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Jun-Yuan Jeng, Kuo-Cheng Chen, Tsung-Yu Chiang, Pei-Ying Lin, Tzung-Da Tsai,
Yun-Chorng Chang, Tzung-Fang Guo,* Peter Chen,* Ten-Chin Wen, and Yao-Jane Hsu
Organometal halide perovskite is an ideal photovoltaic material that exhibits a direct optical bandgap of around 1.5 eV, a
low exciton bonding energy and long diffusion length (1 m),
a broad range of light absorption covering the visible to nearinfrared spectrum (800 nm) with high extinction coefficient
(104 cm1 at 550 nm).[13] Most importantly, organo-lead
halide perovskites behave the ambipolar characteristics and
work very well with organic carrier transport materials, such
as
2,27,7-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9spirobifluorene (spiro-OMeTAD),[4,5] fullerene (C60) and [6,6]phenyl C61-butyric acid methyl ester (PCBM),[611] conjugated
polymers, etc.,[1214] to form a hybrid heterojunction and generate an efficient photovoltaic effect. Organometal halide perovskite-based mesoscopic or planar heterojunction (PHJ) solar
cells present a very promising photovoltaic performance. Recent
reports demonstrated devices based on this material with a high
power conversion efficiency (PCE) of 1215%.[4,5,12,15,16] Several
reports prospectively propose devices that can achieve PCE of
20% in the near future.[17,18] Hybrid PHJ perovskite-based solar
cells have the advantage to be fabricated by low-temperature
and solution processes, and flexible devices with remarkable
efficiency have been demonstrated recently.[8,9,19,20]
Our previous work had successfully demonstrated efficient hybrid solar cells based on the methylammonium lead
iodide (CH3NH3PbI3)/C60 PHJ configuration.[6] Applying C60
J.-Y. Jeng, Dr. K.-C. Chen, T.-Y. Chiang,
P.-Y. Lin, T.-D. Tsai, Prof. Y.-C. Chang,
Prof. T.-F. Guo, Prof. P. Chen
Department of Photonics
National Cheng Kung University
Tainan, Taiwan 701, ROC
E-mail: guotf@mail.ncku.edu.tw;
petercyc@mail.ncku.edu.tw
Prof. T.-F. Guo, Prof. P. Chen
Advanced Optoelectronic Technology Center
National Cheng Kung University
Tainan, Taiwan 701, ROC
Prof. P. Chen
Research Center for Energy Technology and Strategy
National Cheng Kung University
Tainan, Taiwan 701, ROC
Prof. T.-C. Wen
Department of Chemical Engineering
National Cheng Kung University
Tainan, Taiwan 701, ROC
Dr. Y.-J. Hsu
National Synchrotron Radiation Research Center
Hsinchu, Taiwan 300, ROC
DOI: 10.1002/adma.201306217
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Figure 4. (a) The configuration of the hybrid solar cell in this study of
glass/ITO/NiOx/CH3NH3PbI3 perovskite/PCBM/BCP/Al. (b) Diagram
the energy level of each layer.
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VOC
[V]
JSC
[mA/
cm2]
FF
PCE
[%]
PEDOT:PSS/CH3NH3PbI3
(9500 rpm)/PCBM
0.62
9.39
0.66
3.9
b)
7.8
0.92
12.43
0.68
(8000 rpm)/PCBM
0.88
13.53
0.58
6.9
0.72
10.71
0.59
4.6
0.76
9.51
0.66
4.8
0.74
12.95
0.60
5.7
b)
of the surface properties of NiOx film modulates the photovoltaic parameters.[23,26] The hybrid cell fabricated with 2 minutes of UV-ozone treatment exhibits the optimal condition
for fabrication. By UPS measurement, the work functions of
the glass/ITO/NiOx without and with 4 minutes of UV-ozone
treatment have offsets of approximately 0.07 eV smaller and
0.05 eV larger, respectively, than that of the glass/ITO/NiOx with
2 minutes of UV-ozone treatment. It is noted that the changes
in the magnitude of the work functions for the glass/ITO/NiOx
substrates by UV-ozone treatment are relatively marginal comparing with the modulations of device parameters as illustrated
in Table 1. On the other hand, the water contact angles are 79
and 58 for the glass/ITO/NiOx substrates without (untreated)
and with (treated) 2 minutes of UV-ozone treatment, as the
photographs of water contact angle depicted in the insets of
Figure 3. Therefore, we may attribute the marked enhancement
of device parameters by 2 minutes of UV-ozone treatment on
glass/ITO/NiOx to the improvement of surface wetting property, which enables the higher surface coverage of CH3NH3PbI3
perovskite film. However, the prolonged 4-minute UV-ozone
treatment degrades the device parameters, which probably are
associated with excess oxygen content in the NiOx film. This
part of work requires further investigations in order to understand the effect of UV-ozone treatment for the optimization of
device fabrication process. In a summary, the hybrid cell, glass/
ITO/NiOx/CH3NH3PbI3 perovskite (9500 rpm)/PCBM/BCP/Al
exhibits the optimal device performance in this study owning to
the reducing the energy loss in the charge transfer process for
both hole and electron in the PHJ interfaces and the improvement of surface coverage of CH3NH3PbI3 perovskite film upon
glass/ITO/NiOx substrate. Those disclosures pose the direction
to further improve the photovoltaic performance of the hybrid
CH3NH3PbI3 perovskite/PCBM solar cells by the p-type, nickel
oxide electrode interlayer.
Figure 6 illustrates the incident photon to electron conversion efficiency (IPCE) spectrum and the integrated photocurrent calculated under AM 1.5G solar irradiation of the glass/
ITO/NiOx/CH3NH3PbI3 perovskite (9500 rpm)/PCBM/BCP/Al
cell. The hybrid solar cell exhibits the devices spectral response
from the visible to near-infrared (300 to 800 nm) region with
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Experimental Section
Materials and Sample preparation: The ethylammonium lead iodide
(CH3NH3PbI3) perovskite was prepared according to our previous
work[6] and from other reports elsewhere.[3,32]
Fabrication of CH3NH3PbI3 perovskite/[6,6]-phenyl C61-butyric
acid methyl ester (PCBM) planar-heterojunction (PHJ) hybrid solar
cells: The solar cells were fabricated in a standard arrangement by
sandwiching a PHJ of CH3NH3PbI3 perovskite/PCBM structure between
p-type and n-type contact. The p-type contact is made of pre-cleaned
and -patterned transparent glass/indium-tin-oxide (ITO) (RITEK Corp.,
15 /) coated with poly(3,4-ethylenedioxythiophene) poly(styrene
-sulfonate) (PEDOT:PSS) (Baytron P, Bayer AG, Germany) or nickel
oxide (NiOx) film electrode interlayer as the positive electrode. The
n-type contact is made of bathocuproine (BCP) (Aldrich) film (as a
hole-blocking layer, HBL) and aluminum (Al) as the negative electrode.
Figure 4(a) illustrates the device configuration and Figure 4(b)
diagrams the energy level of each layer. Prior to the device fabrication,
the ITO/glass substrates were sequentially cleaned by ultrasonic
treatment in detergent, de-ionized water, acetone and isopropyl alcohol.
The glass/ITO/PEDOT:PSS or glass/ITO/NiOx substrates were preheated at 60 C for 5 min prior to spin-casting the precursor solution
at 8000 rpm or 9500 rpm, 30 s. The CH3NH3PbI3 precursor solution
was prepared by mixing CH3NH3I and lead iodide (PbI2) (Showa
Chemical Inc.) at 1:1 (0.8:2.3 g) equi-molar ratio in 15.8 ml anhydrous
N,N-dimethylformamide (Aldrich) (17.2 wt.% solution) at 60 C,
stirring for 12 hrs implemented inside a nitrogen-filled glove box with
oxygen and moisture levels <1 ppm. The preheating treatment of the
substrate and the high spinning rate (by a customer designed spin
coater of spinning rate up to 9500 rpm, accelerating rate of 30,000 rpm/
sec2-loaded, Model: SP-13035, IVY Semiconductor Engineering, LTD,
Taiwan) for coating ensure the solvent evaporation in a fast regime to
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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
T.F.G. would like to thank the National Science Council (NSC) of Taiwan
(NSC1022682-M-006001-MY3) and P.C. would like to thank the NSC
of Taiwan (NSC1022113-M-006010) for financially supporting this
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