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Chang-Wen Chen, Hao-Wei Kang, Sheng-Yi Hsiao, Po-Fan Yang, Kai-Ming Chiang,
and Hao-Wu Lin*
Organometal halide perovskites (CH3NH3PbI3xClx and
CH3NH3PbI3) have recently attracted tremendous attention as
promising materials for solar energy conversion. The pioneer
devices demonstrated a power conversion efficiency (PCE) of
4%, as reported by Miyasaka and co-workers in 2009.[1] The
PCEs soon evolved to exceed 12% in a few years both in mesosuperstructure-type and planar-type cells.[212] The planar-type
device architecture is particularly interesting due to the simple
cell configuration and possible low-temperature fabrication on
flexible substrates. However, unlike meso-superstructure-type
devices, in which perovskite can be scaffolded by mesoporous
matrices, incomplete and non-uniform coverage of perovskite
films was usually observed in planar-type perovskite solar cells
and has been regarded as the major factor resulting in decreased
device performance.[1315] Many efforts have been made to control the morphology of perovskite thin films including optimization of the annealing time and temperature,[13,16] selection
of the under-layer material and thickness,[4,11,1719] and the use
of alternative deposition methods such as two-step deposition
and vacuum sublimation.[9,10,18,20] Among these methods, the
vacuum thermal co-evaporation of CH3NH3I and PbCl2 (or
PbI2) and the resulting perovskite thin films exhibited the most
homogeneous morphology and the highest thin-film coverage,
leading to a high performance of 1215% PCE.[6,8] Despite the
promising results, however, to date, only limited reports have
utilized this vacuum sublimation technique to fabricate perovskite layers.[6,8] The main reason could be due to the small
molecular weight of CH3NH3I, which results in a random diffusion of molecules inside the vacuum chamber and causes
difficulty with the monitoring and control of the CH3NH3I deposition rate using quartz microbalance sensors.[6,8]
In this paper, we demonstrate a novel method of perovskite
thin-film deposition via a layer-by-layer sequential vacuum sublimation. The process is relatively simpler than the co-evaporation technique; however, surprisingly, very uniform perovskite
thin films with high coverage can be produced. By incorporating these perovskite thin films with a poly(3,4-ethylenediox
ythiophene):poly(styrene sulfonate) (PEDOT:PSS) hole transporting layer and thermal evaporated C60/Bathophenanthroline (Bphen) electron transporting layers (ETLs), the cells with
C.-W. Chang, H.-W. Kang, S.-Y. Hsiao, P.-F. Yang,
K.-M. Chiang, Prof. H.-W. Lin
Department of Materials Science and Engineering
National Tsing Hua University
Hsinchu 30013, Taiwan
E-mail: hwlin@mx.nthu.edu.tw
DOI: 10.1002/adma.201402461
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Figure 1. a) AFM image (30 m by 30 m) of the vacuum-deposited PbCl2 thin film. b) Photographs of the vacuum deposited PbCl2 (left) and perovskite
(right) thin films.
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8x10
6x10
4x10
2x10
* (110)
(220)
4
2
85 C
o
65 C
10
20
30
20
30
40
2 ()
50
60
75 C
60
(b)
-4
-8
-12
-16
o
65 C
o
75 C
o
85 C
-20
-24
100
65 C
o
75 C
o
85 C
0.0
0.2
0.4
600
700
1.2
40
800
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1.0
60
500
0.8
(b)
65 C
o
75 C
o
85 C
20
400
0.6
80
EQE (%)
Wavelength (nm)
6650
70
(a)
Voltage (V)
Absorbance
50
(440)
(330)
40
2 ()
10
1x10
Intensity (Counts)
(a)
Intensity (counts)
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400
500
600
700
800
Wavelength (nm)
Figure 4. a) JV characteristics of perovskite solar cells fabricated at
6585 C substrate temperatures measured under 1 sun AM 1.5G illumination (solid lines) and in the dark (dashed lines). b) The corresponding
EQE spectra of the devices.
JSC
[mA/cm2]
FF
[%]
PCE
[%]
65 C
0.93
14.4
45.4
6.1
75 C (highest)a)
1.02
20.9
72.2
15.4
75 C (average s.d.)b)
85 C
0.98 0.03
1.13
44.6
13.9 0.82
4.5
a)The
highest performing device; b)The average and standard deviation (s.d.) of the
12 cells from 3 different batches processed at the 75 C substrate temperature.
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Experimental Section
Device and Thin-Film Preparation: The devices were prepared on
cleaned ITO substrates by spin coating a PEDOT:PSS (Clevios AI 4083)
thin film. Then, the substrates were loaded into a high vacuum chamber
(base pressure < 1 106 Torr) to evaporate PbCl2, CH3NH3I, C60,
Bphen, Ca, Ag thin films layer-by-layer. The substrates were kept at room
temperature, and all the layers (PbCl2, C60, Bphen, Ca, and Ag) were
fabricated with constant deposition rates except the CH3NH3I layer. The
substrates were controlled at specific temperatures (room temperature,
65 C, 75 C and 85 C), while the CH3NH3I layers were deposited with
a constant source temperature of 85 C. The devices were configured as:
glass substrate/ITO (145 nm)/PEDOT:PSS (30 nm)/CH3NH3PbI3xClx/
C60 (100 nm)/Bphen (6 nm)/Ca (1 nm)/Ag (120 nm). The devices were
encapsulated using a UV-cured sealant (Everwide Chemical Co., Epowide
EX) and a cover glass under an anhydrous nitrogen atmosphere after
fabrication and subsequently characterized in air.
Characterization: Perovskite thin films for SEM, AFM, XRD and
absorption measurements were prepared using the same fabrication
conditions as for the solar cells with layer structures configured as: glass
substrate/ITO (145 nm)/PEDOT:PSS (30 nm)/CH3NH3PbI3xClx. The
SEM images were obtained using a Japan Electron Optics Laboratory
Co., Ltd. (JEOL) JSM-7000F scanning electron microscope. The AFM
images were acquired using a Bruker Dimension Icon atomic force
microscope. The X-ray diffraction was performed using a Rigaku TTRAX
III instrument with Cu K radiation. The absorption spectra were
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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors would like to acknowledge the financial support from
the Ministry of Science and Technology of Taiwan (1022221-E-007
125-MY3, 1012112-M-007017-MY3, 1022633-M-007002, 103-3113E-007-004) and the Low Carbon Energy Research Center, National Tsing
Hua University.
Received: June 3, 2014
Revised: July 18, 2014
Published online: September 1, 2014
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