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Monolayer-like Hybrid Halide Perovskite Films Prepared by

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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Additive Engineering without Antisolvent for Solar Cells
Mengru Wanga+, Bo Lia+, Peter Siffalovicb, Lung-Chien Chenc, Guozhong Caoa, d and Jianjun Tiana*
Searching for a simple method to replace the conventional antisolvent process with the objective of achieving a high-quality
perovskite film is indispensable for the practical manufacture of solar cells. In this work, we explored an antisolvent-free
additive engineering to fabricate compact CH3NH3PbI3 (MAPbI3) perovskite films combining the coordination effect of
methylammonium chloride (MACl) and methylammonium acetate (MAAc). The MACl coordination with organic and metal
halides in the precursor solution has resulted in the perovskite film having a large grain size and a single crystal-like cross-
section profile (monolayer-like). The introduction of MAAc into the precursor solution has reduced the perovskite film

shrinkage after a film deposition, presumably due to an increased nucleation rate. Consequently, we succeeded in
fabricating the high-quality monolayer-like perovskite film with a micro-scale grain size (~2 μm), a smooth surface and an
enhanced crystallinity. The time-resolved photoluminescence (PL) spectra and space-charge limited current (SCLC)
measurements have validated a significantly reduced density of trap states, which has an imminent impact on the perovskite
film quality. As a result, the power conversion efficiency (PCE) of the perovskite solar cells (PSCs) using the mixture additive
rises to 19.64%, which is much large than that of devices using single MACl additive (15.61%). Accordingly, this work would
support a new one-step fabrication method of high-quality perovskite films for the coming generation of PSCs

Introduction polar organic solvent (e.g. N,N-dimethylformamide (DMF)) is

Hybrid lead halide perovskites (e.g., CH3NH3PbX3, X=Cl, Br, I)
possess enormous application prospects due to their excellent
solar performance and cost-effective solution fabrication
process.1-3 Owing to their suitable bandgap, 4, 5 low exciton
binding energy6, long electron-hole diffusion length6, 7 and
outstanding photoluminescence properties8, the solar cells
employing perovskites as an active layer have evolved high
power conversion efficiencies (PCE) starting from 3% to over
20% in only one decade,9, 10 which is comparable to the
performance of crystalline silicon and thin film solar cells.11
Moreover, perovskite solar cells (PSCs) can be combined in
tandem with other solar cells to achieve high PCEs over 25%.12
To accomplish high performance PSCs, the high-quality
perovskite films with a spatially homogenous surface coverage,
large micrometer-size crystals with a suitable crystallographic
texture, and a low defect density are regarded as an
imperative.13-16 The one-step spin-coating procedure is a
common fabrication method of perovskite films, in which the
precursor (a mixture of organic halide and metal halide) in a
a. Institute of Advanced Materials and Technology, University of Science and
Technology Beijing, 100083, Beijing, P.R. China. *Email:
tianjianjun@mater.ustb.edu.cn
b. Institute of Physics, Slovak Academy of Sciences, Bratislava, 84511, Slovakia
c. Department of Electro-optical Engineering, National Taipei University of
Technology, 10608, Taiwan
d. Department of Materials Science and Engineering, University of Washington,
Seattle, WA, 98195-2120, USA
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
+These authors contributed equally to this work.
spin-coated on substrate and transformed into perovskite
crystalline films by means of annealing or vacuum extraction. 17,
18 However, the organic and metal halides have different
solubility in the precursor solution, which could result in an
inhomogeneous crystallization (e.g. branch-like grains) during
the solvent evaporation. The inhomogeneous surface
morphology of branch-like perovskite films, exhibiting a high
roughness and the presence of pinholes (voids in films), is
reflected in a lowered performance of PSCs. 19 To overcome this
issue, the introduction of intermediate phases has been
proposed by using the additive engineering during the
perovskite crystallization process. Either the additives contain a
special functional group that coordinates with Pb 2+ to form the
intermediate phase, resulting in a decreased crystallization rate
of PbI2 or they increase the number of homogenous nucleation
sites and hence improve the surface coverage of the perovskite
film.14, 20 For example, Park and co-workers20 proposed a Lewis
adduct to modulate perovskite morphology by forming the
coordination of MAI-PbI2-DMSO (DMSO: N, N-dimethyl
sulfoxide) due to interactions between a Lewis base DMSO (S=)
and a Lewis acid PbI2 (Pb2+). On the other hand, the sole thermal
annealing or vacuum processing cannot remove the additives
completely, which limits the formation of a pure perovskite
phase due to their strong coordination capacity. Consequently,
the widely adopted antisolvent treatment of perovskite films is
used to assist the removal of additives. In the course of
antisolvent treatment, the upper part of the precursor solution
is rapidly extracted and a dense perovskite film forms on the
top, which prevents a deeper penetration of the antisolvent and

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leads to the formation of shrinkage at the bottom of the
perovskite layer.21 Moreover, the antisolvent is usually dropped
onto the center of the substrate, which leads to a spatially
inhomogeneous nucleation of large perovskite films. This is
detrimental for a large-area solar cell fabrication and a device
reproducibility. In addition, the antisolvent method has an
obvious disadvantage as it generates the volatile organic
compounds, threatening the production environment. As a
result, an alternative simple method, which would replace the
conventional antisolvent treatment employed in fabrication of
high-quality perovskite films, is highly desired. The recently
introduced rapid thermal annealing22, 23 of perovskite films
offers an antisolvent-free method suitable even for the large-
scale PSCs manufacture.
Our previous works15, 24, 25 have already demonstrated that
MACl additive could retard the rate of crystallization to control
the perovskite morphology and enhance the PSCs performance,
meanwhile it can be simply removed by annealing after a one-
step spin coating. The MACl coordination with organic and
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metal halides in the precursor solution results in the nucleation
of large size colloidal clusters and that facilitate the growth of a
perovskite film with an enhanced grain size.15, 26 there are no
boundaries along the cross profile of the perovskite film from
the top to the bottom, thus forming a monolayer-like film. The
monolayer-like perovskite films with large micrometer-sized
grains possessed a lower density of defect traps and a higher
charge mobility, comparable to the single crystal perovskite. 25
However, in absence of any antisolvent method a large number
of pores and pinholes were observed in the monolayer-like
films. It was likely attributed to the low crystallization velocity.
Therefore, the antisolvent usually be adopted to boost the
crystallization velocity.15, 24 According to the discussion above,
however, the antisolvent treatment is not an ideal fabrication
method for a large-scale production.25, 27 We have identified
that the MAAc additive could accelerate the nucleation of
MAPbI3 and thereafter support the formation of spatially
uniform perovskite films due to MAAc is unstable.28-30.
However, the rapid formation of the perovskite intermediate
phases between PbI2 and MAAc leads to a small size of the
perovskite grains (~ 200 nm) and limited crystallinity, which is
not beneficial for the formation of monolayer-like perovskite
films.
In this work, we have developed a novel additive engineering
without antisolvent method to fabricate a compact monolayer-
like perovskite film. The addition of MACl in the precursor
solution results in the nucleation of large size colloidal clusters,
which are an essential prerequisite for the development of the
monolayer-like perovskite film. The MAAc additive has an
effect, equivalent to the antisolvent process, which increases
the crystallization velocity and eliminates the presence of
pinholes and defects in the film. This facile solution-process
based on this particular one-step antisolvent-free method does
not only yield the high-quality perovskite films, but also
immensely improves the fabrication reproducibility. Finally, the
perovskite films with a micro-scale grain size, a smooth surface,
an enhanced crystallinity and a lower trap density were
accomplished. Benefiting from the high quality of perovskite
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films, the photovoltaic devices exhibit an improved PCE
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19.64%, having the following DOI:structure:
10.1039/C8TA04794D glass
substrate/FTO/TiO2/MAPbI3/Spiro-oMeTAD/Ag.
Journal of Materials Chemistry A Accepted Manuscript
Experimental section
Materials Synthesis and Solution Preparation
All the chemicals were purchased, including CH3NH3I (MAI,
99.999%), PbI2 (99.999%), MACl (99.999%), DMF (99.8%) from
the Yingkou You Xuan Trade CO., LTD; and other chemicals were
purchased from Sigma-Aldrich. The compact TiO2 precursor
solution was prepared by diluting titanium diisopropoxide bis
(acetylacetonate) (75 wt% in isopropanol) in ethanol with a
volume ratio of 1:25. Mesoporous TiO2 paste was prepared by
diluting commercial TiO2 nanoparticle paste (Dyesol 36NRT,
Dyesol) in ethanol with a weight ratio of 1:10. The as
synthesized MAI (159 mg) and PbI2 (461 mg) were mixed in
anhydrous N, N-dimethylformamide (DMF) to produce the
standard perovskite precursor solutions, then 33.75 mg of MACl
and different volume ratios of MAAc (in DMF) were added into
pore PVDF syringe filter. The hole-transport layer precursor
solution was a blend of 72.3 mg spiro-MeOTAD, 29 μL 4-tert-
butylpyridine and 17.5 μL Li-TFSI solution (520 mg Li-TFSI in 1
mL acetonitrile) in 1 mL chlorobenzene.
Device fabrication
The etched FTO glasses were cleaned by ultrasonic bath using
deionized water, acetone and ethanol for 15 min, respectively,
and then under UV ozone treatment for 15 min before spray
pyrolysis deposition. A 30 nm compact TiO 2 layer was coated by
spray pyrolysis deposition at 450 °C, followed by annealing for
30 min. Ultrathin mesoporous TiO2 layer was deposition on the
compact TiO2 by spin-coating at 5000 rpm for 30s, then
annealed at 500 °C for 30 min. 40 μL perovskite precursor
solution was spin-coated on the mesoporous TiO2 layer at 4000
rpm for 30 s. Then the wet film was annealed at 100℃ for 50
min on a hotplate. When the substrate was cooled down, 25 μL
spiro-MeOTAD solution was spin-coated on the perovskite film
at 4000 rpm for 30 s. After oxidation 12 h in a desiccator, 50 nm
of Ag electrode was deposited onto the substrate through a
shadow mask by thermal evaporation with the base pressure of
<5×10-5 Pa. The active area of the device is 0.1 cm2
Characterization
Fourier-transform infrared spectroscopy (FTIR) was performed
using a Bruker Vertex 80v spectrometer, and the concentration
of perovskite precursors was 1 M. Scanning electron microscopy
(SEM) measurements were performed using a cold field
emission scanning electron microscope (S4800, Hitachi). Atomic
force microscopy (AFM) images were obtained using a MFP-3D
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Infinity AFM (Asylum Research, Oxford Instruments). The XRD
patterns were measured on X-ray diffractometer (PANalytical,
Netherlands) with a monochromat
λ=1.54056 Å). The absorption spectra were recorded using an
ultraviolet-visible (UV-vis) spectrophotometer (UV-3600,
Shimadzu). The photoluminescence (PL) spectra were
measured using a steady state fluorescence spectrometer
(FLS980, Edinburgh), and the excitation wavelength was 375
nm. The current–voltage characteristics were recorded using a
digital source meter (2400, Keithley Instruments Inc.) under 3 A
grade AM 1.5 G simulated sunlight (100 mW.cm-2) (7-SS1503A,
7 Star Optical Instruments Co., Beijing, China). The incident light
intensity was calibrated with an NREL-calibrated Si solar cell
(Newport, Stratford Inc., 91150V). The external quantum
efficiency (EQE) was measured in the direct current (DC) mode
using a custom measurement system consisting of a 150 W
xenon lamp (7ILX150A, 7 Star Optical Instruments Co., Beijing,
China), a monochromator (7ISW30, 7 Star Optical Instruments
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Co., Beijing, China) and a digital source meter (2400, Kiteley
Instruments Inc.).
Results and discussion
Fig. 1 shows top-view and cross-section scanning electron
microscopy (SEM) micrographs of the perovskite films prepared
by an antisolvent-free process employing a single additive of
MACl (Fig. 1a) and a mixture additive of MACl and MAAc (Fig.
1b). The perovskite grains are up to over one micrometer in size,
which is more than the thickness of the perovskite film. It is
attributed to the effect of MACl in the precursor solution
according to our previous works.15, 24, 25 However, without the
usage of MAAc, there is a large number of pores and pinholes in
the film, which are detrimental for the performance of PSCs.
Fig. 1. Top-view and cross-section SEM images of the perovskite films prepared by the antisolvent-free process using additives: (a) MACl exclusively and (b) the
coordination effect of combined MACl and MAAc.
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Relying on the synergistic effect of MAAc, a continuous pinhole-
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free film with homogeneous perovskite grainsDOI: 10.1039/C8TA04794D
was obtained as
shown in Fig.1b. The perovskite layers prepared by the addition
of MACl additive are free of multi-grain stacks in the cross-
section plane as validated by the SEM images shown in Fig. 1a3
Journal of Materials Chemistry A Accepted Manuscript
and Fig. 1b3. In the view of the transversal charge transport
across the active layer, such a perovskite film can be considered
as a monolithic MAPbI3 film. On the other hand, the large
surface roughness of the perovskite layer fabricated using only
the MACl additive (Fig. 1a3) promotes an increased leakage
current in the final PSCs. In contrast, using the mixture of MAAc
and MACl additives, the resulting perovskite film shows a
uniform and smooth surface. There are no grain boundaries
along the cross-section of the perovskite film (Fig. 1b3) from the
top to the bottom. This suggests an enhanced, low-scatter,
charge carrier transport towards the corresponding electron
and hole transporting layers. The effect of the MAAc content
(from 0 to 5 %) on the perovskite film was also studied as shown
in Fig. S1. When the content of MAAc reaches 4 %, a compact
film forms, free of any pores and pinholes.
The Fourier-transform infrared spectroscopy (FTIR) and the
X-ray diffraction (XRD) were carried out to reveal the formation
of the perovskite films using different additives. The FTIR
spectra shown in Fig. 2a confirm the coordination interaction of
ions and molecules in the precursor solution. In the case of the
standard perovskite precursor, the stretching vibration peak of
the C=O bond appears at 1653 cm-1. With the introduction of a
single additive of MAAc, the vibration peak of C=O bond shifts
from 1653 cm-1 to 1651 cm-1. The addition of a pure MACl
additive shifts the vibration peak of C=O bond from 1653 cm -1
to 1648 cm-1. These results confirm that the affinity of MACl
toward PbI2 is higher than that of MAAc. Our previous work15, 25
demonstrated that MACl induced the formation of the complex
PbI2·MACl·MAI·DMF, which is essential for the preparation of
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monolayer-like perovskite films with a large grain size as shown
in Fig. S1a. Nevertheless, the films prepared using a single MACl
additive displayed the presence of pores and pinholes. The
coordination of MAAc is weaker than that of MACl (see Fig. 2a).
The perovskite films prepared using exclusively the MAAc
additive, exhibit a small grain size (no more than 200 nm) as
shown in Fig. S2. When MAAc is added in the precursor
containing MACl, the vibration peak of C=O bond does not shift
(1648 cm-1). It indicates that the introduction of MAAc cannot
break the coordination of MACl with PbI2. Hence, the use of the
additives MACl and MAAc facilitates the formation of
monolayer-like perovskite films with a desired large grain size
(~1 μm). In addition, we noted that the vibration peak of C=O
bond of DMF molecule shift from 1653 cm-1 to1651 cm-1 after
the introduction of MAAc additive in standard precursor. It
implies that the affinity of MAAc toward PbI2 is higher than that
of DMF and MAI. So the coordination sites of PbI2 may be
occupied by Ac- by partial replacement of the coordinated DMF
and MAI molecules in MAI·PbI2·DMF coordination complexes.
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During the spin coating process, the fast evaporation of
uncoordinated DMF and MAAc in the precursor solution
facilitates the perovskite crystallization as well as the
enhancement of nucleation rate. It can be demonstrated by
Fig.S3. Fig. S3 shows the absorption spectra of the wet
perovskite films prepared using the single additive of MACl and
a mixture of MACl and MAAc additives. There is no obvious
MAPbI3 absorption edge at the wavelength of 780 nm for the
wet film prepared using the single additive of MACl, indicating
that the intermediate phases cannot transfer to MAPbI 3
perovskite. In contrast, the film prepared using the mixture of
additives shows the well-developed MAPbI3 absorption edge,
which means that the intermediate phases have already
transferred to MAPbI3 phase during the spin coating process. It
suggests that the MAAc additive accelerates the phase
transition towards the MAPbI3 perovskite phase and eliminates
the development of pores and pinholes in the film. To further
reveal the effect of mixed additives in the film formation, the
SEM images of the additives induced perovskite film for
different anneal time are shown in Fig. S4. We first compared
the morphology of perovskite intermediate phase films with
additive of MACl and MACl+MAAc after spin coating. In the case
of perovskite film with single additive of MACl, we can clearly
see that there are many voids on the perovskite intermediate
phase films after drying at 60°C for 1 min, as shown in Fig. S4a.
Under the combination effect of MACl and MAAc additives, the
FTO substrate is completely covered by compact perovskite
crystals. It implies that the formation of perovskite crystals are
easy to be induced by MAAc in MACl-based perovskite
precursor. It suggests that MAAc will accelerate the nucleation
of perovskite during the removal of solvent process, which is
consistent with the UV-vis spectra in Fig.S3. We also
investigated the growth of perovskite crystals with additive of
MACl and MACl+MAAc. For the perovskite intermediate phase
film prepared by the mix additives in Fig. S4 (e, f), regular grain
boundaries were formed and tended to growth up to a size of
micro-scale after annealing for 5 min. However, the slower
growth kinetics was observed for the perovskite crystals
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DOI: 10.1039/C8TA04794D
Journal of Materials Chemistry A Accepted Manuscript
Fig. 2. (a) FTIR spectra of solutions with different additives. Standard perovskite
precursor solution contains MAI and PbI2 dissolved in DMF solvent without any additives
(black curve). The red, blue and magenta curves correspond to the MAAc, MACl and
MACl+MAAc additives dissolved in the standard precursor solution, respectively. (b) XRD
patterns of the perovskite films prepared using 0.5 M MACl with the successively
increasing MAAc content ranging from 0 to 5 %.
prepared using single MACl additive. The growth of the crystals
showed the same trend with sample prepared by single MACl
additive only when the annealing time more than 10 min as
shown in Fig.S4 (b, c). These results illustrate that MAAc
accelerates the nucleation and growth of perovskite crystals.
Therefore, our mix additives strategy can release the
coordinated solvent molecules from the formed coordination
complexes in standard perovskite precursor. Then the fast
evaporation of MAAc additive and solvent molecules in turn
results in the favorable environment for the perovskite or
intermediate phase crystallization, which avoid the formation of
voids and shrinkage. And MACl facilitates to form monolayer-
like film during anneal time.
We also investigated the effect of MAAc on the crystallinity
of the perovskite by means of XRD. Fig. 2b shows the XRD
patterns of the perovskite films prepared by employing the
single additive of 0.5 M MACl and a mixture of additives with
the gradually increasing content of MAAc (from 0 to 5 %)
without antisolvent process. There are two main diffraction
peaks located at 14.1° and 28.4°, corresponding to the
reflections from the (110) and (220) lattice planes, respectively.
It indicates a preferential crystallographic orientation of the
perovskite crystal growth.31 In addition, with the increasing
content of MAAc in the precursors, the XRD peaks of perovskite
phase rises remarkably and reaches maximum at the MAAc
content of 4 %. And the full widths at half maximum (FWHM) of
the (110) and (220) planes of the perovskite films prepared by
antisolvent free process using additives of 0.5 M MACl and
different content of MAAc (from 0 to 5%) are shown in Fig. S5.
Comparing the FWHM comprehensively, 4% is the proper
content of MAAc in the precursor containing MACl due to both
the FWHM of (110) and (220) planes of perovskite films are
small. Fig. S6 shows XRD patterns of the perovskite films
prepared by MACl, MAAc and MACl + MAAc additives. The XRD
integral intensity of the perovskite phase, represented by the
major diffraction peaks 110, 220, in the film prepared by the
mixture of MACl and MAAc additives is considerably stronger
than that of the films prepared using single additives. These
results illustrate the indispensable role of the MAAc in the
crystallization of monolayer-like perovskite films under the
synergistic effect of MACl.
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Fig. 3. Schematic illustration of the formation of perovskite film from precursors with
MACl additive and mixed additive of MACl+MAAc. (a)MACl additive; (b) Mix additive of
MACl and MAAc.
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According to our discussion above, we deduced the formation
of perovskite film using mix additive in Fig.3. Fig.3 shows the
schematic illustration of the formation of perovskite film using
single MACl additive and mixed additive of MACl and MAAc. For
the perovskite precursor with MACl additive, the affinity of
MAAc toward PbI2 is higher than that of DMF and MAI (see
Fig.2a), the coordination complex of PbI2·MACl·MAI·DMF was
formed as shown in Fig. 3(a). However, the coordinated DMF
molecules and MACl additive is hard to release during
solidification process, which are unfavorable for the perovskite
nucleation13, 15. For the combination effect of MACl and MAAc
as shown in Fig. 3 (b), the affinity of MAAc toward PbI2 is higher
than that of DMF and MAI, but weaker than that of MACl. So
the coordination sites of PbI2 may be occupied by Ac- by partial
replacement of the coordinated DMF and MAI molecules in
PbI2 · MACl·MAI·DMF coordination complexes. As a result,
during the spin coating process, the fast evaporation of MAAc
in the precursor solution facilitates the perovskite
crystallization as well as the enhancement of nucleation rate to
obtain compact monolayer-like perovskite film.
We further carried out the atomic force microscope (AFM) to
assess the surface roughness of perovskite film. Fig. 4 presents
AFM images of the perovskite films on mesoporous TiO 2
substrates. The film prepared using the single MACl additive has
the RMS (root mean square) roughness of 77.8 nm, which is
much rougher than that of the film prepared using the mixture
of additives (33 nm). The 3D perspective projections of the AFM
images shown in Fig. 4c and Fig. 4d enable a better visualization
of a smaller surface roughness of the perovskite film prepared
using the mixture of additives. The perovskite films casted form
the precursor solution based on the mixture of additives do not
exhibit only a significantly lower roughness but are also free
from pores and pinholes. Fig. S7 presents the photoabsorption
spectra of MAPbI3 perovskite films prepared by the mixture of
additives with constant and varying contents of MACl and
MAAc, respectively. With the increase of MAAc content, the
decreased light scattering in the long wavelength region (above
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DOI: 10.1039/C8TA04794D
Journal of Materials Chemistry A Accepted Manuscript
Fig. 4. The surface morphology of perovskite films prepared on mesoporous TiO2 substr
ate. The AFM images of perovskite films casted from the precursors with following
additives: (a, c) MACl and (b, d) MACl-MAAc
780 nm) is observed. It implies that the roughness of perovskite
films decreases, which is consistent with the surface
morphology measured by AFM.
In order to gain a further insight into the effect of mixture
additives on the perovskite films quality, we characterized the
optoelectronic behavior of the perovskite films by means of the
steady-state photoluminescence (PL) and the time-resolved PL
(TRPL) as shown in Fig. 5a and Fig 5b. It is obvious that both PL
peaks maxima of the samples prepared by the single MACl
additive as well as by the mixture of MAAc and MACl are located
at 766 nm, showing a small blue shift compared to that of the
conventional MAPbI3 perovskite as shown in Fig S8，which is
similar to previous reports.20, 32, 33 Furthermore, the PL intensity
of MACl-based perovskite film was more than doubled by the
introduction of MAAc. These results exemplify that the
perovskite films prepared by the mixture additive have a fewer
band-edge trap states, which is reflected in a spectral blue shift
of the PL maximum and a higher PL intensity.34, 35 The TRPL
measurements shown in Fig. 5b were used to extract the
photogenerated carrier lifetimes. Table S1 summarizes the
fitting results using a double-exponential decay model with a
fast decay lifetime τ1 and a slow decay lifetime τ2. Independent
of the employed additives, all samples exhibit comparable
carrier lifetimes, which means that the introduction of MAAc
retains the long charge carrier lifetime of the MACl-based
perovskite film. It is in agreement with the previous report. 36
Surprisingly, the fast component of lifetime τ1 decreases by the
addition of MAAc, which indicates a lower defect concentration
and hence a lower number of recombination centers.
Consequently, we can conclude that the herein studied
antisolvent-free multiple additives method using MACl and
MAAc delivers high quality perovskite films, suitable even for
the large-scale PSCs manufacture.
We assessed the trap density and the charge-carrier mobility
by using the space-charge limited current (SCLC) analysis. The
current-voltage characteristics (I-V curves) of the single-carrier
devices are given in Fig.5c and Fig. 5d for perovskite films casted
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Fig. 5. (a) Steady-state PL spectra and (b) Time-resolved PL decays of MACl-based and MACl-MAAc-based films on Si substrates; Current density–voltage characteristics of
(c) MACl-based and (d) MACl-MAAc–based perovskite devices with FTO/TiO2/perovskite/PCBM/Ag architecture (electron-only devices); (e) The ideality factor derived from
the light-intensity dependent VOC of PSCs with MACl-based and MACl-MAAc-based perovskite.
from the precursors using a single additive (MACl) and the
mixture additives (MACl + MAAc), respectively. The architecture
of the electron–only single-carrier device is as follows:
FTO/TiO2/MAPbI3/PCBM/Ag. The I-V curves display the three
distinctive stages: Ohmic, trap-filled limited (TFL) and SCLC
regime. At the low bias voltage, there is a linear relationship of
I-V, indicating an Ohmic contact. When the bias voltage
increases, the injected carriers start to fill the traps and reach
the TFL stage25. The threshold voltage between the Ohmic
regime and the TFL regime is known as the trap-filled limit
voltage VTFL, which is determined by the trap state density n trap
37: n 2ε0 ε VTFL
trap = 𝑒L2
, where е is the elementary charge, ε, ε0 and
L are the relative dielectric constant, the vacuum permittivity
and the thickness of perovskite film, respectively. The VTFL
values of MAPbI3 films prepared by the mixture additive (MACl
+ MAAc) and the single additive (MACl) are 0.113 V and 0.451
V, respectively. The corresponding trap density values are 2.25
× 1015 cm-3 and 8.95 × 1015 cm-3, respectively. The defect density
of the MAAc-MACl-based film is approximately fourfold lower
than that of the MACl-based film. In the SCLC regime, the
current shows a quadratic dependence on the voltage. At this
stage, the charge carrier mobility 2can be calculated by the
9 𝑉
Mott–Gurney law38: 𝐽𝐷 = 𝜀0 𝜀𝜇 3 , where μ and V are the
8 𝐿
mobility and bias voltage, respectively. The values of the
electron mobility in the devices prepared by the mixture
additive of MAAc-MACl and the single additive of MACl are
20.2cm2 V-1 S-1 and 11.23 cm2 V-1 S-1, respectively. The MAAc-
MACl based film displays the higher charge carrier mobility,
approaching to that of the MAPbI3 single crystal37. The huge
difference probably originates in the large number of pores and
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C8TA04794D
Journal of Materials Chemistry A Accepted Manuscript
pinholes in the MACl-based perovskite film. The poor quality of
the perovskite film leads to increased leakage currents and
enhanced recombination of electrons and holes.
Furthermore, we compared the dependence of photovoltage
on illumination intensity to probe the recombination process of
free charge carriers in the PSCs devices. Fig. 5e shows the open-
circuit voltage Voc as a function of illumination intensity of the
two samples. For the MACl-based solar cell, the Voc value drops
rapidly with the illumination in the low intensity region (< 0.1
sun), suggesting a predominant trap-assisted recombination
process caused by deep-level trap states.39, 40 In contrast, the
MAAc-MACl-based solar cell exhibits a constant linear
dependence of Voc vs. illumination intensity across all the tested
range, indicating that the introduction of MAAc has effectively
reduced trap-assisted recombination. According to the
q dVoc
equation41: n = , the ideality factors (n) of the MAAc-
kT dln(𝜑)
MACl-based and the MACl-based devices are 1.28 and 1.58,
respectively. It also demonstrates that the interface charge
recombination in MAAc-MACl-based devices is less pronounced
than that of the MACl-based one. This fact points again to the
higher quality of the perovskite film prepared by using a
synergistic effect of a combined action of MAAc and MACl
additives.
Fig. 6 shows the (a) current density–voltage (J-V) curves, (b)
external quantum efficiency (EQE) spectra, (c) stabilized PCE, (d)
statistics of PCE distribution and (e) light stability of PSCs. The
performance of the devices has been measured under 3A grade
solar simulator.
Fig. 6a demonstrates the J-V curves of the best MACl-MAAc
and MACl-based device. The highest PCE of 19.64% has been
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Fig. 6. (a) J-V curves of the best performing PSCs casted from the precursors containing
solely MACl (black) and MACl-MAAc (red) additives; (b) The corresponding EQE spectra
complemented with the integrated current density of the best PSCs; (c) Stabilized current
density and PCE of the best PSCs at a given constant bias related to the maximal power
point; (d) The histogram of PCE, the data were collected from an ensemble of 30 PSCs;
(e) Light stability of PCE for unencapsulated devices tested for 120 minuters under AM
1.5 G 100mW/cm2 in an ambient environment with a humidity of ~15% at room
temperature.
achieved by introducing the mixture additive (MAAc-MACl),
with Jsc of 23.50 mA cm-2, Voc of 1.06 V and high FF of 0.79. As a
reference, the best solar cell assembled by using the MACl-
based perovskite film shows a decreased PCE of 15.6%, with Jsc
of 20.58 mA cm-2, Voc of 1.01 V, and FF of 0.75. The EQE spectra
in Fig. 6b demonstrate the higher quantum conversion
efficiency for MAAc-MACl-based PSCs throughout the entire
wavelength range. The improved PCE and EQE of the MACl-
MAAc-based device may be related to the lower trap density
and a reduced interface charge recombination primarily due to
the high-quality monolayer-like film. The incomplete surface
coverage of the solely MACl-based film results in a high
interface charge recombination and an increased leakage
current, which deteriorates the maximum reachable values of
Jsc and Voc. The J-V curves in Fig. S9 show a minor hysteresis in
reverse and forward scans for the MACl–MAAc-based cell
modified with a PCBM layer, which validates that the hysteresis
is not due to the perovskite material layer.25 For that reason,
the presence of hysteresis may be associated with the TiO 2
layer, which is a poorer electron conductor than PCBM and
leads to an unbalanced electron and hole flux. 42 Fig. 6c shows
the stabilized power output as a function of time under a
constant illumination. The MACl-MAAc-based device has a
higher stabilized PCE of 18.5%, with the corresponding Jsc= 21.4
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mA.cm-2. In contrast, the MACl-based device reached Viewthe PCE
Article of
Online
only 14.9%. As a result, compared to the DOI: 10.1039/C8TA04794D
MACl-based device,
the MAAc-MACl-based device shows a higher current density in
response to the illumination. The improved charge collection
efficiency can be seen in the compact and pinhole-free MAAc-
Journal of Materials Chemistry A Accepted Manuscript
MACl-based perovskite film. During the switching on of the
illumination, the photogenerated carriers in perovskite layer
occupy exclusively the empty trap states. Only after the traps
are filled, the current density reaches the stable value.
Accordingly, the shorter the time to stabilize the photocurrent,
the fewer defects are present in the device.43 The MACl-MAAc-
based device is faster to reach the stable current density value
than the MACl-based device (Fig. 6c). Thus, the introduction of
MAAc into MACl-based additive reduces the density of defects
in the film, which in turn decreases the recombination of charge
carriers. We fabricated 30 PSCs in order to demonstrate the
reproducibility without antisolvent manufacture. The statistical
distribution of the measured PCE values are shown in Fig. 6d.
The narrow PCE distribution, with the maximum of 19.64% and
the average of 17.75%, for the MACl-MAAc-based PSCs points
to an enhanced reproducibility of the herein studied
antisolvent-free fabrication method. Our final study is related
to the temporal light stability of fabricated PSCs. The
unencapsulated devices were continuously tested for 120
minutes under AM 1.5 G 100 mW/cm2 in an ambient
environment with a humidity of ~15% at room temperature, as
shown in Fig. 6e. The MACl-based devices degraded faster,
especially within the first 20 minutes, which may be attributed
to the inferior quality of a perovskite layer, in terms already
discussed above. As a comparison, the MACl-MAAc-based
device retained more than 90% of the initial PCE after 120
minutes. It is conceivable that the late degradation of PCE is
predominantly due to the interdiffusion of silver atoms into the
perovskite layer, which is especially true for the MACl-based
device that exhibits a large interface roughness, as shown in Fig.
1c. To explore the effect of MAAc additive onto PCE in the
absence of MACl, we fabricated a PSC casted from a precursor,
which contained exclusively the MAAc additive. Fig. S10 shows
the J-V curve of PSC prepared by a single MAAc additive. The
PCE is merely 15.4%. This concludes that the PCE of the solar
cell fabricated by using the mixture additive is much higher than
that of the devices produced by a single additive of MACl or
MAAc only. It further confirms that the combined effect of
MACl-MAAc additives on the formation of high-performing
perovskite layers constitutes a basis of an attractive antisolvent-
free fabrication method.
Conclusions
We developed an additive engineering without antisolvent
strategy to realize a facile and convenient fabrication method
for obtaining high-quality perovskite films. By introducing MACl
and MAAc into the pristine CH3NH3PbI3 precursor, monolayer-
like and pinhole-free MAPbI3 films were obtained. The MAAc
additive accelerates the nucleation and growth of perovskite
crystals, which effectively eliminates the development of pores
and pinholes. MACl plays a major role in the growth of
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perovskite crystals during anneal process to promote the
formation of a perovskite film with a large grain size and a single
crystal-like cross-section profile. PSCs fabricated by this method
exhibit a high charge carrier mobility, significantly decreased
density of trap states and an enhanced light stability. The test
devices yielded an impressive average efficiency of 17.75% with
the best efficiency of 19.64% under the standard one sun
illumination. The synergistic effect of the combined action of
two additives (MACl and MAAc) is the core of a novel
antisolvent-free method, which is expected to open new
possibilities of fabricating high performance PSCs. Moreover,
the environmentally friendly footprint of the proposed
antisolvent-free method eliminates the requirement for the use
of volatile solvents, currently employed in standard antisolvent
methods.
Conflicts of interest
There are no conflicts to declare.
Published on 13 July 2018. Downloaded on 7/14/2018 3:26:00 AM.
Acknowledgements
This work was supported by the National Science Foundation of
China (51774034, 51772026 and 51611130063), Beijing Natural
Science Foundation (2182039), Fundamental Research Funds
for the Central Universities (FRF-TP-17-030A1, FRF-TP-17-
083A1, FRF-TP-17-082A1 and TW2018010), and Project funded
by China Postdoctoral Science Foundation (2017M620611,
2018M630068).
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Table of Contents

Monolayer-like Hybrid Halide Perovskite Films Prepared by Additive Engineering without Antisolvent for Solar Cells