Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 3487−3495 pubs.acs.org/journal/ascecg

Binary Solvent Engineering for High-Performance Two-Dimensional

Perovskite Solar Cells
Jianjun Zhang,† Liuyang Zhang,† Xiaohe Li,† Xinyi Zhu,† Jiaguo Yu,*,†,‡ and Ke Fan*,†
†
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 122
Luoshi Road, Wuhan 430070, P. R. China
‡
Department of Physics, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
*
S Supporting Information
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ABSTRACT: Two-dimensional (2D) organic−inorganic hybrid

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perovskite materials have recently attracted tremendous attention

for use in perovskite solar cells (PSCs) by virtue of their
considerable long-term stability. However, the primary stumbling
block for their application in PSC is their relatively lower power
conversion efficiency (PCE) compared with the conventional 3D
perovskite. In this work, through a binary solvent engineering of
dimethylformamide (DMF)/dimethyl sulfoxide (DMSO) in the
precursor solution, high-performance 2D perovskite planar solar cells
are fabricated with beyond 10% PCE and outstanding environmental
stability. In the formation of the 2D perovskite film during the hot-
coating process, heterogeneous nucleation primarily occurs at the
air−liquid interface, contributing to the formation of the thin, flaky
cap layer on the outmost surface of the film. Sequentially, for the
unary solvent DMF, its fast volatilization facilitates homogeneous nucleation, resulting in random-orientated perovskite grains in
the inner layer. In contrast, with the binary solvent engineering of DMF/DMSO, the formation of intermediate can slow the
crystallization process, making the perovskite cap layer serve as the seed that impels the subsequent perovskite crystallization to
be vertically orientated in the inner layer of the perovskite film. These findings provide not only a new understanding of the 2D
perovskite crystallization process but also a simple and effective method to fabricate high-performance 2D perovskite-based
photovoltaics.
KEYWORDS: Two-dimensional perovskite, Perovskite solar cells, Solvent engineering, Slow crystallization

■ INTRODUCTION
Organic−inorganic metal halide perovskite materials have been
a superstar in photovoltatics in the past few years because of
their excellent photoelectric conversion properties as well as low
fabrication cost.1−5 In particular, perovskite solar cells (PSCs)
based on the three-dimensional (3D) perovskite CH3NH3PbI3
(MAPbI3) have achieved remarkable power conversion
efficiencies (PCEs) of up to 22% due to its merits of high
absorption coefficient, appropriate band gap, small exciton
binding energy, and superior charge mobility.6−10 However, the
primary stumbling block for the realistic implementation of the
3D perovskite-based PSCs is their poor long-term environ-
mental stability.11−13 The 3D perovskite materials are extremely
sensitive to moisture and temperature, owning to their low
formation energy and hydrophilic nature; therefore, the organic
frameworks of 3D perovskite are easy to destroy in the ambient
environment.14−16 Many strategies have been employed to
improve the stability of 3D perovskite, including enlarging the
size of the perovskite grains to reduce the grain boundaries,17
modifying the perovskite surface with hydrophobic organics,18
and decreasing the perovskite dimensionality.19 Among these
strategies, utilizing 2D layered Ruddlesden−Popper perovskite
to replace the traditional 3D perovskite is the most effective one
and has become a hotspot in the PSC research area.
2D perovskite materials are obtained normally by incorporat-
ing bulky organic molecules such as phenylethylammonium
(PEA) and C4H9NH3 (BA) into the 3D perovskite MAPbI3,
where the bulky organic molecules can be inserted into Pb−I
octahedron repeat unit to form the ultimate 2D perovskite
materials with the general formula of (PEA)2(MA)n−1PbnI3n+1
and (BA)2(MA)n−1PbnI3n+1, respectively.20,21 The 2D perovskite
materials exhibit superior environmental stability, mainly due to
the capping organic cations (BA+ and PEA+), which form
stronger van der Waals interactions with the {PbI6} units; thus,
more external energy is demanded to destroy the 2D perovskite
cell structure.22 Moreover, organic cations with longer alkyl
chains possess a stronger hydrophobic property, which is
advantageous to moisture stability. Nevertheless, the PSCs
based on 2D perovskite exhibit relatively low PCE, mainly due to
the low absorption coefficient, large exciton binding energy, and
Received: November 5, 2018
Revised: December 21, 2018
Published: January 8, 2019

© 2019 American Chemical Society 3487 DOI: 10.1021/acssuschemeng.8b05734

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Figure 1. Top view (a, c, e, g, i) and cross sectional (b, d, f, h, j) SEM images for the 2D perovskite films obtained from different ratios of DMF and
DMSO.
poor charge transport.23,24 To overcome these obstacles of the
practical application for 2D perovskite materials in PSCs, many
efforts have been made, such as regulating the microstructure,25
controlling the crystallization process,26 and altering the phase
orientation.27 The hot-coating method has succeeded in
controlling the orientation of 2D perovskite,28 where relatively
high photovoltaic performance and efficient charge extraction
can be acquired by adjusting the 2D perovskite orientation
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perpendicular to the substrates. However, the corresponding
crystallization process by this means is not well understood yet,
and the quality of the 2D perovskite film still needs further
improvement.
Herein, we combine the hot-coating method with binary
solvent engineering and successfully synthesize high-perform-
ance 2D (BA)2(MA)3Pb4I13 perovskite based PSCs. The 2D
perovskite film can be optimized by the binary solvent
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Figure 2. (a) Schematic of the horizontal and vertical orientations relative to FTO substrate. (b) Illustration of the crystallization process without
DMSO addition (case 1) and with DMSO addition (case 2) to DMF solvent.
engineering of dimethylformamide (DMF) and dimethyl
sulfoxide (DMSO). A two-step crystallization process of the
2D perovskite is proposed: The first step is the heterogeneous
nucleation at the air−liquid interface, contributing to the thin,
flaky cap layer on the surface. The second step for the unary
DMF and binary solvent DMF/DMSO is diverse. Homoge-
neous nucleation occurs in the unary DMF solvent due to the
fast volatilization of DMF, which leads to random-orientated
perovskite grains in the inner layer of perovskite films. However,
by the binary solvent engineering of DMF/DMSO, the
formation of intermediate CH3CH2 BAI/MAI/PbI2/DMSO
can delay the crystallization process to impel the vertical growth
of subsequent crystallization in the inner layer of perovskite
films. Through the binary solvent engineering, the 2D PSCs
achieve an average PCE of 10.3% (a champion PCE of 11.8%)
with an open-circuit voltage (Voc) of 0.97 V, short-circuit current
density (Jsc) of 18.21 mA cm−2, and fill factor (FF) of 58.2% with
good environmental stability. Our work not only successfully
fabricates high-performance PSCs with high-quality 2D perov-
skite but also provides a new understanding of 2D perovskite
crystallization with binary solvent engineering.
■ RESULTS AND DISCUSSION
The preparation of the 2D (BA)2(MA)3Pb4I13 perovskite film
combines the hot-coating method and binary solvent engineer-
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ing. The perovskite precursors are prepared by dissolving PbI2,
CH3NH3I (MAI), and CH2CH2NH3I (BAI) (4:3:2 molar ratio)
in the binary solvent DMF/DMSO. The perovskite films derived
from 1:0, 3:1, 1:1, 1:3, and 0:1 (volume ratio) of DMF and
DMSO are marked as FO10, FO31, FO11, FO13, and FO01,
respectively. Figure 1 exhibits the obtained morphologies of
(BA)2(MA)3Pb4I13 films. Without DMSO addition, the unary
solvent DMF leads to many cracks and subsidence holes on the
surface of the film (Figure 1a). When 3:1 DMF:DMSO is used as
the precursor solvent, flaky 2D perovskite grains begin appearing
on the surface of the 2D perovskite film (Figure 1c). Cracks and
pinholes gradually decrease with increasing DMSO ratio in the
binary solvent, as shown in parts c, e, g, and i of Figure 1 for
FO31, FO11, FO13, and FO01, respectively. Fewer cracks and
pinholes reduce the recombination centers for the photo-
generated electron−hole pairs, which is helpful for the charge
transport between the 2D perovskite film and the hole-transport
layer. Furthermore, a thinner 2D perovskite layer can be
obtained by increasing the DMSO ratio in the binary solvent. It
has been reported that the most appropriate thickness of a 2D
perovskite layer for PSCs is ∼ 700 nm.29 In our case, FO10 has a
thickness of 860 nm, which is too thick for the charge extraction,
while FO01 processes a thickness of 450 nm, which is too thin
for the light harvesting. In contrast, FO31, FO11, and FO13
have the most suitable thicknesses, ranging from 600 to 700 nm,
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Figure 3. (a−e) AFM images of FO10, FO31, FO11, FO13, and FO01. (f) Root mean square deviation (Rq) and (g) arithmetic mean deviation (Ra) of
the 2D perovskite films.
to keep the balance between the charge extraction and light
harvesting. It is also found that tiny random-orientated
perovskite grains are grown on the TiO2/fluorine-doped tin
oxide (FTO) substrate for FO10 (Figure 1b). Once the DMSO
was added in the DMF solvent, 2D perovskite grains tend to
grow in a vertical orientation perpendicular to the FTO
substrate, and the brick structure is more obvious upon
increasing the DMSO ratio (Figure 1d,f,h,j). Significantly, this
phenomenon implies that DMSO influences the crystallization
of the perovskite and turns 2D perovskite growth from random
into vertical. In the 2D perovskite films, the Pb−I octahedral
units are the transport channel for the photogenerated carriers;
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however, the butyl chains between them, which are essential to
form the ultimate 2D structure, become the barriers for the
charge transport. Thus, the orientation of the 2D perovskite with
these butyl chains will strongly affect the charge transport from
perovskite to the FTO substrate. Figure 2a shows the schematic
of the horizontal and vertical orientations of (BA)2(MA)3Pb4I13
perovskite relative to the FTO substrate. When the 2D
perovskite grows horizontally to the FTO, butyl chains hinder
the charge transfer from perovskite to the FTO. However, this
negative effect can be eliminated if the 2D perovskite can grow
vertically to the FTO, which is beneficial for the charge
extraction.24 On the basis of the above observations, we
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Figure 4. (a) FWHM of the {202} plane for all the 2D perovskite films. (b) UV−vis absorption spectra of 2D perovskite films on TiO2/FTO
substrates. Steady-state PL spectra of the BA2MA3Pb4I13 illuminated from (c) the perovskite film side and (d) the FTO-glass side.
proposed a mechanism for the 2D perovskite crystallization
process, which can be catalogued as cases 1 and 2, as shown in
Figure 2b. In both cases, the heterogeneous nucleation first
occurs at the air−liquid interface, which contributes to the
formation of a thin, flaky cap layer on the surface.30 However, for
the next step, the volatilization of the unary DMF solvent in case
1 is extremely fast during the hot-coating process, which leads to
the homogeneous nucleation of perovskite under the flaky cap
layer, resulting in a random orientation of the perovskite crystals
in the inner film. Meanwhile, in case 2, with DMSO addition to
DMF, the binary solvent volatilization process is slowed
significantly during the hot-coating process, leading to the
heterogeneous nucleation. After the substrates are transferred to
the hot plate for further annealing, the subsequent crystallization
is analogous to seed-induced growth, where the surface
perovskite cap layer serves as the seed, impelling the subsequent
2D perovskite crystallization to be vertically orientated.
AFM images in Figure 3 show that the grain of FO10 is
nanosized, indicating that the unary DMF solvent leads to a
rapid and direct crystallization. Once DMSO is added in the
precursor solution, the flaky perovskite grains on the surface
begin appearing on a micron scale (Figure 3b). Figure 3b−e
shows that the 2D perovskite grains become larger and denser
with increasing DMSO in the binary solvent, which is
advantageous to efficient charge transport.31,32 These results
illustrate that DMSO contributes to a slower crystallization,
which explains the prolonged time for color change of the
perovskite films during the hot-coating process from 3 to 15 s.
Moreover, detailed surface information, including root-mean-
square deviation (Rq) and arithmetic mean deviation (Ra), are
shown in Figure 3f,g and Table S1 (Supporting Information, SI),
revealing the roughness of the perovskite film surface. A sharp
increase of Rq and Ra can be observed in FO31 compared with
FO10, which is attributed to the transformation of the
perovskite grain orientation from random to vertical. 3D AFM
images (Figure S2, SI), the line segments (Figure S3a, SI) and
depth distribution (Figure S3b, SI) reveal that the roughness of
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the perovskite films can be tuned by the binary solvent
engineering of DMSO/DMF.33
The X-ray diffraction (XRD) patterns for the 2D perovskite
films are exhibited in Figure S4 (SI). All the 2D perovskite films
show the diffraction peaks at 14.1° and 28.4°, corresponding to
{111} and {202} lattice planes, respectively.28 No other peaks
can be recognized, revealing that the hot-coating method
achieves well-crystallized 2D perovskite films successfully.34
Meanwhile, the full width at half-maximum (FWHM) of the
{202} plane (Figure 4a) sharply narrows down by increasing
DMSO in the solvent, again implying bigger perovskite grains
and fewer grain boundaries, which are beneficial for the charge
extraction.35 Figure 4b exhibits multiple absorptions in the UV−
vis absorption spectra of all the samples, indicating that multiple
perovskite phases with different n values coexist in the 2D
perovskite BA2MAn‑1PbnI3n+1 (although nominally synthesized
as n = 4).36 Among them, FO10 has the strongest absorption in
the 350−700 nm range due to its extra-thick film thickness of
860 nm (Figure 1b). The 2D perovskite films possess slightly
lower light harvesting due to the reduced film thickness (Figure
S5, SI). However, these 2D perovskite films exhibit stronger
absorption in the wavelength range from 700 to 850 nm (Figure
S6, SI), which is attributed to the scattering effect of the enlarged
perovskite grains on the micron scale.37
In addition, parts c and d of Figure 4 display the steady-state
photoluminescence (PL) spectra of the 2D perovskite films
excited from the perovskite film side and FTO-glass side,
respectively. Here, the huge-n and tiny-n phases exhibit stronger
intensity with the laser beam illuminating from the perovskite
film side (Figure 4e) and the FTO-glass side (Figure 4f),
respectively.36 This phenomenon suggests that the huge-n
perovskite phases mainly locate in the top of the perovskite films,
while the tiny-n perovskite phases majorly distribute in the
bottom of the perovskite films. From the PL spectra, the flaky
structure on the 2D perovskite surface has the strong intensity of
the huge-n phase (n = ∞) (Figure 4e), indicating the 3D
perovskite grains on the surface of the perovskite film. In
contrast, the tiny-n phase of 2D perovskite forms the brick
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structure inside the perovskite films (Figure 4f). Meanwhile, the
distribution of the 2D perovskite phases with different n values
also suggests substantially different crystallization kinetics,
where the formation energy for the components with tiny n
are higher than those with huge n.22 Thus, it can be speculated
that the components with huge n are primarily formed with a fast
solvent volatilization at the air−liquid interface and the
components with tiny n are crystallized subsequently under
the surface of perovskite films. Moreover, normally, 2D
perovskite possesses a larger band gap than 3D perovskite,
ascribing to the increased exciton binding energy caused by the
quantum/spatial and dielectric confinement.38 However, in
Figure 4e, compared with FO10, the strongest emission peak of
n = ∞ for the samples derived from binary solvent DMF/DMSO
shows a red shift, suggesting the narrowed band gap of 2D
perovskite in our research, and Figure S7 (SI) again reflects that
the band gap of the perovskite films decreases from 1.64 eV
(FO10) to 1.60 eV (FO13).
Furthermore, Fourier transform infrared spectra (FTIR)
analysis is conducted to explore the influence of the components
in the binary solvent. The test samples are prepared by dissolving
PbI2, MAI, or BAI powders in the mixed solution of DMF and
DMSO and drying in a vacuum oven overnight (the detailed
preparation process can be found in the Supporting
Information). The as-prepared samples are marked as PbI2/
DMSO, MAI/PbI2/DMSO, BAI/PbI2/DMSO, and BAI/MAI/
PbI2/DMSO. The FTIR spectra of DMSO and all the samples
are shown in Figure 5a. As illustrated in Figure 5b and Table S2
Figure 5. (a) FTIR of DMSO, PbI2/DMSO, MAI/PbI2/DMSO, BAI/
PbI2/DMSO, and BAI/MAI/PbI2/DMSO. (b) Amplifying the region
for the SO vibrations. (c) Sketch diagram for the interaction force
between (I) PbI2 and DMSO, (II) PbI2 and MAI, and (III) PbI2 and
BAI.
(SI), the stretching vibration of SO [ν(SO)] of the bare
DMSO solvent is located at 1042 cm−1, which is shifted to lower
frequencies of 985 cm−1 for PbI2/DMSO, 1012 cm−1 for both
MAI/PbI2/DMSO and BAI/MAI/PbI2/DMSO, and 1010 cm−1
for BAI/PbI2/DMSO. As well-known in the harmonic motion
for the diatomic model, the frequency of vibration is
proportional to the square root of the force constant.39
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Therefore, the decreased stretching frequency of SO implies
the decreased force constant, further suggesting the deceased
bond strength between oxygen and sulfur because of the
presence of intermediate products. To be more visual, the
interaction force between the Lewis acid PbI2 and Lewis base
DMSO is illustrated in Figure 5c. The SO stretching
frequency of PbI2/DMSO is lower than that of the bare
DMSO owing to the interaction between the Pb2+ in PbI2 and
the lone pair electrons on oxygen in DMSO. The SO
stretching frequencies of MAI/PbI2/DMSO, BAI/PbI2/DMSO,
and BAI/MAI/PbI2/DMSO decrease because the I− in MAI and
BAI has an interaction with the Pb2+ in PbI2, which can weaken
the interaction between PbI2 and DMSO. It is found that the as-
coated perovskite films derived from the solvent without DMSO
turn brown immediately in the first 3 s. Upon increasing the ratio
of DMSO in the binary solvent, this color change will be visually
delayed to ∼15 s. The direct and fast volatilization of DMF
causes the homogeneous nucleation inside the perovskite film,
resulting in the random orientation of the crystals. In contrast,
the intermediates of PbI2 with BAI, MAI, and DMSO, which can
slow the crystallization process, are primarily formed before the
thorough crystallization of the perovskite, performing an
essential role in the heterogeneous nucleation and further
urging the crystallization process to proceed according to case 2
(Figure 2b). In case 2, the chemical transformation from the
intermediate adduct to the 2D perovskite is analogous to a seed
growth process, contributing to the vertically orientated and
pinhole-free 2D perovskite film.
Figure 6a exhibits the 2D (BA)2(MA)3Pb4I13-based planar
architecture of FTO/c-TiO2/perovskite/spiro-OMeTAD/Au.
The cross sectional image of the planar perovskite solar cell is
exhibited in Figure S8 (SI), and the band alignment in Figure S9
(SI) ensures that the photogenerated carriers flow smoothly
through the whole PSC device. As shown in Figure 6b, the PSCs
of FO01 perovskite have poor performance, mainly due to the
ultrathin perovskite layer that results in inferior light harvesting.
With increasing DMSO addition in the binary solvent from
FO10 to FO13, the IPCE (Figure 6c) and PCE (Figure 6d) of
PSCs are greatly enhanced owing to the improvement of the
short-circuit current density (Jsc) (Figure 6e) and fill factor (FF)
(Figure 6f), which increase from 11.98 mA cm−2 and 48.0%
(FO10) to 18.21 mA cm−2 and 58.2% (FO13), respectively.
Accordingly, the devices of FO13 achieve the highest average
PCE of 10.3% and best PCE of 11.8%. The boost of Jsc can be
attributed to the more obviously oriented growth of the 2D
perovskite perpendicular to the substrate and the smooth and
large perovskite grains with superior crystallization, which have
been discussed previously.
The dark current of PSCs (Figure 7a) is used to elucidate the
leakage current of the devices. It is evident that the dark current
density of PSC decreases with increasing the ratio of DMSO in
the binary solvent, illustrating the significantly suppressed
leakage current.40,41 Moreover, the Nyquist plots in Figure 7b
are measured in dark, and the visible arcs are corresponding to
the charge recombination resistance. The arcs are enlarged upon
increasing the ratio of DMSO in the binary solvent, and the PSC
based on FO13 possesses the largest arc, suggesting the most
efficient charge extraction.42 The suppressed leakage current
and efficient charge extraction can be due to the high-quality 2D
perovskite film with DMSO modulation, as illustrated in SEM
and AFM analysis, presenting fewer flaws and pinholes to reduce
the charge recombination centers.
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Figure 6. (a) Schematic diagram of the device structure. (b) J−V curves, (c) IPCE spectra, and (d−g) corresponding photovoltatic parameters of PSCs
derived from various ratios of DMF and DMSO. Average performance parameters were acquired based on 40 cells for each type under a standard
illumination (100 mW cm−2, AM 1.5).
The humidity tolerance of PSCs was examined under high
humidity (60 ± 5% RH) at room temperature without any
encapsulation. Figure 7c shows the degradation of PCE, which is
summarized in Figure S10 (SI). After 1 month, the PCE of PSC
based on FO10 decreases to 70% of the initial value, but the PCE
of PSC based on FO13 remains above 90% of the initial value,
showing significantly enhanced humidity tolerance via the
binary solvent engineering. Besides, the thermal stability of the
bare perovskite films is further tested by heating the 2D
perovskite/TiO2/FTO substrates at 80 °C in air atmosphere
with a humidity of 60 ± 5%. Figure 7d displays the XRD patterns
of perovskite films after degrading for 15 h. The peak intensity of
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the {111} lattice plane of FO13 remains the strongest,
suggesting its most superior environmental stability.
■ CONCLUSIONS
In summary, high-performance 2D PSCs are obtained by a hot-
coating method with binary solvent engineering. The PSC with
the FO13 2D perovskite possesses the best PCE of 11.8% due to
its significantly enhanced Jsc and FF. With DMSO modulation in
the binary solvent, the 2D (BA)2(MA)3Pb4I13 perovskite films
exhibit vertical orientation growth, superior charge extraction
ability, and excellent environmental stability. The crystallization
process of the 2D perovskite includes two steps. The primary
step is the formation of the flaky cap layer at the air−liquid
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Figure 7. (a) J−V curves and (b) EIS plots recorded under dark condition for PSCs derived from various ratios of DMF and DMSO. (c) The long-term
stability test of PSCs stored in an air atmosphere with a humidity of 60 ± 5%. (d) The degradation analysis of 2D perovskite films at 80 °C in an air
atmosphere with a humidity of 60 ± 5%.
interface. For the unary solvent DMF, the fast volatilization
causes the homogeneous nuclei inside the perovskite film,
leading to the random orientation of the perovskite crystals in
the film. However, the crystallization process in the binary
solvents DMF/DMSO is significantly slowed due to the
formation of the intermediate product BAI/MAI/PbI2/
DMSO. The subsequent crystallization is analogous to seed-
induced growth, where the perovskite cap layer serves as the
seed impelling the subsequent vertical growth of perovskite. Our
work not only succeeds in preparing high-performance 2D
perovskite solar cells but also provides a new understanding of
the 2D perovskite crystallization for photovoltaics.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b05734.
Experimental methods, including materials, synthesis,
solar cell fabrication, and perovskite characterization
(PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*J.Y. e-mail: jiaguoyu@yahoo.com.
*K.F. e-mail: kefan@kth.se.
ORCID
Jiaguo Yu: 0000-0002-0612-8633
Ke Fan: 0000-0003-2269-4042
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by National Natural Science
Foundation of China (51320105001, 21433007, 51772234,
and 21573170), the Natural Science Foundation of Hubei
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Province (2015CFA001), Innovative Research Funds of
SKLWUT (2017-ZD-4), and the Fundamental Research
Funds for the Central Universities (WUT: 2017 IVA 092).
■
REFERENCES
(1) Li, G.; Zhang, T.; Guo, N.; Xu, F.; Qian, X.; Zhao, Y. Ion-
Exchange-Induced 2D-3D Conversion of HMA(1‑x)FA(x)PbI(3)Cl
Perovskite into a High-Quality MA(1‑x)FA(x)PbI(3) Perovskite. Angew.
Chem., Int. Ed. 2016, 55, 13460−13464.
(2) Guo, D.; Yu, J.; Fan, K.; Zou, H.; He, B. Nanosheet-based
printable perovskite solar cells. Sol. Energy Mater. Sol. Cells 2017, 159,
518−525.
(3) Chang, S. H.; Huang, W.-C.; Chen, C.-C.; Chen, S.-H.; Wu, C.-G.
Effects of anti-solvent (iodobenzene) volume on the formation of
CH3NH3PbI3 thin films and their application in photovoltaic cells.
Appl. Surf. Sci. 2018, 445, 24−29.
(4) Cheng, Y.; Xu, X.; Xie, Y.; Li, H.-W.; Qing, J.; Ma, C.; Lee, C.-S.;
So, F.; Tsang, S.-W. 18% high-efficiency air-processed perovskite solar
cells made in a humid atmosphere of 70% RH. Solar RRL 2017, 1,
1700097.
(5) Kirbiyik, C.; Kara, K.; Kara, D. A.; Yigit, M. Z.; Istanbullu, B.; Can,
M.; Sariciftci, N. S.; Scharber, M.; Kus, M. Enhancing the c-TiO2 based
perovskite solar cell performance via modification by a serial of boronic
acid derivative self-assembled monolayers. Appl. Surf. Sci. 2017, 423,
521−527.
(6) Ma, C.; Leng, C.; Ji, Y.; Wei, X.; Sun, K.; Tang, L.; Yang, J.; Luo,
W.; Li, C.; Deng, Y.; Feng, S.; Shen, J.; Lu, S.; Du, C.; Shi, H. 2D/3D
perovskite hybrids as moisture-tolerant and efficient light absorbers for
solar cells. Nanoscale 2016, 8, 18309−18314.
(7) Kim, W.; Jung, M. S.; Lee, S.; Choi, Y. J.; Kim, J. K.; Chai, S. U.;
Kim, W.; Choi, D.-G.; Ahn, H.; Cho, J. H.; Choi, D.; Shin, H.; Kim, D.;
Park, J. H. Oriented grains with preferred low-angle grain boundaries in
halide perovskite films by pressure-induced crystallization. Adv. Energy
Mater. 2018, 8, 1702369.
(8) Zhang, J. J.; Meng, Z.; Guo, D. P.; Zou, H. Y.; Yu, J. G.; Fan, K.
Hole-conductor-free perovskite solar cells prepared with carbon
counter electrode. Appl. Surf. Sci. 2018, 430, 531−538.
(9) Xing, G.; Mathews, N.; Sun, S.; Lim, S.; Lam, Y.; Gratzel, M.;
Mhaisalkar, S.; Sum, T. Long-range balanced electron- and hole-
DOI: 10.1021/acssuschemeng.8b05734
ACS Sustainable Chem. Eng. 2019, 7, 3487−3495
ACS Sustainable Chemistry & Engineering
transport lengths in organic-inorganic CH3NH3PbI3. Science 2013, 342,
344−7.
(10) Feng, B. J.; Duan, J. X.; Tao, L.; Zhang, J.; Wang, H. Enhanced
performance in perovskite solar cells via bromide ion substitution and
ethanol treatment. Appl. Surf. Sci. 2018, 430, 603−612.
(11) Wang, Z.; Lin, Q.; Chmiel, F. P.; Sakai, N.; Herz, L. M.; Snaith, H.
J. Efficient ambient-air-stable solar cells with 2D-3D heterostructured
butylammonium-caesium-formamidinium lead halide perovskites. Nat.
Mater. 2017, 2, 17135.
(12) Bi, E.; Chen, H.; Xie, F.; Wu, Y.; Chen, W.; Su, Y.; Islam, A.;
Gratzel, M.; Yang, X.; Han, L. Diffusion engineering of ions and charge
carriers for stable efficient perovskite solar cells. Nat. Commun. 2017, 8,
15330.
(13) Meng, Z.; Guo, D. P.; Yu, J. G.; Fan, K. Investigation of Al2O3 and
ZrO2 spacer layers for fully printable and hole-conductor-free
mesoscopic perovskite solar cells. Appl. Surf. Sci. 2018, 430, 632−638.
(14) Conings, B.; Drijkoningen, J.; Gauquelin, N.; Babayigit, A.;
D’Haen, J.; D’Olieslaeger, L.; Ethirajan, A.; Verbeeck, J.; Manca, J.;
Mosconi, E.; De Angelis, F.; Boyen, H. G. Intrinsic thermal instability of
methylammonium lead trihalide perovskite. Adv. Energy Mater. 2015, 5,
1500477.
(15) Sun, M. N.; Liu, X. Y.; Zhang, F.; Liu, H. L.; Liu, X. C.; Wang, S.
R.; Xiao, Y.; Li, D. M.; Meng, Q. B.; Li, X. G. Simple dopant-free hole-
transporting materials with p-pi conjugated structure for stable
perovskite solar cells. Appl. Surf. Sci. 2017, 416, 124−132.
(16) Li, X. H.; Zhang, J. J.; Zhu, X. Y.; Yu, J. G.; Fan, K. Effects of Ti
precursors on the performance of planar perovskite solar cells. Appl.
Surf. Sci. 2018, 462, 598−605.
(17) Hadadian, M.; Correa-Baena, J.; Goharshadi, E.; Ummadisingu,
A.; Seo, J.; Luo, J.; Gholipour, S.; Zakeeruddin, S.; Saliba, M.; Abate, A.;
Gratzel, M.; Hagfeldt, A. Enhancing efficiency of perovskite solar cells
via N-doped graphene: crystal modification and surface passivation.
Adv. Mater. 2016, 28, 8681−8686.
(18) Bai, Y.; Xiao, S.; Hu, C.; Zhang, T.; Meng, X.; Lin, H.; Yang, Y.;
Yang, S. Dimensional engineering of a graded 3D-2D halide perovskite
interface enables ultrahigh Voc enhanced stability in the p-i-n
photovoltaics. Adv. Energy Mater. 2017, 7, 1701038.
(19) Hu, Y.; Zhang, Z.; Mei, A.; Jiang, Y.; Hou, X.; Wang, Q.; Du, K.;
Rong, Y.; Zhou, Y.; Xu, G.; Han, H. Improved performance of printable
perovskite solar cells with bifunctional conjugated organic molecule.
Adv. Mater. 2018, 30, 1705786.
(20) Cohen, B.-E.; Wierzbowska, M.; Etgar, L. High efficiency and
high open circuit voltage in quasi 2D perovskite based solar cells. Adv.
Funct. Mater. 2017, 27, 1604733.
(21) Zhang, X.; Munir, R.; Xu, Z.; Liu, Y.; Tsai, H.; Nie, W.; Li, J.; Niu,
T.; Smilgies, D.-M.; Kanatzidis, M. G.; Mohite, A. D.; Zhao, K.;
Amassian, A.; Liu, S. F. Phase transition control for high performance
Ruddlesden-Popper perovskite solar cells. Adv. Mater. 2018, 30,
1707166.
(22) Quan, L. N.; Yuan, M. J.; Comin, R.; Voznyy, O.; Beauregard, E.
M.; Hoogland, S.; Buin, A.; Kirmani, A. R.; Zhao, K.; Amassian, A.; Kim,
D. H.; Sargent, E. H. Ligand-stabilized reduced-dimensionality
perovskites. J. Am. Chem. Soc. 2016, 138, 2649−2655.
(23) Smith, I. C.; Hoke, E. T.; Solis-Ibarra, D.; McGehee, M. D.;
Karunadasa, H. I. A layered hybrid perovskite solar-cell absorber with
enhanced moisture stability. Angew. Chem., Int. Ed. 2014, 53, 11232−
11235.
(24) Cao, D. H.; Stoumpos, C. C.; Farha, O. K.; Hupp, J. T.;
Kanatzidis, M. G. 2D Homologous Perovskites as Light-Absorbing
Materials for Solar Cell Applications. J. Am. Chem. Soc. 2015, 137,
7843−7850.
(25) Safdari, M.; Svensson, P. H.; Hoang, M. T.; Oh, I.; Kloo, L.;
Gardner, J. M. Layered 2D alkyldiammonium lead iodide perovskites:
synthesis, characterization, and use in solar cells. J. Mater. Chem. A
2016, 4, 15638−15646.
(26) Soe, C. M. M.; Stoumpos, C. C.; Kepenekian, M.; Traore, B.;
Tsai, H.; Nie, W.; Wang, B.; Katan, C.; Seshadri, R.; Mohite, A. D.;
Even, J.; Marks, T. J.; Kanatzidis, M. G. New type of 2D perovskites with
alternating cations in the interlayer space, (C(NH 2 ) 3 )-
3495
Research Article
(CH3NH3)nPbnI3n+1: Structure, properties, and photovoltaic perform-
ance. J. Am. Chem. Soc. 2017, 139, 16297−16309.
(27) Zhang, X. Q.; Wu, G.; Yang, S. D.; Fu, W. F.; Zhang, Z. Q.; Chen,
C.; Liu, W. Q.; Yan, J. L.; Yang, W. T.; Chen, H. Z. Vertically oriented
2D layered perovskite solar cells with enhanced efficiency and good
stability. Small 2017, 13, 1700611.
(28) Tsai, H. H.; Nie, W. Y.; Blancon, J. C.; Stoumpos, C. C. S.;
Asadpour, R.; Harutyunyan, B.; Neukirch, A. J.; Verduzco, R.; Crochet,
J. J.; Tretiak, S.; Pedesseau, L.; Even, J.; Alam, M. A.; Gupta, G.; Lou, J.;
Ajayan, P. M.; Bedzyk, M. J.; Kanatzidis, M. G.; Mohite, A. D. High-
efficiency two-dimensional Ruddlesden-Popper perovskite solar cells.
Nature 2016, 536, 312−316.
(29) Zhang, X.; Ren, X. D.; Liu, B.; Munir, R.; Zhu, X. J.; Yang, D.; Li,
J. B.; Liu, Y. C.; Smilgies, D. M.; Li, R. P.; Yang, Z.; Niu, T. Q.; Wang, X.
L.; Amassian, A.; Zhao, K.; Liu, S. Z. F. Stable high efficiency two-
dimensional perovskite solar cells via cesium doping. Energy Environ.
Sci. 2017, 10, 2095−2102.
(30) Chen, A. Z.; Shiu, M.; Ma, J. H.; Alpert, M. R.; Zhang, D.; Foley,
B. J.; Smilgies, D. M.; Lee, S.-H.; Choi, J. J. Origin of vertical orientation
in two-dimensional metal halide perovskites and its effect on
photovoltaic performance. Nat. Commun. 2018, 9, 1336.
(31) Kim, H. D.; Ohkita, H.; Benten, H.; Ito, S. Photovoltaic
performance of perovskite solar cells with different grain sizes. Adv.
Mater. 2016, 28, 917−922.
(32) Eperon, G.; Burlakov, V.; Docampo, P.; Goriely, A.; Snaith, H.
Morphological control for high performance, solution-processed planar
heterojunction perovskite solar cells. Adv. Funct. Mater. 2014, 24, 151−
157.
(33) Zhao, Q.; Li, G. R.; Song, J.; Zhao, Y.; Qiang, Y.; Gao, X. P.
Improving the photovoltaic performance of perovskite solar cells with
acetate. Sci. Rep. 2016, 6, 38670.
(34) Soe, C. M. M.; Nie, W. Y.; Stoumpos, C. C.; Tsai, H.; Blancon, J.
C.; Liu, F. Z.; Even, J.; Marks, T. J.; Mohite, A. D.; Kanatzidis, M. G.
Understanding film formation morphology and orientation in high
member 2D Ruddlesden-Popper perovskites for high-efficiency solar
cells. Adv. Energy Mater. 2018, 8, 1700979.
(35) Wei, Y. Q.; Li, L. Q.; Fang, W. H.; Long, R.; Prezhdo, O. V. Weak
donor-acceptor interaction and interface polarization define photo-
excitation dynamics in the MoS2/TiO2 composite: Time-domain Ab
initio simulation. Nano Lett. 2017, 17, 4038−4046.
(36) Zhou, N.; Shen, Y.; Li, L.; Tan, S.; Liu, N.; Zheng, G.; Chen, Q.;
Zhou, H. Exploration of crystallization kinetics in quasi two-
dimensional perovskite and high performance solar cells. J. Am.
Chem. Soc. 2018, 140, 459−465.
(37) Zou, H. Y.; Guo, D. P.; He, B. W.; Yu, J. G.; Fan, K. Enhanced
photocurrent density of HTM-free perovskite solar cells by carbon
quantum dots. Appl. Surf. Sci. 2018, 430, 625−631.
(38) Ishihara, T.; Takahashi, J.; Goto, T. Exciton state in two-
dimensional perovskite semiconductor (C10H21NH3)2PbI4. Solid State
Commun. 1989, 69, 933−936.
(39) Ahn, N.; Son, D.-Y.; Jang, I.-H.; Kang, S. M.; Choi, M.; Park, N.-
G. Highly reproducible perovskite solar cells with average efficiency of
18.3% and best efficiency of 19.7% fabricated via lewis base adduct of
lead(II) iodide. J. Am. Chem. Soc. 2015, 137, 8696−8699.
(40) Xue, Q.; Bai, Y.; Liu, M.; Xia, R.; Hu, Z.; Chen, Z.; Jiang, X.;
Huang, F.; Yang, S.; Matsuo, Y.; Yip, H.; Cao, Y. Dual interfacial
modifications enable high performance semitransparent perovskite
solar cells with large open circuit voltage and fill factor. Adv. Energy
Mater. 2017, 7, 1602333.
(41) Zhang, J.; Tong, T.; Zhang, L.; Li, X.; Zou, H.; Yu, J. Enhanced
performance of planar perovskite solar cell by graphene quantum dot
modification. ACS Sustainable Chem. Eng. 2018, 6, 8631−8640.
(42) Kim, H.; Lee, J.; Yantara, N.; Boix, P.; Kulkarni, S.; Mhaisalkar, S.;
Gratzel, M.; Park, N. High efficiency solid-state sensitized solar cell-
based on submicrometer rutile TiO2 nanorod and CH3NH3PbI3
perovskite sensitizer. Nano Lett. 2013, 13, 2412−2417.
DOI: 10.1021/acssuschemeng.8b05734
ACS Sustainable Chem. Eng. 2019, 7, 3487−3495