Article

Cite This: J. Am. Chem. Soc. XXXX, XXX, XXX−XXX pubs.acs.org/JACS

Exploration of Crystallization Kinetics in Quasi Two-Dimensional

Perovskite and High Performance Solar Cells
Ning Zhou,† Yiheng Shen,† Liang Li,† Shunquan Tan,† Na Liu,‡ Guanhaojie Zheng,† Qi Chen,‡
and Huanping Zhou*,†
†
Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, Department of Materials Science and
Engineering, College of Engineering, Peking University No. 5 Yiheyuan Road, Haidian District, Beijing 100871, P. R. China
‡
School of Materials Science and Engineering, Beijing Institute of Technology 5 Zhongguancun South Street, Beijing 100081, P. R.
China
*
S Supporting Information

ABSTRACT: Halide perovskites with reduced-dimensionality

(e.g., quasi-2D, Q-2D) have promising stability while retaining
their high performance as compared to their three-dimensional
counterpart. Generally, they are obtained in (A1)2(A2)n−1PbnI3n+1
thin films by adjusting A site cations, however, the underlying
crystallization kinetics mechanism is less explored. In this
manuscript, we employed ternary cations halides perovskite
(BA)2(MA,FA)3Pb4I13 Q-2D perovskites as an archetypal model,
to understand the principles that link the crystal orientation to
the carrier behavior in the polycrystalline film. We reveal that
appropriate FA+ incorporation can effectively control the perovskite crystallization kinetics, which reduces nonradiative
recombination centers to acquire high-quality films with a limited nonorientated phase. We further developed an in situ
photoluminescence technique to observe that the Q-2D phase (n = 2, 3, 4) was formed first followed by the generation of n =
∞ perovskite in Q-2D perovskites. These findings substantially benefit the understanding of doping behavior in Q-2D
perovskites crystal growth, and ultimately lead to the highest efficiency of 12.81% in (BA)2(MA,FA)3Pb4I13 Q-2D perovskites
based photovoltaic devices.

■ INTRODUCTION
Organic−inorganic halide perovskite materials have attracted
tremendous interest in recent years due to their excellent
optoelectronic properties, such as high absorption coefficient,1
tunable band gap,2 small exciton binding energy,3 excellent
ambipolar charge mobility,4 and long charge-carrier diffusion
lengths.5 These advantages combined with the extremely low
fabrication cost make this kind material suitable as a light
absorber for photovoltaic applications. Also, remarkable
progress in power conversion efficiency (PCE) from 3.81%6
to 22.7%7 has been achieved in perovskite solar cells during the
past several years. However, long-term stability of the materials
and devices remain to be the biggest challenge for the realistic
implementation of perovskite solar cell. The instability of
devices mainly comes from the intrinsic materials property,8−13
where perovskites are susceptible to degradation by exposing
to moisture,14 UV light,15,16 temperature,17 and electrical
field,18 etc. Therefore, continuous development on the
perovskite materials is urgently needed to realize long-term
stable and high efficiency perovskite solar cells.
Recently, in contrast to their three-dimensional counter-
parts, ruddlesden−popper phases layered quasi two-dimen-
sional (Q-2D) perovskite based films and devices have shown
the potential to exhibit improved stability while remaining the
high performance.19−24 Initial work has demonstrated that a
layered (PEA)2(MA)2Pb3I10 (where PEA = phenylethylammo-
nium, MA = methylamine) perovskite was used as light
absorber and was relatively stable in air containing 52% relative
humidity for up to 46 days. However, the corresponding solar
cell exhibited a relatively low PCE of 4.73%,21 probably due to
the inhibition of out-of-plane charge transport by the insulating
spacer cations. Similarly, a different kind of organic cation n-
C4H9NH3+ (BA+) was introduced into MAPbI3 to form a Q-
2D (BA)2(MA)n−1PbnI3n+1 perovskite, in which the perovskites
with n = 1−4 was detailed characterized and a PCE of 4.02%
was obtained from the n = 3 compound.19 The quality of Q-2D
(BA)2(MA)3Pb4I13 perovskite has been substantially improved
by using a more sophisticated deposition method of “hot-
casting”, with crystalline planes aligned along the out-of-plane
orientation, which facilitates efficient charge transport along
the perovskite planes and enables an efficiency of 12.52% with
high reproducibility and excellent operating stability.20 More-
over, the Q-2D structure was employed in lead free materials
system, and a highly oriented tin halide perovskites
(PEA)2(FA)n−1SnnI3n+1 based device yielded a 5.94% PCE
with no appreciable decay in efficiency over 100 h.25 In
contrast to the exploration on new materials, the
Received: October 26, 2017
Published: December 15, 2017

© XXXX American Chemical Society A DOI: 10.1021/jacs.7b11157

J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
Journal of the American Chemical Society
Figure 1. (a) XRD patterns and (b)−(e) SEM images of the (BA)2(MA1−xFAx)3Pb4I13, x = 0, 0.2, 0.4, and 0.6 films, respectively.
(BA)2(MA)3Pb4I13 Q-2D are found to exhibit unique multiple
perovskite phases with n = 2, 3, 4, and ∼∞ natural alignment
in the order of n along the direction perpendicular to the
substrate, which leads to a spontaneous charge (electron/hole)
separation property driven by band alignment. These findings
suggest that the relatively poor transportation or undesirable
energy loss in the Q-2D layered hybrid perovskite materials
could be overcome by tuning the crystal orientation and the
internal phases. Although the Q-2D perovskite can be obtained
by cation engineering on the A site in (A1)2(A2)n−1PbnI3n+1,
e.g., FA+, MA+, Cs+, or Rb+ inspired by the composition
engineering in 3D APbX3,26−36 the underlying crystallization
kinetics mechanism in Q-2D is largely unexplored. It thus
requires enormous work to establish a corresponding
fundamental understanding of the crystallization kinetics and
crystal microstructure, which eventually contributes to
improved carrier behaviors of Q-2D perovskite materials and
remarkably efficient devices.
Here, we design a ternary organic cation based Q-2D
perovskite of (BA)2(MA,FA)3Pb4I13 as an archetype, to
understand the principles for maintaining the crystal
orientation with improved carrier behavior, which is essential
to device optimization. The (BA)2(MA1−xFAx)3Pb4I13 (x = 0,
0.2, 0.4, 0.6) Q-2D perovskites were explored in a systematic
way by gradually replacing MA by FA, and the phase,
morphology, crystallographic behavior, as well as the optical
properties were carefully analyzed. An in situ PL technique was
employed to investigate (BA)2(MA,FA)3Pb4I13 perovskite
materials system for the first time, to probe the formation
sequence of different phases. We also revealed a substantially
different crystallographic orientations and crystallization
kinetics in (BA)2(MA,FA)3Pb4I13 Q-2D perovskite induced
by cation substitution, compared to conventional 3D structure.
By introducing 20% FA+, the doped BA2(MA)3Pb4I13 film
exhibited improved carrier lifetime and remain high crystal
orientation, resulting in a best efficiency of 12.81%. The
understanding of the crystallization kinetics and the doping
effect could significantly benefit the rational design of Q-2D
perovskite materials and the solar cell performance.
■
RESULTS AND DISCUSSION
The Q-2D (BA)2(MA)3Pb4I13 perovskite powder was synthe-
sized from a stoichiometric reaction between PbO, MAI, and
BAI in appropriate ratios in a HI/H3PO2 solvent mixture as
described previously.19 To obtain (BA)2(MA1−xFAx)3Pb4I13 (x
= 0, 0.2, 0.4, 0.6) family of perovskite compounds, we replaced
MAI with FAI and adjusted the reaction temperature. We
B DOI: 10.1021/jacs.7b11157
Article
dissolved the perovskite crystal in DMF solvent and adopted
spin-coating method to fabricate films, and the detailed
information can be found in the Supporting Information
(SI). To simplify the chemical formula, we used FA0, FA0.2,
FA0.4, and FA0.6 to represent (BA)2(MA1−xFAx)3Pb4I13 x = 0,
0.2, 0.4, 0.6, respectively. In order to confirm the actual x value
in the final perovskite film, a 1H nuclear magnetic resonance
(NMR) study of the (BA)2(MA1−xFAx)3Pb4I13 samples
scraped from the film with different FA ratio dissolved in the
dimethyl sulfoxide-d6 (DMSO-d6) solvent was undertaken
(Figure S1). We found that the actual x value in the final
perovskite film was quite close to the ratio from the starting
precursor material.
We investigated the crystal phase and crystallinity of the
(BA)2(MA,FA)3Pb4I13 series perovskite films using X-ray
diffraction (XRD) measurement, as shown in Figure 1a. Two
dominant planes were observed at diffraction angles (2θ) of
14.1ο, 28.4ο, representing the (111), (222) crystallographic
planes of (BA)2(MA,FA)3Pb4I13 series perovskite, respectively.
The (111) peak is shifted from 14.1° to 13.9° and 13.8° for
FA0, FA0.2, and FA0.4 respectively, which is due to the larger
size of the FA cation with respect to the MA cation that
expands the crystal lattice.37,38 This gradual shift in diffraction
peak position indicated that mixed (BA)2(MA,FA)3Pb4I13
perovskites are formed with FA cations inserted in the crystal
lattice. However, when the amount of FA cation was further
increased, a new set of periodic (0k0) peaks were found in the
FA0.6 film. The crystallinity of the FA0.6 film was substantially
decreased, where the presented peaks were obtained after
normalizing the peak intensity. It was assigned to the
unoriented BA2(MA,FA)Pb2I7 Q-2D (n = 2) perovskite in
the FA0.6 film,19 which was also evidenced by the XRD peak
shift between BA2(MA)Pb2I7 and BA2(FA)Pb2I7 (Figure S2).
This limited replacement of MA with FA during 2D
(BA)2(MA,FA)3Pb4I13 perovskite growth is quite different
from the conventional formation of 3D (MA1−xFAx)PbI3
perovskite film over the full compositional space.
Scanning electron microscopy (SEM) and atomic force
microscopy (AFM) measurements are then used to study the
quality of (BA)2(MA,FA)3Pb4I13 series perovskite films.
Different MA:FA ratios also present significant differences in
film uniformity and coverage, as shown in the SEM images
(Figure 1b−e). Accordingly, FA0 and FA0.2 films had
adequate surface coverage and densely packed grains without
visible cracks. The introduction of 20% FA significantly
enlarges the crystal grains from several hundred nanometers
to several micrometers. When substituting MA with 40% FA in
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Figure 2. GIWAXS patterns of the perovskite films of (BA)2(MA1−xFAx)3Pb4I13, x = 0, 0.2, 0.4, and 0.6 films, respectively.

Figure 3. (a) The steady-state PL spectra of the (BA)2(MA,FA)3Pb4I13 series Q-2D perovskite films from front side; (b) TRPL spectra for ITO/
(BA)2(MA,FA)3Pb4I13 series Q-2D perovskite film.

(BA)2(MA,FA)3Pb4I13, the film has larger crystal grains but is
less dense with a considerably increased amount of pinholes
and cracks. Further substituting MA with 60% FA, lots of
microparticals appeared on the film surface, which was
attributed to BA2(MA,FA)Pb2I7 according to the XRD results.
Figure S3 provides the AFM images of the
(BA)2(MA1−xFAx)3Pb4I13 (x = 0, 0.2, 0.4, 0.6) perovskite
film. The root-mean-square (RMS) roughness of the FA0 and
FA0.2 films across a scanned area of 5 × 5 μm2 were
determined to be 7.1 and 3.0 nm, respectively, which suggests
the superior film quality of FA0.2. The RMS roughness of
FA0.4 and FA0.6 film were 5.8 and 18.1 nm, respectively, with
randomly distributed domains and coexisted pinholes. We
consider this phenomenon as a result of the growth kinetic
difference between Q-2D and 3D perovskite. Generally, 3D
perovskites are likely to follow uncontrolled crystal growth in
3D space that lead to a rough surface, while Q-2D perovskite
films are smoother as a result of the space confined effect.25 It
also confirmed that the introduction of FA with a ratio less
than 40% would not change the Q-2D orientation structure.
C DOI: 10.1021/jacs.7b11157
However, if the FA ratio is higher than 40%, then the MA in
Q-2D structure cannot be stoichiometrically replaced by FA.
This indicates a different but interesting effect in crystal
structure evolution induced by dimensional variation due to
the crystal growth kinetic difference between MA and FA
based Q-2D perovskite films, and the underlying crystal growth
kinetics mechanism will be discussed as follows.
To confirm the orientation of the (BA)2(MA,FA)3Pb4I13
perovskite films, we performed grazing incidence wide-angle X-
ray scattering (GIWAXS) analysis using synchrotron radia-
tion.39 The scattering patterns of the different FA ratio in the
(BA)2(MA,FA)3Pb4I13 films are shown in Figure 2a−d. The
FA0 sample shows sharp and discrete Bragg spots, which
indicate the highly oriented crystal grain with (111) planes
parallel to the substrate surface.20 The orientated perovskite
films that are vertically grown on the substrate would form an
efficient carrier transport pathway, probably leading to
improved photovoltaic behavior.25 Films with 20% FA ratios
exhibit the same set of diffraction spots, but with even stronger
intensity in the qz direction, as compared to FA0. The
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integrated intensity plots of the GIWAXS patterns at 14.1°
diffraction angle (Figure S4) further confirmed the retained
orientation of the crystal domains, albeit of considerable
change in relative intensity of the crystallographic plane.
However, when the FA ratio was higher (40% or more),
diffraction rings instead of diffraction spots were observed,
suggesting the highly oriented 2D layered structure trans-
formed to less oriented structure. The less apparent diffraction
rings in the FA0.6 film compared to FA0.4 film is due to its
decreased crystallinity. The presented variation in film quality
induced by FA incorporation is consistent with the XRD, SEM,
and AFM results.
Further, we carried out absorption and photoluminescence
(PL) spectroscopy measurements to detect the absorption and
emission property of the perovskite films. All the films were
spin-coated on the glass substrate. We found that multiple
perovskite phases with various n values coexisted in the 2D
perovskite films (although nominally prepared as “n = 4”), as
evident by multiple absorption and emission peaks in Figures
S5 and 3a (front-excitation), respectively. When the laser beam
hit the perovskite from the glass substrate side (back-
excitation), multiple emission peaks of small n value were
more obvious (Figure S6). The differences in the PL spectra
between front- (Figure 3a) and back-side excitations (Figure
S6) suggested that the small-n phases may majorly locate near
substrate side, and the large-n phase locates at the upper
surface of the film, which is consistent with recent reported
work.40 Besides, the strong emission peak gradually shifted
from 736 nm for FA0, to 773, 790, and 784 nm for FA0.2,
FA0.4, and FA0.6, respectively. This emission peak was defined
as n = ∞ which is close to the 3D perovskite. The red-shift
observed in FA0, FA0.2, and FA0.4 is associated with the
reduced bandgap (Eg) of the (BA)2(MA,FA)3Pb4I13 perovskite,
due to the larger ionic radius of FA+. However, a 6 nm blue-
shift in emission peak was unexpectedly observed by increasing
FA content from 0.4 to 0.6. This indicates that the FA ratio in
the highly oriented (BA)2(MA,FA)3Pb4I13 films has a limit and
the structure of FA0.6 becomes different from the FA0.4
structure which is in accordance with the XRD measurement.
We measured the photoluminescence lifetime of the perovskite
films deposited on nonconductive glass, and the time decay of
the fluorescence signals was fitted to two exponentials in
Figure 3b. The carrier lifetimes for the two components are
summarized in Table 1, and we used the longer carrier lifetime
Table 1. Lifetimes Read from the Time-Resolved PL Decays
life time FA0 FA0.2 FA0.4 FA0.6
τ1 /ns 0.41 1.18 4.6 15.8
τ2 /ns 3.18 30.34 103.6 161.4
for comparison. Strikingly, the emission of FA0.2 perovskite
film decayed with a long lifetime of 30.34 ns, which is
approximately 10 times as that of FA0 based film with 3.18 ns.
Further increasing the FA amount would lead to even longer
carrier lifetime of over 100 ns. The prolongation of the lifetime
in the mixed-cation perovskite most likely contributes to a
better carrier-transport behavior in the device. Notably, the
film with longest carrier lifetime may not guarantee the best
efficiency in the resulting device, by considering the
significantly changed structure and poor film morphology in
the (BA)2(MA,FA)3Pb4I13 with high FA amount, which will be
discussed in the following paragraph.
D DOI: 10.1021/jacs.7b11157
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On the basis of the above phenomenon, it suggests an
effective and unique doping effect in Q-2D structure that is
different from 3D structure, due to the crystallization kinetic
difference. In conventional ABX3 3D perovskite structure, the
A, B, and X ions all obey the goldschmidt tolerance factor, and
the radii of A cation is preferred to be ∼0.16−0.22 nm to
couple with PbI6 octohedral. In this circumstance, MA and FA
can replace each other in any given ratio, whereas the phase
and optoelectronic properties can be tuned systematically.
While in the present study, we observed that the replacement
of MA with FA in the Q-2D structure only occurring in a
limited composition window to remain the orientation
structure (x < 0.4), as shown in Figure 4a. This suggests a
substantially different crystallization kinetics for the multi-
layered Q-2D, which plays a vital role to determine the
microstructure. We then developed an in situ PL measurement
to analyze the growth kinetics of (BA)2(MA)3Pb4I13. The
precursor solution was spin-coated onto the substrate, and
three representative emission peaks with different n value were
detected: n = 2 (585 nm), n = 4 (670 nm), and n = ∞ (780
nm), during the evaporation of DMF.41,42 Through the in situ
PL measurement (Figure 4c), we clearly observed that the
initial precursor film exhibits more n = 2 and n = 4 components
with much less n = ∞ one at first. After 50 s, the n = 2 and n =
4 component began to decrease with the increasing n = ∞
component. It indicates that the Q-2D perovskite was formed
first during crystal growth, and the n = ∞ composition which is
quite close to 3D perovskite gradually generated when extra
cations were inserted into the Q-2D framework. Also, we
carried out the in situ PL to investigate the FA0.2 system
(Figure S7), and the variation tendency is similar to FA0
system. It is worth mentioning that although the formation
energy for the Q-2D component is higher than that of the 3D
component,23 we observed the first formation of the Q-2D
phase (n = 2, 4), suggesting its favorable kinetics compared to
the n = ∞ phase. As a result, the initial Q-2D framework is
very important to the final formed perovskite film, which also
explains the limited doping ratio of FA+ in
(BA)2(MA,FA)3Pb4I13. When the FA ratio is lower than
40%, the MA+ can be substituted by FA+ (Figure 4a).
However, when the FA ratio is higher than 40%, the smaller n
phase in the form of BA2(MA,FA)Pb2I7 (n = 2) is kinetically
favorable, which coexisted with (BA)2(MA,FA)3Pb4I13 (n = 4)
structure in the final film with reduced degree of crystal
orientation (Figure 4b). This was likely due to the fact that the
smaller n phase BA2(MA,FA)Pb2I7 was not vertically oriented,
in contrast to the n = 3,4 perovskites phases.19,43 And the
formation of phases with smaller n, e.g., BA2(MA,FA)Pb2I7,
suggests that FA+ can largely promote the growth of smaller n
perovskite phase, probably originating from its different ionic
radii or the interaction between FA+ and I− compared with
MA+. The promoted formation of the small n phase induced by
FA may further influence the crystallization kinetics of n = ∞
phase, as shown in Figure S7. The underlying crystallization
kinetics mechanism may benefit the fundamental under-
standing and rational design of the multilayered Q-2D
structure as well.
Specifically, we explored (BA) 2 (MA) 3 Pb 4 I 13 and
(BA)2(MA0.8FA0.2)3Pb4I13 perovskite films as light absorbers
for solar cells based on a planar inverted architecture of ITO/
PEDOT:PSS/Perovskite/PCBM/BCP/Ag depicted in Figure
5a. Here, PEDOT:PSS and PCBM serve as the hole and
electron transport layers, respectively. The fabrication details
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Figure 4. Scheme of the (BA)2(MA,FA)3Pb4I13 perovskite structure with different MA/FA doping ratio. (a) (BA)2(MA0.8FA0.2)3Pb4I13; (b)
(BA)2(MA0.4FA0.6)3Pb4I13; and (c) in situ PL measurement for BA2(MA)3Pb4I13 film by detecting the emission peak at 585 nm (n = 2), 670 nm (n
= 4), and 780 (n = ∞).

Figure 5. (a) Device structure of the Q-2D perovskite solar cell; (b) the best J−V curve and (c) EQE spectra of BA2(MA)3Pb4I13 and
(BA)2(MA0.8FA0.2)3Pb4I13 based perovskite solar cells by adopting inverted device structure; (d) and (e) Jsc and Voc as a function of light intensity
for inverted planar perovskite solar cells devices; and (f) the long-term stability test of the Q-2D perovskite solar cells stored in air with humidity
40%−60% for 1300 h by adopting regular device structure.

can be found in the Experimental Section. According to the
cross-sectional SEM image of the device (Figure S8), the
thicknesses of the perovskite is approximately 450 nm. Figure
5b shows the J−V characteristics under simulated AM1.5G
irradiation (100 mW/cm2) for the best performing devices.
The device fabricated by (BA)2(MA)3Pb4I13 perovskite films
gives a PCE of 10.70% with an open circuit voltage (Voc) of
0.954 V, a short-circuit current density (Jsc) of 16.13 mA/cm2,
and fill factor (FF) of 69.51%. The (BA)2(MA0.8FA0.2)3Pb4I13
based device yields an enhanced PCE of 12.81%, with Voc =
0.999 V, Jsc = 18.12 mA/cm2, and fill factor = 70.79%. To the
best of our knowledge, this is the highest efficiency regarding
Q-2D (n = 4) based inverted perovskite solar cell. The derived
PCE from steady state power output measurement of
(BA)2(MA0.8FA0.2)3Pb4I13 based device is 12.6%, while the
device based on (BA)2(MA)3Pb4I13 is 10.2% as shown in
Figure S9. The Voc, Jsc, FF, and PCE statistic distribution of
(BA)2(MA0.8FA0.2)3Pb4I13 and (BA)2(MA)3Pb4I13 based solar
cells are summarized in Figure S10. The incident photon to
current conversion efficiency (IPCE) spectra are shown in
Figure 5c, and the derived integrated current value is plotted
E DOI: 10.1021/jacs.7b11157
on the secondary y-axis. (BA)2(MA0.8FA0.2)3Pb4I13 based cell
gives a current density of 18.5 mA/cm2, which is much higher
than that of the (BA)2(MA)3Pb4I13 based cell of 16.3 mA/cm2.
To be noted, the addition of FA+ in (BA)2(MA)3Pb4I13 could
improve the light harvesting capabilities and reduce the
hysteresis of the cells. The hysteresis index43 (HI) of our
PSCs are decreased from 0.149 (BA2MA3Pb4I13) to 0.072
(BA2(MA0.8FA0.2)3Pb4I13) (Figure S11 and Table S1). The
hysteresis observed in BA2(MA0.8FA0.2)3Pb4I13-based systems
is reduced and may be related to the relatively larger radius and
smaller molecular dipole moment of FA+ when compared to
MA+.44
To probe the losses due to the carrier recombination in the
devices, we measured the corresponding J−V characteristics
under different incident light intensities. Figure 5d shows a
relation of Jsc versus light intensity in a double logarithmic
scale. A slope of 0.750 and 0.798 were observed in the
(BA)2(MA)3Pb4I13 and (BA)2(MA0.8FA0.2)3Pb4I13 based solar
cells, respectively, indicating that the monomolecular recombi-
nation is dominant in both devices. While compared to the
(BA)2(MA)3Pb4I13 cell, the (BA)2(MA0.8FA0.2)3Pb4I13 cell
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displays a more ideal relation between Jsc and illumination
intensity, suggesting the reduced trap density within
(BA)2(MA0.8FA0.2)3Pb4I13 material. Furthermore, we revealed
the carrier recombination mechanism by comparing ideality
factors. Figure 5e showed that the Voc increased monotonically
with light intensity and the ideality factor was greater than 1,
indicating that the recombination is not limited only by the
minority carrier concentration, but also trap-assisted Shock-
ley−Read−Hall (SRH) recombination. In addition, a decrease
in ideality factor from 1.67 to 1.52 was observed upon the
incorporation of 20% FA+ in the absorber materials. This
means the trap-assisted SRH recombination is suppressed in
the (BA)2(MA0.8FA0.2)3Pb4I13 devices, which may also
associate to its reduced trap states.
Additionally, we fabricated perovskite solar cell by employ-
ing ITO/TiO2/Perovskite/Spiro-OMeTAD/Au regular archi-
tecture as shown in Figure S12, and obtained a reverse scan
efficiency of 10.72% for (BA)2(MA)3Pb4I13 and 12.46% for
(BA)2(MA0.8FA0.2)3Pb4I13 based solar cells (Figure S13).
Regular architecture devices were employed to examine the
long-term stability in this study in order to avoid any possible
deterioration induced by Ag diffusion and the thin transport
materials based on inverted structure. The unsealed
(BA)2(MA)3Pb4I13 and (BA)2(MA0.8FA0.2)3Pb4I13 based de-
vices were stored in ambient air with relative humidity of
∼40%−60%. After experiencing 1300 h, both devices displayed
excellent stability, by maintaining 85% and 88% of its original
value for (BA)2(MA)3Pb4I13 and (BA)2(MA0.8FA0.2)3Pb4I13
based devices, respectively, as depicted in Figure 5f. We
consider that the suppressed device degradation could be
associated with the long and bulky hydrophobic organic group
in the Q-2D perovskite structure, which can prevent direct
exposure to moisture and thus increase stability.
■ CONCLUSIONS
In summary, we have fabricated thin films of a series of Q-2D
ternary cations halides perovskite (BA)2(MA,FA)3Pb4I13, in
which MA was gradually replaced by FA. Their phase,
morphology, and optoelectronic properties were systematically
explored. Powder XRD, GIWAXS, and TRPL results reveal
that appropriate FA+ incorporation can effectively control the
perovskite crystallization kinetics to obtain highly oriented
phases, which reduces nonradiative recombination centers in
the resultant films. Moreover, in situ PL techniques are
developed to probe the phase formation sequence for the first
time, wherein the 2D phase (n = 2, 3, 4) was formed early
followed by the generation of n = ∞ perovskite in a Q-2D
perovskite system. These findings substantially benefit the
understanding of doping behavior in Q-2D perovskites in the
context of film growth and have led to fabrication of perovskite
solar cells with a PCE of 12.81%, which is the highest efficiency
based on (A1)2(A2)3Pb4I13 Q-2D perovskites with the inverted
planar heterojunction configuration.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/jacs.7b11157.
Experimental section, materials and methods, additional
results and discussion, including Figures S1−S13, Table
S1, and additional references (PDF)
F DOI: 10.1021/jacs.7b11157
Article
■ AUTHOR INFORMATION
Corresponding Author
*happy_zhou@pku.edu.cn
ORCID
Huanping Zhou: 0000-0003-4220-1161
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge funding support from the National
Natural Science Foundation of China (51722201) (51672008)
(91733301), National Key Research and Development
Program of China Grant No. 2017YFA0206701, Young Talent
Thousand Program, and ENN group. The authors thank
beamline BL14B1 (Shanghai Synchrotron Radiation Facility)
for providing the beam time and help during the experiments.
The authors thank Yihua Chen for helping to draw the scheme.
■
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G DOI: 10.1021/jacs.7b11157
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX