Author's Accepted Manuscript

An up-scalable approach to CH3NH3PbI3 com-

pact Films for High-performance perovskite
solar cells
Zhou Yang, Bing Cai, Bin Zhou, Tingting Yao, Wei
Yu, Frank S. Liu, Wen-Hua Zhang, Can Li

www.elsevier.com/nanoenergy

PII: S2211-2855(15)00243-8
DOI: http://dx.doi.org/10.1016/j.nanoen.2015.05.027
Reference: NANOEN859

To appear in: Nano Energy

Received date: 26 February 2015

Revised date: 18 May 2015
Accepted date: 21 May 2015

Cite this article as: Zhou Yang, Bing Cai, Bin Zhou, Tingting Yao, Wei Yu, Frank S.
Liu, Wen-Hua Zhang, Can Li, An up-scalable approach to CH3NH3PbI3 compact
Films for High-performance perovskite solar cells, Nano Energy, http://dx.doi.org/
10.1016/j.nanoen.2015.05.027

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An Up-Scalable Approach to CH3NH3PbI3 Compact Films for

High-performance Perovskite Solar Cells

Zhou Yanga †, Bing Cai a, b †, Bin Zhou a, Tingting Yao a, Wei Yu a, Frank S. Liu a, c,
Wen-Hua Zhang a * and Can Li a *

a. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy
of Sciences
Dalian National Laboratory for Clean Energy, Dalian 116023, China

b. Carbon Research Laboratory, Liaoning Key Lab for Energy Materials and Chemical
Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology,
Dalian116024,China

c. School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062,
China

† These authors contributed equally.

* Corresponding authors:
Wen-Hua Zhang E-mail: whzhang@dicp.ac.cn
Can Li E-mail: canli@dicp.ac.cn
Phone number: +86-411-84379835
Address: State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Science, Dalian, Liaoning Province 116023, China

1
Abstract
In this work, we describe an up-scalable, two step approach to prepare CH3NH3PbI3
perovskite films with high quality and exceptional uniformity at centimeter-scale (5.0 cm ×
5.0 cm). The resulting solar cells achieve efficiency up to 16% with an average efficiency of
14.3% for small-area devices. Remarkably, devices with size of 1.0 cm ×1.0 cm made on the
5.0 cm × 5.0 cm perovskite films display a very impressive efficiency up to 12.6% with an
average efficiency of 10.9% (for 48 devices), which is significantly superior to previous
reports (< 9.0% efficiency) with centimeter-sized devices. The present approach combines
the advantages of the short reaction time, facile fabrication, exceptional uniformity, good
reproducibility, high device performance and up-scalability, enabling it the potential ability in
large-scale photovoltaic applications.

Graphic abstract

Research highlight

1. A facile, simple and effective way (DCIP) has been developed to fabricate high-quality ，
compact perovskite film.

2. The perovskite film obtained shows exceptional uniformity at size of 5.0 cm ×5.0 cm.

3. The device with active size of 1 cm ×1 cm made from 5.0 cm ×5.0 cm perovskite films can
achieve efficiency as high as 12.6% with an average efficiency of 10.9%.

Keywords

Perovskite, film, solar cells, centimeter-scale uniformity, up-scale

2
Introduction

Organolead halide perovskites (CH3NH3PbX3, X=Br, I) solar cells have recently attracted
dramatic attention due to their high efficiency, cost-effective fabrication, and sufficient
supply of raw materials [1-13]. A prominent feature of perovskite solar cells is that they work
very well in various configurations. For instance, both sensitized devices consisting of TiO2
nanostructures [1, 2, 9, 10, 14, 15] and p-i-n type cells in the forms of Al2O3 supported
meso-superstructure [16, 17], planar heterojunction structures [18, 19] and normal organic
solar cell architecture [20-23] displayed excellent photovoltaic performance. Additionally,
solar cells directly based on the heterojunction of perovskites and n-type semiconductors
have also achieved significant efficiency (> 10%) [24, 25]. Among them, the planar
heterojunction devices (i. e., perovskite film solar cells, the same designation hereafter) are
especially interesting because of their simplified fabrication without using of the oxide
nanostructures and their ability in yielding very high efficiency [18, 19, 26].

To date, a variety of strategies have been exploited to deposit the organolead halide
perovskites for photovoltaic study. One-step spin-coating is a simple way to prepare
perovskite solar cells, while its reproducibility is relatively poor, and the corresponding
device performance is not very high [1, 2, 6, 7, 9-13]. Only coupled with solvent engineering,
can this method produce cells with competitive efficiency [27, 28]. A two-step, solution
sequential deposition was exploited to make perovskite sensitized solar cells with high
efficiency in a reproducible way [29], while it is limited in controlling film thickness and
uniformity that is imperative for perovskite film solar cells. Vacuum co-evaporation of two
precursors (PbCl2 and CH3NH3I) exhibits the ability to generate perovskite films with high
coverage and uniformity, resulting in perovskite film photovoltaic devices with efficiency as
high as 15.4% [18, 19]. However, the vacuum deposition will significantly increase the cost
of large-scale fabrication. It is apparent that a deposition without vacuum technique should be
advantageous for cost-effective perovskite photovoltaics. Combining the advantages of the
two-step solution deposition and vapour evaporation of perovskites, vapour-assisted solution
process (VASP) affords CH3NH3PbI3 films with high uniformity [30, 31], leading to planar
device delivering a power conversion efficiency (PCE or η) up to 12.1%. The VASP was
recently modified to fabricate CH3NH3PbI3 segments within mesoporous TiO2 in a closed
container, resulting in HTM-free solar cells with ~10% efficiency high reproducibility [32].

3
 To make perovskite solar cells viable, it is highly necessary to develop the fabrication
process compatible for large-scale production of perovskite films with excellent film
properties. However, this is a big challenge and very few reports have been documented on
the scaling up of perovskite films and solar cells. Ultra-sonic spray-coating has recently been
implemented for preparation of CH3NH3PbI3-xClx films, resulting in planar-structured devices
with the highest efficiency of 11.1% for the 0.025 cm2 cells [33]. Bolink et al. have fabricated
CH3NH3PbI3-based cells by high-vacuum sublimation, giving rise to devices with highest
efficiency of 12% for 0.09 cm2 cells and 8.27% for the 0.98 cm2 cells [20]. Yoon et al. have
made perovskite film photovoltaic devices by solution deposition coupled with solvent
engineering and LiF insertion. Their CH3NH3PbI3 films were extremely smooth and their
cells achieved the remarkably high efficiency up to 14.1% for 0.04 cm2 device, while the
10-cells serially connected module (with substrate area of 10 cm × 10 cm) shows the highest
PCE of 8.7% [34]. It is notable that the above studies of the scalable perovskite solar cells are
all made in normal organic cell architectures. Qi et al [35] have recently modified the vacuum
vapor deposition of CH3NH3PbI3-xClx for fabrication of semi-transparent CH3NH3PbI3-xClx
films with centimeter-scale superior uniformity (5.0 cm × 5.0 cm). Efficiency up to 9.9% was
obtained for the devices with size of 0.05 cm2 in inorganic thin film configuration (namely,
TCO/TiO2/perovskite film/spiro-MeOTAD/Au). It is well-known that solar cells with smaller
size usually show higher efficiency. Therefore, it is highly desirable to explore the possibility
to fabricate perovskite solar cell devices with centimeter sizes on relative large-area
perovskite films (e. g., 5.0 cm × 5.0 cm) with high-efficiency for future large-scale adoption
of perovskite photovoltaics.

Scheme 1. Schematic illustration of the direct contact and intercalation process (DCIP) for growth of
CH3NH3PbI3 compact film.

4
 In this work, we exploit a simple, but efficient two-step approach to the growth of
CH3NH3PbI3 compact films with superior uniformity at centimeter-scale for high efficiency
perovskite film solar cells in inorganic film configuration. This process was developed on the
basis of the two-step VASP but incorporated with important modification for fabrication of
5.0 cm × 5.0 cm perovskite films [30, 31]. The preformed PbI2 films on substrate was directly
put onto the CH3NH3I layer with unintentionally controlled thickness, leading to the
CH3NH3PbI3 compact films after intercalation reaction at 150 oC in a closed container. We
hence designate this hybrid approach as direct contact and intercalation process (DCIP). The
CH3NH3PbI3 films formed via DCIP are characteristic of large grain size, small surface
roughness, complete surface coverage and high reproducibility, catering for the requirement
for high-efficiency perovskite film solar cells with centimeter-scale. The photovoltaic devices
made of such films achieved PCEs as high as 16.0% with an average value of 14.3%.
Moreover, the DCIP processed perovskite films show exceptional uniformity at
centimeter-scale (5.0 cm × 5.0 cm). The devices with active size of 1.00 cm2 made from 5.0
cm × 5.0 cm perovskite films show the highest efficiency of 12.6% and an average efficiency
of 10.9% (for 48 devices), which are the record efficiency for perovskite solar cells with
similar active size, demonstrating the up-scalability of present approach to perovskite film
solar cells.

Experiment section

Materials: PbI2, Lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI), 4-tert-butyl

pyridine (tBP), chlorobenzene and acetonitrile were obtained from Sigma-Aldrich.
Spiro-MeOTAD [2,2’,7,7’-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9’-spiro-bifluorene]
was provided by Shenzhen Feiming Technology Co.. N, N-dimethylformamide (DMF) and
isopropyl alcohol were bought from Sino Chem Company. CH3NH3I was synthesized
according to literature [9].

Device fabrication

Fabrication of TiO2 blocking layer: A compact layer of TiO2 block layer (bl-TiO2) was
deposited on FTO glass by DC magnetron sputter, using Ar as working gas and O2 as
reacting gas. The volume ratio of Ar/O2 is 1/0.15. The resulting TiO2 coated FTO was
annealed in air at 500 oC for 1h.

5
 Growth of CH3NH3PbI3 films via DCIP: 200 nm thick PbI2 film was first prepared by
spin-coating of 0.462 g/ml PbI2/ DMF solution onto bl-TiO2 coated FTO at 3000 rpm,
followed by annealing for 15 min on a 70 °C hotplate. A flat CH3NH3I powder layer was
spread onto the bottom of a metal container pre-heated at 150 oC, onto which the PbI2 film
was directly flipped. The intercalation reaction was performed for specific durations (2.5, 5.0,
7.5, 10.0, 12.5, 15, 20 and 30 min, respectively) for transition of PbI2 to CH3NH3PbI3 in a
closed container (Scheme 1, Figure S1). After cooled down to room temperature, the
CH3NH3PbI3 perovskite film was washed with isopropyl alcohol and dried by N2, and
CH3NH3PbI3 film with ~360 nm thickness can be obtained if the reaction was lasted over
beyond 30 min.

Assembly of perovskite film solar cells: A spiro-MeOTAD solution was prepared by

dissolving 72.3 mg of spiro-MeOTAD in 1.0 ml of chlorobenzene, into which 28.8 µl of tBP
and 17.5 µl of Li-TFSI solution (520 mg Li-TFSI in 1 ml acetonitrile, Sigma-Aldrich, 99.8%)
were added. The sprio-MeOTAD solution was spin-coated on the perovskite films at 5000
rpm for 30 s. Finally, gold electrode with thickness of ~60 nm was thermally evaporated onto
the spiro-MeOTAD-coated film to finish device fabrication.

Characterizations: X-ray diffraction patterns were obtained from samples of

CH3NH3PbI3 perovskite deposited on the bl-TiO2/FTO substrates using an X-ray
diffractometer (X’Pert Pro) via Cu-Kα radiation λ=1.54Å. A field emission SEM (FEI 200G)
was employed to obtain the SEM images with an electron beam accelerated at 20 kV. Atomic
force microscope (AFM) was performed on Bruker Dimension 5000 Scanning Probe
Microscope (SPM) in ''tapping'' mode.

The photocurrent density–voltage (J–V) characteristics of the solar cells was

characterized in air without encapsulation under an AM 1.5G filter at 100 mW/cm2 using a
Newport Oriel 92192 Solar Simulator, calibrated by a certified silicon photodiode. Black
metal apertures with two different sizes (0.1134 cm2 and 1.00 cm2, slightly smaller than the
corresponding gold electrodes) are used to mask the devices and define the active areas. A
typical voltage scan rate was kept at ~0.1 V/s for both directions. The incident
6
photon-to-current efficiency (IPCE) was measured in AC mode on a QTest Station 2000ADI
system (Crowntech Inc.) with a tungsten-halogen lamp (150 W) as light source. The
monochromatic light intensity for IPCE efficiency was calibrated with a reference silicon
photodiode.

Result and Discussion

PbI2 films with ~200 nm thickness were first spinning-coated onto the compact TiO2
block layer/FTO substrate, followed by directly flipping onto the top of the preheated
CH3NH3I films. The intercalation reaction was proceeded at 150 oC within 30min under
nitrogen atmosphere. The transition process from PbI2 to CH3NH3PbI3 was monitored by
XRD (Figure 1a). The pristine PbI2 film shows strong diffraction peak at 12.6 o,
corresponding to the (001) lattice plane. After 7.5 min reaction, a series of new diffraction
peaks of the tetragonal CH3NH3PbI3 appeared, which was accompanied by reduction of the
peak intensity of the 12.6 o reflection of PbI2 within 12.5 min, meaning that the formation of
crystalline CH3NH3PbI3 perovskite is performed by consuming PbI2. In this stage, both PbI2
and CH3NH3PbI3 co-exist in the film, which was further confirmed by UV-Vis absorption (in
Figure 1b). When the reaction was lasted for above 15min, the intercalation reaction was
finished and pure CH3NH3PbI3 films with thickness of ~360 nm can be obtained. Both XRD
patterns and UV-vis absorption spectra were kept unchanged if further prolonging the
reaction to 20 and 30 min, showing that pure CH3NH3PbI3 can be obtained within 15~30 min
DCIP reaction. This is because of the fact that growth of CH3NH3PbI3 is proceeded by
intercalation of CH3NH3I into PbI2, and the reaction would be stopped if the PbI2 was
consumed up within ~ 15min. During the whole process of intercalation reaction, the color of
the film gradually changed from yellow to red-brown and finally to black as shown by
Figure S2.

7
Figure 1. Evolution of the perovskite films subject to DCIP with varied durations at 150 °C. (a) XRD patterns
and (b) UV-Vis absorption spectra.

Scanning electron microscopy (SEM) was performed to reveal evolution of film

morphologies during the conversion process from PbI2 to CH3NH3PbI3 in the present
experiment. Figure S3 discloses that the pristine PbI2 film (Figure S3a) consists of lots of
polygon crystals along with a number of randomly distributed voids. When PbI2 film was
reacted with CH3NH3I for 7.5 min, most of the voids and the polygon feature of PbI2
disappeared ，which is accompanied by appearance of a lot of new crystals. These results
should be ascribed to formation of CH3NH3PbI3 on the surface of PbI2 film by intercalation
of CH3NH3I into PbI2 crystals, during which the crystal volume has been expanded largely to
reduce the void volume and even make them disappear completely. Further increasing the
reaction period enlarges the crystal sizes gradually due to the coalescence of small perovskite
crystals, making the resulting films quite compact. The cross-sectional SEM images of these
samples in Figure S4 show that bi-layers structures were formed during DCIP within 7.5-10
min: the dense up-layer can be attributed to CH3NH3PbI3 while the down-layer containing
loosely packed plates and voids to the pristine PbI2 film. Upon prolonging the reaction to
12.5 min, the bi-layer structure was hardly observed, and large crystal grains with sizes
ranging from 300 nm to 500 nm were produced. The crystal size can be further increased
after 15 min reaction while did not continue growing up beyond 15 min. In such case, very
8
compact CH3NH3PbI3 perovskite films were formed with features of large crystal sizes,
pinhole-free and complete surface coverage. These characteristics make the perovskite films
very suitable for use as building blocks of solar cells. Our DCIP is different from the
inter-diffusion process for fabricating CH3NH3PbI3 perovskite films,[36] in which delicate
control of the ratio of CH3NH3I/PbI2 is needed to form stoichiometric perovskite. In contrast,
it is not necessary to control the ratio of PbI2/CH3NH3I during the present DCIP growth of
CH3NH3PbI3.The prerequisites for the DCIP formation of pure CH3NH3PbI3 are that the
amount of CH3NH3I is sufficient large and the reaction time is long enough to convert PbI2 to
CH3NH3PbI3, which has been clearly demonstrated in the above section that pure
CH3NH3PbI3 can be obtained within 15~30 min. Therefore, the DCIP is a quite facile
approach to fabricate CH3NH3PbI3 perovskite. The DCIP was performed in a closed
container (Figure S1) with small volume and at temperature pre-set at 150oC, thus the
CH3NH3I gas concentration is relative high in cmparison with the VASP where the reaction
was carried out by covering the samples with a petri dish in a glove box (that means the
reaction is performed in a near open way). The low environmental temperature and long
distance between PbI2 and CH3NH3I source in VASP lead to low CH3NH3I vapor
concentration and slow reaction dynamics, making the reaction consume quite long time to
complete the CH3NH3PbI3 growth. [30, 31]. During DCIP, CH3NH3I layer and PbI2 film was
either intimately contacted or the vapor concentration of CH3NH3I is fairly high, significantly
facilitating the intercalation reaction and reducing the reaction time. This was evidenced in
our experiment in such growth of CH3NH3PbI3 compact film consumed only 15 min while it
took 120 min for Yang’s VASP film [30, 31]. DCIP is highly reproducible method in
fabricating CH3NH3PbI3 compact films, characteristic of time-saving and easy to control,
making it quite suitable for photovoltaic application.

9
Figure 2. (a) Plane-view SEM images of the CH3NH3PbI3 film, (b) AFM image of the same sample, (c)
Cross-section SEM image of the solar cells. The CH3NH3PbI3 film was made by DCIP for 15 min at 150 oC.

The as-prepared pure CH3NH3PbI3 films with ~360 nm thickness were subsequently
applied for film solar cells in configuration of FTO/TiO2 blocking layer/ CH3NH3PbI3/
spiro-MeOTAD/Au, where TiO2 blocking layer (bl-TiO2) works as hole blocking and
electron transport materials (ETM), CH3NH3PbI3 as light harvester, spiro-MeOTAD as hole
extraction and transporting materials (HTM). The plane-viewed SEM images (Figure 2a) of
the perovskite film employed for PV device present the large crystal sizes in the range of 300
nm to over 1 µm and complete surface coverage across the whole ranges. Atomic force
microscopy (AFM) of this sample reveals that the film formed through DCIP shows small
surface roughness of 27 nm (Figure 2b) in the ranges of 5.0 µm × 5.0 µm, which is
comparable to the films made via VASP. Cross-section SEM images of a complete
photovoltaic device in Figure 2c shows the planar architecture with very large perovskite
grains and uniform features in the vertical direction across the whole film, which is of
paramount importance to alleviate surface recombination when charge carriers transport
within the perovskite layer [30, 31], thus very favorable for improving device performance.

10
Figure 3. The characterization of photovoltaic performance for DCIP processed devices: (a) typical J-V curves
obtained from back scan and forward scan for the CH3NH3PbI3 film-formed solar cells with 15 min DCIP. Inset
in (a) shows the digital photograph of the typical devices. (b) Photocurrent density and PCE as a function of
time for the same cell hold at maximum power point, which was at 0.82V. (c) IPCE spectrum for this device. (d)
Power conversion efficiency statistics based on 80 devices. (e) J-V curve for the champion cells of them.

Current density (J)-voltage (V) measurements were performed under simulated AM 1.5G
(100 mW/cm2) to assess the photovoltaic performance of the present CH3NH3PbI3 film solar
cells. The typical J-V curves in Figure 3a were obtained in backward scan, showing short
circuit current density (Jsc) of 19.6 mA/cm2, open circuit voltage (VOC) of 1.0 V, fill factor
(FF) of 74.7% and PCE of 14.7%. Perovskite solar cells often show an unusual hysteresis in
the J-V curves if they are measured in different scan modes, and this is especially prominent
11
for planar heterojunction cells in the architecture of inorganic film devices as studied in this
work [37-39]. The back scan usually leads to overestimation of the device efficiency while
forward scan results in underestimation of the efficiency. The real device performance thus
comprises the data obtained both in the back scan and forward scan [27, 40, 41]. We hence
further characterized it by sweeping the applied voltage in forward scan. The hysteresis was
indeed observed. The corresponding photovoltaic parameters obtained from the forward scan
were 19.6 mA/cm2 (JSC), 0.92V (VOC), 64.5% (FF) and 11.6% (PCE) for this cell. The
performance is apparently lower than that obtained from backward scan, which is in line with
the widely reported results. To check the performance of perovskite solar cell under work
condition, we tested the photocurrent density and the corresponding PCE under its maximum
power point at 0.82V, showing steady JSC of 16.7 mA/cm2 and PCE of 13.7% during 110 s
measurement (Figure 3b), demonstrating the high power output ability of this cell. Origin of
J-V hysteresis could be attributed to ferroelectric property, migration of ions, interfacial
defects, and even to electronic contacts in perovskite solar cells [38, 39, 41]. However, more
efforts should be dedicated to address its exact origin for adoption of perovskite
photovoltaics.

IPCE of this cell (in Figure 3c) shows that the onset of the photocurrent generation
occurred near 800 nm, and rose very quickly around 780 nm, which is consistent with the
1.55eV band gap of the CH3NH3PbI3. The IPCE reaches its peak value of 82.9% at ~480 nm
and keeps high level across the whole visible-light range. The integration of the measured
IPCE spectrum over the solar spectrum estimates a short-circuit current density of 19.1
mA/cm2, very close to that obtained from J-V measurement. To test the reliability of the
DCIP in fabricating perovskite film solar cells, 80 devices were fabricated, showing an
average efficiency of 14.3% with small deviation of ± 0.7% (Figure 3d, Table S1). The
champion cell presents an efficiency of 16.0 % along with JSC of 20.9 mA/cm2, VOC of 1.01 V,
and high FF of 75.7% (Figure 3e). These results demonstrate that DCIP is a highly
reproducible approach to fabricate CH3NH3PbI3 film solar cells with competitive
photovoltaic performance. This is understandable considering the fact that, as discussed
above, the CH3NH3PbI3 perovskite films made via DCIP exhibit very high quality,
characteristic of the large grain size, small surface roughness, complete surface coverage, and
pinhole-free. All these features are essential to increase photocurrent while reduce the charge
recombination across the grain boundaries and interface traps during charge transportation,
thus leading to high VOC and large FF [30, 31].
12
Figure 4. (a) Digital photograph
graph of the 36 sub-cells
sub with small gold electrode area (>0.12 cm2) made on the
5.0cm×5.0 cm substrate prepared via DCIP. (b) J-V curve for the champion cells based on these sub-cells. (c)
Statistical histograph of power conversion efficiency (SH-PCE)
(SH of them. (d) Digital photograph
graph of devices with
relative large gold electrode area (>1.02 cm2) made on the 5.0 cm×5.0 cm substrate. (e) J-V
V curve for the
champion cell of 1.00 cm2 devices measured in a back scan model.
model (f) SH-PCE based on 48 cells with 1.00 cm2
area. (g) Photocurrent density and PCE as a function of time for the same cell hold at maximum power point
(0.74V).

We then checked the uniformity of the perovskite films and its up-scalability
up scalability for
production of perovskite films made via DCIP. A CH3NH3PbI3 film with substrate size of 5.0
cm × 5.0 cm (Figure 4a) was prepared by DCIP, from which 36 sub-cells (active area 0.1134
cm2 determined by mask for each cell) were fabricated. The performance of 36 devices on the
same substrate is highly uniform, showing the highest PCE of 15.0% (shown in Figure 4b)
and an average PCE of 13.9% with a small deviation of ± 0.7% (Figure 4c and Table S1
S1).
These results in turn demonstrate the exceptional uniformity of the CH3NH3PbI3 film derived
from DCIP, endowing it with the potential in fabricating large-area
large area solar cells. We hence
prepared PV devices with relative large size of 1.00 cm2 from the 5.0 cm × 5.0 cm perovskite
13
films, showing an average PCE of 10.9% with a deviation of ±1.4% for 48 sub-cells (Figure
4d-f, Table S1). The champion cell shows PCE of 12.6% (with Jsc of 19.6 mA/cm2, Voc of
0.96V, and FF of 67.1% ) in back scan (Figure 4e) and stabilized efficient of 11.1% under its
maximum power point of 0.74V (Figure 4g). All these data are significantly higher than the
previous report (< 9% efficiency) on cells with relative large size (~1 cm2) [20]. Overall, VOC
and FF of the 1.00 cm2 devices are somewhat lower than that of the smaller ones due to the
relatively large series resistance and the decreased shunt resistance. This may be attributed to
the increased probability of the charge carrier recombination and charge traps during their
transport within the large-area perovskite films, ETMs and HTMs. Therefore, DCIP has the
potential ability to afford large-area perovskite films with high quality and exceptional
uniformity, catering for the requirement for large-scale fabrication of perovskite film solar
cells.

Conclusion

In summary, we have exploited a simple but effective approach, DCIP, to fabricate

CH3NH3PbI3 compact films for perovskite film solar cells. The resulting CH3NH3PbI3 films
exhibit excellent morphology and superior uniformity at centimeter-scale, achieving power
conversion efficiency up to 16% with an average efficiency of 14.3% for small-area solar
cells. It is remarkable that devices with area of 1.00 cm2 made on 5.0 cm × 5.0 cm perovskite
films display an impressive efficiency up to 12.6% (with stabilized efficiency of 11.1%),
demonstrating the up-scalability of DCIP in fabricating high-performance perovskite film
solar cells. Thus, the combination of the facile fabrication, exceptional uniformity, high
power conversion efficiency, and up-scalability of the DCIP-processing perovskite film solar
cells enables DCIP the application potential in large-scale photovoltaic applications or other
optoelectronics in future study.

Supporting Information

Electronic Supplementary Information (ESI) available: SEM pictures of samples during

DCIP process and table for statistical analysis of solar cell devices.

Acknowledgements

We acknowledge the financial support from Natural Science Foundation of China (No.
20873141) and the “Hundred Talents Program” of the Chinese Academy of Sciences.
14
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Authors’ information

Zhou Yang received his Bachelor’s degree in Physics from Hebei Normal
University in 2007, and Ph. D. in Condensed Matter Physics from
University of Science and Technology of China in 2012 supervised by Prof.
Xiaoliang Xu. He is currently a postdoc working with Prof.
Prof. Can Li and Prof.
Wen-Hua
Hua Zhang at Dalian Institute of Chemical Physics, CAS. His research
mainly focuses on the third generation solar cell, including quantum dot
sensitized solar cell, perovskite solar cell.

Bing Cai received his Bachelor’s degree in Chemical engineering from

Dalian University of Technology in 2009. He is currently pursuing his Ph.D.
under the supervision of Prof. Jieshan Qiu at Dalian University of
Technology and Prof. Wen-Hua
Wen Hua Zhang at Dalian Institute of Chemical
Physics, Chinese Acaddemy
Acaddemy of Science. His research interest is mainly
focused on organometal halide perovskite solar cells.

Bin Zhou received his Bachelor’s degree in Chemical Engineering from

Zhejiang University of Technology in 2010. He is currently pursuing his
Ph.D. under
er the supervision of Prof. Can Li and Prof. Wen-Hua
Wen Hua Zhang at
Dalian Institute of Chemical Physics, CAS. His research mainly focuses on
development of new type of nanomaterials for solar energy utilization.

Tingting Yao received his Bachelor’s degree in Chemical Engineering from

Zhengzhou University in 2004, and Ph. D. in Chemical Engineering from the
South China University of Technology in 2012 supervised by Prof. Jian Yang.
She is currently a postdoc working with Prof. Can Li at Dalian Institute of Chemical
Chemical Physics,
CAS. Her research mainly focuses on the photoelectrochemistry water splitting.

Wei Yu received his Bachelor’s degree in Hunan Normal University in

2010, and Ph. D. in Condensed. She is currently pursuing her Ph.D. under
Prof. Can Li at Dal
Dalian
ian Institute of Chemical Physics, CAS. Her research
mainly focuses on the third generation solar cell, including polymer solar
cell, perovskite solar cell.

17
 Shengzhong (Frank) Liu received his Ph.D. degree from Northwestern
University (Evanston, Illinois, USA) in 1992. Upon his postdoctoral research
at Argonne National Laboratory (Argonne, Illinois, USA), he joined
high-tech
tech companies in US for research including nanoscale material
materials, thin
film solar cells, laser processing, diamond thin films, etc. His invention at
BP Solar in semi
semi-transparent
transparent photovoltaic module won R&D 100 award in
2002. In 2011, he was selected into China’s top talent recruitment program and now he is a
professor at Shaanxi Normal University and Dalian Institute of Chemical Physics, Chinese
Academy of Sciences.

Hua Zhang received his Ph.D. degree from Shanghai Institute of

Wen-Hua
Ceramics, Chinese Academy of Sciences (CAS) in 2000. He did
postdoctoral work at University
Unive （ ）
College Cork Ireland and was awarded
Alexander von Humboldt (AvH) Research Fellow at Bochum University
（ ）
Germany during 2004-2007. 2007. He joined Dalian Institute of Chemical
Physics, (DICP) in 2007 and received the “CAS Hundred Talents Program”
priorityy support in 2009, then promoted to full professor. Now his research
is focused on development of new type of photovoltaic materials and
photovoltaic cells.

Can Li received his Ph.D. degree in Physical Chemistry from Dalian

Institute of Chemical Physics,
Physics, Chinese Academy of Sciences, in 1989, and
he joined the same institute and was promoted to full professor in 1993. He
did postdoctoral at Northwestern University and was visiting professor at
Lehigh University, the University of Liverpool, and The Queens Queensland
University, and he was awarded the JSPS Professor at Waseda University
University,
Tokyo University of Technology,
Technology and Hokkaido University
University. He was an
Curie, Paris VI. He was the
invited professor at Université Pierre et Marie Curie,
President of the International Association
Asso of Catalysis Societies (2008−2012).
−2012). Currently, he is
the director of the State Key Laboratory of Catalysis. His research interests include (1) UV
Raman spectroscopy and ultrafast spectroscopy; (2) environmental catalysis and green
catalysis; (3) heterogeneous
terogeneous asymmetric catalysis; and (4) solar energy utilization.

Research highlight
1. A facile, simple and effective way (DCIP) has been developed to fabricate high-quality
high ，
compact perovskite film.
2. The perovskite film obtained shows exceptional uniformity at size of 5.0 cm ×5.0 cm.
3. The device with active size of 1 cm ×1 cm made from 5.0 cm ×5.0 cm perovskite films can
achieve efficiency as high as 12.6% with an average efficiency of 10.9%.

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