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A Dissertation entitled

Spectroscopic Ellipsometry Studies of II-VI Semiconductor Materials and Solar Cells

by Jie Chen

Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Physics

_____________________________________
Dr. Robert W. Collins, Committee Chair

_____________________________________ Dr. Patricia Komuniecki, Dean College of Graduate Studies

The University of Toledo December 2010

Copyright 2010, Jie Chen This document is copyrighted material. Under copyright law, no parts of this document may be reproduced without the expressed permission of the author.

An Abstract of Spectroscopic Ellipsometry Studies of II-VI Semiconductor Materials and Solar Cells by Jie Chen

Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Physics

The University of Toledo December 2010

The multilayer optical structure of thin film polycrystalline II-VI solar cells such as CdTe is of interest because it provides insights into the quantum efficiency as well as the optical losses that limit the short-circuit current. The optical structure may also

correlate with preparation conditions, and such correlations may assist in process optimization. A powerful probe of optical structure is real time spectroscopic

ellipsometry (SE) that can be performed during the deposition of each layer of the solar cell. In the CdCl2 post-deposition treatment process used for thin film polycrystalline

II-VI solar cells, the optical properties of each layer of the cell change during the process due to annealing as well as to the elevated temperature. In this case, ex-situ SE before

and after treatment becomes a reasonable option to determine the optical structure of CdCl2-treated CdTe thin film solar cells. CdTe solar cells pose considerable challenges for analysis by ex-situ SE. iii First, the

relatively large thickness of the as-deposited CdTe layer leads to considerable surface roughness, and the CdCl2 post-deposition treatment generates significant additional oxidation and surface inhomogeneity. Thus, ex-situ SE measurements in reflection from the free CdTe surface before and after treatment can be very difficult. Second, SE from the glass side of the cell is adversely affected by the top glass surface which generates a reflection that is incoherent with respect to the reflected beams from the thin film interfaces and consequently depolarization if collected along with these other beams. In

this research, the first problem is solved through the use of a succession of Br2+methanol treatments that smoothens the CdTe free surface, and the second problem is solved through the use of a 60 prism optically-contacted to the top glass surface that eliminates the top surface reflection. In addition, the succession of a Br2+methanol treatment not only smoothens the CdTe surface but also enables CdTe etching in a layer-by-layer fashion. In this way, it has been possible to track the optical properties of the CdTe

component layer as a function of depth from the surface toward the CdS/CdTe interface in order to gain a better understanding of the film structure. In this study, ex-situ spectroscopic ellipsometry was applied first to investigate the optical properties of the TEC-15 glass substrate, and then to extract the optical properties of thin film CdTe and CdS both as-deposited and CdCl2-treated. After obtaining all the

optical properties of the solar cell component layer materials, a comprehensive ex-situ SE analysis has been applied to extract the optical structure of a single thin film of CdCl2-treated CdTe, and finally to obtain the optical structure of the CdCl2 iv

post-deposition treated CdTe solar cell. Based on the fundamental studies in this thesis, various aspects of the solar cell structure after the complicated CdCl2 treatment have been determined. In future work

the role of the key parameters of CdCl2 post-deposition treatment process will be explored including: the temperature and treatment time. As a result, a correlation will be established between solar cell performance and film structure. Finally, an

understanding of how solar cell structure can be optimized to achieve the highest solar cell performance may be possible through improved control of the CdCl2 post-treatment process.

Table of Contents

Abstract Table of Contents List of Tables List of Figures 1 Introduction to Spectroscopic Ellipsometry

iii vi ix xii 1

1.1 History............1 1.2 Purpose ......2 1.3 Data measured by ellipsometry..3 1.4 Mathematical derivation....5 1.5 Spectroscopic ellipsometer used in the study..10 1.6 Data analysis12 2 Introduction to CdTe-based Solar Cells..18 2.1 CdTe-based solar cell structures .18 2.2 Deposition method and process steps..21 2.3 Application of spectroscopic ellipsometry as an analysis technique ..22 3 Optical Properties of TEC-15 Glass....26 3.1 Introduction..26 vi

3.2 Experimental details.....28 3.3 Data analysis and results......29 4 Verification of the Chemical Etching Process for CdTe Depth Profiling52 4.1 Introduction..52 4.2 Structural evolution of CdTe during etching: experimental details.54 4.3 Structural evolution of CdTe during etching: results and analysis .............57 4.4 Detection of a-Te on etched CdTe: experiment details59 4.5 Detection of a-Te on etched CdTe: results and analysis..60 5 Optical Properties of Thin Film CdTe and CdS before and after CdCl2 Post-deposition Treatment...71 5.1 Introduction..71 5.2 Optical properties of as-deposited CdTe and CdS films deposited on c-Si substrates..72 5.3 Optical properties of CdCl2 post-deposition treated CdTe and CdS78 5.4 Etch-back profiling of CdTe thin film structure after post-deposition treatments... . 84 6 Optical Structure of As-deposited and CdCl2-treated CdTe Superstrate Solar Cells94 6.1 Introduction..94 6.2 Experimental details.96 6.3 Results and discussion: film side and prism side measurements.....97 vii

6.4 Results and discussion: through the glass measurements..113 6.5 Summary119 7 RTSE Analysis of CdTe Solar Cell Structures in the Substrate Configuration.. 120 7.1 Introduction120 7.2 Analysis of CdTe deposition on rough molybdenum121 7.3 Ex situ spectroscopic ellipsometry analysis of a CdTe solar cell in the substrate configuration.138 8 Spectroscopic Ellipsometry Studies of II-VI Alloy Films....152 8.1 Introduction152 8.2 Top cell material candidates: Cd1-xMnxTe and Cd1-xMgxTe...154 8.3 Bottom cell material: Cd1-xHgxTe..172 9 Summary and Future Directions...178 9.1 Summary178 9.2 Future directions183 References Appendix A Dielectric functions 207 196

viii

List of Tables

4.1 Best fit parameters and confidence limits that define Eqs. (4.1) and (4.2) for the dielectric function of a-Te. ....63

5.1 Fitting results for single crystal and thin film polycrystalline CdTe using an analytical model consisting of four critical points and one T-L background

oscillator. ...74

5.2 Fitting results for single crystal and thin film polycrystalline CdS using an analytical model consisting of three critical points and one T-L background

oscillator.75

5.3 Best fit dielectric function parameters comparing single crystal, CdCl2-treated, and as-deposited CdTe samples. ...79

5.4 Best fit dielectric function parameters for as-deposited CdS on a fused silica prism, CdCl2-treated CdS on the prism, and. as-deposited CdS on

c-Si. ....83 ix

6.1 Dielectric function library used in spectroscopic ellipsometry data analyses for CdTe solar cells. ..98

6.2 Best fitting parameters added step by step to improve the mean square error (MSE) in modeling through-the-glass SE measurements of a CdTe solar

cell. ..116

6.3 Multilayer stack thicknesses, non-uniformity, and compositions, the latter expressed in terms of volume fractions, along with parameter confidence limits for the best fit to SE data obtained through the glass. .118

7.1 CdTe bulk and surface roughness layer thicknesses for the top four CdTe bulk layers. ..126

7.2 Five models used to evaluate the Mo overlayer thickness using reference dielectric functions from the literature. ...134

7.3 Best fit critical point and Tauc-Lorentz oscillator parameters describing the inverted dielectric function of polycrystalline ZnTe:Cu. The exponents n are fixed at the single crystal values of Table 7.4. ...143

7.4 Best fit critical point and Tauc-Lorentz oscillator parameters for single crystal ZnTe. ..144

7.5 Best fitting parameters added step by step to improve the standard mean square error (MSE) in the ellipsometric analysis of a CdTe solar cell in the substrate configuration. ..150

8.1 Deposition parameters used to prepare the CdxMg1-xTe and CdxHg1-xTe thin films. 155

8.2 Critical point parameters of transition energy and width obtained in the fits to the dielectric functions of Fig. 8.9. 167

8.3 Critical point energies and E0 broadening parameters for two as-deposited Cd1-xMgxTe alloys from spectroscopic ellipsometry. Also shown are corresponding

results for as-deposited and CdCl2-treated CdTe. 172

8.4 Energy position and width of the critical point generating the strongest peak in 2 for as-deposited thin film Cd1-xHgxTe. ..174

xi

List of Figures

r 1-1 Schematic representation of the electric field vector trajectory E (r0 , t ) for an elliptically

r polarized light wave at a fixed position r0 versus time. Q is the tilt angle between the ellipse major axis a and the p-axis, measured in counterclockwise-positive sense when facing the light source.

is the ellipticity angle given by tan-1(b/a). ...........

..7

1-2 Reflection of a polarized light wave at an interface between two media. ...9

1-3 Spectroscopic ellipsometer used in this research mounted in the ex-situ mode of operation. ...11

1-4 Simplified flow chart of the data analysis procedure. ...13

1-5 Optical model and physical structure of a c-Si wafer used as a substrate. ............ ............14

2-1 The substrate structure for CdTe solar cells. .19 xii

2-2 The superstrate structure for CdTe solar cells. ..19

3-1 The multilayer structure of the TEC-15 glass substrate. ...28

3-2 Simple model deduced from the analysis of the transmittance and ellipsometric (, ) spectra of Figs. 3-3 3-5 for the soda lime glass substrate. The surface roughness is obtained in a best fit of the (, ) spectra. ....31

3-3 Best fit simulated and experimental normal incidence transmittance spectra T vs. photon energy for an uncoated soda lime glass substrate used in the fabrication of TEC glasses. ..31

3-4 Best fit simulated and experimental ellipsometric angle = tan1 (|rp/rs|) vs. photon energy for an uncoated soda lime glass substrate used in the fabrication of TEC glasses. The angle of incidence is 60. ..32

3-5 Best fit simulated and experimental ellipsometric angle = p s vs. photon energy for an uncoated soda lime glass substrate used in the fabrication of TEC glasses. The angle of incidence is 60. ...32

3-6 Index of refraction (left) and extinction coefficient (right) vs. wavelength for the xiii

uncoated soda lime glass substrate.

The index of refraction results are derived from

the ellipsometric spectrum whereas the extinction coefficient results are derived from the transmittance spectrum. The data values are tabulated in Appendix A. ......

33

3-7 Model with best fitting parameters obtained in the analysis of the transmittance and ellipsometric (, ) spectra of Figs. 3.8 and 3.9 for the soda lime glass substrate coated with a single layer of undoped SnO2. .34

3-8 Normal incidence transmittance T vs. photon energy for a soda lime glass substrate coated with a single layer of undoped SnO2, the first layer in the fabrication of TEC glasses. Experimental data (broken line) and a best fit simulation (solid line) are shown. 35

3-9 Ellipsometric angles and vs. photon energy for a soda lime glass substrate coated with a single layer of undoped SnO2. Experimental data (broken lines) and best fit simulations (solid lines) for an angle of incidence of 60 are shown. .. 35

3-10 (a,b) Real and imaginary parts of the dielectric function 1 and 2 vs. photon energy for undoped SnO2 that forms the first layer of TEC glasses; (c) analytical expression xiv

for the complex dielectric function of (a,b) along with the best-fit free parameters and their confidence limits. ...36

3-11 Model adopted for the analysis of the transmittance and ellipsometric (, ) spectra of Figs. 3.12 and 3.13 obtained on the soda lime glass substrate coated with a single layer of SiO2. .37

3-12 Normal incidence transmittance T vs. photon energy for a soda lime glass substrate coated with a single layer of SiO2, which is used as the second layer in the fabrication of TEC glasses; experimental data (broken line) and a best fit simulation (solid line) are shown. ...38

3-13 Ellipsometric angles and vs. photon energy for a soda lime glass substrate coated with a single layer of SiO2, which is used as the second layer in the fabrication of TEC glasses; experimental data (broken lines) and a best fit simulation (solid lines) are shown. ..38

3-14 (a) Real (solid line) and imaginary (broken line) parts of the dielectric function vs. photon energy for SiO2 that forms the second layer of the TEC glasses. The

imaginary part of the dielectric function vanishes; (b) mathematical expression for the dielectric function in (a) along with the best fitting parameters and their xv

confidence limits. ..39

3-15 Real and imaginary parts of the dielectric function vs. photon energy for the SiO2 that forms the second layer of the TEC glasses (solid lines) for comparison with the reference data of a thermally-grown SiO2 on crystalline silicon. .. ..39

3-16 Best fit sample structure for a soda lime glass substrate coated with a two layer stack of undoped SnO2 and SiO2, which are the first two layers used in the fabrication of TEC glasses. ..40

3-17 Ellipsometric angles (, ) at an angle of incidence of 60 and transmittance T at normal incidence plotted versus photon energy for a soda lime glass substrate coated with a two layer stack of undoped SnO2 and SiO2, which are the first two layers used in the fabrication of TEC glasses. ..41

3-18 Best fit multilayer stack for a complete TEC-15 glass sample.

The layered

structure includes thin undoped SnO2, thin SiO2, and thick doped SnO2:F with surface roughness on top. The previously-determined dielectric functions were

used for the soda lime glass and the two thin layers. 43

xvi

3-19 Normal incidence transmittance T vs. photon energy for a complete TEC-15 glass sample consisting of a soda lime glass substrate coated with layers of undoped SnO2, SiO2, and top-most doped SnO2:F. Experimental data (broken line) and a best fit

simulation (solid line) are shown. .43

3-20 Ellipsometric angles and at a 60 angle of incidence plotted vs. photon energy for a complete TEC-15 glass sample consisting of a soda lime glass substrate coated with layers of undoped SnO2, SiO2, and top-most doped SnO2:F. The broken lines indicate experimental spectra and the solid lines indicate the best fit simulation. .44 3-21 Real and imaginary parts of the dielectric function 1 and 2 vs. photon energy for doped SnO2:F that forms the top-most layer of TEC-15 glass. These results are

obtained as a best fit analytical expression at low energies where the film is semitransparent and by an inversion of (, ) data at high energies where the film is opaque. ..44

3-22 (a) The analytical equation for the dielectric function of the top-most SnO2:F layer of TEC-15 that holds below 4.4 eV; also shown is (b) a table of the best fit parameters in the equation and their confidence limits. 45

3-23 Multilayer structure with best-fit parameters for a complete TEC-7 glass sample. xvii

The layered structure includes thin undoped SnO2, thin SiO2, and a thick layer of doped SnO2:F with surface roughness on top. The previously determined dielectric

functions for TEC-15 glass were used here for this TEC-7 glass sample. 47

3-24 Multilayer structure with best-fit parameters for a complete TEC-8 glass sample. The layered structure includes thin undoped SnO2, thin SiO2, and a thick layer of doped SnO2:F with surface roughness on top. The previously determined dielectric

functions for TEC-15 glass were used here for this TEC-8 glass sample. 47

3-25 Transmittance T vs. photon energy for a complete TEC-7 glass sample; experimental data (broken line) and simulated results based on the ellipsometric model (solid line) are shown (left). The difference between the two data sets is shown at the right. ..49

3-26 Normal incidence transmittance T vs. photon energy for a complete TEC-8 glass sample; experimental data (broken line) and simulated results based on the ellipsometric model (solid line) are shown (left). The difference between the two

data sets is shown at the right. ...50

xviii

3-27 For TEC-7 glass, the normal incidence scattering results predicted by combining ellipsometry and normal incidence specular transmittance are shown in comparison with experimental normal incidence integrated scattering data from a diffuse transmission experiment. Different TEC-7 samples were used for the two different

data sets. 51

3-28 For TEC-8 glass, the normal incidence scattering results predicted by combining ellipsometry and normal incidence specular transmittance are shown in comparison with experimental normal incidence integrated scattering data from a diffuse transmission experiment. Different TEC-8 samples were used for the two different

data sets. 51

4-1 A schematic of optical models used to evaluate a CdTe film by optical depth profiling during both deposition and etching processes. ..56

4-2 The evolution of void volume fraction within the top 100 of the bulk layer as a function of CdTe bulk layer thickness obtained during the deposition and etching processes. ...58

4-3 Schematic of the sample structural changes that occur in the last three etching steps for a CdTe film on c-Si. The starting thickness of this CdTe film is 3500 . xix

.60

4-4 Ellipsometric spectra for a smoothened CdTe film on a c-Si wafer measured at angle of incidence of 63. The broken lines represent data measured before the first

additional Br2+methanol etching step, and the solid lines represent data measured after the 6th additional Br2+methanol etching step. the two is 18 seconds. The total etching time between

The starting CdTe thickness before any etching was 3 m. ...

.61

4-5 Ellipsometric spectra for a CdTe thin film on a crystalline Si substrate after the 36th and 37th etch steps for comparison. The starting CdTe film thickness was 3500 . ..

.64

4.6 Ellipsometric spectra for a CdTe thin film on a crystalline Si substrate with a starting thickness of 3500 measured after the 37th (left) and 36th (right) etching steps (data points). Also shown are their best fits (broken lines). .... .64

4-7 Model and best-fit parameters used for the analysis of the ellipsometric spectra of Fig. 4.6 (left panel) collected after the 37th etching step applied to a CdTe film on a crystalline Si substrate. Because the CdTe film is completely removed, this xx

analysis provides the structure of the c-Si substrate.

MSE indicates the mean

square error in the fit. 65

4-8 Model and best fit parameters used for the analysis of the ellipsometric spectra of Fig. 4.6 (right panel) collected after the 37th etching step applied to a CdTe film on a crystalline Si substrate. c-Si substrate. This analysis yields the structure of the a-Te layer on the

The void volume fraction in the a-Te layer has been obtained by

expressing the a-Te layer in this study of polycrystalline CdTe as a mixture of the a-Te obtained in a previous study of single crystal CdTe along with a void component. 65

4-9 Real and Imaginary parts of the dielectric function 1 and 2 vs. photon energy for a-Te generated through Br2+methanol etching of a polycrystalline CdTe film. .65

4-10 A comparison of the a-Te optical properties deduced in this study (see Fig. 4.9) with the literature reference optical properties of a-Te from 1.5~6 eV, the latter obtained by etching single crystal CdTe. .66

4-11 Ellipsometric spectra for a CdTe thin film on a crystalline Si substrate with a starting thickness of 3500 measured after the 35th etch step (left panel). xxi Also shown is

the best fit and associated model deduced in the analysis of the ellipsometric spectra in order to extract the a-Te/CdTe/c-Si structural parameters (right panel). ... .68

4-12 Experimental and best fit spectra (left panel) along with the best fit parameters and model (right panel) for comparison with the results of Fig. 4.11, but without introducing an a-Te component into the model. Such a model leads to a higher MSE. ..68

4-13 Ellipsometric spectra and the best fit (left panel) for a smoothened CdTe film with a starting thickness of 3 m obtained before the first additional etch after smoothening. Also shown is the model and best fit parameters used in the analysis of the ellipsometric spectra over the energy range of 2 to 6 eV in order to deduce the a-Te volume fraction in the surface roughness layer (right panel). ... .69

4-14 Experimental and best fit spectra (left panel) along with the best fit model and parameters (right panel) for comparison with the results of Fig. 4.13, but without introducing an a-Te component into the model. This ellipsometric analysis is

associated with a 3 m thick smoothened CdTe film before the first additional etch after smoothening. .69 xxii

4-15 Ellipsometric spectra and the best fit (left panel) for a smoothened CdTe film with a starting thickness of 3 m obtained after the 6th additional etch after smoothening. Also shown is the model and best fit parameters used in the analysis of the ellipsometric spectra over the energy range of 2 to 6 eV in order to deduce the surface roughness thickness and the a-Te volume fraction in the CdTe structure (right panel). 70

4-16 Experimental and best fit spectra (left panel) along with the best fit model and parameters (right panel) for comparison with the results of Fig. 4.15 but without introducing an a-Te component into the model. This ellipsometric analysis is

associated with a 3 m thick smoothened CdTe film after the 6th additional etch. ... .70

5-1 The room temperature dielectric functions of single crystal CdTe (broken lines) and a CdTe film deposited at 188C (solid lines). The downward arrows point to the energy values of the four critical point transitions E0, E1, E1+1, and E2. .73

5-2 Band structure of CdTe. .....74

xxiii

5-3 The room temperature ordinary dielectric functions of single crystal (wurtzite) CdS (broken lines) in comparison with the polycrystalline thin film CdS deposited on c-Si at 225 C (solid line). The three downward arrows point to the energy values of the critical point transitions. 75

5-4 (left) Best fit analytical models of the room temperature dielectric functions for two CdTe films of thickness approximately 1000 , obtained from the same deposition but with different post-deposition processing: as-deposited (no treatments; broken

line) and CdCl2-treated for 5 min at 387C (solid line); (right) a comparison between the CdCl2-treated CdTe film (solid line) and single crystal CdTe (broken line). .. .78

5-5 A schematic of the sputtering chamber for CdTe/CdS deposition on a fused silica prism. .81

5-6 (left) Best fit analytical models for the room temperature dielectric functions of a CdS film as-deposited on a fused silica prism measured from the prism side and on a c-Si wafer measured from the ambient side; (right) best fit analytical model for the

room temperature dielectric functions of CdS measured from the prism side before and after a 30 min CdCl2 treatment at 387C. ...82

xxiv

5-7 Resonance energies En (upper panel) and linewidths n (lower panel) for the critical point transitions in single crystal CdTe (broken lines) and in db ~ 1000 thick CdTe films sputter-deposited at different temperatures (points), all measured at 15C. 85

5-8 Critical point energies (upper panel) and widths (lower panel) as functions of CdTe bulk layer thickness during etching by Br2+methanol for co-deposited CdTe films processed in three different ways: (i) as-deposited, (ii) annealed in Ar for 30 min, and (iii) CdCl2 treated for 5 min. The deviations at low thickness are due to the onset of semi-transparency at the E1 critical point energy. .86

5-9 Relative void volume fractions as functions of CdTe bulk layer thickness during etching by Br2+methanol for co-deposited CdTe films processed in three different ways: (i) as-deposited, (ii) thermally annealed in Ar for 30 min, and (iii) CdCl2-treated for 5 min. For the as-deposited and annealed films, the void fraction For the CdCl2-treated film,

is scaled relative to the observed highest density film.

the void volume fraction is scaled relative to single crystal CdTe. ... .88

5-10 Energy of the E1 transition (upper panel) and its width E1 (lower panel) as functions of CdTe bulk layer thickness in successive Br2+methanol etching steps for xxv

~3000 thick CdTe films. The two films were processed under identical conditions including fabrication on c-Si wafer substrates and annealing in Ar at 387C for 30 minutes. The data for experiment #1 are the same as those depicted in Fig. 5.8. . .90

5-11 Energy of the E1 transition (upper panel) and its width E1 (lower panel) as functions of CdTe bulk layer thickness in successive Br2-methanol etching steps for ~3000 thick CdTe films. The two films were processed under similar conditions including The data

fabrication on c-Si wafer substrates and CdCl2 treatment for 5 minutes.

for experiment #1 are the same as those depicted in Fig. 5.8. ....................................... .90

5-12 Void volume fraction as a function of CdTe bulk layer thickness in successive Br2-methanol etching steps for ~3000 thick CdTe films in a second experiment for comparison with the results in Fig. 5.9. Two different post-deposition processing

procedures were used: (i) an anneal in Ar for 30 min, and (ii) a CdCl2-treatment for 5 min. For the Ar annealed films, the void fraction is scaled relative to the depth at For the CdCl2-treated film, the void volume

which the highest density is observed.

fraction is scaled relative to single crystal CdTe. The void structure for the film annealed in Ar is attributed to structure in the as-deposited film (as in Fig. 5.8). In

contrast, the void structure for the CdCl2 treated film is associated with extensive xxvi

near-surface roughness. .92

6-1 Evolution of the surface roughness thickness and a depth profile of the void volume fraction plotted versus bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk layer thickness of an as-deposited CdTe component of a solar cell. ..99

6-2 (a, left) Evolution of the surface roughness thickness and a depth profile of the void volume fraction plotted versus bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk layer thickness of the CdCl2-treated CdTe component of a solar cell; (b, right) a schematic structure suggested from (a). .. ...100

6-3 (left) Depth profiles of the critical point energies of the E1, E1+1 and E2 transitions in the as-deposited CdTe layer of a solar cell, plotted versus bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk thickness; (right) depth profiles of the linewidths of the E1, E1+1 and E2 transitions obtained in the same experiment. ...103

6-4 (a, top left) Depth profiles of the critical point energies of the E1, E1+1 and E2 transitions in the CdCl2-treated CdTe layer of a solar cell, plotted versus the bulk xxvii

layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk thickness; (b, top right) depth profiles of the linewidths of the E1, E1+1 and E2 transitions obtained in the same experiment; (c, bottom) a schematic structure suggested from (b). ..104

6-5 Energies of the E1, E1+1, and E2 transitions as functions of CdTe bulk layer thickness in successive etches of a CdCl2 treated CdTe solar cell that reach within 0.1 m of the CdS/CdTe interface. ..106

6-6 Broadening parameters E1, E1+1, and E2 as functions of CdTe bulk layer thickness in successive etches of a CdCl2 treated CdTe solar cell that reach within 0.1 m of the CdS/CdTe interface. ...106

6-7 Experimental pseudo-dielectric function spectra for the CdTe solar cell of Figs. 6.2 and 6.4 after the 15th etching step; also shown is the best fit using the structural model of Fig. 6.8. 109

6-8 Structural model for the CdTe solar cell after the 15th etch step that provides the best fit in Fig. 6.7. ...109

6-9 Ex situ SE spectra in (, ) (symbols) (a) from the free CdTe surface after 8 xxviii

Br2+methanol etching steps and (b) from the prism/glass side without etching. The best fit results (solid lines) yield the structural parameters in Figs. 6.10 and 6.11, including the thicknesses of the CdTe roughness, CdTe bulk, CdTe/CdS interface, and CdS bulk layers, as well as the volume fractions of CdS/CdTe in the interface layer and void in the CdS bulk layer. ..110

6-10 The best fit results from the free CdTe surface after 8 Br2+methanol etching steps yielding the thicknesses of the CdTe roughness, CdTe bulk, CdTe/CdS interface, and CdS bulk layers, as well as the volume fractions of CdS/CdTe in the interface layer and void in the CdS bulk layer. 111

6-11 The best fit results from the prism/glass side without etching yielding the thicknesses of the CdTe roughness, CdTe bulk, CdTe/CdS interface, and CdS bulk layers, as well as the volume fractions of CdS/CdTe in the interface layer and void in the CdS layer. ...111

6-12 CdS and CdTe/CdS interface layer thicknesses deduced from spectra collected through the prism/glass (solid line) and from spectra collected from the CdTe surface in successive etches (points, dotted line extrema). ..113

6-13 Multilayer stack used to model the thicknesses and compositions of the individual xxix

layers of the CdTe solar cell.

The SE beam enters through the glass, and the

reflection from the top surface is blocked since it is incoherent with respect to the reflection from the glass/film interface. ..114

6-14 Step-by-step MSE reduction by adding one fitting parameter at a time.

Starting

with the CdTe thickness as a variable, each additional parameter was subsequently fitted. It was found that fitting the SnO2:F thickness provided the greatest Similar methodology was

improvement in MSE among all 2-parameter attempts.

used for all 12 parameters. Circular points indicate the best n-parameter fit with n given at the top and the added parameter given in Table 6.2. .115

6-15 Ellipsometric spectra (points) in (top) and (bottom) at an angle of incidence of 60 as measured through the glass at a single point on a 3 x 3 cm2 CdTe solar cell sample. The solar cell was treated with CdCl2 but no back contact processing was performed. Also shown is a best fit (lines) using the model structure of Fig. 6.13

with the parameters listed in Table 6.3. ...118

7-1 Time evolution of (, ) at 5 photon energies selected from 706-point spectra acquired during sputter deposition of CdTe on a Mo coated glass slide. The full spectral acquisition time was 2 s and the angle of incidence was 65.68. ..122

xxx

7-2 Flow chart of the three-iteration <MSE> minimization procedure for CdTe film growth on a rough Mo film substrate. .127 7-3 The schematic structure describing the final optical model for deposition on rough Mo. ..128

7-4 The schematic structures describing the interface filling (left) and bulk layer growth (right) models for the first interface layer. ...129

7-5 (Left) MSE, which is a measure of the quality of the fit to RTSE data, for the complete CdTe deposition using optical models for the CdTe film consisting of one bulk layer (broken line) and four bulk layers (solid line). In both cases a one-layer

model for surface roughness was employed; (right) the MSE for the model with four bulk layers is shown on an expanded scale. 130

7-6 Evolution of the surface roughness thickness versus deposition time determined using a four-layer model for CdTe film growth on rough Mo. The spikes in the surface

roughness thickness result from the consideration of each bulk layer individually with an independent surface roughness layer. In this case, the surface roughness

layer on the underlying layer is instantaneously transformed into an interface layer at the vertical broken lines upon initial growth of the overlying layer, whose roughness layer starts from zero thickness. ..132 xxxi

7-7 Time evolution of the CdTe overlayer volume percent during interface filling of the underlying CdTe roughness layer for CdTe growth on Mo. 132

7-8 (Left) Evolution of the individual bulk layer thicknesses versus deposition time determined using a four-layer model for CdTe film growth on Mo; (right) evolution of effective thickness of CdTe, including all bulk, interface, and surface layer components. .133

7-9 Mo dielectric function at a nominal temperature of 200 C acquired by inversion assuming a Mo substrate roughness thickness of 79.6 (solid line). For the

overlying CdTe, four bulk layers and a roughness layer are used to describe the best fit model. For the first bulk layer, the Mo/CdTe interface roughness, the CdTe bulk,

and CdTe surface roughness layer thicknesses di, db, ds, respectively, are determined in a dynamic analysis, in which case the criterion is the minimum average MSE. The Mo/CdTe interface roughness thickness di is taken to be the same as the Mo substrate film roughness thickness. Also shown is the Mo dielectric function at room temperature before heating to the deposition temperature as determined by inversion, again assuming a Mo surface roughness layer thickness of 79.6 (broken line). ... 134

7-10 Real (top panel) and imaginary (bottom panel) parts of the dielectric functions of the xxxii

four layers [(a)-(d)] of a CdTe thin film deposited on rough Mo. These results are determined from inversion, after determining the CdTe roughness and bulk layer thicknesses through minimization of the average MSE obtained throughout the layer analysis; (e) also shown is a comparison of the first layer dielectric function of CdTe deduced in this study with that of CdTe deposited on a smooth c-Si substrate at a nominal temperature of 200 C. In (b)-(d) comparisons are provided between the

dielectric function of a given layer and that of the layer underneath it. ...137

7-11 Comparison of the surface roughness thickness at the end of the deposition for a 1496.5 thick CdTe film on Mo as deduced by RTSE with the relative surface height distribution and rms roughness from AFM. .138

7-12 A comparison of measured pseudo-dielectric functions (solid lines) for Mo thin films deposited by sputtering (a) on glass and (b) on Kapton. Also shown are the fits (broken lines) using a reference dielectric function for dense Mo determined separately, and the multilayer models depicted in the insets. ..140

7-13 Ellipsometric spectra (solid lines) and best fit (broken lines) using the structural model and best fit parameters shown in the inset. The dielectric function is

determined simultaneously using a model assuming a sum of critical point structures. xxxiii

The resulting dielectric function is shown in Fig. 7.14. ..142

7-14 Dielectric function of thin film ZnTe:Cu prepared by magnetron sputtering with 1 wt.% Cu in the ZnTe target (solid lines). A model consisting of four critical points The data points are literature

in the band structure has been used in this analysis.

results for single crystal ZnTe. 144

7-15 Step-by-step MSE reduction by adding one fitting parameter at a time. Starting with the CdTe thickness as a variable, each additional parameter was subsequently fitted. It was found that fitting the CdS thickness provided the greatest improvement in MSE among all 2-parameter attempts. Similar methodology was used for all 14 parameters. Circles connected by the solid line indicate the best n-parameter fit with n given at the top and the added parameter given in Table 7.5. ..147

7-16 Ellipsometric spectra for a CdTe solar cell deposited on Mo in the substrate configuration (points). measurement. The cell was exposed to a CdCl2 treatment before this

The top contact of the solar cell is not incorporated over the area The solid line

probed, leading to the structure: ambient/CdS/CdTe/ZnTe:Cu/Mo.

depicts the optical model shown in Fig. 7.17. .148

7-17 Optical model for a CdTe solar cell in the substrate configuration (excluding the top xxxiv

contact) deposited on a Mo film surface.

This model and the best fit parameters

provide the solid line results in Fig. 7.16. ...151

8-1 Current-voltage and normalized quantum efficiency spectra for a champion 16.5% efficient CdTe/CdS thin-film solar cell. ..152

8-2 Two-terminal tandem cell based on Cd1-xMgxTe and Cd1-xHgxTe absorbers. ...154

8-3 Real (a) and imaginary (b) parts of the pseudo-dielectric functions of RF sputtered CdTe (Eg = 1.50 eV), Cd1-xMnxTe (Eg = 1.63 eV) and Cd1-xMgxTe (Eg = 1.61 eV) films all in the as-deposited state; (c) Pseudo-dielectric function of as deposited Cd1-xMnxTe samples after different storage times in laboratory ambient: (1) immediately after Br2/methanol etch; (2) 3 weeks after deposition; and (3) 1.5 years after deposition. ...158

8-4 Best fit (lines) to the second derivative of the experimental pseudo-dielectric function (points) for the as-deposited Cd1xMnxTe film of Fig. 8.3 (c: immediately after etch). The three CP transitions, E1, E1 + 1, and E2, are indicated by arrows with best fit energies of 3.352, 3.884, and 5.033 eV, respectively. The composition of x=0.06

can be estimated by the empirical relationship between E1, the strongest CP in this xxxv

case, and the composition. ...160

8-5 Variation of the pseudo-dielectric function of as deposited Cd0.94Mn0.06Te with time after Br2/methanol etching, measured in situ at room temperature during exposure to laboratory ambient. ..161

8-6 Pseudo-dielectric functions of as-deposited and one-step and two-step CdCl2 treated Cd0.94Mn0.06Te samples. ...161

8-7 Index of refraction and extinction coefficient of amorphous TeO2. .162

8-8 Pseudo-dielectric functions of as-deposited and CdCl2 treated Cd1-xMgxTe samples. ... ...163

8-9 Approximate dielectric functions, i.e., optical properties deduced with a best attempt to eliminate surface effects, for as-deposited films and CdCl2-treated films obtained by SE after Br2+methanol etching that improves the surface quality (points); (a) CdTe; (b) Cd1-xMnxTe; (c) Cd1-xMgxTe; the solid lines show the results of fits to extract critical point energies and widths. The result for the CdCl2-treated

Cd1-xMnxTe could not be fit with a critical point parabolic band model. .. ...166 xxxvi

8-10 Pseudo-dielectric function obtained directly from experimental (, ) data using a single interface conversion formula for a Cd1-xMgxTe sample prepared from a target of CdTe (80 wt.%) + MgTe (20 wt.%) (CGT42). The solid line describes The deduced

experimental data and the dashed line describes the best fit result.

bulk and surface roughness layer thicknesses are shown. ...169

8-11 Best fit analytical dielectric function obtained from an analysis of the experimental (, ) data for the Cd1-xMgxTe sample of Fig. 8.10 prepared from a target of CdTe (80 wt.%) + MgTe (20 wt.%) (CGT42). ..169

8-12 Pseudo-dielectric function obtained directly from experimental (, ) data using a single interface conversion formula for a Cd1-xMgxTe sample prepared from a target of CdTe (60 wt.%) + MgTe (40 wt.%) (CGT92). The solid line describes experimental data and the dashed line describes the best fit result. The deduced

bulk and surface roughness layer thicknesses are shown. ...170

8-13 Best fit analytical dielectric function obtained from an analysis of the experimental (, ) data for the Cd1-xMgxTe sample of Fig. 8.12 prepared from a target of CdTe (60 wt.%) + MgTe (40 wt.%) (CGT92). ..171

xxxvii

8-14 Band gap of as-deposited thin film Cd1-xHgxTe as a function of the substrate temperatures over the range from 23C to 153C. ..174

8-15 Dielectric functions from mathematical inversion and from the corresponding analytical model fit for as-deposited Cd1-xHgxTe films prepared with different substrate temperatures. 175

8-16 Comparison of the real (left) and imaginary (right) parts of the pseudo-dielectric function of as-deposited and CdCl2 treated CdxHg1-xTe films, including results (a) before and (b) after a single Br2/methanol etching step. .177

xxxviii

Chapter One

Introduction to Spectroscopic Ellipsometry

1.1 History The very first ellipsometric studies were performed by Professor Paul Drude (1863~ 1906), even though the term ellipsometry was not used at that time
[1-1]

Drude was

the first to derive the equations of ellipsometry, and was also the first to perform experimental studies on both absorbing and transparent solids. The optical properties determined in these ellipsometry studies were found to be quite accurate. In fact, when Palik compared Drudes results with those obtained 100 years later, the results were amazingly close [1-2]. Because of the absence of fast computation methods made possible by the modern computer, Drude obtained the optical properties of solids at only a few selected wavelengths [1-1]. After Paul Drudes tremendous impact on ellipsometry development, very little progress was reported in the succeeding 70 years. One exception was a 1945 article authored by Alexandre Rothen who described the half-shade method to detect the polarization state change of light upon reflection from a specular surface, and coined the term ellipsometry[1-3]. When laboratory computers became prevalent in the 1960s and 1

1970s, automated ellipsometers for diverse purposes were developed

[1-4]

. Among the

different types of automated ellipsometers developed at that time, two major types are still widely used in the spectroscopic mode of operation: (i) the rotating element ellipsometer
[1-5],

and (ii) the phase modulation (PM) ellipsometer

[1-6]

The photon

energy range of spectroscopic ellipsometry has increased significantly over the years since D. E. Aspnes and A. A. Studna developed the first rotating analyzer spectroscopic ellipsometer covering the full (near-infrared)-to-(near-ultraviolet) range
[1-7]

At the

same time, the instrument development focus was also placed on increasing the speed of full spectroscopic measurement by incorporating a multichannel detection system in the ellipsometer in order to acquire the entire spectral range essentially simultaneously
[1-8]

As a result of this effort, the technique of real time spectroscopic ellipsometry (RTSE) arose for analysis of thin film growth and materials processing. 1.2 Purpose Spectroscopic ellipsometry is used to obtain the optical properties of materials of interest in optical and electronic applications
[1-9]

. Once optical properties of materials

are available, thin film thicknesses can be measured using optical models for single thin film and multilayer samples. Advanced data analysis often enables measurement of
[1-10, 1-11]

thickness and optical properties simultaneously

The measurable thickness For spectroscopic

range for ellipsometry varies from submonolayer to several microns.

ellipsometry measurements of thickness, a wide spectral range is important since the light must penetrate through the thin film, reflect from an underlying interface, return through 2

the film, and proceed to the detector.

In studies of semiconductors, lower energy gap

materials such as CuInSe2 can be analyzed for thickness when the spectral range extends deeper into the infrared. For energies below the semiconductor band gap, the light

remains unabsorbed and reflects from the bottom interface of the film, enabling wave superposition and phase shifts that allow thickness to be determined. This demonstrates

the advantage of spectroscopic ellipsometers with an extended near-IR spectral range, even below the 1.1 eV band gap of the most common Si diode detectors used in ellipsometers. A similar advantage exists for spectroscopic ellipsometers with an

extended ultraviolet spectral range when characterizing the thickness of metal thin films. In addition to thickness, other properties of a film can be determined through ellipsometric measurements performed in real time during the deposition process
[1-12]

These include roughness thickness on the surface of the film and the optical properties of the film. From the latter, the film density deficit (represented by a volume fraction of

voids in the layer), film crystalline quality (represented by a defect density or average grain size), alloy composition, and temperature may be determined. In fact, real time

measurements may also provide a depth profile of the film structure and properties, and even area uniformity of the film. 1.3 Data measured by ellipsometry An ellipsometric measurement provides the angles (, ), corresponding to the relative amplitude ratio (tan) and phase shift difference () between the complex

r r amplitude reflection coefficients for E p and Es , the orthogonal linear electric field
components of a polarized light wave [1-13]. These electric field components are parallel (The overline arrow denotes a

r r ( E p ) and perpendicular ( Es ) to the plane of incidence.

complex vector in which case each vector component has a real amplitude and phase.)
r r The nature of E p and Es for a light wave will be further elucidated in the next section.

% Thus, the quantity measured by ellipsometry is the ratio of the complex amplitude % reflection coefficients for the p-polarized field component ( Rp ) to that for the s-polarized
% field component ( Rs ):
% = % Rp = tan ei ; % R
s

(1-1)

where
% E p ref % % Rp = inc = Rp exp ( i p ) , % E
p

(1-2)

% E ref % % Rs = s inc = Rs exp ( i s ) . % Es Here, the notational style of these equations will be summarized.

(1-3) Generally, the

subscripts p and s identify the wave characteristics for vector components parallel and perpendicular to the plane of incidence, respectively. For example, p and s represent On the

the phase shifts of each orthogonal electric field component upon reflection.

% other hand E p ( s ) denotes the p (s) orthogonal component of the electric field amplitude. The superscripts ref and inc in Eqs. (1-2) and (1-3) refer to the electric field components of the reflected and incident light waves.

As a result, the angles and are defined by:


tan =

% Rp , % R
s

(1-4) (1-5)

= p s .

% R p ( s ) are also called the complex Fresnel coefficients.

% As a complex variable, R p ( s )

provides information on the amplitude change and phase shift of the p (s) field components of the wave upon its reflection from the sample. In fact, the complex

Fresnel coefficients provide the reflected-to-incident amplitude ratio and the

r reflected-minus-incident phase shift for each orthogonal electric field component E p (or r Es ) of the polarized light wave.

1.4 Mathematical derivation In order to understand the derivation of optical properties from the ellipsometric angles (, ), it is necessary to understand first the mathematics of polarized light. When the most general state of elliptically polarized light wave transmits through or reflects from one or more interfaces between media at a non-normal angle of incidence, the polarization change can be defined in terms of a change in tilt angle and ellipticity angle of the general polarization ellipse. This change depends on the angle of incidence and the optical properties and thicknesses of the media. The elliptically polarized state

of monochromatic light in any medium assumed to be isotropic can be described by

r decomposing the beam into two orthogonal components which are linear and parallel ( E p )

r as well as linear and perpendicular ( Es ) to the plane of incidence.

Both components are

plane waves and a superposition of such components is described by [1-14]:

r r r r r E ( r , t ) = E0 exp [i (q r t ) ] ;
where

(1-6)

r q

is the complex propagation vector,

is the wave frequency,

r and E0 determines the polarization state of the wave. In this linear p-s basis, r r r i E0 = E p + Es = E p e p p + Es ei s s .
(1-7)

r For this general polarization state of the light wave, the endpoint of the vector E0 r traces an ellipse as a function of time t during propagation at a fixed position r0 .
complete cycle is made in a time = A

. The plane wave also travels in space with a

phase velocity of v =

% Re(q)

, and the endpoint of the field vector traverses one full

ellipse after a distance equal to the wavelength =

2 . % Re(q)

% Here is q defined as the

r % complex magnitude of the propagation vector: q = qq .

r r E (r0 , t )

r r r = r0
r Figure 1-1 Schematic representation of the electric field vector trajectory E (r0 , t ) for an r elliptically polarized light wave at a fixed position r0 versus time. Q is the tilt angle between the ellipse major axis a and the p-axis, measured in counterclockwise-positive sense when facing the light source. is the ellipticity angle given by tan-1(b/a). r

r In Equation 1-6, the wavevector q defines the propagation direction. r assumes q is parallel to the z-axis, the wave becomes:

If one

r r % E ( r , t ) = E0 exp [i ( qz t ) ] ;
where

(1-8)

% q = c
2

4 r % 2 r + i = c N ,

(1-9)

or
% % q = N . c

Here c is the speed of light in vacuum. At the light wave frequency , r and r denote the real dielectric function and real optical conductivity of the medium in which the wave
7

% travels, and N is its complex index of refraction, where [1-15]

4 r % N = n + ik = r + i

(1-10)

Here n is the (real) index of refraction, and k is the extinction coefficient of the medium.
% It should be noted that Re(q ) =

n , so the phase velocity of the wave is v =

c and the n

wavelength is =

2 c 2 % % = v as expected. Next q and N are substituted into n

Equation 1-8 to give


r r r nz kz E (r , t ) = E0 exp t . exp i c c

(1-11)

% % In addition to the complex index of refraction N , the complex dielectric function

is another commonly used quantity to describe the macroscopic optical properties of solids [1-15], where:
% % = 1 + i 2 = N 2 ,

(1-12) (1-13) (1-14)

1 = r = n 2 k 2 , 2 =
4 r

= 2nk .

Ellipsometry measures the change in polarization state of the incident light caused by reflection from one or more interfaces. When an incident linearly polarized light wave reflects from a single interface between two media (see Fig. 1.2), the state of polarization of the reflected beam can assume an elliptical state with the tilt and ellipticity angles depending on the optical properties of the sample.

incident wave p

reflected wave p

.
s Medium 0 Medium 1 Plane of sample i s i
% t

.
p s

.
Plane of incidence s

transmitted wave

Figure 1-2

Reflection of a polarized light wave at an interface between two media.

For the ideal situation of a perfectly planar interface on the atomic scale with no roughness, the optical properties of the reflecting medium can be derived from the ellipsometric angles (, ) as long as the optical properties of the incident medium and the angle of incidence are known [1-13]. In the simplest case of reflection and transmission at the perfectly planar interface between two isotropic media (see Fig. 1.2), the ratio of the complex Fresnel reflection coefficients can be written:
% % N s cos i na cos t % % % R p na cos t + N s cos i % = = % % % Rs na cos i N s cos t % % na cos i + N s cos t ,

(1-15)

% where na is the assumed real refractive index of Medium 0 (ambient, see Fig. 1.2), N s is

the complex index of refraction of Medium 1 (substrate, see Fig. 1.2), i is the angle of

% % incidence and t is the complex angle of refraction. cos t can be obtained from sin i ,
9

% na , and N s by using a complex form of Snells Law:


% cos t = % N s 2 na 2 sin 2 i . % N
s

(1-16)

Then, eliminating cos t from Equation 1-15 yields:

% % N s 2 cos i m na N s 2 na 2 sin 2 i % Rp % = = % Rs % % N s 2 cos i na N s 2 na 2 sin 2 i


% = % na sin 2 i m cos i N s 2 na 2 sin 2 i , % n sin 2 cos N 2 n 2 sin 2
a i i s a i

( (

)( n cos )( n cos m
a i a i

% N s 2 na 2 sin 2 i % N s 2 na 2
2

) , (1-17) sin )
i

(1-18)

% and solving for N s 2 yields:


2 % % 2 = n 2 sin 2 1 + 1 tan 2 . Ns a i i % 1+

(1-19)

% As a result, by using the dielectric function definition in Equation 1-12, s can be

obtained from
1 2 % 2 % s = a sin i 1 + tan i . % 1+
2

(1-21)

Therefore, if one knows (i) a the dielectric function of the ambient; (ii) i the angle of incidence, and (iii) (, ) the measured ellipsometric angles, then one can determine the dielectric function of the reflecting medium.

1.5 Spectroscopic ellipsometer used in the study The spectroscopic ellipsometer used for the study described in this thesis was manufactured by J. A. Woollam Company
[1-16]

. The specific model used here was the This

M-2000DI, which is a rotating-compensator multichannel ellipsometer.


10

ellipsometer covers the photon energy range from 0.74 to 6.50 eV. One complete set of spectra in the ellipsometric angles (, ) (0.74~6.5 eV) can be collected as an average over a minimum of two optical cycles in a time of (30.7 Hz)-1 = 32 ms; thus, the single optical period is 16 ms. Here 30.7 Hz is the mechanical rotation frequency of the compensator. In the case of real time SE applications, specifically for monitoring the CdTe or CdS deposition process, acquisition times from 1 to 3 seconds were chosen. In the case of the ex-situ SE applications, the data acquisition time of 10 seconds was chosen to ensure a higher precision in the measured (, ) spectra. As a result of the multichannel detection capability, this spectroscopic ellipsometer is ideal for in-situ process monitoring and quality control, and specifically for studies of the CdTe-based solar cells as described in this thesis.

Figure 1-3 Spectroscopic ellipsometer used in this research mounted in the ex-situ mode of operation.

The angle of incidence is adjustable for this ellipsometer.

For ex-situ studies, the

ellipsometer is set at angles of incidence ranging from 45 to 75 at 5 intervals. 11

Measurements at different angles of incidence enable one to extract optical properties of unknown materials with greater confidence. Analyses of all spectra apply either numerical inversion or least-squares regression algorithms, or even combinations of these two methods.

1.6 Data analysis As described in Section 1.4, the ellipsometry measurement provides two angles (, ), which quantify the change in the state of polarization of the light wave upon oblique reflection from the sample. Ellipsometry does not directly measure the optical properties and thickness of a thin film; however, and are functions of these characteristics, which require data analysis for extraction [1-17]. The starting point for such analysis is an optical model for the sample. procedure is illustrated in Fig. 1.4. The first step in building an optical model for the sample requires identifying the physical sequence of layers of the sample, including each layers thickness and optical properties, the latter either as fixed functions, analytically defined functions with variable parameters, or even continuously variable functions point by point. For each such A general schematic of the analysis

thickness and optical property variable, it is necessary to provide an estimated value to begin the iteration. As an example, an optical model for a simple silicon substrate sample is shown in Fig. 1.5. In general, building an optical model begins with the

simplest structure; however, complexities such as surface and interface roughness layers

12

can be added as required in order to improve the fit to the data and to conform with any previously established understanding of the nature of the sample.

Measurement (, ) versus E (, ) versus i

Construct optical model

Assign initial values to variables

Fit, compare data and model results

Results: n, k versus E thicknesses

Figure 1-4

Simplified flow chart of the data analysis procedure.

13

n, k, (surface roughness) n, k, (film) n, k, (interface) n, k, (substrate) SiO2/void SiO2 SiO2/c-Si c-Si Figure 1-5

ds db di

ds db di

Optical model and physical structure of a c-Si wafer used as a substrate.

Calculated (, ) spectra are first generated using the optical model with the initial values assigned to the unknown parameters. Then these spectra are compared with the experimental (, ) spectra and iterative adjustments of the unknown parameters are performed in a regression analysis intended to minimize the difference between the two pairs of spectra. If the initial values of the unknown parameters differ substantially from the overall best fit solution, however, then the regression algorithm may fail. The role of this algorithm is to compute the corrections to the initial estimates that yield improved agreement between the calculated and experimental spectra and ultimately the overall best fit. What can occur instead is the identification of a local minimum in the quality

of fit when plotted in the space of the unknown free parameters, and as a result the calculated spectra may differ substantially from the experimental spectra. In contrast, if the initial estimates are close enough to the overall best fit solution, then through iterative corrections, the algorithm can identify the global minimum in the quality of the fit, and as 14

a result improved agreement between the calculated and experimental data is possible. For this reason, the flow chart in Fig. 1.4 shows an iteration step not only in the construction of the model but also in the variation of the initial values typically over a grid in parameter space. In addition to the simplest case of thicknesses as unknown parameters, the least-squares regression method is commonly used to extract the complex dielectric function of one or more materials in the model
[1-17]

When an unknown complex

dielectric function can be expressed as an analytically-defined function of several wavelength-independent parameters such as electronic resonance energies (band gaps), resonance amplitudes (oscillator strengths), and broadening parameters (inverse excitation lifetimes), then the fitting procedure is similar to that of fitting simply thicknesses. All the known values of the parameters are fixed in the model, and the wavelength independent unknown parameters are estimated, including the thicknesses and the optical property parameters. The (, ) spectra associated with these initial estimates are calculated and compared with the experimental (, ) spectra. Then, the least-squares regression algorithm is used to adjust the unknown parameters iteratively so as to minimize the difference between the calculated and experimental ellipsometric spectra. A mean square error (MSE) function is used as the criterion; the iterations are terminated when MSE attains its minimum. If the initial estimates of the unknown

parameters are close enough to the correct values, then the global minimum can be reached; if not, a local minimum can lead to erroneous parameter results. 15

In such analyses, the least-squares regression algorithm uses the weighted mean square deviation given by [1-17]:
1 MSE = 2N M cal exp i exp i i =1
N 2 2 ical iexp + exp

(1-22)

where N is the number of (, ) data pairs versus wavelength or photon energy, and M is the number of unknown free parameters determined in the analysis. Thus, the squares

of the differences between each pair of calculated and experimental data ( cal , exp ) and ( cal , exp ) at a given wavelength or photon energy indicated by the subscript i are
exp exp summed and divided by the standard deviations of the experimental data and ,

respectively, for the associated wavelength.

As a result, spectral points that exhibit a

lower signal to noise ratio, typically at the highest photon energies (6.0~6.5 eV) are weighted less heavily. Once the fit for a given model is successful, a number of various models need to be tested in order to improve the global fit to the data. These models generally start with

the simplest structure, e.g., a single film on a substrate, and then progress to more complicated ones that include surface and interface roughness. Some complications Others may be

may be expected based on an understanding of how thin films grow. unexpected and provide new insights.

In particular for complicated models with many

parameters, the overall best fit parameters must be evaluated for their confidence limits and possible pair-wise or multiple correlations. In addition, the best fit parameters must

be physically meaningful; obviously there should be no zero or negative thickness values.

16

For an intrinsic semiconductor, the index of refraction n must decrease smoothly with increasing at wavelengths longer than that associated with the band gap. In this range,

k should remain at zero, because of the lack of absorption at photon energies below the band gap. Obviously, k cannot be negative; otherwise, the light would be amplified in

traversing the material.

17

Chapter Two

Introduction to CdTe-based Solar Cells

2.1 CdTe-based solar cell structures CdTe-based solar cells can be fabricated in both substrate and superstrate configurations [2-1, 2-2, 2-3]. In the substrate configuration, sunlight enters the active layers

of the cell before reaching the underlying substrate, and thus the substrate need not be transparent. A typical substrate-type deposition process would follow the sequence, Indium-tin-oxide (ITO), denoted by the chemical formula

Mo/CdTe/CdS/In2O3:Sn.

In2O3:Sn whereby Sn is the dopant, is a transparent conducting oxide (TCO) thin film that functions as an electrical contact as well as a window layer through which sunlight is transmitted
[2-1]

In the superstrate configuration which is the configuration used by

industry, the sunlight enters the substrate first, and the substrate must be selected for low absorption over the solar spectrum. Typically there will be a trade-off between low A typical deposition sequence in this

absorption and low cost in module manufacturing.

case is glass/SnO2:F/CdS/CdTe/Cu/Au. A common superstrate for the CdTe solar cell is TEC glass manufactured by Pilkington. TEC glass is a soda-lime glass coated with

successive layers of undoped SnO2, SiO2, and F-doped SnO2, SnO2:F, to achieve the 18

desired sheet resistance, optical properties, and chemical stability.

Another TCO used in

place of In2O3:Sn and SnO2:F in both substrate and superstrate solar cells is ZnO:Al, aluminum-doped zinc oxide. Schematic examples of the substrate and superstrate

configurations are shown in Figs. 2-1 and 2-2. Ambient front contact ITO CdS CdTe back contact Figure 2-1 Mo

The substrate structure for CdTe solar cells.


Ambient CdTe CdS SnO2:F SiO2 SnO2 Soda lime glass front contact TEC-15

Cu/Au back contact

Figure 2-2

The superstrate structure for CdTe solar cells.

In this thesis, results for both substrate and superstrate solar cells will be presented; however, the focus has been on solar cells using TEC-15 glass as the superstrate. This glass has been used in module manufacturing and will be described in detail in Chapter 3. The TEC-15 glass is ~ 3 mm thick and serves as a support for the active layers of the solar cell. It is transparent, rigid, and inexpensive, and has the widest applications for

ground mounted PV systems. The critical component is the TCO layer, SnO2:F, which 19

is the top-most layer of the TEC-15 glass and acts as the front contact electrode of the solar cell. The polycrystalline cadmium sulfide (CdS) layer is invariably an n-type semiconductor, and serves as one side of the p-n heterojunction solar cell
[2-1]

. As a

material with a wide band gap of 2.43 eV at room temperature, CdS is transparent to optical wavelengths as short as 510 nm. Because its thickness is relatively small

compared to that of CdTe, typically ~1000 , some fraction of the photons with energy above 2.43 eV will still pass through the CdS layer to reach the CdTe layer. The polycrystalline cadmium telluride (CdTe) is the active absorber layer and serves as the p-type semiconductor of the heterojunction. It is an ideal absorber material

because its 1.5 eV band gap is very close to the theoretically calculated optimum value for a single junction solar cell
[2-4]

under unconcentrated AM1.5 sunlight.

It is an

efficient absorber above its band gap, and its high absorption coefficient results from the direct nature of the band gap transition. Typically, the thickness of the CdTe layer in the solar cell ranges from 2 to 4 m in order to absorb a larger fraction of the light between 633 nm and 832 nm. CdS layer. The p-n junction consists of the CdTe layer in contact with the

Because the doping level in CdTe is much lower than that in the CdS, most

of the depletion region of the device is located within the CdTe layer. The back contact studied in this dissertation uses copper (~ 30 ) and gold (~ 200 ) in forming the electrode. Due to its high conductivity, a large thickness is not needed for the gold layer. 20

2.2 Deposition method and process steps The deposition method pioneered at the University of Toledo utilizes the radio frequency (RF) magnetron sputtering technique for fabrication of both the CdTe and CdS thin films [2-5]. The CdTe or CdS sputtering target, serving as one electrode, is driven by This power source generates a plasma of ionized argon gas between

a RF power source.

the target and the substrate platform, which serves as the second grounded electrode. The RF potential drives the ions towards the surface of the target where they impact, causing atoms to be dislodged from the target. surface where they are deposited. These atoms travel to the substrate

A magnetic field is applied to contain the plasma ions

near the surface of the target in order to increase the sputtering rate. The ions follow helical paths around the magnetic field lines, an effect that enhances the ion density in the plasma near the target. This also allows the plasma to be sustained at lower pressures.

The sputtered species are predominantly neutral atoms and are not affected by the magnetic trap. Solar cell fabrication in the superstrate configuration begins with the deposition of a CdS thin film with a thickness of approximately 1300 on a SnO2:F coated soda lime glass substrate
[2-6]

. Typical sputtering parameters for CdS include 50 Watts RF target

power and 10 mTorr Ar gas pressure. During deposition, the substrates are held at a nominal temperature of 300C. After CdS deposition, a CdTe film with a standard thickness of approximately 2.4 m is deposited on the CdS surface using similar deposition conditions as for CdS. For selected depositions of this study, a nominal 21

substrate temperature of 200C has been used for the CdTe.

After the two

semiconductor depositions, a CdCl2 post-deposition treatment is generally applied to the substrate/CdS/CdTe stack
[2-7]

This treatment consists of exposure to an atmosphere of

vaporized CdCl2 with partial pressure at 3.6 mTorr, and for a standard thickness of CdTe, is carried out for 30 minutes in a tube furnace set at 387 C. The CdCl2 post-deposition

treatment is applied for different durations to cells with different CdTe layer thicknesses, while setting the same treatment temperature [2-8]. layer the treatment time is ~ 15 min. The solar cell is finished with an evaporated Cu-Au back contact. Cu is deposited to 30 thickness and Au to 200 thickness
[2-9]

For example, for a 1 m thick CdTe

The final step requires annealing the In this For

solar cell for 45 minutes in air at 150 C in order to diffuse the Cu into the CdTe.

step, the CdTe layer near the back contact becomes more heavily p-type doped [2-9].

the thinner CdTe cells, the annealing time for Cu diffusion must be reduced in order to achieve the proper dopant distribution in the CdTe layer.

2.3 Application of spectroscopic ellipsometry as an analysis technique In the development of real time spectroscopic ellipsometry (RTSE) as a probe for CdTe-based solar cell characterization, a step-by-step research program is being undertaken in order to separate out the various complexities that occur in the deposition process and in the CdCl2 post-deposition treatment process. For the first real time analyses of CdTe and CdS deposition processes, optical properties of the deposited layers 22

must be established simultaneously with the structural parameters such as bulk layer thickness, void volume fraction profile, and surface roughness thickness. Such initial

analyses are typically done using ultra-smooth crystalline silicon substrates so that the extracted optical properties are as accurate as possible
[2-10]

Substrates with rough

surfaces require incorporation of an interface roughness layer into the film growth model that adds greater uncertainty to the overall analysis. Parameterization of the deposited layer optical properties in terms of useful characteristics such as defect density or grain size, strain, and temperature then yields an optical property database that enables real time analysis of subsequent, more complex deposition processes and substrate structures
[2-11]

In basic research studies on the

deposition process, details of the solar cell structure during its deposition beyond simple thickness can be determined such as CdTe and CdS nucleation and coalescence characteristics, surface roughness evolution versus thickness, void volume fraction depth profile, deposition temperature, film stress, defect density or grain size, and CdTe and CdS interface layer compositional depth profile at the interface between the materials. These features can be used not only for basic research but also for process development and troubleshooting. In addition, the database can be applied to the ex-situ analysis of

post-deposition treatments using a bromine-methanol step-wise etching process for depth profiling. Finally these optical property databases established under ideal conditions of

growth on atomically smooth and well-characterized substrates such as c-Si wafers can be applied on-line for production monitoring of the solar modules or for off-line mapping 23

of completed modules.

Data obtained on the production line could potentially be

applied to monitor and control layer thicknesses, for example, in the production process. In addition to the deposition parameters of the CdTe film, the CdCl2 post-deposition treatment of the CdTe solar cell significantly influences the CdTe film structure and optical properties
[2-12]

The final goal of spectroscopic ellipsometry analysis is to

understand the effects of the key parameters of the CdCl2 post-deposition treatment process, temperature and time, on the optical properties and structure of the CdS/CdTe and relate these to the solar cell performance. Because of the complexity of the final

film structures to be treated, the Br2+methanol stepwise etching in conjunction with ex-situ spectroscopic ellipsometry is a unique capability for characterizing CdTe film depth profiles, such as void fraction and grain structure. Thus, this analysis procedure

makes it possible to perform time-reversed real time spectroscopic ellipsometry while maintaining a smooth surface as the layers of the structure are etched away. Such an

approach in which numerous spectra are collected as a function of thickness during etching provides sufficient information to determine depth profiles of the film properties with confidence. In Chapter 3 through Chapter 5, this thesis will focus on optical property database development. In order to determine the structural parameters of CdTe-based solar cells,

the required database of optical properties must include not only CdTe and CdS but also any substrate components. Chapter 3 will describe how the four sets of optical These materials

properties for the materials of the TEC-15 glass substrate are extracted. 24

include the soda lime glass, undoped SnO2, SiO2, and doped SnO2:F.

In Chapter 4,

validity of stepwise etching for time reversed real time spectroscopic ellipsometry will be demonstrated for the purpose of depth profiling CdTe thin films. Chapter 5 will

describe the determination of the optical properties of CdTe and CdS films before and after the CdCl2 post-deposition treatment process. These results will be applied in

Chapter 6 along with an optical model to deduce the structure for superstrate solar cells. Results in Chapter 7 focus on the development of a database and analysis of the complete solar cell for the substrate configuration. In Chapter 8, the application of spectroscopic

ellipsometry will be described for the characterization of CdTe-based ternary alloys.

25

Chapter Three

Optical Properties of TEC-15 Glass

3.1 Introduction The transparent electrically conducting (TEC) glass manufactured at low cost by Pilkington North America is a durable, pyrolytically coated, soda lime glass. The

coating is available in various thicknesses on 3 mm thick soda lime glass which yields an

Ohms when current passes from one side of a square region of the coating surface or interface to the opposite side, irrespective of the area of the square. Because of the

coating durability, TEC glass plates can be handled just like ordinary uncoated plates. TEC glass can be used in many thermal and electrical applications including frost-free refrigerator windows, defogging mirrors, touch screen displays, static-free windows, liquid crystal displays, and superstrates and substrates for thin film photovoltaics. Among the group of TEC glass products, TEC-15, TEC-7, and TEC-8 are the transparent conducting oxide (TCO) coated products used most extensively in the

26

approximately 5000 /

for TEC-1000. The /

value provides the resistance in

electrical sheet resistance from 6 to 8 Ohms/square (/

) for TEC-7, up to

fabrication of CdTe thin film solar cells in the superstrate configuration. As a widely used thin film transparent conductor, fluorine doped tin-oxide (SnO2:F) is the most important layer of the three-layer TEC glass stack. This layer forms the top contact, and

thus serves to conduct the current generated in the semiconductor layers to the external circuit. SnO2:F is relatively easy to deposit pyrolytically onto a heated substrate and is TEC-15 has the appearance of uncoated glass due to the color

quite stable chemically.

suppression characteristics of the three layer stack. Before multilayer optical analysis can be applied to spectroscopic ellipsometry data collected on thin film CdTe-based superstrate solar cells, a library of dielectric functions = 1 + i2 is needed that includes all the component layers. In this chapter, an ex-situ

spectroscopic ellipsometry investigation is described that provides the four sets of optical properties for the material components of TEC-15 glass. From bottom to top, these In

materials include the soda lime glass substrate, undoped SnO2, SiO2, and SnO2:F.

determining the optical properties of these materials, optical models were used to analyze the measured ellipsometry and transmittance spectra. Because all the TEC glasses

exhibit the same multilayer structure, the optical properties deduced for each layer of the TEC-15 glass are assumed to be applicable for the corresponding layers of the TEC-7 and TEC-8 glasses in order to determine their thicknesses. For the TEC-7 and TEC-8

glasses, comparisons of the experimental and calculated transmission spectra, the latter based on an ellipsometric analysis, will be presented in this Chapter as well. These comparisons provide information on light scattering, so-called haze, and macroscopic 27

roughness. 3-1.

A schematic of the multilayer structure of TEC-15 glass is shown in Fig.

Surface roughness SnO2:F SiO2 SnO2 Soda lime glass

Figure 3-1

The multilayer structure of the TEC-15 glass substrate.

3.2

Experimental details The primary effort was focused on TEC-15 glass which exhibits the thinnest SnO2:F

layer, and thus the smoothest surface among the three glasses explored. As a result, the measured data are least affected by scattering due to macroscopic roughness. In

addition to ex-situ ellipsometric spectra, normal incidence transmittance spectra were collected for the TEC-15 components. The purpose of the latter spectra was to seek

higher accuracy extinction coefficient values for the components of the TEC-15 glass. The ellipsometry measurement is sensitive to small changes in the polarization state of the light, which in turn is measurably affected by even a monolayer change in the thickness of a thin film. Because the ellipsometer measures the change in p-s ratio of

the electric fields of the light wave upon reflection from the sample surface, it is not very sensitive to the extinction coefficient k, when the k-value is small ( 0.1). As a result, a

transmission measurement, which can provide more accurate values of k when its 28

magnitude is low, is used to supplement the ellipsometry measurement. sets are analyzed together using the same optical model.

The two data

TEC glass samples were provided by Pilkington North America; five samples were prepared for this study. These samples include (i) uncoated soda lime glass, (ii)

SnO2/(soda lime glass), (iii) SiO2/(soda lime glass), (iv) SiO2/SnO2/(soda lime glass), and (v) fully coated TEC-15 glass: SnO2:F/SiO2/SnO2/(soda lime glass). separate samples of TEC-7 and TEC-8 glass were provided. In addition,

Variable angle

spectroscopic ellipsometry and normal incidence transmittance measurements were applied to study all samples. Each sample was cut into two pieces. For the first piece, the backside of the sample

was roughened to remove the beam returning from the back side glass/air interface. This beam will distort the ellipsometry spectra in ways that are difficult to model due to the incoherence of this beam relative to the top side reflection. The ellipsometry data

were acquired at angles of incidence of 45, 60 and 75, and each acquisition time at a given angle was 10 seconds. The second sample piece was kept as-is and measured The spectral range of all ellipsometry and

using normal incidence transmittance.

transmission measurements was 0.75~6.5 eV.

3.3 (i)

Data analysis and results Uncoated soda lime glass The deduced substrate structure, which includes the bulk glass and a thin surface 29

roughness or modulation layer, is shown in Fig. 3-2. The best fit value for the thickness of this layer (13 ) is also given in Fig. 3-2. The transmittance spectrum measured on

the soda lime glass was first analyzed in order to determine its extinction coefficient k. By fixing the index of refraction spectra of the soda lime glass using results from a reference database as a first estimate
[3-1]

, numerical inversion could be applied to the Then, the index of

transmittance spectra in order to deduce the extinction coefficient k.

refraction spectrum could be extracted by fitting ellipsometry spectra (, ) as measured on the back-surface roughened glass in a procedure that also provides the surface modulation layer thickness. In this fitting procedure, the spectrum in k was fixed as that This process was iterated by repeating the

obtained from transmittance analysis.

inversion of the transmittance spectra using the index of refraction and sample structure deduced from the ellipsometry spectra. As a check of the final results, an analysis of

both the transmittance and ellipsometric spectra was also applied in order to deduce n and k simultaneously using a 100% weighting level of transmittance relative to and . Once the optical properties have been determined in this analysis procedure, they have been fitted by smooth analytical functions. The results are tabulated in Appendix A.

Experimental spectra for the transmittance, and (broken lines), and their best fit simulations (solid lines) using the final structure and optical properties are shown in Figs. 3-3, 3-4, and 3-5.

30

surface roughness soda lime glass


MSE = 1.85

13.1 0.1 3 mm

Figure 3-2 Simple model deduced from the analysis of the transmittance and ellipsometric (, ) spectra of Figs. 3-33-5 for the soda lime glass substrate. The surface roughness is obtained in a best fit of the (, ) spectra.

1.0

Soda Lime Glass substrate

simulation exp.
i =0
o

0.8

Transmittance

0.6

0.4

0.2

0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 3-3 Best fit simulated and experimental normal incidence transmittance spectra T vs. photon energy for an uncoated soda lime glass substrate used in the fabrication of TEC glasses.

Considering Fig. 3-5, the ellipsometric spectra should be 0 throughout the spectral range when the surface layer thickness is negligible and absorption is weak as is the case for soda lime glass. The 13 surface roughness or modulation layer is justified by the observation of a non-zero spectrum. This layer may also include contributions due to surface contamination and/or differences in the chemical nature of the glass near the surface. As a result, the relatively poor quality of the fit to is likely to be due to

inadequacies in the simple Bruggeman effective medium theory model for the optical 31

properties of the thin modulation layer.

The analytical expressions that best fit the index

of refraction and extinction coefficient spectra for the uncoated soda lime glass are shown in Fig. 3-6.

simulation exp.
i = 60
o

(degree)

soda lime glass substrate


0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 3-4 Best fit simulated and experimental ellipsometric angle = tan1 (|rp/rs|) vs. photon energy for an uncoated soda lime glass substrate used in the fabrication of TEC glasses. The angle of incidence is 60.
soda lime glass substrate

20

(degree)

10

0 0 1 2 3 4 5

simulation exp. o i = 60
6 7

Photon Energy (eV)

Figure 3-5 Best fit simulated and experimental ellipsometric angle = p s vs. photon energy for an uncoated soda lime glass substrate used in the fabrication of TEC glasses. The angle of incidence is 60.

32

1.7

Soda lime glass substrate


1E-4

Soda lime glass substrate

1.6

Extinction Coefficient

Index of Refraction

1E-5

1E-6

1.5

1E-7
0 200 400 600 800 1000 1200 1400 1600 1800

200

400

600

800

1000

1200

1400

1600

1800

Wavelength (nm)

Wavelength (nm)

Figure 3-6 Index of refraction (left) and extinction coefficient (right) vs. wavelength for the uncoated soda lime glass substrate. The index of refraction results are derived from the ellipsometric spectrum whereas the extinction coefficient results are derived from the transmittance spectrum. The data values are tabulated in Appendix A.

(ii)

SnO2/(soda lime glass) Ellipsometry and transmittance spectra were measured on the soda lime glass

substrate coated with a single film of undoped SnO2. The analysis of this coated soda lime glass substrate was performed similarly to that of the uncoated glass and used the optical properties of the soda lime glass shown in Fig. 3-6. The deduced sample

structure is shown in Fig. 3-7, including the bulk glass and a two-layer (roughness/bulk) model for the film. The best fit structural parameters obtained in the analysis are also included in Fig. 3-7. The experimental and best fit simulated transmittance and

ellipsometric (, ) spectra are given in Figs. 3-8 and 3-9, and the optical properties of the undoped SnO2 used in the best fit simulations are shown in Fig. 3-10. property results are also tabulated in Appendix A. The surface roughness layer on the film depicted in Fig. 3-7 is modeled as a mixture 33 These optical

of the underlying undoped SnO2 and void with a variable composition.

The

parameterized expression used for the optical properties of the SnO2 in the fits of Figs. 3-8 and 3-9 employs the parameters given along with their confidence limits in Fig. 3-10. The absorptive properties of the film can be assessed from the imaginary part of the dielectric function 2 shown in Fig. 3-10 (b). Due to the thinness of the SnO2 layer, the

absorption associated with values of 2 below 0.01 is not definitive, however, and can be approximated as 0. In fact, an 2 value of 0.01 at 2.0 eV, corresponds to a k-value of

0.0026, an absorption coefficient of 5.3 x 102 cm-1, and a single pass absorbance of 0.16% in a 310 film. As a result, no significant influence on any of the optical

characteristics of the TEC glass stack results from this approximation.


surface roughness 160 1 0.52 0.01 / 0.48 0.01 SnO2 / void SnO2 Soda Lime Glass MSE = 3.81 226 2 3 mm

Figure 3-7 Model with best fitting parameters obtained in the analysis of the transmittance and ellipsometric (, ) spectra of Figs. 3-8 and 3-9 for the soda lime glass substrate coated with a single layer of undoped SnO2.

34

1.0

SnO2/SLG
0.8

simulation exp.
i = 0
o

Transmittance

0.6

0.4

0.2

0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 3-8 Normal incidence transmittance T vs. photon energy for a soda lime glass substrate coated with a single layer of undoped SnO2, the first layer in the fabrication of TEC glasses. Experimental data (broken line) and a best fit simulation (solid line) are shown.
SnO2/SLG o i= 60
300

16

SnO2/SLG o i = 60

simulation exp.

200

(degree)

(degree)
simulation exp.
0 1 2 3 4 5 6 7

12

100

-100 0 1 2 3 4 5 6 7

Photon Energy (eV)

Photon Energy (eV)

Figure 3-9 Ellipsometric angles and vs. photon energy for a soda lime glass substrate coated with a single layer of undoped SnO2. Experimental data (broken lines) and best fit simulations (solid lines) for an angle of incidence of 60 are shown.

35

4.4

10

(a) SnO2
1
4.0

(b) SnO2

0.1

3.6

2
0.01
3.2

1E-3

Photon Energy (eV)

Photon Energy (eV)

(c) Parameterization of dielectric function: 1 + i2 = ADrudeDrude/(E2+iDrudeE) +

(
n=1

1,T-L,n

+ i 2,T-L,n ) + 1,Gaussian + i 2,Gaussian


E > E gn E E gn

Here: 1,T-L,n =

2,T-L,n () E
2 2

d , and

2,T-L,n 2,T-L,n

Egn

A n E 0n C n (E E gn ) 2 1 = 2 2 2 2 2 (E E 0n ) + C n E E =0
E EGaussian 2 )

1,Gaussian =

( 2 () p 2 2 2 d , 2,Gaussian = A Gaussian (e 0 E

E + EGaussian 2 )

) , and

Gaussian 2 ln(2)
An (eV) E0n (eV) Cn (eV) Egn (eV) ADrude (eV) Drude (eV)

n=1 n=2

20.5641.380 4.8250.052 2.6470.063 3.2360.025 5.3034.020 0.0260.020 0.3570.213 68.1558.90018.9921.31011.8451.200 1.5570.027 AGaussain (eV) EGaussian (eV) Gaussian (eV) 0.2280.016 4.3840.006 0.5220.024

Figure 3-10 (a,b) Real and imaginary parts of the dielectric function 1 and 2 vs. photon energy for undoped SnO2 that forms the first layer of TEC glasses; (c) analytical expression for the complex dielectric function of (a,b) along with the best-fit free parameters and their confidence limits.
36

(iii)

SiO2/(soda lime glass) Transmittance and ellipsometry spectra on a soda lime glass substrate coated with a

single layer of SiO2 were measured and fit simultaneously at the 100% weighting level of transmittance relative to and . fabrication of TEC glasses. The SiO2 is used as the second layer in the

The adopted sample structure, including the bulk glass and The best fit

a two-layer (roughness/bulk) model for the film is shown in Fig. 3-11. structural parameters and their confidence limits are also shown.

The surface roughness

is assumed to be a 0.5/0.5 volume fraction mixture of the underlying SiO2 and void. The experimental transmittance and ellipsometric spectra along with their best-fit simulations are shown in Figs. 3-12 and 3-13. The optical properties of the SiO2 used in these simulations are shown in Fig. 3-14(a), and the data are tabulated in Appendix A. A parameterized expression for the optical properties of the SiO2 is used as shown in Fig. 3-14(b), based on a two term Sellmeier expression and a separate pole term. Figure

3-15 shows the reference dielectric function for thermally-grown SiO2 on crystalline Si
[3-2]

in comparison with the deduced dielectric function of the SiO2 film on the soda lime

glass.
Surface roughness SiO2 Soda Lime Glass MSE = 1.24 35 2 315 4 3 mm

Figure 3-11

Model adopted for the analysis of the transmittance and ellipsometric (, ) 37

spectra of Figs. 3-12 and 3-13 obtained on the soda lime glass substrate coated with a single layer of SiO2.
1.0

SiO2/SLG
0.8

simulation exp.
i= 0
o

Transmittance

0.6

0.4

0.2

0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 3-12 Normal incidence transmittance T vs. photon energy for a soda lime glass substrate coated with a single layer of SiO2, which is used as the second layer in the fabrication of TEC glasses; experimental data (broken line) and a best fit simulation (solid line) are shown.
7.5

SiO2/SLG o i= 60

25

SiO2/SLG o i= 60

20

7.0

(degree)

(degree)

15

6.5

10

6.0
5

simulation exp.
5.5 0 1 2 3 4 5 6 7
0 0 1 2 3 4 5

simulation exp.
6 7

Photon Energy (eV)

Photon Energy (eV)

Figure 3-13 Ellipsometric angles and vs. photon energy for a soda lime glass substrate coated with a single layer of SiO2, which is used as the second layer in the fabrication of TEC glasses; experimental data (broken lines) and a best fit simulation (solid lines) are shown.

38

2.5

2.0

1.5

1, 2
1.0 0.5

(a) SiO2
0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

(b) Parameterization of the real part of the dielectric function:

1 = offset + A0/(E02E2) + Apole/(E2poleE2); 2 = 0; A0 (eV2)


248.876 1.458

E0 (eV)
14.544 0.003

Apole (eV2)
0.0330.001

Epole (eV)
0

offset
1.000 0.009

Figure 3-14 (a) Real (solid line) and imaginary (broken line) parts of the dielectric function vs. photon energy for SiO2 that forms the second layer of the TEC glasses. The imaginary part of the dielectric function vanishes; (b) mathematical expression for the dielectric function in (a) along with the best fitting parameters and their confidence limits.
2.5

2.0

1.5

1, 2
1.0

1 TEC SiO2 2 TEC SiO2 1 thermal SiO2

0.5

2
0.0 0 1 2 3 4

2 thermal SiO2

Photon Energy (eV)

Figure 3-15 Real and imaginary parts of the dielectric function vs. photon energy for the SiO2 that forms the second layer of the TEC glasses (solid lines) for comparison with the reference data of a thermally-grown SiO2 on crystalline silicon[3-2]. 39

(iv)

SiO2/SnO2/(soda lime glass) For the next set of results to be described, the SiO2 layer was deposited instead on the

SnO2/(soda lime glass) structure.

The ellipsometry and transmittance data were fit

simultaneously using 100% weighting of transmittance relative to and for this sample, as well. The optical properties of the soda lime glass, the undoped SnO2, and the SiO2

used in the best-fit simulation are those shown in Figs. 3-6, 3-10, and 3-14, respectively. Figure 3-16 shows the optical model applied in this case along with the best fit parameters and their confidence limits. Figure 3-17 shows the best fit to the

ellipsometric spectra and , obtained using the model of Fig. 3-16.


Surface roughness 144 2 (0.63 0.01)/(0.37 0.01) SiO2/void SiO2 SnO2 Soda Lime Glass MSE = 4.03 253 3 466 1 3 mm

Figure 3-16 Best fit sample structure for a soda lime glass substrate coated with a two layer stack of undoped SnO2 and SiO2, which are the first two layers used in the fabrication of TEC glasses.

40

SiO2/SnO2/SLG
40

300

simulation exp.
i= 60
200
o

32

(degree)

24

(degree)
i= 60
o

100

16

simulation exp.
0 0 1 2 3 4 5 6 7 -100 0 1 2 3 4

SiO2/SnO2/SLG
5 6 7

Photon Energy (eV)

Photon Energy (eV)

1.0

SnO2/SiO2/SLG
0.8

simulation exp.
i= 0
o

Transmittance

0.6

0.4

0.2

0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 3-17 Ellipsometric angles (, ) at an angle of incidence of 60 and transmittance T at normal incidence plotted versus photon energy for a soda lime glass substrate coated with a two layer stack of undoped SnO2 and SiO2, which are the first two layers used in the fabrication of TEC glasses. The effective thicknesses of these layers as indicated in Fig. 3-16, including surface roughness and bulk components, are larger than those of the individual layers. For the

SnO2 layer of the bi-layer the effective thickness is the bulk layer thickness, so that deff(SnO2) = 466 . For the SiO2, one must also include the contribution of the For the individual layers, deff(SnO2) = 309

roughness layer, so that deff(SiO2) = 344 . 41

and deff(SiO2) = 333 . (v) TEC-15 glass with SnO2:F/SiO2/SnO2/ (soda lime glass) structure The assumed sample structure, including the bulk glass and a four-layer model for the TEC-15 multilayer stack is shown in Fig. 3-18. The stack includes two ideal films

for the undoped SnO2 and the SiO2 and two layers -- roughness/bulk -- for the top-most doped SnO2:F film. Figure 3-18 also shows the best-fit structural parameters of the The previously-determined dielectric The

model along with their confidence limits.

functions were used for the soda lime glass, the thin undoped SnO2, and the SiO2.

dielectric function of the SnO2:F and structural parameters were deduced simultaneously in this analysis. In Figs. 3-19 and 3-20, the experimental transmittance and

ellipsometric spectra are shown along with the simulations obtained as the best fit using at a 100% weighting level of transmittance relative to and . The optical properties

of the top-most doped SnO2:F used in the simulation are shown in Fig. 3-21 and tabulated in Appendix A. The minimum 2 value of 0.02 near 2.5 eV corresponds to a k value of

0.0027, an absorption coefficient of 6.8 x 102 cm-1, and a single pass irradiance loss of 2.5%, the latter value typical of high quality transparent conducting oxides. The

analytical expression for the complex dielectric function valid for photon energies below 4.4 eV is given in Fig. 3-22 along with the best fit parameters and their confidence limits. This expression includes a two term Sellmeier expansion, one Lorentz oscillator, and one Drude contribution. The dc electrical conductivity can be deduced from the Drude

amplitude AD according to dc = AD0/ = 2.87 x 103 (cm)1, leading to a resistivity of 42

Surface roughness 273 3 0.60 0.005 / 0.40 0.005 SnO2:F / void SnO2:F SiO2 SnO2 Soda Lime Glass
MSE = 64.65

3533 6 222 3 287 3 3 mm

Figure 3-18. Best fit multilayer stack for a complete TEC-15 glass sample. The layered structure includes thin undoped SnO2, thin SiO2, and thick doped SnO2:F with surface roughness on top. The previously-determined dielectric functions were used for the soda lime glass and the two thin layers.

1.0

SnO2:F/SiO2/SnO2/SLG
0.8

Transmittance

0.6

0.4

0.2

0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 3-19 Normal incidence transmittance T vs. photon energy for a complete TEC-15 glass sample consisting of a soda lime glass substrate coated with layers of undoped SnO2, SiO2, and top-most doped SnO2:F. Experimental data (broken line) and a best fit simulation (solid line) are shown.

43

.
simulation exp.
i= 0
o

3.48 x 10-4 cm and a sheet resistance of ~ 10 /

40

SnO2:F/SiO2/SnO2/SLG

30

simulation exp. o i= 60

SnO2:F/SiO2/SnO2/SLG
300

simulation exp. o i= 60

200

(degree)

20

(degree)

100

10

0 0 1 2 3 4 5 6 7

-100 0 1 2 3 4 5 6 7

Photon Energy (eV)

Photon Energy (eV)

Figure 3-20 Ellipsometric angles and at a 60 angle of incidence plotted vs. photon energy for a complete TEC-15 glass sample consisting of a soda lime glass substrate coated with layers of undoped SnO2, SiO2, and top-most doped SnO2:F. The broken lines indicate experimental spectra and the solid lines indicate the best fit simulation.

7 6 5 4

SnO2:F

fit to analytical expression

exact inversion of (, ) data


1

SnO2:F fit to analytical expression exact inversion of (, ) data

3
0.1

2 1 0
0.01

2
0

Photon Energy (eV)

Photon Energy (eV)

Figure 3-21 Real and imaginary parts of the dielectric function 1 and 2 vs. photon energy for doped SnO2:F that forms the top-most layer of TEC-15 glass. These results are obtained as a best fit analytical expression at low energies where the film is semitransparent and by an inversion of (, ) data at high energies where the film is opaque.

44

(a) Parameterization of the dielectric function E < 4.4 eV:

1 + i2 = offset + A1/(E12E2)+ ALLE0/(E20E2iLE) ADD/(E2+ iDE);


(b) Sellmeier: A1 (eV2) 207.5614.905 Lorentz: AL 1.3320.240 Drude: AD (eV) 21.3110.608 D (eV) 0.0890.002 E0 (eV) 4.6860.077 L (eV) 0.3890.061 E1 (eV) 8.8570.001 offset 1.0030.070

Figure 3-22 (a) The analytical equation for the dielectric function of the top-most SnO2:F layer of TEC-15 that holds below 4.4 eV; also shown is (b) a table of the best fit parameters in the equation and their confidence limits. (vi) TEC-7 and TEC-8 glasses with SnO2:F/SiO2/SnO2/ (soda lime glass) structure The sample structures deduced for TEC-7 and TEC-8 glasses are shown in Figs. 3-23 and 3-24. The best-fit structural parameters are included in the figures, as well. The

dielectric functions previously-determined from TEC-15 glass were used for the soda lime glass, the thin undoped SnO2, thin SiO2, and thick doped SnO2:F layers of the TEC-7 and TEC-8 samples. The incorporation of two additional fitting parameters was attempted in this case because of the larger surface roughness and bulk SnO2:F film thicknesses for the TEC-7 and TEC-8 glasses relative to TEC-15. One parameter is the volume fraction of voids in the SnO2:F layer, which is incorporated due to the expected coarser microstructure of the SnO2:F layers for the TEC-7 and TEC-8 glasses. other parameter describes the thickness non-uniformity of the layers. The

Thickness

non-uniformity arises due to the variation of one or more film thicknesses across the

45

sample surface. If the film thickness varies over the area of the light beam, then the beam on the film surface can be divided into components by a grid selected such that the thickness variation is negligible over a given beam component. The resulting grid size must be larger than the lateral coherence of the beam, estimated to be ~5-10 m, otherwise interference between neighboring beam components will occur. In the absence of

interference, the irradiances associated with all beam components will add and the resulting reflected beam will be partially polarized. parameter can then be determined in the analysis. A thickness non-uniformity This parameter describes the

percentage variation in film thickness within the overall probe beam area according to the definition [(dmaxdmin)/dave]100%. For the TEC-7, the observed ~7% non-uniformity is

not of the macroscopic variety, i.e. not a variation in thickness from one side of the beam to the other, but rather is associated with surface roughness having an in-plane scale that exceeds the lateral coherence length. As support for this interpretation, when thickness

non-uniformity is added as a free parameter into the TEC-15 fitting procedure, however, the best-fit value is zero within confidence limits. This result is consistent with the fact

that this film has an in-plane roughness scale that is smaller than the TEC-7 and TEC-8, which in turn is consistent with its thinner surface roughness layer.

46

Surface roughness 409 4 0.55 0.005 / 0.45 0.005 SnO2:F / void SnO2:F 4708 19 0.97 0.005 / 0.03 0.005 SnO2:F / void SiO2 SnO2 Soda Lime Glass 222 5 302 6 3 mm

Thickness non-uniformity 7.4% 0.8%; MSE = 87.6

Figure 3-23 Multilayer structure with best-fit parameters for a complete TEC-7 glass sample. The layered structure includes thin undoped SnO2, thin SiO2, and a thick layer of doped SnO2:F with surface roughness on top. The previously determined dielectric functions for TEC-15 glass were used here for this TEC-7 glass sample.
Surface roughness 609 7 0.53 0.01 / 0.47 0.01 SnO2:F / void SnO2:F 5672 52 0.92 0.01 / 0.08 0.01 SnO2:F / void SiO2 SnO2 Soda Lime Glass 294 14 335 14 3 mm

Thickness non-uniformity 10.7% 0.8%; MSE = 156.2

Figure 3-24 Multilayer structure with best-fit parameters for a complete TEC-8 glass sample. The layered structure includes thin undoped SnO2, thin SiO2, and a thick layer of doped SnO2:F with surface roughness on top. The previously determined dielectric functions for TEC-15 glass were used here for this TEC-8 glass sample.

The experimental normal incidence transmission data measured for the TEC-7 and TEC-8 samples and the data calculated on the basis of the optical models deduced by ellipsometry are shown in Fig. 3-25 (left) and Fig. 3-26 (left). Due to the existence of 47

thicker surface roughness layers on the TEC-7 and TEC-8 samples, some amount of scattering is expected in the normal incidence transmission measurement. In theory, the transmission spectra calculated on the basis of the model deduced by ellipsometry should be approximately equal to the summation of the experimental normal incidence specular transmission data and the total normal incidence scattering data integrated over all solid angles. In comparison with the close agreement between the calculated and experimental transmission spectra for the TEC-15 sample (Fig. 3-18), the corresponding data sets for TEC-7 and TEC-8 samples differ considerably below 3.5 eV. Considering the values of

the microscopic surface roughness thicknesses of three TEC samples, these results can be easily explained. TEC-15 glass has the smallest microscopic surface roughness

thickness among three samples ~275 , which means it has the smallest macroscopic roughness as well, and thus, the smallest scattering loss. In this case, the experimental

data are closest to the calculated results and in fact, it was valid to use the transmittance as a data component to be fitted in the analysis of Fig. 3-18. TEC-8 glass has the largest microscopic surface roughness thickness, thus the largest macroscopic roughness thickness, and as a result the largest scattering loss. This explains why the experimental transmission for the TEC-8 glass exhibits the greatest deviation from the calculated results. Figures 3-25 (right) and 3-26 (right) show the differences between the calculated and experimental transmission spectra for the TEC-7 and TEC-8 glass samples. 48 This

difference approximates the total normal incidence scattering data integrated over all angles. It is easily recognized that the transmission loss in TEC-8 glass is larger

because of a stronger scattering effect than that in TEC-7 glass. In addition, in Figs. 3-27 and 3-28 the normal incidence scattering data for these samples as predicted by the combination of ellipsometry and normal incidence specular transmission has been compared with experimental normal incidence integrated scattering data. The experimental scattering data were measured at Pilkington in a

diffuse transmission experiment using a different pair of TEC-7 and TEC-8 samples than the ones measured in this investigation. From the comparison in Figs. 3-27 and 3-28,

the experimental scattering results are lower than the predictions over the 400 600 nm and 1200 1500 nm wavelength ranges in both cases. One possible origin of this

difference may arise from the small collection aperture of the ellipsometer used to measure the normal incidence specular transmittance relative to the apertures used to pass the
1.0

0.20

TEC-7 transmission
0.8

simulation exp. data


i = 0

Difference between TEC-7 simulation and exp. data


i = 0

0.15

Transmittance, T

0.6

0.10

0.4

T
0.05 0.00 -0.05

0.2

0.0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Photon Energy (eV)

Figure 3-25 Transmittance T vs. photon energy for a complete TEC-7 glass sample; experimental data (broken line) and simulated results based on the ellipsometric model (solid line) are shown (left). The difference between the two data sets is shown at the right. 49

1.0

TEC-8 transmission
0.8

simulation exp. data


i = 0

0.35 Difference between TEC-8 simulation

and exp. data


0.30 0.25
i = 0

Transmittance, T

0.6

0.20

0.4

0.15 0.10

0.2

0.05 0.00

0.0 0 1 2 3 4 5 6 7

-0.05 0 1 2 3 4 5 6 7

Photon Energy (eV)

Photon Energy (eV)

Figure 3-26 Normal incidence transmittance T vs. photon energy for a complete TEC-8 glass sample; experimental data (broken line) and simulated results based on the ellipsometric model (solid line) are shown (left). The difference between the two data sets is shown at the right. specularly reflected and transmitted beams in the measurement at Pilkington with an integrating sphere. In such a case, near-specular scattering would be considered true

scattering by ellipsometry but rather as part of the specular beam in the integrating sphere measurement, and hence not collected. This difference due to near-specular scattering

amounts to about 5% for TEC-7 and closer to 10% for TEC-8 at the high and low energies. Another possible origin of the difference may arise from different optical properties of the SnO2:F layer in the three different types of TEC glass. If the absorbance in

TEC-7 and TEC-8 are underestimated with the use of the TEC-15 optical properties, then the measured transmittance of the TEC-7 and TEC-8 would be lower than that predicted by ellipsometry. This effect would contribute a positive term to the T spectra in Figs. In fact, it is expected that the

3-25 and 3-26 that is not accountable by scattering.

increasing T values at long wavelengths visible most clearly in Figs. 3-27 and 3-28 are generated by a larger Drude contribution to the absorption in the TEC-7 and TEC-8 50

glasses compared to TEC-15.

Improvements in the analysis of TEC-7 and TEC-8 using

the approach developed here for TEC-15 will be the subject of future research.

0.3

Total integrated scattering

TEC-7 Predicted scattering by ellipsometry and specular transmission


i = 0

0.2

0.1

0.0

Measured scattering by diffuse transmission


0 200 400 600 800 1000 1200 1400

Wavelength (nm)

Figure 3-27 For TEC-7 glass, the normal incidence scattering results predicted by combining ellipsometry and normal incidence specular transmittance are shown in comparison with experimental normal incidence integrated scattering data from a diffuse transmission experiment. Different TEC-7 samples were used for the two different data sets.
TEC-8 Predicted scattering by ellipsometry and specular transmission
i = 0

0.4

0.3

0.2

0.1

0.0

Measured scattering by diffuse transmission


0 200 400 600 800 1000 1200 1400

Wavelength (nm)

Figure 3-28 For TEC-8 glass, the normal incidence scattering results predicted by combining ellipsometry and normal incidence specular transmittance are shown in comparison with experimental normal incidence integrated scattering data from a diffuse transmission experiment. Different TEC-8 samples were used for the two different data sets.

51

Chapter Four

Verification of the Chemical Etching Process for CdTe Depth Profiling

4.1 Introduction A critical step in the fabrication of CdTe-based solar cells is the CdCl2 vapor treatment performed near 400 C in the presence of oxygen. the solar cell efficiency by a factor of two or more [4-1, 4-2]. This process step improves Comparisons of as-deposited

and CdCl2 vapor-treated CdTe thin film materials have revealed significant near-surface, interface, and bulk property differences. Considering the near-surface, the CdCl2

post-deposition treatment generates much thicker roughness and oxidized layers on the treated film in comparison with the as-deposited film. Evidently the exposure to

chlorine and oxygen in the high temperature (~ 400 C) environment during the treatment leads to three-dimensional grain growth and oxidation of the surfaces of the large grains. In addition, many bulk film and interface parameters that may impact the solar cell performance are modified in the post-deposition CdCl2 treatment. These include the

physical characteristics such as thickness, density, and grain size and orientation for both the CdTe and CdS films, as well as the composition profile of the interface region between the two films. Changes also occur in the optical and electronic properties upon 52

treatment including the dielectric functions of the CdTe, CdS, and interface region, the concentration and nature of the defects which control the free electron concentration, and the mobility of photoinjected carriers. Real time spectroscopic ellipsometry can be used to obtain dynamic information on film growth and modification through analysis of the data acquired during thin film deposition or post-deposition processing. During the CdCl2 post-deposition treatment, In fact, the layers that

however, the properties of several layers change simultaneously.

may change in their properties and thickness upon CdCl2 treatment include CdTe and CdS, as well as the surface and interface layers: TCO/CdS, CdS/CdTe, and CdTe/oxide. In order to separate out all the changes that occur during the post-deposition treatment process, real time spectroscopic ellipsometry is avoided in favor of ex-situ spectroscopic ellipsometry, accompanied by chemical etching for depth profiling. A comparison of

the depth profiling results with those obtained in real time on the as-deposited film provides an effective comparison before/after deposition. Depth profiling of the CdCl2-treated thin films by successive Br2+methanol etches of the CdTe thin film layer has been applied in this thesis research. In previous research

the Br2+methanol etch has been successful in removing overlayers including native oxides and surface roughness from opaque single crystal materials, such as CdTe, and HgxCd1-xTe
[4-3]

By performing spectroscopic ellipsometry during the etching process,

one can determine the extent to which oxide and roughness removal has been successful by monitoring the maximum magnitude of the imaginary part of the pseudo-dielectric 53

function denoted <2> after each etching step.

The pseudo-dielectric function is

calculated from the ideal single-interface ambient/bulk model. Thus, as the overlayers are removed, the pseudo-dielectric function maxima determined from the (, ) spectra increase and approach the true values of the complex dielectric function of the opaque CdTe film in this case. Thus, upon complete removal of the overlayers, an inverted

% % form of the complex Fresnel amplitude reflection ratio R p / Rs yields the complex

dielectric function spectra of the opaque film directly from the (, ) spectra.
In order to adapt successfully an etching technique previously demonstrated for single crystals to the polycrystalline films of this study, it must be verified that the chemical etching process does not modify the underlying film structure that one is attempting to measure. In the following paragraphs, an experiment is described to

evaluate the validity of the etching method to be used for the CdCl2 treated CdTe-based solar cell structure as described in Chapters 5 and 6. In fact, optical depth profiling

results for the CdTe film structure from real time spectroscopic ellipsometry are compared with the corresponding results from ex-situ spectroscopic ellipsometry during etch back.

4.2 Structural evolution of CdTe during etching: experimental details Magnetron sputtering of the CdTe thin film used in this study was performed at a radio frequency (rf) target power of 60 W, an Ar pressure of 18 mTorr, and an Ar flow rate of 23 sccm. The substrate was a native oxide-covered crystalline Si (c-Si) wafer

54

held at a nominal temperature of 200C [4-4]. The true temperature of the starting surface just prior to deposition was estimated to be 130 5C, as determined in situ from an analysis of the c-Si E1 and E2 critical points. deposition due to its smoothness. A c-Si wafer substrate was used for this

As a result, complications were avoided due to

substrate-induced surface roughness that evolves into interface roughness during overlying film growth. The design of the commercial rotating-compensator multichannel ellipsometer used in this study is similar to that first developed to study the growth of Si:H-based materials and solar cells [4-5]. The spectral range of the ellipsometer extends from ~0.75 to 6.5 eV,

and complete spectra in the ellipsometric angles (, ) can be collected as an average over a minimum of two optical cycles in a time of (30.7 Hz)-1 = 32.6 ms. is the mechanical rotation frequency of the compensator. Here 30.7 Hz

In the real time experiment

performed on the deposition of the CdTe film to be etched, complete (, ) spectra were collected in 1.95 seconds as an average over 60 such optical cycle pairs. A total of 705

spectral files were collected, corresponding to a set of time points from 2.38 s to 3216.3 s, with a step of 4.56 s. Each spectral file includes 706 values of and , spanning photon energies from 0.743 to 6.50 eV. Thus, during the 3213.9 s deposition time, the

instrument acquired (705)*(706)*(2) = 9.9546x105 experimental data values, filling about 15 Mbytes of computer memory. During the acquisition time for one set of (, ) spectra, an average thickness of CdTe of 2.4 accumulates at the bulk layer deposition rate measured here (1.21 /s). Analyses of all spectra utilized a specialized

(mathematical inversion) / (least-squares regression) algorithm developed previously [4-6]. The angle of incidence for the RTSE measurement was 65.61. 55

Figure 4-1 A schematic of optical models used to evaluate a CdTe film by optical depth profiling during both deposition and etching processes.

The large data set accumulated in this way during the deposition of the CdTe film was analyzed over the energy range of 5~6.5 eV in order to achieve the highest depth resolution possible. The absorption depth ( 1, where is the absorption coefficient)

of single crystal CdTe decreases with increasing photon energy, reaching 100 at 5 eV. A schematic of the optical models used in the analysis of the experiment including the deposition and etching processes is shown in Fig. 4-1. The chemical etch of the CdTe

thin film was performed using a Br2+methanol solution prepared with 0.05 volume percent Br2. Initially, the etching time was fixed at 3 seconds for each etch step, then increased to 30 seconds and fixed.

56

4.3 Structural evolution of CdTe during etching: results and analysis In order to verify the validity of the above approach, the same sample was studied in real time during deposition and ex-situ during sequential etching, without a CdCl2 treatment in between the two measurements. A simple two-layer roughness/bulk model

was applied to analyze SE data collected in real time during deposition as well as ex-situ after each chemical etch step. Figure 4-2 (solid line) shows the evolution of void

volume fraction in the top ~100 of the CdTe bulk layer as a function of the bulk layer thickness (the latter as deduced from lower energy data) during the deposition process. The abrupt upward step in void fraction represents a sharp microstructural transition, characteristic of the relaxation of high compressive strain that occurs in the early stage of film growth. This structural transition is only observed at low substrate temperatures (<

200 C) and the resulting void structures that propagate throughout the film are likely to be detrimental to the final solar cell performance. The discrete points in Fig. 4-2

collected after each etch step match the deposition results (solid line) very well given the confidence limits and depth resolution of the analysis. Thus, for each CdTe bulk

thickness, the sample has the same structural profile as measured during both the deposition and etching processes. This result shows that the etching process is the

reverse of the deposition process, and that etching does not modify the underlying film structure, even when the underlying structure is inhomogeneous and varies significantly with depth.

57

0.25

CdTe growth process CdTe etch process

void volume fraction, fv

0.20 0.15 0.10 0.05 0.00 -0.05

depth resolution 1/ (5eV) ~ 100

one-layer surface roughness model analysis range for fv: 5.0~6.5 eV


0 500 1000 1500 2000 2500 3000 3500

bulk layer thickness, db ()

Figure 4-2 The evolution of void volume fraction within the top 100 of the bulk layer as a function of CdTe bulk layer thickness obtained during the deposition and etching processes.

One detail of interest must be considered in view of these results.

Previous reports

have shown that a thin amorphous Te (a-Te) layer remains on the top surface of CdTe single crystals after a Br2+methanol etch step [4-7,4-8]. The data of Fig. 4-2 show that this

thin a-Te layer, if it does exist for the polycrystalline CdTe film, has only a weak effect on the determination of the sub-surface void fraction within the sample as long as the CdTe layer is much thicker than the a-Te layer. Such conditions are satisfied due to the Another detail

expected thinness of the a-Te layer using the previous report as a guide.

must be addressed considering that, for the data acquired in these two processes, the samples are at different temperatures, 130 C for deposition and 25 C for etching. For

the film structure during deposition, thermal expansion will occur at the elevated temperature, and as a result, a difference in the thickness scales will exist relative to the 58

film structure at room temperature.

Given the thermal expansion coefficient of single

crystal CdTe of 5.9x106 (C)1 at 25 C, the thickness change that a 2000 thick CdTe film undergoes upon heating to 130C is (2000 )[5.9x106 (C)1](105 C) = 1.2 , which is inconsequential in this study.

4.4 Detection of a-Te on etched CdTe: experiment details Two experiments have been designed in order to detect a-Te on etched CdTe films and to extract its optical properties. In the first experiment, a 3 m thick CdTe film was

deposited onto a c-Si wafer, and smoothened by Br2+methanol etching from a starting surface roughness thickness of 500 to 50 , as characterized by spectroscopic ellipsometry over the photon energy range from 0.75 to 1.5 eV. Once the surface

roughness has been reduced to its minimum, additional Br2+methanol etch steps have been applied to this sample with spectroscopic ellipsometry measurements performed before the first additional etch step and after each successive etch. The very rough

region at the surface of the starting CdTe is removed through successive 3 second etches, leaving a smooth surface which increases the sensitivity of the analysis to the surface and underlying CdTe. In the additional etches, also set at 3 second durations, the smooth

CdTe film was removed in a layer-by-layer fashion with a relatively constant roughness thickness. The additional etches and measurements have provided the information

needed to evaluate the presence of an a-Te layer in the Br2+methanol etching process. In the second experiment, a 3500 thick CdTe film was deposited on a c-Si wafer, and a 59

total of 37 Br2+methanol etch steps was applied to this sample until the CdTe thin film was completely removed from the c-Si wafer. Spectroscopic ellipsometry

measurements were performed after each etch step. These measurements have been used to extract the optical properties of the a-Te film generated in the Br2+methanol etching process. The concept of this second experiment is shown in Fig. 4-3 through a These layered structures are applied in the

schematic of the sample structural changes.

modeling of the spectroscopic ellipsometry data.

35th etching a-Te CdTe SiO2 C-Si

36th etching a-Te SiO2 C-Si

37th etching

SiO2 C-Si

Figure 4-3 Schematic of the sample structural changes that occur in the last three etching steps for a CdTe film on c-Si. The starting thickness of this CdTe film is 3500 .

4.5 Detection of a-Te on etched CdTe: results and analysis Previous reports have shown that Br2+methanol treatments leave the surface of single crystal CdTe covered with an optically identifiable amorphous Te layer
[4-7, 4-8]

similar effect is expected for polycrystalline CdTe, which can be seen clearly by the difference in the ellipsometric spectra of Fig. 4-4. Figure 4-4 shows two spectra for the

3 m thick smoothened CdTe film on c-Si wafer measured at angle of incidence of 63. The dashed line represents the data measured before the additional Br2+methanol etching 60

steps when the surface roughness has reached its minimum, and the solid line is acquired after the 6th additional Br2+methanol etch step after a total etching time of 18 seconds. Because the CdTe surface is already smooth after the first set of etching steps and the deduced surface roughness thickness is not changing over the additional etching steps, then the ellipsometric spectra measured after the 6th etch should be similar to that measured before the 1st etch. Obviously, from Fig. 4-4, one concludes that changes have

occurred in the nature of the surface, even though the roughness layer thickness is not changing significantly. It can be proposed that the changes are characterized by the

gradual conversion of a roughness layer associated with CdTe to a roughness layer associated with the a-Te region.

30 25 20 15

(degree)

6 Br+Me etch st Before 1 etch

th

160
(degree)

140 120 100 80

Photon Energy (eV)

Figure 4-4 Ellipsometric spectra for a smoothened CdTe film on a c-Si wafer measured at angle of incidence of 63. The broken lines represent data measured before the first additional Br2+methanol etching step, and the solid lines represent data measured after the 6th additional Br2+methanol etching step. The total etching time between the two is 61

18 seconds.

The starting CdTe thickness before any etching was 3 m.

Based upon such a proposition, analysis is performed on the ellipsometric spectra acquired in the second experiment described in Sec. 4.4 after the 36th and 37th etching steps at an angle of incidence of 65. The two experimental spectra are shown in Fig. 4-5 for comparison. Figure 4-6 shows the two spectra presented separately along with Figures 4-7 and 4-8 also show the best-fit If the real and

the best-fit simulations in each case.

structural parameters of the model along with their confidence limits.

imaginary parts of the dielectric function (1, 2) of the a-Te were extracted from the model of Fig. 4-8 without the assumption of voids, then a relatively weak oscillator amplitude in 2 would be obtained, but with a shape similar to that of the previous reports on single crystal CdTe
[4-7, 4-8]

The weak 2 is attributed, in fact, to the large void

fraction in the a-Te derived from etching away the polycrystalline CdTe in comparison to that derived from bulk single crystal CdTe. In an initial fit of the spectra of Fig. 4-6

(left), the a-Te dielectric function from the previous reports was used as a reference along with a variable void volume fraction. In the final fit, an analytical model for the a-Te

dielectric function was used along with a fixed void fraction deduced from the initial fit. The confidence limits on the void fraction in Fig. 4-8 are derived from the initial fit. The resulting dielectric function deduced for the a-Te layer over the range of 0.75 to 6.5 eV is shown in Fig. 4-9. In Fig. 4-10, a comparison of these best fit spectra is

provided with the corresponding results for a-Te from measurements of single crystal 62

CdTe over the range of 1.5 to 6.0 eV from the previous reports

[4-7, 4-8]

The analytical

expression for the real and imaginary parts of the dielectric function used in the best fit is given as [4-9]:

2 ( E ) = 0; E < Eg
2 ( E ) = G ( E ) L( E ) = ( E Eg ) 2 ( E Eg ) + E p
2 2

(4.1)

AE0E ; E > Eg . ( E E0 2 )2 + 2 E 2
2

(4.2)

1 ( E ) = 1 () +

2 2 () P d , Eg 2 E 2

Here E is the photon energy and Eg is the band gap energy associated with band-to-band transitions in the a-Te. For E>Eg, the imaginary part of the dielectric function includes

the product of two terms, the Lorentz oscillator function L(E) and the band edge function G(E). The latter is based on the assumption of parabolic bands and a constant dipole matrix element. In the Lorentz oscillator expression L(E), A is the amplitude, is the In the band edge function, Ep (> This second

broadening parameter and E0 is the resonance energy.

Eg) defines a second transition energy (in addition to Eg), given by Ep+Eg.

transition energy separates the band edge region from the Lorentz oscillator region and provides flexibility that is lacking in the more common TaucLorentz expression [4-9]. Table 4.1 Best fit parameters and confidence limits that define Eqs. (4.1) and (4.2) for the dielectric function of a-Te.

38.791.97

2.9490.053

2.8670.075

0.9090.103

0.4970.154

2.8190.143

63

An

En (eV)

n (eV)

Eg (eV)

Ep (eV)

()

40 35
(degree)

30 25 20 15 180

36 etch th 37 etch

th

(degree)

160 140 120 100 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 4-5 Ellipsometric spectra for a CdTe thin film on a crystalline Si substrate after the 36th and 37th etch steps for comparison. The starting CdTe film thickness was 3500 .
40 35
(degree) (degree)

40 35 30 25 20 15 180
(degree)

30 25 20 15 180

37 etch fit

th

36 etch fit

th

(degree)

160 140 120 100 0 1 2 3 4 5 6 7

160 140 120 100 0 1 2 3 4 5 6 7

Photon Energy (eV)

Photon Energy (eV)

Figure 4-6 Ellipsometric spectra for a CdTe thin film on a crystalline Si substrate with a starting thickness of 3500 measured after the 37th (left) and 36th (right) etching steps (data points). Also shown are their best fits (broken lines).

64

native SiO2 c-Si


MSE = 5.896

20.5 0.1 2 mm

Figure 4-7 Model and best-fit parameters used for the analysis of the ellipsometric spectra of Fig. 4-6 (left panel) collected after the 37th etching step applied to a CdTe film on a crystalline Si substrate. Because the CdTe film is completely removed, this analysis provides the structure of the c-Si substrate. MSE indicates the mean square error in the fit.
Surface roughness 0.55 0.01 / 0.45 0.01 native SiO2 c-Si
MSE = 7.669

12.3 0.1 a-Te/void 20.5 2 mm

Figure 4-8 Model and best fit parameters used for the analysis of the ellipsometric spectra of Fig. 4-6 (right panel) collected after the 37th etching step applied to a CdTe film on a crystalline Si substrate. This analysis yields the structure of the a-Te layer on the c-Si substrate. The void volume fraction in the a-Te layer has been obtained by expressing the a-Te layer in this study of polycrystalline CdTe as a mixture of the a-Te obtained in a previous study of single crystal CdTe along with a void component.
20 15 10 5 0 15

1 2

10

0 0 1 2 3 4 5 6 7

Photon Energy (eV)

Figure 4-9 Real and Imaginary parts of the dielectric function 1 and 2 vs. photon energy for a-Te generated through Br2+methanol etching of a polycrystalline CdTe film. 65

20 15 10 5 0

a-Te reference

1 2

15 10 5 0 2 3 4 5 6

Photon Energy (eV)

Figure 4-10 A comparison of the a-Te optical properties deduced in this study (see Fig. 4-9) with the literature reference optical properties of a-Te from 1.5 to 6 eV, the latter obtained by etching single crystal CdTe. Now that the optical properties of a-Te have been determined, it is possible to apply the results in a model of spectra collected in the two etching experiments in order to improve the quality of fit to the data. A decrease in the MSE value will provide an

indicator of the correctness of the optical properties of a-Te layer obtained in this study. Figure 4-11 shows the ellipsometric spectra and the best fit for the same etching experiment as that in Fig. 4-6, but after the 35th etch step (left panel). The right panel

shows the optical model consisting of an a-Te/CdTe/c-Si structure along with the best fit parameters, confidence limits, and MSE value. Figure 4-12 shows the modeling results

corresponding to Fig. 4-11 but without introducing an a-Te layer and using CdTe surface roughness in the analysis instead. Similarly, Figures 4-13 and 4-14 compare the best fit of the ellipsometric spectra before the first additional etch for the same experiment as that 66

of Fig. 4-4, comparing the modeling results with and without the a-Te layer.

Finally in

Figs. 4-15 and 4-16 a comparison of the ellipsometric analysis after the 6th additional etch step for the same experiment as that in Figs. 4-13 and 4-14, comparing the modeling results with and without introducing the a-Te component into the model. In all three

situations, introduction of the a-Te component into the model lowers the MSE and thus, improves the quality of the fit to the spectra. As a result, it can be concluded that the

optical properties of a-Te extracted in this study are reliable and useful. Various features of the results of Figs. 4-11 to 4-16 are relevant for this and future investigations. First it can be noted that it is not necessary to include the a-Te

component in order to obtain accurate structural information when the CdTe thickness is much larger than the a-Te surface layer thickness. This is the case in Figs. 4-13-4-16.

In contrast when the CdTe is very thin, it becomes necessary to incorporate the a-Te component for an accurate CdTe void volume fraction. Figs. 4-11 and 4-12. This can be seen by comparing

Second, for the thinner (3500 ) as-deposited CdTe film, the a-Te

layer obtained even after many etching steps is relatively thin (14 ) and dense as can be seen from Fig. 4-11. In contrast, for the thicker (3 m) as-deposited CdTe film, the a-Te

containing layer is thicker (50-60 ), but with a much lower volume fraction of a-Te (0.2-0.3) as can be seen from Figs. 4-13 and 4-15. In spite of the large physical

thickness of the layers in this case, the effective thickness is identical to that of the a-Te layer on the thinner CdTe (13-14 ). This comparison suggests that etching of the very

thick film leads to greater inhomogeneity in the surface layer. 67

35 30
(degree)

25 20 15 180

35 etch fit

th

Surface roughness 0.97 0.03/0.03 0.03 CdTe 0.94 0.01 / 0.06 0.01 native SiO2 c-Si
MSE = 13.33

14 0.4 a-Te / void 109 1 CdTe / void 20.5 2 mm

(degree)

160 140 120 100 0 1 2 3 4 5 6 7

a-Te at surface: deff = 13.5


Photon Energy (eV)

Figure 4-11 Ellipsometric spectra for a CdTe thin film on a crystalline Si substrate with a starting thickness of 3500 measured after the 35th etch step (left panel). Also shown is the best fit and associated model deduced in the analysis of the ellipsometric spectra in order to extract the a-Te/CdTe/c-Si structural parameters (right panel).
35 30
(degree)

25 20 15 180 160

35 etch fit

th

Surface roughness 78 8 0.11 0.01/0.89 0.01 CdTe / void CdTe native SiO2 c-Si
MSE = 22.11

95 1 20.5 2 mm

(degree)

1.16 0.01 / 0.16 0.01 CdTe / void

140 120 100 80

Photon Energy (eV)

Figure 4-12 Experimental and best fit spectra (left panel) along with the best fit parameters and model (right panel) for comparison with the results of Fig. 4-11, but without introducing an a-Te component into the model. Such a model leads to a higher MSE. 68

35 30
(degree)

25 20 15 160

Surface roughness 59 2 0.220.01/0.290.02/0.490.01 a-Te/CdTe/void


before 1 etch fit
st

(degree)

140 120 100 2 3 4 5 6

CdTe 137 12 0.850.01/0/0.150.01 CdTe/a-Te/void CdTe semi infinite substrate 0.95 0.01 / 0.05 0.01 CdTe / void
MSE = 7.181

a-Te at surface: deff = 13 a-Te at sub-surface: deff = 20.5


Photon Energy (eV)

Figure 4-13 Ellipsometric spectra and the best fit (left panel) for a smoothened CdTe film with a starting thickness of 3 m obtained before the first additional etch after smoothening. Also shown is the model and best fit parameters used in the analysis of the ellipsometric spectra over the energy range of 2 to 6 eV in order to deduce the a-Te volume fraction in the surface roughness layer (right panel).
35 30
(degree)

25 20 15 160

before 1 etch fit

st

Surface roughness 84 0.7 0.51 0.01/0.49 0.01 CdTe / void CdTe semi infinite substrate 0.94 0.01 / 0.06 0.01 CdTe / void
MSE = 8.168

(degree)

140 120 100 2 3 4 5 6

Photon Energy (eV)

Figure 4-14 Experimental and best fit spectra (left panel) along with the best fit model and parameters (right panel) for comparison with the results of Fig. 4-13, but without introducing an a-Te component into the model. This ellipsometric analysis is associated with a 3 m thick smoothened CdTe film before the first additional etch after smoothening. 69

35 30
(degree)

25 20 15 160

Surface roughness 0.27 0.01/0.73 0.01

53 2 a-Te / void

6 etch fit

th

CdTe/a-Te 251 11 0.890.01/0.060.01/0.060.01 CdTe/a-Te/void CdTe semi infinite substrate 0.99 0.01 / 0.01 0.01 CdTe / void
MSE = 8.028

(degree)

140 120 100 2 3 4 5 6

a-Te at surface: deff = 14 a-Te at sub-surface: deff = 15

Photon Energy (eV)

Figure 4-15 Ellipsometric spectra and the best fit (left panel) for a smoothened CdTe film with a starting thickness of 3 m obtained after the 6th additional etch after smoothening. Also shown is the model and best fit parameters used in the analysis of the ellipsometric spectra over the energy range of 2 to 6 eV in order to deduce the surface roughness thickness and the a-Te volume fraction in the CdTe structure (right panel).
35 30
(degree)

25 20 15 160

6 etch fit

th

Surface roughness 0.68 0.01/0.32 0.01

100 4 CdTe / void

CdTe semi infinite substrate 1.02 0.01 / -0.02 0.01 CdTe / void
MSE = 39.38

(degree)

140 120 100 80

Photon Energy (eV)

Figure 4-16 Experimental and best fit spectra (left panel) along with the best fit model and parameters (right panel) for comparison with the results of Fig. 4-15 but without introducing an a-Te component into the model. This ellipsometric analysis is associated with a 3 m thick smoothened CdTe film after the 6th additional etch. 70

Chapter Five

Optical Properties of Thin Film CdTe and CdS before and after CdCl2 Post-deposition Treatment

5.1 Introduction A description of the optical properties of the TEC-15 glass substrate components has been provided in Chapter 3. Here in Chapter 5, the focus now shifts to the optical

properties of CdTe and CdS before and after the CdCl2 post-deposition treatment. The optical properties of as-deposited CdTe and CdS films on single crystalline Si (c-Si) substrates were determined as described previously [5-1]. Using this previous work on an

as-deposited CdTe film as a starting point, post-deposition CdCl2 treatment of the same film was performed as part of this thesis, and its optical properties were obtained after the treatment. In the case of CdS, a polycrystalline thin film prepared in the device

configuration on a fused silica prism enables measurements of the same CdS film through the prism before and after CdCl2 treatment, without loss of spectral range. As a first step toward studying the layers of the full solar cell, the CdTe film structural changes upon CdCl2 treatment were investigated using spectroscopic ellipsometry (SE) measurements of a CdTe film on a crystalline silicon (c-Si) substrate. 71

Because the c-Si is very smooth, the complexity of the data analysis is reduced as a result of the smooth, well-characterized interface between the film and substrate. In addition, the absence of an underlying CdS film, which is present in the solar cell structure, avoids the complication of alloying of the CdTe with S due to S in-diffusion. Analyses of CdTe

films in CdCl2 treated solar cell structures are described later in Chapter 6, and in that chapter the issue of S diffusion will be addressed. Upon CdCl2 treatment, it was observed in this study that the optical properties of the CdTe film on c-Si change dramatically as will be described in Sec. 5.3. The

modification experienced by the CdS film in the SiO2/CdS/CdTe structure as a result of the CdCl2 treatment is weaker; however, in this case, additional research needs to be performed in the future to explore the observed substrate dependence of the CdS optical properties and the role of the post-deposition treatment.

5.2 Optical properties of as-deposited CdTe and CdS films deposited on c-Si substrates The polycrystalline CdTe and CdS films of this study were magnetron sputtered under conditions similar to those yielding 14%-efficient solar cells
[5-2]

The CdTe

depositions were performed on native oxide-covered c-Si wafers in a system with two chambers and a load-lock (built by AJA International, Inc.) using 60 W rf power applied to the target, 18 mTorr Ar pressure, 23 sccm Ar flow, and a 10 1 cm target-substrate distance. The CdS depositions were performed similarly on c-Si in the two-chamber

system to obtain reference data, and on a fused silica prism in a separate single-chamber 72

system (built at Univ. Toledo) to explore the role of CdCl2 treatments; (Dr. Victor Plotnikov is acknowledged for assistance in the fabrication of this sample). For both As

CdS depositions, the rf power level was 50 W and the Ar pressure was 10 mTorr.

noted earlier, c-Si substrates and an optical quality fused silica prism were used in both cases due to their consistent optical properties and smoothness; thus, complications in optical analysis arising from substrate-induced surface roughness and film/substrate interface roughness were avoided. The true substrate temperatures T for the CdTe and CdS depositions on c-Si were 188 C and 225 C, respectively, as determined in an in situ SE calibration
[5-3]

The nominal substrate temperature T was 200 C for the CdS In this case, a

deposition on the fused silica prism in the single-chamber system.

measurement of true substrate temperature was not possible since real time SE was not used to probe the film growth process.
16 14 12 10 8
E0 E1 E1+1 E2

1,2

6 4 2 0
_______

-2 -4 1

188 C
2 3 4 5 6

- - - - Single crystal CdTe

photon energy (eV)

Figure 5-1 The room temperature dielectric functions of single crystal CdTe (broken lines) [5-4] and a CdTe film deposited at 188C (solid lines) [5-5]. The downward arrows point to the energy values of the four critical point transitions E0, E1, E1+1, and E2 identified in the band structure of Fig. 5-2. 73

Table 5.1 Fitting results for single crystal and thin film polycrystalline CdTe using an analytical model consisting of four critical points and one T-L background oscillator.
An CP(E0) Single CdTe CP(E1) CP(E2) T-L CP(E0) Film 188 C CP(E1) CP(E2) T-L En (eV) n (eV) n (degree) n EG 7.2830.407 1.4910.004 0.0410.006 20.8062.165 0.0480.003 4.8710.137 3.3100.002 0.3000.011 6.1494.598 1.0890.054 2.9750.343 1.7100.034 0.048 1.089 0.377 1.560 1.710 4.1200.301 5.3200.261 5.1600.003 0.9230.034 31.0568.876 1.5600.094 70.8533.536 4.7900.067 4.7730.380 8.9280.314 1.5270.007 0.0890.018 16.7911.194 2.3950.072 3.1990.018 0.6280.025 75.5015.900 1.8620.092 5.2080.023 0.9580.048 73.0894.033 4.790 3.7330.136 9.5236.253

crystal CP(E1+1) 7.3580.382 3.8940.003 0.2860.010 77.4731.798 0.3770.019

CdTe at CP(E1+1) 6.4580.131 3.9810.019 0.5160.022 96.1175.746

E1 E1+1

E0

E2

Figure 5-2

Band structure of CdTe [5-6].

74

E0
8

E1-A

E1-B

1,2

film CdS Tdep=225 C single crystal CdS

0 0 1 2 3 4 5 6

photon energy (eV)

Figure 5-3 The room temperature ordinary dielectric functions of single crystal (wurtzite) CdS (broken lines) [5-7] in comparison with the polycrystalline thin film CdS deposited on c-Si at 225 C (solid line) [5-1]. The three downward arrows point to the energy values of the critical point transitions. Table 5.2 Fitting results for single crystal and thin film polycrystalline CdS using an analytical model consisting of three critical points and one T-L background oscillator.
An CP(E0) Single CP(E1-A) 2.5810.190 4.8020.004 0.3490.021 50.3937.018 0.7770.085 crystal CP(E1-B) 5.5860.327 5.5180.008 0.6890.046 101.964.870 0.4890.058 CdS T-L CP(E0) 90.7705.560 6.2620.043 3.4210.232 6.7390.071 2.4260.004 0.1270.008 20.6970.621 0.103 0.777 1.5970.103 at 225 C CP(E1-B) 5.4580.112 5.4000.018 0.6200.026 79.6735.466 T-L 94.9318.038 6.262 4.6020.282 0.489 3.501 3.5010.046 1.4630.595 En (eV) n (eV) n (degree) n EG

6.7200.756 2.3990.003 0.2090.008 19.0560.836 0.1030.013

Film CdS CP(E1-A) 2.5330.146 4.9440.009 0.3490.020 55.4033.499

For all dielectric functions in Figs. 5-1 and 5-3, experimental (1, 2) results obtained by inversion of (, ) data were fit using an analytical model consisting of N critical

75

points (N=4 for CdTe and N=3 for CdS).

The locations of the four critical point features E0 represents the

of CdTe are identified in the band structure diagram of Fig. 5-2.

fundamental band gap transition at the zone center point, whereas the E1 complex is attributed to transitions along the L line between the L6 valence and conduction bands and between the L4,5 valence bands and the L6 conduction band. Each critical point was

modeled using an expression derived for Lorentzian broadened transitions between parabolic bands [5-8]:
=A n e(in ) { n /2[E n E i( n /2)]}n (5.1)

Thus each critical point is fit with five parameters, an amplitude An, a phase n, a broadening parameter or linewidth n, a resonance or band gap energy En, and an exponent n. These parameters are given in Table 5.1 for single crystal and thin film Also included

polycrystalline CdTe and in Table 5.2 for corresponding samples of CdS.

in the dielectric function model was a single broad background Tauc-Lorentz oscillator which was used to fit non-parallel-band transitions in energy regions between the critical points. The background is modeled using the expression: A 0 E 0 E E EG 2 = (E 2 E 2 )2 + 2 E 2 (E E G ) , E 0 0
2

(5.2)

where (E E G ) is a unit step function, centered at E=EG such that =1 when E > EG and =0 when E EG. This expression has four variable parameters, EG, the Tauc

band gap, A0, E0, and 0, the Lorentz oscillator resonance amplitude, energy, and broadening parameter, respectively. These parameters are also included in Tables 5.1

76

and 5.2 along with , the constant contribution to the dielectric function. may be due to transitions above the measured spectral range.

This constant

Negative values for

have been observed in similar such analyses of single crystal Si [5-9]; however, the origin of such unphysical values is unclear. The major difference between the polycrystalline thin film CdTe and single crystal CdTe dielectric functions derive from the critical point broadening parameters or linewidths, which are larger for the thin film most likely due to scattering of excited carriers at grain boundaries which reduces the lifetimes. For CdS, however, it is

observed that the single crystal has equal or larger critical point widths than the thin film. This effect is likely to be due to polishing damage at the near surface of the crystal in this case. The differences in the critical point energies are due to in-plane strain in the thin

films, and these strain shifts are currently being quantified in order to use the dielectric function to evaluate strain with the potential for on-line analysis
[5-10]

The strain

probed in this case lies in the plane of the film since the probing optical field, even though impinging on the film at oblique incidence, is strongly refracted so that the optical field lies predominantly in the plane. The differences in the critical point amplitudes can be attributed to either voids or tensile strain which decrease the An values or compressive strain which increase these values. The exponents n and the phases n are

expected to be the same in the film and single crystal, and in fact, the n values are fixed for the thin films at values deduced for the single crystal. The observed differences in the best fit n may be attributed to changes in excitonic interactions due to grain structure 77

or defects.

5.3 Optical properties of CdCl2 post-deposition treated CdTe and CdS In order to characterize the changes in the structure of the thin films of the solar cell upon post-deposition treatment, the optical properties of the treated CdTe and CdS must be obtained and compared to those of Section 5.2. The dielectric function of the

CdCl2-treated CdTe film deposited on a c-Si substrate was extracted in order to avoid complications of S diffusion in the completed solar cell. The optical properties of the treated CdTe are shown in Fig. 5-4.

12 8

12 8

4 0 -4 12

1
4 0 -4 12

CdTe as-deposited CdTe CdCl2 treated

CdTe single crystal CdTe CdCl2 treated

2
4 0 1 2 3 4 5 6 0 1 2 3 4 5 6

Photon Energy (eV)

Photon Energy (eV)

Figure 5-4 (left) Best fit analytical models of the room temperature dielectric functions for two CdTe films of thickness approximately 1000 , obtained from the same deposition but with different post-deposition processing: as-deposited (no treatments; broken line) and CdCl2-treated for 5 min at 387C (solid line); (right) a comparison between the CdCl2-treated CdTe film (solid line) and single crystal CdTe (broken line).

78

Table 5.3 Best fit dielectric function parameters comparing single crystal, CdCl2-treated, and as-deposited CdTe samples.
An CP(E0) Single CdTe CP(E1) CP(E2) T-L CP(E0) CdCl2 CdTe CP(E1) CP(E2) T-L CP(E0) Film 188 C CP(E1) CP(E2) T-L En (eV) n (eV) n (degree) n EG

7.2830.407 1.4910.004 0.0410.006 20.8062.165 0.0480.003 4.8710.137 3.3100.002 0.3000.011 6.1494.598 1.0890.054 2.9750.343 1.7100.034 0.048 1.089 0.377 1.560 1.710 0.048 1.089 0.377 1.560 1.710 4.1200.301 3.7560.175 5.3200.261 5.1600.003 0.9230.034 31.0568.876 1.5600.094 70.8533.536 4.7900.067 4.7730.380 7.7010.169 1.5030.005 0.0610.011 15.6250.449 4.2600.042 3.3210.003 0.3420.006 3.1461.034 4.7560.040 5.2140.003 0.8400.010 22.8850.821 79.2541.208 4.790 4.5760.075 8.9280.314 1.5270.007 0.0890.018 16.7911.194 2.3950.072 3.1990.018 0.6280.025 75.5015.900 1.8620.092 5.2080.023 0.9580.048 73.0894.033 4.790 3.7330.136 9.5236.253

crystal CP(E1+1) 7.3580.382 3.8940.003 0.2860.010 77.4731.798 0.3770.019

treated CP(E1+1) 6.1190.057 3.9130.004 0.2120.005 88.1421.689

CdTe at CP(E1+1) 6.4580.131 3.9810.019 0.5160.022 96.1175.746

As an example of the key role of the CdCl2 treatment, Fig. 5-4 and Table 5.3 compare best-fit analytical results for the room temperature dielectric functions of the single crystal CdTe, as-deposited thin film CdTe, and thin film CdTe with the 5 min CdCl2-treatment. The optical model used here is the same as that described in Section 5.2. The spectra in Fig. 5-4 for the treated film were obtained after a sufficient number of etch cycles, so that its thickness matched that at which the as-deposited film was measured (~ 1000 ). It is clear from Table 5.3 that the CdCl2-treatment leads to a

significant narrowing of the critical points so as to be nearly indistinguishable from the single crystal as shown in Fig. 5-4. This is an indication of an increase in grain size and

/or a reduction in defect density upon treatment. 79

The narrower higher energy critical points for the treated film may be due to its higher quality surface compared to the single crystal. Also in Table 5.3 the critical point

energies of the treated film approach those of the single crystal, indicating that strain in the film is relaxed as a result of the CdCl2 treatment. As a result, the primary difference

between the dielectric function of the CdCl2-treated film and the single crystal is the presence of a small volume fraction of voids (0.01 0.002) that exist preferentially near the surface and reduce the amplitudes of the higher energy critical points. It is more difficult to perform the corresponding experiment for CdCl2 treatment of the CdS film. First, the effectiveness of the etching procedure which is used to remove

the thick oxide and surface roughness layers for determination of the treated CdTe dielectric function, in fact, has yet to be successfully demonstrated for CdS. Second, in order for post-deposition treatment studies of the CdS to be at all relevant for device structures, the CdS must be capped with a layer of CdTe, as this layer is likely to have a significant impact on the structural change upon treatment. Because an overlying CdTe

layer significantly attenuates the light irradiance entering the CdS from the CdTe/ambient side at photon energies above the band gap of the CdTe, the use of a prism arrangement has been explored in order to study the effect of treatment on the CdS. In this study,

CdS with an intended thickness of 3000 is deposited directly onto one face of a 60 fused silica prism held at a nominal temperature of 200C, and then over-deposited with CdTe to an intended thickness of 5.0 m. The true temperature of the surface of the

film is difficult to assess in this case and should be much lower than 200C due to the 80

different geometry of the substrate holder necessitated by the prism and the lack of a real time SE analysis capability on the deposition chamber (see Fig. 5-5). Finally the sample

structure and CdS dielectric function are measured by spectroscopic ellipsometry through the prism side before and after the CdCl2-treatment.

Sputtering chamber

Substrate holder Heating wire

Plasma CdTe Target Ground Shield

Fused silica prism substrate

CdS Target

Figure 5-5 A schematic of the sputtering chamber for CdTe/CdS deposition on a fused silica prism (reproduced with permission from Victor Plotnikov, Ph.D. Thesis, University of Toledo, 2009).

Figure 5-6 (left) shows the analytically derived dielectric function of CdS as-deposited on the prism and measured from the prism side, in comparison with that of CdS as-deposited on c-Si at 225C and measured from the ambient side. The dielectric

function of the CdS as-deposited on the prism is suppressed significantly in amplitude at the higher energies, and the high energy critical point structure is very broad. Because

the light beam does not penetrate very deeply into the CdS at these higher energies, the results are characteristic of the CdS at the prism interface which is apparently either a low 81

density material due to incomplete space filling during nucleation or instead a physical mixture of the substrate material with CdS due to microscopic roughness. Alternatively,

a chemical mixture may occur at the interface due to intermixing induced by the impact of sputtered species. The extensive broadening of the high energy critical points E1-A

and E1-B would suggest a nanocrystalline CdS character at the interface; however other explanations for this such as a chemical interaction and diffusion are certainly possible. Figure 5-6 (right) shows that the CdCl2 treatment process appears to densify the CdS, but the material exhibits a similar interface nature as the as-deposited film.

8 6 4 2 0 8 6 4 2 0 1 2 3 4 5 6

8 6 4 2

CdS as deposited on prism CdS as deposited on c-Si

CdS as deposited CdS CdCl2 treated

on prism

0 1 2 3 4 5 6

Photon Energy (eV)

Photon Energy (eV)

Figure 5-6 (left) Best fit analytical models for the room temperature dielectric functions of a CdS film as-deposited on a fused silica prism measured from the prism side and on a c-Si wafer measured from the ambient side; (right) best fit analytical model for the room temperature dielectric functions of CdS measured from the prism side before and after a 30 min CdCl2 treatment at 387C.

82

Table 5.4 Best fit dielectric function parameters for as-deposited CdS on a fused silica prism, CdCl2-treated CdS on the prism, and. as-deposited CdS on c-Si.
An CP(E0) CdS as deposited on prism En (eV) n (eV) n (degree) n 0.103 0.1980.023 3.501 EG

6.2360.030 2.4980.001 0.2260.003 24.2680.297

CP(E1-A) 0.3160.051 4.8800.100 1.1780.284 32.19439.738 1.8610.858 CP(E1-B) 4.4740.129 5.2860.026 1.0840.090 108.212.472 T-L 57.7115.145 6.262 14.828 0.3240.005

CdCl2 treated CdS on prism

CP(E0)

2.1800.106 2.4530.004 0.4860.013 34.0413.277 0.4730.030 9.1534.829 1.8040.021 0.103 0.777 0.489 3.501 1.5970.103

CP(E1-A) 1.6280.498 4.9230.223 2.5070.271 123.8810.262 1.1970.195 CP(E1-B) 11.9614.281 5.3540.007 0.9440.114 172.964.398 0.1480.092 T-L CP(E0) 75.4275.834 6.8100.262 9.1451.009 6.7390.071 2.4260.004 0.1270.008 20.6970.621

CdS as deposited on c-Si

CP(E1-A) 2.5330.146 4.9440.009 0.3490.020 55.4033.499 CP(E1-B) 5.4580.112 5.4000.018 0.6200.026 79.6735.466 T-L 94.9318.038 6.262 4.6020.282

Table 5.4 shows a comparison of the parameters used in the analytical model for the three dielectric functions of Fig. 5-6. A comparison of the critical point energies reveals

that the CdCl2 treatment leads to a reduction in the E0 energy from the as deposited value to a value closer to the single crystal. This effect would appear to be characteristic of The situation

strain relaxation, as also occurs in the case of CdCl2 treatment of CdTe. for the E1A transition is likely to be more complicated.

A single, broad E1 peak for the

as-deposited film on the fused silica prism is an indication of a film without preferential orientation of the crystallites. In contrast, the clear E1A-E1B doublet for the as-deposited The observed significant

film on c-Si is an indication of preferential c-axis orientation.

shift of oscillator strength to higher energy upon treatment could also be due to a change

83

in the grain texture that leads to preferential c-axis orientation.

Clearly further work

needs to be undertaken, in particular to understand whether the differences in the as-deposited dielectric functions of CdS on c-Si and CdS on fused silica are due to top-surface vs. back surface measurement method or due to differences in the nature of deposition on the two substrates.

5.4 Etch-back profiling of CdTe thin film structure after post-deposition treatments Analysis results are presented next that focus on the effects of post-deposition processing on the structural depth profile of CdTe films deposited on native oxide-covered c-Si substrates. Sequential etching was applied to three ~ 3000 thick These films were exposed to

CdTe films co-deposited on c-Si substrates held at 188C.

the following post-deposition processing conditions: (i) as-deposited (i.e., no treatments), (ii) thermally annealed at 387C in an atmosphere of Ar for 30 min, and (iii) CdCl2 treated also at 387C, but for 5 min. etching was 0.05 vol.% in methanol. The Br2 concentration used in this study for For each sample, the etch-profiling method was

performed using successive immersion steps in Br2+methanol, with each etch step leading to a ~ 300 reduction in the bulk layer thickness. Because of the relative smoothness of the as-deposited CdTe on c-Si substrates (compared, for example, to depositions on rough TEC glasses), the successive etching treatments led to very smooth surfaces from which high accuracy dielectric function determinations were possible. In

addition, the absence of an underlying CdS film in this case avoided the complication of 84

alloying of CdTe due to S in-diffusion that may be especially notable in the later stages of etching as the CdTe is fully removed. This complication will be discussed further in Chapter 6.

Figure 5-7 Resonance energies En (upper panel) and linewidths n (lower panel) for the critical point transitions in single crystal CdTe (broken lines) and in db ~ 1000 thick CdTe films sputter-deposited at different temperatures (points), all measured at 15C [5-10] .

Figure 5-7 highlights the consistent differences between the critical point parameters of as-deposited CdTe films and the single crystal. 85 The latter is characteristic

of CdCl2-treated CdTe as shown in Fig. 5-6 (right).

Results for five different

as-deposited films prepared at different substrate temperatures from 188 C to 304 C reveal the following characteristics relative to the single crystal: (i) higher energy E0, E1+1, and E2 critical point transitions, (ii) lower energy E1 transitions such that the spin orbit splitting energy is larger than in the single crystal, and (iii) broader critical points with the E1 transition showing the largest variation with substrate temperature. In the

next paragraph, the focus will be on the E1 critical point in an evaluation of the effect of the CdCl2 treatment on the structural depth profile of the CdTe film.

etching etching

Figure 5-8 Critical point energies (upper panel) and widths (lower panel) as functions of CdTe bulk layer thickness during etching by Br2+methanol for co-deposited CdTe films processed in three different ways: (i) as-deposited, (ii) annealed in Ar for 30 min, and (iii) CdCl2 treated for 5 min. The deviations at low thickness are due to the onset of semi-transparency at the E1 critical point energy. 86

Figure 5-8 presents the depth profiles in the E1 critical point energy and width relative to those of the single crystal values. These results provide information on the New

depth profiles in the strain and grain size, respectively, throughout the film. experimental results
[5-11]

suggest that the E1 transition shifts to lower energy with With this new insight, Similarly, Fig.

increasing strain consistent with a stress shift of (0.2 eV/GPa).

the depth profiles in the critical point energies take on greater meaning.

5-9 presents depth profiles in the void fraction that provide information on the structural uniformity. For the as-deposited CdTe film, the red-shift of E1 relative to the single crystal value in the top panel of Fig. 5-8 suggests significant strain in this film over the studied depth range of 1500-2000 ; (the depth is measured relative to the substrate interface at 0 ). The maximum E1 energy shift of 0.12 eV at a depth of 1500 corresponds to a

stress level of 0.6 GPa, which is consistent with results for these as-deposited films in Fig. 5-7. The depth profile in the void volume fraction in Fig. 5-9 provides additional The film is observed to undergo a structural transition

indirect evidence for this strain.

near 1500 whereby the strain is ultimately relaxed (after 2000 thickness) through generation of voids and their continued evolution with thickness as shown in Fig. 5-9. The lower panel of Fig. 5-8 shows that the as-deposited film has a very large broadening parameter E1 ~ 0.6 0.15 eV which appears to be decreasing with increasing thickness (or distance from the substrate interface). This is indicative of a very small grain size (~ 10 nm) which appears to be increasing with thickness [5-11]. 87

Upon annealing of the CdTe film in Ar, the strain nearest the substrate is significantly reduced as the grain size increases (reduced E1). Even after 30 min of

annealing in Ar, however, there is no significant reduction in the grain size within 500 of the surface, and the strain in this region increases somewhat relative to the as-deposited film (as indicated by the lower E1 energy). Figure 5-9 shows that the void

fraction in the surface region is reduced upon annealing in Ar and thus, the structure of the film becomes more uniform throughout the thickness.

Figure 5-9 Relative void volume fractions as functions of CdTe bulk layer thickness during etching by Br2+methanol for co-deposited CdTe films on c-Si processed in three different ways: (i) as-deposited, (ii) thermally annealed in Ar for 30 min at 387C, and (iii) CdCl2-treated for 5 min at 387C. For the as-deposited and annealed films, the void fraction is scaled relative to the observed highest density film. For the CdCl2-treated film, the void volume fraction is scaled relative to single crystal CdTe.

88

A 5 min CdCl2 treatment leads to an E1 energy within 10 meV (i.e., within experimental error) of the single crystal value throughout the thickness, suggesting a fully strain-relaxed film. In addition, E1 has been reduced significantly to a constant value

of E1 ~ 0.30 0.02 eV throughout the bulk of the film, indicating a significant increase in grain size. Finally the CdCl2 treatment leads to a uniform void volume fraction 0.05 0.02. Considerably more scatter exists

throughout most of the bulk of the film:

in these CdCl2 treated data, however, compared with those of the other samples, possibly an effect of the Br2+methanol etching of a large-grained, relatively thin film. Figure 5-9

shows that voids have been pushed to the near-surface region of the CdCl2 treated film which is likely to be the result of a much larger surface roughness layer thickness. Finally, it should be noted that the void fractions for the as-deposited and Ar annealed films in Fig. 5-9 are plotted relative to that of the as-deposited film at the minimum thickness of ~1250 . For this material, which is under significant compressive stress For the

(0.6 GPa), the apparent density is ~0.03 higher than that of single crystal CdTe.

CdCl2 treated film, the observed void fraction of 0.05 0.02 is scaled relative to the single crystal.

89

Annealed CdTe Experiment # 1 Experiment # 2

Annealed CdTe Experiment # 1 Experiment # 2

Figure 5-10 Energy of the E1 transition (upper panel) and its width E1 (lower panel) as functions of CdTe bulk layer thickness in successive Br2+methanol etching steps for ~3000 thick CdTe films. The two films were processed under identical conditions including fabrication on c-Si wafer substrates and annealing in Ar at 387C for 30 minutes. The data for experiment #1 are the same as those depicted in Fig. 5-8.

CdCl2 treated Experiment # 1 Experiment # 2 CdCl2 treated Experiment # 1 Experiment # 2

Figure 5-11 Energy of the E1 transition (upper panel) and its width E1 (lower panel) as functions of CdTe bulk layer thickness in successive Br2-methanol etching steps for ~3000 thick CdTe films. The two films were processed under similar conditions including fabrication on c-Si wafer substrates and CdCl2 treatment for 5 minutes. The data for experiment #1 are the same as those depicted in Fig. 5-8. 90

The results of Figs. 5-8 and 5-9 can be clearly understood in terms of CdTe grain growth and strain relaxation effects of the CdCl2 treatment, and can even identify clear differences in behavior between the CdCl2 treatment and simply annealing in Ar. In

further experiments, the reproducibility of the etch-profiling studies of such films has been explored with the goal being to corroborate the above interpretation. Figure 5-10 shows the Ar annealing behavior of thin (3000-3300 ) CdTe films on c-Si substrates from two independent experiments for comparison. The solid squares

are the same results as shown in Fig. 5-8, and the open triangles denote the results of a second experiment performed on a different sample prepared and annealed under identical conditions. The annealing behavior is reasonably well reproduced in the two experiments, considering that the film thickness in the second experiment is somewhat lower. In both experiments, the E1 energy lies ~ 20 meV lower than that of single

crystal CdTe, indicating residual stress of ~0.1 GPa, and the width E1 increases toward the surface, indicating a smaller near-surface grain size in both experiments. Figure 5-11 shows results for E1 and E1 from the two experiments on CdTe films in which CdCl2 treatments were applied for 5 min. been presented earlier in Fig. 5-8. The results of the first experiment have

This first experiment was performed with a CdCl2

treatment temperature of 387C, whereas the second was performed using a higher temperature of 397C. Another difference between the two experiments -- the age of the More importantly, for both

prepared CdCl2 sources -- was deemed insignificant.

experiments, the treatment was the first one for each of the two CdCl2 vapor sources. 91

Although the overall results of the two experiments of Fig. 5-11 are similar, certain details in the second experiment suggest an effect of the higher temperature. First, for

the second experiment, the grain size increases more significantly toward the surface than in the first experiment. In fact, the broadening parameter in the top 500 of the film

drops below that of single crystal CdTe. This effect may reflect a dielectric function for the single crystal CdTe from the reference
[5-4]

that may be influenced either by Second, a comparison of Fig.

experimental errors or by greater near-surface damage.

5-12 with Fig. 5-9 shows that the void profile in the second experiment is not nearly as uniform as in the first. This feature is likely due to the higher temperature which leads

to a densification of the underlying large grain crystalline material at the expense of significant roughness with surface connected voids that extend well into the film. A hint

of this effect appears for the CdCl2 treated film in Fig. 5-9, but the effect appears quite strongly in Fig. 5-12.
Experiment #2 CdCl2 treated CdTe film Experiment #2 Ar annealed CdTe film

Figure 5-12 Void volume fraction as a function of CdTe bulk layer thickness in successive Br2-methanol etching steps for ~3000 thick CdTe films in a second experiment for comparison with the results in Fig. 5-9. Two different post-deposition 92

processing procedures were used: (i) an anneal in Ar for 30 min, and (ii) a CdCl2-treatment for 5 min. For the Ar annealed films, the void fraction is scaled relative to the depth at which the highest density is observed. For the CdCl2-treated film, the void volume fraction is scaled relative to single crystal CdTe. The void structure for the film annealed in Ar is attributed to structure in the as-deposited film (as in Fig. 5-8). In contrast, the void structure for the CdCl2 treated film is associated with extensive near-surface roughness. In the above studies, it is clear that a short 5 min CdCl2 treatment is observed to have a more significant effect in relaxing strain and enhancing grain growth than a 30 min anneal in Ar. This reveals the reactive nature of the CdCl2 treatment. These studies

suggest clear directions for future work which should involve the effects of treatment time and temperature on the depth profiles of the strain and grain size. This may enable

one to study the kinetics of grain growth and the separate roles of the surface and substrate interface in this process.

93

Chapter Six

Optical Structure of As-deposited and CdCl2-treated CdTe Superstrate Solar Cells

6.1 Introduction The multilayer optical structure of thin film solar cells is of interest because it provides insights into the optical quantum efficiency as well as the optical losses that limit the short-circuit current
[6-1]

The optical structure may also identify

process-property relationships that assist in process optimization. A powerful probe of optical structure is real time spectroscopic ellipsometry (SE) [6-2] that can be performed during the deposition of each layer of the solar cell as well as during post-deposition processing. In some circumstances, however, the deposition or processing geometry

precludes optical access; in this case, ex-situ SE becomes the only option. The CdTe solar cell poses considerable challenges for analysis by ex-situ SE
[6-3]

First, the relatively large thickness of the as-deposited CdTe layer leads to considerable surface roughness, and the conventional CdCl2 post-deposition treatment generates significant additional oxidation and surface inhomogeneity. Thus, ex-situ SE

measurements in reflection from the free CdTe surface can be very difficult if not impossible. Second, SE performed from the glass side of the solar cell is adversely 94

affected by the top glass surface which generates an incoherent reflection and consequent depolarization. In this research, the problem of the free CdTe surface is solved through the use of Br2+methanol treatments that etch and smoothen the CdTe [6-4]. The problem of the free

glass surface is solved through the use of a 60 prism optically-contacted to the top glass surface that eliminates the top surface reflection. In an additional approach, the top surface reflection is eliminated through spatial filtering of the reflected beam, which is possible due to the relatively thick glass substrate. In this chapter, comprehensive ex-situ spectroscopic ellipsometry studies are described that have been applied to investigate the multilayer optical structure of thin film CdTe solar cells in the superstrate configuration before and after the CdCl2 treatment. Dielectric functions have been obtained by SE for all layers of these cells as described in previous chapters. is available. As a result, a reference library for ex-situ analysis of CdTe solar cells With the

The library used in this chapter is shown in Table 6.1.

Br2+methanol layer-by-layer etching, it has been possible to gain a better understanding of the underlying structure for the as-deposited CdTe film by tracking the optical properties of the CdTe layer as a function of depth from the surface and proximity to the CdS/CdTe interface. In order to evaluate the role of the CdCl2 treatment, such In the latter

experiments have also been performed on the treated solar cell.

experiments, ex-situ SE is performed from the CdTe film side in the etching process and also from the glass side either by (i) using a 60 fused silica prism optically contacted to 95

the soda lime glass substrate with index matching fluid, or (ii) blocking the top surface reflection using an iris.

6.2 Experimental details In this study, the CdS and CdTe layers of the cells were prepared by rf magnetron sputtering
[6-5]

but no back contact deposition and anneal were performed.

The CdS

depositions were performed directly on TEC-15 glass substrates at a nominal deposition temperature of 160C using 50 W rf power applied to the target, 10 mTorr Ar pressure, 23 sccm Ar flow, and a 10 1 cm distance between the target and the substrate. The CdTe

depositions were performed similarly on each CdS film, with the exception that the nominal deposition temperature was 180 C; (Dr. Jennifer Drayton is acknowledged for deposition of these samples). Thus, the layered structure of the cells studied here Some of these cell Ex-situ SE has been

includes TEC-15 glass coated with sputtered CdS and CdTe. structures were subjected to a 30-min. CdCl2 treatment at 387C.

applied for analysis of the CdTe-based solar cells before and after the CdCl2 treatment. In order to perform reliable measurements from the CdTe free surface, the rough surface region was removed through successive Br2+methanol etches, leaving a much smoother surface suitable for SE measurements. In a series of etches applied to the CdTe cell

structures, the CdTe layer was also removed step by step, which provided a useful method for optical depth profiling of the structures.

96

Additional experiments were carried out in which the same CdCl2 treated solar cell structure was probed in two ex-situ SE measurements, one from the CdTe film side and the other from the glass substrate side. In order to perform reliable measurements from

the glass side of the solar cell in this comparison, a 60 fused silica prism was contacted with index-coupling fluid to the soda lime glass of the solar cell substrate, thus suppressing the incoherent reflection from the top ambient/glass interface. These two measurements can be compared to achieve greater confidence in the analysis of glass side measurement, which could be adversely affected by stress in the prism and glass substrate as well as by imperfect index-matching to the prism. Furthermore, experimental SE

measurements from the free CdTe side performed in successive etches can be used (i) for assessing the confidence limits on the parameters that describe the underlying structure, as well as (ii) for depth profiling of the CdTe high energy critical point parameters as has been described previously in Chapter 5.

6.3 Results and discussion: film side and prism side measurements By performing numerous etching/measurement cycles, this process simulates a real time spectroscopic ellipsometry measurement, but reversed in time. Figure 6-1 shows the CdTe surface roughness layer thickness and bulk layer void volume fraction during etching of the as-deposited solar cell. Each point represents an etching step that leads to a reduction in the bulk layer thickness of the CdTe, starting from an initial value of 2.4 m. The thickness of the CdTe is determined from an analysis of spectroscopic data at 97

low energies ( 1.45 eV) where thin film interference oscillations are present.

The

surface roughness thickness and bulk layer void volume fraction are determined from the data at high energies ( 3 eV) where the CdTe is opaque and high surface sensitivity is attained.

Table 6.1 Dielectric function library used in spectroscopic ellipsometry data analyses for CdTe solar cells. Material Description File name Soda lime TEC-15 SLG_pilkington_TEC15_20c_userdefined_02162006.mat glass component TEC-15 SnO2 SnO2_pilkington_TEC15_20c_drudecppb_09172009.mat component TEC-15 SiO2 SiO2_pilkington_TEC15_20c_cauchypole_02172006.mat component TEC-15 SnO2:F SnO2F_pilkington_TEC15_20c__inver.go_09152009.mat component Sputtered nominal 400 C CdS CdS_UT_Tser320C_20C_GO_12032005.mat (Figs. 6-1, 6-2, 6-7, 6-9) Sputtered nominal 200 C (Figs 6-2, 6-4); CdTe CdTe_UT_Tser188C_20C_inver_06212004.mat Single crystal (Figs. 6-1, 6-3, 6-5, 6-6, 6-7, 6-9)

Figure 6-1(a) shows that after about 7 etching steps the surface roughness and void fraction stabilize with very small variations thereafter. With successive etching steps,

the surface roughness shows random fluctuations over the range of 42-47 whereas the void fraction (scaled relative to that at the etch step when the highest density CdTe is obtained) lies in the narrow range of 0.01-0.02. 98 The void fraction for this sample is

uniform over a wide range of bulk layer thicknesses, from 0.4 to 1.6 m.

For a CdTe

film of this starting bulk layer thickness (2.4 m), there is also a thick region of surface-connected microvoids that extends 0.8 m into the film and is interpreted in the model as a bulk layer. A very high void fraction (~ 0.3) is obtained in the top 0.2 m

of the bulk layer. This material is readily removed in the etching process. Figure 6-2 shows the CdTe surface roughness layer thickness and bulk layer void volume fraction during etching of the CdCl2 treated solar cell. These results show that

after about 5 etching steps the surface roughness and void fraction stabilize with weak variations thereafter. In this case with successive etching steps, the surface roughness

shows random fluctuations over the range of 20-40 whereas the void fraction (scaled relative to single crystal CdTe) lies in the range of 0.01-0.06, and is tentatively attributed to a density deficit in the grain boundary regions. proposed schematic of the film structure. Figure 6-2 (b) shows a

The surface roughness thickness and void

fraction exhibit greater fluctuations for the CdCl2 treated solar cell possibly due to the larger grained structure which leads to greater non-uniformity in the etching process.
70

surface roughness thickness, ds () void volume fraction, fv

asc42 as deposited CdTe:etching process low Energy for db: 1.0 ~ 1.45 eV high E range for (ds, fv): 3.0 ~ 6.5 eV

60

50

40 0.3 0.2 0.1 0.0 4000

depth resolution 1/ (3 eV) ~ 400

8000

12000

16000

20000

24000

CdTe bulk thickness, db ()

Figure 6-1

Evolution of the surface roughness thickness and a depth profile of the void 99

volume fraction plotted versus bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk layer thickness of an as-deposited CdTe component of a solar cell.
0.5 void fraction
120

0.01 m

surface roughness thickness, ds ()

100 80 60 40 20

asc34 treated etching process low E range for db : 1.0 ~ 1.45 eV high E range for (ds, fv) : 3.0 ~ 6.0 eV

0.20-0.30 void fraction

0.3 m

1.8 m 2.1 m
depth resolution 1/(3 eV) ~ 400

void volume fraction, fv

0.30

0.15

0.02-0.05 void fraction


0.00 5000 10000 15000 20000

bulk layer thickness, db ()

(a)

(b)

Figure 6-2 (a, left) Evolution of the surface roughness thickness and a depth profile of the void volume fraction plotted versus bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk layer thickness of the CdCl2-treated CdTe component of a solar cell; (b, right) a schematic structure suggested from (a). Additional information on the depth profile of the structure can be deduced from analyses of the energies and widths of the critical point transitions. The results of such

analyses when applied to the as-deposited CdTe solar cell, are depicted in Fig. 6-3. The critical point energies show a systematic variation with etching to a bulk layer depth of 0.5 m. This can be attributed to an increase in compressive strain with increasing Figure 6-3 also shows that the broadening

thickness for the as-deposited CdTe film.

parameter values (or linewidths) are relatively constant, but are quite large compared with those of the CdCl2 treated CdTe of Fig. 6-4. 100 For the E1, E1+1, and E2 transitions, the

broadening values for the as-deposited film at 0.8 m are 0.45, 0.48, and 1.08 eV, respectively. The corresponding values for the CdCl2-treated films are 0.30, 0.30, and These results suggest that the as-deposited CdTe film has a

0.98 eV, respectively. smaller grain size.

For the corresponding Br2+methanol etching results shown in Fig. 6-4(a), obtained on the CdCl2-treated solar cell, the energies remain essentially constant with etching from below the surface region to a depth of 0.8 m. This result shows that the effects of the

CdCl2 treatment in the CdTe solar cell are not only to increase the grain size, but also to relax strain in the film. A second experiment performed with higher depth resolution,

however, shows that as the CdS interface is approached, detectable shifts occur that may be attributed either to residual interface strain and/or to the presence of S in the CdTe. Unfortunately, it is not possible to probe through the CdS/CdTe interface since etching studies of a single CdS film show that it is severely roughened and ultimately delaminated by the Br2+methanol etch. Figure 6-4(b) shows results for the depth profile of the linewidths of the prominent E1, E1+1, and E2 critical points. The widths associated with the surface layer are

typically broader possibly due to the presence of an inhomogeneous region generated by the CdCl2 treatment. The widths reach a minimum once the surface layer is removed It should be noted that the E1

and the bulk film void fraction stabilizes below 0.06.

linewidth shows behavior opposite to this possibly due to correlation with the nearby E1+1 linewidth. As etching of the CdTe progresses toward the CdS interface, all three 101

broadening parameters increase.

This effect may be attributed to CdTe crystallite

growth in the CdCl2 treatment that progresses from the surface to the CdS interface, leaving a structure such as that shown in the schematic of Fig. 6-4(c). Alternatively, an

alloying effect of S with CdTe may be a possible explanation; however; this explanation is not favored due to the lack of systematic variations in the critical point energies. The results in Fig. 6-4(b) for the critical point widths can be understood using a simple model of independent line broadening mechanisms each described by hi ~ h/i (in photon energy), whereby the resulting transition lifetime is given as: 1/ = 1/1 + 1/2 + 1/3 +
[6-6]

Here 1, 2, and 3 indicate, for example, the processes of phonon The latter process can be

scattering, impurity scattering, and grain boundary scattering.

written as 1/3 = /R, where is the electron group velocity and R is the average grain radius. For a polycrystalline material in which grain boundary scattering controls the

variation in linewidth, the result h = b + (h/R) is obtained, where (h/R) is the grain boundary scattering term and b is the single crystal width
[6-6]

In fact b is

typically controlled by phonon scattering, which leads to a dependence of b on the measurement temperature. Thus, the simple schematic of the sample structure in Fig.

6-4(c), could account for the increase in transition widths with increasing depth as shown in Fig. 6-4(b). When impurity scattering is the dominant mechanism, for example,

considering S atoms in a random CdTe1-xSx (x < 0.1) alloy, then R can be considered as proportional to the average distance between atoms.

102

Figure 6-3 (left) Depth profiles of the critical point energies of the E1, E1+1 and E2 transitions in the as-deposited CdTe layer of a solar cell, plotted versus bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk thickness; (right) depth profiles of the linewidths of the E1, E1+1 and E2 transitions obtained in the same experiment.

103

3.38 3.36

asc34 treated: etching process low E range for db : 1.0 ~1.45 eV energy of E1 transition (3.310 eV)
E1 (eV)

0.40 0.35 0.30 0.25 0.35


E1+1 (eV)

E1 (eV)

3.34 3.32 3.900

high E range for (E1, E1+1, E2) : 3.0 ~ 6.0 eV

asc34 treated: etching process low E range for db : 1.0 ~1.45 eV high E range for (E1, E1+1, E2) : 3.0 ~ 6.0 eV width of E1 transition (3.310 eV)

energy of E1+1 transition (5.894 eV) E1+1 (eV)


3.896 3.892 5.20

width of E1+1 transition (5.894 eV)

0.30 1.05

5.18 5.17 8000 12000 16000 20000

E2 (eV)

E2 (eV)

5.19

energy of E2 transition (5.160 eV)

1.00 0.95

width of E2 transition (5.160 eV)

8000

12000

16000

20000

(a)

0.5 void fraction 0.20-0.30 void fraction

0.01 m

(b)

1.5 m 2.1 m

0.02-0.03 void fraction

(c)

Figure 6-4 (a, top left) Depth profiles of the critical point energies of the E1, E1+1 and E2 transitions in the CdCl2-treated CdTe layer of a solar cell, plotted versus the bulk layer thickness obtained in successive Br2+methanol etching steps that reduce the bulk thickness; (b, top right) depth profiles of the linewidths of the E1, E1+1 and E2 transitions obtained in the same experiment; (c, bottom) a schematic structure suggested from (b).

A similar analysis was applied to a second CdCl2-treated solar cell structure co-deposited with the structure of Figs. 6-2 and 6-4 again using the high energy range of 104

bulk layer thickness, db ()

bulk layer thickness, db ( )

the spectra collected during etching to determine depth profiles in the energies and linewidths of the CPs. The purpose of this analysis is to assess the reproducibility of the observed behavior in Fig. 6-4 while achieving a greater depth resolution and approaching closer to the CdS/CdTe interface. Figure 6-5 shows the energies of the E1, E1 + 1, and E2 transitions versus CdTe thickness all from successive etches. The data in the energies in Fig. 6-5 show relatively weak variations; however, as the CdS interface region is approached, E2 -- which appears to be a more sensitive indicator of structural deviations from the single crystal -increases systematically, possibly due to interface compressive strain or to in-diffusion of S. The very weak shifts in E1, E1 + 1, which appear only at the end of etching below a bulk layer thickness of 2000 , are not consistent with compressive strain; thus, in-diffusion of S seems to be a more likely possibility to explain the behavior of the E2 transition. The broadening parameters corresponding to each critical point have also been investigated. Figure 6-6 shows that E1, E1 + 1, and E2 all increase gradually, an effect

which corroborates similar results obtained from the co-deposited solar cell presented previously in Fig. 6-4(b). This effect may be due to grain size reductions and/or to the

effects of S alloying when the interface is approached, as in the case of the energy E2 described in the previous paragraph. Given the small differences in the energies in Fig.

6-5 compared to crystal CdTe, strain is unlikely to cause the significant broadening effects in Fig. 6-6. 105

c-CdTe E1+1 = 3.894 eV

Figure 6-5 Energies of the E1, E1+1, and E2 transitions as functions of CdTe bulk layer thickness in successive etches of a CdCl2 treated CdTe solar cell that reach within 0.1 m of the CdS/CdTe interface.

Figure 6-6 Broadening parameters E1 , E1+1, and E2 as functions of CdTe bulk layer thickness in successive etches of a CdCl2 treated CdTe solar cell that reach within 0.1 m of the CdS/CdTe interface. In order to understand better the variation of the critical point parameters in CdTe solar cell structures, the results of Figs. 6-5 and 6-6 can be considered in view of similar

106

results on thin films in Chapter 5.

First, the Chapter 5 results (Fig. 5-8, top) suggest that

interface strain is not a significant factor for the CdCl2-treated sample structure, and thus, any weak variations in the energies in Fig. 6-5 may be more likely due to alloying. Second, considering the depth profile of the broadening parameters in Fig. 5-8 (bottom), such results for the Ar annealed film are interpreted to suggest that grain boundaries remain fixed at the surface but grain growth occurs sub-surface. In contrast, the CdCl2

treatment is shown to generate a more rapid grain growth effect not only well into the bulk but also on the surface. Thus, a key role of the CdCl2 treatment is to generate The results in Figs. 6-4 (b) and 6-6

uniform grain growth throughout the thickness.

suggest that grain growth does not extend all the way to the CdS interface in the solar cell, possibly due to the role of the CdS in pinning the grain boundaries or the diffusion of S which may suppress grain growth. Alternatively, the CdCl2 treatment for the cells of Figs. 6-4 (b) and 6-6 may not be fully optimized. In addition to the structural analyses of Figs. 6-1 6-6 that focus on the high energy SE data for the CdTe surface roughness and structural depth profiles, it is also possible to extract characteristics of the underlying CdS and its layered structure from the low energy data. This information is obtained from the same low energy data range that provides the CdTe bulk layer thicknesses, plotted along the abscissas in Figs. 6-1 6-6. Figure

6-7 shows the deduced pseudo-dielectric function (solid lines) from SE measurement after the 15th etch step for the CdCl2 treated sample of Figs. 6-2 and 6-4. Also shown in A simple

Fig. 6-7 is the least-squares regression analysis best fit (broken lines). 107

multilayer model that leads to this best fit with a relatively small number of free parameters, seven in all, is shown in Fig. 6-8. It incorporates the glass substrate, including (i) a fixed optical structure as obtained in a previous analysis of uncoated TEC-15 consisting of SnO2 (267 ); SiO2 (215 ); and SnO2:F (3178 ); (ii) an interfacial roughness layer of fixed thickness between the TEC-15 and the CdS whose fixed thickness is chosen to match the surface roughness thickness measured from the uncoated TEC-15 (296 ) and whose composition is a fixed 0.5/0.5 effective medium mixture of the overlying and underlying materials; (iii) a CdS layer of variable thickness and void volume fraction; (iv) a single interface layer of variable thickness between the CdS and CdTe modeled as an effective medium of the two materials with variable composition; and (v) the bulk CdTe and its 0.5/0.5 CdTe + void surface roughness layer, both of variable thickness. The amorphous Te layer on the etched surface is neglected

in this study since it has little effect on the deduced parameters when the CdTe layer is thick. Because the starting TEC-15 transparent conducting oxide exhibits a surface roughness layer with a thickness of approximately 300 , roughness is sure to propagate throughout the structure and thus occurs at each interface. As a result, any layers that

are generated at the critical CdS/CdTe interface by the chemical interaction between the CdS and CdTe are modulated by roughness. Thus, as a first approximation, a single

effective medium layer of CdS+CdTe of variable composition is used to represent the layer at the CdS/CdTe interface. 108

10

10 5

Fit
asc34 15th step asc34 etch 15th

<1>

Fit asc34 etch 15th

<1> <2>
2.0

0 -5 10 5 0

<2>

-5

1.0

1.5

-5

PHOTON ENERGY (eV)

PHOTON ENERGY (eV)

Low energy data provide: CdTe, CdS, and interface thicknesses, along with their compositions

High energy data provide: CdTe surface roughness CdTe composition and grain size or defect density

Figure 6-7 Experimental pseudo-dielectric function spectra for the CdTe solar cell of Figs. 6-2 and 6-4 after the 15th etching step; also shown is the best fit using the structural model of Fig. 6-8.
CdTe surface roughness CdTe bulk CdTe/CdS interface CdS bulk CdS/SnO2:F interface SnO2:F SiO2 SnO2 Soda lime glass

CdTe/void = 0.5/0.5 CdTe/void=0.960.01/0.040.01 CdTe/CdS = 0.510.02/0.490.02 CdS/void = 0.930.01/0.070.01 CdS/SnO2:F = 0.5/0.5 SnO2:F = 1.00 SiO2 = 1.00 SnO2 = 1.00 glass = 1.00

35 0.4 14529 32 935 10 1247 25 296 3178 215 267 semi-inf. Fixed TEC15 structure

Figure 6-8 Structural model for the CdTe solar cell after the 15th etch step that provides the best fit in Fig. 6-7.

109

After the structural analysis of Figs. 6-7 and 6-8 was performed, confidence in the method was sought by performing two more analyses on a second CdCl2 treated solar cell structure deposited under the same conditions, one analysis from the film side and the other from the glass substrate side through a prism in optical contact with the free surface of the glass. Separate sample pieces from the same solar cell deposition were studied in The previously deduced dielectric function library in Table 6.1 was

these two analyses.

used in the analysis of the ex-situ SE data in Fig. 6-9 acquired from the CdTe free surface after 8 etching steps and from the prism/glass substrate side without CdTe etching. The structural models of Figs. 6-10 and 6-11 used in the analysis of both data sets shown in Fig. 6-9 are the same as that of Fig. 6-8; simple models with six free parameters yielded the fits in Fig. 6-9.
16 12
(degree)

(a)
60
(degree)

(b)

45 30 15

8 4 0 300

Data: 8 etch Fit

th

Data: glass side Fit

300
(degree)

(degree)

150

150

-150 0.9

1.0

1.1

1.2

1.3

1.4

1.5

-150 0.9

1.0

1.1

1.2

1.3

1.4

1.5

Photon Energy (eV)

Photon Energy (eV)

Figure 6-9 Ex situ SE spectra in (, ) (symbols) (a) from the free CdTe surface after 8 Br2+methanol etching steps and (b) from the prism/glass side without etching. The best fit results (solid lines) yield the structural parameters in Figs. 6-10 and 6-11, including the thicknesses of the CdTe roughness, CdTe bulk, CdTe/CdS interface, and CdS bulk layers, as well as the volume fractions of CdS/CdTe in the interface layer and void in the CdS bulk layer. 110

Figure 6-10 The best fit results from the free CdTe surface after 8 Br2+methanol etching steps yielding the thicknesses of the CdTe roughness, CdTe bulk, CdTe/CdS interface, and CdS bulk layers, as well as the volume fractions of CdS/CdTe in the interface layer and void in the CdS bulk layer.

Figure 6-11 The best fit results from the prism/glass side without etching yielding the thicknesses of the CdTe roughness, CdTe bulk, CdTe/CdS interface, and CdS bulk layers, as well as the volume fractions of CdS/CdTe in the interface layer and void in the CdS layer.

Figures 6-10 and 6-11 show the multilayer models of the sample structures, the latter depicting the placement of a 60o fused silica prism on top of the free surface of the glass substrate. In this configuration, an index-matching fluid proves vital in eliminating

unwanted incoherent reflections. Considering the assumptions and simplifications of the model, the agreement in the structural parameters listed in the two figures is excellent. Good agreement is obtained even in the CdTe/CdS interface layer composition although 111

this layer should require a more complex model that includes not only interface roughness modeled using an effective medium approximation, but also interdiffusion [6-7] modeled using stable phase CdTe1-xSx and CdS1-xTex alloy dielectric functions. As final supporting results for the overall approach, the CdS layer and CdTe/CdS interface thicknesses have been deduced from spectra collected at the CdTe free surface in 24 successive etches as shown in Fig. 6-12. In the 25 analyses, the same model was

used for all the spectra, now obtained as a function of CdTe bulk thickness before and after each etching step. These fits should provide independent values for CdS/CdTe

interface layer thickness and CdS bulk layer thickness since the unprocessed (, ) spectra data vary rapidly with CdTe bulk layer thickness due to variations in the interference pattern as shown in Fig. 6-9 (left panel). In fact, these independent values

should be constant since the etching does not affect the sub-surface material, and any variations provide a measure of the uncertainty in these values. For the selected optical

model to be justified, the confidence limits for the interface thickness and composition must be smaller than the values themselves. In fact maximum deviations of 2-3%

from the average values are obtained and the average values lie within the confidence limits of the analyses performed on spectra collected through the prism/glass.

112

Figure 6-12 CdS and CdTe/CdS interface layer thicknesses deduced from spectra collected through the prism/glass (solid line) and from spectra collected from the CdTe surface in successive etches (points, dotted line extrema). Among the key final results of Fig. 6-12 include a 1000 thick interface region of (CdS+CdTe) and a 1030 thick layer of CdS. The (CdS+CdTe) interface layer for this

sample is found to be a 0.7/0.3 vol. fraction mixture of CdTe/CdS; however, this mixture merely provides a dielectric function that approximates that of the interface region and should not be interpreted physically. interface are in progress [6-8]. Further studies of the optical properties of the

6.4 Results and discussion: through the glass measurements SE measurements directly through the top glass have been performed using a method in which the reflection from the glass/film-stack interface is collected whereas the reflection from the ambient/glass interface is blocked. Invasive prism attachment is

avoided by eliminating the top glass surface reflection, an approach that is more practical for off-line or on-line cell and module mapping applications. An example of such SE 113

data analysis for a magnetron sputtered CdTe solar cell is demonstrated here in a step-by-step process in which additional fitting parameters are introduced while observing a measure of the quality of the fit. The goal is to increase the complexity of

the optical model systematically over the six and seven parameter models of Figs. 6-8, 6-10, and 6-11 by incorporating additional thicknesses and volume fractions and determining the parameters that are most important in ensuring a good fit. The most complicated optical model used for analysis of through-the-glass SE spectra collected on CdTe solar cells on glass superstrates shown in Fig. 6-13 includes a total of 12 variable parameters with satisfactory confidence limits on all parameters.
(, )

Soda lime glass

(ambient) TEC-15 structure

SnO2 (d) SiO2 (d) SnO2:F + CdS (d & fCdS) CdS +void (d & fv) CdTe/CdS interface (d & fCdTe ) CdTe (d, d/d)

Surface roughness

(d, fv)

Figure 6-13 Multilayer stack used to model the thicknesses and compositions of the individual layers of the CdTe solar cell. The SE beam enters through the glass, and the reflection from the top surface is blocked since it is incoherent with respect to the reflection from the glass/film interface.

114

0.22 1 0.20 0.18

6 7 8 9 10 11 12 number of fitting parameters

MSE

0.16 0.14 0.12 0.10

Step-by-step MSE reduction


0 10 20 30 40 50 60

Steps Figure 6-14 Step-by-step MSE reduction by adding one fitting parameter at a time. Starting with the CdTe thickness as a variable, each additional parameter was subsequently fitted. It was found that fitting the SnO2:F thickness provided the greatest improvement in MSE among all 2-parameter attempts. Similar methodology was used for all 12 parameters. Circular points indicate the best n-parameter fit with n given at the top and the added parameter given in Table 6.2.

The SE spectra collected at one spot on the 3 x 3 cm2 CdTe solar cell and at angles of incidence of 60 and 65 were modeled over the spectral range from 0.75 to 3.0 eV, below the glass absorption onset. Figure 6-14 shows the step-by-step reduction in mean

square error (MSE), expressed in terms of the deviations in the real and imaginary parts of tan exp(i), obtained by adding best fitting parameters one at a time. Table 6.2

shows the sequence of fitting parameters that are introduced in order of importance to obtain the best n-parameter fit (n = 2, 3, 412). best final 12-parameter fit. Figure 6-15 shows the SE data and the

The best fit parameters are shown in Table 6.3 along with 115

their confidence limits. Table 6.2 Best fitting parameters added step by step to improve the mean square error (MSE) in modeling through-the-glass SE measurements of a CdTe solar cell. Best fitting parameter to add to improve MSE CdTe thickness SnO2:F thickness CdTe non-uniformity CdS thickness CdTe surface roughness (50/50) Void fraction in CdTe roughness CdS volume fraction in SnO2:F SiO2 thickness Void volume fraction in CdS CdS/CdTe interface thickness (50/50) SnO2 thickness CdTe volume fraction in CdS/CdTe interface

# of fitting parameters 1 2 3 4 5 6 7 8 9 10 11 12

MSE 0.2208 0.1735 0.1565 0.1448 0.1363 0.1134 0.1056 0.1010 0.0968 0.0883 0.0881 0.0860

The fitting parameter sequence in Table 6.2 is understandable in that the thickest layers have the greatest impact in the step-by-step fitting procedure. As a result this new analysis approach also provides information on the starting TEC-15, namely, the thicknesses of the SnO2 at the glass interface, the intermediate SiO2 layer, and the doped 116

conducting SnO2:F layer without assuming fixed values.

For the solar cell, the analysis

provides additional information on possible modification of the SnO2:F by over-deposition of CdS, as well as the standard parameters of CdS thickness, its void fraction, the combined CdS/CdTe interface roughness-interaction thickness, and the CdTe thickness. As shown in Fig. 6-13, a mixture of SnO2:F and CdS is used to model the

interaction between the two materials when CdS is deposited on the TEC-15; however, the exact nature of this interaction will be the subject of more detailed future studies. It

is not clear if the modification is simulating the effect of CdS penetrating the roughness and near surface void structure or, alternatively, if there is a uniform modification of the SnO2:F properties. Other approaches to describe the interaction, e.g., a modification in the free electron density or mobility in SnO2:F has not yet achieved success. The

interaction layer between the CdS and the CdTe has been described as a simple effective medium of the two materials that simulates interface roughness, although a more realistic approach may be to use alloy layers in addition to the effective medium layer as described previously. It should be noted that the deduced CdS thickness of 1225 14

is in good agreement with the intended CdS thickness of 1300 .

117

Figure 6-15 Ellipsometric spectra (points) in (top) and (bottom) at an angle of incidence of 60 as measured through the glass at a single point on a 3 x 3 cm2 CdTe solar cell sample. The solar cell was treated with CdCl2 but no back contact processing was performed. Also shown is a best fit (lines) using the model structure of Fig. 6-13 with the parameters listed in Table 6.3. Table 6.3 Multilayer stack thicknesses, non-uniformity, and compositions, the latter expressed in terms of volume fractions, along with parameter confidence limits for the best fit to SE data obtained through the glass. Soda lime glass SnO2 thickness SiO2 thickness SnO2:F thickness CdS volume fraction CdS thickness Void volume fraction CdTe/CdS interface thickness CdTe volume fraction CdTe bulk thickness CdTe thickness nonuniformity CdTe surface roughness thickness Surface void fraction Ambient The new analysis procedure, through-the-glass SE, is useful in determining the 118 339 13 157 5 3123 24 2.3% 0.5% 1225 14 13.5% 0.6% 868 32 73.3% 1.6% 19702 43 3.1% 0.1% 851 16 28.4% 0.7%

optical structure of CdTe solar cells for off-line or on-line analysis in a mapping mode. This method is useful because it is non-destructive, and the large roughness layer thickness of the CdTe does not present a problem. Analysis of the SE data using a step-by-step analysis methodology identifies the important thicknesses and compositional parameters for successful optical characterization of the solar cell.

6.5 Summary Ex-situ spectroscopic ellipsometry has been applied to perform multilayer analyses of CdTe solar cell structures. This capability exploits a database obtained from both

ex-situ and in-situ measurements that includes the dielectric functions of all component layers of the cell. As a supplementary tool, Br2+methanol etching was used to reduce the CdTe bulk layer thickness in a layer-by-layer fashion for depth profiling purposes. The SE measurements made after a variable number of etching steps enables tracking of changes in the critical point energies and broadening parameters near the surface, in the bulk CdTe, and near the CdS/CdTe interface. This capability was used to smoothen the

CdTe free surface so that measurements of the multilayer stack can be performed for correlation with through-the-glass measurements of the solar cell. Good agreement is

obtained between the CdS thickness and CdS/CdTe interface layer thickness between the two measurement approaches. Thus, the validity of the through-the-glass method of

solar cell analysis has been supported through this study.

119

Chapter Seven

RTSE Analysis of CdTe Solar Cell Structures in the Substrate Configuration

7.1 Introduction In the conventional configuration for thin film CdTe solar cells used in both research and manufacturing, one starts with a glass superstrate which is coated with a transparent conducting oxide top contact
[7-1]

. In this configuration, the CdS window layer of the

heterojunction is deposited on the transparent conductor first and the CdTe active photovoltaic layer is deposited on top of the CdS. In this sequence, the heterojunction is protected from the ambient by the much thicker layer of CdTe. Furthermore, since the

CdTe surface is exposed to the ambient in this configuration, the CdTe layer can be treated with CdCl2 just prior to p+ back contact formation. In the reverse or substrate configuration, one cannot apply the same sequence of operations. In this case, because the CdTe layer is deposited first, the back contact is

formed simultaneously with the deposition process, rather than as a separate step. Furthermore the CdCl2 treatment must then be performed either after the CdTe deposition, which is not likely to leave an optimum surface for subsequent heterojunction formation, or after the CdS deposition, which is not likely to produce a favorable effect on the CdS 120

surface for subsequent top contact formation.

As a result CdTe solar cells in the

substrate configuration have not reached the level of performance of cells in the superstrate configuration [7-2]. In this Chapter, results of a real time spectroscopic ellipsometry (SE) study of CdTe film growth on Mo, which is a standard back contact metal used in the substrate configuration, are presented, and the information content of such SE measurements will be discussed in detail. Ex situ SE results for a completed solar cell in the same substrate

configuration will also be presented and discussed.

7.2 Analysis of CdTe deposition on rough molybdenum Figure 7-1 shows the time evolution of (, ) at 5 photon energies selected from the 706 spectral positions acquired during CdTe sputter deposition at 50 W target power and 18 mTorr Ar pressure; (Dr. Anthony Vasko is acknowledged for deposition of this sample, and additional measurement assistance of Dr. Jian Li is acknowledged). The substrate

was a glass slide coated with thin film Mo, held at a nominal temperature of 200C. This corresponds to a true temperature of 237C when a crystalline Si wafer substrate is used. The full spectral acquisition time was 2 s and the angle of incidence of the This was the first real time experiment performed during The Mo film was also

measurement was 65.68.

CdTe deposition using the SE system described in Chapter 1.

prepared by magnetron sputtering and was found to exhibit a surface roughness ~80

121

80
0.743 eV 1.166 eV 1.166eV 2.637 eV 1.653 eV 6.500 eV 6.500 eV 1.653 eV 2.637 eV 0.743 eV

300

60
(degree)

200
(degree)

40

100

20

0 0 10 20 30 40 50 0 10 20 30 40 50

-100

Time (min)

Time (min)

Figure 7-1 Time evolution of (, ) at 5 photon energies selected from 706-point spectra acquired during sputter deposition of CdTe on a Mo coated glass slide. The full spectral acquisition time was 2 s and the angle of incidence was 65.68.

thick. The analysis results obtained here for the Mo optical properties can be applied in future studies of solar cells in the substrate configuration.

7.2.1 MSE minimization for the analysis of CdTe/Mo The analysis of the spectra for the experiment of Fig. 7-1 used a two-variable, time-averaged, mean-square error (MSE) minimization procedure over selected time intervals. The time averaged MSE serves as a criterion to obtain the correct structural

evolution as well as the optical properties of the deposited CdTe film, as a multilayer within the selected time intervals. Even the structure and optical properties of the Mo thin film can be determined in the procedure. Each selected time interval during

deposition has been separated into two components in the average MSE minimization 122

procedure.

In one component, film growth occurs as a bulk/roughness structure with

variables db and ds which are the bulk and surface roughness layer thicknesses, respectively. In the other component, film growth occurs through the filling of the

rough interface between the underlying and growing materials as an interface/roughness structure with variables fi and ds, where fi is the volume fraction of new material filling the roughness of the underlying material and ds is the surface roughness layer thickness on the growing film. Additional details on the two analysis components will be given in the following paragraphs. In order to achieve the desired results, one seeks to maintain In this analysis

the MSE value below ~5 throughout the time range of the deposition.

procedure, four time intervals have been selected in all, leading to four individual layers in the CdTe film growth process, and the average MSE minimization procedure has been applied to the growth of each layer. For the first CdTe layer, the time interval for the average MSE minimization procedure was 3.303~13.936 min and the energy range in the MSE calculation was 0.74~6.5 eV. Minimization of the average MSE for this layer requires the following

nine steps, grouped in three iterations. Iteration A: Estimate Mo roughness thickness Step 1. substrate. Step 2. Numerical inversion software is applied to the in-situ experimental data (, A value di is estimated for the surface roughness thickness on the Mo

) collected before initiation of the deposition to deduce the dielectric function (1, 2) of 123

the bulk Mo based on the value di from Step 1. Step 3. A least-squares regression model is created, using a previously-determined
[7-3]

reference dielectric function for CdTe

as an initial approximation.

A dynamic

growth analysis is performed over the 3.303~13.936 min time range and the time-averaged MSE, denoted <MSE> is determined. The starting time is selected to

ensure that filling of the substrate/film interface roughness has occurred as described later, and the ending point is selected to maintain an acceptable MSE versus time, typically less than 5. Step 4. The di value is adjusted and Steps 2 and 3 are repeated. The two results for

the <MSE> are compared and continued iterative adjustments in di are made until the minimum <MSE> is found. Finally, di is fixed at the value that minimizes <MSE>.

Iteration B: Estimate CdTe structure and optical properties Step 5. With the optimum di value fixed from Iteration A, further estimates are

made for a pair of values for the CdTe bulk and surface roughness layer thicknesses (db, ds). Step 6. Inversion of the experimental data (, ) is performed next to deduce the

dielectric function (1, 2) of CdTe at the ending time 13.936 min. Step 7. Using the inverted CdTe dielectric function, dynamic growth analysis is

performed over the time range 3.303~13.936 min, in order to determine <MSE>. Step 8. Steps 6 and 7 are iterated using successive adjustments in (db, ds) within a The minimum <MSE> then

two-dimensional grid, until the minimum <MSE> is found. 124

yields the best fit results for {db(t), ds(t)} and for the inverted CdTe dielectric function. Iteration C: Refine Mo roughness thickness as well as the CdTe structure and

optical properties Step 9. Next, rather than using the CdTe reference dielectric function of Step 3, the This

inverted dielectric function of Step 8 is used in a repetition of Steps 1, 2, 3, and 4. refinement provides an improved value of di. with the refined di value.

Steps 5, 6, 7, 8, and 9 are then repeated

A final iteration is performed for internal consistency. The minimum average MSE and the

The final results of Steps 19 are as follows.

interface roughness thickness are given by: <MSE>min = 2.98 and di = 79.6 . The best fit bulk and surface roughness layer thicknesses at the ending time of 13.936 min are db = 423 ; ds = 56.7 . These results are summarized in the first entry of Table 7.1.

The average MSE minimization procedure has also been applied for the other three CdTe layers. For each of these three layers, the minimization steps were performed in a

similar way as those in the analysis of the first CdTe growth layer; however, now di can be fixed at the final result from the first layer analysis and only Iteration B is needed. Thus, one only need to estimate the pair of (db, ds) values and invert the experimental (, ) data to obtain the dielectric function (1, 2) of the CdTe at the ending time. With the

resulting CdTe dielectric function, dynamic growth analysis is performed, the <MSE> is extracted, and the process is iterated through adjustments of (db, ds) until <MSE>min is found. For the growth analysis with <MSE> = <MSE>min the db and ds values are

correct and the associated inverted dielectric function for CdTe is also correct. 125

These three successive <MSE> minimizations based on Iteration B have yielded the following results. The second CdTe layer covered the time range of 15.229~23.024 min,

and analysis employed the energy range 1.2~6.5 eV; <MSE>min was obtained at db = 313 and ds = 54.5 . The third CdTe layer analysis used the ranges 24.246~34.480 min and 1.0 ~ 6.5 eV; <MSE>min was obtained at db = 404 ; ds = 66.0 . The fourth and

topmost CdTe layer analysis used the ranges 36.002~40.948 min and 1.5~6.5 eV; <MSE>min was obtained at db = 108 ; ds = 67.0 . summarized in Table 7.1. These results for all four layers are

Table 7.1 layers.

CdTe bulk and surface roughness layer thicknesses for the top four CdTe bulk

Time range (min) 3.303~13.936 15.229~23.024 24.246~34.480 36.002~40.948

db () 423 313 404 108

ds () 56.7 54.5 66.0 67.0

Data analysis energy range (eV) 0.74~6.5 1.20~6.5 1.00~6.5 1.50~6.5

<MSE>min 2.98 2.60 8.71 1.30

The overall <MSE> minimization can be described by a flow chart as shown in Fig. 7-2 for the most complicated case of the first CdTe layer. The schematic structure of the full CdTe layer stack is shown in Fig. 7-3.

126

Iterations

Step 1. Estimate di, the Mo substrate surface roughness layer thickness.

Step 2. Apply inversion routine to the exp. data (, ) obtained just prior to deposition to deduce the dielectric function (1, 2) of the bulk Mo. Step 3. Apply reference dielectric function for CdTe, and A perform dynamic growth analysis over the time range 3.303~13.936 min, to extract the average MSE. Step 4. Minimum <MSE> ? N Adjust the di value. Y

Minimum <MSE>; best fit di. C Step 5. Fix di at the best fit value, and estimate CdTe (db, ds) at the ending time t = 13.936. Step 6. Perform inversion of the exp. data (, ) to deduce the dielectric function (1, 2) of CdTe. Step 7. Perform dynamic CdTe growth B analysis over the time range 3.303~13.936 min, to determine the average MSE. Step 8. Minimum <MSE> ? N Adjust the (db, ds) values. Y

Minimum <MSE>; best fit di, (db, ds) Y Minimum <MSE> ? N Use the CdTe dielectric function deduced in Step 7 instead Step 9. of the reference CdTe dielectric function, and return to Step 1 in order to refine di value; minimum. Minimum <MSE>; best Mo, CdTe structures and dielectric functions Final results : <MSE>=2.98; di=79.6 ; db=423 ; ds=56.7 .

Figure 7-2 Flow chart of the three-iteration <MSE> minimization procedure for CdTe film growth on a rough Mo film substrate. 127

Ambient ds db4 d2j+1 = d2j,end + (0.5fi)d2j,end + 0.5ds d2j = d2j-1,end + 0.5(dsd2j-1,end) + db d4 = d3,end + 0.5(dsds3,end) + db d3 = d2,end + (0.5fi)ds2,end + 0.5ds d2 = d1,end + 0.5(dsds1,end) + db d1 = (0.5fi)di + 0.5ds di4 db3 di3 db2 di2 db1 di1 Mo surface roughness fourth CdTe bulk layer fourth interface roughness third CdTe bulk layer third interface roughness second CdTe bulk layer second interface roughness first CdTe bulk layer first interface roughness

Figure 7-3 The schematic structure describing the final optical model for deposition on rough Mo.

Each of the four CdTe bulk layers will be associated with an interface layer adjacent to the underlying material which is filled in upon deposition of the overlying material. During each interface filling time, db is set to zero. The Bruggeman EMA has been used to model the dielectric function of the interface layer. The volume percent void in the

interface layer is one fitting parameter which is varied in the interface filling analysis for modeling purposes. Therefore, during each interface filling time, the void volume

percent should decrease from 50% to 0% as the overlying material volume percent increases from 0% to 50%. The first interface layer is a three-component composite of

materials including Mo (50%), (void + CdTe) (50%), and the other three topmost interface layers are three-component composites of materials including the lower CdTe 128

film (50%), and (void + the upper CdTe film) (50%).

For the interface layer filling

analysis, the first interface layer (0~3.277 min) used the energy range (0.74~6.5 eV). The second, third, and fourth interface layers spanned the time ranges of (14.012~15.229 min), (23.024~24.246 min), and (34.480~36.002 min), respectively, using the energy ranges of 1.5~6.5 eV in all cases. A detail of the structural evolution of the first

interface and bulk CdTe layers is shown in Fig. 7-4. ds (0.5/0.5): (CdTe #1/void) db
Mo

Mo

ds (0.5/0.5): (CdTe #1/void) di (0.5/0.5fi/fi): (Mo/CdTe #1/void)

di

(0.5/0.5): (Mo/CdTe #1)

Figure 7-4 The schematic structures describing the interface filling (left) and bulk layer growth (right) models for the first interface layer.

7.2.2 Structural evolution The fit quality is given by the magnitude of the MSE which degrades rapidly for deposition times t > 15.5 min. This result is shown in Fig. 7-5 (left) (broken line). The goal of the multilayer model is to determine if this MSE degradation can be attributed to the evolution of the dielectric function with accumulated bulk layer thickness. Such an

effect can be modeled using a succession of layers, each having a dielectric function determined independently, whereas the same model for the surface roughness layer can be used throughout. Figure 7-5 (right) includes the results for the MSE from the four-layer model (solid line) on an expanded scale in which case the quality of the fit remains very good (MSE<5) 129

for the full ~40 min deposition process. In the final film structure, the effective thicknesses of the four layers including the interface filling regions are (interface to surface) 491, 369, 465, and 174 , for a total effective thickness of 1499 . The sharp

minima at 14, 23, 34.4, and 37.5 min in the four-layer MSE indicate the times at which the dielectric functions of the four layers were determined.

Figure 7-5 (Left) MSE, which is a measure of the quality of the fit to RTSE data, for the complete CdTe deposition using optical models for the CdTe film consisting of one bulk layer (broken line) and four bulk layers (solid line). In both cases a one-layer model for surface roughness was employed; (right) the MSE for the model with four bulk layers is shown on an expanded scale. Figures 7-6, 7-7 and 7-8 show the final results of such modeling, in which case four separate bulk layers are used along with a single evolving surface roughness layer. Although the best fit leads to an improvement in MSE as shown in Fig. 7-5 (left) (i.e., by a factor of ~40), the exact origin of the improvement requires further study as will be seen from an inspection of the four dielectric functions in Sec. 7.2.3. The evolution of the surface roughness layer thickness (Fig. 7-6), the overlying material volume fraction during the interface filling region (Fig. 7-7), the bulk layer thickness for all four CdTe 130

component layers (Fig. 7-8, left), and the effective thickness or mass per unit area (Fig. 7-8, right) versus deposition time have all been deduced using the four-layer model for the CdTe film. The broken line jumps in the surface roughness thickness ds result from

the consideration of each bulk layer individually with an independent surface roughness layer thickness. At the jumps, the surface roughness on the underlying layer is

instantaneously transformed into an interface roughness layer with the subsequent development of roughness on the overlying layer starting from ds = 0 . The continuity

of ds before generation and after filling of the interface layers is an indication of the internal consistency of the analysis. The evolution of the accumulated effective

thickness versus deposition time is determined from adding the following components: (i) First interface filling layer: d1 = (0.5fi) *di+0.5*ds, where db=0, 0 fi 0.5, t0 t < t1; (ii) First bulk layer: d2 = d1,end + 0.5*(dsds1,end) + db, where t1 t < t2; (iii) Second interface filling layer: d3 = d2,end + (0.5fi)*ds2,end + 0.5*ds, where t2 t < t3; (iv) Second bulk layer: d4 = d3,end + 0.5*(dsds3,end) + db, where t3 t < t4 In these equations, dj,end and dsj,end are the values of the effective thickness and the surface roughness thickness at the end of the time range for layer j. The end of the time

range for the jth bulk layer t2j is defined somewhat arbitrarily in order to maintain an MSE that is acceptably low (e.g. less than ~ 5), and the end of the time range for the jth interface filling layer t2j+1 is defined such that the void fraction fi reaches zero. In

addition, the interface void fraction fi is related to the overlying material volume fraction 131

fm=0.5fi.

Figure 7-6 Evolution of the surface roughness thickness versus deposition time determined using a four-layer model for CdTe film growth on rough Mo. The spikes in the surface roughness thickness result from the consideration of each bulk layer individually with an independent surface roughness layer. In this case, the surface roughness layer on the underlying layer is instantaneously transformed into an interface layer at the vertical broken lines upon initial growth of the overlying layer, whose roughness layer starts from zero thickness.
50 40

f (%) fm m

30 20 10 0 0 10 20
Time (min)

30

Figure 7-7 Time evolution of the CdTe overlayer volume percent during interface filling of the underlying CdTe roughness layer for CdTe growth on Mo.

132

Figure 7-8 (Left) Evolution of the individual bulk layer thicknesses versus deposition time determined using a four-layer model for CdTe film growth on Mo; (right) evolution of effective thickness of CdTe, including all bulk, interface, and surface layer components. 7.2.3 Optical properties In Fig. 7-9, the Mo dielectric function is shown, valid for the nominal deposition temperature of 200 C. These results were deduced by inversion after determination of the Mo surface roughness thickness value of 79.6 , through the 3D <MSE> minimization procedure. In this <MSE> minimization procedure, an independent

dynamic analysis provides interface, bulk, and surface roughness thicknesses, di, db, ds, respectively, that describe the structural evolution of CdTe growth on the rough Mo film.

133

5 0

-5 -10 50 40

inversion di = 79.6 at nom. 200 C inversion di = 79.6 at R.T.

30 20 10 0 0 1 2 3 4 5 6 7

Photon energy (eV)

Figure 7-9 Mo dielectric function at a nominal temperature of 200 C acquired by inversion assuming a Mo substrate roughness thickness of 79.6 (solid line). For the overlying CdTe, four bulk layers and a roughness layer are used to describe the best fit model. For the first bulk layer, the Mo/CdTe interface roughness, the CdTe bulk, and CdTe surface roughness layer thicknesses di, db, ds, respectively, are determined in a dynamic analysis, in which case the criterion is the minimum average MSE. The Mo/CdTe interface roughness thickness di is taken to be the same as the Mo substrate film roughness thickness. Also shown is the Mo dielectric function at room temperature before heating to the deposition temperature as determined by inversion, again assuming a Mo surface roughness layer thickness of 79.6 (broken line). In an attempt to corroborate the surface roughness thickness on Mo from the starting room temperature (, ) spectra, reference dielectric functions for Mo [7-4], MoO3 [7-5] and MoOx [7-5] were applied in conjunction with the models of Table 7.2. Table 7.2 Five models used to evaluate the Mo overlayer thickness using reference dielectric functions from the literature.
Ambient ds Mo/void Mo Model 1 ds 91.2 2.5 [fi/(1fi)] 50%/50% MSE 238.5 Ambient MoO3/void Mo Model 2 81.9 2.9 50%/50% 273.1 Ambient MoOx/void Mo Model 3 86.4 2.9 50%/50% 267.6 Ambient MoO3/Mo Mo Model 4 117.4 2.3 50%/50% 190.9 Ambient MoOx/Mo [fi/(1fi)] Mo Model 5 121.6 2.3 50%/50% 188.4

134

The results of Table 7.2 show that the Mo substrate roughness thickness of 79.6 deduced through the 3D <MSE> minimization procedure is close (within 12 ) to the corresponding model that applies reference dielectric function results (Model 1). Figure 7-10 (a-d) shows the real (top) and imaginary (bottom) parts of the dielectric functions of the four CdTe layers that comprise the film deposited on the Mo covered glass substrate. Each of these CdTe dielectric functions has been determined by

numerical inversion, incorporating the full underlying film structure and after determining the surface roughness and bulk layer thicknesses through minimization of the <MSE> in a dynamic analysis of the growing layer. Figures 7-10(b-d) include Comparison of the

comparisons of the dielectric functions of two successive layers. successive dielectric functions leads to two observations.

First, using the range of

energies greater than ~2.5 eV, no significant differences in the void fraction, critical point energies, and critical point widths are observed. This suggests a relatively uniform layer throughout the thickness. Second, for the range of energies below 2.5 eV, artifacts are These two

observed, and these increase in amplitude with the increase in layer number.

observations lead to the conclusion that the increase in MSE in Fig. 7-5 for the one bulk layer model is not due to non-uniformity with depth, but rather other features of the measurement or model such as a spatial distribution of thicknesses over the surface of the beam or inadequacies of the model for the Mo substrate interface. Such features do not

affect the data quality in the opaque regime above 2.5 eV for each layer.

135

For comparison in Fig. 7-10(e), the solid line is the dielectric function deduced in a study of CdTe deposited on a c-Si substrate as reported by Li
[7-6]

. The sample on c-Si

was deposited at a substrate temperature of 188 C, an rf power of 60 W, and an Ar pressure of 18 mTorr. The 1 spectra at low energies suggest that the void volume In fact,

fraction is consistently higher for the component layers of the CdTe film on Mo.

the first layer CdTe film material on Mo can be described as an effective medium of the CdTe film material on Si plus voids; the deduced volume fraction of voids is 0.10. This

result indicates that the void volume fraction in thin film CdTe may depend on the substrate and in particular its surface roughness thickness. Because the comparison in

Fig. 7-10(e) is for the first CdTe bulk layer on Mo, it appears that in the case of the Mo substrate, voids develop immediately in the deposition process, likely an effect of shadowing by the roughness on the Mo. Later in this chapter, an ex situ spectroscopic

ellipsometry analysis of a CdTe solar cell on ZnTe:Cu/Mo will be performed to evaluate the ability to characterize the full solar cell in the substrate configuration.

12 10 8 6 4 2 0 -2 10 8 6

(a)

CdTe/Mo layer # 1

12 10 8 6 4 2 0 -2 10 8 6

(b)

CdTe/Mo layer # 2 CdTe/Mo layer # 1

4 2 0 0 1 2 3 4 5 6 7

4 2 0 0 1 2 3 4 5 6 7

Photon energy (eV)

Photon energy (eV)

136

12 10 8 6 4 2 0 -2 10 8

12

(c)

CdTe/Mo layer # 3 CdTe/Mo layer # 2

10 8 6 4 2 0 -2 10 8

(d)

CdTe/Mo layer # 4 CdTe/Mo layer # 3

1 2

6 4 2 0 0 1 2 3 4 5 6

6 4 2 0

Photon energy (eV)


12 10 8 6

Photon energy (eV)


CdTe/Mo layer #1 CdTe/c-Si

(e)

1 2

4 2 0 -2 12 10 8 6 4 2 0 0 1 2 3 4 5 6 7

Photon energy (eV)

Figure 7-10 Real (top panel) and imaginary (bottom panel) parts of the dielectric functions of the four layers [(a)-(d)] of a CdTe thin film deposited on rough Mo. These results are determined from inversion, after determining the CdTe roughness and bulk layer thicknesses through minimization of the average MSE obtained throughout the layer analysis; (e) also shown is a comparison of the first layer dielectric function of CdTe deduced in this study with that of CdTe deposited on a smooth c-Si substrate at a nominal temperature of 200 C [7-6]. In (b)-(d) comparisons are provided between the dielectric function of a given layer and that of the layer underneath it. 7.2.4 Comparison of RTSE and AFM Lastly, it is of interest to compare the roughness thickness for the final CdTe film on the Mo coated glass substrate as deduced by RTSE with that obtained by atomic force microscopy (AFM) using a 1 x 1 m2 image area. The RTSE/AFM comparison results

are in reasonable agreement as shown in Fig. 7-11, where the root-mean-square (rms) 137

value from AFM is indicated. Considering the surface height distribution from AFM, it is clear that spectroscopic ellipsometry is not sensitive to area fractions of surface asperities and depressions at the level of ~ 0.3 or less.
Roughness ds = 67.1

depressions

asperities

Figure 7-11 Comparison of the surface roughness thickness at the end of the deposition for a 1496.5 thick CdTe film on Mo as deduced by RTSE with the relative surface height distribution and rms roughness from AFM.

7.3

Ex situ spectroscopic ellipsometry analysis of a CdTe solar cell in the substrate configuration The goal of ex situ spectroscopic ellipsometry (SE) studies of solar cells in the

substrate configuration is two-fold.

First, the substrate configuration precludes Thus, a reflection

transmission measurements for optical analysis of the solar cells.

measurement is the only choice for optical analysis, and ellipsometry is the most powerful reflection measurement available. With such a measurement, it may be

possible to establish a sufficient in-depth understanding of the growth processes so that they can be optimized for highest efficiency solar cells. 138 Second, SE may be developed

as an in-line monitor of substrate-type solar cells, for example in a roll-to-roll process. 7.3.1 Metallic back contact for CdTe solar cells in the substrate configuration Figure 7-12 shows a comparison of measured pseudo-dielectric functions (solid lines) for the Mo thin films deposited (a) on glass and (b) on Kapton, two possible substrates used for rigid and flexible solar modules, respectively. Thus, these Mo films

serve as the first deposited or back contact layer of the CdTe solar cells in the substrate configuration. The pseudo-dielectric functions of Fig. 7-12 are calculated directly from the ellipsometry spectra using an optical model consisting of a single perfect interface between the ambient and the film. Thus, the pseudo-dielectric function approaches the

true dielectric function of the film only when the film is opaque and its surface is atomically smooth and oxide-free. Both oxides and surface roughness on an opaque film lead to deviations of the pseudo-dielectric function from the true dielectric function. In addition, semitransparent films also generate strong differences between the two due to the presence of back reflected light and associated interference fringes. In the real time SE studies described earlier in this Chapter, the dielectric function for Mo at room temperature has been established and this has been used in the optical modeling of the pseudo-dielectric functions in Fig. 7-12. In fact, the Mo sample used as

a reference was fabricated on a smooth glass substrate and was analyzed using a (surface roughness)/(semi-infinite bulk) optical model. Using this reference, the ex situ

ellipsometric spectra of Fig. 7-12 can be analyzed by applying the corresponding optical model to deduce the microscopic structure of these samples. 139 The results at the left in

Fig. 7-12 are for the Mo film deposited on glass, and reveal an excellent fit to the data
5 0

Exp. data fit data

-5

<1>

-10

-15

Exp. data fit data


0

<1>

30

84 3 Mo/void = 0.54 0.02/0.46 0.02 ds db semi-inf Mo MSE = 17.9

608 3 Mo/void = 0.49 0.01/0.51 0.01


10

ds db

semi-inf

Mo/void = 0.32 0.01/0.69 0.01 MSE = 28.2

<2>

10

<2>
(b)
6 7 0 0

20

(a)
0 0 1 2

PHOTON ENERGY (eV)

PHOTON ENERGY (eV)

Figure 7-12 A comparison of measured pseudo-dielectric functions (solid lines) for Mo thin films deposited by sputtering (a) on glass and (b) on Kapton. Also shown are the fits (broken lines) using a reference dielectric function for dense Mo determined separately, and the multilayer models depicted in the insets.

(broken lines) using a model of bulk Mo (no density deficit relative to the reference) with a 84 thick surface roughness layer on top. This is consistent with the results for the

reference Mo film which was prepared under similar conditions and exhibited a roughness thickness of ~ 80 , as determined in the analysis of CdTe over-deposition. The results at the right in Fig. 7-12 are for Mo deposited on Kapton; these results are considerably different, particularly in terms of the overall magnitude of the dielectric function at low energies. energies. In addition, 1 does not become negative for this film at low

This suggests that the film lacks conducting channels in the plane of the film In

and so the electrons behave as bound electrons at the frequencies of the optical field.

fact, a fit to the ellipsometric data suggests a very thick roughness layer (~ 600 ) which 140

is nearly opaque.

Beneath this layer there appears to be a region of even larger density It is not clear whether this density deficit is due to The impact of the

deficit (~70%) in the bulk Mo film.

true voids or to roughness at the interface to the Kapton substrate.

resulting microstructure on solar cell performance is unclear; however, it is evident that ex situ SE can be used to characterize the substrate metal optical properties and structure and the effects of the substrate on overlying film optical properties and structure.

7.3.2 Transparent p+ back contact for CdTe solar cells In order to develop a complete optical model for the CdTe solar cell in the substrate configuration, it is also necessary to extract the optical properties of the ZnTe p+ semiconductor back contact in a structure that is easier to analyze than the completed solar cell. As a result, these studies were performed using ZnTe deposited by magnetron

sputtering directly onto a glass substrate; (Dr. Viral Parikh is acknowledged for the deposition of this sample). Doping ZnTe p-type was possible using Cu, and the Cu Figure 7-13 shows the raw ellipsometric

content in the ZnTe sputtering target is 1 wt.%.

spectra and the best fit that provides the bulk and surface roughness layer thicknesses (5237 and 90 , respectively). In this analysis the dielectric function is modeled as a

sum of four critical point structures, three to match the peaks observed most clearly in in Fig. 7-13 and the fourth to simulate the gradual absorption onset. A fifth

Tauc-Lorentz oscillator simulates a broad background absorption centered above 6 eV. The best fit result is shown in Fig. 7-14 as the solid lines. 141 Handbook data [7-7] for single

crystal ZnTe are also shown in Fig. 7-14 as the points.

Significant differences can be

observed between the results for the doped thin film sample presented here and the

30

(degree)

20 10

exp.data fit

exp.data fit

0 300 200

(degree)

100 0

ZnTe:Cu glass
0

5236.6 1 mm
6

-100

PHOTON ENERGY (eV)

PHOTON ENERGY (eV)

Figure 7-13 Ellipsometric spectra (solid lines) and best fit (broken lines) using the structural model and best fit parameters shown in the inset. The dielectric function is determined simultaneously using a model assuming a sum of critical point structures. The resulting dielectric function is shown in Fig. 7-14. handbook results for the single crystal. The differences are likely to be due to the heavy The three higher

Cu doping as well as the fine-grained polycrystallinity of the thin film.

energy critical points at 3.61, 4.15, and 5.27 eV mirror those in the single crystal, but are consistently broader; however, the band gap critical point expected at ~ 2.2 eV in the thin film could not be detected in spite of considerable efforts to incorporate it into the model. Instead, an oscillator at ~ 1.8 eV with a very large width of ~ 1 eV is needed to fit the low energy spectra. Thus, the disappearance of the 2.2 eV band gap structure is interpreted

as a true effect, not an artifact of the analysis, since the band gap critical points in 142

ZnTe:Cusurface roughness 90.4

0.9 1.1

undoped CdTe-based alloys of similar thickness on glass are easily observable using the same method of analysis. As a result, the severely broadened band edge absorption is

interpreted as an effect of the Cu incorporation in the film which is likely to be significantly greater than typical doping levels in semiconductors. Tables 7.3 and 7.4

provide the parameterized results for polycrystalline ZnTe:Cu and single crystal ZnTe assuming four critical point oscillators and one Tauc-Lorentz oscillator, the latter serving as the broad back ground. The critical point oscillator expression is given by: = n [Anexp(in)] [n/(2En2Ein)]n. (7.1)

The free parameters include amplitudes, resonance energies, broadening parameters, phases, and exponents, respectively: (An, En, n, n, n); n = 1, 2, 3, 4. For the thin

film ZnTe:Cu, the exponents n are fixed at the best fit values from the analysis of single crystal ZnTe data. Table 7.3 Best fit critical point and Tauc-Lorentz oscillator parameters describing the inverted dielectric function of polycrystalline ZnTe:Cu. The exponents n are fixed at the single crystal values of Table 7.4.
CPPB oscillator 1 2 3 4 An 4.10 0.42 2.69 0.06 11.86 0.67 6.64 0.23 En(eV) 1.78 0.14 3.61 0.01 4.14 0.01 5.27 0.01 n(eV) 0.96 0.22 0.72 0.01 0.55 0.02 1.28 0.02 n 124.34 10.76 112.82 3.34 45.02 2.92 19.90 3.10 n 0.08 2.09 0.38 1.52 2.79 0.61 1 offset

T-L oscillator 1

An 36.24 11.89

En (eV) 6.35 0.18

n (eV) 4.28 0.46

Eg (eV) 1.49 0.49

143

Table 7.4 Best fit critical point and Tauc-Lorentz oscillator parameters for single crystal ZnTe [7-7].
CPPB oscillator 1 2 3 4 An 8.05 0.45 4.85 0.09 16.09 1.01 3.43 0.20 En(eV) 2.21 0.03 3.58 0.01 4.25 0.02 5.22 0.02 n(eV) 0.20 0.03 0.50 0.01 0.51 0.03 0.77 0.05 n 37.31 9.34 78.30 3.48 137.85 9.29 35.46 7.67 n 0.08 2.09 0.38 1.52 -3.64 0.75 1 offset

T-L oscillator 1

An 219.76 19.98

En (eV) 4.74 0.06

n (eV) 2.86 0.06

Eg (eV) 2.48 0.06

Figure 7-14 Dielectric function of thin film ZnTe:Cu prepared by magnetron sputtering with 1 wt.% Cu in the ZnTe target (solid lines). A model consisting of four critical points in the band structure has been used in this analysis. The data points are literature results for single crystal ZnTe [7-7]. 7.3.3 Optical analysis of the CdTe solar cell in the substrate configuration In the optical analysis of the CdTe solar cell in the substrate configuration, a device is studied here that is complete with the exception of the top contact; (Dr. Anthony Vasko is acknowledged for deposition of this sample, and Dr. Jian Li is acknowledged for

144

measurement assistance).

Thus, the top surface from which the light beam reflects is

CdS, which is relatively rough. After the CdS deposition, this solar cell was treated with CdCl2 at a temperature of 387 C for a duration of 30 min. In order to analyze the structure of the solar cell, a reference set of dielectric functions is adopted including CdS obtained at room temperature using in situ SE for a film prepared in the same sputtering chamber at a substrate temperature of 310 C, a rf power level at the target of 50 W, an Ar pressure of 10 mTorr, and an Ar flow of 23 sccm. The spacing between the target and

the substrate was ~ 10 cm and the substrate was a smooth c-Si substrate for ease of analysis. Single crystal CdTe was also used as a reference, as obtained from real time
[7-8]

SE of a film prepared by molecular beam epitaxy in a literature study

. The two

other dielectric functions include that of ZnTe:Cu, obtained as described above (see Figs. 7-13 and 7-14), and Mo, obtained in the real time SE study of CdTe deposition on Mo/glass. In the latter analysis, correction was made for the surface roughness layer on

the Mo film. A step-by-step analysis, in which one free parameter is introduced at a time, was developed specifically for ex situ studies of CdTe solar cells. As each parameter is

introduced, a measure of the quality of the fit is observed, with the goal being to increase the complexity of the optical model by incorporating additional thicknesses and compositions, and in this way, determine which parameters are most important for a high quality fit and which parameters are unnecessary. Figure 7-15 shows the step-by-step reduction in the mean square error (MSE) 145

obtained by adding best fitting parameters one at a time. The MSE is expressed in terms of the standard deviations of the real and imaginary parts of tan exp(i). Figure

7-16 shows the experimental spectroscopic ellipsometry data for the CdTe solar cell on the Mo surface in the substrate configuration. The data from 0.75 to 2.5 eV are shown The fringe

on an expanded scale relative to those over the range from 2.5 to 6.5 eV.

pattern over the range from 0.75 to 1.5 eV provides information on the CdTe thickness and the modulation of these fringes provides information on the optical properties and thicknesses of the materials underneath the CdTe. The single fringe over the range from

1.5 to 2.3 eV provides information on the CdS thickness and the modulation of this fringe provides information on the underlying (opaque) CdTe. information on the critical points of the CdS. The data above 2.5 eV provides

Even very small details of the cell

structure can be inferred from the raw data, as described next. First, the critical points of the CdS are broadened compared to the film deposited on crystal Si from which the reference data were obtained. This broadening may be due to

oxidation at the surface as a result of the CdCl2 treatment. Alternatively, the effect may be due to a smaller grain size in the CdS when it is deposited on a CdTe thin film as compared to when it is deposited on bulk crystal Si. interdiffusion of the CdS and CdTe. Finally, the effect may be due to

A second observation is that the CdS band gap

appearing in the data is lower than that in the model, suggesting either interdiffusion or differences in strain between the reference film deposited on crystal Si and the solar cell of Fig. 7-16 deposited on CdTe. In spite of these small deviations, a reasonably good fit 146

(solid line) can be obtained using the model shown in Fig. 7-17.

It should be

emphasized that this represents a first attempt at analyzing solar cells in the substrate configuration and improved results are expected by breaking the structure down and developing optical properties more relevant to the structure. For example, the optical

properties of the CdS can be obtained from a single-layered sample that has been exposed to the same CdCl2 treatment as the solar cell.

0.8 1

7 9 10 11 1213 14 8 number of fitting parameters

0.6

MSE/1000

0.4

0.2

Step-by-step MSE reduction


0 10 20 30

Steps

40

50

60

70

80

Figure 7-15 Step-by-step MSE reduction by adding one fitting parameter at a time. Starting with the CdTe thickness as a variable, each additional parameter was subsequently fitted. It was found that fitting the CdS thickness provided the greatest improvement in MSE among all 2-parameter attempts. Similar methodology was used for all 14 parameters. Circles connected by the solid line indicate the best n-parameter fit with n given at the top and the added parameter given in Table 7.5.

147

40 30 20 10 0 300 200 100 0 -100 0.5 1.0 1.5

Exp. data fit

(degree)

Exp. data fit

(degree)

2.0

PHOTON ENERGY (eV)

PHOTON ENERGY (eV)

Figure 7-16 Ellipsometric spectra for a CdTe solar cell deposited on Mo in the substrate configuration (points). The cell was exposed to a CdCl2 treatment before this measurement. The top contact of the solar cell is not incorporated over the area probed, leading to the structure: ambient/CdS/CdTe/ZnTe:Cu/Mo. The solid line depicts the optical model shown in Fig. 7-17. The fitting parameter sequence in Table 7.5 is understandable in that the thickest layers have the greatest impact in the step-by-step fitting procedure. When the initial

estimate of a fitting parameter is close to its best fitting result, this fitting parameter will be added into the model at a lower priority in the sequence, an example being the ZnTe thickness. The results provide information on the ZnTe thickness and void fraction, the

ZnTe/Mo interface thickness, its Mo volume fraction, as well as the CdS thickness, and 148

void fraction, the combined CdS/CdTe interface roughness-interaction thickness, its CdTe fraction, and the CdTe thickness, and void fraction, all shown in Fig. 7-17. Also

determined is the percent non-uniformity, which describes the thickness distribution over the area of the probe beam. The following comments can be made regarding the deduced structure of Fig. 7-17. The high void fraction in the Mo substrate is consistent with the study of individual such layers as noted above. Apparently these voids are not completely filled in by the

overlying deposition of ZnTe:Cu. The model is not able to discern roughness at the CdTe/ZnTe:Cu interface, not because it does not exist, but rather, because the optical properties of the two materials do not exhibit sufficient contrast to detect it. The ~1300

thick interface layer between the CdS and CdTe is attributed to a combination of interface roughness and alloying. The volume fractions in the layers of the structure The CdTe

also convey some information; however, some results require closer scrutiny.

(3% void) of this substrate solar cell structure appears to be similar in density to that typically observed in CdCl2 treated superstrate cells (typically 1-3% voids). The CdS in the substrate cell appears to be denser than that in superstrate cells. Finally, the low

volume fraction of Mo in the Mo/ZnTe interface layer seems incongruous in view of the higher Mo fraction in the surface layers of the bare Mo film as shown in Fig. 7-12. result needs to be studied in greater detail in future analyses. This

Generally such difficult

analyses are a work in progress -- like the cell itself -- and will improve as more is learned about the optical properties and microstructure. 149 For example, a three

component effective medium approximation may be needed to describe the ZnTe:Cu/Mo interface, consisting of Mo, ZnTe:Cu, and finally void. substrate interface can be quantified. Table 7.5 Best fitting parameters added step by step to improve the standard mean square error (MSE) in the ellipsometric analysis of a CdTe solar cell in the substrate configuration. # of fitting parameters 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Best fitting parameter added to improve MSE CdTe thickness CdS thickness Mo void volume fraction CdS roughness thickness (50/50) ZnTe/Mo interface thickness (50/50) CdTe void volume fraction Mo volume fraction in ZnTe CdS roughness void volume fraction CdTe non-uniformity CdS/CdTe interface thickness (50/50) CdS void volume fraction CdTe volume fraction in CdS/CdTe interface ZnTe void volume fraction ZnTe thickness Standard MSE 764.2 475.7 214 113.3 86.05 67.84 53.02 40.05 36.4 35.54 34.93 34.33 33.95 33.87 In this way, voids trapped at the

150

CdS surface roughness thickness Surface void fraction CdS thickness Void volume fraction CdS/CdTe interface thickness CdTe volume fraction CdTe thickness Void volume fraction CdTe thickness non-uniformity CdTe/ZnTe interface thickness ZnTe thickness Void volume fraction ZnTe/Mo interface thickness Mo volume fraction Mo void volume fraction

159 5 0.25 0.01 2433 9 0.007 0.003 1348 20 0.835 0.009 13715 66 0.030 0.003 3.8% 0.2% 0 1120 114 0.026 0.011 293 63 0.195 0.061 0.395 0.027

Figure 7-17 Optical model for a CdTe solar cell in the substrate configuration (excluding the top contact) deposited on a Mo film surface. This model and the best fit parameters provide the solid line results in Fig. 7-16.

151

Chapter Eight

Spectroscopic Ellipsometry Studies of II-VI Alloy Films

8.1 Introduction In the single junction superstrate solar cell configuration, the highest efficiency for a CdTe device prepared by sputtering is 14%
[8-1]

and the corresponding result for

close-spaced sublimation is 16.5% [8-2]. The latter champion solar cell has the following characteristics: VOC = 845 mV, JSC = 25.9 mA/cm2, and FF (fill factor) = 75.5%. The

current-voltage (J-V) and quantum efficiency (QE) curves of the champion cell are shown in Figure 8-1.

Figure 8-1 Current-voltage and normalized quantum efficiency spectra for a champion 16.5% efficient CdTe/CdS thin-film solar cell [8-2]. 152

In order to improve on these cell efficiencies, materials and devices for tandem cell structures have been investigated in the research laboratory
[8-3]

Instead of using a

single junction device based on CdTe with a near-optimum band gap of 1.5 eV, the top cell absorber material of the tandem must have a wider band gap, and the bottom cell absorber material must have narrower band gap. A practical conversion efficiency of

25% has been predicted for a two-junction two-terminal polycrystalline thin-film tandem cell with energy band gaps of 1.14 eV for the bottom cell and 1.72 eV for the top cell [8-4]. CdTe-based ternary alloy materials, such as Cd1-xMgxTe and Cd1-xMnxTe are attractive due to the flexibility of controlling their band gaps through the molar composition x, and as a result, these materials have been considered as wide band gap top cell candidates for such tandem cells as shown in Fig. 8-2. In addition to the II-VI alloys with wide band

gaps, the alloy Cd1-xHgxTe is a possible narrow band gap bottom cell candidate. Cd1-xHgxTe is flexible enough to tailor the band gap from 0.15 eV for x = 1, i.e. semimetallic, to 1.5 eV for x = 0 [8-5]. Spectroscopic ellipsometry is an excellent non-contacting technique for investigating thin-film semiconductor optical properties, electronic structure, and surface and bulk microstructure. This technique has been applied for materials evaluation in order to explore the opportunities and identify the potential difficulties in the fabrication of II-VI materials for top cells in two-junction devices with either monolithic two-terminal (see Fig. 8-2) or mechanically stacked four-terminal structures. In this research, two top cell

materials, Cd1-xMnxTe and Cd1-xMgxTe, the latter with a band gap as wide as 1.98 eV, 153

were measured.

These films were obtained by sputtering in order to assess their The widest band gap Also in

suitability in tandem PV devices with a Cd1-xHgxTe bottom cell.

Cd1-xMgxTe was obtained from a target of 60 wt.% CdTe and 40 wt.% MgTe.

this research, Cd1-xHgxTe thin films with a band gap variation from 0.81 eV to 1.58 eV were measured. These films were obtained by sputtering using a target of 60 wt.%

CdTe and 40 wt.% HgTe through a variation of the deposition temperature.

glass ZnO CdS Cd1-xMgxTe ZnTe ZnO CdS Cd1-xHgxTe Cu/Au

Figure 8-2

Two-terminal tandem cell based on Cd1-xMgxTe and Cd1-xHgxTe absorbers.

8.2 Top cell material candidates: Cd1-xMnxTe and Cd1-xMgxTe 8.2.1 Cd1-xMnxTe and Cd1-xMgxTe preparation The Cd1-xMnxTe and Cd1-xMgxTe films described in this section were magnetron sputtered on soda-lime glass substrates from targets fabricated from 87 wt. % CdTe and 13 wt. % MnTe, and from 80 wt. % CdTe and 20 wt. % MgTe, respectively; (Viral Parikh is acknowledged for the deposition of these samples). A first estimate of the

composition of the as-deposited alloys films was made on the basis of the optical 154

absorption edge determined from the transmission spectra.

The Cd1-xMnxTe film

thickness was typically about 1 m; Cd1-xMgxTe films were thinner -- about 0.2 m. The deposition conditions for CdxMg1-xTe are shown as the first two entries of Table 8.1. Table 8.1 films. Deposition parameters used to prepare the CdxMg1-xTe and CdxHg1-xTe thin

CdTe CdxMg1-xTe (20 wt.% MgTe) CdxMg1-xTe (40 wt.% MgTe) CdxHg1-xTe CdxHg1-xTe CdxHg1-xTe CdxHg1-xTe CdxHg1-xTe CdxHg1-xTe

Rf power (W) 20 50 50 27 27 27 27 27 27

Pressure (mTorr) 18 20 5 10 10 10 10 10 10

Substrate temp (C) 250 200 290 23 44 70 85 97 153

A CdCl2 post-deposition treatment was performed as an important step in fabricating solar cells using the alloys as the active layers. Several effects of the CdCl2 treatment

are believed to enhance the solar cell performance of the alloy films, including relaxing the strain, increasing the grain size, improving the alloy/CdS interface, and reducing the lattice mismatch there [8-6]. For evaluation purposes, the CdCl2 treatment was performed

on a 2 cm 3 cm piece of each sample placed in a 2.5 cm diameter quartz tube. The CdCl2 source was fabricated by forming a saturated methanol solution of the chloride and evaporating it from the surface of a heated glass plate. The sample was placed above

155

the source plate with the film side facing the plate and a 1 mm gap between the two.

typical 30 minute CdCl2 treatment was performed on the Cd1-xMgxTe films at a temperature of 387C. were evaluated. To treat the Cd1-xMnxTe films, two post-deposition approaches

In one approach, the CdCl2 vapor treatment was carried out on the In the other, a two-step process was

films under the same conditions as for Cd1-xMgxTe.

applied in which a high temperature annealing step was carried out at 520C for 10 minutes under 2% H2/Ar, followed by the standard CdCl2 vapor treatment at 385C for 30 minutes in dry air. In order to compare the optical results before and after CdCl2 treatment, pure CdTe films of more than 1 m in thickness were magnetron sputtered onto soda-lime glass at 250C. For these CdTe films, a CdCl2 treatment in dry air ambient was performed at a

temperature of 387C with different times optimized depending on the film thicknesses.

8.2.2 Data analysis and results A rotating compensator multichannel spectroscopic ellipsometer with a 0.75 - 6.5 eV photon energy range was used to investigate the optical properties of the as-deposited and annealed films. The information extracted from SE measurements is very useful for

assessing the surface and bulk characteristics of the samples. As-deposited Cd1-xMgxTe and Cd1-xMnxTe optical properties Figure 8-3(a-b) shows the pseudo-dielectric functions of RF magnetron sputtered CdTe, Cd1-xMnxTe, and Cd1-xMgxTe films in the as-deposited state. The thicknesses of 156

CdTe, Cd1-xMnxTe and Cd1-xMgxTe films are 1.41 m, 1.0 m and 0.18 m, respectively. The band gaps of 1.63 eV for the Cd1-xMnxTe film and 1.61 eV for the Cd1-xMgxTe film were estimated from optical transmission measurements. These two alloy films as well

as the CdTe film are transparent below their band gaps, and the spectral density of interference fringes in the lower energy range of ~ 0.75 eV to 2.0 eV scales with the film thickness. In the high energy range of 2.0 eV to 6.5 eV, features are observed

corresponding to the higher energy band gaps at the critical points (CPs) in the joint density of states. The nature of these CPs and the information that can be extracted

from them will be discussed shortly. A comparison of pseudo-dielectric functions over the high energy range for the Cd1-xMnxTe film of Fig. 8-3(a-b) after Br2/methanol etch and after selected times of long term laboratory storage is given in Fig. 8-3(c). The freshly-deposited sample exhibits

higher amplitudes in < > than a sample that has been stored for a period of time. The data for the Cd1-xMnxTe sample in Figure 8-3(a-b) were taken one week after film deposition. Thus, it is reasonable to interpret the relatively low dielectric function By tracking <2 > values during

amplitudes of the stored samples to surface oxidation.

Br2/methanol chemical etching processes, one can develop an optimum procedure to remove the oxide, and achieve the most abrupt interface to the ambient as this leads to maximum <2 >. For the results in Figure 8-3(c), the E1, E1 + 1, and E2 critical-point

structures can be seen clearly in all spectra. The sample measured immediately after etching by Br2/methanol chemical solution showed the highest amplitudes of the 157

pseudo-dielectric function in the higher energy region. Fig. 8-3(c) are in accord with those of epitaxial films

In fact, the maximum values in


[8-7]

and bulk crystals

[8-8]

Thus,

the pseudo-dielectric function after etching is expected to be very close to true dielectric function with only small deviations due to residual surface roughness or a thin Te-rich surface layer generated by the etching process.
16 12 8 4 0 16 12 1 2 3 4 5 6

CdTe CdTe

8 4 0 -4 1 8 2 3 4 5

CdTe CdTe

<> <2e 2 >

<e>> < 11

8 4 0 16 12 8 4 0 1 2 3 4 1 2 3 4

CdMnTe Cd1-xMnxTe

4 0 -4

Cd1-xMnxTe CdMnTe

8
Cd1-xMgxTe CdMgTe

4 0 -4
CdCdMgTe 1-xMgxTe

Energy (eV)

Energy (eV)

(a)
12 10 8

(b)
12 10

1 2 3

E1 E 1+ 1
< 2>

E 1 E 1+ 1

E2

8 6 4 2 0

< 1>

6 4 2 0 -2 2

E2

1 2 3

Energy (eV)

-2

(C)

Energy (eV)

Figure 8-3 Real (a) and imaginary (b) parts of the pseudo-dielectric functions of RF sputtered CdTe (Eg = 1.50 eV), Cd1-xMnxTe (Eg = 1.63 eV) and Cd1-xMgxTe (Eg = 1.61 eV) films all in the as-deposited state; (c) Pseudo-dielectric function of as deposited Cd1-xMnxTe samples after different storage times in laboratory ambient: (1) immediately after Br2/methanol etch; (2) 3 weeks after deposition; and (3) 1.5 years after deposition. 158

Once the maximum value of <2> is obtained through etching, the resulting spectra as in Fig. 8-3(c) (immediately after etch), interpreted as an approximation to the true dielectric function, can be further interpreted through CP analysis. Although the imaginary part of the dielectric function is most closely related to the absorptive behavior of films and thus the joint density of electronic states, however, both real and imaginary parts encode this information due to the Kramers-Kronig relationships. The fundamental and higher band

gap energies determined from the CP features provide information on the alloy composition and strain whereas the broadening energies of the CP features provide information on the crystalline grain size arising from the polycrystalline structure. The band structure parameters of a single CP, including the band gap and broadening energies can be deduced from both parts of (E) by fitting to a standard analytic line shape [8-9]

( E ) = Aei / [(2 E 2 E0 + i) ] ,

(8-1)

where A is the CP amplitude, and are the Lorentzian broadening energy and phase angle, and E0 and are the threshold energy and exponent, the latter defined by the nature of the singularity in the electronic joint density of states. These parameters are readily determined by fitting second-derivative spectra d2(E)/dE2. For the ternary alloy

system, once relationships have been established between the molar composition x and the CP energies in the band structure, as determined from the dielectric function (E), usually from studies of single crystals, such relationships can be used to estimate the composition of any unknown alloy
[8-9,8-10]

Figure 8-4 shows the experimental

second-derivative spectra in the pseudo-dielectric function <(E)> of an as-deposited

159

Cd1-xMnxTe sample, along with best fit results obtained using Eq. (8-1).
d < 1 >/d d < 2 >/d
2 2 2 2

100

d < >/ d

-100

E 2 (5.033 eV) E 1 + 1 (3.884 eV) E 1 (3.352 eV)


2 3

Energy (eV)

Figure 8-4 Best fit (lines) to the second derivative of the experimental pseudo-dielectric function (points) for the as-deposited Cd1xMnxTe film of Fig. 8-3 (c: immediately after etch). The three CP transitions, E1, E1 + 1, and E2, are indicated by arrows with best fit energies of 3.352, 3.884, and 5.033 eV, respectively. The composition of x=0.06 can be estimated by the empirical relationship between E1, the strongest CP in this case, and the composition [8-7]. Returning to the results of Fig. 8-3(c), very large changes in the pseudo-dielectric function induced by sample exposure to laboratory ambient can be observed by SE. This effect can be explored in greater detail by RTSE. Figure 8-5 shows the continuous

variation in the pseudo-dielectric function of the 3-week-old Cd0.94Mn0.06Te sample immediately after Br2/methanol etching and upon exposure to air. For such

measurements, the native oxide layer was removed by 0.01-0.02% Br2/methanol in a few seconds of etching time. Upon exposure of the resulting clean sample to air, the

pseudo-dielectric function does not change much during the initial several minutes; however, with increasing time both real and imaginary parts of the pseudo-dielectric function gradually decrease. In fact, the imaginary part of the pseudo-dielectric function

near the E1 + 1 CP energy (~ 3.88 eV) decreased by 5% over a one hour period. 160

18 16 14
Time increasing

8 6 4
0.5 3.5 6.5 9.5 18 38 58 m in m in m in m in m in m in m in

12

< 1>

10 8 6 4 2 0 -2 1 2 3 4

< 2>

2 0 -2 -4 -6 -8

Energy (eV)

Energy (eV)

Figure 8-5 Variation of the pseudo-dielectric function of as deposited Cd0.94Mn0.06Te with time after Br2/methanol etching, measured in situ at room temperature during exposure to laboratory ambient.
20 16 12
As-deposited One-step o 385 C 30 min with CdCl2 Two-step o first 520 C 10 min in H2, then 385 C 30 min with CdCl2
o

20 16 12

As-deposited One-step o 385 C 30 min with CdCl2 Two-step o first 520 C 10 min in H2, then 385 C 30 min with CdCl2
o

<1>

8 4 0 1 2

Energy (eV)

< 2 >

8 4 0

-4 1 2 3 4 5 6

Energy (eV)

Figure 8-6 Pseudo-dielectric functions of as-deposited and one-step and two-step CdCl2 treated Cd0.94Mn0.06Te samples. Optical properties of CdCl2-treated and Cd1-xMnxTe and Cd1-xMgxTe Figure 8-6 shows the pseudo-dielectric function of as-deposited (3-week-old) and annealed Cd0.94Mn0.06Te samples. Using the dielectric functions obtained from the

Br2/methanol-etched Cd0.94Mn0.06Te sample and assuming Te oxide (TeO2) on the surface, the latter shown in Fig. 8-7
[8-11]

, a simple 3-layer model of oxide/Cd0.94Mn0.06Te/glass

could be employed to fit the experimental results for the as-deposited sample. The 161

Tim e increasing

0.5 3.5 6.5 9.5 18 38 58

min min min min min min min

12 10

thickness of TeO2 layer was found to be ~ 35 .

For the annealed sample, however, it

was difficult to fit the experimental data due to lack of reference dielectric functions for the surface layer components. In particular, for the sample that was vapor treated with

CdCl2 at 385C, the pseudo-dielectric function was much different from that of the as-deposited samples. It was further observed that even after the treated films were

etched using several etching steps of 0.04 volume % Br2 in methanol, the pseudo-dielectric function showed much different spectral behavior from that of the as-deposited sample. This suggests that the top layer is substantially modified during

treatment, both chemically and morphologically; however, there remains the possibility that the behavior is due to a thick metallic oxide generated during treatment that does not respond to the Br2 methanol etch in the same way as the native oxide.

Figure 8-7

Index of refraction and extinction coefficient of amorphous TeO2.

162

20 16 12 8 4 0 1 2 As-deposited o 387 C 30 m in CdCl2 treated

20 16 12

As-deposited o 387 C 30 m in CdCl2 treated

< 1>

< 2>
3 4 5 6

8 4 0

-4

Energy (eV)

Energy (eV)

Figure 8-8 samples.

Pseudo-dielectric functions of as-deposited and CdCl2 treated Cd1-xMgxTe

Figure 8-8 shows the pseudo-dielectric function of as-deposited and CdCl2-treated Cd1-xMgxTe samples. For the CdCl2-treated Cd1-xMgxTe sample, much less deterioration in the bulk optical characteristics is observed compared with CdCl2 treated Cd1-xMnxTe, suggesting that the CdCl2 treatment is effective for Cd1-xMgxTe PV devices. Most

importantly, the critical point structure of the Cd1-xMgxTe is retained upon treatment with a clear narrowing of the widths. Dielectric functions of as-deposited and CdCl2 treated samples over the energy range of 3.0 ~ 6.0 eV are accumulated in Fig. 8-9 (a-c). For these measurements, the films

were previously etched using one or more steps, each consisting of brief immersion in a 0.04 volume % Br2 in methanol solution. The original intent of this process was to

remove oxides that are observed to develop on as-deposited and CdCl2-treated CdTe films due to their exposure to the laboratory and treatment ambients. Interestingly, for

CdTe it has been found that successive etching steps lead to a significant step-wise smoothening of the film surface simultaneously with decreasing bulk layer thickness due 163

to step-wise film dissolution. In fact, a roughness layer of thickness of up to a micron or more can be eliminated in several successive etching steps, and ultimate stabilization of the roughness thickness at ~20-40 can be observed. It is under stable, smooth-surface Under these

conditions that the measurements on CdTe of Fig. 8-9(a) are made.

conditions, the dielectric function deduced from the measured ellipsometry spectra is reasonably representative of the true dielectric function, enabling determination of the critical point energies and widths by dielectric function fitting. etching treatments lead to a Te-rich surface layer (~10 )
[8-12]

It is known that the ; however, its effect is

expected to be smaller than that of the residual roughness and has been neglected in this study. Figure 8-9(c) compares the approximate dielectric function of Br2/methanol-etched Cd1-xMgxTe in the as-deposited (left) and CdCl2-treated (right) states. This Cd1-xMgxTe film was sputter-deposited to a thickness of 0.18 m on a soda-lime glass slide. The

results in Fig. 8-9(c) may differ somewhat from the true dielectric function due to the presence of the residual roughness and a Te-rich surface layer. The key observation in the comparison of the panels of Fig. 8-9(c) is that noted earlier in Fig. 8-8, namely, the critical points E1, E1+1, and E2 are clearly observed at similar energy positions in both sample states. effects. Any observed shifts may be due to incomplete accounting of surface

In fact, all critical points become sharper upon CdCl2 treatment. This is an

indication that the composition of the film is retained upon treatment and that the crystalline grain size increases significantly, as well. 164 For comparison, in Fig. 8-9(a),

which depicts the corresponding results for CdTe (i.e., with no alloying), similar behavior is observed. In contrast, for Cd1-xMnxTe in Fig. 8-9(b), the CdCl2 treatment leads to a

complete loss of the critical point structures and these cannot be recovered by continued etching. This demonstrates that the treatment leads to a significant chemical

modification of the Cd1-xMnxTe film, most likely phase segregation and oxidation of the Mn, which can account for its poor performance when incorporated into actual devices. The fact that the Cd1-xMgxTe does not experience such a modification upon CdCl2 treatment and retains the band structure characteristics of the as-deposited film (along with a significant increase in grain size) has demonstrated its promise for the development of devices from this material. Quantitative information can be obtained from fits to the approximate dielectric functions of Figs. 8-9(a) and 8-9(c) which provide the energy positions and widths of the dielectric function peaks. These results are given in Fig. 8-9 as the solid lines for all

films except for the CdCl2-treated Cd1-xMnxTe in which case the critical point structure is lost. The critical point parameters including the energy positions Ej and widths j are Among the key observations of Table 8.2 include:

presented in Table 8.2.

(i) retention of the critical point structure for Cd1-xMgxTe upon CdCl2 treatment without a significant change in the energy positions (in consideration of surface variations), indicating success of alloying in the CdCl2-treated films; (ii) reduction of the critical point transition widths upon CdCl2 treatment for the CdTe and Cd1-xMgxTe, an indication of an increase in grain size or a reduction in defect 165

density;

(a)

(b)

(c)

Figure 8-9 Approximate dielectric functions, i.e., optical properties deduced with a best attempt to eliminate surface effects, for as-deposited films and CdCl2-treated films obtained by SE after Br2+methanol etching that improves the surface quality (points); (a) CdTe; (b) Cd1-xMnxTe; (c) Cd1-xMgxTe; the solid lines show the results of fits to extract critical point energies and widths. The result for the CdCl2-treated Cd1-xMnxTe could not be fit with a critical point parabolic band model. 166

(iii) increase of the critical point transition widths for the as-deposited alloys compared with the as-deposited CdTe, possibly due to a smaller grain size in the as-deposited alloy films; and (iv) similar critical point widths for the CdCl2-treated CdTe and Cd1-xMgxTe, indicating the effectiveness of the treatment in improving the alloy. Table 8.2 Critical point parameters of transition energy and width obtained in the fits to the dielectric functions of Fig. 8-9. CdTe as-dep. 1.497 3.274 0.411 3.844 0.484 5.193 0.993 CdTe CdCl2-treat. 1.499 3.331 0.200 3.883 0.368 5.208 0.796 Cd1-xMgxTe as-dep. 1.615 3.354 0.480 3.901 0.520 5.179 1.252 Cd1-xMgxTe CdCl2-treat. 1.633 3.303 0.216 3.878 0.309 5.197 0.879 Cd1-xMnxTe as-dep. 1.548 3.363 0.430 3.914 0.483 5.182 1.215 Cd1-xMnxTe CdCl2-treat. ---------------

E0 (eV) E1 (eV) (1) (eV) E1+1 (eV) (E1+1) (eV) E2 (eV) (E2) (eV)

Furthermore, two additional Cd1-xMgxTe samples prepared by magnetron sputtering from alloy targets were studied in detail by ex situ SE. The goal of this study was to

compare the previously-described as-deposited film prepared with low Mg content and band gap of Eg = 1.615 eV with those prepared under conditions leading to higher Mg content. This comparison was performed on as-deposited films without CdCl2 treatment. For the sample labeled CGT42, the target was CdTe (80 wt.%) + MgTe (20 wt.%), and Cd1-xMgxTe deposition was performed on a soda lime glass substrate at a temperature of 200C using 50 W rf power at the target, 20 mTorr Ar pressure, and 30 sccm Ar flow.

167

The deposition time was 2 hours, and the final Cd1-xMgxTe film thickness was ~ 0.3 m. For the much higher Mg content sample labeled CGT92, the target was CdTe (60 wt.%) + MgTe (40 wt.%), and Cd1-xMgxTe deposition was performed on an aluminosilicate glass substrate at a temperature of 290C using 50 W rf power at the target, 5 mTorr Ar pressure, and 30 sccm Ar flow. In this case, the deposition time was 6 hours, and the

Cd1-xMgxTe film thickness was ~ 2.9 m. Spectroscopic ellipsometry was performed on these two samples at angles of incidence of 60 and 65, respectively. 0.74~6.50 eV. The photon energy range was standard:

A two-layer surface-roughness/bulk model for the film was used to

analyze the experimental data (, ). The dielectric function of the bulk layer was modeled using a sum of critical point oscillator terms, each of the form of Eq. (8-1), given by

= TL + 4j=1 [Ajexp(ij)][j/(2Ej 2E ij)]j.

(8-1)

Here oscillators labeled j = 1, 2, 3, 4 correspond to the E0 (band gap), E1, E1+1, and E2 critical point transitions. An additional oscillator, denoted TL, is modeled using the Tauc-Lorentz expression in order to simulate a broad background in . Each of the

critical point oscillators has five free parameters: amplitude Aj, energy Ej, width j, phase

j, and exponent j. In this analysis, the focus is on the critical point energies Ej and the
width 0 of the lowest band gap critical point.

168

12

<1>
8

CdMgTe 42 Cd1-xMgxTe
CGT42

<2> <1, 2>


4
ambient

roughness CdMgTe

ds = 94 db = 2908

-4

glass

Photon Energy (eV)

Figure 8-10 Pseudo-dielectric function obtained directly from experimental (, ) data using a single interface conversion formula for a Cd1-xMgxTe sample prepared from a target of CdTe (80 wt.%) + MgTe (20 wt.%) (CGT42). The solid line describes experimental data and the dashed line describes the best fit result. The deduced bulk and surface roughness layer thicknesses are shown.

E0 = 1.71 eV , E0 = 0.13 eV
1 2

CdMgTe 42 Cd1-xMgxTe
CGT42

1, 2

0 0 1 2 3 4 5 6 7 Photon Energy (eV)

Figure 8-11 Best fit analytical dielectric function obtained from an analysis of the experimental (, ) data for the Cd1-xMgxTe sample of Fig. 8-10 prepared from a target of CdTe (80 wt.%) + MgTe (20 wt.%) (CGT42). The energies can provide information on the band gaps, alloying, and strain, whereas the width of the E0 critical point provides information on defects, grain size, and disorder. 169

Figure 8-10 shows the pseudo-dielectric function data for the lower Mg content Cd1-xMgxTe sample (CGT42) and the best fit to these data. Figure 8-11 shows the true dielectric function of this Cd1-xMgxTe film which is extracted in the best fit. deduced band gap, 1.71 eV, and the broadening parameter is 0.13 eV. The

This band gap

corresponds to a molar composition of x = 0.15 using the relationship established previously


[8-7]

Optical transmission spectroscopy yielded a band gap value in

agreement with the SE result.

<1>

CdMgTe 92 Cd1-xMgxTe

<2>

CGT92

< 1, 2 >

ambient

roughness CdMgTe glass

ds = 137 db = 28887

Photon Energy (eV)

Figure 8-12 Pseudo-dielectric function obtained directly from experimental (, ) data using a single interface conversion formula for a Cd1-xMgxTe sample prepared from a target of CdTe (60 wt.%) + MgTe (40 wt.%) (CGT92). The solid line describes experimental data and the dashed line describes the best fit result. The deduced bulk and surface roughness layer thicknesses are shown.

170

E0 = 1.98 eV, E0 = 0.16 eV 8


1 2

CdMgTe 92 Cd1-xMgxTe
CGT92

1, 2

Photon Energy (eV)

Figure 8-13 Best fit analytical dielectric function obtained from an analysis of the experimental (, ) data for the Cd1-xMgxTe sample of Fig. 8-12 prepared from a target of CdTe (60 wt.%) + MgTe (40 wt.%) (CGT92). Figures 8-12 and 8-13 show the corresponding results for the higher Mg content sample (CGT92). 0.16 eV. The band gap of this film is 1.98 eV, and the broadening parameter is

The band gap corresponds to a composition [8-7] of x = 0.30, indicating a linear

relationship between film molar and target wt. % composition for CdTe and the two alloy samples with a slope of 0.0075/wt.% MgTe. Table 8.3 shows the values of the fundamental gap energy E0 and its width, as well as the energies of the higher energy critical points E1, E1+1, E2, for the two Cd1-xMgxTe samples. Also shown for comparison are the corresponding results for pure CdTe before

and after the CdCl2 treatment. The shifts in the energies of critical points upon CdCl2 treatment for CdTe in this case are due to relaxation of strain and the narrowing of the E0 peak is due to an increase in grain size. It is clear that the E0 band gap increases as the

target alloy composition increases; the use of 20 wt.% MgTe in the target does not lead to 171

significant broadening of the E0 transition relative to pure untreated CdTe.

However, 40

wt.% MgTe leads to a significant broadening effect as a result of either a smaller grain size or increased disorder in the film due to alloying. The non-monotonic behavior observed in the E1 and E1+1 higher energy gaps with alloying are likely to be due to changes in electronic structure as well as to strain in the films. Table 8.3 Critical point energies and E0 broadening parameters for two as-deposited Cd1-xMgxTe alloys from spectroscopic ellipsometry. Also shown are corresponding results for as-deposited and CdCl2-treated CdTe. CdTe CdCl2-treat. E0 (eV) (E0) (eV) E1 (eV) E1+1 (eV) E2 (eV) 1.503 0.061 3.321 3.913 5.214 CdTe Untreated 1.527 0.089 3.199 3.981 5.208 Cd1-xMgxTe 42 (20 wt.% MgTe) 1.710 0.128 3.567 3.725 5.175 Cd1-xMgxTe 92 (40 wt.% MgTe) 1.983 0.161 3.479 3.816 5.143

8.3 Bottom cell material: Cd1-xHgxTe 8.3.1 Cd1-xHgxTe film preparation Efforts have also focused on the optical characterization of as-deposited Cd1-xHgxTe films grown at different substrate temperatures for use as a bottom cell absorber material. The Cd1-xHgxTe films were deposited by rf magnetron sputtering as described in Table 8.1 on 1 mm thick soda-lime glass, using a sputtering target containing CdTe (60 wt.%) + HgTe (40 wt.%). Individual films were grown at substrate temperatures of 23C, 44C, This substrate deposition temperature range is of

70C, 85C, 97C, and 153C.

172

greatest interest in order to avoid metallic Hg inclusions

[8-13]

All such films were

deposited at an Ar pressure of 10 mTorr and an RF power of 27 W; (Dr. Viral Parikh is acknowledged for deposition of these samples). In addition, CdCl2 post-deposition The higher temperature of the

treatments were performed on the Cd1-xHgxTe films.

post-deposition process in CdTe has been shown to increase the grain size and thus improve the efficiency of the cells. A two stage process was explored for the

Cd1-xHgxTe consisting of an anneal in an inert gas at 387C and then a CdCl2 vapor treatment at the same temperature. Optical characterization was performed in order to Thus, ex situ

determine the band gap variation with substrate temperature.

spectroscopic ellipsometry data were acquired on as-deposited and CdCl2-treated Cd1-xHgxTe films before and after Br2/methanol etching.

8.3.2 Results and discussion Figure 8-14 shows the band gaps of the Cd1-xHgxTe films in the as-deposited state for different substrate temperatures, whereas Fig. 8-15 shows comparisons of the dielectric functions from the inversion process and from the corresponding analytical model fit. Table 8.4 also shows the energy and width of the critical point with the strongest peak in

2 as described in Fig. 8-15.

173

1.6

1.4

Bandgap (eV)

1.2

1.0

0.8 20 40 60 80 100 120 140 160

Substrate Temperature (C)

Figure 8-14 Band gap of as-deposited thin film Cd1-xHgxTe as a function of the substrate temperatures over the range from 23C to 153C. Table 8.4 Energy position and width of the critical point generating the strongest peak in 2 for as-deposited thin film Cd1-xHgxTe. Temperature (C) 23 44 70 85 97 153 E (eV) 3.30 3.11 3.44 3.47 3.49 3.51

(eV) 1.97 2.50 1.64 1.89 1.77 0.85

174

14 12 10 8

g.o. fit inversion inversion

14 12 10 8

g.o. fit inversion inversion

Ts = 23C Eg = 1.58 eV
e1,e2

Ts = 44C Eg = 1.57 eV

e1,e2

6 4 2 0 -2 0 1 2 3 4 5 6 7

6 4 2 0 -2 0 1 2 3 4 5 6 7

eV
14 12 10 8

eV

g.o. fit inversion inversion

14 12 10 8

g.o. fit inversion inversion

Ts = 70C Eg = 1.51 eV
e1,e2

Ts = 85C Eg = 1.15 eV

e1,e2

6 4 2 0 -2 0 1 2 3 4 5 6 7

6 4 2 0 -2 0 1 2 3 4 5 6 7

eV
14 12 10 8 14 12 10 8

eV

g.o. fit inversion inversion

g.o. fit inversion inversion

Ts = 97C Eg = 1.37 eV
e1,e2

Ts = 153C Eg = 0.81 eV

e1,e2

6 4 2 0 -2 0 1 2 3 4 5 6 7

6 4 2 0 -2 0 1 2 3 4 5 6 7

eV

eV

Figure 8-15 Dielectric functions from mathematical inversion and from the corresponding analytical model fit for as-deposited Cd1-xHgxTe films prepared with different substrate temperatures. The agreement between the two methods for dielectric function determination supports the validity of the functional form of the analytical model. 175 Figure 8-14 shows

that the band gap decreases abruptly at a substrate temperature of about 75C.

At low

temperatures the band gaps are close to that of CdTe, however, the dielectric function shape is inconsistent with polycrystalline CdTe. It is possible that nanoscale Hg The

inclusions exist, giving rise to a broad plasmon resonance centered near 3.5 eV.

semiconductor component of all films except that grown at the highest temperature must have a very small grain size or high defect density in accordance with the large broadening values. In the film prepared at the highest temperature of 153C,

semiconducting Cd1-xHgxTe with x ~ 0.4 appears to have been obtained with a larger grain size
[8-14]

These trends are confirmed by XRD measurements which reveal that

the films grown at 85C and 97C consist of small grains coalesced to form larger grains with diffuse grain boundaries. Figure 8-16 presents a comparison of the pseudo-dielectric functions of as-deposited and CdCl2 treated Cd1-xHgxTe films, including the results for each of the two samples before and after a single Br2+methanol etching step. The key observations of Fig. 8-16

include (i) the blue shift of the critical point energies for Cd1-xHgxTe upon CdCl2 treatment, indicating the loss of Hg content in the alloy film after the treatment; and (ii) reduction of the critical point transition widths for the Cd1-xHgxTe upon CdCl2 treatment, an indication of an increase in grain size or a reduction in defect density. This

post-deposition treatment has proven to be the most challenging aspect of Cd1-xHgxTe and other alloy film preparation and further work is needed to optimize these processes specifically for the alloys. 176

12
16 14 12 10

As developed st As developed 1 etch step CdCl2 treated CdCl2 treated 1 etch step
st

10 8 6

Cd1-xHgxTe critical points blue shift after CdCl2 treatment E1+1 E2 E1

<1>

8 6 4 2 0 -2 0 1 2 3 4 5 6 7

< 2 >

4 2 0 -2 -4 -6 0 1 2 3

E1 E1+1

E2

As developed st As developed 1 etch step CdCl2 treated CdCl2 treated 1 etch step
4 5 6 7
st

Photon energy (eV)

Photon energy (eV)

Figure 8-16 Comparison of the real (left) and imaginary (right) parts of the pseudo-dielectric function of as-deposited and CdCl2 treated CdxHg1-xTe films, including results (a) before and (b) after a single Br2/methanol etching step.

177

Chapter Nine

Summary and Future Directions

9.1

Summary The most significant accomplishment of this thesis research is the first demonstration

of ex-situ spectroscopic ellipsometry (SE) performed through the glass superstrate for non-destructive evaluation of CdTe solar cells in the configuration used widely by industry. This measurement approach avoids the problem of the very rough free surface

of CdTe, which makes quantitative optical measurements from the film side extremely difficult, if not impossible. The validity of such through-the-glass measurements has

been corroborated by ex-situ SE measurements from the film side of the solar cell performed destructively after smoothening the CdTe film surface with a succession of Br2+methanol etching steps. The measurement approach in which the CdTe solar cell is

probed non-destructively through the glass has a wide variety of applications including: (i) off-line mapping of large area coated glass plates, (ii) on-line monitoring of such plates, as well as (iii) interpreting quantum efficiency measurements in terms of optical and electronic losses.

178

In Chapter 3 of this thesis, ex-situ SE was shown to provide the four sets of optical properties of the materials that comprise the Pilkington TEC-15 glass superstrate of the CdTe solar cell. These materials include the soda lime glass superstrate material, and

the SnO2, SiO2, and SnO2:F thin film materials deposited in on-line coating processes. The dielectric functions of these four materials were measured from the film side in each case, and they serve as a database that enables analysis of CdCl2-treated and untreated CdTe solar cells in measurements through the glass or from the film side. Both

ellipsometry and transmittance experiments have been performed on the set of TEC-15 samples, and the optical models have been selected for each material so as to fit the measured ellipsometry and transmittance spectra simultaneously and thereby provide accurate dielectric functions of the component materials of the superstrate. In the thesis research described in Chapter 4, a Br2+methanol step-wise chemical etching process has been developed that both reduces the bulk thickness of the CdTe and smoothens its surface, but without introducing measurable changes in the underlying thin film structure. In studies that demonstrate this capability, in-situ real time SE and

ex-situ SE measurements have been compared, the latter in conjunction with repetitive chemical etching. By comparing the CdTe thin film structure during deposition as

monitored by real time SE with that during the etching process using ex-situ SE, it has been shown that the etching process is the reverse of the deposition process. This means

that for each CdTe bulk layer thickness during growth or etching, the underlying bulk layer of the sample has the same void fraction profile. 179

In Chapter 5, the Br2+methanol etching procedure has been demonstrated for the analysis of CdTe structural modifications by CdCl2 treatments. This approach is

preferred over in-situ real time SE studies of CdCl2 treatment because in the real time studies many aspects of the sample structure are likely to change simultaneously, making interpretation extremely difficult. In Chapter 5, the power of Br2+methanol etch

profiling was demonstrated first in studies of ~3000 thick CdTe films on crystalline Si substrates processed in three different ways: (i) as-deposited, (ii) thermally annealed in Ar gas for 30 min, and (iii) CdCl2 treated for 5 min. For such films, depth profiles in the

relative void volume fraction and the critical point energies and widths as functions of CdTe bulk layer thickness during etching by Br2+methanol have provided information on microstructure, grain size, and strain. As a result, it has been demonstrated that the

CdCl2 treatment relaxes the strain in the CdTe network and generates a relatively uniform grain structure throughout the thickness of the thin films. Differences in the depth

profiles between Ar annealed and CdCl2 treated films suggest that in the former case, a fine grained structure is retained at the surface. Also in Chapter 5, the optical properties of CdCl2 treated CdTe and CdS were presented, and comparisons made with the optical properties of the as-deposited films. The changes that occur in the optical properties of CdTe and CdS upon CdCl2 treatment are significant and demonstrate the necessity of expressing these optical properties in terms of photon-energy independent parameters that describe the critical point features. These parameters in turn can be expressed in terms of the physical properties such as 180

mean free path or grain size and stress.

With such a database, it then becomes possible

to use the physical properties as free parameters in the optical analysis of CdCl2-treated solar cells. This more advanced approach will be undertaken in future work.

In the research effort described in Chapter 6, the database consisting of optical properties of the TEC-15 and semiconductor components of the CdTe solar cell has been applied to analyze the CdS/CdTe solar cell structure obtained after CdCl2 post-deposition treatment. The measurements of the solar cell structure were performed

non-destructively from the glass superstrate side using a 60 prism contacted to the glass superstrate with index matching fluid. As described earlier in this summary, the

metrological capability developed here is the most significant accomplishment of this thesis research due to its potential application for on-line monitoring and off-line mapping of complete modules. Also in Chapter 6, the application of ex-situ spectroscopic ellipsometry was described for analyzing the structure of the thin film CdTe solar cell destructively using a succession of Br2+methanol etching treatments. In this way, the optical properties of the

CdTe component of the cell could be determined as a function of depth from the surface and proximity to the CdS/CdTe interface. Using this method of depth profiling, a better

understanding of the overall film structure could be obtained in comparison with the non-destructive method. In addition to providing a depth profiling capability, the

destructive method has also been useful in corroborating the structure measured non-destructively through the glass superstrate. 181

In Chapters 7 and 8, the application of ex-situ spectroscopic ellipsometry to more advanced problems in the development of CdTe-based solar cell materials and devices was described. First, in the research described in Chapter 7, ex-situ SE has provided the thicknesses and structural properties of CdTe solar cells in the substrate configuration in which case the CdTe is deposited directly on opaque Mo metal. Although ex-situ SE in the

substrate configuration has the advantage that there is no overlying glass to limit the spectral range that reaches the semiconductors, the basic problem in this configuration is the surface roughness on the top-most transparent conductor, or CdS layer in the full or partial device configuration, respectively. There is less motivation at this time to

address these issues since all current manufacturing processes for CdTe solar cells exploit the superstrate configuration. Second, in the research described in Chapter 8, ex-situ SE has been applied to study the CdTe based ternary alloys Cd1-xMnxTe, Cd1-xMgxTe, and Cd1-xHgxTe, which are potential absorber layer components of sputtered II-VI tandem solar cells. In this study

it was shown that ex-situ SE could provide the critical point band gaps and broadening parameters from which the success of alloying could be assessed. By repeating such

measurements after the CdCl2 treatments, the ability of such treatments to generate the desired increase in grain size while maintaining the desired alloy composition and band gap could also be assessed. As a result, it was shown that ex-situ SE could be used in

182

conjunction with absorber materials fabrication for the development of sputtering and post-deposition processes to be adopted in device structures.

9.2

Future directions The most pressing goal of future research is to identify a robust optical model that

can be used for all CdTe based solar cells such that small changes in materials properties such as CdS and CdTe layer thicknesses, void fractions, mean free paths or grain sizes, strain, and uniformity can be determined non-invasively in the actual solar cell configuration. Possible modifications of the TCO layers of the superstrate by CdS over-deposition is also of interest. sensitivity to changes is a key goal. Although accuracy is not necessarily needed, If the optical model can be optimized, then it may

be possible to achieve accuracy and sensitivity simultaneously. Along the way, it will be helpful to correlate spectroscopic ellipsometry (SE) results with other methods such as cross-sectional transmission electron microscopy (XTEM) and secondary ion mass spectrometry (SIMS) in order to better understand the nature of the interactions at the CdS/CdTe and SnO2:F/CdS interfaces in the solar cells. In particular, it is important to

improve the SnO2:F/CdS interface model and understand how the SnO2:F may be modified by CdS over-deposition and post-deposition treatments. In this section, more

detailed suggestions for future studies to continue this thesis research will be reviewed in order of the relevant chapter.

183

Additional improvement in the analysis of TCO-coated glass superstrates, an extension of the TEC glass studies of Chapter 3, is an important direction for future research. For the complete TCO stack, the simulated spectra are not in close agreement The largest

with experimental data over two regions of the photon energy range.

deviations occur at the lowest energies (< 1.0 eV) where the Drude behavior dominates. Four different complexities may be evaluated in greater detail in the future so as to improve the fitting in this region: (i) additional layers in the optical model, such as interface roughness between pairs of bulk layers; (ii) additional terms in the analytical model for the top-most SnO2:F, which is the most strongly absorbing layer; (iii) non-uniformity over the area of the beam due to macroscopic scale roughness; and (iv) non-uniformity with depth due, for example, to a void volume fraction or free carrier concentration gradient. Although some of these approaches have been attempted Also in the region near

individually, they have not been evaluated in combination.

4.50-4.75 eV, where a transition from SnO2:F semi-transparency to opacity is observed, improved modeling results will require a closer match between the regimes where an analytical function is assumed for the dielectric function and where exact inversion is applied. This may require (i) an improved analytical model for the absorption onset

and/or (ii) more advanced inversion methods that incorporate not only the surface roughness thickness, but also the bulk layer thickness. The focus in this thesis has been on the development of an optical database for TEC-15, the most common coated superstrate used for CdTe solar cells. 184 Other types of

coated TEC glass deserve similar attention, such as TEC-7 and TEC-8, as well as coated glass from other manufacturers. TEC-7 and TEC-8 may be used for solar cells in which light scattering or "haze" is desirable, e.g., cells with thin (< 1 m) CdTe layers or with thin film silicon absorber layers. Results reported in Chapter 3 suggest that the optical

properties of the top-most SnO2:F of TEC-7 and TEC-8, differ from those of TEC-15, and these TEC glass types should be reanalyzed on the basis of this assumption. Of recent

interest are the high resistivity transparent top layers typically undoped or weakly doped SnO2, called "HRT" or "buffer" layers, which are incorporated as a fourth layer of experimental TEC glass stacks. The ultimate challenge is to characterize the optical properties of these layers in the full multilayer configuration consisting of glass/SnO2/SiO2/SnO2:F/HRT. In summary, future research must involve standardizing

the analysis procedure for TEC-15 so that it is applicable for other TEC glasses. Furthermore, standardized procedures are also needed for the analysis of the four-layer stacks, applied to cases in which samples of the HRT layer on simpler substrates are unavailable. In Chapter 4, step-wise Br2+methanol etching was evaluated for depth-profiling of CdCl2 treated and untreated CdTe thin film materials and solar cells while retaining a smooth surface for high quality optical measurements throughout the process. In this

chapter, it was shown how a residual amorphous tellurium (a-Te) layer ~13-14 in effective thickness could be detected and characterized under certain circumstances. The presence of this layer was neglected in the depth-profiling studies of CdTe thin film 185

materials in Chapter 5 and solar cells in Chapter 6. This simplification was based on modeling performed for very thick CdTe layers, namely that the impact of the a-Te layer on the deduced film structure is minimal. Further work needs to be done, however, in For

order to evaluate the validity of this simplification under all circumstances.

example, when the surface roughness region of a CdTe solar cell is completely etched away, the void fraction in the CdTe reaches a sharp minimum. Future work must be

performed to determine if this minimum continues to be observed when a-Te is included in the optical model, or if it is an artifact of neglecting the a-Te. In addition, the effect

on critical point analyses that results from incorporating a-Te in the optical model must be evaluated. A more detailed analysis involving analytical removal of a known

thickness of a-Te may provide a better understanding of the CdTe solar cell depth profiles in the mean free path or grain size and film strain. Although very good consistency has been observed in the depth profiles for the CdTe material in Chapter 5, the depth profiles for the CdTe solar cells in Chapter 6, in particular the critical point energies, were not easily interpretable, possibly as a result of simultaneous variations in film strain and sulfur in-diffusion. Very accurate critical point analyses will be needed in the future to

separate out these effects. In Chapter 5, clear differences between the optical properties of CdCl2 treated and untreated CdTe have been characterized and understood in terms of differences in strain, which shifts the critical point energies, and differences in defect density or grain size, which changes the broadening parameters. For CdS, however, the dielectric function of 186

a thin film as-deposited on a fused silica prism and measured through the prism differs considerably from those of thin films as-deposited on crystalline Si substrates and measured from the film side at a thickness of 500 . The motivation for such a study

was to characterize the change in dielectric function of CdS upon CdCl2 treatment using a configuration that corresponds more closely to the actual device, i.e., an underlying oxide and an overlying CdTe layer such that the free surface of the CdS is not exposed during the treatment. In the prism deposition experiment described in Chapter 6, the origin of

the differences in the as-deposited materials must be studied in greater detail in the future through additional experimentation. The low amplitude of the dielectric function in the Even the CdCl2 treatment does not restore

high energy range is of particular interest.

this amplitude to the level observed for CdS deposited on crystalline Si and measured from the film side. Future experiments may determine if this effect is (i) due to extrinsic

differences in the deposition process, e.g., higher interface contamination levels or lower substrate temperature associated with deposition on the prism, (ii) specific to the interface structure of CdS on fused SiO2, or (iii) intrinsic to the CdS interface in general which becomes evident using light from the substrate side with a very short penetration depth (photon energies > 4 eV). The future directions designed to extend studies of the step-wise etching for materials and solar cells decribed in Chapters 5 and 6, respectively, must focus on the role of temperature and time in the Ar annealing and CdCl2 treatment processes. For the

thinner CdTe materials on crystalline substrates, one may be able to establish the nature 187

of the grain growth processes.

For example, in the case of annealing in Ar gas, grain

growth appears to start from the substrate interface with pinned grain boundaries at the surface, whereas for CdCl2 treatment, the mechanism is clearly different with both near-surface and sub-surface grain growth occurring. In the case of the solar cell

structures, by exploring the kinetics versus temperature and time one may be able to separate out effects of grain growth in CdTe from those of CdS in-diffusion. In the research described Chapter 7, a novel approach for real time spectroscopic ellipsometry (RTSE) analysis has been applied to a CdTe deposition in the substrate configuration on Mo. In this analysis, which involves a synthesis of exact inversion and

least squares regression analysis methods, excellent fits to the data have been obtained with a low mean square error. In spite of these excellent fits, the resulting inverted

dielectric functions show artifacts indicating that improvements in the multilayer model for the substrate/film are required. These improvements may include (i) incorporation

of thickness non-uniformity over the cross-section of the optical beam or (ii) application of a multilayer or graded model to describe the CdTe/Mo interface or even an alternative effective medium theory. Because of the uncertainty involved in modeling rough

interfaces between the CdTe and its substrate, a case in point being the CdTe/Mo interface, subsequent studies to extract high accuracy dielectric functions of the CdTe have used the smoothest possible substrates -- single crystal silicon wafers. In the future,

if complete solar cells are to be studied successfully by real time SE, such issues involving rough interfaces must addressed comprehensively. 188

As described in the inroductory pararaph of this section, the key studies in Chapters 6 and 7 on ex situ SE of CdTe solar cells in the superstrate and substrate configurations represent works in progress, and significant improvements are to be expected through additional future studies. Promising future directions will be outlined in the following paragraphs. This discussion provides a roadmap that future research should follow, It is also

continuing from the foundation established through this initial thesis research.

recommended, because of the complexity of the models being developed, that a step-by-step procedure be undertaken as described in Chapters 6 and 7 in which case the number of free parameters of the model is increased successively. With this approach,

the success or failure of the suggestions for improvement made below can be quantitatively evaluated.

Tin side characteristics of the glass superstrate Analysis of through-the-glass spectroscopic ellipsometry on superstrate CdTe solar cells may benefit from a detailed analysis of the reflection from the Sn side of the glass, i.e., the side through which the light enters. The modeling of the bare soda lime glass as

described in Chapter 3 was performed using uncoated glass from the side opposite to the Sn side. The focus of an improved analysis will be on characterization of the optical

properties of the Sn side using the dielectric function of the opposite side from Chapter 3 as the underlying base material. One or two layers may be required to characterize the

residual Sn clusters on the glass surface as well as atomic Sn diffused into the glass. 189

The Sn side reflection must be taken into account carefully when considering the polarization changes that occur when the incident and specularly reflected light beams, the latter from the glass/film interface, crosses the Sn side interface. In addition to the

more detailed analysis of the Sn side of the glass for through-the-glass SE, it will also be important to characterize the strain in the glass. The effect of strain in the superstrate

glass is similar to that of strained windows in real time ellipsometry, and the successful correction procedures are expected to consist of zone averaged measurements as well as an offset correction in the ellipsometric angle . SnO2:F/CdS interface The surface roughness on the TEC-15 SnO2:F is up to ~300 thick, and when high resistivity transparent layers are added to the top of the TEC glass, the roughness can increase even further. This surface roughness is likely to appear as interface roughness As the superstrate of the CdTe

when the CdS is deposited on the superstrate surface.

solar cell becomes rougher, it becomes more difficult to determine all the characteristics of the solar cell because one must use thicker effective medium layers at the rough interfaces, and effective medium theories generally involve considerable uncertainty. In

the analysis of the superstrate solar cell, however, when one attempts to incorporate a SnO2:F/CdS effective medium mixture as an interface roughness layer, the thickness of this layer expands to the entire thickness of the SnO2:F, and the CdS volume fraction decreases to relatively small values. The interpretation of this observation is that the

dominant effect of the interaction between the SnO2:F and CdS is not interface roughness, 190

but rather modification of the SnO2:F layer either in the CdS deposition process or in the CdCl2 treatment. Future experiments for modeling improvement include characterizing

TEC-15 glass not only before solar cell deposition, but also after all cell processing, in the latter case after removing both the CdTe and CdS layers by etching. In such

experiments, one may be able to identify the optical characteristics of the SnO2:F layer that change upon cell processing, e.g., free carrier concentration, optical absorption onset, and/or void fraction, as well as the key processing parameters that lead to the change in optical properties. Once this information is available, then it may be possible to include

both interface roughness and SnO2:F modification in the ex situ SE modeling of the solar cell. Optical properties of CdS and CdTe The poorer fits to the ex situ ellipsometric spectra for the superstrate and substrate solar cells in the neighborhood of the CdTe and CdS fundamental band gaps and high energy critical points may be attributed to mean free paths, grain sizes, or strain levels in the solar cell layers that may be different than those in the layers used to extract the reference dielectric functions. differences. Layer interdiffusion may also contribute to the

As a result, improvements in fitting can be expected if such effects can be For example, for the superstrate solar cell of Chapter 6,

incorporated in the modeling.

the fringe pattern in just below the band gap is more pronounced in the data than in the model, an indication of a longer mean free path or larger grain size in the solar cell than in the CdTe material used for reference data. 191 Furthermore, for the substrate solar cell

analysis of Chapter 7, the CdS layer band gap is noticeably lower and the CdTe band gap is higher in the experimental data than in the model, possibly indicating that the stress in the CdS is lower and that in the CdTe is higher than in the reference materials. These simple observations made on the basis of (, ) comparisons could be made quantitative through a parameterization of the CdS and CdTe reference dielectric functions explicitly in terms of mean free path, stress, and alloying generated by inter-diffusion. CdS/CdTe interface thickness The thickness of the CdS/CdTe interface layer for both superstrate and substrate solar cells has been observed to lie in the range of 800-1400 . In the case of the superstrate

solar cells, this thickness is significantly greater than the expected interface roughness layer if the thin CdS layer were to conformally cover the SnO2:F of the TEC-15 without generation of additional roughness. As an alternative approach to using a single layer

model for the CdS/CdTe, a three layer model may be implemented in future research. The layers at the interfaces to the bulk CdS and CdTe layers would be CdS-rich and CdTe-rich layers, respectively, representing the interdifusion regions, and the intervening layer would represent the interface roughness. It would be reasonable to fix the

composition of the latter at ~0.5/0.5 CdS/CdTe for stability in the modeling when using three interface layers. Two different approaches could be used for modeling the optical functions of the two interface layers in the three layer model. The first method is the simplest, involving the

use of effective medium theories that incorporate small volume fractions of CdTe in CdS 192

and CdS in CdTe.

This approach may be applicable if interdiffusion occurs through the

grain boundaries, and thin regions at the boundary regions then assume the composition of the adjoining layer. Alternatively, ternary alloys of CdS1-x Tex with a small Te content

in CdS, and CdTe1-xSx with a small S content in CdTe could be assumed based on a model of uniform bulk interdiffusion. .For this latter approach, the dielectric functions of metastable ternary alloys are available; however. future efforts must focus on determining the dielectric functions of the stable alloy phases that form at the elevated temperatures of solar cell processing. CdTe properties and roughness thickness For future improvement of the ex situ analysis of both superstrate and substrate CdTe solar cells, the ability to incorporate void profiles of various functional forms must be included in the modeling. As detailed in Chapters 4-6, real time SE measurements have

shown clearly that complicated void profiles can exist in the as-deposited CdTe films and solar cells, and that these profiles are suppressed in the CdCl2 treatment processes. The

results of Chapter 6 do suggest small deviations in density for the CdCl2 treated CdTe, however, which may lead to significant effects in ex situ modeling when accumulated throughout the thickness of 2-3 m films. Also for the superstrate solar cell analyzed through the glass in Chapter 6, the surface roughness on the CdTe at the back of the solar plays an important role due to its effect on the back-reflected light beam. In fact, the

CdTe roughness parameters are the fifth and sixth most important ones in the 12-parameter model. Improvements may be possible in this case through the use of 193

multiple layers to describe the roughness, or even a graded layer.

It is also of interest to

test effective medium approximations other than that of Bruggeman for comparisons of the fitting quality. The p+ doped back contact For the CdTe solar cell in the superstrate configuration studied by ex situ SE analysis (Chapter 6), the p+ back contact treatment consisting of in-diffusion of a 30 layer of Cu has not been applied. It is of interest to explore the optical properties of this back contact material to determine if changes can be detected in the mean free path as derived from the widths of the critical points. Such an experimentation is best performed after CdCl2 treatment followed by a Br2+methanol etch that leads to a smooth and well-characterized surface, from which it is easiest to detect changes upon Cu in-diffusion. For the CdTe solar cell in the substrate configuration, as described in Chapter 7, the p+ back contact ZnTe:Cu has been studied in detail. This thin film material shows clear In

evidence of heavy doping in the form of a significantly broadened absorption onset.

fact, if this material is to be used as a transparent back contact, improvements in optical properties will be needed since a significant absorption tail exists even below 2 eV. Reduction in low energy absorption may be possible through a reduction in the doping level. Finally, analysis of the p+ back contacts used in superstrate and substrate solar

cells may benefit from infrared spectroscopic ellipsometry which may be able to detect the free carrier absorption in the contact regions or in discrete heavily doped layers. 194

A final area of research that deserves additional future study follows from the alloy research of Chapter 8. In general for future progress in this area, a closer correlation

between the ex situ SE measurements of the alloys before and after CdCl2 treatment and the device measurements would be helpful in order to establish the relationships between fundamental materials properties and device performance. Both real time SE

measurements and Br2+methanol etching experiments would also be helpful to establish the role of the CdCl2 treatment in modifying the structure of the film throughout the depth. Such experiments may help to guide future improvements in the post-depositon Finally, solar cell depositions using individual binary targets would

treatment processes.

enable continuous compositional ranges to be obtained in a single deposition across the superstrate surface, and such materials and cells can then be characterized by mapping SE in terms of their band gaps. This approach would enable expeditious study and

subsequent optimization of alloy composition not possible with discrete ternary targets.

195

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206

Appendix A Dielectric functions A.1


mn

Dielectric function of uncoated soda lime glass


k 1.65E-05 1.77E-05 1.91E-05 2.06E-05 2.24E-05 2.43E-05 2.64E-05 2.87E-05 3.12E-05 3.39E-05 3.68E-05 3.99E-05 4.32E-05 4.67E-05 5.03E-05 5.42E-05 5.82E-05 6.23E-05 6.66E-05 7.09E-05 7.53E-05 7.98E-05 8.43E-05 8.88E-05 9.33E-05 9.77E-05 0.00010202 0.00010622 0.00011026 0.00011413 0.0001178 0.00012124 0.00012444 0.00012737 0.00013002 0.00013237 0.00013442 0.00013617 0.0001376 0.00013873 254.04 255.63 257.22 258.8 260.39 261.98 263.57 265.16 266.74 268.33 269.92 271.51 273.1 274.69 276.28 277.87 279.46 281.05 282.64 284.23 285.82 287.41 289 290.59 292.18 293.77 295.36 296.95 298.54 300.13 301.72 303.31 304.9 306.49 308.08 309.68 311.27 312.86 314.45 316.04 317.63 1.5725 1.5715 1.5704 1.5694 1.5684 1.5674 1.5664 1.5655 1.5646 1.5637 1.5628 1.5619 1.5611 1.5603 1.5595 1.5587 1.5579 1.5571 1.5564 1.5556 1.5549 1.5542 1.5535 1.5529 1.5522 1.5515 1.5509 1.5503 1.5497 1.5491 1.5485 1.5479 1.5473 1.5468 1.5462 1.5457 1.5451 1.5446 1.5441 1.5436 1.5431 0.00013957 0.00014012 0.00014042 0.00014049 0.0001404 0.00014013 0.00013962 0.00013884 0.00013778 0.00013641 0.00013473 0.00013275 0.00013045 0.00012785 0.00012497 0.0001218 0.00011837 0.0001147 0.00011081 0.00010673 0.00010247 9.81E-05 9.36E-05 8.90E-05 8.43E-05 7.97E-05 7.50E-05 7.04E-05 6.58E-05 6.14E-05 5.70E-05 5.27E-05 4.86E-05 4.47E-05 4.10E-05 3.74E-05 3.40E-05 3.08E-05 2.78E-05 2.50E-05 2.25E-05 319.22 320.81 322.41 324 325.59 327.18 328.77 330.36 331.95 333.55 335.14 336.73 338.32 339.91 341.5 343.1 344.69 346.28 347.87 349.46 351.05 352.64 354.24 355.83 357.42 359.01 360.6 362.19 363.78 365.38 366.97 368.56 370.15 371.74 373.33 374.92 376.51 378.1 379.69 381.29 382.88 1.5426 1.5422 1.5417 1.5412 1.5408 1.5403 1.5399 1.5395 1.539 1.5386 1.5382 1.5378 1.5374 1.537 1.5366 1.5362 1.5359 1.5355 1.5351 1.5348 1.5344 1.5341 1.5337 1.5334 1.5331 1.5328 1.5324 1.5321 1.5318 1.5315 1.5312 1.5309 1.5306 1.5303 1.53 1.5297 1.5295 1.5292 1.5289 1.5286 1.5284 2.01E-05 1.79E-05 1.59E-05 1.41E-05 1.24E-05 1.10E-05 9.62E-06 8.43E-06 7.37E-06 6.43E-06 5.61E-06 4.88E-06 4.25E-06 3.70E-06 3.23E-06 2.81E-06 2.46E-06 2.16E-06 1.90E-06 1.68E-06 1.50E-06 1.34E-06 1.21E-06 1.09E-06 9.99E-07 9.20E-07 8.53E-07 7.97E-07 7.49E-07 7.08E-07 6.74E-07 6.44E-07 6.18E-07 5.96E-07 5.76E-07 5.59E-07 5.43E-07 5.28E-07 5.15E-07 5.03E-07 4.91E-07

190.76 192.33 193.91 195.49 197.06 198.64 200.22 201.8 203.37 204.95 206.53 208.11 209.69 211.27 212.85 214.43 216.01 217.59 219.18 220.76 222.34 223.92 225.51 227.09 228.67 230.26 231.84 233.42 235.01 236.59 238.18 239.76 241.35 242.94 244.52 246.11 247.69 249.28 250.87 252.45

1.649 1.6458 1.6428 1.6398 1.6369 1.6341 1.6313 1.6287 1.6261 1.6236 1.6212 1.6189 1.6166 1.6144 1.6123 1.6102 1.6081 1.6062 1.6042 1.6024 1.6006 1.5988 1.5971 1.5954 1.5938 1.5922 1.5906 1.5891 1.5877 1.5862 1.5848 1.5835 1.5821 1.5808 1.5796 1.5783 1.5771 1.5759 1.5748 1.5736

207

384.47 386.06 387.65 389.24 390.83 392.42 394.01 395.6 397.19 398.78 400.37 401.96 403.55 405.14 406.73 408.32 409.91 411.5 413.09 414.68 416.27 417.86 419.45 421.04 422.63 424.22 425.81 427.4 428.99 430.57 432.16 433.75 435.34 436.93 438.52 440.11 441.7 443.28 444.87 446.46 448.05 449.64 451.22 452.81 454.4

1.5281 1.5279 1.5276 1.5274 1.5271 1.5269 1.5266 1.5264 1.5262 1.5259 1.5257 1.5255 1.5253 1.525 1.5248 1.5246 1.5244 1.5242 1.524 1.5238 1.5236 1.5234 1.5232 1.523 1.5228 1.5226 1.5224 1.5222 1.522 1.5219 1.5217 1.5215 1.5213 1.5212 1.521 1.5208 1.5206 1.5205 1.5203 1.5202 1.52 1.5198 1.5197 1.5195 1.5194

4.81E-07 4.70E-07 4.61E-07 4.51E-07 4.42E-07 4.34E-07 4.26E-07 4.18E-07 4.10E-07 4.02E-07 3.95E-07 3.88E-07 3.81E-07 3.74E-07 3.68E-07 3.61E-07 3.55E-07 3.49E-07 3.43E-07 3.37E-07 3.32E-07 3.27E-07 3.21E-07 3.16E-07 3.11E-07 3.07E-07 3.02E-07 2.98E-07 2.93E-07 2.89E-07 2.85E-07 2.81E-07 2.77E-07 2.74E-07 2.70E-07 2.67E-07 2.64E-07 2.60E-07 2.57E-07 2.54E-07 2.52E-07 2.49E-07 2.46E-07 2.44E-07 2.42E-07

455.99 457.58 459.16 460.75 462.34 463.93 465.51 467.1 468.69 470.27 471.86 473.45 475.04 476.62 478.21 479.8 481.38 482.97 484.56 486.14 487.73 489.31 490.9 492.49 494.07 495.66 497.24 498.83 500.42 502 503.59 505.17 506.76 508.34 509.93 511.51 513.1 514.68 516.27 517.85 519.44 521.02 522.61 524.19 525.78

1.5192 1.5191 1.5189 1.5188 1.5186 1.5185 1.5183 1.5182 1.5181 1.5179 1.5178 1.5176 1.5175 1.5174 1.5172 1.5171 1.517 1.5169 1.5167 1.5166 1.5165 1.5164 1.5162 1.5161 1.516 1.5159 1.5158 1.5156 1.5155 1.5154 1.5153 1.5152 1.5151 1.515 1.5149 1.5147 1.5146 1.5145 1.5144 1.5143 1.5142 1.5141 1.514 1.5139 1.5138

2.40E-07 2.37E-07 2.35E-07 2.34E-07 2.32E-07 2.30E-07 2.29E-07 2.27E-07 2.26E-07 2.25E-07 2.24E-07 2.22E-07 2.22E-07 2.21E-07 2.20E-07 2.19E-07 2.19E-07 2.18E-07 2.18E-07 2.18E-07 2.18E-07 2.18E-07 2.18E-07 2.18E-07 2.18E-07 2.19E-07 2.19E-07 2.20E-07 2.20E-07 2.21E-07 2.22E-07 2.23E-07 2.24E-07 2.25E-07 2.27E-07 2.28E-07 2.30E-07 2.31E-07 2.33E-07 2.35E-07 2.36E-07 2.38E-07 2.41E-07 2.43E-07 2.45E-07

527.36 528.95 530.53 532.12 533.7 535.28 536.87 538.45 540.04 541.62 543.21 544.79 546.37 547.96 549.54 551.12 552.71 554.29 555.87 557.46 559.04 560.63 562.21 563.79 565.37 566.96 568.54 570.12 571.71 573.29 574.87 576.46 578.04 579.62 581.2 582.79 584.37 585.95 587.53 589.12 590.7 592.28 593.86 595.45 597.03

1.5137 1.5136 1.5135 1.5134 1.5133 1.5132 1.5131 1.513 1.5129 1.5129 1.5128 1.5127 1.5126 1.5125 1.5124 1.5123 1.5122 1.5121 1.5121 1.512 1.5119 1.5118 1.5117 1.5116 1.5116 1.5115 1.5114 1.5113 1.5112 1.5112 1.5111 1.511 1.5109 1.5108 1.5108 1.5107 1.5106 1.5105 1.5105 1.5104 1.5103 1.5103 1.5102 1.5101 1.51

2.47E-07 2.50E-07 2.53E-07 2.55E-07 2.58E-07 2.61E-07 2.64E-07 2.67E-07 2.71E-07 2.74E-07 2.77E-07 2.81E-07 2.85E-07 2.89E-07 2.92E-07 2.97E-07 3.01E-07 3.05E-07 3.09E-07 3.14E-07 3.19E-07 3.23E-07 3.28E-07 3.33E-07 3.38E-07 3.44E-07 3.49E-07 3.54E-07 3.60E-07 3.66E-07 3.72E-07 3.78E-07 3.84E-07 3.90E-07 3.97E-07 4.03E-07 4.10E-07 4.17E-07 4.23E-07 4.31E-07 4.38E-07 4.45E-07 4.52E-07 4.60E-07 4.68E-07

208

598.61 600.19 601.78 603.36 604.94 606.52 608.1 609.69 611.27 612.85 614.43 616.01 617.6 619.18 620.76 622.34 623.92 625.5 627.09 628.67 630.25 631.83 633.41 634.99 636.58 638.16 639.74 641.32 642.9 644.48 646.06 647.65 649.23 650.81 652.39 653.97 655.55 657.13 658.71 660.29 661.88 663.46 665.04 666.62 668.2

1.51 1.5099 1.5098 1.5098 1.5097 1.5096 1.5096 1.5095 1.5094 1.5094 1.5093 1.5092 1.5092 1.5091 1.509 1.509 1.5089 1.5088 1.5088 1.5087 1.5087 1.5086 1.5085 1.5085 1.5084 1.5084 1.5083 1.5082 1.5082 1.5081 1.5081 1.508 1.508 1.5079 1.5078 1.5078 1.5077 1.5077 1.5076 1.5076 1.5075 1.5075 1.5074 1.5074 1.5073

4.76E-07 4.84E-07 4.92E-07 5.00E-07 5.09E-07 5.17E-07 5.26E-07 5.35E-07 5.44E-07 5.53E-07 5.62E-07 5.72E-07 5.81E-07 5.91E-07 6.01E-07 6.11E-07 6.21E-07 6.32E-07 6.42E-07 6.53E-07 6.64E-07 6.74E-07 6.86E-07 6.97E-07 7.08E-07 7.20E-07 7.31E-07 7.43E-07 7.55E-07 7.67E-07 7.80E-07 7.92E-07 8.05E-07 8.17E-07 8.30E-07 8.43E-07 8.56E-07 8.70E-07 8.83E-07 8.97E-07 9.11E-07 9.25E-07 9.39E-07 9.53E-07 9.67E-07

669.78 671.36 672.94 674.52 676.1 677.68 679.26 680.85 682.43 684.01 685.59 687.17 688.75 690.33 691.91 693.49 695.07 696.65 698.23 699.81 701.39 702.97 704.55 706.13 707.71 709.29 710.87 712.45 714.03 715.61 717.19 718.77 720.35 721.93 723.51 725.09 726.67 728.25 729.83 731.41 732.99 734.57 736.15 737.73 739.31

1.5072 1.5072 1.5071 1.5071 1.507 1.507 1.5069 1.5069 1.5068 1.5068 1.5067 1.5067 1.5066 1.5066 1.5065 1.5065 1.5064 1.5064 1.5064 1.5063 1.5063 1.5062 1.5062 1.5061 1.5061 1.506 1.506 1.5059 1.5059 1.5058 1.5058 1.5058 1.5057 1.5057 1.5056 1.5056 1.5055 1.5055 1.5055 1.5054 1.5054 1.5053 1.5053 1.5052 1.5052

9.82E-07 9.96E-07 1.01E-06 1.03E-06 1.04E-06 1.06E-06 1.07E-06 1.09E-06 1.10E-06 1.12E-06 1.13E-06 1.15E-06 1.17E-06 1.18E-06 1.20E-06 1.22E-06 1.23E-06 1.25E-06 1.27E-06 1.28E-06 1.30E-06 1.32E-06 1.34E-06 1.35E-06 1.37E-06 1.39E-06 1.41E-06 1.43E-06 1.44E-06 1.46E-06 1.48E-06 1.50E-06 1.52E-06 1.54E-06 1.55E-06 1.57E-06 1.59E-06 1.61E-06 1.63E-06 1.65E-06 1.67E-06 1.69E-06 1.71E-06 1.73E-06 1.75E-06

740.89 742.47 744.05 745.63 747.21 748.78 750.36 751.94 753.52 755.1 756.68 758.26 759.84 761.41 762.99 764.57 766.15 767.73 769.31 770.88 772.46 774.04 775.62 777.2 778.77 780.35 781.93 783.5 785.08 786.66 788.24 789.81 791.39 792.97 794.54 796.12 797.7 799.27 800.85 802.42 804 805.58 807.15 808.73 810.3

1.5052 1.5051 1.5051 1.505 1.505 1.505 1.5049 1.5049 1.5048 1.5048 1.5048 1.5047 1.5047 1.5046 1.5046 1.5046 1.5045 1.5045 1.5045 1.5044 1.5044 1.5043 1.5043 1.5043 1.5042 1.5042 1.5042 1.5041 1.5041 1.5041 1.504 1.504 1.504 1.5039 1.5039 1.5038 1.5038 1.5038 1.5037 1.5037 1.5037 1.5036 1.5036 1.5036 1.5035

1.77E-06 1.79E-06 1.81E-06 1.83E-06 1.85E-06 1.87E-06 1.89E-06 1.91E-06 1.93E-06 1.95E-06 1.97E-06 1.99E-06 2.01E-06 2.03E-06 2.05E-06 2.07E-06 2.09E-06 2.12E-06 2.14E-06 2.16E-06 2.18E-06 2.20E-06 2.22E-06 2.24E-06 2.26E-06 2.28E-06 2.31E-06 2.33E-06 2.35E-06 2.37E-06 2.39E-06 2.41E-06 2.43E-06 2.45E-06 2.47E-06 2.50E-06 2.52E-06 2.54E-06 2.56E-06 2.58E-06 2.60E-06 2.62E-06 2.64E-06 2.66E-06 2.69E-06

209

811.88 813.45 815.03 816.6 818.18 819.75 821.33 822.9 824.47 826.05 827.62 829.19 830.77 832.34 833.91 835.49 837.06 838.63 840.2 841.77 843.35 844.92 846.49 848.06 849.63 851.2 852.77 854.34 855.91 857.48 859.05 860.62 862.19 863.76 865.32 866.89 868.46 870.03 871.59 873.16 874.73 876.29 877.86 879.43 880.99

1.5035 1.5035 1.5034 1.5034 1.5034 1.5033 1.5033 1.5033 1.5033 1.5032 1.5032 1.5032 1.5031 1.5031 1.5031 1.503 1.503 1.503 1.5029 1.5029 1.5029 1.5029 1.5028 1.5028 1.5028 1.5027 1.5027 1.5027 1.5026 1.5026 1.5026 1.5026 1.5025 1.5025 1.5025 1.5024 1.5024 1.5024 1.5024 1.5023 1.5023 1.5023 1.5022 1.5022 1.5022

2.71E-06 2.73E-06 2.75E-06 2.77E-06 2.79E-06 2.81E-06 2.83E-06 2.85E-06 2.87E-06 2.89E-06 2.91E-06 2.94E-06 2.96E-06 2.98E-06 3.00E-06 3.02E-06 3.04E-06 3.06E-06 3.08E-06 3.10E-06 3.12E-06 3.14E-06 3.16E-06 3.18E-06 3.20E-06 3.22E-06 3.24E-06 3.25E-06 3.27E-06 3.29E-06 3.31E-06 3.33E-06 3.35E-06 3.37E-06 3.39E-06 3.41E-06 3.43E-06 3.44E-06 3.46E-06 3.48E-06 3.50E-06 3.52E-06 3.53E-06 3.55E-06 3.57E-06

882.56 884.12 885.68 887.25 888.81 890.38 891.94 893.5 895.06 896.62 898.19 899.75 901.31 902.87 904.43 905.99 907.55 909.1 910.66 912.22 913.78 915.34 916.89 918.45 920 921.56 923.11 924.67 926.22 927.77 929.33 930.88 932.43 933.98 935.53 937.08 938.63 940.18 941.73 943.27 944.82 946.37 947.91 949.46 951

1.5022 1.5021 1.5021 1.5021 1.5021 1.502 1.502 1.502 1.502 1.5019 1.5019 1.5019 1.5019 1.5018 1.5018 1.5018 1.5017 1.5017 1.5017 1.5017 1.5016 1.5016 1.5016 1.5016 1.5015 1.5015 1.5015 1.5015 1.5015 1.5014 1.5014 1.5014 1.5014 1.5013 1.5013 1.5013 1.5013 1.5012 1.5012 1.5012 1.5012 1.5011 1.5011 1.5011 1.5011

3.59E-06 3.60E-06 3.62E-06 3.64E-06 3.66E-06 3.67E-06 3.69E-06 3.71E-06 3.72E-06 3.74E-06 3.76E-06 3.77E-06 3.79E-06 3.81E-06 3.82E-06 3.84E-06 3.85E-06 3.87E-06 3.88E-06 3.90E-06 3.91E-06 3.93E-06 3.94E-06 3.96E-06 3.97E-06 3.99E-06 4.00E-06 4.02E-06 4.03E-06 4.05E-06 4.06E-06 4.07E-06 4.09E-06 4.10E-06 4.11E-06 4.13E-06 4.14E-06 4.15E-06 4.17E-06 4.18E-06 4.19E-06 4.20E-06 4.22E-06 4.23E-06 4.24E-06

952.55 954.09 955.63 957.18 958.72 960.26 961.8 963.34 964.88 966.41 967.95 969.49 971.02 972.56 974.09 975.63 977.16 978.69 980.22 981.75 983.28 984.81 986.34 987.87 989.4 990.92 992.45 993.97 995.49 997.01 998.54 1000.1 1012.3 1015.8 1019.2 1022.6 1026.1 1029.5 1032.9 1036.3 1039.8 1043.2 1046.6 1050 1053.5

1.5011 1.501 1.501 1.501 1.501 1.5009 1.5009 1.5009 1.5009 1.5009 1.5008 1.5008 1.5008 1.5008 1.5007 1.5007 1.5007 1.5007 1.5007 1.5006 1.5006 1.5006 1.5006 1.5006 1.5005 1.5005 1.5005 1.5005 1.5005 1.5004 1.5004 1.5004 1.5002 1.5002 1.5001 1.5001 1.5001 1.5 1.5 1.4999 1.4999 1.4998 1.4998 1.4998 1.4997

4.25E-06 4.26E-06 4.28E-06 4.29E-06 4.30E-06 4.31E-06 4.32E-06 4.33E-06 4.34E-06 4.36E-06 4.37E-06 4.38E-06 4.39E-06 4.40E-06 4.41E-06 4.42E-06 4.43E-06 4.44E-06 4.45E-06 4.46E-06 4.47E-06 4.48E-06 4.49E-06 4.50E-06 4.51E-06 4.51E-06 4.52E-06 4.53E-06 4.54E-06 4.55E-06 4.56E-06 4.57E-06 4.63E-06 4.65E-06 4.67E-06 4.68E-06 4.70E-06 4.72E-06 4.73E-06 4.75E-06 4.76E-06 4.78E-06 4.79E-06 4.81E-06 4.82E-06

210

1056.9 1060.3 1063.8 1067.2 1070.6 1074 1077.5 1080.9 1084.3 1087.7 1091.2 1094.6 1098 1101.5 1104.9 1108.3 1111.7 1115.2 1118.6 1122 1125.4 1128.9 1132.3 1135.7 1139.2 1142.6 1146 1149.4 1152.9 1156.3 1159.7 1163.2 1166.6 1170 1173.4 1176.9 1180.3 1183.7 1187.2 1190.6 1194 1197.4 1200.9 1204.3 1207.7

1.4997 1.4996 1.4996 1.4996 1.4995 1.4995 1.4994 1.4994 1.4994 1.4993 1.4993 1.4993 1.4992 1.4992 1.4991 1.4991 1.4991 1.499 1.499 1.499 1.4989 1.4989 1.4989 1.4988 1.4988 1.4988 1.4987 1.4987 1.4987 1.4986 1.4986 1.4986 1.4985 1.4985 1.4985 1.4984 1.4984 1.4984 1.4983 1.4983 1.4983 1.4982 1.4982 1.4982 1.4981

4.84E-06 4.85E-06 4.86E-06 4.88E-06 4.89E-06 4.90E-06 4.91E-06 4.93E-06 4.94E-06 4.95E-06 4.97E-06 4.98E-06 4.99E-06 5.00E-06 5.02E-06 5.03E-06 5.04E-06 5.06E-06 5.07E-06 5.08E-06 5.10E-06 5.11E-06 5.12E-06 5.14E-06 5.15E-06 5.16E-06 5.17E-06 5.19E-06 5.20E-06 5.21E-06 5.22E-06 5.24E-06 5.25E-06 5.26E-06 5.27E-06 5.28E-06 5.29E-06 5.30E-06 5.31E-06 5.32E-06 5.33E-06 5.34E-06 5.35E-06 5.36E-06 5.36E-06

1211.2 1214.6 1218 1221.5 1224.9 1228.3 1231.7 1235.2 1238.6 1242 1245.5 1248.9 1252.3 1255.8 1259.2 1262.6 1266.1 1269.5 1272.9 1276.4 1279.8 1283.2 1286.7 1290.1 1293.5 1297 1300.4 1303.8 1307.3 1310.7 1314.1 1317.6 1321 1324.4 1327.9 1331.3 1334.7 1338.2 1341.6 1345 1348.5 1351.9 1355.4 1358.8 1362.2

1.4981 1.4981 1.4981 1.498 1.498 1.498 1.4979 1.4979 1.4979 1.4978 1.4978 1.4978 1.4978 1.4977 1.4977 1.4977 1.4976 1.4976 1.4976 1.4976 1.4975 1.4975 1.4975 1.4975 1.4974 1.4974 1.4974 1.4973 1.4973 1.4973 1.4973 1.4972 1.4972 1.4972 1.4972 1.4971 1.4971 1.4971 1.4971 1.497 1.497 1.497 1.497 1.4969 1.4969

5.37E-06 5.38E-06 5.39E-06 5.39E-06 5.40E-06 5.40E-06 5.41E-06 5.41E-06 5.41E-06 5.41E-06 5.42E-06 5.42E-06 5.42E-06 5.42E-06 5.42E-06 5.42E-06 5.42E-06 5.41E-06 5.41E-06 5.41E-06 5.40E-06 5.40E-06 5.40E-06 5.39E-06 5.38E-06 5.38E-06 5.37E-06 5.36E-06 5.35E-06 5.34E-06 5.33E-06 5.32E-06 5.31E-06 5.30E-06 5.28E-06 5.27E-06 5.26E-06 5.24E-06 5.23E-06 5.21E-06 5.19E-06 5.18E-06 5.16E-06 5.14E-06 5.12E-06

1365.7 1369.1 1372.5 1376 1379.4 1382.9 1386.3 1389.7 1393.2 1396.6 1400 1403.5 1406.9 1410.4 1413.8 1417.2 1420.7 1424.1 1427.6 1431 1434.5 1437.9 1441.3 1444.8 1448.2 1451.7 1455.1 1458.6 1462 1465.4 1468.9 1472.3 1475.8 1479.2 1482.7 1486.1 1489.6 1493 1496.5 1499.9 1503.4 1506.8 1510.2 1513.7 1517.1

1.4969 1.4969 1.4969 1.4968 1.4968 1.4968 1.4968 1.4967 1.4967 1.4967 1.4967 1.4966 1.4966 1.4966 1.4966 1.4966 1.4965 1.4965 1.4965 1.4965 1.4964 1.4964 1.4964 1.4964 1.4964 1.4963 1.4963 1.4963 1.4963 1.4963 1.4962 1.4962 1.4962 1.4962 1.4961 1.4961 1.4961 1.4961 1.4961 1.496 1.496 1.496 1.496 1.496 1.4959

5.11E-06 5.09E-06 5.07E-06 5.05E-06 5.03E-06 5.01E-06 4.98E-06 4.96E-06 4.94E-06 4.92E-06 4.90E-06 4.87E-06 4.85E-06 4.83E-06 4.81E-06 4.78E-06 4.76E-06 4.73E-06 4.71E-06 4.69E-06 4.66E-06 4.64E-06 4.62E-06 4.59E-06 4.57E-06 4.54E-06 4.52E-06 4.50E-06 4.47E-06 4.45E-06 4.43E-06 4.40E-06 4.38E-06 4.36E-06 4.33E-06 4.31E-06 4.29E-06 4.27E-06 4.25E-06 4.23E-06 4.21E-06 4.19E-06 4.17E-06 4.15E-06 4.13E-06

211

1520.6 1524 1527.5 1530.9 1534.4 1537.8 1541.3 1544.7 1548.2 1551.7 1555.1 1558.6 1562 1565.5 1568.9 1572.4 1575.8 1579.3 1582.7 1586.2 1589.7 1593.1 1596.6 1600 1603.5 1606.9 1610.4 1613.9 1617.3 1620.8 1624.2 1627.7 1631.2 1634.6 1638.1 1641.5 1645 1648.5 1651.9 1655.4 1658.9 1662.3 1665.8

1.4959 1.4959 1.4959 1.4959 1.4959 1.4958 1.4958 1.4958 1.4958 1.4958 1.4957 1.4957 1.4957 1.4957 1.4957 1.4956 1.4956 1.4956 1.4956 1.4956 1.4956 1.4955 1.4955 1.4955 1.4955 1.4955 1.4955 1.4954 1.4954 1.4954 1.4954 1.4954 1.4953 1.4953 1.4953 1.4953 1.4953 1.4953 1.4952 1.4952 1.4952 1.4952 1.4952

4.11E-06 4.09E-06 4.07E-06 4.05E-06 4.04E-06 4.02E-06 4.00E-06 3.99E-06 3.97E-06 3.95E-06 3.94E-06 3.92E-06 3.91E-06 3.90E-06 3.88E-06 3.87E-06 3.86E-06 3.85E-06 3.83E-06 3.82E-06 3.81E-06 3.80E-06 3.79E-06 3.78E-06 3.77E-06 3.76E-06 3.75E-06 3.74E-06 3.73E-06 3.72E-06 3.71E-06 3.70E-06 3.69E-06 3.68E-06 3.67E-06 3.66E-06 3.65E-06 3.64E-06 3.63E-06 3.62E-06 3.60E-06 3.59E-06 3.58E-06

1669.3 1.4952

3.56E-06

212

A.2
eV

Dielectric function of SnO2


1 3.3297 3.3326 3.3362 3.3405 3.3456 3.3515 3.3581 3.3655 3.3738 3.3828 3.3927 3.4034 3.4149 3.4272 3.4404 3.4544 3.4691 3.4846 3.5009 3.5178 3.5355 3.5537 3.5725 3.5919 3.6116 3.6318 3.6522 3.6728 3.6935 3.7141 3.7347 3.7549 3.7748 3.7941 3.8127 3.8306 3.8475 2 1.1928 1.1992 1.2058 1.2127 1.2197 1.2269 1.2341 1.2414 1.2487 1.256 1.2632 1.2702 1.2771 1.2836 1.2899 1.2958 1.3012 1.3061 1.3105 1.3142 1.3173 1.3196 1.3211 1.3217 1.3214 1.3201 1.3178 1.3145 1.31 1.3045 1.2979 1.2902 1.2814 1.2716 1.2609 1.2494 1.2372 4.9743 4.9429 4.9118 4.8811 4.8508 4.8209 4.7913 4.7621 4.7332 4.7047 4.6765 4.6486 4.6211 4.5939 4.567 4.5405 4.5142 4.4882 4.4626 4.4372 4.4121 4.3873 4.3627 4.3384 4.3144 4.2907 4.2672 4.244 4.221 4.1983 4.1758 4.1536 4.1315 4.1098 4.0882 4.0669 4.0458 4.0249 3.8634 3.8783 3.8921 3.905 3.9169 3.9282 3.939 3.9496 3.9604 3.9717 3.9838 3.997 4.0117 4.0279 4.0457 4.065 4.0858 4.1077 4.1304 4.1536 4.1767 1.2246 1.2116 1.1987 1.1859 1.1736 1.1618 1.1509 1.141 1.1319 1.1238 1.1164 1.1096 1.1029 1.0961 1.0887 1.0802 1.0702 1.0584 1.0444 1.0279 1.0089 4.0042 3.9837 3.9635 3.9434 3.9235 3.9039 3.8844 3.8652 3.8461 3.8272 3.8085 3.79 3.7716 3.7534 3.7355 3.7176 3.7 3.6825 3.6652 3.648 3.631 3.6142 3.5975 3.5809 3.5646 3.5483 3.5322 3.5163 3.5005 3.4848 3.4693 3.4539 3.4387 3.4236 3.4086 3.3938 3.3791 3.3645 4.2701 0.47692 4.2587 0.45382 4.2467 0.43215 4.2343 0.41186 4.2217 0.39288 4.2089 0.37512 4.196 4.1704 0.35851 0.3284 4.1832 0.34297 4.1578 0.31474 4.1453 0.30191 4.133 4.109 0.28984 0.26775 4.1209 0.27847 4.0973 0.25761 4.0858 0.24802 4.0746 0.23894 4.0635 0.23033 4.0527 0.22216 4.042 0.2144 4.0316 0.20703 4.0214 0.20003 4.0113 0.19337 4.0014 0.18704 3.9917 0.18103 3.9822 0.17531 3.9728 0.16989 3.9636 0.16473 3.9546 0.15985 3.9458 0.15521 3.9371 0.15083 3.9285 0.14668 3.9202 0.14275 3.912 3.896 3.8807 0.13905 0.13228 0.1263 3.9039 0.13556 3.8883 0.12919

6.5004 6.4471 6.3947 6.3432 6.2924 6.2425 6.1933 6.1448 6.0972 6.0502 6.0039 5.9584 5.9135 5.8692 5.8257 5.7827 5.7404 5.6987 5.6575 5.617 5.577 5.5376 5.4987 5.4604 5.4226 5.3853 5.3485 5.3122 5.2764 5.241 5.2062 5.1717 5.1378 5.1042 5.0711 5.0384 5.0062

4.1992 0.98722 4.2207 0.96303 4.2407 0.93647 4.2589 0.90779 4.2749 0.87732 4.2885 0.84541 4.2996 0.81247 4.3079 4.3137 0.7789 0.7451

4.3168 0.71142 4.3174 0.67821 4.3158 0.64576 4.312 0.6143 4.3064 0.58403 4.2992 0.55508 4.2906 0.52755 4.2808 0.50149

213

3.35 3.3357 3.3215 3.3074 3.2934 3.2795 3.2658 3.2522 3.2386 3.2252 3.212 3.1988 3.1857 3.1727 3.1599 3.1471 3.1345 3.1219 3.1095 3.0971 3.0849 3.0727 3.0607 3.0487 3.0368 3.025 3.0134 3.0018 2.9902 2.9788 2.9675 2.9563 2.9451 2.934 2.923 2.9121 2.9013 2.8905 2.8799

3.8733 0.12359 3.8661 0.12106 3.859 3.8454 0.11871 0.1145 3.8521 0.11652 3.8389 0.11264 3.8325 0.11093 3.8263 0.10937 3.8204 0.10795 3.8147 0.10664 3.8093 0.10534 3.804 0.10406 3.7989 0.10279 3.7939 0.10154 3.7891 0.1003 3.7844 0.099079 3.7798 0.09787 3.7754 0.096675 3.771 0.095493 3.7667 0.094324 3.7626 0.093169 3.7585 0.092027 3.7545 0.090898 3.7506 0.089782 3.7468 0.088678 3.743 0.087586 3.7393 0.086507 3.7357 0.08544 3.7321 0.084385 3.7286 0.083341 3.7252 0.08231 3.7218 0.081289 3.7185 0.08028 3.7153 0.079283 3.7121 0.078296 3.7089 0.07732 3.7058 0.076355 3.7027 0.075401 3.6997 0.074457

2.8693 2.8588 2.8483 2.838 2.8277 2.8175 2.8074 2.7973 2.7873 2.7774 2.7676 2.7578 2.7481 2.7384 2.7289 2.7194 2.7099 2.7006 2.6913 2.682 2.6728 2.6637 2.6547 2.6457 2.6368 2.6279 2.6191 2.6103 2.6016 2.593 2.5844 2.5759 2.5675 2.559 2.5507 2.5424 2.5342 2.526 2.5178

3.6968 0.073523 3.6939 0.0726 3.691 0.071687 3.6881 0.070784 3.6853 0.069891 3.6826 0.069008 3.6799 0.068134 3.6772 0.06727 3.6745 0.066415 3.6719 0.06557 3.6694 0.064734 3.6668 0.063906 3.6643 0.063088 3.6618 0.062279 3.6594 0.061479 3.6569 0.060687 3.6546 0.059904 3.6522 0.059129 3.6499 0.058363 3.6476 0.057605 3.6453 0.056856 3.643 0.056114 3.6408 0.055381 3.6386 0.054655 3.6364 0.053937 3.6343 0.053227 3.6321 0.052525 3.63 0.05183 3.6279 0.051143 3.6259 0.050463 3.6238 0.049791 3.6218 0.049126 3.6198 0.048468 3.6178 0.047817 3.6159 0.047173 3.6139 0.046536 3.612 0.045906 3.6101 0.045283 3.6082 0.044667

2.5098 2.5017 2.4937 2.4858 2.4779 2.4701 2.4623 2.4546 2.4469 2.4393 2.4317 2.4242 2.4167 2.4092 2.4018 2.3945 2.3872 2.3799 2.3727 2.3655 2.3584 2.3513 2.3443 2.3373 2.3303 2.3234 2.3165 2.3097 2.3029 2.2961 2.2894 2.2827 2.2761 2.2695 2.263 2.2564 2.2499 2.2435 2.2371

3.6063 0.044057 3.6045 0.043454 3.6026 0.042858 3.6008 0.042268 3.599 0.041684 3.5972 0.041107 3.5955 0.040536 3.5937 0.039971 3.592 0.039412 3.5903 0.03886 3.5886 0.038313 3.5869 0.037773 3.5852 0.037238 3.5835 0.036709 3.5819 0.036186 3.5802 0.035669 3.5786 0.035157 3.577 0.034651 3.5754 0.034151 3.5738 0.033656 3.5722 0.033166 3.5707 0.032682 3.5691 0.032203 3.5676 0.03173 3.5661 0.031262 3.5646 0.030799 3.5631 0.030341 3.5616 0.029888 3.5601 0.02944 3.5586 0.028998 3.5572 0.02856 3.5557 0.028127 3.5543 0.027699 3.5529 0.027276 3.5515 0.026857 3.5501 0.026444 3.5487 0.026035 3.5473 0.025631 3.5459 0.025231

214

2.2307 2.2244 2.2181 2.2118 2.2056 2.1994 2.1932 2.1871 2.181 2.175 2.1689 2.163 2.157 2.1511 2.1452 2.1393 2.1335 2.1277 2.1219 2.1162 2.1105 2.1048 2.0992 2.0936 2.088 2.0825 2.077 2.0715 2.066 2.0606 2.0552 2.0498 2.0444 2.0391 2.0338 2.0286 2.0233 2.0181 2.0129

3.5445 0.024836 3.5432 0.024445 3.5418 0.024059 3.5405 0.023677 3.5392 0.0233 3.5379 0.022927 3.5365 0.022558 3.5352 0.022194 3.534 0.021834 3.5327 0.021478 3.5314 0.021126 3.5301 0.020779 3.5289 0.020435 3.5276 0.020096 3.5264 0.01976 3.5251 0.019429 3.5239 0.019101 3.5227 0.018778 3.5215 0.018458 3.5202 0.018142 3.519 0.01783 3.5179 0.017522 3.5167 0.017218 3.5155 0.016917 3.5143 0.01662 3.5132 0.016327 3.512 0.016037 3.5108 0.015751 3.5097 0.015468 3.5086 0.015189 3.5074 0.014914 3.5063 0.014642 3.5052 0.014373 3.5041 0.014108 3.503 0.013846 3.5019 0.013588 3.5008 0.013333 3.4997 0.013081 3.4986 0.012833

2.0078 2.0027 1.9976 1.9925 1.9874 1.9824 1.9774 1.9724 1.9675 1.9625 1.9577 1.9528 1.9479 1.9431 1.9383 1.9335 1.9288 1.924 1.9193 1.9146 1.91 1.9053 1.9007 1.8961 1.8915 1.887 1.8825 1.878 1.8735 1.869 1.8646 1.8601 1.8557 1.8514 1.847 1.8427 1.8383 1.834 1.8298

3.4975 0.012588 3.4964 0.012346 3.4954 0.012107 3.4943 0.011872 3.4933 0.01164 3.4922 0.01141 3.4912 0.011184 3.4901 0.010961 3.4891 0.010741 3.4881 0.010524 3.4871 0.010311 3.486 0.0101 3.485 0.0098917 3.484 0.0096867 3.483 0.0094847 3.482 0.0092855 3.481 0.0090893 3.4801 0.0088959 3.4791 0.0087053 3.4781 0.0085175 3.4771 0.0083325 3.4762 0.0081503 3.4752 0.0079709 3.4742 0.0077941 3.4733 0.0076201 3.4723 0.0074488 3.4714 0.0072801 3.4705 0.0071141 3.4695 0.0069507 3.4686 0.00679 3.4677 0.0066318 3.4667 0.0064762 3.4658 0.0063231 3.4649 0.0061726 3.464 0.0060246 3.4631 0.0058791 3.4622 0.005736 3.4613 0.0055955 3.4604 0.0054573

1.8255 1.8213 1.817 1.8128 1.8087 1.8045 1.8004 1.7962 1.7921 1.7881 1.784 1.7799 1.7759 1.7719 1.7679 1.7639 1.76 1.756 1.7521 1.7482 1.7443 1.7405 1.7366 1.7328 1.729 1.7252 1.7214 1.7176 1.7139 1.7101 1.7064 1.7027 1.699 1.6954 1.6917 1.6881 1.6844 1.6808 1.6772

3.4595 0.0053216 3.4586 0.0051883 3.4578 0.0050575 3.4569 0.0049289 3.456 0.0048027 3.4551 0.0046789 3.4543 0.0045574 3.4534 0.0044382 3.4526 0.0043213 3.4517 0.0042067 3.4508 0.0040943 3.45 0.0039842 3.4492 0.0038763 3.4483 0.0037706 3.4475 0.0036671 3.4467 0.0035658 3.4458 0.0034667 3.445 0.0033697 3.4442 0.0032749 3.4434 0.0031821 3.4426 0.0030915 3.4417 0.003003 3.4409 0.0029166 3.4401 0.0028322 3.4393 0.0027499 3.4385 0.0026696 3.4377 0.0025913 3.437 0.0025151 3.4362 0.0024408 3.4354 0.0023685 3.4346 0.0022982 3.4338 0.0022299 3.4331 0.0021635 3.4323 0.002099 3.4315 0.0020365 3.4308 0.0019759 3.43 0.0019171 3.4292 0.0018602 3.4285 0.0018052

215

1.6737 1.6701 1.6666 1.663 1.6595 1.656 1.6525 1.6491 1.6456 1.6422 1.6387 1.6353 1.6319 1.6285 1.6252 1.6218 1.6185 1.6152 1.6118 1.6085 1.6053 1.602 1.5987 1.5955 1.5922 1.589 1.5858 1.5826 1.5795 1.5763 1.5731 1.57 1.5669 1.5637 1.5606 1.5576 1.5545 1.5514 1.5484

3.4277 0.0017521 3.427 0.0017008 3.4262 0.0016514 3.4255 0.0016037 3.4248 0.0015579 3.424 0.0015139 3.4233 0.0014716 3.4226 0.0014311 3.4218 0.0013924 3.4211 0.0013555 3.4204 0.0013202 3.4197 0.0012867 3.419 0.001255 3.4183 0.0012249 3.4176 0.0011965 3.4169 0.0011698 3.4162 0.0011448 3.4155 0.0011215 3.4148 0.0010998 3.4141 0.0010798 3.4134 0.0010613 3.4127 0.0010445 3.412 0.0010294 3.4113 0.0010158 3.4107 0.0010038 3.41 0.0009934 3.4093 0.0009846 3.4086 0.0009773 3.408 0.0009716 3.4073 0.0009674 3.4067 0.0009648 3.406 0.0009636 3.4054 0.000964 3.4047 0.0009659 3.4041 0.0009693 3.4034 0.0009742 3.4028 0.00098 3.4022 0.0009858 3.4015 0.0009917

1.5453 1.5423 1.5393 1.5363 1.5333 1.5303 1.5273 1.5244 1.5214 1.5185 1.5156 1.5127 1.5098 1.5069 1.504 1.5011 1.4983 1.4954 1.4926 1.4898 1.487 1.4842 1.4814 1.4786 1.4758 1.4731 1.4703 1.4676 1.4649 1.4622 1.4595 1.4568 1.4541 1.4514 1.4487 1.4461 1.4435 1.4408 1.4382

3.4009 0.0009975 3.4003 0.0010034 3.3997 0.0010093 3.3991 0.0010153 3.3985 0.0010212 3.3978 0.0010272 3.3972 0.0010332 3.3966 0.0010392 3.396 0.0010453 3.3954 0.0010513 3.3948 0.0010574 3.3943 0.0010636 3.3937 0.0010697 3.3931 0.0010759 3.3925 0.001082 3.3919 0.0010882 3.3913 0.0010945 3.3907 0.0011007 3.3902 0.001107 3.3896 0.0011133 3.389 0.0011196 3.3885 0.001126 3.3879 0.0011323 3.3873 0.0011387 3.3868 0.0011451 3.3862 0.0011516 3.3856 0.001158 3.3851 0.0011645 3.3845 0.001171 3.384 0.0011776 3.3834 0.0011841 3.3829 0.0011907 3.3823 0.0011973 3.3818 0.0012039 3.3812 0.0012106 3.3807 0.0012172 3.3801 0.0012239 3.3796 0.0012306 3.3791 0.0012374

1.4356 1.433 1.4304 1.4278 1.4252 1.4227 1.4201 1.4176 1.4151 1.4125 1.41 1.4075 1.405 1.4025 1.4 1.3976 1.3951 1.3927 1.3902 1.3878 1.3854 1.383 1.3806 1.3782 1.3758 1.3734 1.371 1.3687 1.3663 1.364 1.3616 1.3593 1.357 1.3547 1.3524 1.3501 1.3478 1.3455 1.3433

3.3785 0.0012441 3.378 0.0012509 3.3774 0.0012577 3.3769 0.0012646 3.3764 0.0012714 3.3759 0.0012783 3.3753 0.0012852 3.3748 0.0012922 3.3743 0.0012991 3.3738 0.0013061 3.3732 0.0013131 3.3727 0.0013201 3.3722 0.0013271 3.3717 0.0013342 3.3712 0.0013413 3.3706 0.0013484 3.3701 0.0013556 3.3696 0.0013627 3.3691 0.0013699 3.3686 0.0013771 3.3681 0.0013844 3.3676 0.0013916 3.3671 0.0013989 3.3666 0.0014062 3.3661 0.0014135 3.3656 0.0014209 3.3651 0.0014283 3.3646 0.0014357 3.3641 0.0014431 3.3636 0.0014505 3.3631 0.001458 3.3626 0.0014655 3.3621 0.001473 3.3616 0.0014805 3.3611 0.0014881 3.3606 0.0014957 3.3601 0.0015033 3.3596 0.0015109 3.3591 0.0015186

216

1.341 1.3388 1.3365 1.3343 1.3321 1.3299 1.3277 1.3255 1.3233 1.3211 1.3189 1.3167 1.3146 1.3124 1.3103 1.3081 1.306 1.3039 1.3018 1.2997 1.2976 1.2955 1.2934 1.2913 1.2893 1.2872 1.2851 1.2831 1.2811 1.279 1.277 1.275 1.273 1.271 1.269 1.267 1.265 1.263 1.2611

3.3586 0.0015263 3.3582 0.001534 3.3577 0.0015417 3.3572 0.0015495 3.3567 0.0015572 3.3562 0.001565 3.3557 0.0015729 3.3553 0.0015807 3.3548 0.0015886 3.3543 0.0015965 3.3538 0.0016044 3.3534 0.0016123 3.3529 0.0016203 3.3524 0.0016282 3.3519 0.0016363 3.3515 0.0016443 3.351 0.0016523 3.3505 0.0016604 3.35 0.0016685 3.3496 0.0016766 3.3491 0.0016848 3.3486 0.0016929 3.3482 0.0017011 3.3477 0.0017093 3.3472 0.0017176 3.3468 0.0017258 3.3463 0.0017341 3.3459 0.0017424 3.3454 0.0017507 3.3449 0.0017591 3.3445 0.0017675 3.344 0.0017759 3.3436 0.0017843 3.3431 0.0017927 3.3426 0.0018012 3.3422 0.0018097 3.3417 0.0018182 3.3413 0.0018267 3.3408 0.0018352

1.2591 1.2572 1.2552 1.2533 1.2514 1.2494 1.2475 1.2456 1.2437 1.2418 1.2399 1.2249 1.2207 1.2166 1.2126 1.2085 1.2045 1.2005 1.1965 1.1926 1.1887 1.1848 1.1809 1.1771 1.1732 1.1695 1.1657 1.1619 1.1582 1.1545 1.1509 1.1472 1.1436 1.14 1.1364 1.1328 1.1293 1.1258 1.1223

3.3404 0.0018438 3.3399 0.0018524 3.3395 0.001861 3.339 0.0018697 3.3386 0.0018783 3.3381 0.001887 3.3377 0.0018957 3.3372 0.0019044 3.3368 0.0019132 3.3363 0.0019219 3.3359 0.0019307 3.3323 0.0020028 3.3313 0.0020232 3.3303 0.0020437 3.3293 0.0020644 3.3283 0.0020852 3.3274 0.0021062 3.3264 0.0021273 3.3254 0.0021485 3.3244 0.0021699 3.3234 0.0021914 3.3225 0.0022131 3.3215 0.0022349 3.3205 0.0022568 3.3195 0.0022789 3.3185 0.0023011 3.3176 0.0023235 3.3166 0.002346 3.3156 0.0023687 3.3147 0.0023915 3.3137 0.0024145 3.3127 0.0024376 3.3118 0.0024608 3.3108 0.0024842 3.3098 0.0025078 3.3089 0.0025315 3.3079 0.0025553 3.3069 0.0025793 3.306 0.0026035

1.1188 1.1154 1.1119 1.1085 1.1052 1.1018 1.0984 1.0951 1.0918 1.0885 1.0853 1.082 1.0788 1.0756 1.0724 1.0692 1.0661 1.0629 1.0598 1.0567 1.0536 1.0506 1.0475 1.0445 1.0415 1.0385 1.0355 1.0326 1.0296 1.0267 1.0238 1.0209 1.018 1.0152 1.0123 1.0095 1.0067 1.0039 1.0011

3.305 0.0026278 3.3041 0.0026522 3.3031 0.0026768 3.3021 0.0027016 3.3012 0.0027265 3.3002 0.0027515 3.2993 0.0027767 3.2983 0.0028021 3.2974 0.0028276 3.2964 0.0028533 3.2954 0.0028791 3.2945 0.0029051 3.2935 0.0029312 3.2926 0.0029575 3.2916 0.002984 3.2907 0.0030106 3.2897 0.0030374 3.2888 0.0030643 3.2878 0.0030914 3.2868 0.0031186 3.2859 0.003146 3.2849 0.0031736 3.284 0.0032013 3.283 0.0032292 3.2821 0.0032573 3.2811 0.0032855 3.2802 0.0033139 3.2792 0.0033424 3.2782 0.0033711 3.2773 0.0034 3.2763 0.003429 3.2754 0.0034582 3.2744 0.0034876 3.2734 0.0035171 3.2725 0.0035468 3.2715 0.0035767 3.2706 0.0036067 3.2696 0.0036369 3.2687 0.0036673

217

0.99836 3.2677 0.0036979 0.99561 3.2667 0.0037286 0.99287 3.2658 0.0037595 0.99015 3.2648 0.0037905 0.98744 3.2638 0.0038218 0.98475 3.2629 0.0038532 0.98208 3.2619 0.0038847 0.97941 3.2609 0.0039165 0.97677 0.97413 0.97151 3.26 0.0039484 3.259 0.0039805 3.258 0.0040128

0.90118 3.2296 0.005027 0.89893 3.2286 0.0050647 0.8967 3.2276 0.0051027 0.89447 3.2266 0.0051408 0.89226 3.2256 0.0051791 0.89006 3.2246 0.0052177 0.88787 3.2236 0.0052564 0.88569 3.2226 0.0052953 0.88351 3.2216 0.0053344 0.88135 3.2206 0.0053737 0.8792 3.2196 0.0054132 0.87707 3.2186 0.0054529 0.87493 3.2176 0.0054928 0.87282 3.2166 0.0055328 0.87071 3.2156 0.0055731 0.86861 3.2146 0.0056136 0.86652 3.2136 0.0056543 0.86444 3.2126 0.0056951 0.86237 3.2115 0.0057362 0.86031 3.2105 0.0057775 0.85826 3.2095 0.0058189 0.85622 3.2085 0.0058606 0.85419 3.2075 0.0059025 0.85217 3.2064 0.0059446 0.85016 3.2054 0.0059868 0.84815 3.2044 0.0060293 0.84616 3.2034 0.006072 0.84417 3.2023 0.0061149 0.8422 3.2013 0.006158 0.84023 3.2003 0.0062013 0.83828 3.1992 0.0062448 0.83633 3.1982 0.0062885 0.83439 3.1972 0.0063325 0.83246 3.1961 0.0063766 0.83054 3.1951 0.0064209 0.82862 3.1941 0.0064655 0.82672 0.82482 3.193 0.0065102 3.192 0.0065552

0.82106 3.1899 0.0066458 0.81919 3.1888 0.0066914 0.81732 3.1878 0.0067372 0.81547 3.1867 0.0067832 0.81362 3.1857 0.0068294 0.81179 3.1846 0.0068759 0.80996 3.1836 0.0069225 0.80814 3.1825 0.0069694 0.80632 3.1815 0.0070165 0.80452 3.1804 0.0070638 0.80272 3.1793 0.0071114 0.80093 3.1783 0.0071591 0.79915 3.1772 0.0072071 0.79737 3.1762 0.0072553 0.79561 3.1751 0.0073037 0.79385 0.7921 3.174 0.0073523 3.1729 0.0074011

0.96891 3.2571 0.0040452 0.96632 3.2561 0.0040778 0.96374 3.2551 0.0041106 0.96117 3.2542 0.0041436 0.95862 3.2532 0.0041768 0.95608 3.2522 0.0042101 0.95356 3.2513 0.0042436 0.95105 3.2503 0.0042773 0.94855 3.2493 0.0043112 0.94607 3.2483 0.0043452 0.94359 3.2474 0.0043794 0.94113 3.2464 0.0044138 0.93869 3.2454 0.0044484 0.93625 3.2444 0.0044832 0.93383 3.2435 0.0045182 0.93142 3.2425 0.0045533 0.92902 3.2415 0.0045886 0.92664 3.2405 0.0046241 0.92427 3.2395 0.0046598 0.9219 3.2385 0.0046957 0.91956 3.2376 0.0047317 0.91722 3.2366 0.004768 0.91489 3.2356 0.0048044 0.91258 3.2346 0.004841 0.91028 3.2336 0.0048778 0.90798 3.2326 0.0049149 0.9057 3.2316 0.004952 0.90344 3.2306 0.0049894

0.79035 3.1719 0.0074502 0.78862 3.1708 0.0074995 0.78689 3.1697 0.007549 0.78517 3.1686 0.0075987 0.78345 3.1676 0.0076486 0.78174 3.1665 0.0076988 0.78004 3.1654 0.0077492 0.77835 3.1643 0.0077998 0.77667 3.1632 0.0078507 0.77499 3.1621 0.0079018 0.77332 3.1611 0.0079531 0.77165 0.77 0.7667 3.16 0.0080046 3.1589 0.0080563 3.1567 0.0081605

0.76835 3.1578 0.0081083 0.76507 3.1556 0.008213 0.76344 3.1545 0.0082656 0.76181 3.1534 0.0083185 0.7602 3.1523 0.0083717 0.75859 3.1512 0.008425 0.75698 3.1501 0.0084786 0.75539 3.149 0.0085325

0.82294 3.1909 0.0066004

218

0.7538

3.1478 0.0085865

0.75221 3.1467 0.0086408 0.75064 3.1456 0.0086954 0.74907 3.1445 0.0087501 0.7475 3.1434 0.0088051 0.74594 3.1423 0.0088604 0.74439 3.1411 0.0089158 0.74285 3.14 0.0089715

219

A.3
eV

Dielectric function of SiO2


1 2.4689 2.4629 2.4571 2.4515 2.4461 2.4408 2.4357 2.4307 2.4259 2.4213 2.4167 2.4123 2.408 2.4039 2.3998 2.3959 2.3921 2.3883 2.3847 2.3812 2.3777 2.3744 2.3711 2.3679 2.3648 2.3618 2.3588 2.3559 2.3531 2.3504 2.3477 2.345 2.3425 2.34 2.3375 2.3351 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5.0062 4.9743 4.9429 4.9118 4.8811 4.8508 4.8209 4.7913 4.7621 4.7332 4.7047 4.6765 4.6486 4.6211 4.5939 4.567 4.5405 4.5142 4.4882 4.4626 4.4372 4.4121 4.3873 4.3627 4.3384 4.3144 4.2907 4.2672 4.244 4.221 4.1983 4.1758 4.1536 4.1315 4.1098 4.0882 4.0669 2.3328 2.3305 2.3283 2.3261 2.3239 2.3218 2.3198 2.3178 2.3158 2.3139 2.312 2.3101 2.3083 2.3065 2.3048 2.3031 2.3014 2.2998 2.2982 2.2966 2.295 2.2935 2.292 2.2906 2.2891 2.2877 2.2863 2.285 2.2837 2.2823 2.2811 2.2798 2.2785 2.2773 2.2761 2.2749 2.2738 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4.0458 4.0249 4.0042 3.9837 3.9635 3.9434 3.9235 3.9039 3.8844 3.8652 3.8461 3.8272 3.8085 3.79 3.7716 3.7534 3.7355 3.7176 3.7 3.6825 3.6652 3.648 3.631 3.6142 3.5975 3.5809 3.5646 3.5483 3.5322 3.5163 3.5005 3.4848 3.4693 3.4539 3.4387 3.4236 3.4086 2.2726 2.2715 2.2704 2.2693 2.2683 2.2672 2.2662 2.2652 2.2642 2.2632 2.2622 2.2613 2.2603 2.2594 2.2585 2.2576 2.2567 2.2558 2.255 2.2541 2.2533 2.2525 2.2517 2.2509 2.2501 2.2493 2.2486 2.2478 2.2471 2.2463 2.2456 2.2449 2.2442 2.2435 2.2429 2.2422 2.2415 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3.3938 3.3791 3.3645 3.35 3.3357 3.3215 3.3074 3.2934 3.2795 3.2658 3.2522 3.2386 3.2252 3.212 3.1988 3.1857 3.1727 3.1599 3.1471 3.1345 3.1219 3.1095 3.0971 3.0849 3.0727 3.0607 3.0487 3.0368 3.025 3.0134 3.0018 2.9902 2.9788 2.9675 2.9563 2.9451 2.934 2.2409 2.2402 2.2396 2.239 2.2383 2.2377 2.2371 2.2365 2.2359 2.2354 2.2348 2.2342 2.2337 2.2331 2.2326 2.232 2.2315 2.231 2.2304 2.2299 2.2294 2.2289 2.2284 2.2279 2.2274 2.227 2.2265 2.226 2.2256 2.2251 2.2247 2.2242 2.2238 2.2233 2.2229 2.2225 2.2221 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

6.5004 6.4471 6.3947 6.3432 6.2924 6.2425 6.1933 6.1448 6.0972 6.0502 6.0039 5.9584 5.9135 5.8692 5.8257 5.7827 5.7404 5.6987 5.6575 5.617 5.577 5.5376 5.4987 5.4604 5.4226 5.3853 5.3485 5.3122 5.2764 5.241 5.2062 5.1717 5.1378 5.1042 5.0711 5.0384

220

2.923 2.9121 2.9013 2.8905 2.8799 2.8693 2.8588 2.8483 2.838 2.8277 2.8175 2.8074 2.7973 2.7873 2.7774 2.7676 2.7578 2.7481 2.7384 2.7289 2.7194 2.7099 2.7006 2.6913 2.682 2.6728 2.6637 2.6547 2.6457 2.6368 2.6279 2.6191 2.6103 2.6016 2.593 2.5844 2.5759 2.5675 2.559

2.2216 2.2212 2.2208 2.2204 2.22 2.2196 2.2192 2.2188 2.2184 2.2181 2.2177 2.2173 2.2169 2.2166 2.2162 2.2159 2.2155 2.2152 2.2148 2.2145 2.2141 2.2138 2.2135 2.2131 2.2128 2.2125 2.2122 2.2118 2.2115 2.2112 2.2109 2.2106 2.2103 2.21 2.2097 2.2094 2.2091 2.2088 2.2085

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

2.5507 2.5424 2.5342 2.526 2.5178 2.5098 2.5017 2.4937 2.4858 2.4779 2.4701 2.4623 2.4546 2.4469 2.4393 2.4317 2.4242 2.4167 2.4092 2.4018 2.3945 2.3872 2.3799 2.3727 2.3655 2.3584 2.3513 2.3443 2.3373 2.3303 2.3234 2.3165 2.3097 2.3029 2.2961 2.2894 2.2827 2.2761 2.2695

2.2082 2.2079 2.2077 2.2074 2.2071 2.2068 2.2066 2.2063 2.206 2.2058 2.2055 2.2052 2.205 2.2047 2.2045 2.2042 2.204 2.2037 2.2035 2.2032 2.203 2.2027 2.2025 2.2023 2.202 2.2018 2.2016 2.2013 2.2011 2.2009 2.2007 2.2004 2.2002 2.2 2.1998 2.1996 2.1993 2.1991 2.1989

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

2.263 2.2564 2.2499 2.2435 2.2371 2.2307 2.2244 2.2181 2.2118 2.2056 2.1994 2.1932 2.1871 2.181 2.175 2.1689 2.163 2.157 2.1511 2.1452 2.1393 2.1335 2.1277 2.1219 2.1162 2.1105 2.1048 2.0992 2.0936 2.088 2.0825 2.077 2.0715 2.066 2.0606 2.0552 2.0498 2.0444 2.0391

2.1987 2.1985 2.1983 2.1981 2.1979 2.1977 2.1975 2.1973 2.1971 2.1969 2.1967 2.1965 2.1963 2.1961 2.1959 2.1957 2.1955 2.1953 2.1951 2.1949 2.1948 2.1946 2.1944 2.1942 2.194 2.1938 2.1937 2.1935 2.1933 2.1931 2.193 2.1928 2.1926 2.1924 2.1923 2.1921 2.1919 2.1918 2.1916

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

2.0338 2.0286 2.0233 2.0181 2.0129 2.0078 2.0027 1.9976 1.9925 1.9874 1.9824 1.9774 1.9724 1.9675 1.9625 1.9577 1.9528 1.9479 1.9431 1.9383 1.9335 1.9288 1.924 1.9193 1.9146 1.91 1.9053 1.9007 1.8961 1.8915 1.887 1.8825 1.878 1.8735 1.869 1.8646 1.8601 1.8557 1.8514

2.1914 2.1913 2.1911 2.1909 2.1908 2.1906 2.1905 2.1903 2.1901 2.19 2.1898 2.1897 2.1895 2.1893 2.1892 2.189 2.1889 2.1887 2.1886 2.1884 2.1883 2.1881 2.188 2.1878 2.1877 2.1875 2.1874 2.1872 2.1871 2.187 2.1868 2.1867 2.1865 2.1864 2.1862 2.1861 2.186 2.1858 2.1857

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

221

1.847 1.8427 1.8383 1.834 1.8298 1.8255 1.8213 1.817 1.8128 1.8087 1.8045 1.8004 1.7962 1.7921 1.7881 1.784 1.7799 1.7759 1.7719 1.7679 1.7639 1.76 1.756 1.7521 1.7482 1.7443 1.7405 1.7366 1.7328 1.729 1.7252 1.7214 1.7176 1.7139 1.7101 1.7064 1.7027 1.699 1.6954

2.1855 2.1854 2.1853 2.1851 2.185 2.1849 2.1847 2.1846 2.1845 2.1843 2.1842 2.1841 2.1839 2.1838 2.1837 2.1835 2.1834 2.1833 2.1831 2.183 2.1829 2.1828 2.1826 2.1825 2.1824 2.1822 2.1821 2.182 2.1819 2.1817 2.1816 2.1815 2.1814 2.1812 2.1811 2.181 2.1809 2.1808 2.1806

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1.6917 1.6881 1.6844 1.6808 1.6772 1.6737 1.6701 1.6666 1.663 1.6595 1.656 1.6525 1.6491 1.6456 1.6422 1.6387 1.6353 1.6319 1.6285 1.6252 1.6218 1.6185 1.6152 1.6118 1.6085 1.6053 1.602 1.5987 1.5955 1.5922 1.589 1.5858 1.5826 1.5795 1.5763 1.5731 1.57 1.5669 1.5637

2.1805 2.1804 2.1803 2.1802 2.18 2.1799 2.1798 2.1797 2.1796 2.1794 2.1793 2.1792 2.1791 2.179 2.1789 2.1787 2.1786 2.1785 2.1784 2.1783 2.1782 2.1781 2.1779 2.1778 2.1777 2.1776 2.1775 2.1774 2.1773 2.1772 2.177 2.1769 2.1768 2.1767 2.1766 2.1765 2.1764 2.1763 2.1762

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1.5606 1.5576 1.5545 1.5514 1.5484 1.5453 1.5423 1.5393 1.5363 1.5333 1.5303 1.5273 1.5244 1.5214 1.5185 1.5156 1.5127 1.5098 1.5069 1.504 1.5011 1.4983 1.4954 1.4926 1.4898 1.487 1.4842 1.4814 1.4786 1.4758 1.4731 1.4703 1.4676 1.4649 1.4622 1.4595 1.4568 1.4541 1.4514

2.1761 2.1759 2.1758 2.1757 2.1756 2.1755 2.1754 2.1753 2.1752 2.1751 2.175 2.1749 2.1748 2.1747 2.1745 2.1744 2.1743 2.1742 2.1741 2.174 2.1739 2.1738 2.1737 2.1736 2.1735 2.1734 2.1733 2.1732 2.1731 2.173 2.1729 2.1728 2.1727 2.1726 2.1725 2.1724 2.1723 2.1722 2.1721

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1.4487 1.4461 1.4435 1.4408 1.4382 1.4356 1.433 1.4304 1.4278 1.4252 1.4227 1.4201 1.4176 1.4151 1.4125 1.41 1.4075 1.405 1.4025 1.4 1.3976 1.3951 1.3927 1.3902 1.3878 1.3854 1.383 1.3806 1.3782 1.3758 1.3734 1.371 1.3687 1.3663 1.364 1.3616 1.3593 1.357 1.3547

2.1719 2.1718 2.1717 2.1716 2.1715 2.1714 2.1713 2.1712 2.1711 2.171 2.1709 2.1708 2.1707 2.1706 2.1705 2.1704 2.1703 2.1702 2.1701 2.17 2.1699 2.1698 2.1697 2.1696 2.1695 2.1694 2.1693 2.1693 2.1692 2.1691 2.169 2.1689 2.1688 2.1687 2.1686 2.1685 2.1684 2.1683 2.1682

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

222

1.3524 1.3501 1.3478 1.3455 1.3433 1.341 1.3388 1.3365 1.3343 1.3321 1.3299 1.3277 1.3255 1.3233 1.3211 1.3189 1.3167 1.3146 1.3124 1.3103 1.3081 1.306 1.3039 1.3018 1.2997 1.2976 1.2955 1.2934 1.2913 1.2893 1.2872 1.2851 1.2831 1.2811 1.279 1.277 1.275 1.273 1.271

2.1681 2.168 2.1679 2.1678 2.1677 2.1676 2.1675 2.1674 2.1673 2.1672 2.1671 2.167 2.1669 2.1668 2.1667 2.1666 2.1665 2.1664 2.1664 2.1663 2.1662 2.1661 2.166 2.1659 2.1658 2.1657 2.1656 2.1655 2.1654 2.1653 2.1652 2.1651 2.165 2.1649 2.1648 2.1647 2.1647 2.1646 2.1645

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1.269 1.267 1.265 1.263 1.2611 1.2591 1.2572 1.2552 1.2533 1.2514 1.2494 1.2475 1.2456 1.2437 1.2418 1.2399 1.2249 1.2207 1.2166 1.2126 1.2085 1.2045 1.2005 1.1965 1.1926 1.1887 1.1848 1.1809 1.1771 1.1732 1.1695 1.1657 1.1619 1.1582 1.1545 1.1509 1.1472 1.1436 1.14

2.1644 2.1643 2.1642 2.1641 2.164 2.1639 2.1638 2.1637 2.1636 2.1635 2.1634 2.1634 2.1633 2.1632 2.1631 2.163 2.1622 2.162 2.1618 2.1616 2.1614 2.1612 2.161 2.1608 2.1606 2.1604 2.1602 2.16 2.1598 2.1595 2.1593 2.1591 2.1589 2.1587 2.1585 2.1583 2.1581 2.1579 2.1577

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1.1364 1.1328 1.1293 1.1258 1.1223 1.1188 1.1154 1.1119 1.1085 1.1052 1.1018 1.0984 1.0951 1.0918 1.0885 1.0853 1.082 1.0788 1.0756 1.0724 1.0692 1.0661 1.0629 1.0598 1.0567 1.0536 1.0506 1.0475 1.0445 1.0415 1.0385 1.0355 1.0326 1.0296 1.0267 1.0238 1.0209 1.018 1.0152

2.1575 2.1573 2.1571 2.1569 2.1566 2.1564 2.1562 2.156 2.1558 2.1556 2.1554 2.1552 2.155 2.1548 2.1546 2.1543 2.1541 2.1539 2.1537 2.1535 2.1533 2.1531 2.1529 2.1527 2.1525 2.1522 2.152 2.1518 2.1516 2.1514 2.1512 2.151 2.1508 2.1506 2.1503 2.1501 2.1499 2.1497 2.1495

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1.0123 1.0095 1.0067 1.0039 1.0011 0.99836 0.99561 0.99287 0.99015 0.98744 0.98475 0.98208 0.97941 0.97677 0.97413 0.97151 0.96891 0.96632 0.96374 0.96117 0.95862 0.95608 0.95356 0.95105 0.94855 0.94607 0.94359 0.94113 0.93869 0.93625 0.93383 0.93142 0.92902 0.92664 0.92427 0.9219 0.91956 0.91722 0.91489

2.1493 2.1491 2.1488 2.1486 2.1484 2.1482 2.148 2.1478 2.1476 2.1473 2.1471 2.1469 2.1467 2.1465 2.1463 2.146 2.1458 2.1456 2.1454 2.1452 2.1449 2.1447 2.1445 2.1443 2.1441 2.1438 2.1436 2.1434 2.1432 2.143 2.1427 2.1425 2.1423 2.1421 2.1418 2.1416 2.1414 2.1412 2.1409

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

223

0.91258 0.91028 0.90798 0.9057 0.90344 0.90118 0.89893 0.8967 0.89447 0.89226 0.89006 0.88787 0.88569 0.88351 0.88135 0.8792 0.87707 0.87493 0.87282 0.87071 0.86861 0.86652 0.86444 0.86237 0.86031 0.85826 0.85622 0.85419 0.85217 0.85016 0.84815 0.84616 0.84417 0.8422 0.84023 0.83828 0.83633 0.83439 0.83246

2.1407 2.1405 2.1403 2.14 2.1398 2.1396 2.1394 2.1391 2.1389 2.1387 2.1384 2.1382 2.138 2.1377 2.1375 2.1373 2.1371 2.1368 2.1366 2.1364 2.1361 2.1359 2.1357 2.1354 2.1352 2.135 2.1347 2.1345 2.1342 2.134 2.1338 2.1335 2.1333 2.1331 2.1328 2.1326 2.1323 2.1321 2.1319

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

0.83054 0.82862 0.82672 0.82482 0.82294 0.82106 0.81919 0.81732 0.81547 0.81362 0.81179 0.80996 0.80814 0.80632 0.80452 0.80272 0.80093 0.79915 0.79737 0.79561 0.79385 0.7921 0.79035 0.78862 0.78689 0.78517 0.78345 0.78174 0.78004 0.77835 0.77667 0.77499 0.77332 0.77165 0.77 0.76835 0.7667 0.76507 0.76344

2.1316 2.1314 2.1311 2.1309 2.1307 2.1304 2.1302 2.1299 2.1297 2.1294 2.1292 2.129 2.1287 2.1285 2.1282 2.128 2.1277 2.1275 2.1272 2.127 2.1267 2.1265 2.1262 2.126 2.1257 2.1255 2.1252 2.125 2.1247 2.1245 2.1242 2.124 2.1237 2.1235 2.1232 2.1229 2.1227 2.1224 2.1222

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

0.76181 0.7602 0.75859 0.75698 0.75539 0.7538 0.75221 0.75064 0.74907 0.7475 0.74594 0.74439 0.74285

2.1219 2.1217 2.1214 2.1211 2.1209 2.1206 2.1204 2.1201 2.1198 2.1196 2.1193 2.1191 2.1188

0 0 0 0 0 0 0 0 0 0 0 0 0

224

A.4
eV

Dielectric function of SnO2:F


1 2 5.0062 6.5153 3.2727 4.0458 4.6146 0.11577 3.3938 4.1528 0.033239 3.2482 4.0249 4.5946 0.10925 3.3791 4.1447 0.032638 3.1561 4.0042 4.5753 0.10334 3.3645 4.1368 0.032069 3.0728 3.9837 4.5568 0.097956 3.35 4.129 0.03152 2.9625 3.9635 4.5388 0.093011 3.3357 4.1213 0.030999 2.8423 3.9434 4.5215 0.088501 3.3215 4.1137 0.030498 2.8191 3.9235 4.5048 0.08436 3.3074 4.1062 0.030019 2.713 3.9039 4.4885 0.080529 3.2934 4.0989 0.029569 2.666 3.8844 4.4728 0.077006 3.2795 4.0917 0.029131 2.5396 3.8652 4.4575 0.073734 3.2658 4.0845 0.028709 2.3692 3.8461 4.4427 0.070718 3.2522 4.0775 0.028309 2.17 3.8272 4.4283 0.067919 3.2386 4.0706 0.027921 1.9544 3.8085 4.4143 0.065308 3.2252 4.0637 0.027551 1.7318 3.79 4.4007 0.062875 3.212 4.0569 0.027199 1.5118 3.7716 4.3875 0.060622 3.1988 4.0502 0.026859 1.3012 3.7534 4.3747 0.058505 3.1857 4.0436 0.02654 1.1047 3.7355 4.362 0.056515 3.1727 4.0371 0.026221

6.5004 3.9713 6.4471 3.8365 6.3947 4.0079 6.3432 4.041 6.2924 4.1187 6.2425 4.1532 6.1933 4.1876 6.1448 4.2819 6.0972 4.3261 6.0502 4.3707 6.0039 4.4314 5.9584 4.5232 5.9135 4.5773 5.8692 4.6024 5.8257 4.6925 5.7827 5.7404 5.6987 4.755 4.828 4.891

4.0149 4.9743 6.5892 3.9148 4.9429 6.6857 3.9887 4.9118 6.7541 4.0674 4.8811 6.8624 3.9552 4.8508 6.8828 3.9855 4.8209 6.9286 3.9881 4.7913 6.8787 3.9916 4.7621 6.8868 3.9426 4.7332 6.8607 3.9117 4.7047 6.8106 3.868 4.6765 6.7108 3.9396 4.6486 6.5733 3.8937 4.6211 6.4086 3.872 4.5939 6.2269 3.8377 4.567 6.0375 3.8735 4.5405 5.8478 3.8227 4.4882

3.8354 4.5142 5.6671 0.92812 3.7176 4.3498 0.054663 3.1599 4.0307 0.025929 5.501 0.77349 3.7 4.3378 0.052917 3.1471 4.0243 0.02564 4.018 0.025359 0.0251 0.0246 3.7736 4.4626 5.3554 0.64218 3.6825 4.3262 0.051279 3.1345 3.8102 4.4121 5.1496 0.455

5.6575 4.9459 5.617 5.0635 5.577 5.1365 5.5376 5.2317 5.4987 5.2471 5.4604 5.3437 5.4226 5.4337 5.3853 5.5346 5.3485 5.62 5.3122 5.6826 5.2764 5.7345 5.241 5.7963 5.2062 5.8783 5.1717 5.9604 5.1378 6.0616 5.1042 6.1636 5.0711 6.2959 5.0384 6.3878

3.8069 4.4372 5.2368 0.53621 3.6652 4.3147 0.049737 3.1219 4.0119 3.7544 4.3873 5.1007 0.40485 3.631 4.2927 0.04693 3.0971 3.9997

3.648 4.3036 0.04829 3.1095 4.0057 0.024849 4.282 0.045637 3.0849 3.9936 0.024369

3.7339 4.3627 4.9976 0.36189 3.6142

3.7248 4.3384 4.9634 0.32464 3.5975 4.2716 0.044418 3.0727 3.9877 0.02415 3.7151 4.3144 4.9301 0.29291 3.5809 4.2614 0.043262 3.0607 3.9818 0.023929 3.6793 4.2907 4.8976 0.26542 3.5646 4.2514 0.042167 3.0487 3.9761 0.02373 3.5867 4.2672 4.8663 0.24169 3.5483 4.2416 0.041141 3.0368 3.9703 0.02353 3.5601 3.5325 4.244 4.8361 0.22099 3.5322 4.2319 0.040162 3.025 3.9647 0.023341 3.959 0.023159 3.948 0.022821 4.221 4.8071 0.20295 3.5163 4.2225 0.03923 3.0134

3.5341 4.1983 4.7793 0.18707 3.5005 4.2132 0.03834 3.0018 3.9534 0.022989 3.4751 4.1758 4.7528 0.17307 3.4848 4.2042 0.037502 2.9902 3.5094 4.1536 4.7272 0.16065 3.4693 4.1952 0.036701 2.9788 3.9425 0.02266 3.4719 4.1315 4.7029 0.14965 3.4539 4.1865 0.035942 2.9675 3.9371 0.02251 3.4253 4.1098 4.6794 0.13975 3.4387 4.1778 0.03522 2.9563 3.9317 0.022359 3.389 4.0882 4.657 0.13093 3.4236 4.1693 0.03453 2.9451 3.9264 0.02222 4.161 0.033871 2.934 3.9212 0.02209 3.3222 4.0669 4.6353 0.12296 3.4086

225

2.923

3.916 0.02196 2.5507 3.7402 0.02016

2.263 3.5951 0.022001 2.0338 3.4625 0.025969

2.9121 3.9108 0.02184 2.5424 3.7362 0.02018 2.2564 3.5916 0.02208 2.0286 3.4592 0.026101 2.9013 3.9057 0.02172 2.5342 3.7322 0.02019 2.2499 3.5881 0.022159 2.0233 3.4559 0.026229 2.8905 3.9006 0.02161 2.8799 3.8956 2.8693 3.8906 2.8588 3.8856 2.526 3.7283 0.02021 2.2435 3.5846 0.02224 2.0181 3.4525 0.026349 0.0224 2.0078 3.4459 0.02661 0.0215 2.5178 3.7244 0.02023 2.2371 3.5811 0.02232 2.0129 3.4492 0.026479 0.0214 2.5098 3.7204 0.02025 2.2307 3.5777 0.0213 2.5017 3.7166 0.02027 2.2244 3.5742 0.02249 2.0027 3.4426 0.026741 0.0203 2.2181 3.5707 0.02257 1.9976 3.4392 0.026871

2.8483 3.8808 0.02121 2.4937 3.7127

2.838 3.8759 0.02113 2.4858 3.7088 0.02032 2.2118 3.5673 0.02266 1.9925 3.4359 0.027011 2.8277 3.8711 0.02104 2.4779 3.7049 0.02035 2.2056 3.5638 0.02275 1.9874 3.4327 0.027139 2.8175 3.8663 0.02097 2.4701 3.7011 0.02038 2.1994 3.5604 0.02284 1.9824 3.4293 0.02728 2.8074 3.8615 0.02089 2.4623 3.6973 0.02042 2.1932 2.7873 3.8521 0.02076 2.4469 3.6897 0.02049 2.7774 3.8475 0.02069 2.4393 3.6859 0.02052 2.7578 3.8382 0.02058 2.4242 3.6783 0.02061 2.7481 3.8337 0.02053 2.4167 3.6746 0.02065 3.557 0.022929 1.9774 3.426 0.02741 2.7973 3.8568 0.02082 2.4546 3.6935 0.02045 2.1871 3.5535 0.02302 1.9724 3.4227 0.027549 2.181 3.5501 0.02312 1.9675 3.4194 0.027691 2.175 3.5466 0.023211 1.9625 3.4161 0.027829 2.163 3.5398 0.023411 1.9528 3.4095 0.028111 2.157 3.5364 3.533 0.0235 1.9479 3.4062 0.028259 0.0236 1.9431 3.4029 0.0284

2.7676 3.8428 0.02063 2.4317 3.6821 0.02056 2.1689 3.5433 0.023309 1.9577 3.4128 0.027971

2.7384 3.8292 0.02048 2.4092 3.6709 0.02069 2.1511 2.7194 3.8202

2.7289 3.8247 0.02044 2.4018 3.6672 0.02074 2.1452 3.5296 0.02371 1.9383 3.3996 0.02854 0.0204 2.3945 3.6635 0.02079 2.1393 3.5262 0.02381 1.9335 3.3963 0.02869 3.393 0.028841 1.924 3.3897 0.028989 2.7099 3.8158 0.02036 2.3872 3.6598 0.02084 2.1335 3.5228 0.02391 1.9288 2.7006 3.8114 0.02033 2.3799 3.6561 0.02089 2.1277 3.5195 0.02402 2.6913 2.682 3.8026 0.02027 2.3655 3.6488 2.6637

3.807 0.02029 2.3727 3.6524 0.02094 2.1219 3.5161 0.024119 1.9193 3.3864 0.02914 0.021 2.1162 3.5127 0.02423 1.9146 3.3831 0.029289 1.91 3.3798 0.029441 3.506 0.024449 1.9053 3.3765 0.029589 0.0299

2.6728 3.7983 0.02024 2.3584 3.6451 0.02105 2.1105 3.5093 0.02434 3.794 0.02022 2.3513 3.6415 0.02111 2.1048 2.6547 3.7897

0.0202 2.3443 3.6379 0.02117 2.0992 3.5026 0.02456 1.9007 3.3732 0.02974 2.088 3.4959 0.02478 1.8915 3.3667 0.030059 1.887 3.3633 0.03021 3.36 0.030371 1.878 3.3567 0.030532 1.869 3.3502 0.03085 2.077 3.4892 0.025011 1.8825

2.6457 3.7855 0.02018 2.3373 3.6342 0.02123 2.0936 3.4992 0.02467 1.8961 3.3699 2.6368 3.7812 0.02017 2.3303 3.6307 0.02129 2.6191 3.7729 0.02015 2.3165 3.6235 0.02142 2.6016 3.7646 0.02014 2.3029 3.6163 0.02156 2.5844 3.7564 0.02014 2.2894 3.6092 2.6279 3.7771 0.02016 2.3234 3.6271 0.02136 2.0825 3.4925 0.024901 2.6103 3.7687 0.02014 2.3097 3.6199 0.02149 2.0715 3.4858 0.025131 2.593 3.7605 0.02014 2.2961 3.6128 0.02163 2.0606 3.4791 0.025361 2.5759 3.7523 0.02014 2.2827 3.6057 0.02177 2.0498 3.4725

2.066 3.4825 0.02524 1.8735 3.3534 0.030691

0.0217 2.0552 3.4758 0.025481 1.8646 3.3468 0.031012 0.0256 1.8601 3.3436 0.031179

2.5675 3.7482 0.02015 2.2761 3.6022 0.02185 2.0444 3.4692 0.025729 1.8557 3.3403 0.031339 2.559 3.7443 0.02015 2.2695 3.5986 0.02192 2.0391 3.4658 0.025849 1.8514 3.3369 0.031512

226

1.847 3.3337 0.03167 1.6917

3.204 0.03899 1.5606 3.0711 0.047926 1.4487 2.9333 0.058515

1.8427 3.3303 0.031842 1.6881 3.2007 0.039202 1.5576 3.0675 0.048184 1.4461 2.9296 0.05881 1.8383 3.3271 0.032009 1.6844 3.1974 0.039408 1.5545 3.0641 0.048432 1.4435 2.9259 0.059115 1.834 3.3238 0.032178 1.6808 3.194 0.039618 1.5514 3.0606 0.048679 1.4408 2.9224 0.059407 0.0597 1.8298 3.3205 0.032352 1.6772 3.1906 0.039828 1.5484 3.0571 0.048943 1.4382 2.9188 1.8213 3.3138 0.032692 1.6701 3.1839 0.04026 1.5423 3.0501 0.049451 1.8128 3.3073 0.033038 1.8045 3.3007 0.0334

1.8255 3.3172 0.03252 1.6737 3.1872 0.040042 1.5453 3.0537 0.049189 1.4356 2.9152 0.060001 1.433 2.9115 0.060301 0.0606 1.817 3.3106 0.032868 1.6666 3.1804 0.040472 1.5393 3.0466 0.049713 1.4304 2.9079

1.663 3.1771 0.040688 1.5363 3.0431 0.049973 1.4278 2.9043 0.060898 1.656 3.1704 0.041129 1.5303 3.0362 0.050491 1.4227 2.897 0.061512

1.8087 3.3039 0.033221 1.6595 3.1737 0.040909 1.5333 3.0396 0.050222 1.4252 2.9007 0.061195 1.8004 3.2973 0.033571 1.6525 3.167 0.041348 1.5273 3.0327 0.050748 1.4201 2.8934 0.061807

1.7962 3.2941 0.033748 1.6491 3.1635 0.041572 1.5244 3.0291 0.051013 1.4176 2.8897 0.062122 1.7921 3.2908 0.033928 1.6456 3.1602 0.041789 1.5214 3.0257 0.051268 1.4151 2.8862 0.062414 1.7881 3.2874 0.034112 1.6422 3.1567 0.042012 1.5185 3.0221 0.051541 1.4125 2.8825 0.062727 1.784 3.2841 0.0343 1.6387 3.1534 0.042227 1.5156 3.0186 0.051803 1.41 2.8788 0.063039 1.405 2.8715 0.063659 1.4 2.8642 0.064284 1.7799 3.2808 0.034478 1.6353 3.15 0.042458 1.5127 3.0151 0.052074 1.4075 2.8752 0.063349 3.008 0.052613 1.4025 2.8679 0.063977 3.001 0.053148 1.3976 2.8605 0.064603 2.994 0.053697 1.3927 2.8531 0.065244

1.7759 3.2775 0.034659 1.6319 3.1466 0.042688 1.5098 3.0115 0.052344 1.7719 3.2741 0.03485 1.6285 3.1432 0.042907 1.5069 1.7679 3.2708 0.035039 1.6252 3.1397 0.043141 1.7639 3.2675 0.035218 1.6218 3.1364 0.043368 1.5011 1.756 3.2609 0.035598 1.6152 3.1295 0.043833 1.4954 1.504 3.0045 0.052881

1.76 3.2642 0.035411 1.6185 3.1329 0.043601 1.4983 2.9974 0.053423 1.3951 2.8569 0.064917 1.7521 3.2575 0.035789 1.6118 3.1262 0.044057 1.4926 2.9904 0.05397 1.3902 2.8495 0.065546 1.7482 3.2542 0.035989 1.6085 3.1227 0.044297 1.4898 2.9868 0.054252 1.3878 2.8458 0.06587 1.7443 3.2509 0.036178 1.6053 3.1192 0.044533 1.7405 3.2475 0.036372 1.487 2.9832 0.054533 1.3854 2.8421 0.066193 1.383 2.8384 0.066525 2.831 0.067165 1.602 3.1158 0.044771 1.4842 2.9797 0.054803

1.7366 3.2442 0.036569 1.5987 3.1124 0.044998 1.4814 2.9761 0.055082 1.3806 2.8347 0.066845 1.7328 3.2409 0.036761 1.5955 1.7252 3.2342 0.037162 3.109 0.045241 1.4786 2.9726 0.05536 1.3782 1.729 3.2375 0.036962 1.5922 3.1056 0.045476 1.4758 2.9691 0.055646 1.3758 2.8273 0.067493 1.589 3.1021 0.045718 1.4731 2.9655 0.055932 1.3734 2.8236 0.06781 2.962 0.056207 1.371 2.82 0.068136 0.0565 1.3687 2.8162 0.068474 1.364 2.8087 0.069133 1.7214 3.2308 0.037361 1.5858 3.0987 0.045958 1.4703

1.7176 3.2275 0.03756 1.5826 3.0953 0.046198 1.4676 2.9583

1.7139 3.2241 0.037762 1.5795 3.0917 0.046454 1.4649 2.9547 0.056783 1.3663 2.8125 0.068797 1.7101 3.2208 0.037959 1.5763 3.0883 0.046691 1.4622 2.9511 0.057074 1.7027 3.2141 0.03837 1.57 3.0814 0.047181 1.4568 1.7064 3.2175 0.03817 1.5731 3.0849 0.046937 1.4595 2.9475 0.057364 1.3616 2.8051 0.069454 2.944 0.057654 1.3593 2.8014 0.069787 1.357 2.7976 0.07012 1.699 3.2108 0.038579 1.5669 3.0779 0.047433 1.4541 2.9404 0.057942

1.6954 3.2074 0.038783 1.5637 3.0745 0.047676 1.4514 2.9368 0.058229 1.3547 2.7939 0.070461

227

1.3524 2.7901 0.070791 1.3501 2.7864 0.071129 1.3478 2.7827 0.071467 1.3455 2.779 0.071803

1.269

2.642 0.084723 1.1364

2.342 0.11632 1.0123 1.9556 0.16289

1.267 2.6381 0.085101 1.1328 2.3327 0.11737 1.0095 1.9451 0.16424 1.265 2.6343 0.085477 1.1293 2.3232 0.11845 1.0067 1.9346 0.16559 1.263 2.6305 0.085851 1.1258 2.3137 0.11952 1.0039 1.9241 0.16695 0.1206 1.0011 1.9137 0.1683 1.903 0.16968

1.3433 2.7751 0.072153 1.2611 2.6265 0.086244 1.1223 2.3042 1.3388 2.7676 0.072834 1.2572 2.6188 0.087015 1.1154 1.3365 2.7639 0.073165 1.2552 1.3343 2.7601 0.07352 1.2533 2.6111 0.087782 1.1085 2.285

1.341 2.7714 0.072486 1.2591 2.6227 0.086616 1.1188 2.2947 0.12168 0.99836

0.1228 0.99561 1.8925 0.17106

2.615 0.087385 1.1119 2.2756 0.12388 0.99287 1.8819 0.17245 2.266 0.12499 0.99015 1.8713 0.17384 1.85 0.17665

1.3321 2.7563 0.073864 1.2514 2.6071 0.088167 1.1052 2.2561 0.12614 0.98744 1.8607 0.17524 1.3299 2.7525 0.074216 1.2494 2.6034 0.088542 1.1018 2.2466 0.12724 0.98475 1.3277 2.7487 0.074567 1.2475 2.5995 0.088935 1.0984 1.3255 2.237 0.12836 0.98208 1.8393 0.17806

2.745 0.074908 1.2456 2.5956 0.089327 1.0951 2.2273 0.12951 0.97941 1.8286 0.17949

1.3233 2.7412 0.075257 1.2437 2.5917 0.089717 1.0918 2.2175 0.13065 0.97677 1.8179 0.18092 1.3211 2.7374 0.075614 1.2418 2.5878 0.090106 1.0885 2.2078 0.13179 0.97413 1.8071 0.18236 1.3189 2.7337 0.07596 1.2399 2.5839 0.090494 1.0853 2.1978 0.13298 0.97151 1.7963 0.18381 1.3167 2.73 0.076305 1.2249 2.5522 0.093724 1.082 2.1882 0.13412 0.96891 1.7855 0.18526 0.1882 1.3146 2.7261 0.076665 1.2207 2.5435 0.094619 1.0788 2.1783 0.13531 0.96632 1.7746 0.18673 1.3124 2.7224 0.077017 1.2166 2.5346 0.09554 1.0756 2.1684 0.13648 0.96374 1.7638 1.3081 2.7148 0.077724 1.2085 2.5167 0.097396 1.0692 2.1487 0.13884 0.95862 1.306 2.711 0.078089 1.2045 2.5076 0.098342 1.0661 2.1386 0.14006 0.95608 1.3039 2.7071 0.078452 1.2005 2.4987 0.099281 1.0629 2.1288 0.14125 0.95356 1.3018 2.7033 0.078815 1.1965 2.4897 0.10022 1.0598 2.1188 0.14247 0.95105 1.2997 2.6995 0.079176 1.1926 2.4806 0.10119 1.0567 2.1088 0.14369 0.94855 1.3103 2.7185 0.077384 1.2126 2.5255 0.096477 1.0724 2.1585 0.13766 0.96117 1.7529 0.18968 1.742 0.19116 1.731 0.19266 1.72 0.19416 1.709 0.19567 1.698 0.19719

1.2976 2.6956 0.079535 1.1887 2.4714 0.10216 1.0536 2.0988 0.14491 0.94607 1.6869 0.19872 1.2955 2.6918 0.079904 1.1848 2.4624 0.10313 1.0506 2.0886 0.14617 0.94359 1.6758 0.20025 1.2934 2.6881 0.080261 1.1809 2.4533 0.1041 1.0475 2.0787 0.1474 0.94113 1.6647 0.2018 1.2913 2.6843 0.080626 1.1771 2.4441 0.10509 1.0445 2.0685 0.14866 0.93869 1.6536 0.20335 1.2893 2.6803 0.081008 1.1732 2.4351 0.10606 1.0415 2.0583 0.14992 0.93625 1.6424 0.20491 1.2872 2.6766 0.081361 1.1695 2.4257 0.10707 1.0385 2.0482 0.15118 0.93383 1.6312 0.20648 1.2851 2.6728 0.081723 1.1657 2.4166 0.10806 1.0355 2.0381 0.15244 0.93142 1.2811 2.665 0.082478 1.1582 2.3982 0.11008 1.0296 2.0176 1.62 0.20805 1.2831 2.6689 0.082101 1.1619 2.4075 0.10906 1.0326 2.0276 0.15375 0.92902 1.6088 0.20963 0.155 0.92664 1.5975 0.21123 1.279 2.6613 0.082845 1.1545 2.3889 0.1111 1.0267 2.0072 0.15631 0.92427 1.5862 0.21283

1.277 2.6574 0.08322 1.1509 2.3794 0.11215 1.0238 1.9969 0.15762 0.9219 1.5749 0.21444 1.275 2.6535 0.083592 1.1472 2.3702 0.11317 1.0209 1.9866 0.15892 0.91956 1.5635 0.21605 1.273 2.6497 0.083974 1.1436 2.3608 0.11422 1.271 2.6458 0.084344 1.018 1.9764 0.16023 0.91722 1.5521 0.21768 1.14 2.3514 0.11527 1.0152 1.9658 0.16158 0.91489 1.5407 0.21931

228

0.91258 1.5293 0.22095 0.83054 1.0622 0.29172 0.76181 0.55339 0.37653 0.91028 1.5178 0.2226 0.82862 1.0498 0.29371 0.7602 0.53972 0.37891 0.90798 1.5064 0.22426 0.82672 1.0372 0.29572 0.75859 0.52609 0.38129 0.9057 1.4948 0.22593 0.82482 1.0246 0.29773 0.75698 0.51249 0.38367 0.90344 1.4833 0.2276 0.82294 1.012 0.29975 0.75539 0.49874 0.38608 0.3909 0.3958 0.4007 0.90118 1.4717 0.22929 0.82106 0.99934 0.30178 0.7538 0.48502 0.38849 0.89893 1.4601 0.23098 0.81919 0.98667 0.30382 0.75221 0.47133 0.89447 1.4369 0.23439 0.81547 0.9613 0.30793 0.74907 0.44369 0.89226 1.4252 0.23611 0.81362 0.94859 0.89006 1.4135 0.23783 0.81179 0.93576 0.31207 0.74594 0.41607 0.88569 0.8967 1.4485 0.23268 0.81732 0.97405 0.30587 0.75064 0.45749 0.39336 0.31 0.7475 0.42991 0.39824

0.88787 1.4017 0.23957 0.80996 0.92297 0.31416 0.74439 0.40216 0.40318 1.39 0.24131 0.80814 0.91012 0.31627 0.74285 0.3882 0.40567 0.88351 1.3782 0.24306 0.80632 0.89732 0.31836 0.88135 1.3664 0.24482 0.80452 0.8844 0.32048 0.8792 1.3546 0.24659 0.80272 0.87151 0.3226 0.87707 1.3427 0.24837 0.80093 0.85858 0.32474 0.87493 1.3308 0.25016 0.79915 0.8456 0.32688 0.87282 1.3188 0.25195 0.79737 0.83265 0.32904 0.87071 1.3069 0.25376 0.79561 0.81958 0.3312 0.86861 1.2949 0.25557 0.79385 0.80654 0.33337 0.86652 1.2829 0.25739 0.7921 0.79346 0.33557 0.86444 1.2709 0.25922 0.79035 0.7804 0.33775 0.86237 1.2589 0.26106 0.78862 0.76723 0.33996 0.86031 1.2468 0.26291 0.78689 0.75408 0.34216 0.85826 1.2347 0.26477 0.78517 0.74087 0.34439 0.85622 1.2225 0.26664 0.78345 0.7277 0.34662 0.85419 1.2104 0.26851 0.78174 0.71448 0.34885 0.85217 1.1982 0.2704 0.78004 0.70121 0.3511 0.85016 1.1859 0.27229 0.77835 0.6879 0.35337 0.84815 1.1737 0.27419 0.77667 0.67454 0.35564 0.84616 1.1614 0.2761 0.77499 0.66118 0.35792 0.84417 1.1492 0.27802 0.77332 0.6478 0.36021 0.8422 1.1368 0.27995 0.77165 0.63443 0.36252 0.84023 1.1245 0.28189 0.83828 0.77 0.62094 0.36484 1.112 0.28384 0.76835 0.60748 0.36716

0.83633 1.0996 0.28579 0.7667 0.59403 0.36948 0.83439 1.0872 0.28776 0.76507 0.58046 0.37183 0.83246 1.0747 0.28973 0.76344 0.56691 0.37418

229

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