Electrical Characterization of N-Type Gallium Nitride Grown

by Metalorganic Vapor Deposition (MOCVD) on Sapphire

A Dissertation
Presented to the Faculty of the Graduate School
of
Yale University
in Candidacy for the Degree of
Doctor of Philosophy
Gabel Chong
Dissertation Director: Professor Mark A. Reed
December 2000
2000 by Gabel Chong
All rights reserved.
Abstract
Electrical Characterization of N-Type Gallium Nitride Grown by Metalorganic Vapor
Deposition (MOCVD) on Sapphire
Gabel Chong
2000
Gallium nitride and related alloys are wide bandgap materials attractive for high
temperature, high power and high frequency electronic applications. Although great
achievements have been made in optoelectronic devices, there is an incomplete
understanding of the basic material properties. In a highly defective materials system
such as this, proper assessment of the electrical parameters is needed. In this thesis, the
room temperature electrical characteristics of the intentionally n-doped and
unintentionally samples are examined. For the latter, capacitance voltage profiling reveals
a higher doped region near the substrate, and a transition layer towards lighter doping
towards the substrate. Two-layer and a modified two-layer analysis of thin films of
successive thickness are employed to the inhomogeniety along the growth direction of the
film. Temperature-dependent carrier concentration is analyzed using the charge-balance
equation. The Matthiesen rule is used to fit the experimental mobility values. The
additional effects of charged dislocation scattering and two-layer conduction are included
in the analysis, showing a dominant effect due to the latter, but the scattering effect from
dislocations seemed to be overestimated. At a wide range of temperature the samples
exhibit the properties of the classic impurity band conduction for a series of silicon
doping concentration. In the low temperature range, Mott hopping is observed and that
silicon concentration strongly affects the hopping behavior. In comparison, the
unintentionally doped samples show transport through the bottom layer.
Figure 1. 1 Cross-sectional TEM of Nichia LED structure.
Figure 1. 2 Microstructure Model of the GaN film. a) Side View showing relative tilt of
(0001) direction. b) Plan View showing twist of columns in (112n) directions.
Figure 1. 3 Schematic diagram of factors affecting lateral transport in gallium nitride.
Figure 2. 1 Home-built horizontal flow MOCVD growth chamber.
Figure 2. 2 GaN growth temperature vs time.
Figure 2. 3 Homebuilt variable temperature Hall cryostat
Figure 2. 4 Mercury probe profiling setup.
Figure 2. 5 A typical electrochemical profiling setup. Courtesy of Blood [ 2 ].
Figure 2. 6 Reactions in a plasma etching system.
Figure 2. 7 Photograph of etching system.
Figure 2. 8 Gas flow plan for system.
Figure 2. 9 Purge Gas Manifold (Left) and Corrosives Manifold (Right).
Figure 2. 10 Contaminants on chamber insulator likely due to reaction of Delrin.
Figure 2. 11 Post-etch corrosion showing moisture accumulation on etched metal mask.
Figure 2. 12 Etch rate vs DC Bias with fixed power, flow rate and pressure.
Figure 2. 13 Dependence on Etch Rate for two different flow rates (5sccm for Diamonds,
15 sccm for Squares).
Figure 2. 14 SEM micrograph of masked square with surround material etched away.
Figure 2. 15 SEM micrograph of etched pit.
Figure 2. 16 Microdisk lasers Fabrication Flow Process
Figure 2. 17 Short Etch Low100W 5sccm 80mTorr 250V
Figure 2. 18 Short Etch Low100W 5sccm 80mTorr 300V
Figure 2. 19 Long Etch with Metal Mask - 100W 5sccm 80mTorr 250V
Figure 2. 21 Long Etch Low100W 5sccm 80mTorr 325V
Figure 2. 22 CCD images of microdisk showing light scattering from edges.
Figure 2. 23 Output vs Input Power Threshold Measurement of Sample A (smooth
sidewalls) and Smaple B (rough sidewalls). Sample A has lower spontaneous to
stimulated emission threshold.
Figure 3. 1 Model of the Schottky Diode (Right Figure) and the Equivalent circuit (Left
Figure).
Figure 3. 2 Conductance (G) Vs Voltage (Inset) showing breakdown of Schottky Diode,
the extracted free carrier concentration N
D
is no longer accurate beyond breakdown.
Figure 3. 3 Hall Van der Pauw Sample Cross-sectional view (Top Figure), and Top view
showing clover-leaf shape (Bottom Figure).
Figure 3. 4 Map of interference fringes, Hall and CV data distribution on a quarter wafer.
Figure 3. 5 Distribution of Hall data for Unintentionally Doped samples showing poor
long-term reproducibility.
Figure 3. 6 Hall Carrier Density Vs Silane Flowrate for Silicon Doped Samples.
Figure 3. 7 Carrier concentration (n) by Hall Vs Surface net doping concentration (N
D
)
by C-V showing discrepancy in low surface concentration regime.
Figure 3. 8 Carrier Concentration Profile of a single unintentionally doped sample as
measured by C-V.
Figure 3. 9 Mercury probe C-V profiles of original unetched (circles) and 0.6microns
etched (triangles) unintentionally doped film.
Figure 3. 10 SEM micrograph of the 0.25 micron sample.
Figure 3. 11 SEM Micrograph of the 0.5 micron sample.
Figure 3. 12 Mercury probe C-V profile of three films of successive thickness (0.55, 1.1
and 2.2 microns).
Figure 3. 13 Fitting of the dopant profile shown previously in Figure 3.12.
Figure 3. 14 CV Profile of unetched and etched back silicon doped sample.
Figure 3. 15 Polaron Electrochemical Profiling data showing a silicon doped gallium
nitride depth profile (continuous) Vs an unintentionally doped sample (crosses)
Figure 3. 16 Fitting of (n
s *
) product Vs total film thickness using the Two-Layer
Model.
Figure 3. 17 Room temperature conductance vs thickness of successively etched back
silicon doped sample.
Figure 3. 18 Fitting of Hall mobility Vs total film thickness using the Two-Layer
Model.
Figure 3. 19 Plot of fitted Hall Carrier Density Vs total film thickness using the Two-
Layer Model.
Figure 3. 20 Fitting of (n
s
) product Vs total film thickness using the Modified Two
Layer Model(dashed line) with the Two-Layer Model (continuous line) as comparison.
Figure 3. 21 Plot of fitted Hall Mobility Vs total film thickness using the Modified Two
Layer Model(dashed line) with the Two-Layer Model (continuous line) as comparison.
Figure 3. 22 Plot of fitted Hall Carrier density Vs total film thickness using the Modified
Two Layer Model(dashed line) with theTwo-Layer Model (continuous line) as
comparison.
Figure 3. 23 Simulation of Composite Vs Surface (Top Layer) concentration, where
and N
D
of the bottom n
+
layer and the mobility of top layer are fixed.
Figure 3. 24 Simulation of the effect of variation of top layer doping on resulting
Composite Mobility due to Two-Layer Conduction.
Figure 3. 25 Simulation of Composite Concentration as a function of Bottom (n+) Layer
carrier concentration of an unintentionally doped sample.
Figure 3. 26 Simulation of Composite Mobility as a function of Bottom (n+) Layer
carrier concentration of unintentionally doped sample.
Figure 3. 27 Simulation of Composite Concentration as a function of Bottom (n
+
) Layer
thickness of an unintentionally doped sample.
Figure 3. 28 Simulation of Composite Concentration as a function of Bottom (n+) Layer
thickness of an unintentionally doped sample. Figure 3. 29 SIMS data for an
unintentionally doped sample.
Figure 3. 30 Mobility Vs Carrier Density showing the theory (with compensation ratios 0
and 0.4) with data.
Figure 4. 1 Energy diagram in the vicinity of the dislocation [24].
Figure 4. 2 Fraction of filled traps from Wiemann, Eastman et al[16]
Figure 4. 3 Fraction of filled traps from Leung, Wright et al[27] for the nitrogen rich
growth environment.
Figure 4. 4 Diagram of the Hall bridge
Figure 4. 5 Calibration of two cryostats.
Figure 4. 6 Hall carrier density vs inverse Temperature for undoped samples (1/2 and 2
microns) uncorrected (Top Figure). Hall carrier density vs inverse Temperature for
undoped samples (1/2 and 2 microns) corrected by the two layer model (Bottom Figure).
Figure 4. 7 Mobility vs Temperature for 2 micron undoped sample (top) without and
(bottom) with correction from the two-layer effect of the 0.5 micron sample.
Figure 4. 8 Top: Hall mobility vs Temperature for Si-doped samples (2 microns).
Bottom: Hall carrier concentration vs Temperature for Si-doped samples (2 microns).
Figure 4. 9 AFM scan of Sample 5 showing dislocations (top) dislocation density of this
sample is ~1-2 x109 cm-2. Profile of surface depression on AFM scan is shown in the
bottom figure.
Figure 4. 10 Mobility due to Phonon Scattering
Figure 4. 11 Mobility vs temperature for a) Samples 3 and b) Sample 4.
Figure 4. 12 Fitting of Sample 4 with Hall scattering factor.
Figure 4. 13 a) Fitting Undoped sample using phonon and ionized impurity scattering.; b)
Fitting Undoped sample using phonon and dislocation scattering of 10
9
/cm
2
; c) Fitting
Undoped sample using phonon and dislocation scattering of density 2 x10
8
/cm
2
, and
ionized impurity scattering (acceptor concentration 4x10
16
cm
-3
.
Figure 4. 14 Mobility vs carrier concentration considering the effect of dislocation
scattering and Gaskills [36] prediction.
Figure 5. 1 Conductance Successively Etched back of Silicon-Doped sample in the high
temperature regime.
Figure 5. 2 Room temperature conductance vs thickness of successively etched back
silicon-doped sample.
Figure 5. 3 Conductivity vs 1/T for silicon-doped samples from 20-290K showing E1 and
the transition to E2 or E3.
Figure 5. 4 Liquid Helium Temperature Sheet conductance vs room temperature Hall
concentration for silicon-doped samples.
Figure 5. 5 Conductivity vs 1/T for silicon-doped samples from 300 1.5 K showing
single activation is not a good fit for the data.
Figure 5. 6 Conductivity vs 1/T
1/4
for silicon-doped samples from 300 1.5 K showing
excellent fit for samples 3-5.
Figure 5. 7 Conductivity vs 1/T
1/2
for silicon-doped samples from 300 1.5 K showing
reasonable fitting, but not as good as Figure 5.6.
Figure 5. 8 Conductance of unintentionally doped sample of successive thickness in the
high temperature regime.
Figure 5. 9 Room temperature Conductance of unintentionally doped sample of
successive thickness vs thickness
Figure 5. 10 Conductance of unintentionally doped sample of successive thickness in the
low temperature regime.
Figure 5. 11 Liquid Helium sheet conductance vs room temperature sheet conductance
for unintentionally doped samples. Data point for lightly Si-doped sample #5 is also
included (shown by arrow).
Figure 5. 12 Conductivity vs 1/T for undoped samples.
Figure 5. 13 Conductivity vs 1/T
1/4
for undoped samples
Table 2.1 Boiling point of typical etch products which contains Fluorine (F) and
Chlorine (Cl).
Table 3. 1 Two Layer Analysis
Table 4. 1 Literature survey of electrical properties of unintentionally doped and silicon
doped gallium nitride.
Table 4. 2 Results of charge-balance equation fitting.
Table 4. 3 Physical Parameters of GaN
Table 4. 4 Temperature-dependence of various scattering mechanisms.
Table 5.1 Carrier Density and Mobility Values of Samples 1-5
Table 5.2 Correlation of Various Hopping Dependence
Table 5.3 Mott Hopping Parameters
Table 5.4 Mott Hopping Parameters for Samples 3-5 Using 2
nd
Approach are listed.
Table 5.5 Carrier Density and Mobility Values of Undoped samples
Table 5.6 Extracted hopping lengths for undoped samples.
1
Chapter 1 Introduction
1.1 Motivation
Gallium nitride and its related alloys are wide bandgap materials that are attractive for
high temperature, high power and high frequency electronic applications. Although great
achievements have been made in optoelelectronic [1] (such as UV and blue green lasers, light
emitting diodes and detector) as well as microwave [2] devices, there is an incomplete
understanding of the basic material properties. In order to engineer electronic devices for best
performance, doping level needs to be well controlled. In a highly defective material system like
the group III-nitride, proper assessment of the electrical parameters such as mobility and
background carrier density in relation to the material properties is needed to achieve this goal.
1.2 Electrical Properties of Gallium Nitride
The lack of a suitable substrate for gallium nitride is the first and foremost difficulty in
growing high crystalline quality material. The insolubility of nitrogen in gallium at equilibrium is
one of the reasons why only limited-sized bulk gallium nitride can be grown at extremely high
pressure of ~15 kbar of N
2
over gallium melt at a temperature ~1400 C [3]. The alternative
choice of substrate suffers lattice and thermal mismatch, as well as different stacking order from
III-V nitrides. Despite the 13% lattice mismatch with GaN and a different crystal structure,
sapphire is the substrate of choice for most metalorganic chemical vapor deposition (MOCVD)
methods due to its availability, low cost, surface morphology and high temperature stability
compared to other substrates such as silicon carbide. The crucial progress was made when
Akasaki [4] successfully employed a two-step buffer layer process to improve the quality of the
MOCVD gallium nitride film, a method which has been widely adopted by most MOCVD
processes, molecular beam epitaxy (MBE) to a lesser degree due to limited success [5]. The low
temperature buffer layer optimizes the transition between the substrate and the gallium nitride
2
layer by means of a high nucleation density and an alternate surface arrangement from the
substrate such that the nitride layer can assume its own structure. During the initial growth of the
nucleation layer, the film consists of disordered short hexagonal islands [4]. After the initial low
temperature buffer layer, a ramp up to high temperature anneals the film and nominal epilayer
growth can proceed. During the high temperature anneal, the crystalline quality of the buffer layer
dramatically improves. Different groups have reported single crystalline, mixed cubic and
hexagonal phases [6] and pockets of amorphous regions [7]. Nonetheless, the crystallinity and
morphology of first few hundred angstroms of the film significantly affect the quality of the final
film. Numerous studies have been performed to optimized the thickness of the buffer layer [7],
the temperature at which it is grown [4][7], its growth rate [9], the rate of the ramp up [9], and the
substrate preparation process in place of [HVPE] or before the buffer growth [10]. The structural
quality (mosaicity, morphology and extended defects characteristics) is very affected by this
bottom layer as shown in all these studies. The V/III ratio (adopted by many groups as the flow
rates in mols/min of nitrogen-bearing precursors to gallium-bearing precursors) [11] during
growth is also another parameter to be optimized, and greatly affects the film quality. The quality
and stoichiometery of the material could vary depending on the true active nitrogen and gallium
species in the growth environment as well as their growth dynamics.
The distinguishing feature in this material system is the high density of defects in the
material grown by various methods. Figure 1. 1 shows a typical cross-sectional transmission
electron microscopy (TEM) view of a gallium nitride film on sapphire. Such is an example of a
commercial light emitting diode (LED) structure by Nichia showing the highly defective
interfacial region between the substrate and the epilayer, and threading dislocations all
propagating along the growth direction. Many films contain higher concentrations of dislocations
3
of close to the substrate than other regions. These dislocations terminate within a certain growth
thickness of the film, while the surviving dislocations continue throughout the entire thickness
towards the film surface. Another type of defect of much lower density is the hollow "nanopipe"
grown by MOCVD [12] and other methods [13].
Figure 1. 1 Cross-sectional TEM of Nichia LED structure. (Courtesy of Ponce, Xerox Corp)
On some plan view TEM micrographs and atomic force microscopy (AFM) studies, the
dislocations appear to form the boundaries of cells [14][15]. These columnar structures may not
be polycrystalline in the strictest sense, but good structural coherence exists within each column.
The columns in the film can be visualized as being tilted with respect to each other in the (0001)
direction on a side view and twisted with respect to each other in (112n) directions on a plan view
(Figure 1. 2).
4
Figure 1. 2 Microstructure Model of the GaN film. a) Side View showing relative tilt of (0001) direction. b)
Plan View showing twist of columns in (112n) directions. From [16].
In a material with multiple structural defect types, understanding electrical properties is a
complex task. This thesis work is a participation of the on-going understanding of how the defects
manifest themselves electrically. The following diagram ( Figure 1. 3 ) can help visualize the
properties of the gallium nitride film that influence lateral electronic transport.
Current
Sapphire
2
m
0.2-0.5
m
Point Defects
Dislocations
Buffer Layer
Figure 1. 3 Schematic diagram of factors affecting lateral transport in gallium nitride.
As-grown gallium nitride is unintentionally doped n-type by hydride vapor phase epitaxial
(HVPE) and most MOCVD growth methods. For this reason, nitrogen vacancies were (and still
5
are by some) believed as the dominant native point defects which are donors. Recent calculations
show that gallium vacancies (acceptors) are likely to be the dominant defect for undoped n-GaN
grown in a nitrogen-rich environment [17]. Oxygen and silicon which are both shallow donors in
n-GaN can be the causes for unintentional n-type doping as supported by secondary ions mass
spectroscopy (SIMS) [18]. This is consistent with calculations that their formation energy in n-
type material is low [17]. Unlike silicon, which is a shallow donor, oxygen as a donor substituting
the nitrogen site is likely to be a localized donor state [14]. Carbon incorporated during growth
could add to the background acceptor level [19]. However, to this day, the nature of the
unintentional doping is still being debated.
As for n-type intentional doping, silicon (on the gallium site) is the most common shallow
donor of choice employed by various growth methods [20][21], although use of germanium
doping have been reported [20]. For MOCVD, inclusion of silane flow in the chamber during
growth has been successful, similarly with disilane [22]. A few reports have used group IV
elements like oxygen [23] (substituting the nitrogen site) as their intentional doping source.
In terms of the structural properties, the region close to the substrate can be highly
defective. A parallel electron conduction path to lateral transport is seen in HVPE films [25] due
to the defective interfacial region. Some studies of MOCVD grown material (e.g. [26]) suggest
similar behavior, although the physical origin of this layer is not well established.
Electrical activity at dislocations of gallium nitride has been seen with various methods. A
combination of AFM, TEM, cathodoluminescence (CL) and scanning capacitance microscopy
(SCM) are used to study the electrical properties of gallium nitride as related to the surface
morphology of the films [27] [28]. The SCM study [28] shows the presence of negative charge in
the vicinity of dislocations, which the authors suggested to be either acceptor-like states
6
associated with, or segregation of charged impurities near the dislocations. Wavelength-resolved
cathodoluminescence correlated with AFM and TEM measurements to conclude that the
inhomogeneity in the luminescence intensity of the films near band edge can be due to non-
radiative recombination near threading dislocations [27]. Electrical activity at these dislocations is
revealed after wet-etching under uv excitation which generates holes during the process. Under
moderately diffusion-limited conditions, the etching is impeded [15] leaving whisker-like
structures after etching.
Theoretical calculations of the nature of these dislocations are varied (that these
dislocations are charged [30] or electrically inactive [31]), and atomic resolution TEM studies are
emerging to observe the dislocation core structures [32]. One calculation has suggested the
threading edge dislocation cores be made up of gallium vacancies for n-type material under
nitrogen-rich growth conditions, whereas nitrogen vacancies should be energetically favorable
under gallium-rich environments [30]. Both cases show that electrons can accumulate at the
multiple-charged state defect levels. These charged dislocations could affect the transverse
mobility of the material.
Assessment of this effect in gallium nitride has been suggested by Wienmann et al [35]
using the formulation from Read [33] and Podor [34], and their later work (Ng et al [35]) is a
study on the temperature dependence of Hall data. Look has extended the study to calculate the
scattering due to dislocations and quantitatively fitted the variable temperature Hall data of two
MOCVD samples [37]. All of the above transport studies are based on the assumption that in n-
type material, each of the dislocations (most likely to be gallium vacancies) is made up of one
electron trap per dangling bond that accept carriers from the bulk and become negatively charged
when filled. A recent Z-contrast TEM study by Xin et al [32] shows that the threading dislocation
7
cores are likely to be made up of gallium vacancies, but the actual line density of the vacancies is
much less than predicted by the above theory. While the nature of the dislocations is still not fully
understood to allow unambiguous quantification of their scattering effect based on the above
assumption, the model describes the trends in Hall mobility vs carrier concentration and is
consistent with the electrical characteristics inferred by techniques (e.g. CL, SCM).
AFM measurements of MOCVD gallium nitride show that edge dislocations can form low
angle grain boundaries. In films that contain high dislocation densities, hexagonal columns are
seen by TEM and the individual dislocations could no longer be resolved [38]. In this case, the
material can be modeled as polycrystalline. Fehrer et al [39] analyzed their ECR MBE samples
which consist of a wide range of highly dislocated materials from very low doping (< 1x 10
15
cm
-
3
) to n-type ( 1x 10
18
cm
-3
), showing grain boundaries transport.
In terms of low temperature transport studies variable temperature Hall measurements
from room temperature to 4-10K (see for example [24] [37]) have been done to investigate the
effect of the defect band or the impurity band. A few reports have suggested hopping behavior in
the low temperature conductivity measurements [41], most without detailed analysis [42] [43].
The last chapter of this thesis is an in-depth study hopping conduction at liquid helium
temperatures. This should not be confused with detailed investigations related to hopping which
are done in a vastly different doping level and the high temperature regimes (> 100 K). The
examples are the investigation of highly compensated semi-insulating MBE gallium nitride [44]
and the study of reversed biased p-n junction of MOCVD GaN above room temperature [45].
Scatter amongst electrical data for unintentionally doped samples are huge due to different
compensation levels, interfacial layer properties and structural properties (dislocation densities).
Care should be taken in comparing films grown by different methods. The other variable is the
8
film thickness that can affect material quality (measured by x-ray diffraction or
photoluminescence) [46]. Nonetheless, comparing the various unintentionally doped materials,
MOCVD and HVPE samples reported have unintentionally doping level of ~1x 10
17
cm
-3
(mostly
due to residual silicon or high oxygen content as supported by SIMS data). The exceptions are the
outstanding from Nichia [46] and the Warsaw University group [47], both by MOCVD on
sapphire. These films have with room temperature free carrier density of ~1x 10
16
cm
-3
. In
general, the dislocation densities for MOCVD [48] and HVPE [49] films are low (best-reported
value of 2 x10
8
cm
-2
, whereas for MBE, the values are 1-2 orders of magnitude higher). The
significance of the growth conditions can affect the nature of the various types of defects and the
electrical properties.
The most two most outstanding data for wurzite gallium nitride achieved by Nichia and
University of Warsaw have achieved peak mobility of 4000 cm
2
/V-s ~ 70 K and mobility of ~900
cm
2
/V-s at room temperature. This is an implication that compensation is low, and the both
groups have indicated that the buffer layer growth conditions are very optimized. Although the
dislocation densities are not available, it is very likely that the values are one order magnitude
lower compared to the others. Moreover, the defective layer conduction may not constitute a large
fraction of the transport.
Finally, the relationship between mobility and free carrier density has been calculated
theoretically, mostly for 300 K. The calculations by Rode shows that without compensation, the
Hall mobility vs electron carrier concentration trend should be similar to GaAs [51]. The
anomalous behavior of low experimental values at low doping concentration is explained by a)
the bottom conduction pathway and b) structural defects.
9
1.3 Overview of this work
In this thesis, the room temperature electrical characteristics of the intentionally n-doped
and unintentionally samples are examined. For the unintentionally doped sample, capacitance
voltage profiling reveals a higher doped region near the substrate, and a transition layer towards
lighter doping towards the substrate. A two-layer and a modified two-layer analysis of thin films
of successive thickness are employed to the inhomogeniety along the growth direction of the film.
Hall measurements (from 77-300 K) of the intentionally n-doped and unintentionally doped
gallium nitride are also examined. Temperature-dependent carrier concentration is analyzed using
the charge-balance equation. The Matthiesen rule is used to fit the experimental mobility values,
both at room temperature and variable temperature to various theoretical scattering mechanisms.
The additional effects of charged dislocation scattering and two-layer conduction are included in
the analysis. The room temperature and variable temperature Hall data shows a dominant effect
due to the transition-layer, but the scattering effect due to charged dislocations seems to be
overestimated due to incomplete understanding of its electrical nature.
At a wide range of temperature, the silicon-doped samples exhibit the properties of the
classic impurity band conduction in the study of the transport characteristics of in gallium nitride
for a series of intentional doping concentration. In the higher temperature range, activation
energies for thermal generation of electrons from the silicon impurity band into the conduction
band are measured. In the low temperature range, Mott hopping is observed and doping
concentration for the silicon-doped samples strongly affects the hopping behavior. In comparison,
the unintentionally doped samples show transport through the bottom layer.
10
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43. P. Hacke et al, Japanese Journal of Applied Physics, 33 6443 (1994).
44. D. C. Look, et al Journal of Applied Physics 80 (5) 2960 (1996)
45. D. V. Kukensenkov et al Applied Physics Letters 72 p1365 (1998)
46. J. N. Kunnia, M. A. Khan, D. T. Olson, Journal of Applied Physics 73 4700(1993) S.
Nakamura, M. Senoh, S. Nagahama, Applied Physics Letters 67, 1869, (1995).
47. K. Pakua, J. M. Baranowski, M. Leszczy~ski, B. Suchanek and M. Wojdak, MRS Internet J.
Nitride Semiconductors Research 3 23 (1998).
48. D. Kapolnek, X. H. Wu, B. Heying, S. Keller, B. P. Keller, U. K. Mishra, S. P . DenBaars and
J. S. Speck Applied Physics Letters 67 1541 (1995).
49. L. T. Romano, B.S. Krusor, R. J. Molnar, Applied Physics Letters 71 2151 (1997).
50. K. Saarinen et al, Applied Physics Letters 73, (22) 3255 (1998).
51. D. K. Gaskill, K. Doverspike L.B. Rowland and D. Rode, International Symposium on
Compound Semiconductors edited by H. Goronkin (IOP Bristol) p101 (1995).
14
Chapter 2 Experimental Procedure
2.1 Introduction
This chapter is a description of the experimental methods done for this thesis work. It is
organized as follows, firstly the introduction of gallium nitride material growth by
MOCVD, followed by the extensive electrical characterization techniques (mercury
probe capacitance voltage (C-V) profiling, Hall measurements both room temperature and
variable temperature, low temperature conductivity measurements, electrochemical
profiling). Also included is a discussion of materials characterization by atomic force
microscopy (AFM) to determine structural defects and secondary ions mass spectroscopy
(SIMS) to determine chemical composition. Finally, the chapter ends with processing
techniques, especially reactive ion etching (RIE) for material fabrication.
2.2 Sample Growth
A brief description of the sample growth is presented in this section. The samples were
grown on c-plane sapphire in the home-built horizontal-flow metalorganic chemical
deposition (MOCVD) system at Yale University, with quartz as the growth chamber.
During growth the sample was placed in a silicon carbide coated graphite susceptor
heated by radio-frequency excitation. Trimethylgallium and ammonia were the host atom
sources for the undoped samples and silane was the gas for the n-type doping. The
trimethylgallium source was maintained at 5 t1C while palladium-purified hydrogen
was bubbled through it to provide the gallium-bearing molecular species. The nitrogen-
bearing species were supplied from the equilibrium vapors over liquid ammonia. No pre-
growth activation was applied to the sources. Hydrogen was used as a carrier gas at a
15
flow rate of 8slm to transport the growth precursors to the reaction chamber where the
system pressure was held at 100 Torr.
To begin the discussion, a standard two-step growth process was used for all
gallium nitride samples in the study. Akasaki and co-workers [1] pioneered this process
leading to improvement of morphology and defect density of the films via the two-step
growth method on lattice mismatched sapphire substrate. Before sample loading, the
sapphire substrate was subjected to standard solvent clean followed by a 15-minute soak
in 1:1 phosphoric and sulfuric acid mixture at 180C followed by a rinse in deionized
water. The sample was then loaded into the chamber, followed by a 10-minute in-situ
bake-out at 1040C with a hydrogen flow rate of 8 slm. A low temperature buffer layer of
thickness 25-30 nm was first deposited at 553-556 C for 55 sec, followed by a ramp up
to the nominal growth temperature of 1030C. The flow rate of ammonia was 4 slm (or
178 mmol/min) and trimethylgallium was 50 t3 mol/min for all samples, implying
nitrogen-rich growth environment having typical a V-III flow ratio of 3.5 x10
3
. For the n-
doped samples, the silane source was turned on during the high temperature growth and
its flow rate ranged from 4 x 10
-3
to 0.1 slm. The susceptor heater was switched off to
allow the sample to cool down, while the ammonia continued to flow until ~350 C to
prevent decomposition of the gallium nitride film. The average growth rate of 0.5 nm/sec
was attained at this temperature, as measured by weight change before and after growth.
A typical growth run is shown in Figure 2. 2 for growth temperature vs time.
The next section is devoted to the characterization techniques used to study the
films grown by the method discussed here.
16
RF Coil For
Heating
Susceptor
Gas Sources - NH
3
and (CH
3
)
3
Ga
Sample On
Graphite
Susceptor
Figure 2. 1 Home-built horizontal flow MOCVD growth chamber.
Temperature
C
minutes
Figure 2. 2 GaN growth temperature vs time
17
2.3 Electrical Setup
The following section describes the various techniques to characterize the electrical
properties of the gallium nitride epitaxial films. These methods are mercury probe
capacitance voltage (C-V) profiling, Hall measurements both room temperature and
variable temperature, low temperature conductivity measurements, electrochemical
profiling.
2.3.1 Variable Temperature Cryostat
A commercial Janis variable-temperature He
4
cryostat setup was used for the
conductivity measurements from room temperature to below 4K. The stainless steel
sample chamber was used as the compartment for the helium exchange gas, with the
outer liquid nitrogen dewar as the radiation shield. A ceramic ten-pin connector was
mounted on the flange, and thin magnum wires of low resistance were used to connect
these pins to the sample socket header. A calibrated Lakeshore silicon diode thermometer
DT470-SD controlled by the Lakeshore 330 Autotuning temperature controller was used
to measure the temperature of the exchange gas. Four-probe measurements were
performed using the HP 4145B Semiconductor Parameter Analyzer.
The following procedure was undertaken for using the helium cryostat for
variable-temperature zero magnetic field measurements. Pump-purging of the chamber
was done via the two-valve system for 5-6 times, with helium as the purge gas and a
vacuum of below 30 mTorr for each pump cycle. Then the sample was first cooled with
liquid nitrogen immersion of outer chamber. Liquid helium was transferred in the middle
dewar, and afterwards introduced into the sample chamber through needle valve at a rate
18
of 10 K drop every 10-20 minutes to ensure small thermal gradient during cool down.
When the temperature reached 4.2 K, the pump valve was adjusted to pump on the
sample chamber with the introduction of a small helium flow via the needle valve. In this
way, superfluid conditions at which temperatures below 1.5 K could be attained.
Conductivity measurements were done during the warm-up cycle. The temperature
control in the range of 1.5-4.2 K was manually done, and current sweeps were performed
using the HP 4145B Semiconductor Parameter Analyzer. Between 4 K to ~20 K, the
temperature rise was fast due to the liquid-gas transition of helium, the temperature was
adjusted manually by introducing slight flow into the sample chamber. From 20-295 K,
the helium valve was opened slightly to allow a small flow such that the sample and
vapor temperatures were almost equal. Automation of the measurement process was done
using the LabView data acquisition program which triggered the Semiconductor
Parameter Analyzer I-V sweeps every temperature interval of 10 K. The entire system
was allowed to warm up to room temperature as the helium evaporated.
2.3.3 Variable Temperature Hall Setup
The room temperature measurements were done in the Hall measurement setup with the
following components. Each sample was mounted on a sample stick/removable-flange
assembly inside a stainless steel chamber. The stainless steel sample chamber was
mounted between the two pole faces of the Harvey Well electromagnet capable of
manual switching between north and south polarities. The sample was always placed
such that the film surface was perpendicular to the magnetic field. The electromagnet was
controlled by a Kepco power supply at a setting of 25 V and 17 A. The commercial
19
electronics measurement unit from Keithley Instruments was made up of a 220
Programmable Current Source, Keithley 614 Electrometers and a switch box.
This same Hall setup was modified for the variable temperature measurements
from room to liquid nitrogen temperatures (Figure 2. 3) in conjunction with a home-built
cryostat system. The stainless steel sample chamber was the same used for the room
temperature measurements, but a different top flange was used to make a vacuum tight
compartment for the helium exchange gas. A ceramic ten-pin connector was mounted on
the top of the flange, and thin magnum wires of resistance were used to connect the pins
to the sample socket header. The temperature of the exchange gas was measured by a
Lakeshore silicon diode thermometer DT 470 SD using four-wire resistance technique at
a constant current of 10 A. The thermometer was calibrated to within t 1K of the
standard thermometer used in the Janis cryostat system. The thermometer was placed in
close proximity to the sample to ensure accuracy of the sample temperature.
The following procedure was undertaken for using this nitrogen cryostat for
variable-temperature Hall measurements. Pump-purging of the chamber was done via the
two-valve system for 5-6 times, with helium as the purge gas and a vacuum of below 30
mTorr for each pump down. Then the sample was first cooled down with immersion of
sample chamber in an external small dewar filled with liquid nitrogen. After the
temperature had reached equilibrium, the dewar was incrementally lowered to decrease
the level of liquid nitrogen immersion, causing a gradual rise in temperature of the
exchange gas in the chamber. At a rate of 10 K rise every 10-20 minutes, the temperature
dependent Hall measurements were made.
20
Figure 2. 3 Homebuilt variable temperature Hall cryostat
21
2.3.4 Mercury Probe C-V Setup
The MSI mercury-probe set-up was used to provide a temporary Schottky contact
for the C-V measurements without subjecting the film to high temperature metallization.
Each time the mercury contact was formed by mercury rising up two small glass tubings
to a lateral contact scheme through orifices on the holder chuck. With the sample faced
down towards the chuck, mercury was forced against the sample with a very weak
vacuum of 6 in of Hg as shown in the diagram (Figure 2. 4).
The measurement procedure was as follows. To ensure reproducibility of the
mercury dot area, the vacuum level of 6" Hg was used each time. The center dot with
area 2.03 x 10
3
cm
2
served as the Schottky contact, and the outer ring with area >30
times that of former means that its capacitance would not contribute significantly to the
measured values. A thermal oxide of thickness 5200 was used as calibration, the
extracted thickness from mercury probe C-V in accumulation is ~5500. Capacitance and
conductance were measured with a reverse-biased voltage sweep from 0 V to 40 V with
step voltage 0.1-0.5 V using the HP LCR meter, the peak-to peak ac excitation voltage
chosen to be 10mV with a frequency range between 10 Hz-1 MHz.
22
Sapphi re/
GaN
Mer cur y
Cont act s
Figure 2. 4 Mercury probe profiling setup
Figure 2. 5 A typical electrochemical profiling setup. Courtesy of Blood [ 2 ] .
23
2.3.5 Electrochemical Profiling (Polaron)
The Biorad PN4300PC Electrochemical C-V Profiler at Purdue University was used by
Vidyut Gopal to perform the measurements. The technique is unique in its ability to
provide carrier concentration measurements to unlimited depth in a multitude of
semiconductor structures. The electrolyte in which the sample is immersed is the etching
solution, and the process conditions are controlled by an applied potential across the
electrochemical cell. Since electrolytic etching depends on the presence of holes for n-
type semiconductors, illumination above bandgap is necessary. This process is similar to
the photoenhanced wet etching described in previous sections [6][7]. The electrolyte
provides an electrochemical Schottky contact without the need for metal Schottky
contacts. The depth to which the semiconductor is etched depends on the measured
dissolution current as a function of time:
dt I
A zF
M
d
t
dis

.
An electrochemical profiling setup similar to Figure 2. 5 was used. The
semiconductor wafer was pressed against a sealing ring such that a small dot about 1 mm
in radius was exposed to the electrolyte or the equivalent of the Schottky contact. For this
setup, etching was performed using a solution of 0.2 Molar of H
2
SO
4
under uv
illumination. At a small reversed bias and a small excitation ac voltage (30Hz in this
case), the capacitance of the surface space charge region in the gallium nitride was
measured across the platinum wire immersed in the electrolyte and the back contact
located in the dry portion of the wafer. Etching took place over hours for profiling the
entire 2 m films, and agitation was required to prevent the accumulation of bubbles on
the surface of the sample.
24
2.4 Other Measurements
2.4.1 Atomic Force Microscopy (AFM)
In the introductory chapter, the importance of structural defects in gallium nitride has
been discussed. The presence of threading dislocations could affect the transport
properties of the film, and an estimate of their average density is very useful. According
to Rosner et al [3] and Hansen et al [4] the atomic scale surface depressions revealed
from AFM measurements correspond to the threading dislocations on the as-grown
gallium nitride film. Thus, an AFM scan can provide a simple and non-destructive way to
count the average threading dislocations in gallium nitride.
The AFM technique takes images by running an atomically sharp tip over the
surface to be scanned and works as follows. The AFM tips are typically made from
silicon nitride or silicon and extend down from the end of a cantilever. A laser beam
reflects off the tip end of the cantilever and into a split photodetector which measures the
difference voltage between the upper and lower photodetectors. This signal is sent via a
feedback loop to a piezoelectric ceramic, which is mounted beneath the substrate to
maintain a constant cantilever deflection. The movement of the piezoelectric device
tracks the topography of the surface. The forces of interaction between tip and surface
can reveal the sample's topography in a three-dimensional way, down to the atomic level.
Typical forces between tip and sample are from 10
-11
to 10
-6
N.
For gallium nitride, the measurements need to be done in the tapping rather than
contact mode. In contact mode AFM, the dragging motion of the probe tip exerts a
lateral force on the surface. Because gallium nitride is a very hard material compared to
the tip, such motion can break the tip and imaging is hindered. This problem is solved by
25
the tapping mode AFM. With this technique, patented by Digital Instruments, the vertical
separation between the probe tip and the surface is rapidly oscillated such that the probe
taps the surface lightly at the bottom of each oscillation. The discontinuous contact
eliminates any damage to the tip.
The measurements were done at Stanford Nanofabrication Facility using the
Tapping Mode AFM by Digital Instruments Nanoscope Dimension 3000. The tapping
mode resonance frequency used was 220-320 kHz, and a scan rate of 2 Hz was employed
to provide scan surface of 1-3 m square using a silicon tip.
2.4.2 Secondary Ion Mass Spectroscopy (SIMS)
In order to gain good insight into chemical constituents of the film, and correlating them
to the electric properties, SIMS measurements are essential. The samples were sent to
Charles Evans & Associates for the measurements. For this characterization technique,
the principle is as follows. An energetic primary ion beam sputters a sample surface,
while the secondary ions formed in this sputtering process are extracted from the sample
and analyzed in a double-focusing mass spectrometer system. As the sample surface is
slowly sputtered away continuously, information is collected as a function of time (then
converted to depth), giving a depth profile of resolution 50 -100 . The bombarding
primary ion beam species useful in SIMS include Cs
+
, O
2+
, O
+
, Ar
+
, and Ga
+
at energies
between 1 and 30 keV.
In order to convert the secondary ion signals useful information like impurity
concentration in the film, careful calibration methods using standard films are needed.
Ion yields depend on the sputtering species (eg electropositive Cs
+
enhances the yield for
26
electronegative elements in the material). Moreover, the different elements to be analyzed
in a given sample or matrix show great variation in ion yield as much as the variation of
the same element in different matrices and thus separate conversion factors or relative
sensitivity factors RSF's were measured for each in the past. In order to eliminate the
matrix effect, CsM
+
ion detection is used rather than M
t
ions (M being the element to be
analyzed). In this process, the ion of interested is produced under Cs
+
primary ion
bombardment of the sputtered neutral atoms M. Given a series of known concentrations
of the element (e.g. implanted In) in a standard substrate (e.g. GaAs), the relative ion
yield of CsIn
+
is normalized to the CsAs
+
standard.
The limitations for the SIMS measurement technique are the following. The SIMS
detection limits for most trace elements are between 10
12
and 10
16
atoms/cc. If the SIMS
instrument introduces the analyte element, then the introduced level constitutes
background-limited sensitivity. Oxygen, carbon and hydrogen, present as residual gas in
vacuum systems, are all examples of elements with background limited sensitivity. As a
result, the background levels measured are usually high 10
16
, low 10
16
, and high 10
17
cm
-3
for O, C and H respectively as given by the Charles Evans & Associates.
Other considerations regarding the interpretation of the SIMS results are
important. Firstly, SIMS provides information of impurity concentration, and not the
electrically active impurity concentration, so care should be taken in the comparison of
the SIMS profile with that of the free carrier concentration. The other point is that if the
dopant specie is not a foreign impurity, but rather, a stoichiometric defect, SIMS would
not be able to detect it.
27
In this section, the various electrical measurement setups and other supporting
characterization techniques such as AFM and SIMS were discussed. The next section will
be devoted to fabrication techniques for structure and simple device realization.
2.5 Fabrication - Reactive Ion Etching System
2.5.1 Background
The process of dry etching involves various mechanisms that lead to a choice of different
approaches (ion milling, plasma etching, reactive ion etching etc). Within each specific
method of etching, the choice of controllable parameters (typically, power, pressure, flow
rate) can affect the results. This section provides the background and some of the
motivation for the approach taken for drying etching gallium nitride.
The variety of processes that can happen in the chamber as well as on the sample
surface for dry etching in general are as follows. Cracking of the chemical species into
reactive neutrals and ions by any form of excitation occurs, followed by positive ion
impingement and damage of the substrate. Adsorption of atoms, radicals and neutral
species occurs on the sample surface. The adsorbates can diffuse around the surface
sample or beneath the surface. Chemical reactions, which could be assisted by catalysts,
occur among cracked chemical species and the sample atoms. Competing reactions
among cracked species in the chamber environment also happen. Desorption of products
and by products of the reactions occur and physical sputtering of the above items and the
sample atoms play an important role in removal of the sample material.
28
Initial
e
-
impact
Inelastic
and Elastic
Collisions
Surface-Plasma
Reactions (Adsorption)
(Ion Bombardment)
(Desorption)
Principles of Dry Etching
Plasma
Figure 2. 6 Reactions in a plasma etching system.
In order to achieve common end goals of rapid etch rates (especially for deep
etches), high etch-selectivity, high spatial resolution and control over profile, a choice of
the approaches between the two extremes has to be made. Dry etching is the balance
between chemical etching, which utilizes the chemical reactions, and physical etching,
which relies on ions as the dominant etch mechanism. Chemical etching usually results in
materials selectivity, volatile etch products and low damage whereas physical etching
gives good anisotropy control and is insensitive to surface or geometry.
The detailed description of reactive ion etching (RIE) will follow in later sections,
only brief introduction is provided here. Essentially, the plasma inside the reactive ion
etcher is generated between two parallel plates via RF excitation of 13.6MHz. The
sample is placed on the powered electrode and is etched by chemical reactions between
29
the reactive species in the plasma and the sample. Sputter desorption of products is
enhanced by impinging ions that have a DC bias in the typical range of a few hundred
volts.
The challenge in gallium nitride processing is that there is no simple wet etch
except for particular crystallographic directions [5], or unless there is high concentration
holes generated in the material by UV excitation [6][7]. Therefore, dry etching is a crucial
option for device fabrication. Low chemical reactivity, reflected in its high
decomposition temperature at ~900
o
C and high bond strength (8.92eV/atom), results in
difficulty etching using the traditional plasma systems like RIE. The resulting etch rate of
~500 /min at moderate bias is about an order of magnitude lower than GaAs under the
same kind of conditions. Reports of GaN etching using reactive ion etching, chemically
assisted ion beam etching and high-density plasma etching (e.g. ECR, ICP, MRIE) have
been published (see review article [8]). In general, the chemical species density is a
limiting factor for etching gallium nitride in RIE. Higher etch rates and anisotropy can
only come about through higher physical bombardment energies, causing increased
roughness and damage to the sample. Among the different methods, etch rates are highest
(1-2 orders of magnitude higher than RIE) in high-density plasma systems (plasma
density 2-3 orders of magnitude higher than RIE). These are the electron cyclotron
resonance etching [16] in which the plasma is generated efficiently by a microwave ECR
source at low pressures, inductively coupled plasma in which the plasma is generated in a
dielectric vessel encircled by an inductive coil ICP [10] and MRIE [11]. The smoothest
morphologies can be attained in the chemically assisted ion beam etching (CAIBE)
30
systems [ 12 ] which is etching in a reactive gas ambient with a few hundred volts argon
ion beam directed at the sample.
Table 2.1Boiling point of typical etch products which contains Fluorine (F) and Chlorine (Cl). The
sublimation temperature is denoted by T
s
.
Element F Compound T boil (C) Cl Compound T boil (C)
Al AlF
3
1291 AlCl
3
177 (T
s
)
As AsF
3
-63 AsCl
3
63
Ga GaF
3
1000 GaCl
3
201
In InF
3
1200 InCl
3
300 (T
s
)
Ni NiF
2
1000 NiCl
2
973 (T
s
)
Si SiF
4
-86 SiCl
4
58
Product-desorption proves to be a limitation that affects the choice of gas
chemistry. When gallium nitride reacts with the etch gas, the typical limiting products are
the gallium-containing compounds with the boiling point of GaF
3
being 1000
o
C and
GaCl
3
being 201
o
C, the latter being more volatile. Compare these values to the volatile
nitrogen-containing products, NF
3
the boiling point of which is 129
o
C and NCl
3
of
which is 71
o
C. For that reason, chlorine based system is the choice for our system. Other
chemistries like bromine and iodine are very corrosive and relatively lower in purity than
chlorine gases, but have been used successfully in etching gallium nitride [13]. Other
chemistries like Cl
2
/H
2
[14] , Cl
2
/CH
2
/H
2
/Ar [15] , BCl
3
/H
2
/Ar [16] have been successful
in ECR and ICP etching for etching gallium nitride.
The motivation for using reactive ion etching is availability and relatively low
cost (also true for this work). Successful etching of gallium nitride using chlorine- based
31
chemistries (e.g. SiCl
4
/SiF
4
[17] , SiCl
4
/SF
6
[18 ], BCl
3
[18] , CHF
3
and CCl
2
CIF
5
[20] )
have been published. These chemistries and others exhibit higher etch rate with a
nitrogen additive in Cl
2
/N
2
and BCl
3
/N
2
due to charge exchange of N
2
+
with the reactive
gas species and resulting in an increase in ionization efficiency of the reactive gas.
Boron trichloride (BCl
3
) is the reactive gas used in our system. The experimental
threshold for RIE of gallium nitride for our system is ~150 eV below which no etching is
measurable. In a study of ionization cross-sections of BCl
3
by electron impact, electron
energies above 35 eV, the most abundant fragment is BCl
2
+
, followed by Cl
+
, and BCl
3
+
,
both of which have similar cross sections [ 24 ] . These fragments are heavy ions that can
provide physical component for etching without additives. One possible ion
fragmentation mechanism is: BCl
3
+ e
-
BCl
2
+
+ Cl
-
The chlorine neutral species are also produced in the glow discharge by the following
fragmentation: BCl
3
+ e
-
BCl
2
+ Cl + e
-
The etching of gallium nitride, enhanced by ion damage, can then occur with the chlorine
radicals: 2GaN + 6Cl 2GaCl
3
+ N
2
Although the chlorine-containing by-product is important, nitrogen-containing by-
products like NCl
3
in chlorine-based etching can be rate-limiting [21] :
GaN + 6Cl GaCl
3
+ NCl
3
This conclusion was drawn upon the results that NF
3
with its boiling point much lower
than that of NCl
3
could be the by-product in chlorine-based etching with fluorine-
containing reactive gas as additives.
32
2.5.2 System Description
The chamber design is a planar diode reactor in the center (its description will
follow in the next section) with four ports to the sides serving individual purposes. They
are: A) the pump port where the chamber connects to the turbomolecular pump via the
non-sealing throttle valve; B) the loadlock port where the manual gate valve isolates the
chamber from the loadlock chamber during standby mode; C) the viewport where the
quartz view glass is attached to the chamber for good viewing during sample transfer and
processing; and D) the analyzer port which has a T-connection ports for analysis tools
attachment in the future.
The general description of the system is provided here. The turbo pump is needed
to pump down the system to below 10
-6
Torr during standby mode to prevent moisture
accumulation and hence corrosion in the chamber. Since it takes time for the
turbomolecular pump to power up and down, it is not usually shut off during processing.
The fact that the inlet pressure of the turbo pump cannot exceed 300 mTorr (doing so
especially during reactive gas flow will destroy the bearings), great care is taken to set
upper limits for the flow rate and pressure. The former is controlled by the mass flow
controller ( MFC ), and the latter controlled by the throttle valve together with
commercial MKS pressure regulation system.
Great care has to be taken to keep moisture out of the chamber for chlorine-based
system. This is included in the design of the system itself, such as using the turbo pump
mentioned previously. Bearings are routinely regreased and constantly purged with
nitrogen during processing. The backing pump uses Fomblin oil that is filtered
33
chemically in the pump. The other important design is the loadlock system built to
provide isolation between the chamber and the atmosphere. The loadlock chamber is
usually pumped down to below 25 mTorr before the manual gate valve opens it up to the
sample chamber. Routine cleaning of the gate valve is needed to prevent leak into the
chamber. The docking of the sample holder into the slot inside the chamber is done via a
transfer stick.
D. Port Behind
the chamber
B. Loadlock Port
With Gate Valve
A. Pump Port
Connected to
Throttle Valve
and Turbo Pump
C. View Chamber
(see blue argon
plasma)
Figure 2. 7 Photograph of etching system
34
The gas manifold and system design is shown in Figure 2. 8. The system has been
designed for the provision of eight separate gas sources, which are grouped into two
separate manifolds The arrows indicate the direction of flow. The lines that are currently
installed are the boron trichloride, argon and nitrogen in the bottom manifold and oxygen
in the upper one. The sources are of 5.0 grade 99.999% purity and the moisture content
has to be low. House oxygen and argon are tapped as sources, but nitrogen is provided
separately for this system because it is used as the purge gas that for all the gas lines in
the manifold inside the cleanroom. Connection of nitrogen line to both sides of each
mass flow controller allows purging before taking it off-line for maintenance.
The detailed process procedure is provided in the process manual, but a few
points related to operation will be mentioned. Several valves have to be opened before
flow can be supplied to the system ensures safety working with the system. Chlorine-
containing residuals remain in the system after processing even when the reactive gas
flow is turned off. The system requires pump-purging the chamber and gas lines with
nitrogen 5 times before the standby mode.
Figure 2.9 shows the manifold in the Gas House, which consists of the inert purge
gas and the corrosive source. The Venturi valve is used to provide a 30 vacuum to pump
out the line. Each section of the manifold here can be access for pumping and purging
separately so that when sources are about to be changed no residue gas will be exposed to
the personnel. The vapor pressure of boron trichloride is 4.4 psi, and an absolute pressure
regulator made of Monel is used to prevent corrosion. The pneumatic valve, which
controls the gas flow, is interlocked with the switch on the top of the gas cabinet. This
35
system is connected with an interlock system that controls the emergency shut down of
all cleanroom gas lines.
Figure 2. 8 Gas flow plan for system.
36
Figure 2. 9 Purge Gas Manifold (Left) and Corrosives Manifold (Right). The purge gas manifold
provides nitrogen to PURGE the lines in the Corrosives manifold. The venturi valve relies on the
high flow and pressure from the nitrogen cylinder to create a small vacuum to PUMP the lines in the
Corrosives Manifold.
37
2.5.3 Chamber Design
The reactive ion etcher is a planar diode design with the upper electrode and chamber
walls grounded, and the lower (isolated) electrode powered by the radiofrequency
generator. The upper electrode is attached to the lid of the chamber by the support of the
threaded gas feedthrough assembly and two stainless steel tubings. The height of this
upper ground electrode assembly is adjustable so that the spacing between the grounded
the powered electrodes can be reduced for optimization of electric field. The process gas
is introduced into the chamber via the showerhead from the upper electrode. This design
ensures even flow distribution of the process gas covering the entire circular area directly
above the sample platen at the lower electrode. In this way, the maximum percentage of
the process gas is within the electric field and the reactive species (both chemical and
physical) are in close proximity of sample. Electrically, the upper electrode is grounded
with the chamber. Since it is anticipated that the maximum electric field occurs between
this electrode and the lower electrode directly beneath it, this electrode is cooled by
chilled water circulation.
The next part of the chamber design is the floating power electrode assembly that
is connected to the RF power supply. It contains the top hard-anodized aluminum surface
for corrosion prevention, bolted down to the stainless steel power electrode plate. A
threaded diameter copper rod is screwed into this plate on one end, and connected to
the power supply via the load-match tuning capacitor. The electrode plate is electrically
isolated from the surrounding grounded chamber via a Delrin spacer. The anodized
38
aluminum platen has been designed to the appropriate height for sample holder docking
into the chamber via the home-built loadlock system.
The maximum temperature of the platen is not measured, but care has to be taken
in operation and maintenance regarding heating. However, despite the cooling water
circulation on the platen, the Viton O-ring that serves to seal the cooling water
compartment between the platen and the stainless steel case needs to be replaced over
time. It is recommended that viton O-rings do not operate over 170 C for more than six
hours at a time. Similar concerns regarding overheating Delrin spacer which also melts
at 170 C. High power (>100W input power) processes should not be done continuously
for more than 30 minutes.
Unfortunately, a problem with using Delrin as the insulator material, despite its
mechanical and electrical properties, is that it is not really recommended for highly acidic
environments. It is an acetyl resin in the form of crystalline plastic made by the
polymerization of formaldehyde. Although it has not been tested under boron trichloride
plasma conditions, it is likely going to decompose from its original form. It is subjected
to direct ion bombardment during processing in BCl
3
, as seen by the plasma sheath
extended from the top of the sample platen down to the topmost 1cm of the cylindrical
spacer. (Figure 2. 10) Moreover, regular patterned brown residual is seen on the white
Delrin surface, which is likely to be caused by the electric field near the spacer. At
Cornell Nanofabrication Facility (CNF), a similar system utilizes Teflon as the
insulator spacer, which is not directly exposed to bombardment, and even then brown
deposits are seen after prolonged used. According to CNF, etch performance is hindered
39
when that happens, and regular scrubbing is necessary to rid the system of contaminants.
This means one has to physically open up the system and expose it to the moisture in the
atmosphere, which could introduce sources for corrosion for the chloride-based system.
The problem in our system is more severe, and the spacer will be replaced another
material that can withstand chemical and physical erosion (e.g. ceramic) in the future.
Figure 2. 10 Contaminants on chamber insulator likely due to reaction of Delrin.
Figure 2. 11 Post-etch corrosion showing moisture accumulation on etched metal mask.
40
2.5.4 Etch Characterization
In this section, the problems related to etching in this system will be described.
The issues of etch mask material, post-etch corrosion, excessive polymerization and
choice etch parameters will be discussed here.
The common choices for mask material for etching are photoresist, dielectrics and
refractory metal. However, at high DC bias excessive polymerization occurs when
photoresist is used as the mask, rendering it insoluble even in H
2
SO
4
/H
2
O
2
. At the time of
this work, the cleanroom facility did not have the capability to routinely deposit
dielectrics, leaving metal masks as the common choice. In choosing an appropriate mask
material for selectivity, the desorption-product should have a high boiling point. The
boiling points of the metal chlorides are shown in Table I. For a few typical metallization
schemes available, nickel works best from our experiments, giving selectivity to gallium
nitride >30:1.
The other important problem related to etching in this system is post-etch
corrosion. Moisture gradually accumulates on sample and metal mask within minutes due
to post chlorine etching corrosion even after chamber pump/purging. This sample is
viewed under scanning electron microscope (SEM) after etching (Figure 2. 11). Post-etch
soak has been experimented using with 10% ammonium hydroxide NH
4
OH, buffered
oxide etchant (BOE) overnight soak, but the most effect method is a 30 min soaking in
hot deionized water.
Next, the problem of excessive polymerization in this system is addressed. A
series of unpatterned gallium arsenide samples were etch for half an hour and
41
roughness/grass on the sample was found and the features did not vary with etch
parameters. On the etched samples, carbon contamination after etch was high as
confirmed by Auger electron spectroscopy. The excessive polymerization was likely due
to the Delrin-spacer in direct contact with the plasma, making it a contamination source.
The solution is the descumming of the chamber using low power oxygen plasma either
before sample loading or after etching. Short etches of 15 minute-duration were
performed.
In terms of etch parameters, DC bias, RF power, chamber pressure, gas flow rate
were varied, shown in the plot of Etch Rates vs DC bias in Figure 2. 12. Typical etch
rates of <500/min of gallium nitride were achieved. The conditions were 40mTorr base
pressure, flow rate of 10sccm of BCl
3
and the RF power of 100 t20W. As mentioned
before, the DC bias was used as the variable parameter and was manually tuned such that
reflected power was below 2.5W. The increase in etch-rate with DC bias is consistent
with the picture that physical sputtering is a dominant component of the RIE etching
process [8]. The results could be compared to a recent study of the etching fundamentals
of gallium nitride using in-situ monitoring of the etch-product GaCl
2
mass peaks as a
function of with respect to dc bias and power for a chlorine-based ECR etching process
[25]. Product formation is favored with an increase in incident energy (as measured by
DC bias).
In Figure 2. 13, the increase in etch rate with respect to increasing pressure is
shown. The flow rate and manual DC bias were held constant during the experiments.
When the RF power was held between 100 t20 W, loadmatch tuning was done manually
42
instead of automatically. Even though the reflected power was always kept at a level of
below the limit set by the power supply for safe operation, the reflected power was not at
its peak tuning parameters. At a given high RF power and high DC bias, high reflected-
power occurred. However, the DC bias was kept at the desired set level while pressure of
the chamber was varied. This was opposite to what could happen in most systems
whereby the automatic DC self-bias would decrease with pressure due to the increasing
mean free path of the ions. Moreover, an increase in pressure should in principle reduce
desorption of volatile products and thereby reducing the etch rate. Since the plasma
density of our RIE could be low for etching gallium nitride under the typical etch
conditions, the end effect of increasing pressure in our system was the increase in etch
rate through increasing the number density of reactive species.
The increase in flow rate was investigated to see if the concentration of reactive
species could be increased. In the graph of etch rate vs pressure (Figure 2. 13), the effect
of increased flow rate showed no notable difference, implying that residence time of the
species did not varied very much in these conditions. Under these conditions the increase
in flow rate did not increase density of the reactive species. Typical SEM pictures of
etched samples are shown in Figure 2. 14 and Figure 2. 15, showing quite good etched
surfaces. The imperfection in the mask was transferred in the etch process. At this DC
bias, no major sidewalls striations could be seen.
43
0
50
100
150
200
250
300
350
-300 -200 -100 0
DC Bias in V
E
t
c
h

R
a
t
e

i
n

A
n
g
s
t
r
o
m
s
/
m
i
n
Figure 2. 12 Etch rate vs DC Bias with fixed power, flow rate and pressure.
Pressure Dependence on Etch Rate
0
50
100
150
200
250
300
350
0 20 40 60 80 100
Pressure in mTorr
E
t
c
h

R
a
t
e

i
n

A
n
g
s
t
r
o
m
s
/
m
i
n
100W 100W
5sccm 15sccm
-250V -250V
Figure 2. 13 Dependence on Etch Rate for two different flow rates (5sccm for Diamonds, 15 sccm for
Squares).
100W
10sccm
40mTorr
44
Figure 2. 14 SEM micrograph of masked square with surround material etched away.
Figure 2. 15 SEM micrograph of etched pit.
100W
5sccm
30mTorr
-250V
100W
5sccm
80mTorr
-250V
45
2.6 Application of RIE
2.6.1 Microdisk Lasers
The main motivation for using microdisk lasers is the low lasing threshold for
Whispering Gallery Mode whereby Q factor of the cavity (Energy stored in the
cavity/Energy loss per cycle of light in the cavity) is very high [26] due to total internal
reflection. Many examples of microdisk lasers were fabricated in semiconductor system
(GaAs, InAs). Moreover, gallium nitride theoretically can have low stimulated emission
threshold for systems designed with two-dimensional spatial confinement [27].
Furthermore the bandgap of the gallium nitride system is a direct one spanning the wide
range of wavelength up to the UV regime, making it attractive for short wavelength laser
application [28]. Compared to conventional Fabry-Perot cavity lasers in gallium nitride
[29][30], the microdisk lasers fabricated here has lower lasing threshold due to microdisk
cavity effect and pumping configuration [31] [32].
The process flow diagram is shown in Figure 2. 16, and the specifications for the
gallium nitride microdisk were as follows. Nominally two-micron etch depth was
required for complete removal of material not protected by the mask. For the etching
conditions, this implied reasonable etch rate, so a higher a power was chosen while the
mask had to hold up during the entire etching process. Estimated mask selectivity >15:1
was required so that metal mask deposition needed was no more than a 4000 . The
critical dimension was ~2 m for large feature sizes of a few hundred microns in
diameter. Smooth sidewalls would be desirable, implying low etch damage needed and
therefore, low DC bias was needed while achieving reasonable etch rate. Finally, the
sidewall profile was not really specified and may not be too critical for this set of
46
optically pumped mcirodisk lasers because the optical mode resides mostly within a few
thousand angstroms of the film surface due to lack of optical confinement in the design.
1 Growth
2m
GaN epilayer
Sapphire
Substrate
Buffer layer
uv
2 Optical Lithography
Optical Mask
Photoresist
4 Lift-Off
Nickel Mask
5 Reactive Ion Etching
+ + + +
3 Metallization
Nickel
Developed
Photoresist
Figure 2. 16 Microdisk lasers Fabrication Flow Process
The mask material used in the process was required to hold up during the entire
long etch process. In the literature, metal masks of nickel (any others) or dielectric masks
are used in chlorine based etching. In terms of etch selectivity ( mask etch time: GaN etch
time ), the two thermal evaporated metal masks were compared and were found to be
47
2.8:1 for gold and 30:1 for nickel. Photoresist was also attempted, and after 10 min
exposure to the plasma at >300V bias, the resist turned into an black residual product
that could not be removed by soaking overnight in piranha (sulfuric acid and peroxide
mixture).
Figure 2. 17 Short Etch Low100W 5sccm 80mTorr 250V
Figure 2. 18 Short Etch Low100W 5sccm 80mTorr 300V
The optimal etch parameters used for microdisk laser fabrication was 100W
5sccm 80mTorr -250V, yielding an etch rate of 320 /min. The long etch time was a
48
crucial determining factor for the choice of high etch rate parameters (relatively moderate
bias and pressure). The DC bias values were picked to ensure low damage to the
sidewalls. As a comparison, another sample was fabricated with the same parameters
except for the DC bias, which was 325V. An important point is that the sidewall
roughness for the short etches (15 min) vs the duration to etch the gallium nitride epilayer
completely were very different for 325V sample. The short etches shown in Figure 2.
17 and Figure 2. 18 contained imperfection due to transfer of mask imperfection into the
etch material, but little striations could be seen. In long etches the rough sidewalls were
due to extended bombardment as well as mask erosion (Figure 2. 19 - Figure 2. 21).
In general the problem of using a slow etch plasma process (e. g. RIE) for long
etches at high bias is the erosion of the etch mask as compared with cleaner techniques
like CAIBE which can give mirror smooth surfaces for laser facets [33].
49
Figure 2. 19 Long Etch with Metal Mask - 100W 5sccm 80mTorr 250V
Figure 2. 20 Long Etch Low100W 5sccm 80mTorr 250V
50
Figure 2. 21 Long Etch Low100W 5sccm 80mTorr 325V
2.6.2 Optical Performance of Microdisk Cavity
The fabricated microdisk lasers were optically excited. Optical pumping was
performed perpendicular to the disk by the third harmonic (= 355 nm) or the fourth
harmonic (=266nm) of a Q-switched Nd:YAG laser. The output light emission form the
structures were collected by a reflecting objective (NA=0.5) located 80 from the surface
normal, dispersed by using a 0.5 m focal-length spectrometer and detected by a gated
intensified charge-coupled device detector for output intensity measurements from a
specific part of the microdisk. For imaging the spatial information of the light output
from a side view, rather than the reflecting objective only the camera lens were used.
51
The fact that the edge of sample A (the smoother of the two) is not perfect
contributes to scattering loss. This is revealed in the CCD images of showing the
intensity of the 375 nm stimulated emission/lasing peak light output for input intensity of
10 MW/cm
2
in Figure 2. 22. If there is no diffused light from the scattering surfaces, the
light should come out tangentially at two spots.
Comparing the smooth and rough edged microdisks, output vs input power
measurements were made. The output intensity of the two samples for the peak intensity
of 375 nm light is shown as in Figure 2. 23. From these two plots, the sublinear to
superlinear back to sublinear regimes on this log-log plot turnover (the lasing threshold)
happens at 1MW/cm
2
for sample A. For sample B continued increase in pump power
resulted in disintegrating the sample. The results of Sample A are explained by the well-
described spontaneous emission (SP) (first sublinear regime at low input power) to
stimulated emission (SE) (superlinear regime) to lasing (the sublinear regime at high
input power) where gain-pinning occurs [34]. Comparison of the two samples (see
arrows) rougher sample seems to have a lower spontaneous to stimulated emission
threshold. From the experiments in which the pumping beam is ring-shaped with varying
diameters, the SP to SE emission threshold correlates well with lasing threshold [35].
From those experiments one can infer that the sidewall roughness increases the lasing
threshold and reduces the performance of the microdisk laser. However, both samples are
flood pumped, the most favored mode excitation are not closest to the circumference and
therefore may not be the most optimal experiments to compare the effects of scattering
due to rough sidewalls.
52
Figure 2. 22 CCD images of microdisk showing light scattering from edges.
53
SampleA Sample B
GaN
Laser Beam
To Detector
SE Peak Intensity
of Sample A
-250V bias
1
10
100
1000
10000
0.1 1 10 100
Pump Power (MW/cm^2)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Lasing
Threshold
SE Threshold
54
Figure 2. 23 Output vs Input Power Threshold Measurement of Sample A (smooth sidewalls) and
Smaple B (rough sidewalls). Sample A has lower spontaneous to stimulated emission threshold.
2.7 Summary
In conclusion, the experimental methods used in this thesis work were discussed.
Based on the information in this chapter regarding materials development, the next three
chapters will be devoted to the measurements by the characterization techniques
described here.
SE Peak Intensity
of Sampl e B
-325 V bi as
10
100
1000
10000
100000
0.1 1 10 100
Pump Power (MW/ cm^2)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
SE Threshold
55
2.8 Reference
1. I. Akasaki, Journal of Crystal Growth 98 p109 (1989).
2. P. Blood, Semiconductor Science and Technology 1 7 (1986).
3. S. J. Rosner, E. C. Carr, M. J. Ludowise, G. Girolai, H.I. Erikson, Applied Physics
Letters 70 420 (1997).
4. P J. Hansen, Strausser, Y E. Erickson, A N. Tarsa, E J. Kozodoy, P. Brazel, E G.
Ibbetson, J P. Mishra, U. Narayanamurti, V. DenBaars, S P. Speck, J S. Applied
Physics Letters. v 72 n 18 May 14 1998. p 2247-2249
5. D. A. Stocker and E.F. Schuber, J. M Redwing, Applied Physics Letters Vol 73, No.
18, 2654 (1998).
6. M. S. Minsky, M.White and E.L. Hu, Applied Physics Letters Vol 68, No. 11, 1531
(1996).
7. C. Youtsey and I. Adesida, G. Bulman, Applied Physics Letters Vol 71, No. 15, 2151
(1997)
8. J C. Zolper, R J. Shul, Implantation and dry etching of group-III-nitride
semiconductors MRS Bulletin. v 22 n 2 Feb 1997. p 36-42
9. S. J. Pearton, C. R. Abernathy and F. Ren, Applied Physics Letters Vol 64, No. 17,
2294 (1994).
10. S. A. Smith et al Applied Physics Letters Vol 71, No. 25, 3631 (1997).
11. G. F. Mclane and L. Casas, S. J. Pearton and C. R. Abernathy. Applied Physics
Letters Vol 66, No. 24, 3328 (1995).
12. A. T. Ping, C. Youtsey, and I. Adesida, M. A. Khan and J. N. Kuznia. Journal of
Electronic Materials Vol 24, No. 4, 229 (1995).
13. B. Vartuli, S. Pearton et al, Applied Physics Letters Vol 69, No. 10, 1426 (1996).
14. H. Cho, C. B. Vartuli et al, Journal of Electronic Materials Vol 27, No. 4, 166 (1998).
15. R. J. Shul and A. J. Howard, S. J. Pearton, C. R. Abernathy, C. B. Vartuli, Journal of
the Electrochemical Society, Vol 143, No. 10, 3285 (1996).
16. S. J. Pearton, C. R. Abernathy and F. Ren, Applied Physics Letters Vol 64, No. 17,
2294 (1994).
17. I. Adesida et al, Applied Physics Letters Vol 63, No. 20, 2777 (1993).
18. G. Franz, C. Hoyler, J. Kaindl, Journal of Vacuum Science and Technology B Vol
14, No. 1, 126 (1996).
56
19. M. E. Lin, Z. F. Fan, A. Ma, L. H. Allen and H. Morkoc, Applied Physics Letters Vol
64, No. 7, 887 (1994).
20. H. Lee and J. Harris, Journal of Electronic Materials Vol 27, No. 4, 185 (1998).
21. F. Karouta et al, Electrochemical and Solid-State Letters Vol 2, No. 5, 240 (1999).
22. M. E. Lin, Z. F. Fan, A. Ma, L. H. Allen and H. Morkoc, Applied Physics Letters Vol
64, No. 7, 887 (1994).
23. H. Lee and J. Harris, Journal of Electronic Materials Vol 27, No. 4, 185 (1998).
24. Q. Jiao, R. Nagpal,P. Haaland, Chemical Physics Letters Vol 265, 239(1997).
25. Eddy C., MRS Internet J. Nitride Semicond. Res. 4S1, G10.5 (1999).
26. R. E. Slusher, S. L. McCall, U. Mohideen, A. F. Levi, Microdisk lasers Proceedings
of SPIE -The International Society for Optical Engineering, Published by Society of
Photo-Optical Instrumentation Engineers, Bellingham, WA, USA. v 2145 p 36-45
(1994).
27. S. Bdinyk, T. J. Schmidt, B. D. Little, J. J. Song, Applied Physics Letters 74, 1
(1999).
28. S. Nakamura, Proceedings of SPIE - the International Society for Optical
Engineering. v 3749 1999. p 2-3
29. R. Dingle, K.L. Shaklee, R. F. Leheny, R. B. Zetterstrom, Applied Physics Letters
19, 5 (1971).
30. X. H. Yang, T. J. Schmidt, W. Shan, J. J. Song, and B. Goldenberg, Applied Physics
Letters 66, 1 (1995).
31. S. Chang, N. Rex and R. K. Chang, G. Chong and L. J. Guido, 1999 Conference on
Lasers and Electro Optics.
32. S. Chang, N.B. Rex, R. K. Chang, G. Chong and L. J. Guido Applied Physics Letters
v 75 n 2 166 (1999).
33. F. Binet et al, Applied Physics Letters 72, 960 (1998).
34. A. E. Siegman, Lasers (University Science Books, Sausalito, 1986).
35. N. Rex (private communication).
57
Chapter 3 Two-Layer Effect
3.1 Introduction
In this chapter, the effect of the bottom n
+
layer (between the epi-film and the buffer
layer) is quantified by capacitance-voltage (C-V) and Hall measurements at room
temperature for intentionally n-doped and unintentionally doped gallium nitride. The
issue of variability within a sample and among different runs is assessed by these two
techniques at room temperature. This will be important in comparing samples at low
temperatures to be discussed in chapters to follow. The discrepancy in carrier
concentration measured by these two methods for unintentionally doped samples will be
explained by the vertical inhomogeneity along the thickness of the film due to the bottom
layer. Measurements of the carrier density profile by a) mercury probe Schottky C-V on a
single sample, b) mercury probe C-V on samples with successive thickness, c) mercury
probe C-V on successively etched back samples and d) electrochemical etching will be
presented. In general, the profile shows two layers of different doping levels with
electrically non-abrupt boundaries. Using a two-layer model and a modified two-layer
model, Hall measurements of samples with successive thickness will be analyzed. The
corrected values of Hall mobility Vs carrier density enable us to continue the discussion
of the electrical properties at lower temperatures in the next two chapters.
58
3.2 Experimental Procedures
3.2.1 Capacitance-Voltage Measurement Technique
Differential Capacitance-Voltage (C-V) measurements are performed to measure
the carrier concentration close to the surface of the Schottky contact. If desired, the depth
profile of the carrier density can be measured by continuous sweeping of the reverse-bias
until the Schottky contact breaks down. The reverse-biased voltage V on the Schottky
barrier produces a space-charge region thickness W with capacitance
dV
dQ
C
s
where
Q
s
is the semiconductor charge. The incremental charge can be expressed as
dW W qN dQ
d s
) ( where N
D
(W) is the carrier density at the edge of the space-charge
region. This region can also be modeled as a parallel plate capacitor with capacitance
W
A
C
0

. Differentiating this expression of C with respect to voltage, and combining

with the former expression of C gives the well-known method to extract carrier density
profile by differential capacitance:
) / (
) (
2
0
3
dV dC A q
C
W N
d

.
In this formulation, the contribution from minority carriers is assumed to be
negligible and the majority carriers consist of the donors that are almost fully ionized.
The differential capacitance measures the incremental charge variation at the edge of the
space-charge region as the ac probe voltage exposes more or less ionized donors. The
charges that actually move in response to the ac voltage are the free carriers, not the
donor ions. Therefore, if the doping profile has a large gradient, the majority carrier
distribution will not be abrupt due to screening. Thus the spatial resolution (~ a few
59
Debye lengths) poses a limit on the accuracy of the measurement. Simulations of the
electrical properties of a silicon n-n
+
junction have shown that poor agreement between
majority carrier and actual doping profile if the doping profile is abrupt. However, good
agreement occurs for a doping step of low-high ratio of 1:10 that linearly ramps within 5
Debye lengths of the higher doping density [1]. For n-GaN of relative dielectric constant
~10.4, the doping gradient of our film typically varies between 1 x 10
16
- 1 x 10
17
cm
-3
.
As long as the profile steps do not vary more than 5 Debye lengths (5x 0.012 m) of the
higher doping, the profile should be accurate.
The Schottky diode is modeled as the circuit in Figure 3. 1. The capacitance (C)
of the space-charge region is in parallel with the conductance ( G ) due to leakage current
through the Schottky diode. Large series resistance (r
s
) from the substrate can be present
in materials with high resistivity or high contact resistance (serious for undoped samples).
However, the measured values of capacitance and conductance (C
m
and G
m
) are shown in
the equivalent circuit Figure 3. 1. Both (C
m
and G
m
) can be expressed as a function of C,
G, r
s
and frequency f. From the conductance Vs voltage characteristics (with zero-bias as
starting voltage), the data can be considered accurate up to the point where the condition
r
s
G <<1 is no longer met. The effect of leakage current on the extracted carrier
concentration is shown in a typical conductance Vs reverse-bias (inset) graph, with the
corresponding carrier concentration Vs depth in Figure 3. 2. The carrier concentration
data is affected by the irregularities of the reverse current and the Schottky breakdown
characteristics, rendering profiling inaccurate beyond the indicated voltage.
60
Figure 3. 1 Model of the Schottky Diode (Right
Figure) and the Equivalent circuit (Left
Figure). The relationship between these two
circuits are expressed as follows:
2 2
2
2 2
) 2 ( ) 1 (
) 2 ( ) 1 (
) 2 ( ) 1 (
C fr G r
fC r G r G
G
C fr G r
C
C
s s
s s
m
s s
m

+ +
+ +

+ +

Figure 3. 2 Conductance (G) Vs Voltage (Inset) showing breakdown of Schottky Diode, the extracted
free carrier concentration N
D
is no longer accurate beyond breakdown. Also shown is the good
agreement between uncorrected and corrected N
D
due to series resistance effect.
61
The limitation of profiling moderately to highly doped samples is the small
depletion width given by
0
1

D
N q
kT
W . It implies earlier breakdown of the
Schottky diode at smaller reverse-bias, the higher the doping level N
D
. For the undoped
samples where the carrier density profile gradually increases with depth, as shown in
etched-back Hydride Vapor Phase Epitaxy (HVPE) and MOCVD samples, the space-
charge width gets smaller and smaller with incremental increase in reverse-bias sweep.
To ensure that the measured values are not affected by the series resistance of the
film, the condition that 2 f r
s
C <<1 needs to be satisfied. At high frequencies, large
errors can occur due to series resistance, so usually low frequencies are favored. From
our experiments, the value for r
s
was measured at high forward-bias of the Schottky
junction where the depletion was minimal. In a frequency range of 1KHz 1MHz
commonly chosen due to noise performance, the above criteria was met. In general, the
difference between capacitance values measured at 1MHz and 1KHz was <4%. For an
undoped sample the forward-biased series resistance value was measured to be 500 .
The problem with epitaxy on insulating substrates is the issue of lateral contact
scheme due to lack of substrate contact. When profiling lightly doped films on insulating
substrates, the series resistance problem emerges with progressively thinner space-charge
regions with increasing reverse-bias [2]. As mentioned in the introduction, the bottom
layer is more conductive than the top layer of the undoped epitaxial film. Therefore,
series resistance problem discussed here may not be as relevant as thicker films.
Nonetheless, its problems in C-V profiling measurements where r
s
G <<1 is satisfied, but
2 f r
s
C<<1 may not. In particular, the violation of the second condition occurs when r
s
62
and C are varying with bias. By monitoring the phase ) / ( tan
1
m m
G C

, the dopant
profile can be extracted. Note also that if there is any series resistance in the
measurement, the phase shift will be different from the otherwise undistorted capacitance
measurement:
1
]
1

,
_

dV
d
C
dV
dC
A q
C
W N
m
m
m
A

cot 2 sin
) (
4
2
0
3
;
m
C
A e
W

2
0
sin

Our data (Figure 3. 2) shows no big difference between the corrected and the uncorrected
profile, indicating that the problem is not serious.
The other source of error is the trapping of free carriers by defect levels. In our
experiments, the measurements were taken with consideration that trapping could play a
role. It should be noted that the measurements were all performed in the dark to prevent
electrons trapping in defect levels within the bandgap. Previously, the electron trap
lifetime was estimated to be in order of seconds to days (< 1 Hz) from persistent
conductivity measurements [3]. Therefore, in high frequency range of 1 KHz - 1 MHz the
traps would not be able to respond to the ac excitation. A sweep rate of 0.1 V/s,
translation to a range of 0.2 - 1 seconds each voltage increment, was used.
Finally, zero-bias depletion depth occurs in the Schottky diode due to the
difference in built-in potential between the metal and the semiconductor. This poses a
limit to profiling close to the sample surface. The surface condition of the sample can
cause some slight variation on the zero-bias depletion depth as well. For the
unintentionally doped samples, this depth was measured to be 0.2 - 0.5 m. True surface
carrier density of the film could not be profiled unless low leakage current could be
63
guaranteed under forward bias. Therefore, the use of MOS type structure can probe this
region, although caution needs to be taken in analyzing the profile in the accumulation
regime [2]. Nonetheless, the concentration on the surface does not seem to be varying as
drastically as the region close to the substrate.
The Schottky diode provided by the MSI mercury-probe was used to measure C-V
characteristics of the films, and the set-up was described in the last chapter. Capacitance (
C ) and conductance ( G ) were measured with reverse-biased voltage sweep from 0 V to
40 V with step voltage 0.1-0.5V using the HP LCR meter. The peak-to peak ac
excitation voltage chosen to be 10 mV with a frequency range between 10 Hz - 1 MHz.
Before each voltage sweep, a ten-minute wait time was exercised to allow the capacitance
to stabilize to equilibrium. Four-wire technique was used to minimize the cable
impedance. The open circuit correction option on the HP LCR was performed in
conjunction with the mercury probe setup by placing a piece of sapphire as a perfect
insulator. Short circuit correction was performed with the four cables shorted to each
other before connection to the mercury probe. With these two correction procedures
performed at the beginning of every experiment, any stray capacitance was zeroed out to
ensure accuracy.
3.2.2 Room Temperature Hall measurements
Hall Measurements were performed using the van der Pauw with cloverleaf geometry in
the setup described in the Experimental Chapter. The standard measurement procedure
(ASTM Standard F76) was followed, showing every permutation of the physical position
of the current and voltage probes on the sample ( Figure 3. 3 ). With zero-magnetic field,
64
the average of the V/I values of switch positions 1-4 gave the measurement of the sheet
resistance. The average of the measured V/I values for switch positions 5 and 6 was used
to calculate the Hall Coefficient and the zero-field values served as correction for the
errors due to misalignment of the contacts. Both positive and negative currents, with both
polarities of the magnetic field, were used.
Figure 3. 3 Hall Van der Pauw Sample Cross-
sectional view (Top Figure), and Top view
showing clover-leaf shape (Bottom Figure).
Current
I
Voltage
V
#1 1,2 3,4
# 2 2,3 4,1
# 3 3,4 1,2
# 4 4,1 2,3
#5 1,3 4,2
# 6 2,4 1,3
The important point for films with non-uniform doping is that Hall measurement
gives the averaged electrical characteristics of the composite film if there is doping
inhomogeniety, with
H
mobility and carrier density n
H
given by
s
s Hs
s Hs H
R
R

2

;
1
]
1

1
]
1

d
d
H
dx x x n
dx x x n
d
0
0
2
) ( ) (
) ( ) (
) (

2
2
1
s Hs
s
Hs
Hs
qR
d qR
n

;
1
]
1

1
]
1

d
d
dx x x n
dx x x n
Hs
d n
0
2
2
0
) ( ) (
) ( ) (
) (

65

s
is the sheet conductivity, R
HS
is the Hall coefficient (R
Hs
=1/qn
s,
where n
s
is the sheet
carrier concentration). This issue will be discussed in greater detail in the later sections.
3.2.3 Electrochemical Profiling Measurements
The setup of the electrochemical profiling measurements was described in the
Chapter 2. The capacitance of the space-charge region in the gallium nitride was
measured across the platinum wire immersed in the electrolyte, with the ground contact
located in the dry portion of the wafer. The capacitance was measured using a small
reverse-bias to probe the surface concentration as described by C-V profiling technique in
a previous section. A small excitation ac voltage at 30 Hz was used in this case. Since in
n-type GaN the relative magnitude of the photoconductive current could be less than 1 %
at 300K, the measurement at small bias should not be greatly affected by the illumination.
Moreover, the relaxation time of the slow traps is in order of hours, so the ac voltage of
30 Hz should be too fast for them to affect the measurements.
Perhaps the effective contact area is a major source of error for the
electrochemical profiling technique, affecting both the dopant concentration and the
measured etch depth. The dopant concentration is a function of the square of the
area:
) / (
) (
2
0
3
dV dC A q
C
W N
d

. The measured depth W by capacitance-voltage

method is the sum of the small depletion depth plus the etched depth that depends on the
monitored dissolution current as a function of time:
dt I
A zF
M
C
A
W
t
dis

+
0
0

[2]. If
there is any crater-formation from non-uniform etching, a gradual increase in area with
66
time can occur. Also, the result would be that the area A and the depletion depth are
underestimated, and that the doping concentration N
D
is overestimated. Moreover,
towards the substrate where the material is very defective, interpretation of the data is
complicated.
3.3 Results
3.3.1 Uniformity across Wafer
The electrical and optical properties of the epilayer could vary due to non-uniform
gas flow dynamics and temperature gradient across the sample, even though small
substrates (quarter of a 2-diameter sapphire wafer) was during each growth. From
photoluminescence studies, the map of the radiative efficiency across an unintentionally
doped sample when growth conditions were not optimized (early 1997) shows a band
edge efficiency variation about 15%, the ratio bandedge to yellow defect band efficiency
could be as much as 65%[4].
Moreover, the spatial variation of the film thickness shown by interference fringes
is reproduced here in Figure 3. 4. Under direct fluorescent lighting each interference band
corresponds to a change of thickness:t 1/n where n is the refractive index (~2.4 for
GaN). From the standard color charts for thermally grown SiO
2
of n~1.465, the thickness
change between different distinguishable color bands for a 1.5-m thick film was
estimated to be in the order of 500 . Therefore, the thickness between each interference
band for GaN should be about 0.08m. Figure 3. 4 d) shows the measured carrier
concentration of the top 0.5 m for samples grown in August 1999.
67
One can see variations in the electrical characteristics by Hall measurements. For
a few calibration samples, Hall measurements showed 15 % variation for and 25% for
n. One can see that the left lower corner of the quarter wafer is in general higher in
concentration than the other regions. (Figure 3. 4 b and c). The greatest variation for n
measured by C-V was 108% between the left lower corner and the other parts of the
sample. All three measurements of Hall, C-V and PL show greater variation in this
particular region of the sample where the sample was estimated to be slightly thinner than
the center. Great care was taken to make van der Pauw Hall measurements from the same
location on each sample. This was not possible for the larger Hall bridge bar samples.
3.3.2 Run-to-run Reproducibility
The 2-m unintentionally doped samples, of which all variable growth parameters
(growth temperature, flow rates, pressure, buffer layer growth procedure etc) were kept
the same, served as calibration for the variability in the reactor. Figure 3. 5 shows all the
Hall data of all the undoped samples grown within a 15-month period, the scatter among
the undoped samples (the circles) is large. The long-term reproducibility of the samples is
not very good and the electrical properties cannot be readily correlated with any change
in the reactors condition. The short-term reproducibility, however, is acceptable that
samples grown within a 1-2 week period show similar electrical properties. Therefore,
when a set of samples were grown, calibration samples (undoped) were usually grown
both before and afterwards to ensure reproducibility.
68
Direction of
Source Flow
Series of Bands
2mm around the edge
~1mmThick
band
~2mm
1
a)
b) Carrier Concentration in units of 10
18
cm
-3
1.63

1.64 1.65 1.8

2.12 1.84

1
c) Mobility in units of cm
2
/Vs
67

59 58 57

52 59

d) Carrier Concentration in units of x 10
15
cm
-3
3.5

3.5
3
4
10
Figure 3. 4
a) Interference Fringes of a Typical Undoped Sample.
b)Hall Carrier Concentration Map (in 1 x 10
18
cm
-3
) , c) Hall Mobility Map (in cm
2
/V-s) of another
undoped sample for which the growth conditions were not optimized.
d) Map of Near-surface Free Carrier Concentration measured by C-V (in 1 x 10
15
cm
-3
) for a
different sample.
69
Figure 3. 5 Distribution of Hall data for Unintentionally Doped samples showing poor long-term
reproducibility.
The scatter of the electrical properties is typical in unintentionally doped samples
in the gallium nitride community regardless of growth method. It is likely to be due to the
variation in the bottom layer and will be discussed later on in the thesis. Evidence to
support this is the much-improved reproducibility of the samples using
photoluminescence as a figure of merit, indicating only a small variation in optical
quality in the top layer.
70
For the silicon-doped samples, the reproducibility seems to be much better. For
these samples, the flow of silane (diluted in hydrogen) was introduced at the start of the
high temperature growth, after annealing of the ~30 nm thick low temperature buffer
layer. All the conditions were kept the same as the unintentionally doped samples except
for the presence of silane. The silane flow rate during growth is plotted against Hall
carrier in Figure 3. 6. It shows the three sample-sets grown at different periods and the
monotonic increase in the carrier density with silane flow. This is an indication of very
good long-term and short-term reproducibility.
1.E+16
1.E+17
1.E+18
1.E+19
1.E+20
0.1 1 10 100
SiH
4
/H
2
Flow ( sccm )
n (Hall) in
cm-3
Si Dec 97
Si June 98
Si Oct 98
Figure 3. 6 Hall Carrier Density Vs Silane Flowrate for Silicon Doped Samples.
71
3.3.3 SIMS Measurements
As mentioned in the introduction the possible donors in gallium nitride are
silicon, oxygen and nitrogen vacancies. The characteristics of Hall carrier density Vs
Silane flow (Figure 3. 6) suggest that silicon could be the main donor responsible for the
n-type intentional doping of most of these samples. The questionable data points are the
one with the highest silane flow rate and the lowest one. For a moderately doped sample
the silicon incorporation into the sample measured by SIMS is 3 x 10
18
cm
-3
, which
compares well with Hall measurement of 3.8 x 10
18
cm
-3
. The background level of
oxygen is at least one order of magnitude lower, so silicon is the dominant donor.
However, for the highest silane flow (ie highest doped) sample with free carrier
concentration ~2 x 10
19
cm
-3
by Hall technique, the surface of the sample is very rough.
SIMS measurement for this sample shows that the top 0.5 m contains a silicon level of
~5 x 10
19
cm
-3
and a high oxygen level >10
21
cm
-3
. From the literature, high
concentrations of structural defects are typically seen in highly doped samples around 2 x
10
19
cm
-3
. It is reasonable to suspect that the structural quality is poor for this sample, and
therefore one cannot isolate the electrical effect of silicon incorporation from this sample.
As for the silicon-doped sample with the lowest silane flow rate, even though no
SIMS data is available, the data for unintentionally doped samples can suggest what one
would expect. The main problem with the measurements of the low silane flow sample is
that the carrier concentration level measured by Hall technique is similar those of the
unintentionally doped samples. This implies background level likely due to either
residuals of silicon or oxygen. As mentioned in Chapter 2, in order to determine the
72
atmospheric contaminant levels (eg O, C, H) by SIMS, great care must be taken to reduce
the system base pressure of the SIMS instruments to a minimum.
3.3.4 Schottky C-V Measurements
The C-V data for doped and undoped samples is presented in this section. As mentioned
before, the Schottky C-V measurements give the differential change in N
D
at the edge of
the depletion region as the depletion depth is increased by the increasing reverse-bias.
Measurement at low reverse-bias gives the surface carrier concentration information of
the film. Since the donors may not be completely ionized at room temperature, the N
D
as
measured by C-V can be slightly larger than the free carrier concentration (n). As for Hall
measurement, the average free carrier concentration (n) of the composite film is
measured. For our data, the good agreement between the carrier concentration (Hall) and
the near-surface net doping concentration (C-V ) breaks down at the low surface dopant
densities as shown Figure 3. 7. The discrepancy between the C-V and Hall techniques is
indicative of parallel conductive path, with a higher carrier concentration and lower
mobility towards the interface. Therefore, carrier concentration profile Vs depth will help
quantify the electrical properties of the film.
73
1.00E+15
1.00E+16
1.00E+17
1.00E+18
1.00E+19
1.00E+15 1.00E+16 1.00E+17 1.00E+18 1.00E+19
ND by CV (cm
-3
)
n by Hall
(cm
-3
)
Silicon Doped
Unintentionally doped
nCV=nHall
Figure 3. 7 Carrier concentration (n) by Hall Vs Surface net doping concentration (N
D
) by C-V
showing discrepancy in low surface concentration regime.
For the unintentionally doped samples, the carrier density of the sample rises
dramatically from the zero-biased depletion value of ~5 x 10
15
cm
-3
(typically near 1 x
10
16
cm
-3
) to close to 1 x 10
17
cm
-3
at ~1.5 m from the surface as seen in Figure 3. 8.
The qualitative trend of greater than one order of magnitude increase in carrier density
within ~1.5 m from the surface is typically observed, although the absolute depth of the
concentration rise varies from sample to sample.
74
Figure 3. 8 Carrier Concentration Profile of a single unintentionally doped sample as measured by C-
V.
10
15
2
4
6
8
10
16
2
4
6
8
10
17
2
4
6
8
10
18
N
D

i
n

c
m
-
3
1.5 1.0 0.5 0.0
Depth in m
Unintentionally Doped Sample
#9809291
As the reverse-bias is increased, the profiling measurements are prone to error due
to diode breakdown, Debye length limit, series resistance, stray capacitance and leakage
current as discussed in Section 3.2. The near-surface capacitance is very reliable, and
precautions have been taken to minimize errors in the extraction of depth profile N
D
.
However, comparison with etched-back and thinner films is important to assess the data.
75
Figure 3. 9 Mercury probe C-V profiles of original unetched (circles) and 0.6microns etched
(triangles) unintentionally doped film. The estimated etch depth of 0.6 microns was included in the
depletion depth in order to construct the entire profile.
10
15
2
4
6
8
10
16
2
4
6
8
10
17
2
4
6
8
10
18
N
D

i
n

c
m
-
3
1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0
Depth in m
Etched Film
Unetched Film
Fit
Profiling measurements were done on an unintentionally doped sample with and
without reactive ion etching (Figure 3. 9). The conditions of the etched sample were
100W, -250V, pressure and flow rate in BCl
3
, and approximately 0.6 (t0.150) m was
etched away. For the etched profile, a leftward shift of 0.6m is added such that the
profiles of the unetched and etched samples are overlaid to reconstruct the entire carrier
concentration depth-profile. No adjustment in depth or extracted carrier concentration is
made in the overlaying procedure. An almost continuous profile is seen, starting at ~ 1 x
10
16
cm
-3
near the surface, and gradually rising to ~ 1 x 10
17
cm
-3
at 1.2 m from the top
76
surface. This compares well with the continuous profile of the unintentionally doped
sample in Figure 3. 8. The surface roughness can increase the surface area, resulting in a
lower carrier density and smaller depth, a factor not accounted for in Figure 3. 9.
Moreover, the Schottky barrier formed between mercury and the etch-damaged surface
breaks down at low voltages.
In order to probe the profile beyond the Debye-length and Schottky diode
breakdown limits, the profiles of a series of thin films of thickness 0.55 to 2.2 m were
measured. More details of these samples will be given regarding the two-layer model
analysis. The thin undoped samples were grown in the same fashion as the 2.2-m
calibration films. The procedures for the low-temperature buffer layer and high
temperature epilayer growth and sample cool-down were exactly the same for these
samples. The first set of three samples of thickness 0.25, 0.55, 1.1 m were grown within
a three-day period, and the last sample of 2.2m was grown about ten days previously.
Comparison of samples grown in approximately similar time frame ensures short-term
reproducibility.
The growth of GaN on a lattice-mismatched substrate involves the initial
formation of 3-D islands that eventually coalesce into a continuous film [5]. SEM
pictures (Figure 3. 10) show that the morphology of the thin sample (0.25m sample)
looks different from the specular 2-m calibration layers. Compared to other MOCVD
material in the literature, completely continuous film formation happens at 0.4m [6]. As
seen in Figure 3. 10, the 0.25-m sample shows hexagonal islands and its continuity is
questionable and will not be used in the analysis.
77
Figure 3. 10 SEM micrograph of the 0.25 micron sample.
Figure 3. 11 SEM Micrograph of the 0.5 micron sample.
78
Our 0.5 m sample shows a continuous film (Figure 3. 11), but the SEM picture
reveals that it contains what appears to be voids (~ 1-m in lateral diameter) that do not
occur in thicker films in which all the gaps are filled up. It is unclear how deep these
voids originate. The thin films will likely show a different low temperature (below carrier
freeze-out) characteristic than the embedded first 0.55 m of a thicker film, but at room
temperature it is likely that these unfilled gaps on the surface are large scale geometric
effects. [7] No surface structures could be seen under the SEM for the 1.1 and 2.2 m
samples.
The assumption of this analysis is the identical electrical properties of the
embedded bottom-most layer for all these undoped samples, which may not be a good
one. Moreover, it has been shown that the structural (quantified by X-ray rocking curves)
and optical properties (by PL), gradual improvement with increasing film thickness
occurs [8]. Decrease in full width half maximum (FWHM) for the X-ray and PL data
continues up to 4 m in MOCVD films after which no additional improvement occurs
any more. If the two-layer analysis works well using this assumption, research may be
needed to solve this apparent paradox.
In any case, the C-V profiles of the three samples (of thickness 0.55, 1.1 and 2.2
m) are overlaid like Figure 3. 9. Both profiles of the 0.55-m and the 2.2-m samples
were not adjusted at all for the carrier concentration and thickness. The profile of 1.1-m
sample was shifted 0.1 m leftward (to an equivalent of 1.0 m thickness) to construct a
continuous profile. This is reasonable because a thickness error margin of t 0.1 m is
79
expected for these films. From these two profiling methods, it seems that successive etch
back or successive increasing film thickness can provide reliable carrier concentration Vs
depth information.
Figure 3. 12 Mercury probe C-V profile of three films of successive thickness (0.55, 1.1 and 2.2
microns).
10
15
2
4
6
8
10
16
2
4
6
8
10
17
2
4
6
8
10
18
N
D

i
n

c
m
-
3
2.0 1.5 1.0 0.5 0.0
Depth from top surface in m
Data from 2.2 micron
sample
Data from 1.1
micron
Sample
Data from
0.55 micron
Sample
In terms of how the voids in the 0.55-m film affect the C-V profiling, the
following assessment is made. When the mercury contact is applied to the film, surface
tension prevents the mercury from filling the voids. The equivalent capacitance can be
written as the capacitance of the filled film (with dielectric constant of gallium nitride) in
80
parallel with the capacitance of the pockets (with dielectric constant of air).
d
A
d
A
C C C
GaN GaN voids air
GaN voids total

0 0
+ +
. Using the formulation
for the extraction of doping profile N
A
(W) and depletion depth W shown in Section 3.2.1,
the error for these two quantities can be estimated. The area of the voids (average lateral
diameter of 1m) consists of ~7-8% of the total cross-sectional surface of the film. As a
result, the doping concentration error is ~+ 7%, and the depth error is ~-7%.
The carrier concentration profiles in Section 3.3.3 all show a similar gradual
transition region towards the bottom of the substrate, but there is not enough information
about the film towards the interface of GaN and sapphire. The best method is the overlaid
profiles of a series of thin films of successive thickness. For the 0.55-m, the carrier
density does not rise sharply in this film, although precise information at the
GaN/sapphire interface is still not available. For modeling purposes, one can think of the
2.2-m sample as a having two layers, one lighter doped and one higher doped with a
gradual transition between them. For the region from ~ 1.4 to 1.7 m, the variation of the
carrier density is quite dramatic. This profile bears some resemblance to an n-n
+
junction
in equilibrium where the space charge is in the form
2
2
1

,
_

D
s
L
x
qn

[ 8]
where n
s
is the excess sheet charge on the n-n
+
boundary.
When using differential C-V technique at a reverse-bias to incrementally change
the depletion depth, the ac probe voltage exposes more or less ionized donors. As
mentioned previously, the spatial resolution of a few Debye lengths poses a limit on the
accuracy of the measurement. Simulations of profiles for a silicon n-n
+
junction have
81
shown good agreement between the majority and doping profile if the doping profile of
low-high ratio 1:10 linearly ramps up within 5 Debye lengths of the higher doping
density [1]. As seen in Figure 3. 12, the doping gradient of our film typically varies
between 1 x 10
16
- 1 x 10
17
cm
-3
. The excess charge would be within a few Debye
lengths of the higher doped layer of ~1 x 10
17
cm
-3
, yielding L
D
=0.012 m. As
mentioned in section 3.2, as long as the dopant profile step of one order magnitude occurs
within 5 Debye lengths (~0.062m), the C-V profile shown here should be a good
indication of the dopant profile.
The following the empirical relationship was best fitted to the profile Figure 3. 12
for the lighter doped region, and bears resemblance to the equilibrium space charge of n-
n
+
junction [8] mentioned previously: 4
2
1
) 1 (
) (
3
2
K
K
x N
K
K x
+
+

. The
parameter K
2
indicates the distance from top surface where the lower doped region (layer
1) begins, and K
4
gives the background doping level of the lower doped (layer 1) film. K
1
corresponds to the charge density at x= K
2
, so K
1
the density of the n
+
layer (layer 2). K
3
is similar to the concept of the Debye length L
D
, serving as a measure of the spatial extent
of the doping transition. The values of the empirical parameters are K
1
=1.5 x 10
17
cm
-3
,
K
2
=1.8m, K
3
= 0.12 m and K
4
= 8.6 x 10
15
cm
-3
. The C-V profiles of a single sample
and the overlaid profile of the RIE etched sample can be fitted in this form, although the
absolute information of the thickness of the n
+
layer is more uncertain in these plots than
Figure 3. 12 (thin series).
For C-V profiling of moderately to highly doped samples, the limitation is the
relatively small depletion width, implying early breakdown of the Schottky diode at small
82
reverse-bias. Profiling depth greater than 2000 for the sample with near surface
concentration of 2 x 10
17
cm
-3
could not be obtained. In order to assess the possible two-
layer conduction, the silicon-doped sample with this doping level was etched back, and
the C-V profile compared with the unetched portion of the sample. However, the
increased concentration towards the bottom of the film was not observed. In fact, Figure
3. 14 shows a decrease in concentration after etching, an effect of the increased surface
area due to RIE.
Figure 3. 13 Fitting of the dopant profile shown previously in Figure 3.12.
10
15
2
4
6
10
16
2
4
6
10
17
2
83
Figure 3. 14 CV Profile of unetched and etched back silicon doped sample. Only a small profiling
depth is possible in moderate doping levels due to Schottky breakdown.
3.3.5 Electrochemical Profiling Data
The absolute value of the depth measured by Polaron electrochemical profile
(Figure 3. 15) is very different from the C-V profile measured by the mercury probe
technique. The data for an unintentionally doped sample (n
H
~ 4 x 10
16
cm
-3
) is
compared with a silicon doped sample (n
H
~ 1.5 x 10
17
cm
-3
). Qualitatively, the general
upward profile agrees with that of the mercury probe measurement in Figure 3. 12 (thin
series) and Figure 3. 9 (RIE etched back). However, the Polaron depth axis, at least in the
region of gradual rising concentration with depth, is severely underestimated. Since
depletion depth is directly proportional to area, it is likely that net surface area increases
due to non-uniform etching. In photochemical etching preferential etching of the material
away from dislocations is seen by the remaining whisker-like structures [10] suggested
by the decrease in hole-concentration due to charges near threading dislocations
84
preventing efficient etching. During electrochemical profiling measurement, the
retardation of etching near the dislocations can give rise to increased surface area.
Comparison with mercury probe profiling could not be made due to the breakdown of the
mercury Schottky diode. However, the bottommost ~1.5 m of gradual depleting region
shown in the Polaron data seems to be contradictory to existence of the parallel
conductive path near the interface.
In the literature, silicon doping has been found to change the distribution of
dislocations and improves the structural quality of the resulting doped MOCVD gallium
nitride grown with an AlN buffer layer [11]. In the future, when the technique by
electrochemical profiling for this experiment is better developed, the possible difference
between the transition layers of the samples could be explored.
Figure 3. 15 Polaron Electrochemical Profiling data showing a silicon doped gallium nitride depth
profile (continuous) Vs an unintentionally doped sample (crosses)
85
3.4 Two-Layer Model Analysis
The highly defective interfacial region between the substrate and the gallium for
MOCVD and MBE films, thicker in hydride vapor deposition (HVPE) films, is found in
all heteroepitaxial grown samples. In a gallium nitride sample grown by HVPE this
region has been shown to be rich in electron concentration by cathodoluminescence [12].
In terms of lateral electron transport, it can provide a parallel conduction path for HVPE
gallium nitride films and MOCVD films.
A survey of the two-layer studies of the HVPE-grown GaN films is as follows.
Goetz et al [13] measure the near-surface carrier concentration (using C-V techniques) of
a progressively polished HVPE film grown using gallium chloride pretreatment and find
that the carrier density measured by Hall techniques does not scale with thickness. They
have found that at the bottom-most 10% thickness (1.2m) of their 12-m film, the C-V
concentration is two orders of magnitude higher than the near-surface region. Aside from
the threading dislocations shown to continue throughout the entire film, the TEM data of
these films shows a distinct 0.25-m region with mostly stacking faults [14], consistent
with the literature. Above this region, TEM data has revealed a high concentration of
various types of dislocations which decrease gradually after ~ 0.8m towards the
substrate. Goetz et al [15] conclude the ~ 0.25-m faulted region as a source of the
parallel conduction path, with some possible contribution from oxygen contamination
from sapphire. Along the same line of study, Goetz et al also have utilized a series of
variable thickness films to study thick HVPE samples with zinc oxide pretreatment of
initial thickness ~0.2 m [13]. Again, the films have been found to contain threading
86
dislocations that continue throughout the entire thickness. In contrast to the GaCl
pretreated films, no distinct zinc oxide region has been observed in a typical thick film,
but rather, a bottom layer with high concentration of dislocation loops annihilating within
2-3 m. They compare the gallium chloride and zinc oxide pretreated HVPE samples,
and find that a two-layer model fits the former and a transition layer for the latter. Look et
al [16] have used the standard multiband [17] (or mulitlayer ) analysis to extract the Hall
data for the top layer of the HPVE film from temperature independent Hall mobility and
carrier concentration values at low temperature (<30K). The discrepancy between the
corrected and the uncorrected values is found to be ~ 15% for mobility throughout the
entire temperature range, and ~ 5-10 times for carrier density.
For our undoped samples, low temperature conductivity (1.5 - 30 K)
measurements did not show a degenerate, electrically temperature-independent transition
layer ( see Chapter 5), unlike the ZnO pretreated HVPE sample analyzed by Look [16].
In fact, as will be seen in Chapter 5, the conductivity below 30 K shows continuous
decrease at the lowest temperature (1.5 K). The two-layer extraction from low
temperature Hall data may not be applicable to our data. Instead, a series of thin films
was chosen to assess the electrical properties of the bottom layer.
3.4.1 Two Distinct Layers Model Formulation and Analysis
The model describes the film as having two-layers with distinct mobility and carrier
density with abrupt boundaries, and will be simply referred as two-layer model unless
stated otherwise. For the general case, the measured Hall mobility and carrier density as
follows:
87
1
]
1

1
]
1

d
d
H
dx x x n
dx x x n
d
0
0
2
) ( ) (
) ( ) (
) (

Therefore, for the two-layer mode,

2 2 2 1 1 1
2 2
2
2 1 1
2
1
d n d n
d n d n
H H H H
H H H H
H

+
+
, where d
1
is
the thickness of the top film and d
2
is that of the bottom film.
The sheet carrier concentration n
Hs
of the composite film thickness d is given as
follows, in contrast to n
H
which is the carrier concentration:
1
]
1

1
]
1

d
d
dx x x n
dx x x n
d
Hs
n
0
2
2
0
2
) ( ) (
) ( ) (
) (

For a two layer model,

2 2
2
2 1 1
2
1
2
2 2 2 1 1 1
) (
d n d n
d n d n
d n
H H H H
H H H H
H


+
+

Finally, to extract the corrected values of the top epilayer from the measurements,
we can rewrite the above expressions as:
2 2 2
2 2
2
2
2
1
d n d n
d n d n
H H H H
H H H H
H

;
2 2
2
2
2
2
2 2 2
1 1
) (
d n d n
d n d n
d n
H H H H
H H H H
H

The results of the Hall measurement is in Table 3. 1, with the extracted top layer mobility

H1
and normalized carrier concentration n
H1
using the mobility and carrier density of the
0.55m and 1.1m as layer 2. These values bode well with the near surface concentration
by C-V measurements (n
CV
).
88
The bottom layer cannot be applied to extract the information of samples grown
in a different time period due to variability of the bottom layer. Take for an example, a
2.2 m undoped sample of concentration ~1 x 10
16
cm
-3
by CV,
H
=132 cm
2
/Vs and n
H
=3.7 x 10
16
cm
-3
(sample number 9711181, grown more than 12 months prior to the 0.55
m sample). The conductivity alone is smaller than the conductivity of the 0.55 m
sample shown here.
Thickness
(m )
Measured
n
H
(cm
-3
)
Measured

H
(cm
2
/Vs)
*n
H1
in
cm
-3
*
H1
in
cm
2
/Vs
n
H1
in cm
-3

H1
in
cm
2
/Vs
n
C-V
in
cm
-3
0.55
1.82 x 10
17
165 - - - - 3 x 10
17
1.1
7.30 x 10
16
218 8.42 x 10
15
(8 x 10
15
<n<4 x 10
16
)
537.545
(320<<
830)
- - 3 x 10
16
2.2
3.70 x 10
16
317 1.20 x 10
16
t0.7 x 10
16
528.542 1.43
x 10
16
525.84 1 x 10
16
* Calculated using the 0.55 m as Layer 2. Calculated using the 1.1 m as Layer 2
Table 3. 1 Two Layer Analysis
In order to see the applicability of the two-layer model, the product of
H
and n
Hs
are plotted Vs d the total thickness of the samples. Note that it is easier to analyze the
data in terms of thickness as measured from the bottom of the film, whereas for carrier
density profiling, the convention is to express the data in terms of depth as measured
89
from the surface of the film. A linear fit of the product
H *
n
Hs
Vs total thickness (d)
(like the one shown in Figure 3. 16) implies that the two-layer model is a good one:
2 2 2 2 1 1
0
) ( ) ( ) ( ) ( d n d d n dx x x n d n
H H H H
d
Hs H
+
1
]
1

One important way to think about the two-layer model is the following. It may
helpful to rewrite the product of
H
and n
Hs
as:
2 1 1 2 2 1 1
) ( ) ( d n n d n d n
H H H H H H Hs H
+
Equation 1
This formulation adds some new insight to our discussion of the two-layer model through
the x-intercept of the linear fit of
H*
n
Hs
Vs total thickness (d). When the x-intercept of is
positive, it implies that
H2
n
H2
>
H1
n
H1
. Typically for the unintentionally doped film
(see for example [16]), even though the top layer mobility
H1
is a few times higher than
that of the bottom layer
H2
, the carrier concentration for the top layer n
H1
can be one
order of magnitude lower than n
H2
. The end result is that indeed the
H
n
H
-product is
higher for the bottom layer (layer 2) than the top layer (layer 1), yielding a positive x-
intercept frequently seen in the unintentionally doped samples (see also Figure 3. 16). As
a result, there is a parallel conductive path in the bottom layer.
In other cases where the doping level difference is not drastic (ie n
H2
~ n
H1
), the
difference in the
H
n
H
-product may not necessarily be large, and the intercept can be
small. In the extreme case where the doping level of the top layer is much higher than the
bottom layer, the result is that n
H2
<< n
H1
. Even if the mobility of the bottom layer is
several times lower due to structural defects, the end result could be that
H2
n
H2
<
H1
n
H1
, yielding a negative x-intercept in
H
n
Hs
Vs total thickness (d). Such can be the case
90
when the intentional doping level of the top layer is high. The bottom layer can then be
thought of as a more resistive layer.
Figure 3. 16 Fitting of (n
s *
) product Vs total film thickness using the Two-Layer Model.
4x10
15

3
2
1
0
n
s
*

p
r
o
d
u
c
t


(
c
m

-
2
c
m
2
/
V
s

)
250x10
-6
150 100 50 0
Thickness in cm
Data
Two Layer fit
91
2.0x10
-3
2.0x10
-3

1.5 1.5
1.0 1.0
0.5 0.5
0.0 0.0

2.5x10
-4
2 1.5 1 0.5 0
film thickness in cm
R
o
o
m

T
e
m
p
e
r
a
t
u
r
e

C
o
n
d
u
c
t
a
n
c
e

(
1
/
O
h
m
s
)
Figure 3. 17 Room temperature conductance vs thickness of successively etched back silicon doped
sample.
Figure 3. 17 is the data for a silicon-doped etched back sample that could be in
this latter category, and will be discussed in greater detail in Chapter 5 which explains the
temperature dependence conductivity. In Figure 3. 14 the profile of this etched-back
silicon-doped sample has been shown. From the room temperature conductivity, C-V and
variable temperature analysis, the silicon-doped samples should not be dominated by the
two-layer problem.
Finally, the important point regarding the linear fit of
H
n
Hs
Vs total thickness (d)
is that if the thickness of the bottom layer d
2
is small compared to the total thickness, the
x-intercept will be small. This means that the net effect of the bottom layer will be small,
be it a parallel conductive path or a dead layer.
92
Now that Equation 1 and its implications have been explained, the fitting of the
series of unintentionally doped samples is as follows. Referring back to Figure 3. 16, one
can extract the slopes and the x-intercept. With the best estimated value of the bottom
layer thickness d
2
as 0.55m (or, another way to think about it, the bottom layer starts at
1.65m from the surface of the film if the total thickness is 2.2 m). Thus,
H1
n
H1
and

H2
n
H2
can be found. Then,
H
Vs total thickness (d) (Figure 3. 18) is plotted and fitted,
all the parameters
H1
, n
H1
,
H2
and n
H2:
can be solved according to :
2 2 2 2 1 1
2 2
2
2 2 1
2
1
) (
) (
) (
d n d d n
d n d d n
d
H H H H
H H H H
H

+
+

Figure 3. 18 Fitting of Hall mobility Vs total film thickness using the Two-Layer Model.
400
300
200
100
0
M
o
b
i
l
i
t
y

i
n

c
m
2
/
V
-
s
250x10
-6
150 100 50 0
Thickness in cm
Data
Two Layer Model
93
Figure 3. 19 Plot of fitted Hall Carrier Density Vs total film thickness using the Two-Layer Model.
10
16
2
3
4
5
6
10
17
2
3
4
5
H
a
l
l

C
a
r
r
i
e
r

C
o
n
c
e
n
t
r
a
t
i
o
n
i
n

c
m
-
3
250x10
-6
150 100 50 0
Thickness in cm
Fit (Two Layer Model )
Data
S
a
p
p
h
i
r
e
The extracted mobility and electron concentration is as follows. The values of the
top film (layer 1) are
H1
= 504 cm
2
/Vs and n
H1
= 1.3 x 10
16
cm
-3
, and for the bottom film
(layer 2)
H2
= 158 cm
2
/Vs and n
H2
= 1.63 x 10
17
cm
-3
. A plot of the calculated n
H
(d) Vs
total film thickness (d) using the fitted parameters shows excellent agreement with the
experimental data (Figure 3. 19). The values for the mobility and carrier density extracted
are very reasonable.
An estimate of the largest range of the mobility and carrier density values of the
top layer can be assessed considering the errors of the measurements. Taken into account
were systematic errors from all three samples and statistical ones. The errors from this
analysis are estimated from the t20% error for the mobility data. The largest error for
94
carrier density comes from error in the estimation of the thickness. In the actual Hall
measurement, sheet carrier density is measured, and the carrier density is then normalized
from the thickness value. In this way, the error of the carrier density is assessed with the
error due to the thickness, which is ~ t 0.1 m. If the assumption is made that the
bottom layer starts 1.65t 0.1 m from the surface of the film, an estimate of the range of
mobility and carrier density values of the top layer can be assessed considering the errors
of the measurements. The errors for mobility and carrier density are less than 10% and
20% respectively. In summary, the resulting range of values are 322 - 678 cm
2
/Vs for
mobility of the top layer and 5.8 x 10
15
- 1.7 x 10
16
cm
-3
carrier density of the top layer
considering the above measurement errors.
3.4.2 Modified Two Layer Model Formulation and Analysis
From C-V profiling, it has been shown that the undoped film consists of a higher
doped region of < 0.5m embedded in near the GaN/sapphire interface, and a gradual
transition to light doping as the thickness increases. In recognition of the non-abruptness
of the two-layers, the two-layer model in the previous section is modified to include the
gradual transition and is referred as modified two-layer from here on. The gradual
transition has been measured by the mercury-probe profiling technique. In order to prove
the applicability of the modified two-layer model, the product of
H
and n
Hs
is plotted Vs
d (the total thickness of the samples). The x co-ordinates are changed such that they
represent thickness instead of depth. Therefore, the zero-point in the x-axis is the bottom
of the ~2.2 m film. The carrier density of the top layer (n
1
) is replaced by the best-fitted
empirical form:
95

'

< <
< < +

m d n d n
m d K
K
d n
H H
K
d
H

55 . 0 0 ) (
2 . 2 55 . 0
) 1 (
) (
2
4
2
55 . 0
1
3
The various K's are all fitted parameters. The boundary condition at the interface need not
be met because there is not enough information for modeling the bottom layer, so n
H2
is
taken to be an average value of the carrier density of the bottom layer.
The mobility profile is unknown, but it has been suggested to follow the
exponential function, similar to the carrier concentration [13], its approximation by the
Taylor expansion is chosen here for simpler calculation.

'

< <
< <
+
+
m d d
m d
d C
B
A d
H H
H


55 . 0 0 ) (
2 . 2 55 . 0
) 55 . 0 ( 1
) (
2
The product of mobility-sheet carrier density of the measured films is
therefore,
D dx x x n d n
d
d
Hs H
+

2
) ( ) ( ) (
1 1

where 55 . 0
2 2 H H
n D .
The mobility-sheet carrier density product can be expressed as a function the fitting
parameters A, B, C and D, and the integral is written in its analytical form as evaluated by
Mathematica. The difficulty in fitting with only three data points requires some estimate
of the parameters. The best fit is achieved with the additional constraint that
H2
= 165
cm
2
/Vs is also the boundary condition value of
H
(0.55). The fitted value of parameter D
can be solved to give the value of
H2
.
96
The fitting results give the mobility of the upper layer in the form
) 55 . 0 ( 6980 1
797
962 ) (
+

d
d
H
, and a transition layer of maximum carrier density n=
1.2 x 10
17
cm
-3
. Using the values of the fitted parameters, mobility and carrier density
both as a function of thickness are plotted with the measured values, with the fitted lines
from the two-layer model as comparison.
Figure 3. 20 Fitting of (n
s
) product Vs total film thickness using the Modified Two Layer
Model(dashed line) with theTwo-Layer Model (continuous line) as comparison.
4x10
15

3
2
1
0
n
s
*

p
r
o
d
u
c
t


(
c
m

-
2
c
m
2
/
V
s

)
250x10
-6
150 100 50 0
Thickness in cm
Data
Two Layer fit
Transition/Two Layer
97
Figure 3. 21 Plot of fitted Hall Mobility Vs total film thickness using the Modified Two Layer
Model(dashed line) with theTwo-Layer Model (continuous line) as comparison.
400
300
200
100
0
M
o
b
i
l
i
t
y

i
n

c
m
2
/
V
-
s
250x10
-6
150 100 50 0
Thickness in cm
Data
Two Layer Model
Transition/Two Layer Fit
98
Figure 3. 22 Plot of fitted Hall Carrier density Vs total film thickness using the Modified Two Layer
Model(dashed line) with theTwo-Layer Model (continuous line) as comparison.
10
16
2
3
4
5
6
10
17
2
3
4
5
200x10
-6
150 100 50 0
Thickness in cm
Data
Two Layer Model
Transition/Two Layer
Hall
Carrier
Concen-
tration
In cm
-3
As one can see in Figure 3. 19- 3.21, the original two-layer model is a better fit
than this modified two-layer model. The reason is that for the latter, the bottom layer
information is not clear. More importantly, the mobility profile could be inaccurate. In
order to assess truly the variation of mobility with thickness, best method is a structure
like a MOSFET in which drift mobility profile can be estimated from the channel
resistivity measurement with variable gate voltage and carrier density profile using
capacitance voltage measurements. This method requires a good quality dielectric with
low interface trap density for reliable measurements.
The parameters the modified two-layer model for the carrier profile can shed
some light on the variations of the film electrical properties. For an ideal film where the
99
parallel conductive path effect is to be minimized, the thickness K
2
should be as close to
the total thickness as possible, meaning that the thickness of the n
+
layer compared to the
total thickness should be minimized. This implies that by growing a thicker film, the
effect can be reduced. Similarly, the spatial extent of the transition layer measured by K
3
should also be small. The concentration of the n
+
film as measured by K
1
should be low.
For a film with background doping as indicated by K
4
, a comparable level as the n
+
doping level means that there is no large gradient in the profile, and therefore minimizing
the parallel conductive path.
3.5 Variability of Samples
For simplicity, the two-layer model is employed to explain the variability among
samples, firstly in terms of doping concentration. As a simulation exercise the following
properties are used. The room temperature mobility of the bottom n
+
layer of 0.55m is
165 cm
2
/Vs and the carrier density is 1.82 x 10
17
cm
-3
, while the mobility of the top 1.65-
m layer is 529 cm
2
/Vs. These are values from the two layer analysis (Table 3. 1). Using
the two-layer model, the average carrier density of the entire composite 2.2 m sample is
calculated as a function of the carrier density of the top layer ranging from 5 x 10
15
to 1 x
10
18
cm
-3
and plotted in Figure 3. 22. The disagreement between the two carrier
concentrations can be seen in the deviation of the composite n

from the unity line
(dotted). In particular, for the lightly doped top layer the composite carrier concentration
n is almost an order of magnitude higher than the top surface concentration N
D
. This
simulation bears resemblance to Figure 3. 7 in which Hall carrier density is plotted
against that measured by C-V. The discrepancy occurs for light doping levels as well. In
Figure 3. 23 the effect of variation in the doping of the top layer on the resulting
100
composite mobility for the entire 2.2-m film is plotted. The composite mobility is
consistently lower than top layer mobility throughout the entire range of simulated top
layer concentration, most seriously at or below 1 x 10
16
cm
-3
where the composite
mobility is a few times less than the top layer mobility.
Now suppose the background doping of the top layer of the unintentionally doped
sample is well controlled at 1 x 10
16
cm
-3
which is realistic considering that the C-V data
for the unintentionally doped samples usually falls within this doping level. The next
question to ask is what would the averaged composite n and of the 2.2 m sample be
when the thin n
+
layer varies in doping concentration within one order of magnitude (1 x
10
17
to 1 x 10
18
cm
-3
). In the next simulation shown in Figure 3. 25 and Figure 3. 26, the
mobility values of the top and bottom layers are assumed to be 529 and 165 cm
2
/Vs,
respectively. The variation in the simulated composite carrier concentration is about one
order of magnitude with one order of magnitude change in n
+
layer concentration. The
composite mobility variation is about a factor of two.
The variation of the thickness of the n
+
layer is shown in Figure 3. 26 and 3.27
when the mobility values of the top and bottom layers are assumed to be 529 and 165
cm
2
/Vs. The concentration the top and bottom layers are 1.2 x 10
16
cm
-3
and 1.82 x 10
17
cm
-3
. For a variation of the thickness of the n
+
layer from 0.4-0.75 m, variation in the
simulated composite carrier concentration is about a factor of two whereas the composite
mobility variation is about a factor of 1.25. (Figure 3. 27 and Figure 3. 28).
101
Figure 3. 23 Simulation of Composite Vs Surface (Top Layer) concentration, where and N
D
of the
bottom n
+
layer and the mobility of top layer are fixed. Top layer N
D
is varied to see the discrepancy
due to Two layer effect.
1E+15
1E+16
1E+17
1E+18
1.00E+15 1.00E+16 1.00E+17 1.00E+18
ND of Top Layer (cm-3)
Composite
N
D
(cm-3)
Composite ND
Line of Composite N
D
=SurfaceN
D
200
300
400
500
600
700
1.00E+15 1.00E+16 1.00E+17 1.00E+18
ND of Top Layer (cm-3)
Mobility
cm
2
/V-s
Composite Mobility
Top Surface Mobility
Figure 3. 24 Simulation of the effect of variation of top layer doping on resulting Composite Mobility
due to Two-Layer Conduction. The Top surface Mobility serves as a comparision. The and N
D
of
the bottom n
+
layer and the of the top layer are the same.
102
Figure 3. 25 Simulation of Composite Concentration as a function of Bottom (n+) Layer carrier
concentration of an unintentionally doped sample. Background concentration of the top layer is
shown in dashed line.
1E+15
1E+16
1E+17
1E+18
1.00E+17 1.00E+18
Carrier Concentration of Bottom n
+
Layer(cm
-3
)
Concen
-tration
cm
-3
Top Layer Concentration
Composite Concentration
200
300
400
500
600
700
1.00E+17 1.00E+18
Carrier Concentration of Bottom n
+
Layer(cm-3)
Mobility
cm
2
/V-s
Composite Mobility
Top Surface Mobility
Figure 3. 26 Simulation of Composite Mobility as a function of Bottom (n+) Layer carrier
concentration of unintentionally doped sample. Background concentration of the top layer is shown
in dashed line. The values and N
D
of the top layer and of bottom n
+
layer are the same as in
Figure 3.23.
103
Figure 3. 27 Simulation of Composite Concentration as a function of Bottom (n
+
) Layer thickness of
an unintentionally doped sample. Background concentration of the top layer is shown in dashed line.
1E+15
1E+16
1E+17
1E+18
0.00004 0.00005 0.00006 0.00007 0.00008
Thickness of n+ layer in microns
Composite
Concen
-tration
(cm
-3
)
Composite Carrier Concentration
Top Layer Concentration
200
300
400
500
600
700
0.00004 0.00005 0.00006 0.00007 0.00008
Thickness of n+ layer in microns
Mobility
cm
2
/V-s
Composite Mobility
Top Layer Mobility
Figure 3. 28 Simulation of Composite Concentration as a function of Bottom (n+) Layer thickness of
an unintentionally doped sample. Background concentration of the top layer is shown in dashed line.
104
3.6 Origin of the Non-uniform Doping Layer
In the literature, the origin of the conductive layer or conductive transition layer has been
suggested. In some studies the bottom parallel path has been suggested to correlate with
the region full of stacking faults in the HVPE samples [16][18]. For zinc oxide pretreated
HVPE sample, Goetz et al have suggested a possible correlation between the electrical
defects and the dislocations within less than 1 m from the interface, the density of
dislocations decreasing rapidly with distance from the GaN/sapphire interface [19].
Cathodoluminescence data of a 40 m HVPE film shows a thin interfacial region of 0.5-1
m of non-radiative recombination centers [12]. Interestingly, they have found a quasi-
continuous layer made up of small columns of height up to 10m from the GaN/sapphire
interface. They estimate the electron concentration of this layer to be a few 10
19
cm
-3
, and
have suggested that the non-uniform electron concentration could be due to structural
imperfections (point defects such as the nitrogen vacancy), or decoration by impurity
atoms introduced through growth. Goetz et al [13] compare the level of oxygen (~1 x 10
18
cm
-3
) in the bottom 0.5 m measured by SIMS with the electron concentration of the
bottom layer measured by C-V. They conclude that the concentration is too small to be
the only cause of the high electron concentration. Other authors have used the SIMS data
to show that oxygen diffuses from the sapphire into the MOCVD gallium nitride film
[20] which does not seem to be very reasonable.
For our samples, no structural analysis on the interfacial region has been
performed, so it is not possible to conclude structural defects to be the source of this
layer. From the literature, MOCVD materials usually do not have large regions of
105
stacking faults, but in general contain higher concentration of dislocations of screw and
mixed types up to 0.5 m [21]. Oxygen is a possible cause of contamination in our film,
as shown in the gradual increase in SIMS oxygen level (~1 x 10
18
cm
-3
) towards the
bottom 0.5 m of our samples in Figure 3. 29. Coincidentally, similar electron
concentration level and profile is seen from C-V profiling of the thin series, although
preferential sputtering of the aluminum oxide substrate is also a likely cause for the data.
Figure 3. 29 SIMS data for an unintentionally doped sample.
1.E+15
1.E+16
1.E+17
1.E+18
1.E+19
1.E+20
1.E+21
0.00E+00 5.00E-01 1.00E+00 1.50E+00 2.00E+00 2.50E+00
Depth in Microns
C
o
n
c
e
n
t
r
a
t
i
o
n

(
c
m
-
3
)
Si
C
O
H
GaN
106
It is possible that gradual incorporation of impurities (like oxygen) from the 300
nm thick buffer layer occurs as the individual growth islands gradually join up to form a
continuous film. As the SEM view of the thin samples shows that coalescence is still not
complete up to 0.55 m, there is a possibility of the contamination from the buffer even
up to this thickness.
3.7 Hall Mobility Vs Carrier Concentration
In the introduction, the
Hall
and n
Hall
trend of gallium nitride is considered
anomalous in the upward slope in the low carrier density regime. The Boltzmann
transport equation is solved iteratively by Gaskill et al [22] and a theoretical trend of
mobility Vs concentration at room temperature should bear similar shape than for
example, gallium arsenide. The effect of two different compensation ratios is shown.
Ionized impurity scattering is an important scattering mechanism at high concentrations,
so a higher compensation means more ionized charges, and the two mobility curves
would differ. The silicon doped samples show decent agreement with the theory, if
compensation is the same throughout the intentional doping range. It is also quite likely
that the actual background compensator concentration does not vary much, resulting in a
net increase in compensation ratio with decreasing concentration. This could be a better
explanation of the data. At low concentrations, ionized impurity scattering should not be
a strong effect, so the theoretical mobility for both compensation ratios should be at
similar values.
107
The theoretical mobility shows a much higher mobility at low concentrations than
normally attained in the literature. In order to explain this discrepancy, the effect of the
measurement error posed by the parallel conduction path is illustrated in Figure 3. 30.
The analysis from this chapter for this set of three data points is shown. The undoped data
for the 1.1-m and 2.2-m sample (the latter happens to have one of the highest mobility
for among the undoped samples grown in this reactor) are shown with the corrected
values. By the two-layer analysis, the disagreement between theory and the data narrows
for these samples. More data points of various values of thickness (up to a few microns)
can improve the two-layer analysis. Finally, in order to generate a trend, analysis of more
undoped samples would be needed to show statistical significance of the behavior.
108
Figure 3. 30 Mobility Vs Carrier Density showing the theory (with compensation ratios 0 and 0.4)[22]
with data. Shown also are the 1 and 2 microns unintentionally doped sample and the correction with
the two layer model.
5 5
6 6
100 100
2 2
3 3
4 4
5 5
6 6
1000 1000
2 2
M
o
b
i
l
i
t
y

i
n

c
m
2

/
V
-
s
10
15
10
16
10
17
10
18
10
19
10
20
Carrier Density in cm
-3
Theoretical Calculation NA/ND=0
Theoretical Calculation NA/ND=0.4
Si Doped Unintentionally doped
Corrected Unintentionally doped
3.8 Summary
In this section, the room temperature electrical characteristics of the intentionally
n-doped and unintentionally samples have been examined. For the unintentionally doped
sample, capacitance voltage profiling shows a higher doped region near the substrate, and
a transition layer towards lighter doping towards the substrate. The two-layer model
essentially is analogous to two resistors in parallel, with the bottom layer more
109
concentrated with electrons and therefore is of a lower resistance, making it a favorable
path for electrons to travel. The problem with this bottom path is that the mobility is low,
causing the measured composite mobility to be much lower that if the top layer (high
structural quality) were measured by itself. Therefore, a two-layer analysis of thin films
of successive thickness has been employed to assess the inhomogeniety along the growth
direction of the film to extract the top layer electrical properties. The corrected data
shows a higher mobility and lower carrier concentration than the as-measured values, and
accounts for some of the discrepancy between the theory and the experimental data in the
anomalous behavior of Hall mobility Vs free carrier concentration. Unfortunately, there
is yet a universal consensus regarding the electrical nature (carrier type and transport
mechanisms) in the bottom layer, where defects of all kinds (namely, point defects and
impurities, dislocations and the stacking faults) are all present. In the next chapter, the
presentation of the mobility and carrier density characteristics in light of the scattering
mechanisms of the film will follow.
110
Reference
1. W. C. Johnson, P.T. Panousis, IEEE Trans. Electron Devices ED-18 195 (1972).
2. D. K. Schroder, Semiconductor Material and Device Characterization, John Wiley &
Sons, Inc., 1990.
3. C H Qiu, J I Pankove, Applied Physics Letters. Vol 70 n 15 Apr 14 1997. P 1983-
1985.
4. Peter Mitev, PhD Thesis 1997.
5. I. Akasaki, Journal of Crystal Growth 98 p109 (1989).
6. X. H. Wu, E. J. Tarsa, C. R. Elsass, P. Fini, S. P . DenBaars and J. S. Speck Journal
of Crystal Growth 180/190 231 (1998).
7. N. F. Mott and E. A. Davis, Electronic Processes in Non-crystalline Materials, 2
nd
Edition, Oxford University Press, Oxford, (1979).
8. J. N. Kunnia, M. A. Khan, D. T. Olson, Journal of Applied Physics 73 4700(1993)
AlN and GaN buffer XRD, buffer thickness, total thickness and XRD)
9. R. S. Muller, T. I. Kamins, "Device electronics for integrated circuits" 2nd ed. New
York : Wiley, 1977, c1986.
10. C. Youtsey and I. Adesida, G. Bulman, Applied Physics Letters Vol 71, No. 15, 2151
(1997).
111
11. S. Ruviov, Z. Liliental-Weber, T. Susuki, J. W. Ager III, J. Washburn, J. Krueger, C.
Kisielowski, E. R. Weber, H. Amano, I .Akasaki Applied Physics Letters 69 990
(1996).
12. T. Paskova, E. M. Goldys, B. Monemar, Journal of Crystal Growth Vol 203 p1
(1999).
13. W. Goetz, J. Walker, L. T. Romano, N. M. Johnson, and R.J. Molnar, Material
Research Society Symposium Proceedings, vol 499, 525 (1997).
14. L. T. Romano, B.S. Krusor, R. J. Molnar, Applied Physics Letters 71 2151 (1997).
15. W. Goetz et al, Applied Physics Letters 68 1869 (1996).
16. D. C. Look and R. J. Molnar, Applied Physics Letters 70 3379 (1997).
17. M. A. Reed, W. P. Kirk, and P. S. Kobiela, IEEE Jour. Quant. Elect QE22, 1753
(1986).
18. W. Goetz et al, Applied Physics Letters 69, 242 (1996). (HVPE)
19. W. Goetz et al, Applied Physics Letters 72, 1214 (1998). (HVPE)
20. X. L. Xu et al Applied Physics Letters 76 152 (2000).
21. D. Kapolnek, X. H. Wu, B. Heying, S. Keller, B. P. Keller, U. K. Mishra, S. P .
DenBaars and J. S. Speck Applied Physics Letters 67 1541 (1995).
22. D. K. Gaskill, K. Doverspike L.B. Rowland and D. Rode, International Symposium
on Compound Semiconductors edited by H. Goronkin (IOP Bristol) p101 (1995)
112
Chapter 4 Carrier Transport
4.1 Introduction
In this chapter, Hall measurements of the intentionally n-doped and
unintentionally doped gallium nitride will be examined. From the acceptor concentration
obtained from the mobility fit, the temperature-dependent carrier concentration will be
analyzed using the charge-balance equation. The Matthiesen rule is used to fit the Hall
electron mobility data to various theoretical scattering mechanisms both at room
temperature and variable temperature (from 77-300 K). In addition to the well-known
scattering mechanisms due to ionized impurities, acoustic phonons (deformation
potential), acoustic phonons (piezoelectric) and optical polar phonon, the two additional
transport effects are charged dislocation scattering and bottom layer conduction. Our
room temperature (see previous chapter) and variable temperature scattering data shows a
dominant effect due to the bottom n
+
layer, and correction of unintentionally doped data
will be shown. Also, the scattering effects due to charged dislocations would be
examined using the estimate of their density obtained from representative AFM
measurements. Finally, the relationship between Hall mobility and carrier density will be
re-examined.
113
Table 4. 1 Literature survey of electrical properties of unintentionally doped and silicon doped gallium nitride.
Group
/Author
Growth
Method
Ref. Buffer
layer
Doping
level
Thick-
ness
(m)
RT

RT n Peak
Temp
Peak

N
D
Cm-3
N
A
E
D
(meV)
Ndis
Cm-2
How was it
analyzed
Undoped
Xerox (Goetz) MOCVD 1 (uit Si
10
17
)
4.5 568 2.00x10
17
150 950 3x 10
17
1x10
16
17 High Temp ~T
-1.6
UCSB MOCVD 2 Nitridation 2 590 1.50x10
17
140 1100 3.1x10
17
1x10
17
4 x10
8
Warsaw MOCVD 3 GaN - 3 to 6 900 1.00x10
16
90 4000 High Temp ~T
-2
Nakamura TF-
MOCVD
4 GaN - 4 900 3.00x10
16
70 3000 High Temp ~T
-1
Yale MOCVD GaN - 2.2 317 3.7x10
16
145 473 1-2 x10
9
Look-Molnar HVPE 5 Pre-treat
ZnO
- 20 633 1.90x10
17
140 1700 2.1x10
17
5x10
16
16 Degenerate Layer
High Temp ~T
-2.8
Xerox (Goetz) HVPE 6 Pre-treat
GaCl
13 460 2.00x10
17
130 1210 1.7x10
17
18 3 x10
8
Degenerate Layer
Si Doped
Warsaw MOCVD 7 GaN >1x10
17
8 780 2.60x10
16
115 2000
Xerox (Goetz) MOCVD 1 >1x10
17
2 to 3 500 1.00x10
17
160 764 9x10
16
1x10
17
15 Power Law
High Temp ~T
-x
X=1.3-1.6
Yale MOCVD GaN 1.8x10
17
2.2 527 1.8x10
17
150 950 1-2 x10
9
Uof I (Morkoc) MBE 8 Undoped
templates
>1x10
17
1.5 280 5.50x10
17
130 690 1.3x10
17
8x10
16
9
BU (Ng) MBE 9 - 0.5 - 2 200 2.00x10
16
340 230 8x10
9
BU MBE 10 >1x10
17
0.5 - 2 300 3.00x10
17
424 13-15 8e9
114
4.2 Comparison of Data for Temperature Dependent Hall Measurements
In the introduction, the various growth techniques of gallium nitride and their respective
general characteristics were described. In order to understand our data within the larger
context of the community, the following data has been compiled. Listed in Table 4. 1 are
Hall carrier density and mobility values for wurzite gallium nitride. Comparing the
various unintentionally doped materials, MOCVD and HVPE samples reported generally
have unintentionally doping level of ~1x10
17
cm
-3
(mostly due to residual silicon as
supported by SIMS data). The exception are the outstanding MOCVD materials from
Nichia and the Warsaw University group, both with room temperature free carrier density
of ~1x10
16
cm
-3
after successful efforts in growth optimization. The fact that MOCVD
reactors are not high vacuum systems, incorporation of atmospheric contaminants is not
uncommon. While most MOCVD uses a two-step buffer layer process to improve the
quality of the MOCVD gallium nitride film, the buffer layer is less common in MBE due
to varying degrees of success [1]. The V/III ratio (adopted by many groups as the flow
rates in mols/min of nitrogen-bearing precursors to gallium -bearing precursors) during
growth is one parameter that greatly varies because it depends on the growth method and
the nature of the sources (whether or not they are pre-activated). In general, MBE has a
wider range of V/III ratios at their disposal, and many have reported lower V/III ratio
than MOCVD [11]. The significance of the growth conditions can affect the nature and
density of native point defects and dislocations.
In general, the dislocation densities for MOCVD and HVPE materials are lower
(best-reported value of 2 x 10
8
cm
-2
) than MBE by 1-2 orders of magnitude. Theoretical
calculations of the nature of these dislocations are varied (that these dislocations are
115
charged [12] or electrically inactive [13]), and atomic resolution TEM studies only are
emerging to observe the dislocation core structures [14]. The nature of the dislocations is
still not fully understood to allow unambiguous quantification of their scattering effect.
However, the studies of by Weinmann et al [15] and Ng et al [9] correctly describe the
trends in (MBE) transverse Hall mobility vs carrier density and their relative dependence
with respect to temperature. Their findings are consistent with the electrical
characteristics at the dislocations for various growth methods inferred by other
techniques (e.g. CL[16], SCM [17]).
As far as MOCVD material, the most two most outstanding data have been
achieved by Nichia [18] and University of Warsaw [3]. Both groups have achieved peak
mobility values (~ 4000 cm
2
/V-s) three to four times higher than and occurring at
temperatures ~ 60 K lower than the next tier of high-mobility material (compare with
peak mobility of ~1000 cm
2
/V-s at 140 K [2]). This is an implication that the former
material has low compensation, and the authors have indicated the crystalline quality of
the film is high. Although the dislocation densities are not available, it is very likely that
the values are one order magnitude lower compared to the others.
With this broader context in mind, the analysis of Yale MOCVD material will be
presented, and this list will be revisited to compare our material with the published data.
4.3 Scattering Mechanisms
In order to assess the scattering effects of gallium nitride, a theoretical background is
provided in this section. The various electron scattering mechanisms important in gallium
nitride transport are ionized impurity, acoustic phonon (deformation potential), acoustic
116
phonon (piezoelectric potential), polar optical phonon and dislocations. The Matthiesen
rule is used to add individual contributions to the total mobility, if all the relaxation times
<> are independent of energy E:
( )

i
i
total 1
1

;
* m

A better approximation is to calculate the average relaxation time integrated over all
energies.

0
2 / 3
0
2 / 3
dE E
dE E

The relaxation time is a good approximation for all scattering mechanisms except
for the optical polar phonon scattering rate (and hence mobility) which needs to be
approximated by the variational solution to the Boltzmann equation. Basic formulation of
the relaxation time and mobility are based on the standard works and textbooks such as
Ziman [19], Blakemore[20], Look[21].
4.3.1 Acoustic Phonon (Deformation Potential)
Interaction of electrons and acoustic phonons causes deformation of the lattice, changing
the bandgap in various points of the crystal. The electron scattering by this type of
phonon is elastic, with its corresponding mobility approximated by the following
expression:
2
3
2
5
) ( *) ( 3
2 2
2
1
2 2
T k m E
e s
B
dp
h

;
) ( *) ( 2
2 / 3 2
1
2 / 1 2 2
T k m E
E s
B
dp

117
The deformation potential is a function of the crystal mass density, s the velocity of
sound and E
1
the deformation potential.
4.3.2 Acoustic Phonon (Piezoelectric Potential)
Interaction of electrons and acoustic phonons caused by strain in the material, especially
for crystals lacking inversion symmetry, introduces the piezoelectric effect. This form of
phonon scattering is also elastic, with the corresponding mobility approximated by the
following expression :
2
1
2
3
) ( *) )( ( 3
2 16
2 2
T k m eh
e s
B s pz
pe

;
) ( *) )( (
2 2
2
1
2 / 1 2 2
T k m eh
eE s
B s pz
pe

This scattering mechanism also depends on , s and E

1
, with the additional h
pz
term
which is the piezoelectric constant. Even though the expression for mobility bears
resemblance to the mobility due to acoustic deformation potential, the temperature
dependence is different.
4.3.3 Optical Polar Phonon (Using variational approach)
In ionic crystals like GaN, the optical phonon modes must be accompanied by large
polarization field due to large contra motions of ions of opposite charge. The large
phonon energy absorbed or emitted in this process makes scattering inelastic. Therefore,
the relaxation time approach is not a good approximation, considering that measurement
range is well below Debye temperature of 1044 K. In order to solve the Boltzmann
equation for this mechanism, Rode iterative technique can be used, but does not reduce to
analytical form. The variational technique is used by Ziman [19] to enable manipulation
118
of the first two terms in the mobility. It was solved by Howarth and Sondheimer (see
explanation in Look[21]). Ehrenreich derived a similar expression. The mobility is
approximated as follows:
) )( ( *) (
) / ( ] 1 ) / [exp( ) ( 2
1 1
0 0
2 2 / 9
2
3
2
1

s B
B
po
T k m e
T T T T T k

h
The polar optical phonon scattering is a function of low and high frequency
dielectric constants (
s
,

). The (T
0
/T) term is a slow varying function with respect to
temperature, and has been approximated as
2
0 0 0
) / ( 2920 . 0 ) / ( 5841 . 0 1 ) / ( T T T T T T +
for 0T
0
/T5
) / ( 8 / 3 ) / (
0 0
T T T T
for 5T
0
/T
4.3.4 Ionized Impurity
The previous three scattering mechanisms affect the semiconductor at high temperature.
Electron scattering by the Coulomb potential of ionized impurities is a dominant
mechanism at low temperature in semiconductors. The potential of the charged ions is
reduced due to Thomas-Fermi screening. The formulation follows Brooks-Herring
derivation as follows [22]:

[ ] ) 1 ( ) 1 ln( *) (
) ( 2 128
2
1
2
3
2
2
b b b m Z N
T k
I
B s
ii
+ +

where N
I
N
D
+ N
A
;
119
'
) ( * 24
2
2
n e
T k m
b
B s
h

;
n' (the effective screening concentration) is given by n' = n + ( N
D
- N
A
- n )(n + N
A
)/
N
D
4.3.5 Charged Line dislocation
Electron scattering by the Coulomb potential of charged line dislocations could also be
important at low temperature in semiconductors. Wienmann et al [15] calculated the
extent to which the traps inside each dislocation are filled (as expressed by the fraction of
filled traps f) using the formulation from Read [23]. The assumption used is that each
dislocation line contains an electron trap (acceptor) for every c-lattice spacing, so f
depends on the number of available free electrons that can be trapped. The other
important assumption is that the energy level of the defect-state of the dislocation is
known, which these authors took to be the defect band energy (also known as the yellow
band) from photoluminescence measurements. For most groups this level is about
~2.2eV, so the authors assigned the trap level E
t
to be 2.2eV below the conduction band.
The origin and nature of this yellow band is a topic under intensive research, so the
assumption used in the model may be questionable. In any case, the potential energy of
the electron on the dislocation increases as the sites are filled until the electrostatic energy
E
s
(from electron-electron repulsion, electron-ionized donor attraction and ionized donor
repulsion) increases to the point where it is no longer energetically favorable to do so.
Therefore, f can be calculated by minimization of free energy per site: f x (E
t
E
F
+E
s
(f)
). The energy diagram is illustrated in Figure 4. 1[15].
120
On a rigorous level, Wright et al [24] have calculated the formation energies of
the defect levels at a threading edge dislocation in gallium nitride taking into account
both gallium-rich and nitrogen-rich growth conditions. Like Van de Walle et al [25], their
study indicates that for the latter condition (our MOCVD materials are probably grown
under such conditions), it is energetically favorable for the dislocations to be made up of
gallium vacancies (and nitrogen vacancies for the gallium rich growth condition). Built
on this theory, Leung, Wright and Stechel have also calculated the various charge states
and the number of electrons/site with respect to dopant density, equivalent to the fraction
of filled trap f [26].
Figure 4. 1 Energy diagram in the vicinity of the dislocation[23].
E
t
E
F
Distance from
Dislocation
E
C
121
Figure 4. 2 Fraction of filled traps from Figure 4. 3 Fraction of filled traps from Leung,
Wiemann, Eastman et al[15] Wright et al[26] for the nitrogen rich growth
environment where gallium vacancies are
energetically favorable.
The effect of transport due to these line-dislocations is treated like the ionized
impurity scattering mechanism that is relatively dominant at low temperatures. This
mechanism is strongly screened by the available free carriers in the bulk, and depends on
the density of the charged traps. The mobility is given by [27]:
D Dis
B s
Dis
m e f N
c T k

2
1
2
3
*) (
) ( 2 30
3 2
2
2
;
'
) (
2
n e
T k
B
D

where N
Dis
is the density of dislocation, c is the lattice constant perpendicular to the plane
of transport,
D
is the Debye length, n' is the effective screening concentration. The
accuracy of this analysis in gallium nitride depends on the understanding of the electrical
nature of the dislocations in this material, if indeed they are electron traps, the defect
levels, reasonable estimate of the actual number density and the fraction of filling.
122
In the next section, the experimental details and data analysis will be presented
based on the various scattering mechanisms discussed here.
4.4 Experimental Details
Figure 4. 4 Diagram of the Hall bridge
3
1 2
4 5
12mm
Evaporated Ti/Al
Contact
3.5mm 1.5mm
0.5mm
1mm
The setup of these experiments was described in Section 2.5.2 of Chapter 1. The Hall
Bridge structures were used for the variable-temperature Hall experiments (77 - 290 K)
and the low temperature conductivity measurements (1.5 - 290 K) to be discussed in
section 4. Fabricated by abrasive removal just like the clover leaf Hall structures
described in Chapter 2, the dimensions of the six-contact Hall bar were 12mm by 1.5mm
long for the current injection large contacts (1,2), with the two voltage probe branches
(3&4, 5&6) 3.5mm apart.
In these experiments, the HP 34401A Multimeter was used. The resistance across
points (3&4) was measured with a current excitation of 10-100 A from points (1&2).
Hall resistance was measured across points (4&5) for both N and S polarities of the B
field, and the zero-field resistance was measured to account for the misalignment of the
contacts. Ohmic contacts of 200 Ti/1000 Al was fabricated by lift-off, after which the
samples were annealed at 900 C for 30s. The samples were mounted securely onto a 16-
123
pin ceramic header with cement glue and contacts were connected to the pins by
indium/silver alloy solder and thin copper wire. Good Ohmic behavior in the low
temperature I-V sweeps was ensured before the measurement was made for the entire
temperature range.
Figure 4. 5 Calibration of two cryostats.
Data taken with 020
Cryostat (See Chapter 4)
Data taken with Hall
Setup in this Chapter
1/ T
The reliability of the measurements of this setup was measured against the room
temperature Hall setup in Room 500 with the same van der Pauw sample. The same
averaging technique was done for the sample using the Multimeter setup, and the
agreement for the carrier concentration was 9% and 1% for mobility. However, the same
averaging technique was not used for the bridge samples, due to the limitation of sample
124
area. Furthermore, the Hall Bridge samples were not fabricated from any particular
location of the sample. As shown in Chapter 3, the variability of Hall mobility and carrier
density was shown across the wafer. In fact, a few samples were indeed taken from the
corner piece that has higher Hall carrier concentration and mobility. In terms of
conductivity the error was estimated to be 15% if comparing the bridge samples with the
star samples. The reliability of the temperature control was measured against the cryostat
in 020 using the same Hall Bridge samples. Figure 4. 5 is a comparison of the variable
temperature resistance plot of the two setups when the temperature warmed up slowly to
ensure thermal equilibrium.
4.5.1 Results of Hall Measurement
I. Unintentionally doped Samples
Hall measurements of two unintentionally doped samples of different thickness are
presented in Figure 4. 6 in which the log of carrier density versus inverse temperature is
plotted. The fact that both samples are not straight lines in this plot implies that the
relationship is more complex than a single energy activation behavior. Further analysis
using the charge-balance equation will follow to find the compensation ratio and donor
energy level. The mobility data can be analyzed to first order by empirical power laws in
the high and low temperature regimes. The room temperature carrier densities of the 0.5-
m and the 2-m samples are 1.8 x10
17
and 3x10
16
, and the peak mobility values are 188
and 473 cm
2
/V-s occurring at (160 K and 145 K) respectively.
125
Figure 4. 6 Hall carrier density vs inverse Temperature for undoped samples (1/2 and 2 microns)
uncorrected (Top Figure). Hall carrier density vs inverse Temperature for undoped samples (1/2 and
2 microns) corrected by the two layer model (Bottom Figure).

micron
2 micron
uncorrected
2 micron
corrected
126
Figure 4. 7 Mobility vs Temperature for 2 micron undoped sample (top) without and (bottom) with
correction from the two-layer effect of the 0.5 micron sample.
127
In Chapter 3, the two-layer analysis has been employed for the unintentionally
doped sample in the 1x10
16
range, to provide an estimate of the discrepancy between the
top layer mobility and average composite mobility. Using the same analysis, the extracted
carrier concentration and mobility of the unintentionally doped sample is re-plotted with
respect to temperature in Figure 4. 6 and Figure 4. 7. A low carrier concentration value
of 3 x 10
16
cm
-3
and peak mobility of 490 cm
2
/V-s at a relatively low temperature of 140
K has been measured for the undoped sample (uncorrected). The mobility information
implies that the quality of the material is good. According to Figure 4. 7, the mobility
value is shifted down as a result of the transition layer conduction. The temperature shift
of the peak mobility seems to be subtle, but no drastic change in temperature dependence
is noted. The peak mobility of the corrected data is 742 cm
-2
/V-s at 130 K. The result of
the transition layer analysis in Chapter 3 clearly shows that the corrected room
temperature mobility of the 2.2-mm undoped sample 322-678 cm
2
/V-s. Considering the
variability between runs and across the sample, this is within 20% agreement.
II. Silicon Doped Samples
The mobility and carrier concentration data for the silicon-doped Samples 3-5 is plotted
in Figure 4. 8. The log of carrier density versus inverse temperature is usually plotted to
show single energy activation behavior. The fact that the data deviates from a straight
line implies that the relationship is more complex, and the fitting analysis will follow.
The mobility data can be analyzed to first order by empirical power laws in the
high and low temperature regimes. The power factor x (~ T
x
) in the high temperature
regime for Samples 3, 4 and 5 are -1.5, -1.3 and -1.4 respectively. There is more
variability in the low temperature regime for Samples 3, 4 and 5, with powers of 1.1, 0.9
128
and 1.3 respectively. This is an indication of the variation in compensation ratio. The
samples 3, 4 & 5 show room temperature free carrier concentration values of descending
order (1.8 x10
17
, 1.5 x10
17
, and 7x10
16
), and peak mobility values of 790, 950, 650
cm
2
/V-s occurring at (160 K, 150 K and 145 K) respectively. The peak temperature
position correlates with the free carrier concentration at room temperature, and yet the
peak mobility level does not. The lower than expected mobility of Sample 5 implies that
the transition layer conduction does play a role in the transport of this sample. Our data
show similar temperature-dependent Hall characteristics compared to similar material
grown elsewhere [1]. A similar trend in peak temperature and peak mobility for
comparable doping levels has been seen by the study as well. The high temperature
power dependence varies from -1.3 to -1.6. Of course, this method of analysis depends on
the available temperature range of the data, and the power dependence can be
underestimated in the roll-off transition region between the high and low temperature
regimes.
In Chapter 3, the measured mobility of lightly doped of top layer is shown to be
seriously affected by the two-layer effect. In Figure 3.31, showing the mobility vs carrier
concentration, even the silicon doped samples in the lower concentration range deviates
from the theoretical values. Due to issues of long-term reproducibility and the possibility
of difference between the transition layer of doped and unintentionally doped samples,
across the board two-layer correction for all data sample is not possible using any given
thin undoped sample. Like the analysis shown in Figure 4. 7, the shift in temperature of
the peak mobility is expected be small. As a result of the transition layer conduction, the
mobility could be underestimated by ~15%.
129
Figure 4. 8 Top : Hall mobility vs Temperature for Si-doped samples (2 microns). Bottom: Hall
carrier concentration vs Temperature for Si-doped samples (2 microns).
2
3
4
5
6
7
8
9
1000
5 6 7 8 9
100
2 3
=T
-1.3
=T
0.9
Peak @ 150K
2
3
4
5
6
7
8
9
1000
5 6 7 8 9
100
2 3
=
1.3
Peak @ 145K
=
1.4
Sample 5
Sample 3
Sample 4
2
3
4
5
6
7
8
9
1000

m
o
b
i
l
i
t
y

c
m

2
/
V
s
5 6 7 8 9
100
2 3
Temperature
=
1.5
=
1. 1
Peak @ 160K
130
4.5.2 Results of AFM
The assessment of the threading dislocation density is best done by a combination of
cross-sectional TEM which allows the distinction among various types of dislocations
(e.g. threading, screw and mixed), and plan view TEM which gives the actual area
density of the dislocations. However, since TEM sample preparation is very involved,
other methods have been used to estimate the dislocation densities. Rosner et al [16] has
shown correlation of fine morphological features (~30nm diameter) among AFM, plan
view TEM to characterize threading dislocations in gallium nitride. Kaponlnek et al have
found the same order of magnitude estimate of dislocation density with the AFM and
TEM measurements [28]. Photochemical etching studies show the correlation among the
whisker-like structures after etching, dislocations by AFM, and threading dislocations by
cross-section and plan-view TEM [29].
A typical AFM image of an uncontaminated gallium nitride sample is shown in
Figure 4. 9. The color scale represents the height of the sample, showing bands of color
indicative of atomic steps. The black dots which are surface depressions are correlated
with TEM to be individual dislocations [28] and have in general two different sizes of
total dislocation density ~1-2 x 10
9
cm
-2
. For our samples, the larger ones (~ 300 - 500
in diameter [28][16]), that are more dominant are likely to be mixed and screw
dislocations and are measured to be >400 for our samples (Figure 10). The smaller ones
are likely to be edge dislocations in 150 diameter. Note also that the smaller edge
dislocations are unevenly distributed, but they appear in arrays to form a grain boundary.
The surface depressions are predicted to be formed at the surface terminations of
dislocations due to strain energy density associated with the dislocation [11].
131
Figure 4. 9 AFM scan of Sample 5 showing dislocations (top) dislocation density of this sample is ~1-
2 x109 cm-2. Profile of surface depression on AFM scan is shown in the bottom figure.
Array of small depression
(edge typedislocation ) to
make up a grain boundary
Individual larger depression
(mixed type)
Profile of surface depression
0
20
40
60
80
100
120
140
0 0.01 0.02 0.03 0.04 0.05
distance in microns
A
r
b
i
t
u
a
r
y

u
n
i
t
s
The surface could not be completely cleaned for some samples even after
extensive ultrasonic agitation during acetone dip. The protrusions on the surface of the
scale >3nm are most likely to be contaminants. However, we are still able to distinguish
132
the black surface depression features from the contaminant ones. The dislocation density
of this sample is ~1-2 x10
9
cm
-2
.
The distribution of dislocations is in good agreement with X-ray diffractometer
data shows FWHM values of 468 arcsec for asymmetric reflection and 216 acrsec for
symmetric reflection. This indicates a higher density of dislocations having a screw
component as measured by the symmetric case as opposed to the dislocations having an
edge component shown in the asymmetric reflection [28]. The data is similar to other
high the temperature range between 77 - 190 K, activation behavior is observed (see
quality MOCVD gallium nitride on sapphire [28].
4. 6 Hall Carrier Concentration Fitting
In this section, the Hall carrier concentration is fitted with the charge-balance equation. In
plot of n vs 1/T ( Figure 4. 8 ) and plot of ln vs 1/T ( Figure 5.3, Chapter 5). Since
transport in this regime is described by well-established characteristics of carrier
concentration and mobility, both of which varying quite dramatically above 77 K, the
trend in the activation energies extracted from the conductivity can only provide
qualitative insight on effect of increasing silicon doping. The conductivity activation
energies are 4.6 meV for the highly doped sample (#1) which is past the Mott transition,
12 meV for the intermediately doped sample (Sample 2) and gradually increase to ~17
meV for the lightly doped samples for Samples 3,4,5.
Variable-temperature Hall data shown in Figure 4. 8 for lighter doped samples #
3, 4 & 5 will be analyzed. These measurements serve as comparison to material quality
grown by other groups, as well as to give us an idea of the compensation ratios of our
133
films. From optical measurements, it is believed that there are two shallow donors
[Error! Reference source not found.] and an acceptor. The carrier concentration data is
fitted with the charge neutrality equation with two independent donors and compensators
according to:

,
_

+
+
2
1
exp 1
i Di
C
i
Di
comp
kT
E
N
n g
N
N n
where n, N
A
ND1, ED1, ND2, ED2, and g, are the
concentration of the electrons, compensating acceptors, shallow donor, activation energy
of the shallow donor, deep donor, activation of the deep donor, and the degeneracy factor.
The conduction band effective density of states is given by NC = 4.3x 10
14
T
1.5
.
The shallow donor level and its concentration have been determined from least-
squares fit with all five parameters (ND1, ED1, Ncomp, ND2, ED2 ) floating, and in other
cases Ncomp is fixed to determined the rest of the parameters. The extracted shallow
donor ED1 activated energy varies between 11 22 meV (for sample 3, 4 5 and the
unintentionally doped 2.2-mm sample after correction) are consistent with other MOCVD
grown silicon doped samples [1] of which the data is analyzed by solving the charge-
balance equation (Table 4. 2). Alternatively, the fitting can be done with the assumption
of a single donor [30], and the slope of log carrier concentration vs inverse temperature is
extracted. The extracted donor ionization energy is half the slope, yielding ~ 26 meV for
Sample 4, in good agreement with the literature [30]. However, the accuracy of this
method is not clear. Using the first method, the donor energies are small compared to the
ionization energy from a hydrogenic donor in gallium nitride ~28 meV calculated from
the Bohr radius. Such discrepancy is also seen [5][31] in other material, and has been
134
attributed to the effect of the fluctuating potential of the ionized donors on the bandgap
energy, resulting in E
D
=28meV a
e
N
D
1/3
. The value of a
e
was estimated to be 2.1x10
-5
meV/cm [31], in good agreement with our estimates.
The less precisely determined deeper donor level from this fit is between 39 and
75 meV, as compared to 37 meV from previous Hall measurements [1], suggested by
some as the resonant donor level due to oxygen [Error! Reference source not found.].
All samples show comparable compensation ratio N
A
/N
D
to be <0.3 from this fit, but
again with uncertainty. When the values of compensation are fitted to be very low, which
may not be realistic, addition constraints such as 0.1<N
A
/N
D
0.4, E
D1
> 10meV,
E
D2
<100meV need to be used. As a result the fitted value of N
A
is more than one order of
magnitude than the first fitting method. In this case, the fitting of the carrier concentration
is still good indicated by only a 10% increase in the root mean square error. As for
Sample 5, the Hall measurements is likely to be affected by the two-layer effect, so it is
not clear how accurate the analyzed values are. The analysis of unintentionally doped
(2.2m) sample with the two-layer correction is also shown.
Table 4. 2 Results of charge-balance equation fitting.
Sample N
D1
Cm
-3
N
D2

cm
-3
E
D1
meV
E
D2
meV
N
A
cm
-3
Root mean
Square
Error
cm
-3
Interaction
factor
meV/cm
# 3 (Si-doped) 2x10
17
1.68x10
17
15.6 75 <1x10
16
2.3x10
15
2.05x10
-5
2.3x10
17
1.5x10
17
11 65 4x10
16
2.5x10
15
2.71x10
-5
# 4(Si-doped) 1.7x10
17
4.3x10
16
15.6 39 1.2x10
16
1.2x10
14
2.17x10
-5
# 5(Si-doped) 4.2x10
16
4.7x10
16
20 66 <1x10
15
3.6x10
14
2.19x10
-5
6.2x10
16
4.7 x10
16
14.7 65 2x10
16
3.9x10
14
3.26x10
-5
UID (2.2mm
corrected)
9.9x10
15
3.6x10
15
22.5 56 1.4x10
15
1.7x10
14
2.38x10
-5
135
4.7 Mobility Analysis - Scattering Mechanisms
In the earlier section, the various physical mechanisms regarding gallium nitride have
been discussed. The following parameters are used in calculating the various
contributions. The limitation of fitting mobility is that many scattering mechanisms are
involved, and each material-related parameter (Table 4. 3) needs to be known quite
accurately. With the available estimates of the above, the Matthiesen rule is used to ad up
the various contributions of the average relaxation time, hence, drift mobility. However,
the drift mobility is related to Hall mobility by Hall scattering factor which is not
extensively established either. Extensive modeling is needed, and it is well beyond the
scope of this work. We have estimated the Hall scattering factor to simulate the data.
Table 4. 3 Physical Parameters of GaN [32] [33]
Parameter Symbol(Units) GaN
Dielectric Constant (High Freq.)

(F/m) 5.47
0
Dielectric Constant (Low Freq.) (F/m) 10.4
0
Polar phonon Debye Temperature T
po
(K) 1044
Mass Density (kg m
-3
) 6.10 x10
3
Speed of Sound s (m/s) 6.59 x10
3
Piezoelectric Constant h
pz
(
14
) (Cm
-3
) 0.5
Acoustic Deformation Potential E
1
(eV) 9.2
Electron effective mass m* (kg) 0.22
136
Table 4. 4 Temperature dependence of various scattering mechanisms.
Mechanism Temperature Dependence
Acoustic Deformation Potential Phonon T
1.5
Acoustic Piezoelectric Phonon T
0.5
Optical Polar Phonon T
1.5 to 2
Ionized Impurity T
1.5
Charged Dislocations (?) T
1
In Section 4.3, we have discussed the theoretical expressions for the various
scattering mechanisms for gallium nitride. Theoretically, for a pure gallium nitride
without any structural defects, the scattering should only be affected by the phonon
scattering shown as the first three items in
Table 4. 4. The mobility due to these mechanisms is plotted in Figure 4. 10 on
solid lines to highlight their effect. The effect of ionized impurity scattering (dashed) of
donor concentration of 10
16
cm
3
with compensating acceptors of 5 x 10
15
cm
3
is
plotted as an example of how this scattering mechanism looks like.
137
Figure 4. 10 Mobility due to Phonon Scattering
100
1000
10000
100000
1.00E+01 1.00E+02 1.00E+03
Temperature in K
Mobility in cm-2/V-s
Total of phonon scattering
Piezoelectric Acoustic Phonon
Optical Polar Phonon
Acoustic Deformation Potential
Ionized impurity
scattering
4.8 Mobility Fitting
4.8.1 Silicon-Doped Samples
The analysis of the temperature dependent mobility is as follows. Figure 4. 11
show the data for Sample 3 & 4 with room temperature Hall carrier concentration of 1.8 x
10
17
cm
3
and 1.5 x 10
17
cm
3
respectively. The high quality unintentionally doped
material by other groups [2] has similar overall and peak mobility value, as well as the
peak mobility temperature compared to our silicon doped sample #4. Using the
Matthiesen Rule for adding up the ionized impurity, optical and acoustic phonon
138
(deformation & piezoelectric), the calculation still does not account for the high
temperature portion.
a) Mobility fit for Sample 3
0
200
400
600
800
1000
1200
50 150 250 350
T
Mobility
b) Mobility fit for Sample 4
0.00E+00
2.00E+02
4.00E+02
6.00E+02
8.00E+02
1.00E+03
1.20E+03
0 50 100 150 200 250 300
T(K)
Mobility in
cm2/V-s with
no Ndis
Figure 4. 11 Mobility vs temperature for a) Samples 3 and b) Sample 4.
Aside from the fitting method discussed previously, the other method of retaining
the general shape of the curve involves dividing the entire theoretical curve by a
numerical factor (1.79 for Sample 3, 1.68 for Sample 4 in Figure 4. 11). Using this
139
method, the N
A
is found to be ~ 6x10
16
and 8x10
16
cm
-3
respectively. However, by the
same analysis as before, the two-layer effect can cause an underestimation in the
measured mobility values. Another reason was attributed to large area contacts by Look
[34]. If this were an experimental artifact, it should be easily corrected. However, our
silicon-doped samples show similar behavior as in the literature [1].
Just for the sake of completeness, the Matthiesen Rule with the inclusion of
dislocation scattering is used to fit the data without good agreement. The dislocation
density is 1x10
9
cm
-2
in the best case, assuming that the all traps are filled for dopant
concentration in the 1 x 10
17
cm
-3
range according to Figure 4. 2. When the estimated
Hall factor is included in Figure 4. 12, the theoretical values still is fitted to within 20%
of the data, and N
A
is estimated to be 8 x 10
16
cm
-3
.
Figure 4. 12 Fitting of Sample 4 with Hall scattering factor.
Sample 4
0
200
400
600
800
1000
1200
0 100 200 300
Temperature (K)
Mobility (cm^2/V-s)
4.8.2 Unintentionally Doped Samples
For the unintentionally doped sample used in this analysis, the room temperature
carrier density is 3 x 10
16
cm
-3
and the corrected value is 1 x 10
16
cm
-3
from the two-
140
layer analysis. The background carrier concentration is lower than the average
unintentionally doped material reported in the literature, and our peak mobility occurs at
140 K. The data could not be fitted with any reasonable model satisfactorily.
Method 1) It was mentioned in the previous section that the numerical factor can
account for some of the discrepancy of the data due to the two-layer effect. If N
A
of 1.6 x
10
16
cm
3
is used to fit the uncorrected data, a numerical factor of ~6 is needed to divide
the entire mobility data. The resulting corrected room temperature mobility will be over
1000 cm
2
/V-s which is inconsistent with the transition layer analysis which gives a range
300 - 678 cm
2
/V-s, not enough to explain the discrepancy.
Method 2) The theoretical mobility due to phonon scattering is much higher that
the measured values. Figure 4. 13a shows that if the low temperature range is fitted with
ionized impurity scattering with acceptor concentration of 1.2 x 10
17
cm
-3
. Adding the
mobility due to ionized impurities does not fully account for the data both the high and
the low temperature regions at the same time.
Method 3) Similar to Method 2, inclusion of effect due to charged dislocation
does not fully account for the data both the high and the low temperature regions at the
same time. As discussed in Section 4.3.5, the accuracy of the analysis of dislocation
scattering in gallium nitride depends on the understanding of the electrical nature of the
dislocations, if indeed they are electron traps, the defect levels, and reasonable estimate
of the actual number density and the fraction of filling. For our undoped samples with
nominal net doping carrier concentration of 1.6 x 10
16
cm
-3
(after two-layer correction),
the dislocation density is in the range of 1-2 x 10
9
cm
-2
from AFM. Assuming for the
141
moment that there is indeed one trap per c-lattice, the acceptor density is 2 - 4 x 10
16
cm
-
3
, implying that a donor density before compensation around 3 - 5 x 10
16
cm
-3
. For a
rough estimate from the theory by Leung et al (see Figure 4. 3) at a doping density level
equal to or higher than the above, the fraction of filled traps should be close to 1 and the
resulting dislocation scattering should be significant.
In Figure 4.13 b, it shows the fitting using phonon and dislocation scattering. The
calculation of the mobility due to dislocation is similar to Look's [35] in which f =1 was
also assumed. The difference between the data Look analyzed for the sample grown at
UCSB [35] and ours is that the background carrier density is about an order of magnitude
lower, and their dislocation density is 4 x 10
8
cm
-2
which means that the contribution of
dislocation scattering is small. For our calculation here, the dislocation density is taken to
be the best case value of 1 x 10
9
cm
-2
as measured by AFM and that the scattering of the
dislocations is severely overestimated in the low temperature regime. The effect of
ionized impurity scattering is not shown because of negligible contribution to the total
mobility fit even if the acceptor concentration is 1 x 10
17
cm
-3
. Both the high and low
temperature regimes cannot be fitted properly.
Figure 4.13 c shows both contributions of the ionized impurity and dislocation
scattering, with fitted dislocation density of 2x 10
8
cm
-2
, and acceptor concentration is 4 x
10
16
cm
-3
. Again, f is also estimated to be 1 from Figure 4.3.Both the high and low
temperature regimes also cannot be fitted properly.
142
Figure 4. 13 a) Fitting Undoped sample using phonon and ionized impurity scattering. Both the high
and low temperature regimes cannot be fitted properly.
1.E+02
1.E+04
10 100 1000
Temperature (K)
Mobility
(cm-
2
/V-s)
Total fitted Mobility
Ionized Impurity NA=1.2e17cm-3
Phonon Mobility (Acoustic and Optical)
Data
1.E+02
1.E+04
10 100 1000
Temperature (K)
Mobility
(cm-
2
/V-s)
Total fitted Mobility
Dislocation scattering, NDis=1e9 cm
-2
Phonon Mobility (Acoustic and Optical)
Data
Figure 4.13 b Fitting Undoped sample using phonon and dislocation scattering of 10
9
/cm
2
. Effect of
ionized impurity scattering is not shown because of negligible contribution to the total mobility fit.
Both the high and low temperature regimes cannot be fitted properly.
143
1.E+02
1.E+04
10 100 1000
Temperature (K)
Mobility
(cm-
2
/V-s)
Ionized Impurity NA=4e16cm
-3
Phonon Mobility (Acoustic and Optical)
Dislocation Scattering NDi s=2e8 cm
-2
Total Fitted Mobility
Data
Figure 4. 14c Fitting Undoped sample using phonon and dislocation scattering of density 2 x10
8
/cm
2
,
and ionized impurity scattering (acceptor concentration 4x10
16
cm
-3
.Both the high and low
temperature regimes cannot be fitted properly.
4.8.3 Hall Mobility vs Carrier Concentration
The anomalous behavior of Hall mobility Vs Carrier concentration at 300K is discussed.
This relationship should be viewed in conjunction with poor fitting of the variable
temperature mobility characteristics. Among the many calculations regarding this
relationship, as much a factor of 1.5 difference in the theoretical value of an
uncompensated gallium nitride with doping level 1x10
16
cm
-3
. The difference is their
calculation of the Hall scattering factor [33], estimation of the optical polar phonon
scattering effect [36], and the use of relaxation time as opposed to iterative solution to the
Boltzmann equation [37]. Figure 4. 14 shows the simulation by Gaskill et al [36] with
144
compensation ratios N
A
/N
D
=0 and 0.4. As one can see, the corrected data due to the two-
layer model of the transition layer pushes the data closer to the theoretical simulation. To
first order, the data is explained by the transition layer effect.
Figure 4. 14 Mobility vs carrier concentration considering the effect of dislocation scattering and
Gaskills [36] prediction.
5 5
6 6
100 100
2 2
3 3
4 4
5 5
6 6
1000 1000
2 2
M
o
b
i
l
i
t
y

i
n

c
m
2

/
V
-
s
10
15
10
16
10
17
10
18
10
19
10
20
Carrier Density in cm
-3
Theoretical Calculation NA/ND=0
Theoretical Calculation NA/ND=0.4
Si Doped Unintentionally doped
Corrected Unintentionally doped
Dislocation Scattering f=1

145
The effect of dislocations using for dislocation density of 1 x 10
9
cm
-2
(best case
for our data, usually can be up to 2 x 10
9
cm
2
) can be assessed to see how this
relationship is changed. The fraction of filled trap f = 1 is used as the best estimate for the
dislocation density at particular doping range using Leung et al's simulation. At room
temperature, the dominating scattering effect is the optical phonon scattering, so the
effect of the dislocation is not as easily seen as the low temperature data. In Figure 4. 14,
the dependence of dislocation scattering on carrier concentration is weaker than the data
suggested, i.e. the data shows a much sharper roll-off with carrier concentration. Perhaps
if the data at 77K is plotted, the disagreement would be even more dramatic. More
importantly, the effect of dislocation scattering using this formulation has already been
shown to underestimate severely the variable temperature Hall mobility in the previous
section.
4.8.4 Discussion
Poor agreement between the data and the theoretical calculation for Hall mobility Vs
temperature and Hall mobility Vs carrier concentration are seen. The inclusion of
dislocation scattering, using the estimation of the fraction of filled traps by Leung et al
[26], still does not satisfactorily explain the data. In fact, the two-layer correction seems
to be much more important than the explanation by dislocation scattering effect that
underestimates the mobility at low temperature.
Recall that the mobility due to dislocation scattering is as follows:
D Dis
B s
Dis
m e f N
c T k

2
1
2
3
*) (
) ( 2 30
3 2
2
2
;
'
) (
2
n e
T k
B
D

146
where N
Dis
is the density of dislocation, c is distance between adjacent traps at any
dislocation line (assumed to be the same as the lattice constant perpendicular to the plane
of transport),
D
is the Debye length, n' is the effective screening concentration.
The uncertainty for the calculation of dislocation scattering is firstly, the possible
wrong assumption of the number of traps per dislocation. In fact, recent Z-contrast TEM
studies [14] have shown that at the dislocation core, the likely line defect density (likely
to be made up of gallium vacancies) could be as low 15% of the value used in the
assumption. That means c lattice parameter used in the formulation is too small.
The second problem is the complex charge accumulation calculations of the
fraction of filled traps f by Leung et al [26]. For one, it depends on the accurate estimate
of the distance between adjacent defects along the direction of the threading dislocations,
i.e. the value of c which is taken to be the lattice constant of gallium nitride along the
growth direction. As explained previously, f is calculated by minimization of free energy
per site. The potential energy of the electron on the dislocation increases as the sites are
filled until the electrostatic energy E
s
(from electron-electron repulsion, electron-ionized
donor attraction and ionized donor repulsion) increases to the point where it is no longer
energetically favorable. Moreover, the estimate of f also requires an estimate of the trap
energy levels that have been calculated by the same group [24]. At this point, it is not
clear whether the f values (or the trap levels) calculated are correct or not. Unfortunately,
samples of low doping levels, the effect of f on the mobility could larger than the highly
doped samples, and the accuracy of mobility calculations would be compromised by the
uncertainty of the fraction of filled traps.
147
The last problem is that even if the values of f calculated by Leung et al are not
too far off, it is still not simple to analyze the mobility. It is because f depends on doping
level, dislocation density, and more importantly, the identity of the defect (gallium
vacancy or nitrogen vacancy). Throughout the thesis, it has been mentioned that although
many researchers favor gallium vacancy as the native point defect, it is still not a proven
fact.
Therefore, when estimating the effect of dislocation scattering in gallium nitride,
these uncertainties in the formulation need to be taken into consideration.
4.10 Summary
In this chapter, Hall measurements of the intentionally n-doped and
unintentionally doped gallium nitride have been examined. The temperature-dependent
carrier concentration has been analyzed using the charge-balance equation with the
assumption of two shallow donors and a single acceptor level for the silicon doped
samples. The unintentionally doped sample (2.2 mm) corrected for the two-layer effect is
also analyzed with this method. The fitted donor levels are in good agreement with the
literature, but the accuracy fitted acceptor concentration is unclear.
The effect of the travelling electrons impeded by the defects and the lattice has
been examined using Hall mobility with respect to temperature. For the silicon doped
samples, the effect of electron scattering by ionized impurities and phonons have been
observed. For the unintentionally doped sample, the bottom conductive path containing
high concentration of slow electrons plays a large role in the reduction of the measured
mobility, consistent with the discussion in Chapter 3. Dislocation lines are expected to
148
contain charges which repel the travelling electrons and scattering could contribute
additionally to the difference between the theory and the data corrected for the bottom
layer. However, this effect does not seem to drastically reduce the mobility of our
undoped samples as expected, in particular at low temperature where this effect is
supposed to be very dominant. Quantitative calculation of temperature-dependent
mobility is difficult because of the uncertainty in the identity of the defect at the
dislocations, the line density of the defects at any dislocation, and the built-up charge
density along the dislocation. All these questions point to the limitation of the current
understanding of the electrical nature of threading dislocations which badly needs to be
addressed by the community.
4.11 Reference
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149
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152
Chapter 5 Hopping Conduction
5.1 Introduction
In the Introduction Chapter, the effects of defects on the electronic transport of
gallium nitride have been discussed. The purpose of this section is to study the transport
characteristics of impurity conduction in gallium nitride over a wide range of temperature
for a series of doping concentration, and these silicon-doped samples exhibit the classic
properties of impurity conduction. In the higher temperature range, activation energies
for thermal generation of electrons from the silicon impurity band into the conduction
band have been measured. In the low temperature range, Mott hopping (with T
1/4
dependence) is observed typically between 1.5 to 16 K due to impurity conduction. It will
be shown in this chapter that the doping concentration for the silicon-doped samples
strongly affects the hopping behavior. In comparison, the unintentionally doped samples
show transport through the bottom layer, consistent with the analysis from the previous
two chapters.
5.2 Background
Impurity conduction is a classic example of non-crystalline material because of
the random nature of the impurity sites. This topic has been extensively studied and the
reader is referred to Mott and Davis [1]. In a doped semiconductor (n-type for all the
samples studied), conductivity is described by:
kT
E
e
kT
E
e
kT
E
e
3 2 1
3 2 1

As shown in Chapter 4, the transport properties are given separately by well-
characterized carrier statistics and mobility in the high temperature regime. In the above
153
equation, E
1
is the ionization energy from the donor impurity band to the conduction
band. In the low temperature regime carrier transport usually happens within the impurity
band [1]. The convention for carrier transport is in terms of conductivity.
At intermediate to high doping levels, overlap between hydrogen-like wave
functions of neighboring donor states is high. Depending on the doping level, the states of
the conducting electrons in the impurity band may not be degenerate, and there are
electronic states that are localized due to the random position of donor centers and/or due
to the random potential from any compensating centers. The energy level demarcating the
localized states at the wide band tail and extended (degenerate) states of the impurity
band is called the mobility edge, and its level with respect to the Fermi level affects on
the transport. If the Fermi level lies in the region of extended state, metallic behavior of
the impurity band occurs. If the Fermi level lies in the region of localized states, the
activation energy E
2
describes the excitation from localized states to the extended states
at the mobility edge. If the overlap between states changes (due to changing donor
concentration, stress or magnetic field) the position of the mobility edge varies.
Experimentally, E
2
has been observed to increase with decreasing doping concentration
[2] in doped germanium with arsenic. The mechanism E
2
is seen in a temperature regime
between those of E
1
and E
3
[2], and would not occur at very low doping level.
At low temperature, the mechanism related to the third term E
3
occurs, and is also
known as nearest neighbors hopping [3]. It represents the Coulomb barriers overcome by
the hopping electrons amongst localized states near the Fermi level. For very lightly
doped samples in which donor wave functions are too far apart to overlap, electrons are
localized and the bandwidth is due to the fluctuating potential due to compensating
154
centers. For highly doped material even without compensation, hopping of this type
occurs among localized states near the Fermi level. It is measure of the bandwidth, and E
3
increases with increasing concentration where the degree of overlap of neighboring donor
wave function increases.
At even lower temperature, instead hopping to its nearest neighbor represented by
E
3
, the electron near the Fermi level jumps to a site further away in order to minimize the
hopping energy W, hence the name variable range hopping by Mott [4]. The
minimization of the energy with respect to distance results in conductivity with a
temperature dependence of exp(T
-1/4
) [1]. If the temperature is so low such that the
average thermal energy is small compared to the Coulomb interaction among hopping
electrons, the other mechanism Efros-Shlovskii hopping appears [5] with a characteristic
temperature dependence of exp(T
-1/2
) on conductivity.
The effect of dislocations by moderate amount of plastic deformation on the low
temperature conduction of germanium has been investigated [6] for a lightly doped
sample where impurity band broadening (and hence increase in E
3
) with increasing
structural disorder and increasing compensation by dislocations. Hopping conduction is
suggested to be via impurities between dislocations.
Low temperature transport data for gallium nitride [7][8] reported are variable
temperature Hall measurements from room temperature to 4-10K to investigate the effect
of the defect band or the impurity band. A few reports have suggested hopping behavior
in the low temperature conductivity measurements [9], most without detailed analysis
[10][11]. This chapter is an in-depth study of hopping conduction at liquid helium
155
temperatures. In our samples, transport through a wide range of temperature resembles
that of classic impurity conduction in the intermediate to high doping range, and hopping
is seen only below carrier freeze-out. Multi-phonon hopping has observed in other
semiconductors [12] at high temperature. However, it is not a phenomenon applicable to
our experiments since at liquid helium temperature, the thermal energy available involves
hopping via a single phonon. This study should not be confused with detailed
investigations related to hopping which are done in a vastly different doping level and the
high temperature regimes (>100K), such as the investigation of highly compensated
semi-insulating MBE gallium nitride [13].
5.3 Experimental Details
The measurements were done with the variable temperature cryostat setup
described in section 2.5.1 in Chapter 2. The same Hall-bridge structures used for variable
temperature Hall experiments were used for the low temperature four-point conductivity
here. Points 1&2 served as current probes where the current is swept from -10 A to 10
A at 400 point steps, the differential voltage was taken between probes 3&4 using the
HP4145B. Ohmic contacts of 200A Ti/1000A Al was fabricated by lift-off, after which
the samples were annealed at 900C for 30s. The samples were mounted securely onto a
header with cement glue and contacts were connected to the pins by indium/silver alloy
solder and thin copper wire. Good Ohmic behavior in the low temperature I-V sweeps
was ensured before the measurement was made for the entire temperature range.
5.4 Si-doped samples
The run-to-run reproducibility for the unintentionally doped samples is not satisfactory
(see Chapter 3), whereas the silicon-doped samples show good long and short-term
156
reproducibility. Moreover, the despite the good agreement of the surface concentration
measured by CV and Hall techniques at room temperature, the data shows lower than
expected probably due to the two-layer effect for doping in the 1 x 10
17
cm
-3
range.
5.4.1 Results i) Progressively Etched Back Sample
Figure 5. 1 shows the temperature-dependent conductance a progressively etched-back
silicon-doped sample. The fact that peak conductance does not vary much implies that
etching back the sample changes the thickness of the sample. This analysis does not
support a strong evidence of a higher doped bottom layer like the unintentionally doped
sample. The assumption of this experiment is that the top etched region for all 3 samples
are the same. Even though it is difficult to assess the damage due to etching, this
assumption is fine since there is not much change in temperature dependence
conductance at the temperature range shown in Figure 5. 1.
157
Figure 5. 1 Conductance Successively Etched back of Silicon-Doped sample in the high temperature
regime.
2.0x10
-3
2.0x10
-3

1.5 1.5
1.0 1.0
0.5 0.5
0.0 0.0

2.5x10
-4
2 1.5 1 0.5 0
film thickness in cm
R
o
o
m

T
e
m
p
e
r
a
t
u
r
e

C
o
n
d
u
c
t
a
n
c
e

(
1
/
O
h
m
s
)
Figure 5. 2 Room temperature conductance vs thickness of successively etched back silicon-doped
sample.
158
In Figure 5. 2 room temperature conductance scales linearly with thickness, but
does not show a finite conductance at zero depth. Together with Figure 5. 1, this result
implies that there is no parallel conductive path, rather possibly a dead layer due to
etching. From the analysis of the last two sections, and this data, it is reasonable to
conclude that most of the silicon-doped samples are not strongly affected by the
conductive bottom layer. On the other hand, the lightly doped Sample 5 and the
unintentionally doped samples are definitely affected in even in this temperature regime.
ii) Series of Doping levels (N
D
~ 7x 10
16
4x 10
18
cm
-3
)
The data for the silicon-doped samples with the doping range N
D
~ 7x 10
16
4x
10
18
cm
-3
is presented in . In the temperature range between 77 - 190 K, activation
behavior is observed in the plot of ln vs 1/T. Similarly, in the analysis of Chapter 4, the
plot of ln n vs 1/T has been plotted. The assumption is that only a single donor is present
in the GaN film, but may not be correct. Nonetheless, the trend in the activation energies
extracted from the temperature-dependent conductivity can provide information
regarding silicon doping. The activation energies extracted from Figure 5. 3 are 4.6 meV
for the highly doped sample (#1), 12meV for the intermediately doped sample (Sample 2)
and gradually increase to ~17meV for the lightly doped samples (Table 5.1). Compare
this values with the donor ionization energy given by E
d
= m
e
e
4
/(4
0
)
2
, which is
27.6 meV for gallium nitride.
Below 80K, Sample #1 exhibits no temperature dependence, indicating that the
impurity band conduction is in the metallic side of the Mott transition. The Bohr radius a
H
of the ground state of hydrogenic donor in the semiconductor is given by 4
0
/m
e
e
2
yielding 26 for gallium nitride (compared to 31 for silicon and 80 for germanium).
159
The estimated critical concentration of metal insulator transition should occur at n
c
1/3
a
H
~ constant, for 0.3 1x 10
18
cm
3
for silicon. It should happen about 2x 10
18
cm
3
for
gallium nitride.
At the lower temperature regime from about 50-20K (inverse temperature 20-50 x
10
-3
1/K), there is a transition from E
1
to either E
2
(excitation to mobility edge for the
higher doped samples) or E
3
(hopping conduction). It is usually difficult to determine this
region accurately. As an estimate, the hopping energy in this temperature regime is
estimated to be decreasing with decreasing doping as shown in Table 5.1, which is
opposite to what characteristic excitation to mobility edge ( E
2
) should behave like. It is
likely that this temperature regime is only a transition to the transport mechanism
dominant at lower temperature. Therefore, a larger range of at temperature is necessary to
understand the transport.
160
0.1
1
10
100
C
o
n
d
u
c
t
i
v
i
t
y

(
1
/
o
h
m
-
c
m
)
50x10
-3
40 30 20 10
1/Temperature (1/K)
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Figure 5. 3 Conductivity vs 1/T for silicon-doped samples from 20-290K showing E1 and the
transition to E2 or E3.
Table 5.1 Carrier Density and Mobility Values of Samples 1-5
na: not applicable
n
hall
@300
K cm
2
/Vs
@300
K
cm
2
/Vs
n
CV

cm
-3
E
1
()
meV
E
50-20K
meV
#1 3.7x 10
18
261 4x10
18
4.57 na
# 2 4.55x10
17
421 6.5x10 12.86 1.05
# 3 1.8x 10
17
524 3x10
17
17.45 0.94
# 4 1.5x 10
17
543 2.5x10 17.57 1.00
# 5 6.6x 10
16
355 7x10
16
17.36 0.51
161
Previous work has explored the conductivity dependence in the 10 - 40 K regime
in silicon-doped gallium nitride [10] by MOCVD. Metallic impurity band behavior has
been observed for a sample with room temperature concentration of 1.1x 10
18
cm
-3
, but
samples in the 1x 10
17
cm
-3
range have been suggested to be due to hopping without
much analysis because of the limited temperature range. As a comparison, a different
study shows resistivity of HVPE and MOCVD gallium nitride plotted from room
temperature to ~ 5 K. The clear distinction of metallic behavior due to the thin
degenerate layer at the GaN/sapphire interface of HVPE is seen, as opposed to activated
behavior at low temperatures due to hopping [9] of MOCVD material.
5.4.2 Low Temperature Transport
Our study here is unique in that the conductivity measurements have been done at
a low temperature of 1.5 K, enabling the study of the transport mechanisms. Before the
discussion of these results, it should be pointed out that the effect of the bottom layer for
the lightest intentionally doped sample ( Sample #5) seems be a significant contribution
to the overall conductivity. It is not clear how the impurity band conduction of the top
layer competes with the bottom layer at low temperature, but the electrical thickness and
absolute value of conductivity could be in error. In order to assess this effect, an
unintentionally doped sample grown around the same time as Samples 4 and 5 has been
measured and the sheet conductance is several times lower than those two silicon-doped
samples at 4K. The monotonically increasing trend of 4K sheet conductance with room
temperature Hall carrier concentration (see Figure 5. 4 ) implies that conduction of these
samples at low temperature are mainly due to contribution from the donor impurities.
Sample 5 is an exception since its conductance through the top layer is not conclusively
determined.
162
0.000001
0.00001
0.0001
0.001
0.01
0.1
1.00E+16 1.00E+17 1.00E+18 1.00E+19
Room Temperature Hall Concentration (cm-3)
4
K

S
h
e
e
t

c
o
n
d
u
c
t
a
n
c
e
Silicon doped
Unintentionally Doped
Figure 5. 4 Liquid Helium Temperature Sheet conductance vs room temperature Hall concentration
for silicon-doped samples. The three samples grown in the same period are shown by the arrows;
diamonds represent the silicon-doped samples and squares represent the unintentionally doped
samples.
Now the low-temperature conductivity of the silicon doped samples is presented.
Referring back to Figure 5. 3, the conductivity deviates clearly from activated conduction
band transport the low temperature range (below 50K). In the extended temperature range
to 1.5K for Samples 2-5 shown in Figure 5. 5, the plot of ln against inverse temperature
is continuously decreasing. This would not otherwise have been determined in Figure 5.
163
3. The distinction from high temperature activated behavior to the distinctly different
low temperature behavior is evident.
0.01
2
4
6
8
0.1
2
4
6
8
1
2
4
6
8
10
C
o
n
d
u
c
t
i
v
i
t
y

i
n

(
o
h
m

c
m
)
-
1
0.7 0.6 0.5 0.4 0.3 0.2 0.1
1/Temperature (1/K)
50.0 10.8 6.0 4.2 3.2 2.6 2.2 1.9 1.7 1.5 1.3
10
1
0.1
0.01
T (K

)
Sample 2
Sample 3
Sample 5
Sample 4
Figure 5. 5 Conductivity vs 1/T for silicon-doped samples from 300 1.5 K showing single activation
is not a good fit for the data.
In general
0
T
m
exp -(T
0
/T )
p
where 1 0 p and the T dependence on m is
negligible. Regardless of p, the slope of ln (T) decreases with increasing doping.
Moreover, the conductivity behavior of the lower doped samples # 3 and 4 appear
identical at room temperature, but the overall conductivity (
0
) of Sample 4 departs with
164
decreasing temperature from Sample 3. Theoretically the values of p should be 1, , as
explained in the background section. Also, the dependence of conductivity is fitted using
a number of different candidate mechanisms (e.g., different p). The conductivity is
expressed in its equivalent form ln ln
0
- (T
0
/T)
p
. Firstly, from Figure 5. 5, the log
conductivity dependence as a function of 1/T ( p=1 ) is analyzed yielding correlation
factors for a least squares fit of ~0.95 (see Table 5.2). However, the fitting is best for
Sample 2 because a smaller range of temperature was used. Figure 5. 6 shows a fit using
Mott Hopping with p=1/4 and average correlation of >0.998 for Samples 3-5 for a wide
range of temperature. Figure 5. 7 shows a fit with Efros-Shklovskii Hopping with p=1/2
giving an average correlation of >0.98 for Samples 3-5 at a wide range of temperature.
Table 5.2 Correlation of Various Hopping Dependence
Sample N
hall
@300
K in cm
-3
Single
Activation p=1
Mott
p=1/4
Efros & Shklovskii
p=1/2
#2 4.53x 10
17
0.98 - -
# 3 1.8x 10
17
0.96 0.998 0.993
# 4 1.5x 10
17
0.95 0.995 0.982
# 5 6.6x 10
16
0.93 0.997 0.985
The difficulty in distinguishing between the three transport mechanisms is that in
general contributions from all are present. The first term (
1
) has been described
previously to be 12-17 meV for the unintentionally doped samples. In the low
temperature regime considered here (k
B
T < 2 meV), the contribution from this term is
negligible, and the 2
nd
and 3
rd
terms will be discussed.
165
0.01
2
4
6
8
0.1
2
4
6
8
1
2
4
6
8
10
C
o
n
d
u
c
t
i
v
i
t
y

i
n

(
o
h
m

c
m
)
-
1
0.9 0.8 0.7 0.6 0.5 0.4
1/T
1/4
(1/K
1/4
)
39.1 24.4 16.0 10.9 7.7 5.6 4.2 3.2 2.4 1.9 1.5
C
o
n
d
u
c
t
i
v
i
t
y

i
n

(
o
h
m

c
m
)
-
1
10
1
0.1
0.01
T (K

)
Sample 2
Sample 3
Sample 5
Sample 4
Figure 5. 6 Conductivity vs 1/T
1/4
for silicon-doped samples from 300 1.5 K showing excellent fit for
samples 3-5.
166
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2
1/Temperature
1/2
(1/K
1/2
)
2
3
4
5
6
7
8
9
0.1
2
3
4
5
6
7
8
9
1
2
C
o
n
d
u
c
t
i
v
i
t
y

(
1
/
O
h
m
-
c
m
)
25.00 13.72 8.65 5.95 4.34 3.31 2.60 2.10 1.73 1.45 1.23
0.1
1
Sample 2
Sample 3
Sample 5
Sample 4
Figure 5. 7 Conductivity vs 1/T
1/2
for silicon-doped samples from 300 1.5 K showing reasonable
fitting, but not as good as Figure 5.6.
For sample 2, conductivity in the lower temperature changes continuously with
temperature. Although the conductivity for Sample 2 is included in both Figure 5. 6 and
Figure 5. 7, the continuous curvature of conductivity on log scale for both the and
temperature dependence indicates that the fitting may not well suited. In the literature,
samples at high doping tend to have a more significant contribution from E
2
due to the
high degree of wave functions overlap, and hopping is seen at lower temperature than a
167
lighter doped sample. The unsuccessful fitting using any of the three p values for a
reasonable large temperature range for sample 2 means that there could be a series of
transition from E
2
to nearest neighbor hopping to variable range hopping in this order. In
order to observe hopping in this sample, even lower temperature maybe needed.
Nonetheless, E
3
(i.e. p=1) is related to hopping conduction [1] which is a
thermally activated process by which electrons move from one localized state to another
immediate neighbor. Their electronic wave functions overlap each other, and the energy
of the hopping electron is absorbed from a phonon. The hopping rate is proportional to
the transition probability due to hopping among hydrogen-like localized states of the
impurity sites. This hopping energy is approximately the bandwidth of the impurity band
conductivity. For Sample 2, the best estimated extracted is the activation energy of ~ 0.08
meV within the small temperature range from 4 to 1.5 K. If this is indeed hopping
among nearest neighbors, the distance between sites is 3(4N
D
/3), yielding a value of
81 for room temperature Hall carrier concentration of 4.53x 10
17
cm
-3
. Assuming the
bandwidth of the impurity band due to overlap integral of the resonance states, then the
integral is given by I = -e
2

2
R /6
0
exp(- R) [1]. The localization length is equal to
the Bohr radius, and a good agreement of the overlap integral of ~0.09 meV with the
activation energy (~ 0.08 meV ) shows that hopping is the transport mechanism in the
regime in interest. For Samples 3-5 it seems that a better fit is achieved for p=1/4.
Mott Hopping with (p = 1/4 ) is the best fit of Samples 3-5. The assumption of
this model is that at the temperature regime Coulomb interaction energy () among the
localized states is negligible ( k
B
T >> ), the density of states within t k
B
T of the Fermi
168
level is approximately constant. The hopping conductivity is proportional to:
( ) kT W R
ph
/ 2 exp , where is the tunneling decay exponent of the hydrogen-like
localized states exponent (a measure of localization), and v
ph
depends on the strength of
the interaction with phonons. To minimized the hopping energy W (which is a function of
R), the electrons seek out a larger values of hopping distance R, so the end result of the
exponential has the temperature dependence of the form exp (-T
0
/T
1/4
) instead of exp(-
E/kT)[ 4].
In one approach, Allen and Adkins [14] extract the parameters N(E
F
) and from
the slope T
0
and prefactor
0
of ln vs T
1/4
to arrive at an expression for the conductivity:

,
_

,
_

4 / 1
3
2 / 1
9
4 5 2
0
5
2
1
2
)
) (
( 063 . 2 exp
) (
2
) ( 576 kT E N kT E N s
E e
F F

h
Based on the reasoning above and the higher correlation factor for Samples 3-5, the
values of , N(E
F
), R, and W are determined. The constants , E
1
and s are density,
deformation potential and velocity of sound of gallium nitride (see Chapter 4). For
example, for Sample 3 with room temperature carrier density of 1.8x 10
17
cm
-3
, the wave
function decay constant of the localized states
1
is 400 30 and the density of states
is 2.94 0.6 x 10
18
eV
-1
cm
-3
. The results for the rest of the samples are shown Table
5.3. Using these values, the hopping energy is calculated to be 0.35 meV, an average
hopping distance of 570 . The values of the hopping distance are slightly large, and the
N(E
F
) values are small compared to estimates to be discussed in next. An unresolved
question that needs further investigation is the increase
-1
with decreasing doping; it is
169
expected that
-1
should increase with increasing doping because of delocalization
resulting from increased overlap among wave functions.
An alternative approach to calculate
-1
is to measure the density of states using
methods like electron spin resonance technique and then calculate the localization length
from the relation

,
_

4 / 1
3
)
) (
( 063 . 2 exp
kT E N
F

. Since there is no data on the density

of states, the assumption for transport is via impurity conduction. The concentration
levels of the donors (6.6x 10
16
- 4x 10
17
cm
-3
) in these silicon-doped samples are not
low enough to fall under the regime of very lightly doped material. The latter doping
concentration is 1-2 orders of magnitude that of critical metallic concentration n
c
(~2 x 10
18
cm
-3
). Therefore the analysis of extracting density of states by Shlovskii [15] or Miller
and Abrahams [3] are not applicable here. Impurity conduction via localized donor states
are assumed, and a good estimation of N(E
F
) is approximately N
D
/W, that is, the number
of donor sites within the bandwidth of energy or hopping energy. Then the localization
length values

1
are extracted from the slopes of the Mott hopping plots in Figure 5. 6.
Table 5.4 is a summary of the analysis. The estimated localization lengths are between
the Bohr radius and the distance among impurity centers. This is consistent with impurity
conduction in the literature for germanium [14] and silicon [16]. If the average nearest
neighbor hopping distance R of 81 from Sample 2 is included, the hopping distance
increases with decreasing concentration.
170
Table 5.3 Mott Hopping Parameters
N
hall
@300
K in cm
-3

-1
in N(Ef)
(eV/cm
-3
)
R in W meV
# 3 1.8x 10
17
400 2.9 x10
18
570 0.438
# 4 1.5x 10
17
630 4.1 x10
17
1050 0.505
# 5 6.6x 10
16
570 5.7x 10
17
940 0.5
Table 5.4 Mott Hopping Parameters for Samples 3-5 Using 2
nd
Approach are listed. Hopping
distance of Sample 2 estimated from room temperature Hall concentration assuming nearest
neighbor hopping.
n
hall
@300K
in cm
-3
N(Ef)*
(eV/cm
-3
)

-1
in
R
in
N
D1
+N
D2
in
cm
-3
N(Ef)**
(eV/cm
-3
)

-1
in
R in
# 2 4.53x10
17
81
# 3 1.8x 10
17
5.69x10
20
86 131 4.68x10
17
1.07x 10
21
63 83
# 4 1.5x 10
17
4.15x 10
20
59 129 2.31x10
17
4.22x 10
20
53 100
# 5 6.6x 10
16
1.87x10
20
86 173 8.9x 10
16
1.78x 10
20
78 136
*N(Ef) calculated from n/ W from Table 5.3.
**N(Ef) calculated from (N
D1
+N
D2
)/W, N
D1
+N
D2
from Chapter4.
The final hopping model given by Efros and Shklovskii [5] describes hopping
behavior to sites further away at an even lower temperature regime in which k
B
T < (the
Coulomb interaction among the localized states). The density of states within t k
B
T of the
Fermi level is a quadratic function, and is considered a Coulomb gap observed in
phosphorus doped silicon [17]. The conductivity is proportional to exp (-T
0
/T
1/2
), and the
slope of ln vs T
1/2
. However, from the poor fitting in Figure 5. 7, this is an unlikely
mechanism because the temperature regime for it to occur is lower than our setup.
In sum, for the silicon-doped samples in the doping range N
D
~ 7x 10
16
4x 10
18
cm
-3
, classic behavior of impurity conduction is observed for a wide temperature range
[18]. At high doping level (Sample #1), the transport is on the metallic side of the Metal-
insulator transition, showing no temperature dependence in the impurity band. At
171
moderate doping levels (Samples # 2-4) the dominant transport mechanism for moderate
doping for gallium nitride is observed to be hopping due the donor impurities. For the
lowest doped sample (#5), it is likely that the bottom n
+
layer contributes to the
conduction. Perhaps the experiment to quantify this point is to compare the data for a
doped silicon sample grown on undoped template to isolate the bottom layer effect.
5.5 Unintentionally doped sample
5.5.1 Films with successive thickness
The series of 0.55 -2.2 m films is the basis of the two-layer analysis in
Chapter 2. In Figure 5. 8, the relationship between conductance and temperature is
presented. The peak conductance varies up to 45 K, likely due to the two-layer
conduction problem. This is compared to the temperature-dependent conductance of the
silicon-doped samples (Figure 5. 1), which shows within 10 K variation. From variable
temperature Hall measurements, the mobility of the undoped 0.5 and 2.2 m samples are
very different, while the Hall carrier density shows similar temperature dependence. To
compare with the silicon-doped etched back samples, the conductance Vs thickness (
Figure 5. 9 ) relationship shows an approximately linear relationship in the high
temperature regime (300 K), where at zero depth the conductance is still quite large. The
assumption made is that the top and bottom layers for all three samples are the same. Of
course, there is great variability for the properties of the unintentionally doped samples
that cannot be controlled, and therefore, only samples that are grown in the same period
are analyzed as a set.
172
Figure 5. 8 Conductance of unintentionally doped sample of successive thickness in the high
temperature regime.
2
3
4
5
6
7
8
9
10
-4
2
C
o
n
d
u
c
t
a
n
c
e

i
n

m
h
o
s
14x10
-3
12 10 8 6 4
1/Temperature (in 1/K)
Unintentionally Doped Sample
2m
1m
1/2m

200x10
-6

150
100
50
0
C
o
n
d
u
c
t
a
n
c
e

i
n

1
/
o
h
m
s
250x10
-6
200 150 100 50 0
Thickness in cm
Figure 5. 9 Room temperature Conductance of unintentionally doped sample of successive thickness
vs thickness
173
10
-6
2
3
4
5
6
7
8
10
-5
2
3
4
5
6
7
8
10
-4
C
o
n
d
u
c
t
a
n
c
e

i
n

m
h
o
s
0.7 0.6 0.5 0.4 0.3 0.2 0.1
1/Temperature (in 1/K)
Unintentionally Doped Sample
2m
1m
1/2m

Figure 5. 10 Conductance of unintentionally doped sample of successive thickness in the low
temperature regime. The 0.5 m shows a different characteristic than the 1.1 and 2.2 m samples
possibly due to voids in the film.
The conductance characteristics of the series of undoped samples can provide
important information on the properties of the film. In Figure 5. 10, it shows that the
conductance does not scale with thickness at low temperature. Unfortunately, the thinnest
sample (0.55 m) shows a conductance level higher than the thicker samples. In fact, the
film contains some unfilled voids means can affect the low temperature transport, and the
effect of the bottom layer cannot be isolated from transport due to these voids. However,
if the data for 1.1 and 2.2 m samples are compared, the conductance does not scaled
accordingly. This implies transport at low temperature is confined to the bottom of the
film.
174
5.5.2 Collection of Unintentionally Samples
10
-6
2
3
4
5
6
7
10
-5
2
3
4
5
4
K

s
h
e
e
t

c
o
n
d
u
c
t
a
n
c
e

i
n

1
/
O
h
m
-
s
q
0.0001
2 3 4 5 6 7 8 9
0.001
room temperature sheet conductance in 1/(ohm-sq)
Figure 5. 11 Liquid Helium sheet conductance vs room temperature sheet conductance for
unintentionally doped samples. Data point for lightly Si-doped sample #5 is also included (shown by
arrow).
With the hypothesis that most of the conductance measured at low temperature is
due to the bottom layer, the undoped samples will be analyzed. The sheet conductance at
4 K is plotted against the values at room temperature in Figure 5. 11. The sheet
conductance is plotted because conductance is a better representation than conductivity
due to the fact that the actual electrical thickness is not known. Also, since the samples
are made into both Van der Pauw and Hall Bridge structures, the data can be normalized
and compared in terms of sheet conductance. The correlation between the room
temperature sheet conductance and low temperature conductance is interesting. Using the
two-model analysis in Chapter 3, the bottom layer accounts for ~70% of the room
175
temperature sheet conductance of the 2.2 m sample in the successive thickness film
series. Included is the lightly intentionally doped sample # 5.
Figure 5. 12 Conductivity vs 1/T for undoped samples.
3
4
5
6
0.1
2
3
4
5
6
1
2
3
C
o
n
d
u
c
t
i
v
i
t
y

50x10
-3
40 30 20 10
1/T (1/K)
2.2 micron sample in thin series
1.1 micron sample in thin series
Sample 9711181
Sample 9710211
Sample 9809291-1
Table 5.5 Carrier Density and Mobility Values of Undoped samples
n
hall
@300K
in cm
-3
@300K
cm
2
/Vs
n
CV

cm
-3
E1() meV
9901251-1 (2.2m) 3.7x 10
16
317 1x 10
16
13.5
9902061-1 (1.1m) 7.3x 10
16
218 3x 10
16
14.8
9809291 (2.2m) 4.7x 10
16
254 8x 10
15
13.6
9711181 (2.2m) 3.7x 10
17
132 1x 10
16
14.2
9712011 (2.2m) 7.6x 10
16
123 1x 10
16
15.3
176
The conductivity data for the undoped samples are shown in Figure 5. 12 in the
higher temperature regime. The extracted activation energy is shown in Table 5.5 with
the room temperature Hall and CV data. Lower temperature data is shown in Figure 5.
13, and activation behavior of p=1 does not seem to be good fit because of the continuous
curvature of the conductivity characteristic.
Figure 5. 13 Conductivity vs 1/T
1/4
for undoped samples
0.01
2
3
4
5
6
7
0.1
2
3
4
5
C
o
n
d
u
c
t
i
v
i
t
y

(
1
/
o
h
m
-
c
m
)
0.9 0.8 0.7 0.6 0.5 0.4
1/Temperature
1/4
(1/K
1/4
)
2.2 micron sample in thin series
1.1 micron sample in thin series
Sample 9711181
Sample 9710211
Sample 9809291-1
The data for the Mott Hopping analysis undoped samples is shown Figure 5. 13.
Similar to the analysis for the silicon doped samples (see Table 5.4), the values of slope
and prefactor using the 2
nd
method of analysis are shown in Table 5.6. The inconsistency
of this set of data is that if the top layer contributes to impurity conduction hopping, the
177
slopes T
0
should be at least a few times lower than the silicon-doped samples that are
about an order magnitude of top layer concentration [2][14]. As mentioned before, the
actual electrical thickness, the absolute magnitude of the conductivity and the prefactor
could be in error due to the bottom layer conduction. The density of states is estimated to
be ~ 4.8 x 10
20
cm
-3
/eV by assuming the concentration of 2 - 4x 10
17
cm
-3
for the bottom
layer from room temperature CV profiling. The hopping lengths are listed in Table 5.6.
Table 5.6 Extracted hopping lengths for undoped samples.
n
hall
@300K
in cm
-3
Hopping
length R in

-1
MottHopping

0
Mott
Hopping T
0
9901251-1 (2.2m) 3.7x 10
16
114 59 1.465 242
9809291 (2.2m) 4.7x 10
16
114 58 2.224 256
9711181 (2.2m) 3.7x 10
17
123 78 1.164 104
9712011 (2.2m) 7.6x 10
16
110 50 1.927 392
The nature of the bottom layer has been determined to be highly n-type in Chapter
2, but the reason for the doping is not clear due to high density of dislocations in that
region of the film. One thing for sure, the material is not amorphous even though there
can be rare pockets or regions of polycrystallinity from TEM. The observed behavior
could be due to the hopping of electrons between point defect donor-like in nature
(possibly nitrogen vacancies V
N
) concentrated in bottom. Hopping of electrons among
dislocations with V
N
in cores in the bottom layer (possible 1 order of magnitude more in
bottom) can be another explanation. Thirdly, hopping of electrons near gallium vacancies
V
Ga
is possible if indeed the gallium nitride film is grown in a nitrogen rich environment;
178
since it is the dominant defect is an acceptor, electron transport may happen at donors
near dislocations.
In the transport for the silicon-doped and the unintentionally doped samples, the
possibility of transport over grain boundaries is not considered to be likely. Firstly, the
samples not dislocated enough to be considered polycrystalline as shown by AFM.
Furthermore, the hopping energy barriers measured in this study are a fraction of a meV
at low temperatures, since transport is via a small range of states at the Fermi level.
Energy barriers over grain boundaries in semiconductors should be in order of a fraction
of eV (3 orders of magnitude higher). Hopping of localized states at dislocations or grain
boundaries at high temperature regimes in our samples is small compared to impurity
conduction (especially excitation of donor electrons to conduction band). In order to
isolate the effect of these higher energy barriers, one could utilize a reversed biased
MOCVD GaN p-n junction such that the effects of impurities are minimized [19], and
apparently ac hopping conduction among localized states was observed above room
temperature.
5.6 Summary
In summary, in the high temperature regime (77- 290K), carrier excitation from
the donor band to the conduction band has been observed. At low temperature (below
20K) at which thermal energy is no longer available to sustain this excitation process,
electrons travel through the medium by the Mott Hopping mechanism. The density of
states and localization lengths of the electron wave functions have been estimated for
non-degenerate silicon-doped samples and the hopping length increases with decreasing
doping. Therefore, it is concluded that silicon doping strongly affects the hopping
179
behavior and that the electrons hop among the donor impurity sites within the material.
For the unintentionally doped samples, the bottom n
+
layer dominates the transport
behavior, consistent with the findings in the last two chapters. However, the origin of this
bottom layer is not conclusive defects of all kinds (namely, point defects and impurities,
dislocations and the stacking faults) are all present.
180
References
1. N. F. Mott and E. A. Davis, Electronic Processes in Non-crystalline Materials, 2
nd
Edition, Oxford University Press, Oxford, (1979).
2. E.A. Davis and W. D. Compton, Physical Review, 140, A2183 (1965).
3. A. Miller and E. Abrahams, Physical Review 120, 745 (1960).
4. N. F. Mott, Journal of Non-Crystalline Solids, 1, 1 (1968).
5. A.L. Efros and B. I. Shkilovskii Journal of Physics C, 8, L49 (1975)
6. M. L. Kozhukh, J of Physics: Condensed Matter 5 2351(1993).
7. D. C. Look and R. J. Molnar, Applied Physics Letters 70 3379 (1997).
8. D. C. Look and J. R. Sizelove, Physical Review Letter, Vol 82, No. 6, 1237 (1999).
9. D. C. Look, Materials Science and Engineering B50 50 ( 1997).
10. P. Hacke et al, Japanese Journal of Applied Physics, 33 6443 (1994).
11. R. J. Molnar, T. Lei and T.D. Moustakas, Applied Physics Letters 62 72 (1993).
12. D. Emin, Physical Review Letters 32(6) p303 (1974).
13. D. C. Look, et al Journal of Applied Physics 80 (5) 2960 (1996)
14. F. R. Allen and C. J. Adkins , Philosophical Magazine, 24 1027 (1972)
15. B. I. Shkilovskii Soviet Physics- Semiconductors JETP 6 1053 (1973).
181
16. J. Zhang, et al Physical Review B48 (4) 2312 (1993).
17. J. G. Massey and M. Lee, Physical Review Letters 75(23) p4266 (1995).
18. N. F. Mott, Metal-insulator Transition, London : Taylor & Francis ; New York :
Barnes & Noble Books, (1974).
19. D. V. Kukensenkov et al Applied Physics Letters 72 p1365 (1998)
182
Chapter 6 Conclusion
In Chapter 2, the room temperature electrical characteristics of the intentionally n-
doped and unintentionally samples have been examined. For the unintentionally doped
sample, capacitance voltage profiling has shown a higher doped region near the substrate,
and a transition layer towards lighter doping towards the substrate. This chapter questions
the use of Hall data (mobility and carrier concentration) as the only figure of merit for the
reported electrical data of the gallium nitride films. The extensive C-V measurements
done in Chapter 2 have shown to be a useful addition to the Hall data, implying that
surface carrier concentration measured by C-V should be reported as well.
A great deal of effort has been made to explain the two-layer effect. The two-
layer model essentially is analogous to two resistors in parallel, with the bottom layer
having much more concentrated with electrons and therefore lower resistance, making it
a favorable path for electrons to travel. The problem with this bottom path is that the
mobility is low, causing the measured composite mobility to be much lower that if the top
layer (high structural quality) were measured by itself. The corrected data shows a higher
mobility and lower carrier concentration than the as measured values. This means that for
those samples which are dominated by the two-layer effect, the electrical properties are
not as bad as measured by Hall technique. In Chapter 2, it has been explained that the
contribution of the bottom parallel conductive layer can be made small if its thickness is
small compared to the total thickness, implying the reduction of the two-layer by growing
thick films. Also, good quality devices can be made if the bottom layer can be isolated
183
from the top layer. For example, if a lightly intentionally doped film is needed, one could
first grow a thick undoped film as template before the doped film deposition.
In Chapter 3, Hall measurements of the intentionally n-doped and unintentionally
doped gallium nitride have been examined. Temperature-dependent carrier concentration
has been analyzed using the charge-balance equation. The Matthiesen rule was used to fit
the experimental mobility values, both at room temperature and variable temperature
(from 77-300 K) to various theoretical scattering mechanisms. In addition to the well-
known scattering mechanisms due to ionized impurities, acoustic phonons (deformation
potential), acoustic phonons (piezoelectric) and optical polar phonon, the two additional
transport effects were considered: charged dislocation scattering and two-layer
conduction. The room temperature and variable temperature scattering data showed a
dominant effect due to the transition-layer, and correction of unintentionally doped data
was necessary. Dislocation scattering is likely to be a second order effect for the mobility
reduction of our undoped material. With the temperature-dependent Hall data analysis,
the mobility vs carrier concentration relationship for room temperature was revisited.
From Chapter 3, the two-layer effect explained most of the discrepancy between the
theory and the data. Charged dislocation scattering could contribute additionally to the
difference but did not seem to drastically reduce the mobility of our undoped samples as
expected. Quantitative calculation of temperature dependent mobility is difficult because
of the uncertainty in the identity of the defect at the dislocations, the line density of the
defects at any dislocation, and the built-up charge density along the dislocation. All these
questions point to the limitation of the current understanding of the electrical nature of
threading dislocations which badly needs to be addressed by the community.
184
Moreover, since the dislocation scattering has shown to be merely a second order
effect for the reduction of Hall electron mobility, the benefits for improvement of
electrical properties through reduction of dislocations need to be carefully examined. For
example, the methods of lateral overgrowth to reduce threading dislocations are very
much under intensive research, and have been shown to be very promising through
improved leakage current characteristics of electrical devices. Perhaps more study of the
electrical properties in these systems can reveal the correlation between the dislocation
density and electron scattering.
Finally, in the last chapter, we showed that the silicon-doped samples exhibit the
properties of the classic impurity band conduction in study the transport characteristics of
impurity conduction in gallium nitride over a wide range of temperature for a series of
doping concentration. In the higher temperature range, activation energies for thermal
generation of electrons from the silicon impurity band into the conduction band were
measured. In the low temperature range, we observed Mott hopping (with T
1/4
dependence) typically between 1.5 to 16 K due to impurity conduction. We estimated the
density of states near the Fermi level and the wave function decay constant of the
localized states. The important observation is that the doping concentration for the
silicon-doped samples strongly affects the hopping behavior. Transport through these
films is among the impurity sites. In comparison, the unintentionally doped samples show
transport through the bottom layer. However, as discussed in Chapter 2, there is yet a
universal consensus regarding the electrical nature (carrier type and transport
mechanisms) in the bottom layer, where defects of all kinds (namely, point defects and
impurities, dislocations and the stacking faults) are all present.
185
In a material with multiple structural defect types, understanding electrical
properties is a complex task. This thesis work was a participation of the on-going
understanding of how the defects manifest themselves electrically. To this day, the nature
of the unintentional doping is still being debated. Although common properties are
observed by the gallium nitride material (such as mostly n-type unintentional doping,
lattice mismatched substrates, defective interface, high density of threading dislocations),
the variations of the sample preparation method and the material quality are still quite
large. Therefore, there is yet a universal consensus regarding the electrical nature of the
defects in gallium nitride. With the exploding amount of various optical and structural
measurements, the nature of the many types of defects is beginning to be revealed.
Perhaps until the convergence of material quality through improved material
understanding can we sort out the various kinds of transport behavior and fully utilize the
material for the best device performance in the future.