Article

pubs.acs.org/cm

From Nano- to Micrometer Scale: The Role of Antisolvent Treatment

on High Performance Perovskite Solar Cells
S. Paek,† P. Schouwink,† E. Nefeli Athanasopoulou,‡ K. T. Cho,† G. Grancini,† Y. Lee,† Y. Zhang,†
F. Stellacci,‡ Mohammad Khaja Nazeeruddin,*,† and P. Gao*,†
†
Group for Molecular Engineering of Functional Materials, EPFL Valais Wallis, Sion, CH-1951 Switzerland
‡
Supramolecular Nano-Materials and Interfaces Laboratory, EPFL, Lausanne, CH 1015 Switzerland
*
S Supporting Information
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ABSTRACT: To date, antisolvent treatment has become one of the most important means to fabricate high efficiency
perovskite solar cells (PSCs); however, the few reported antisolvents have not been analyzed on a uniform platform, and there is
hitherto no clear reasoning in the choice of antisolvents toward high performance PSCs. Here, we study the role of the
antisolvents in the nucleation kinetics of perovskite solutions and their residual influence on perovskite crystal growth, film
formation, and device performance. Through X-ray diffraction analysis on the complicated double mixed perovskite, we
qualitatively evaluate the impact of thermal annealing and antisolvent treatment (A.S.T.) on the phase composition and
microstructure of the films. By using miscible antisolvents with high boiling point instead of immiscible low boiling point
solvents, we obtain homogeneous and almost pinhole-free perovskite films. When using trifluorotoluene (TFT) to replace
toluene and chlorobenzene as a novel antisolvent, we achieve a power conversion efficiency (PCE) of 20.3% under optimized
device fabrication conditions with a composite perovskite as active layer. The conclusions from this study should assist in
establishing reproducible fabrication processes and finding better antisolvent candidates for perovskite solar cells.

1. INTRODUCTION (A.S.T.),10,11 solvent vapor annealing,12,13 and vacuum treat-

It has been calculated that the solar energy harvested by 0.4% of
the world’s surface area would be sufficient to meet the global
energy demands, assuming an average solar energy conversion
efficiency of 15% can be popularized.1 Very recently, the
dominating photovoltaic community based on crystalline,
inorganic semiconductors was agitated by the fast development
of perovskite solar cells (PSCs).2,3 The surge in the perovskite
based photovoltaic technology is evidenced by the abnormally
rapid update of the record efficiencies in three years.4 As a
latecomer, despite the short time spent on the optimization of
the perovskite devices, the huge amount of efforts dedicated by
scientists from all over the world led to rapid improvements in
the device engineering methods. It has been recognized that the
morphology of the perovskite layer is one of the most crucial
parameters that determine the final performance of a PSC
device.5 Among the many different methods introduced to
improve the surface morphology of perovskite film, gas-
blowing,6 amino halide additive,7−9 antisolvent treatment
ment14 have been the most widely used post-treatment
methods. Enlightened by organic photovoltaic (OPV) device
engineering,15 the A.S.T. is at the origin of several reported
world record efficiencies.11,16−20
Normally, the perovskite precursors are dissolved in high
boiling point (BP) polar aprotic solvents such as dimethyl
sulfoxide (DMSO), dimethylformamide (DMF), dimethylace-
tamide (DMAc), N-methyl-2-pyrrolidone (NMP), and γ-
butyrolactone (GBL). Antisolvents assisting perovskite film
formation include a larger scope of solvents that cannot
dissolve any precursor of the perovskite recipe and the
perovskite itself. It is known that the working mechanism of
an antisolvent is to speed up heterogeneous nucleation via the
creation of an instantaneous local supersaturation on the
Received: December 18, 2016
Revised: March 25, 2017
Published: March 26, 2017

© 2017 American Chemical Society 3490 DOI: 10.1021/acs.chemmater.6b05353

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spinning substrate.10 During the treatment of antisolvents,
complicated interactions are happening simultaneously under
the influence of several physicochemical properties of both
solvents (Table S1). Xiao et al. screened 12 different kinds of
solvents for the treatment of spinning methylammonium lead
iodide (MAPbI3) perovskite films.10 However, some of these
solvents can dissolve the ammonium halide salt and destroy the
final perovskite film. Zheng et al. evaluated three different
antisolvents and various interval dropping times on the final
morphology of methylammonium lead bromide (MAPbBr3).21
To date, the most popular antisolvents for perovskite film
formation are toluene (Tol),16 chlorobenzene (CB),18 and
diethyl ether (ether).20 Interestingly, these three solvents have
dramatically different physicochemical properties but still
perform efficiently with different perovskite films. However,
in these reports, no thorough study on the interaction between
different antisolvents as shower solvent and solution solvents as
bath solvent was conducted. More importantly, these popular
antisolvents have not been evaluated on the same type of
perovskite film to make a fair comparison and elucidate the
limitations of each solvent. A complete understanding of these
issues is crucially important for advancing our ability of
controlling perovskite film morphology and improving solar cell
performance.
To shed light on this perspective, in this study, a series of six
antisolvents including trifluorotoluene (TFT), toluene (Tol),
chlorobenzene (CB), p-xylene (Xyl), diethyl ether (ether), and
dichloromethane (DCM) with different dielectric constants (ε,
solvating abilities) and other physicochemical properties are
chosen to treat the spinning composite perovskite films
deposited from a mixed DMSO and DMF solution (1:4)
(Figure 1, Table S1). The kinetics of the treatment process was
Figure 1. Schematic molecular structures and miscibility behavior of
bath solvents (DMSO and DMF) and shower solvents (TFT,
chlorobenzene, toluene, p-xylene, DCM, and ether).
simulated by observing the change in absorbance at 550 nm.
The morphology and composition of the resulting intermediate
and perovskite films were studied by optical microscopy (OM),
scanning electron microscopy (SEM), X-ray diffraction (XRD),
and atomic force microscopy (AFM). Our findings reveal that
the antisolvent has a substantial effect on the perovskite crystal
growth kinetics and film morphology on a micrometer scale
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due to differences in boiling point (BP), miscibility, and
dielectric constants. Antisolvents with both low boiling point
and poor miscibility with solution solvents will lead to lower
efficiency and reproducibility comparing the antisolvents with
higher boiling point and good miscibility with DMF/DMSO.
By using high boiling point and miscible antisolvents under
optimized conditions, we could always obtain compact
perovskite films with full coverage on the substrate providing
decent power conversion efficiencies (PCE) above 18%. When
using TFT to replace Tol and CB as a novel antisolvent, we
achieve a PCE of 20.3% under optimized conditions with
composite perovskite as active layer, measured under one sun
illumination.
2. RESULTS AND DISCUSSION
2.1. Kinetic Study of Solvent−Solvent Interaction
Effect on Perovskite Phase Formation. One of the major
variables during the antisolvent treatment is the interaction
between the solution solvent and the antisolvent. We designed
an experiment to monitor the kinetics of this process by
recording the increase in absorbance at 550 nm as a function of
time, when the freshly spin-coated perovskite intermediate films
from DMSO/DMF (1:4) were treated with the six kinds of
antisolvents (Figure 2a−f).22 Depending on the mutual
miscibility and dielectric constants, the six antisolvents
exhibited dramatically different kinetic behavior in terms of
the increment and the time constant in the relative absorbance
change. The kinetic traces can be fitted with mono-, bi-, and
triexponential functions, and the corresponding time constants
can be deduced (Table S2). Generally, the data shows a steep
rise of the absorbance upon the addition of the antisolvents
(1−42 s), which is indicative of an accelerated heterogeneous
nucleation and growth process to different extents accompany-
ing the fast solvent (mobile) extraction. This fast component
(τ1) is followed by an approximate plateau that indicates the
completion of nucleation and local crystal growth, when the
solvent extraction reaches a state of equilibrium. The small
additional increase that occurs on a slow component of about
50−1000 s (τ2 and/or τ3) contributes only little to the total
change in absorbance and is attributed to the slow diffusion of
remaining solution solvents (complexed) out of the film and
slow growth of large crystals leading to enhanced light-
scattering. Figure 2b,c,f shows that the fast increase of
perovskite absorption at 550 nm is practically complete within
a few seconds (<15 s) with the DMSO/DMF miscible solvents
TFT, Tol, CB, and DCM. The fast increase in absorbance
(optical density) indicates the rapid formation of perovskite
crystals. On the other hand, for the DMSO/DMF immiscible
solvents (xylene and ether), the fast components are slower
(30−40 s) and the absorbance at the plateau stage is much
lower. Xylene showed the lowest absorbance due to the fact
that it is immiscible with all of the solution solvents. This
behavior is reasonable, as the interaction, and therefore the
exchange rate between the solution solvents and antisolvents, is
much weaker or slower when they are immiscible.
The perovskite films are annealed at 100 °C after the kinetic
absorbance study and before UV−vis absorption and photo-
luminescence (PL) are measured. The latter two are shown in
Figure 2g. The relative absorbance at 550 nm of the films
before and after thermal annealing is extracted and plotted in
Figure 2h. The time nodes for absorbance in the dynamic traces
are chosen according to the optimized device procedure (vide
infra). It is interesting to see that, although the absorbance
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Figure 2. Kinetic traces at 550 nm showing the change in absorbance during the treatment of antisolvents (a) TFT, (b) toluene, (c) chlorobenzene,
(d) xylene, (e) ether, and (f) DCM as a function of time. (Orange spots indicate the absorbance at the time node before thermal annealing and after
A.S.T. in the real device fabrication step, the delay time, vide infra. The x-axis is shown as logarithmic scale.) (g) Steady-state absorption spectra of
perovskite film prepared under different antisolvents treatment after annealing (absorbance at 550 nm is highlighted as the brown spots). (h) Bar
chart showing the change in absorbance at 550 nm before and after annealing.

Figure 3. Schematic processing scheme for perovskite films with and without antisolvent treatment (A.S.T.). (a) The speed-time profile for the spin
coating process with and without the various A.S.T. Optical micrographs (OM) illustrating oriented growth of needle shaped crystals with distinct
size variation before thermal annealing as a function of various antisolvents (b−g) and without A.S.T. (h). Scale bar, 300 μm.

recorded before annealing is fluctuating among different
antisolvent treatments, the absorbance reached almost the
same level after thermal annealing, except in the case of ether;
this exception owed to a poor film morphology (vide infra).
Also, there is no prominent change in the position of PL
spectra.
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2.2. Perovskite Film Formation with Antisolvent
Treatment. The effects of different antisolvent treatment are
characterized in making device scale thin layers. Figure 3 shows
a schematic representation of the device fabrication processes
involving different kinds of antisolvent treatment. DMF and
DMSO as cosolvents (4:1) containing 1.15 M PbI2, 1.10 M
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Figure 4. XRD patterns of perovskite films treated with different antisolvents and without antisolvent (w/o A.S.) treatment before (a) and after (b)
thermal annealing at 100 °C for 90 min. In (d), the fwhm of Bragg peaks (before annealing) representing two different directions (c) is shown, as
well as the ratio of integral intensities. The peak widths of samples after annealing and their integral intensities are given in (e) and (f). *, δ, #, ●, and
(hkl) denote diffraction peaks corresponding to the MAI-FAI-PbI2-PbBr2-DMSO (Pb3I(Br)8 polymorphs) and nonperovskite phases of FAPbI3,
PbI2, FTO, and perovskite, respectively.

FAI, 0.2 M PbBr2, and 0.2 M MABr are prepared. After
initializing a high-speed spin-coating step at 6000 rpm,
antisolvents were drop-casted on the spinning film in one
shot with different, optimized delay time to reach the highest
PCE (Figure 3a). The total spin span (Tspin) at 6000 rpm is 30
s for processes with and without A.S.T. and can be divided into
two stages as spreading time (Tspread) and antisolvent treating
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time (Ttreat). After the entire process, all the antisolvent treated
films showed orange color while the film without A.S.T was
yellow. Before thermal annealing, the films exhibited dramat-
ically different textures as seen by optical microscopy (Figure
3b−g). Low boiling point (<50 °C) antisolvent (ether and
DCM) treatment leads to a nonuniform central area in the film
(Figure S1). This could be due to the fact that there is no
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thermal contact between the vacuum holder of the spin-coater
and the substrate and the evaporative cooling leds to quicker
evaporation in the central region of the substrate (particularly
with low bp solvents). After treatment by miscible antisolvents
(TFT, toluene, chlorobenzene, and DCM), needle shaped
crystals grew in the form of a radial pattern or starburst with
TFT and DCM having the highest needle density. The lengths
of the needles were in the range of 200 to 500 μm (Figure 3b−
d,g). On the other hand, the films treated with immiscible
solvents (p-xylene and ether) showed much shorter (∼40 nm)
needle crystals (Figure 3e,f). The needle crystals after p-xylene
treatment are more homogeneously distributed and denser than
those from ether treatment. This phenomenon indicates that
nucleation kinetics is dominating compared to crystal growth.
The differences in crystal size after the treatments by two
distinct kinds (miscible and immiscible) of solvent are in
agreement with the absorbance maxima observed in the kinetic
study, as the crystal growth speed is much slower with the latter
(Figure 2). Just after spin-coating, the composite perovskite
film without any A.S.T. treatment showed a wet surface covered
with sparsely distributed short yellow needle-like and cubic
dark crystals on top indicating a very deficient and
inhomogeneous heterogeneous nucleation kinetic10 (Figure
3h).
2.3. X-ray Diffraction Study. The impact of thermal
annealing and A.S.T. on the phase composition and micro-
structure of the films was investigated by powder X-ray
diffraction (XRD). Figure 4 shows wide angle XRD patterns of
the composite perovskite film deposited on top of TiO2-coated
FTO glass substrates by means of different antisolvents before
(a) and after (b) thermal annealing. During thermal treatment,
solvent molecules are driven out of the precursors in order to
form the final perovskite film. It is seen that, upon thermal
annealing for 1.5 h at 100 °C, transformation from the
precursors to the perovskite phase is nearly complete in all
cases. Minor impurities arising from the diffraction of the
photoinactive δ-phase of FAPbI3 and PbI2 can be found at 11.6°
and 12.7°, respectively. These impurities are inherent to the
vast majority of reported FA based perovskites assembled in
such films, evidencing difficulties of complete conversion into
the photoactive phase of the perovskite. The literature on the
respective end members of the 4-component phase diagram,
FA, MA, I, and Br, is also ambiguous. Single crystal studies on
the room temperature phase α-FAPbI3 have reported it as
trigonal in space group P3m1,23,24 volume per formula unit (V/
f.u.) = 256.3 Å3. Neutron powder diffraction studies have
established a cubic Pm-3m phase with a V/f.u. of 257.5 Å3.25
Cubic Pm-3m FAPbBr3 has a much lower V/f.u. at 214.8 Å3,26
and tetragonal I4/mcm MAPbI3 has been reported at 243 Å3, at
298 K;27 very recently, the space group I4/mcm has been
corrected to a subgroup, I422.28 Moreover, the substitution FA
by MA or vice versa follow’s Vegard’s law,29 meaning that
presently a simultaneous substitution on both the A-cation and
anion site are compatible with the volume reported herein,
since a pure A-site substitution FA by MA of 15% of the organic
molecule would, according to Vegard, result in a unit cell
volume of approximately 255 Å3 (Table S3).
We have herein attempted to solve and refine the specific
perovskite structure based on our powder diffraction data but
without success. The inherent problems of preferred
orientation on deposited thin films, significant structural
disorder, low intensity laboratory data, and the coexistence of
very strong scatterers (Pb, Br, and I) next to very weak ones
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(H, C, and N) render this impossible at this time. Though an
unambiguous quantitative investigation of the microstructure is
not possible without accurate intensities, some qualitative
observations do allow us to conclude on different aspects.
Therefore, the following discussion attempts to describe results
in a rather qualitative way.
Given the lack of an accurate structural model (and space
group symmetry), a general evaluation of these diffractions was
made based on the reduced cubic lattice parameter from the
annealed samples by Le Bail fits, using Topas 5.30 These fits
were performed in cubic, tetragonal, and trigonal (rhombohe-
dral) space groups but yielded insignificantly different R values
and were thus inconclusive regarding the space group
symmetry and associated metric. The determined volume per
formula unit of perovskite under study is, nevertheless, a
reliable quantity and amounts to 249.9 Å3 at 298 K, the
deviation from this value is within e.s.d.’s for all A.S.T. samples
after annealing. This value is perfectly compatible with a slight
change of unit cell dimensions compared to the respective end
members and in agreement with 241 Å3 at 170 K reported
recently for the single crystal of (FAPbI3)0.85(MAPbBr3)0.1531
(Table S3). Supported by the lack of occurring superstructure
reflections, this evidences that the identical discrete chemical
composition is formed regardless of which solvent is applied.
Importantly, this also proves that the variation in photovoltaic
quantities arises entirely due to the interaction with the solvent,
not from the chemical composition.
From the XRD patterns before and after annealing (Figure
4a,b), we observe signals at approximately 14.1, 20.0, and 24.5°
(2θ, Cu radiation). Though they relate to different lattice
planes in different symmetries, they correspond to orientations
of the perovskite octahedral framework along octahedral
corners (14.1°), octahedral edges (20.0°), and octahedral
faces (24.5°), respectively, regardless of the precise structure or
tilt pattern of the octahedral framework (Figure 4c). Since the
unit cell parameters are identical for all materials, we do not
expect the integrated intensities to change due to changes in
the crystal chemistry. Therefore, intensity changes should arise
due to different orientations of the crystallites on the substrate.
In Figure 4a, with the exception of the strong diffractions
from the FTO substrate, the remaining Bragg signals can be
assigned to a highly crystalline intermediate phase formed by
MABr-FAI-PbI2-PbBr2-DMSO.11 A similar intermediate phase
was recently solved as a Pb3I(Br)8 polymorph with two cations
and intercalated DMSO molecules32,33 (Figure S3). For the
films without A.S.T., the prominent peak at 9.2° is the
characteristic diffraction from the intercalated Pb3I(Br)8
polymorph marked by asterisk in Figure 4a, whose phase
yield decreases after treatments with immiscible antisolvents (p-
xylene and ether) and almost disappears if the antisolvent is
miscible with DMSO/DMF (TFT, toluene, chlorobenzene, and
DCM).
Figure 4d summarizes the line widths at fwhm (full width at
half-maximum) and peak intensities resulting from profile fits
on data collected before thermal annealing. Two immediate
observations are striking. While the peak width of signals
representing the lattice direction along octahedral edges is
approximately constant throughout all samples, both films
treated with the immiscible antisolvents xylene and ether show
pronounced broadening for the diffractions that relate to
corners, suggesting a smaller domain length in this direction,
which is in good agreement with OM images in Figure 3.
Second, the intensity ratio between edge- and corner-related
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reflections is significantly lower for TFT and toluene treated During thermal annealing, the solvent molecules are driven
samples compared to the rest (the intensity of the 14° out of the films, while the perovskite phase proceeds its growth.
reflection of the w/o A.S. data set was not sufficient to be As shown in Figure 4b, after thermal annealing at 100 °C for 90
fitted). This alludes to grains becoming attached on the min, all the intermediate phases have converted to the typical
substrate preferentially along the octahedral edges rather than composite perovskite regardless of the A.S.T. XRD data
corners, upon A.S. treatment with TFT and toluene, and before collected from the films after thermal annealing show similar
thermal annealing. Interestingly, these are the two solvents crystallinity of A.S. treated samples with respect to the
performing best in photovoltaic measurements (Table 1). untreated one as suggested by the line widths at fwhm (Figure
4e). Though diffraction line broadening is less easily discussed
Table 1. Summary of Photovoltaic Parameters Derived from without accurate crystal structures, we can conclude, again
J−V Measurements of Composite Perovskite Based based on the prerequisite of identical chemical compositions,
Champion Devices that the antisolvent treatment does have an impact on the
coherent domain size responsible for Bragg diffraction. First, it
VOC JSC series resistance
antisolvent (V) (mA cm−2) FF η (%)a (Rs) (Ω/cm2) can be seen that, independent of the antisolvent, the crystal
w/o A.S.T. 0.98 19.6 0.74 14.4 95.8
growth direction along octahedral edges (20.0°, 2θ) produces a
trifluorotoluene 1.10 23.3 0.79 20.3 40.4
larger domain length. We note that no reported photovoltaic
toluene 1.10 23.3 0.77 19.7 46.0 perovskite phase can be found, where the 14.1° Bragg signal is
chlorobenzene 1.09 23.0 0.75 18.8 68.0 composed of a doublet and where the signals at 20.0° and 24.5°
p-xylene 1.08 21.9 0.75 17.8 52.0 are both singlets, which allows us to eliminate systematic errors
ether 1.05 22.0 0.76 17.6 47.1 due to neglected peak convolutions. In space group symmetries
a
Performance of organic−inorganic cells was measured with 0.16 cm2
I4/mcm and P3m1, the 14.1° signal is in fact composed of a
working area. doublet (110, 002, and 011 and −111, respectively). However,
only in the case of P3m1, the 20.0° Bragg signal is a single peak,
but the 001 and −111 reflections have an intensity ratio of 5/

Figure 5. Typical AFM images of perovskite films in an area of 10 × 10 μm. The films were deposited on a FTO/c-TiO2/meso-TiO2 substrate
treated with five different antisolvents, TFT (a), toluene (b), chlorobenzene (c), xylene (d), ether (e), and a film without treatment (f). Line
segments from each scan (marked with redline) (g) and the statistics of RMS from five different areas of each film (h) (Table S4).

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95; they are hence approximately a singlet in observed
experimental data. A further peak located around 31.8° (2θ)
was inspected regarding its fwhm, corresponding to a
crystallographic direction which is tilted by 15° with respect
to the octahedral edges. Indeed, the width of this signal comes
to lie at similar values as that corresponding to edges.
The intensity variations from the films after thermal
annealing are shown in Figure 4f. The lack of real systematics
in relative intensities between peaks manifests that the influence
of antisolvent on the orientations of the crystallites can be
eliminated by thermal annealing. However, a further general
qualitative observation on the peak shapes suggests a decrease
in domain size upon thermal annealing (Figure 4d,e),
manifested in the slightly broader edge-related and significantly
broader corner-related Bragg peaks post-annealing. These
changes most likely arise from solid−solvent interaction and
potential domain cracking due to solvent diffusion processes
and exchange reactions, which take place during the thermally
induced crystal growth. As stated throughout this discussion,
we do not attempt to quantify genuine potentially anisotropic
size effects, since they can currently not be separated from
stress and strain related broadening, inhibiting more
sophisticated analysis. Since anisotropic growth has been
reported before, we do assume that size effects dominate the
line broadening.
2.4. Atomic Force Microscopy Study of Film Top-
ography. Due to the unstable nature of the intermediate
phase, it is difficult to study further the topography of the films
on a nanometer scale just after A.S.T. and before annealing
without destroying the sample. We show SEM images of the
respective annealed perovskite films with different A.S.T. in
Figure S2. DCM showed poor texture and low reproducibility
of alike films, owed to the low boiling point and high density, so
in this work, no further optimization of the processing
conditions was carried out. It is worth noting that, after
thermal annealing, all the films treated with high boiling point
antisolvents formed perovskite films with a similar grain density
and coverage on a nanometer scale, as can be seen from Figure
S2a−d. However, the films treated by ether or without A.S.T.
are full of pin-holes (Figure S2e,f). This emphasizes again the
necessity and applicability of A.S.T. for the film formation of
composite perovskite. We further characterized the films after
different A.S.T. by atomic force microscopy (AFM) (Figure 5).
We calculated the root mean-squared (RMS) roughness of the
perovskite films treated with TFT (a), toluene (b),
chlorobenzene (c), p-xylene (d), ether (e), and a film without
treatment (f) to be 45.1 ± 4.3, 39.9 ± 2.8, 40.2 ± 1.5, 35.9 ±
1.9, 85.5 ± 15.5, and 105.4 ± 40.5 nm, respectively, based on
five different areas of 10 × 10 μm from each film. The
roughness of films treated with high boiling point solvents
(TFT, toluene, chlorobenzene, and p-xylene) is greatly reduced
compared to the film treated with a low boiling point solvent
(ether) or without A.S.T., as is evident from both, AFM line
segments (Figure 5g) and RMS statistics (Figure 5h). It is
noteworthy that, due to the existence of pinholes, both the
ether-treated and untreated films showed a large surface
inhomogeneity. In addition, the RMS statistics representative
of five different areas of each film exhibit a narrower
distribution in the films treated by high boiling point solvents,
regardless of the miscibility.
2.5. Photovoltaic Property Evaluation of Different
Antisolvent Treatments. Perovskite solar cells were
fabricated using the perovskite films prepared from the different
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A.S.T. The results for the optimized devices are summarized in
Figure 6a. The cross section of the devices was verified by SEM
Figure 6. Current (J)−voltage (V) curves of the optimized cells (a).
Statistical deviation of the PCEs for 25 different solar cells (b) from
different antisolvents treatment under AM 1.5 conditions (100 mW/
cm2).
and is shown in Figure S4. All the photovoltaic devices have a
structure of FTO/compact TiO2/meso-porous TiO2/perov-
skite/Spiro-OMeTAD/Au (80 nm) as shown in Figure S5.
Device fabrication and measurement details are given in the
Supporting Information. The cross-section determined by SEM
shows that all films treated with miscible solvents (TFT,
toluene, and chlorobenzene) exhibit a similar capping perov-
skite thickness around 485 nm. This capping layer thickness is
increased to 510, 495, and 567 nm upon treatment with the
immiscible xylene, ether, or without A.S.T. The photocurrent
J−V curves of the best devices of a respective A.S.T. as well as
of the untreated device are shown in Figure 6a, with the
corresponding metrics reported in Table 1. Optimized PCEs
were obtained with different delay times after antisolvent
dripping: 20 s (trifluorotoluene, 110 μL), 15 s (chlorobenzene,
100 μL), 15 s (toluene, 600 μL), 15 s (xylene, 900 μL), and 10
s (diethyl ether, 200 μL), respectively, before the end of the
procedure. As shown in Table 1, the champion PCEs under
optimized conditions for perovskites with TFT, toluene,
chlorobenzene, p-xylene, ether, and without treatment are
20.3%, 19.7%, 18.8%, 17.8%, 17.6%, and 14.4%, respectively. It
is noteworthy that the VOC of solar cells after antisolvent
treatment are generally higher than that of the reference cell.
This can be understood by the AFM images in Figure 5 and
SEM images in Figure S2. We can see that the number of holes
is significantly higher without antisolvent treatment, which will
increase the contact between the hole transporting materials
with TiO2 and enhance charge recombination inside the device.
Figure 6b demonstrates the statistical distribution of power
conversion efficiency (PCE) for 25 different cells with different
A.S.T., indicating an outstanding reproducibility for each
respective antisolvent condition. The PCEs we achieved with
toluene and chlorobenzene are on par with the reported values
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Chemistry of Materials
in the literature with similar device structure and perovskite
composition.16,18,19,34 TFT, xylene, and ether are used as
antisolvents for the first time herein to treat composite
perovskite films. Among them, TFT has the highest ε and
gave the highest PCE of 20.3%, outperforming toluene and
chlorobenzene. Although p-xylene and ether have ε values
comparable to other solvents, their immiscibility with DMSO
and/or DMF leads to different nucleation and growth
behaviors. However, the PCEs from the devices treated by
the two immiscible solvents gave reasonably good PCEs of
17.8% and 17.6%, respectively. Importantly, all devices with
A.S.T. gave PCEs superior to those of nontreated devices
(14.4%). The difference can be reflected in the contact quality
with Spiro-OMeTAD, which determines the series resistance
(Rs) of the total device. Devices with TFT treatment exhibited
the lowest Rs, while the devices without A.S.T. showed the
highest Rs, which can well explain the difference in FF and JSC,
highlighting the importance of choosing appropriate anti-
solvents in achieving high quality composite perovskite films. A
hysteresis study was performed, and the results are shown in
Figure S7. No significant hysteresis was observed from the
devices involving all the selected antisolvent, indicating trivial
influence of solvent types.
Through this work, we have unraveled the kinetic procession
of the solvent−solvent interaction during perovskite thin film
formation and thermodynamically induced crystal domain
transition and, in addition, presented a new effective antisolvent
to treat the perovskite film resulting in devices with PCEs above
20%. The critical parameters that determine the choice of
antisolvent are the boiling point, miscibility, and dielectric
constant. As shown in Figure S5, only miscible solvents with
dielectric constants higher than 5 promoted the formation of
perovskite crystal during bulk solvent−solvent extraction.
3. CONCLUSION
In summary, we have systematically studied the role of
antisolvent treatment during composite perovskite film
crystallization before and after thermal annealing by revealing
the correlations between boiling point, miscibility, dielectric
constant, perovskite grain orientation, microstructure, and
nanostructure. We found that a suitable A.S.T. serves not
only to speed up heterogeneous nucleation in the early stages
of film deposition but also to influence the initial crystal growth,
leading to a pinhole free homogeneous film morphology during
the thermal annealing. By using miscible antisolvents with high
boiling point (TFT, toluene, and chlorobenzene), we balanced
nucleation, film smoothness, and surface coverage, which in
turn led to better device performance. TFT as a new antisolvent
candidate showed promising PCE of 20.3% under optimized
conditions. The study presented here demonstrates the criteria
for selection of a good antisolvent and the possibility of further
increasing the quality of perovskite films by choosing a different
antisolvent, which is crucial for achieving higher efficiency
polycrystalline thin film solar cells.
■
ASSOCIATED CONTENT
* Supporting Information
S (6) Huang, F.; Dkhissi, Y.; Huang, W.; Xiao, M.; Benesperi, I.;
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.6b05353.
General methods, central area of the film, table of solvent
properties, top surface and cross sectional SEM images,
3497
Article
fitted time constant values, calculated XRD data, reduced
cubic unit cell volume per formula unit, cross-sections of
full devices, photo images of precipitation experiments,
RMS statistics, dependence of dielectric constant with
ratio of DMF, and hysteresis study (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: peng.gao@epfl.ch.
*E-mail: mdkhaja.nazeeruddin@epfl.ch.
ORCID
S. Paek: 0000-0002-2671-2909
G. Grancini: 0000-0001-8704-4222
F. Stellacci: 0000-0003-4635-6080
Mohammad Khaja Nazeeruddin: 0000-0001-5955-4786
P. Gao: 0000-0002-4963-2282
Author Contributions
S.P. designed the experiment, fabricated the devices, and made
the corresponding characterization. S.P. and P.G. designed and
performed the kinetic studies. E.N.A. conducted and analyzed
the AFM data. G.G. and K.T.C. carried out the PL and SEM
characterization. P.G. and P.S. analyzed the XRD data. P.G.
wrote the initial draft of the manuscript. M.K.N. directed the
research for this work. All the authors contributed to the
discussion and writing of the final paper.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
S.P. designed the experiment, fabricated the devices, and made
the corresponding characterization. S.P. and P.G. designed and
performed the kinetic studies. E.N.A. and F.S. conducted and
analyzed the AFM data. G.G. and K.T.C. carried out the PL and
SEM characterization. P.G. and P.S. analyzed the XRD data.
Y.L. and Y.Z. helped with the device fabrication. P.G. wrote the
initial draft of the manuscript.M.K.N. directed the research for
this work. All the authors contributed to the discussion and
writing of the final paper.
■
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3498 DOI: 10.1021/acs.chemmater.6b05353

Chem. Mater. 2017, 29, 3490−3498