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COMMUNICATION
Millisecond-pulsed photonically-annealed tin oxide electron
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transport layers for efficient perovskite solar cells
Received 00th January 20xx, a,b a,b
Accepted 00th January 20xx Menghua Zhu,§, Weiwei Liu,§, Weijun Ke, Sarah Clark, Ethan B. Secor, Tze-Bin Song,
b,c *,a
Mercouri G. Kanatzidis, Xin Li, and Mark C. Hersam
DOI: 10.1039/x0xx00000x
www.rsc.org/
In recent years, hybrid organic-inorganic halide perovskite solar
cells (PVSCs) have emerged as leading candidates for next-
generation photovoltaic technologies. The architecture of PVSCs
rely on charge transport layers to enable optimal efficiency and
stability. In particular, tin oxide (SnO2) has been shown to be an
effective electron transport layer (ETL) due to favorable energy
level alignment, relatively wide band gap, and high environmental
and thermal stability. However, traditional processing of SnO2
necessitates a high-temperature and/or long-duration sintering
step that limits substrate choice and introduces manufacturing
challenges. To overcome this limitation, we present here a rapid,
low-temperature, solution-based method for SnO2 film fabrication
based on intense pulsed photonic annealing. Following a
comprehensive survey of the precursor solution and photonic
annealing conditions, light exposure as short as 20 milliseconds is
shown to provide a high-quality nanocrystalline SnO2 film at room
temperature, enabling PVSCs with low hysteresis and high power
conversion efficiencies exceeding 15%. Overall, this work
establishes a processing pathway for SnO2-based PVSCs that is
compatible with flexible substrates and high-throughput, roll-to-
roll manufacturing.
Introduction
Hybrid organic-inorganic halide perovskites have attracted
significant attention for photovoltaics due to their superlative,
compositionally-tunable electronic and optical properties
1-5
6
including bipolar transport and long photogenerated carrier
diffusion lengths.
7,8
In recent years, through improved
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Journal of Materials Chemistry A Accepted Manuscript
c b b c
*,b,c
materials and processing parameters, the power conversion
efficiency (PCE) of hybrid organic-inorganic halide perovskite
9 10
solar cells (PVSCs) has risen from 3.8% to 22.1%, with the
11
potential to surpass that of crystalline silicon solar cells. Most
of the reported high-efficiency PVSCs are based on either
planar or mesoporous metal-oxide electron transport layers
(ETLs) such as compact titanium dioxide (TiO2). This type of ETL
typically requires a high-temperature (~500°C) and/or long-
duration (1-3 hours) sintering step to increase crystallinity and
12,13
achieve sufficiently high charge carrier mobility. However,
these sintering conditions have significant drawbacks for high-
throughput, low-cost production and integration with
14,15
mechanically flexible substrates.
Several strategies have been pursued to realize low-
temperature processing of high-performance ETLs for PVSCs,
using alternative film preparation methods or replacing TiO2
with other metal oxides.16-19 For example, a low-temperature
magnetron sputtering process has been employed to prepare
high-density TiO2 layers with the resulting PVSCs exhibiting
PCEs as high as 15.1% on plastic substrates.20 In addition,
planar PVSCs have been demonstrated using a low-
temperature, solution-processed zinc oxide (ZnO) nanoparticle
ETL with PCEs up to 15.7%.16 Recently, there has been
significant interest in employing SnO2 as an ETL for PVSCs due
to its superior stability,16, 21-29 wide band gap, and high electron
mobility compared to ZnO, TiO2, and other metal oxides.22
Indeed, planar PVSCs have been realized using solution-
processed nanoparticle SnO2 ETLs with an average PCE of
16.0%.24 Furthermore, PCEs in excess of 18% have been
achieved by using atomic layer deposition (ALD) to prepare
SnO2 ETLs.22 Using an ultraviolet-ozone treatment, Huang et al.
also demonstrated a low-temperature, sol-gel SnO2 ETL for
PVSCs, resulting in an efficiency as high as 16.2%.28 Although
these early reports have shown that high-quality SnO2 ETLs
enable high-performance PVSCs, these methods necessitate
long annealing or growth times. These long processing times
present a bottleneck for rapid, large-scale manufacturing,
which is a key motivation and cost driver for widespread
deployment of PVSCs.
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In this regard, intense pulsed photonic annealing presents a
compelling fabrication capability to dramatically improve
process throughput and compatibility. This method uses short
millisecond-scale, high-intensity pulses of broadband light,
typically from a xenon flash lamp, to selectively and rapidly
30
anneal optically absorbing materials. The short duration of
the process enables high local temperatures in the optically
absorbing material without damaging thermally sensitive
31
substrates, such as flexible plastics. Moreover, the large-area
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nature of this technique, combined with its short duration and
substrate compatibility, is ideally suited for versatile
32
integration in roll-to-roll fabrication platforms. Due to their
compelling benefits for efficient manufacturing, rapid light-
based annealing strategies have been demonstrated
previously for PVSCs. For example, near-infrared annealing of a
co-deposited Al2O3-CH3NH3PbI3 PVSC for 2.5 seconds achieved
a PCE of 10.0% compared to 10.9% for a 45 minute oven-
33
annealed device. Subsequent work utilized flash photonic
annealing with a reduced processing time of 1.15 milliseconds,
resulting in PCEs up to 11.3% compared to a PCE of 15.2% for
34
hotplate-annealed devices. Using a 2 millisecond light pulse
to anneal a CH3NH3PbI3 film on a layer of thermally-sintered
mesoporous TiO2, a champion PCE of 12.3% has also been
35
achieved. However, these demonstrations still employ ETLs
requiring high temperature (~500 °C) processing, limiting the
benefits afforded by photonic annealing. For direct application
to the ETL, photonic annealing has been shown only for TiO2,
35, 36
resulting in a PCE as high as 15.0% for planar PVSCs. Given
the aforementioned benefits of SnO2, namely improved charge
carrier mobility, wide band gap, and environmental stability,
the extension of this strategy to SnO2 ETLs presents an
important development for scalable, high-throughput
fabrication of PVSCs with broad process and material
compatibility.
Here, we present a low-temperature, solution-based
method combined with intense pulsed photonic annealing to
rapidly fabricate high-quality SnO2 ETL films on fluorine-doped
tin oxide (FTO) substrates. With an optimized concentration of
SnO2 precursor solution and corresponding photonic annealing
time, we achieve PVSC PCEs up to 15.3% when measured
under reverse voltage scan. The SnO2 ETL photonic annealing
process occurs following only 20 milliseconds of light
exposure, without the need for additional thermal annealing,
offering promise for integration with roll-to-roll manufacturing
processes on flexible substrates. This work advances the
prospects for PVSCs in practical solar energy applications.
Experimental
Materials
Unless stated otherwise, all materials were purchased from
Sigma-Aldrich and used as received. Fluorine-doped tin oxide
-1
(FTO) with a sheet resistance of 14 Ω sq on glass was
purchased from Asahi Glass (Japan). The purity of the gold
used for the top contact is 99.99%.
Solar Cell Fabrication
2 | J. Name., 2012, 00, 1-3
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The SnCl4-based precursor solution was prepared by diluting
anhydrous SnCl4 with ultrapure H2O to the desired
concentration. The FTO substrates were treated with
ultraviolet ozone for 15 min preceding SnO2 film formation.
Journal of Materials Chemistry A Accepted Manuscript
For optimal SnO2 ETL film fabrication, 0.1 M SnCl4 precursor
solution was spin-coated onto the FTO substrate at 2,000 rpm
for 30 sec, followed by photonic annealing for 20 ms (Xenon
2 2
Sinteron 2010-S; power = 2.3 kW/cm , total energy = 46 J/cm ,
see Fig. S1 for more details). Photonic annealing leads to the
formation of SnO2 films according to the following reaction:
SnCl4 + 2H2O → SnO2 + 4HCl
The perovskite CH3NH3PbI3 films were prepared by the two-
3
step method. First, 462 mg PbI2 dissolved in 1 mL
dimethylformamide was stirred at 70 °C for 12 h. The solution
was then spin-coated onto the FTO substrates with and
without SnO2 ETLs at a low speed of 500 rpm for 3 s followed
by a high speed of 2,000 rpm for 30 s. Second, the substrates
were dipped into a 10 mg/mL solution of CH3NH3I dissolved in
isopropanol for 5 min and then dipped into clean isopropanol
at room temperature. Finally, the films were annealed in air at
70 °C for 30 min.
The PTAA film was prepared by spin-coating PTAA (EM index,
MW = 17,500 g/mol) / toluene (15 mg/mL) solution with 13.6
μL Li-bis(trifluoromethanesulfonyl) imide (Li-TFSI) / acetonitrile
(28.3 mg/mL) and 6.8 μL 4-tert-butylpyridine (tBP) at 2,000
rpm. Following spin-coating, the as-prepared film was
thermally annealed at 70 °C for 5 min. Finally, an 80 nm thick
Au layer was deposited by thermal evaporation. The active
area of the solar cell was defined by a metal mask with a 0.09
2
cm aperture.
Characterization
X-ray diffraction (XRD) spectra of the prepared films were
measured using a Rigaku SmartLab X-ray diffractometer, while
XRD experiments of the powder isolated as an intermediate
phase were performed using a Rigaku Ultima IV with an X-ray
tube (Cu Kα λ=1.5406Å). Ultraviolet-visible absorption spectra
were recorded on a Shimadzu UV-3101 spectrophotometer in
the 200 nm to 800 nm wavelength range at room temperature.
BaSO4 was used as a non-absorbing reflectance reference. The
morphologies of the surfaces of bare FTO and the SnO2-coated
FTO substrates were characterized by atomic force microscopy
(AFM) (SPM-9500j3). Scanning electron microscopy (SEM)
measurements were performed with a Hitachi SU8030
scanning electron microscope equipped with an Oxford X-max
80 SDD EDS detector. Data were acquired with an accelerating
voltage of 15 kV. J-V characteristics were measured using a
solar simulator (Spectra-Nova Class A Xenon Arc Lamp) with
-2
AM 1.5 G optical irradiation (100 mW cm ), calibrated with a
Si-reference cell certified by NREL. A Keithley 2400 source
meter was used for electrical characterization. External
quantum efficiency (EQE) was characterized using an Oriel
model QE-PV-SI instrument equipped with a NIST-certified Si
diode. Monochromatic light was generated from an Oriel 300
W lamp.
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Figure 1. (a) Schematic, (b) energy diagram, and (c) cross-sectional SEM image of
a SnO2-based perovskite solar cell.
Results and discussion
The SnO2 films were prepared through solution processing. In
particular, a SnCl4-based precursor solution was spin-coated
and then immediately annealed preceding drying via exposure
to high-intensity optical pulses from a xenon lamp as shown in
Fig. S1. To improve substrate wetting and increase infiltration
of the aqueous SnCl4 precursor solution, the FTO substrates
were treated with ultraviolet ozone for 15 min prior to spin-
coating. To examine the efficacy of these photonically-
annealed SnO2 films as an ETL in PVSCs, planar devices with
the configuration FTO/SnO2/CH3NH3PbI3/PTAA/Au were
fabricated. The device structure using PTAA as the hole
transport layer (HTL) is illustrated in Fig. 1a, with the
37
accompanying energy band diagram shown in Fig. 1b. Fig. 1c
includes a cross-sectional SEM image of the completed device,
which shows that each layer forms a conformal contact with its
adjacent layers. The measured film thicknesses of the SnO2
and perovskite layers are ~50 nm and ~500 nm, respectively.
Further details on the process for forming the photonically-
annealed SnO2 ETL is presented in Fig. 2a. The SEM image in
Fig. 2b shows the resulting morphology and coverage of the
SnO2 thin film on the FTO substrate. In addition, Fig. S2
provides AFM images of the SnO2 film before and after
photonic annealing. The AFM-measured surface roughness
value before and after photonic annealing are 32.4 nm and 22.9
nm, respectively, indicating that the SnO2 film is smoother
following photonic annealing. These results confirm that
photonic annealing results in compact, nanocrystalline SnO2
that is suitable for templated casting of perovskite films (Fig.
2c).
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Journal of Materials Chemistry A Accepted Manuscript
Figure 2. (a) Schematic illustration of the SnO2 ETL fabrication process. (b)
Top-view SEM image of a SnO2-coated FTO substrate. (c) Top-view SEM
image of a CH3NH3PbI3 perovskite film coated on the SnO2/FTO substrate.
The inset provides a higher-resolution SEM image of the same surface.
Figure 3. XPS spectra for a SnO2 film coated on an FTO substrate and
photonically annealed for 0.02 seconds: (a) survey, (b) Sn 3d, (c) O 1s, and
(d) Cl 2p.
X-ray photoelectron spectroscopy (XPS) was conducted in
order to assess the conversion of SnCl4 to SnO2 after photonic
annealing. The full XPS survey spectrum contains elemental O,
Cl, and Sn peaks as shown in Fig. 3a. The binding energies of
487.2 eV and 495.7 eV correspond to the Sn 3d5/2 and Sn 3d3/2
peaks, respectively (Fig. 3b). Furthermore, the binding energy
2-
of 531.1 eV can be attributed to O 1s, which is the O state in
SnO2 (Fig. 3c). The higher binding energy can be assigned to
38
the hydroxyl group OH bond. As shown in Fig. 3d, only trace
amounts of chlorine remain after the SnO2 films are
photonically annealed, indicating near complete conversion of
18,39
the SnCl4 to SnO2.
On top of the photonically annealed SnO2 ETL, CH3NH3PbI3
3
films were deposited via an established two step method. A
top-view SEM image of a representative perovskite film
deposited on the SnO2/FTO substrate is provided in Fig. 2c,
revealing a continuous film free of holes or crevices between
grains. The inset in Fig. 2c shows a higher-magnification SEM
image of the perovskite film surface, indicating that the grain
size is ~500 nm. XRD measurements, provided in Fig. S3,
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confirm that the film is composed of the perovskite phase as

well as residual PbI2, the presence of which has been shown to
benefit device performance by suppressing carrier
40
recombination. Fig. 4 shows the absorption and

Journal of Materials Chemistry A Accepted Manuscript

photoluminescence (PL) spectra of the CH3NH3PbI3 film on the
SnO2/FTO substrate. The absorption spectrum shows a sharp
41
band edge at ~760 nm as expected. The second absorption
peak located at ~500 nm has been attributed to a double-
7 42,43
valence band or charge-transfer excited state. The
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photoluminescence peak at ~773 nm agrees well with values Figure 5. (a) J-V curves measured under forward and reverse scans, and (b)
3 EQE spectrum of the optimized perovskite CH3NH3PbI3-based solar cell with
reported in the literature for high-quality perovskite films.
photonically-annealed SnO2 ETL.

Table 1. Photovoltaic parameters of the optimized perovskite CH3NH3PbI3-

based solar cell with photonically-annealed SnO2 ETL under different scan
directions.
-2
Voc (V) Jsc (mA m ) FF PCE(%)
Forward 1.01 20.4 0.65 13.4
Reverse 1.06 21.4 0.67 15.3
Average 1.03 20.9 0.66 14.3

Figure 4. (a) UV-vis absorption spectrum and (b) photoluminescence

spectrum of a CH3NH3PbI3 film deposited on a FTO/SnO 2 substrate.
The photovoltaic device parameters for different SnO2
photonic annealing times are summarized in Table S1, and the
corresponding photocurrent density-voltage (J-V) curves are
displayed in Fig. S4. Suboptimal photovoltaic performance was
observed for photonic annealing times of 5 ms. However,
increasing the photonic annealing time to 20 ms significantly
improved all of the photovoltaic parameters of the resulting
cells, boosting the PCE from 9.7% to 15.3%. Further increasing
the SnO2 photonic annealing time again reduced the efficiency
of the corresponding PVSCs. Evidently, the SnO2 photonic
annealing time is a key parameter in controlling the
44
effectiveness of the ETL and thus PVSC performance. The XPS
analysis in Fig. S5 provides chemical insight into the effect of
photonic annealing time on the SnO2 film. Specifically, the
survey and Cl 2p XPS spectra reveal that the chlorine is fully
photolyzed after 20 ms of photonic annealing. Importantly,
this annealing condition is compatible with plastic substrates
such as PET and PEN, offering compelling prospects for
leveraging this strategy to enable lightweight, flexible PVSCs
(Figure S6). In this regard, the development of low-
temperature and short-duration fabrication routes for high-
performance ETLs is a key challenge for flexible PVSC
45
development, and critical for realizing the benefits of high-
throughput, roll-to-roll processing desired for widespread
deployment of solution-processed photovoltaics.
46
In addition to the photonic annealing time, the ETL thickness
is critical to PVSC performance. The thickness of the ETL is
tuned by the concentration of the original SnCl4 solution.
Therefore, to study the effect of film thickness on device
performance, several SnCl4-based precursor solutions were
prepared with SnCl4 concentrations varying from 0.05 M to 0.2
M.
Fig. S7 shows the PVSC performance for different
concentrations of SnCl4 with the photovoltaic parameters
summarized in Table S2. At low SnCl4 concentrations, the
coverage of the SnO2 film on the FTO surface is incomplete,
allowing for direct contact between the perovskite and the
FTO substrate. Direct contact is well-known to increase
35,47
recombination, resulting in deleterious decreases in open-
circuit voltage (Voc) and fill factor (FF). Conversely, for high
SnCl4 concentrations and thus thicker SnO2 films, photonic
annealing is unable to completely convert the SnCl4 precursor
solution to SnO2. In addition, larger ETL thicknesses increase
47,48
the series resistance, which further reduces PCE. The best
performance was obtained for the 0.1 M SnCl4-based
precursor solution.
Representative J-V curves and external quantum efficiency
(EQE) measurements for the optimized cell (0.1 M SnCl4; 20 ms
photonic annealing time) are shown in Fig. 5. The average of
the J-V curves from the forward and reverse voltage scans (Fig.
5a) possesses a short-circuit current (Jsc), Voc, FF, and PCE of
-2
20.9 mA cm , 1.03 V, 0.64, and 14.0%, respectively, under the
-2
standard AM 1.5 G optical irradiation condition (100 mW cm ).
The respective parameters for the forward and reverse voltage
-2
scans are 20.4 mA cm , 1.01 V, 0.66, and 12.79% versus 21.4
-2
mA cm , 1.06 V, 0.67, and 15.3%, which indicate relatively low
hysteresis (87.6% forward/reverse) for photonically-annealed
SnO2 ETLs. The EQE curve shows a strong spectral response in
the range from 350 nm to 750 nm with a peak EQE close to
-2
83%. The integrated current density (20.7 mA cm ) from the
-2
EQE curve agrees well with the Jsc (20.9 mA cm ) obtained
from the J-V curve.
Conclusions
In summary, we have demonstrated a rapid, low-temperature
photonic annealing approach for preparing SnO2 ETLs for

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efficient PVSCs. Systematic exploration of the processing phase
space revealed that the photonic annealing time and SnCl4-
based precursor solution concentration are the key
parameters in controlling the morphology, chemistry, and
performance of the resulting SnO2 ETL. The optimized
processing conditions (0.1 M SnCl4; 20 ms photonic annealing
time) yielded PVSCs with low hysteresis and high PCE (15.3%),
-2
Voc (1.06 V), Jsc (21.4 mA cm ), and FF (0.67) under the
standard AM 1.5 G optical irradiation condition. This rapid,
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low-temperature, solution-processing methodology is ideally
suited for ongoing efforts to realize large-scale, roll-to-roll
manufacturing of low-cost, high-performance, and
mechanically flexible PVSCs.
Acknowledgement
This work was supported as part of the Argonne-Northwestern
Solar Energy Research (ANSER) Center, an Energy Frontier
Research Center funded by the U. S. Department of Energy,
Office of Science, Basic Energy Sciences under Award No. DE-
SC0001059. We also thank the Specialized Research Fund for
the Doctoral Program of Higher Education (20122302110043)
and the State Key Laboratory of Urban Water Resource and
Environment of the Harbin Institute of Technology
(2016DX07). Menghua Zhu gratefully acknowledges financial
support from the Joint Educational PhD Program of the
Chinese Scholarship Council (CSC). This work made use of the
experimental facilities of the Northwestern University NUANCE
Center, which has received support from the Soft and Hybrid
Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-
1542205); the MRSEC program (NSF DMR-1121262); the
International Institute for Nanotechnology (IIN); the Keck
Foundation; and the State of Illinois.
Notes and references
1 M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami and H. J.
Snaith, Science, 2012, 338, 643-647.
2 L. Etgar, P. Gao, Z. Xue, Q. Peng, A. K. Chandiran, B. Liu, M. K.
Nazeeruddin and M. Grätzel, J. Am. Chem. Soc., 2012,134,
17396-17399.
3 J. Burschka, N. Pellet, S.J. Moon, R. Humphry-Baker, P. Gao,
M. K. Nazeeruddin and M. Grätzel, Nature, 2013, 499, 316-
319.
4 C. Wehrenfennig, G. E. Eperon, M. B. Johnston, H. J. Snaith
and L. M. Herz, Adv. Mater., 2014, 26, 1584-1589.
5 P. W. Liang, C. Y. Liao, C. C. Chueh, F. Zuo, S. T. Williams, X. K.
Xin, J. Lin and A. K. Y. Jen, Adv. Mater., 2014, 26, 3748-3754.
6 P. Docampo, F. C. Hanusch, S. D. Stranks, M. Döblinger, J. M.
Feckl, M. Ehrensperger, N. K. Minar, M. B. Johnston, H. J.
Snaith and T. Bein, Adv. Energy Mater., 2014, 4, 1600474.
7 G. Xing, N. Mathews, S. Sun, S. S. Lim, Y. M. Lam, M. Grätzel,
S. Mhaisalkar and T. C. Sum, Science, 2013, 342, 344-347.
8 S. D. Stranks, G. E. Eperon, G. Grancini, C. Menelaou, M. J.
Alcocer, T. Leijtens, L. M. Herz, A. Petrozza and H. J. Snaith,
Science, 2013, 342, 341-344.
9 A. Kojima, K. Teshima, Y. Shirai and T. Miyasaka, J. Am. Chem.
Soc., 2009, 131, 6050-6051.
10 NREL chart, www.nrel.gov/ncpv/images/efficiency_chart.jpg.
This journal is © The Royal Society of Chemistry 20xx
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11 H. J. Snaith, J. Phys. Chem. Lett., 2013, 4, 3623-3626.
12 T. Leijtens, G. E. Eperon, S. Pathak, A. Abate, M. M. Lee and
H. J. Snaith, Nat. Commun., 2013, 4, 2885.
13 B. Wu, K. Fu, N. Yantara, G. Xing, S. Sun, T. C. Sum and N.
Mathews, Adv. Energy Mater., 2015, 5, 1500829.
Journal of Materials Chemistry A Accepted Manuscript
14 B. S. Ong, C. Li, Y. Li, Y. Wu and R. Loutfy, J. Am. Chem. Soc.,
2007, 129, 2750-2751.
15 Z. M. Beiley and M. D. McGehee, Energy Environ. Sci., 2012,
5, 9173-9179.
16 D. Liu and T. L. Kelly, Nat. Photonics, 2014, 8, 133-138.
17 M. J. Carnie, C. Charbonneau, M. L. Davies, J. Troughton, T.
M. Watson, K. Wojciechowski, H. Snaith and D. A. Worsley,
Chem. Commun., 2013, 49, 7893-7895.
18 D. Muñoz-Rojas, H. Sun, D. C. Iza, J. Weickert, L. Chen, H.
Wang, L. Schmidt-Mende and J. L. MacManus-Driscoll, Prog.
Photovoltaics, 2013, 21, 393-396.
19 M. Dürr, A. Schmid, M. Obermaier, S. Rosselli and A. Yasuda,
G. Nelles, Nat. Mater., 2005, 4, 607-611.
20 D. Yang, R. Yang, J. Zhang, Z. Yang, S. F. Liu and C. Li, Energy
Environ. Sci., 2015, 8, 3208-3214.
21 Z. Zhu, X. Zheng, Y. Bai, T. Zhang, Z. Wang and S. Xiao, S.
Yang, Phys. Chem. Chem. Phys., 2015, 17, 18265-18268.
22 J. P. C. Baena, L. Steier, W. Tress, M. Saliba, S. Neutzner, T.
Matsui, F. Giordano, T. J. Jacobsson, A. R. S. Kandada and S.
M. Zakeeruddin, Energy Environ. Sci., 2015, 8, 2928-2934.
23 H. S. Rao, B. X. Chen, W. G. Li, Y. F. Xu, H. Y. Chen, D. B.
Kuang and C. Y. Su, Adv. Funct. Mater., 2015, 25, 7200.
24 W. Ke, G. Fang, Q. Liu, L. Xiong, P. Qin, H. Tao, J. Wang, H.
Lei, B. Li and J. Wan, J. Am. Chem. Soc., 2015, 137, 6730-
6733.
25 L. Zuo, Z. Gu, T. Ye, W. Fu, G. Wu, H. Li and H. Chen, J. Am.
Chem. Soc., 2015, 137, 2674-2679.
26 H. Zhou, Q. Chen, G. Li, S. Luo, T.-B. Song, H.-S. Duan, Z.
Hong, J. You, Y. Liu and Y. Yang, Science, 2014, 345, 542-46.
27 S. S. Shin, W. S. Yang, J. H. Noh, J. H. Suk, N. J. Jeon, J. H.
Park, J. S. Kim, W. M. Seong and S. I. Seok, Nat. Commun.,
2015, 6, 6432.
28 L. Huang, X. Sun, C. Li, J. Xu, Rui Xu, Y. Du, J. Ni, H. Cai, J. Li, Z.
Hu and J. Zhang, ACS Appl. Mater. Interfaces, 2017, 9, 21909-
21920.
29 M. Abulikemu, M. Neophytou, J. M. Barbé, M. L. Tietze, A.E.
Labban, D. H. Anjum, A. Amassian, I. McCulloch and S. D.
Gobbo, J. Mater. Chem. A, 2017, 5, 7759-7763.
30 K. A. Schroder, S. C. McCool and W. F. Furlan, NSTI-Nanotech.,
2016, 3, 198.
31 S. Wunscher, R. Abbel, J. Perelaerabd and U. S. Schubert, J.
Mater. Chem. C, 2014, 2, 10262-10267.
32 D. Angmo, T.T. Larsen-Olsen, M. Jørgensen, R. R.
Søndergaard and F. C. Krebs, Adv. Energy Mater., 2013, 3,
172-175.
33 E. B. Secor, B. Y. Ahn, T. Z. Gao, J. A. Lewis and M. C. Hersam,
Adv. Mater., 2015, 27, 6683-6688.
34 J. Troughton, C. Charbonneau, M. J. Carnie, M. L. Davies, D.
A. Worsley and T. M. Watson, J. Mater. Chem. A, 2015, 3,
9123-9129.
35 J. Troughton, M. J. Carnie, M. L. Davies, C. Charbonneau , E.
H. Jewell , D.A. Worsley and T. M. Watson, J. Mater. Chem. A,
2016, 4, 3471-3478.
36 S. Das, B. Yang, G. Gu, P. C. Joshi, I. N. Ivanov, C. M. Rouleau,
T. Aytng, D. B. Geohegan and K. Xiao, ACS Photonics, 2015, 2,
680-686.
37 K. Basu, D. Benetti, H. Zhao, L. Jin, F. Vetrone, A. Vomiero
and F. Rosei, Sci. Rep., 2016, 6, 346.
38 B. Bob, T.-B. Song, C.-C. Chen, Z. Xu and Y. Yang, Chem.
Mater., 2013, 25, 4725-4730.
39 M. Zhu, X. Li, W. Liu and Y. Cui, J. Power Sources, 2014, 262,
349-355.
J. Name., 2013, 00, 1-3 | 5
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Journal ofdo not adjustChemistry
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40 Q. Chen, H. Zhou, T.-B. Song, S. Luo, Z. Hong, H.-S. Duan, L.

Dou, Y. Liu and Y. Yang, Nano Lett., 2014, 14, 4158-4163.
41 Z. Guo, J. S. Manser, Y. Wan, P. V. Kamat and L. Huang, Nat.
Commun., 2015, 6, 7471.
42 K. G. Stamplecoskie, J. S. Manser and P. V. Kamat, Energy

Journal of Materials Chemistry A Accepted Manuscript

Environ. Sci., 2015, 8, 208-215.
43 J. A. Christians, P. A. Miranda Herrera and P. V. Kamat, J. Am.
Chem. Soc., 2015, 137, 1530-1538.
44 M. Zhu, F. Hao, L. Ma, T.-B. Song, C. E. Miller, M. R.
Wasielewski, X. Li and M. G. Kanatzidis, ACS Energy Lett.,
2016. 1, 469-473.
Published on 10 November 2017. Downloaded by University of Windsor on 11/11/2017 01:52:15.

45 F. D. Giacomo, A. Fakharuddin, R. Josec and T. M. Brown,

Energy Environ. Sci., 2016, 9, 3007-3014.
46 H. Tan, A. Jain, O. Voznyy, X. Lan, F. P. Arquer, J. Z. Fan, R.
Quintero-Bermudez, M. Yuan, B. Zhang, Y. Zhao, F. Fan, P. Li,
L. Quan, Y. Zhao, Z. Lu, Z. Yang, S. Hoogland and E. H.
Sargent, Science, 2017, 355, 719-722.
47 J. Shi, J. Dong, S. Lv, Y. Xu, L. Zhu, J. Xiao, X. Xu, H. Wu, D. Li
and Y. Luo, Appl. Phys. Lett., 2014, 104, 063901.
48 W. A. Laban and L. Etgar, Energy Environ. Sci., 2013, 6, 3249-
3253.

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