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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 c b b c
Accepted 00th January 20xx Menghua Zhu,§, Weiwei Liu,§, Weijun Ke, Sarah Clark, Ethan B. Secor, Tze-Bin Song,
b,c *,a *,b,c
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 materials and processing parameters, the power conversion
cells (PVSCs) have emerged as leading candidates for next- efficiency (PCE) of hybrid organic-inorganic halide perovskite
9 10
generation photovoltaic technologies. The architecture of PVSCs solar cells (PVSCs) has risen from 3.8% to 22.1%, with the
11
rely on charge transport layers to enable optimal efficiency and potential to surpass that of crystalline silicon solar cells. Most
stability. In particular, tin oxide (SnO2) has been shown to be an of the reported high-efficiency PVSCs are based on either
effective electron transport layer (ETL) due to favorable energy planar or mesoporous metal-oxide electron transport layers
level alignment, relatively wide band gap, and high environmental (ETLs) such as compact titanium dioxide (TiO2). This type of ETL
and thermal stability. However, traditional processing of SnO2 typically requires a high-temperature (~500°C) and/or long-
necessitates a high-temperature and/or long-duration sintering duration (1-3 hours) sintering step to increase crystallinity and
12,13
step that limits substrate choice and introduces manufacturing achieve sufficiently high charge carrier mobility. However,
challenges. To overcome this limitation, we present here a rapid, these sintering conditions have significant drawbacks for high-
low-temperature, solution-based method for SnO2 film fabrication throughput, low-cost production and integration with
14,15
based on intense pulsed photonic annealing. Following a mechanically flexible substrates.
comprehensive survey of the precursor solution and photonic Several strategies have been pursued to realize low-
annealing conditions, light exposure as short as 20 milliseconds is temperature processing of high-performance ETLs for PVSCs,
shown to provide a high-quality nanocrystalline SnO2 film at room using alternative film preparation methods or replacing TiO2
temperature, enabling PVSCs with low hysteresis and high power with other metal oxides.16-19 For example, a low-temperature
conversion efficiencies exceeding 15%. Overall, this work magnetron sputtering process has been employed to prepare
establishes a processing pathway for SnO2-based PVSCs that is high-density TiO2 layers with the resulting PVSCs exhibiting
compatible with flexible substrates and high-throughput, roll-to- PCEs as high as 15.1% on plastic substrates.20 In addition,
roll manufacturing. 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
Introduction significant interest in employing SnO2 as an ETL for PVSCs due
Hybrid organic-inorganic halide perovskites have attracted to its superior stability,16, 21-29 wide band gap, and high electron
significant attention for photovoltaics due to their superlative, mobility compared to ZnO, TiO2, and other metal oxides.22
compositionally-tunable electronic and optical properties
1-5 Indeed, planar PVSCs have been realized using solution-
6
including bipolar transport and long photogenerated carrier processed nanoparticle SnO2 ETLs with an average PCE of
diffusion lengths.
7,8
In recent years, through improved 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 The SnCl4-based precursor solution was prepared by diluting
compelling fabrication capability to dramatically improve anhydrous SnCl4 with ultrapure H2O to the desired
process throughput and compatibility. This method uses short concentration. The FTO substrates were treated with
millisecond-scale, high-intensity pulses of broadband light, ultraviolet ozone for 15 min preceding SnO2 film formation.

Journal of Materials Chemistry A Accepted Manuscript

typically from a xenon flash lamp, to selectively and rapidly For optimal SnO2 ETL film fabrication, 0.1 M SnCl4 precursor
30
anneal optically absorbing materials. The short duration of solution was spin-coated onto the FTO substrate at 2,000 rpm
the process enables high local temperatures in the optically for 30 sec, followed by photonic annealing for 20 ms (Xenon
2 2
absorbing material without damaging thermally sensitive Sinteron 2010-S; power = 2.3 kW/cm , total energy = 46 J/cm ,
31
substrates, such as flexible plastics. Moreover, the large-area see Fig. S1 for more details). Photonic annealing leads to the
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nature of this technique, combined with its short duration and formation of SnO2 films according to the following reaction:
substrate compatibility, is ideally suited for versatile SnCl4 + 2H2O → SnO2 + 4HCl
32
integration in roll-to-roll fabrication platforms. Due to their The perovskite CH3NH3PbI3 films were prepared by the two-
3
compelling benefits for efficient manufacturing, rapid light- step method. First, 462 mg PbI2 dissolved in 1 mL
based annealing strategies have been demonstrated dimethylformamide was stirred at 70 °C for 12 h. The solution
previously for PVSCs. For example, near-infrared annealing of a was then spin-coated onto the FTO substrates with and
co-deposited Al2O3-CH3NH3PbI3 PVSC for 2.5 seconds achieved without SnO2 ETLs at a low speed of 500 rpm for 3 s followed
a PCE of 10.0% compared to 10.9% for a 45 minute oven- by a high speed of 2,000 rpm for 30 s. Second, the substrates
33
annealed device. Subsequent work utilized flash photonic were dipped into a 10 mg/mL solution of CH3NH3I dissolved in
annealing with a reduced processing time of 1.15 milliseconds, isopropanol for 5 min and then dipped into clean isopropanol
resulting in PCEs up to 11.3% compared to a PCE of 15.2% for at room temperature. Finally, the films were annealed in air at
34
hotplate-annealed devices. Using a 2 millisecond light pulse 70 °C for 30 min.
to anneal a CH3NH3PbI3 film on a layer of thermally-sintered The PTAA film was prepared by spin-coating PTAA (EM index,
mesoporous TiO2, a champion PCE of 12.3% has also been MW = 17,500 g/mol) / toluene (15 mg/mL) solution with 13.6
35
achieved. However, these demonstrations still employ ETLs μL Li-bis(trifluoromethanesulfonyl) imide (Li-TFSI) / acetonitrile
requiring high temperature (~500 °C) processing, limiting the (28.3 mg/mL) and 6.8 μL 4-tert-butylpyridine (tBP) at 2,000
benefits afforded by photonic annealing. For direct application rpm. Following spin-coating, the as-prepared film was
to the ETL, photonic annealing has been shown only for TiO2, thermally annealed at 70 °C for 5 min. Finally, an 80 nm thick
35, 36
resulting in a PCE as high as 15.0% for planar PVSCs. Given Au layer was deposited by thermal evaporation. The active
the aforementioned benefits of SnO2, namely improved charge area of the solar cell was defined by a metal mask with a 0.09
2
carrier mobility, wide band gap, and environmental stability, cm aperture.
the extension of this strategy to SnO2 ETLs presents an Characterization
important development for scalable, high-throughput X-ray diffraction (XRD) spectra of the prepared films were
fabrication of PVSCs with broad process and material measured using a Rigaku SmartLab X-ray diffractometer, while
compatibility. XRD experiments of the powder isolated as an intermediate
Here, we present a low-temperature, solution-based phase were performed using a Rigaku Ultima IV with an X-ray
method combined with intense pulsed photonic annealing to tube (Cu Kα λ=1.5406Å). Ultraviolet-visible absorption spectra
rapidly fabricate high-quality SnO2 ETL films on fluorine-doped were recorded on a Shimadzu UV-3101 spectrophotometer in
tin oxide (FTO) substrates. With an optimized concentration of the 200 nm to 800 nm wavelength range at room temperature.
SnO2 precursor solution and corresponding photonic annealing BaSO4 was used as a non-absorbing reflectance reference. The
time, we achieve PVSC PCEs up to 15.3% when measured morphologies of the surfaces of bare FTO and the SnO2-coated
under reverse voltage scan. The SnO2 ETL photonic annealing FTO substrates were characterized by atomic force microscopy
process occurs following only 20 milliseconds of light (AFM) (SPM-9500j3). Scanning electron microscopy (SEM)
exposure, without the need for additional thermal annealing, measurements were performed with a Hitachi SU8030
offering promise for integration with roll-to-roll manufacturing scanning electron microscope equipped with an Oxford X-max
processes on flexible substrates. This work advances the 80 SDD EDS detector. Data were acquired with an accelerating
prospects for PVSCs in practical solar energy applications. 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
Experimental Si-reference cell certified by NREL. A Keithley 2400 source
Materials meter was used for electrical characterization. External
Unless stated otherwise, all materials were purchased from quantum efficiency (EQE) was characterized using an Oriel
Sigma-Aldrich and used as received. Fluorine-doped tin oxide model QE-PV-SI instrument equipped with a NIST-certified Si
-1
(FTO) with a sheet resistance of 14 Ω sq on glass was diode. Monochromatic light was generated from an Oriel 300
purchased from Asahi Glass (Japan). The purity of the gold W lamp.
used for the top contact is 99.99%.

Solar Cell Fabrication

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Journal of Materials Chemistry A Accepted Manuscript

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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
Figure 1. (a) Schematic, (b) energy diagram, and (c) cross-sectional SEM image of image of a CH3NH3PbI3 perovskite film coated on the SnO2/FTO substrate.
a SnO2-based perovskite solar cell. The inset provides a higher-resolution SEM image of the same surface.

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 Figure 3. XPS spectra for a SnO2 film coated on an FTO substrate and
includes a cross-sectional SEM image of the completed device, photonically annealed for 0.02 seconds: (a) survey, (b) Sn 3d, (c) O 1s, and
which shows that each layer forms a conformal contact with its (d) Cl 2p.
adjacent layers. The measured film thicknesses of the SnO2
and perovskite layers are ~50 nm and ~500 nm, respectively. X-ray photoelectron spectroscopy (XPS) was conducted in
Further details on the process for forming the photonically- order to assess the conversion of SnCl4 to SnO2 after photonic
annealed SnO2 ETL is presented in Fig. 2a. The SEM image in annealing. The full XPS survey spectrum contains elemental O,
Fig. 2b shows the resulting morphology and coverage of the Cl, and Sn peaks as shown in Fig. 3a. The binding energies of
SnO2 thin film on the FTO substrate. In addition, Fig. S2 487.2 eV and 495.7 eV correspond to the Sn 3d5/2 and Sn 3d3/2
provides AFM images of the SnO2 film before and after peaks, respectively (Fig. 3b). Furthermore, the binding energy
2-
photonic annealing. The AFM-measured surface roughness of 531.1 eV can be attributed to O 1s, which is the O state in
value before and after photonic annealing are 32.4 nm and 22.9 SnO2 (Fig. 3c). The higher binding energy can be assigned to
38
nm, respectively, indicating that the SnO2 film is smoother the hydroxyl group OH bond. As shown in Fig. 3d, only trace
following photonic annealing. These results confirm that amounts of chlorine remain after the SnO2 films are
photonic annealing results in compact, nanocrystalline SnO2 photonically annealed, indicating near complete conversion of
18,39
that is suitable for templated casting of perovskite films (Fig. the SnCl4 to SnO2.
2c). 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

Fig. S7 shows the PVSC performance for different
spectrum of a CH3NH3PbI3 film deposited on a FTO/SnO 2 substrate.
concentrations of SnCl4 with the photovoltaic parameters
The photovoltaic device parameters for different SnO2 summarized in Table S2. At low SnCl4 concentrations, the
photonic annealing times are summarized in Table S1, and the coverage of the SnO2 film on the FTO surface is incomplete,
corresponding photocurrent density-voltage (J-V) curves are allowing for direct contact between the perovskite and the
displayed in Fig. S4. Suboptimal photovoltaic performance was FTO substrate. Direct contact is well-known to increase
35,47
observed for photonic annealing times of 5 ms. However, recombination, resulting in deleterious decreases in open-
increasing the photonic annealing time to 20 ms significantly circuit voltage (Voc) and fill factor (FF). Conversely, for high
improved all of the photovoltaic parameters of the resulting SnCl4 concentrations and thus thicker SnO2 films, photonic
cells, boosting the PCE from 9.7% to 15.3%. Further increasing annealing is unable to completely convert the SnCl4 precursor
the SnO2 photonic annealing time again reduced the efficiency solution to SnO2. In addition, larger ETL thicknesses increase
47,48
of the corresponding PVSCs. Evidently, the SnO2 photonic the series resistance, which further reduces PCE. The best
annealing time is a key parameter in controlling the performance was obtained for the 0.1 M SnCl4-based
44
effectiveness of the ETL and thus PVSC performance. The XPS precursor solution.
analysis in Fig. S5 provides chemical insight into the effect of Representative J-V curves and external quantum efficiency
photonic annealing time on the SnO2 film. Specifically, the (EQE) measurements for the optimized cell (0.1 M SnCl4; 20 ms
survey and Cl 2p XPS spectra reveal that the chlorine is fully photonic annealing time) are shown in Fig. 5. The average of
photolyzed after 20 ms of photonic annealing. Importantly, the J-V curves from the forward and reverse voltage scans (Fig.
this annealing condition is compatible with plastic substrates 5a) possesses a short-circuit current (Jsc), Voc, FF, and PCE of
-2
such as PET and PEN, offering compelling prospects for 20.9 mA cm , 1.03 V, 0.64, and 14.0%, respectively, under the
-2
leveraging this strategy to enable lightweight, flexible PVSCs standard AM 1.5 G optical irradiation condition (100 mW cm ).
(Figure S6). In this regard, the development of low- The respective parameters for the forward and reverse voltage
-2
temperature and short-duration fabrication routes for high- scans are 20.4 mA cm , 1.01 V, 0.66, and 12.79% versus 21.4
-2
performance ETLs is a key challenge for flexible PVSC mA cm , 1.06 V, 0.67, and 15.3%, which indicate relatively low
45
development, and critical for realizing the benefits of high- hysteresis (87.6% forward/reverse) for photonically-annealed
throughput, roll-to-roll processing desired for widespread SnO2 ETLs. The EQE curve shows a strong spectral response in
deployment of solution-processed photovoltaics.
46 the range from 350 nm to 750 nm with a peak EQE close to
-2
In addition to the photonic annealing time, the ETL thickness 83%. The integrated current density (20.7 mA cm ) from the
-2
is critical to PVSC performance. The thickness of the ETL is EQE curve agrees well with the Jsc (20.9 mA cm ) obtained
tuned by the concentration of the original SnCl4 solution. from the J-V curve.
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
Conclusions
M. 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 11 H. J. Snaith, J. Phys. Chem. Lett., 2013, 4, 3623-3626.
space revealed that the photonic annealing time and SnCl4- 12 T. Leijtens, G. E. Eperon, S. Pathak, A. Abate, M. M. Lee and
H. J. Snaith, Nat. Commun., 2013, 4, 2885.
based precursor solution concentration are the key 13 B. Wu, K. Fu, N. Yantara, G. Xing, S. Sun, T. C. Sum and N.
parameters in controlling the morphology, chemistry, and Mathews, Adv. Energy Mater., 2015, 5, 1500829.

Journal of Materials Chemistry A Accepted Manuscript

performance of the resulting SnO2 ETL. The optimized 14 B. S. Ong, C. Li, Y. Li, Y. Wu and R. Loutfy, J. Am. Chem. Soc.,
processing conditions (0.1 M SnCl4; 20 ms photonic annealing 2007, 129, 2750-2751.
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-2 5, 9173-9179.
Voc (1.06 V), Jsc (21.4 mA cm ), and FF (0.67) under the 16 D. Liu and T. L. Kelly, Nat. Photonics, 2014, 8, 133-138.
standard AM 1.5 G optical irradiation condition. This rapid, 17 M. J. Carnie, C. Charbonneau, M. L. Davies, J. Troughton, T.
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low-temperature, solution-processing methodology is ideally M. Watson, K. Wojciechowski, H. Snaith and D. A. Worsley,

suited for ongoing efforts to realize large-scale, roll-to-roll Chem. Commun., 2013, 49, 7893-7895.
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This work was supported as part of the Argonne-Northwestern
21 Z. Zhu, X. Zheng, Y. Bai, T. Zhang, Z. Wang and S. Xiao, S.
Solar Energy Research (ANSER) Center, an Energy Frontier Yang, Phys. Chem. Chem. Phys., 2015, 17, 18265-18268.
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the Doctoral Program of Higher Education (20122302110043) Kuang and C. Y. Su, Adv. Funct. Mater., 2015, 25, 7200.
and the State Key Laboratory of Urban Water Resource and 24 W. Ke, G. Fang, Q. Liu, L. Xiong, P. Qin, H. Tao, J. Wang, H.
Environment of the Harbin Institute of Technology Lei, B. Li and J. Wan, J. Am. Chem. Soc., 2015, 137, 6730-
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(2016DX07). Menghua Zhu gratefully acknowledges financial 25 L. Zuo, Z. Gu, T. Ye, W. Fu, G. Wu, H. Li and H. Chen, J. Am.
support from the Joint Educational PhD Program of the Chem. Soc., 2015, 137, 2674-2679.
Chinese Scholarship Council (CSC). This work made use of the 26 H. Zhou, Q. Chen, G. Li, S. Luo, T.-B. Song, H.-S. Duan, Z.
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