Journal of
Materials Chemistry A
COMMUNICATION
Binary organic spacer-based quasi-two-
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Cite this: J. Mater. Chem. A, 2019, 7,
dimensional perovskites with preferable vertical
9542 orientation and efficient charge transport for high-
Received 28th December 2018 performance planar solar cells†
Accepted 26th March 2019
Shi Chen,‡a Nan Shen,‡a Luozheng Zhang,a Weiguang Kong,ab Lihua Zhang,a
DOI: 10.1039/c8ta12476k
Chun Cheng *a and Baomin Xu *a
rsc.li/materials-a
Quasi-two-dimensional (Q-2D) perovskites ((RNH3)2MAn!1PbnI3n+1,
RNH3 represents the organic spacer (mostly phenethylammonium
(PEA) and n-butylammonium (BA)) and MA ¼ methylammonium) have
shown great potential for application in solar cells due to their intrinsic
stability, where the organic spacer dominantly determines the Q-2D
perovskite ambient stability and device performance. Current studies
merely concentrate on unary organic spacer Q-2D perovskites, either
using BA or PEA. Herein, for the first time, we have successfully
designed and fabricated (PEA1!xBAx)2MA3Pb4I13 binary spacer-based Q-
2D perovskite films, and demonstrated that the device using binary
organic spacer-based Q-2D perovskite films has substantially better
performance than that using either of the unary organic spacer-based
Q-2D perovskite films. The (PEA0.8BA0.2)2MA3Pb4I13 binary spacer
device yields a maximum power conversion efficiency of 15.7%, which
outperforms the efficiency record (12–14%) for unary spacer (PEA or
BA) Q-2D perovskite devices. In particular, a peak open-circuit voltage
of 1.21 V is achieved due to a non-radiative recombination loss of
#100 mV, the lowest reported loss value for Q-2D perovskite devices.
The high device performance results from binary-spacer-induced
intensified film surface quality, preferable vertical orientation of crys-
tals and improved film optoelectronic properties as well as obviously
decreased device recombination losses. These findings open up a new
avenue for the rational design of Q-2D perovskite materials with
polynary organic spacer.
1 Introduction
Solar cells based on three-dimensional (3D) organic–inorganic
hybrid perovskites have shown promise as next-generation
a
Department of Materials Science and Engineering, Southern University of Science and
Technology, Shenzhen, Guangdong Province, 518055, China. E-mail: chengc@sustc.
edu.cn; xubm@sustc.edu.cn
b
Hebei Key Laboratory of Optic-Electronic Information Materials, College of Physics
Science and Technology, Hebei University, Baoding, 071002, China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c8ta12476k
‡ These authors contributed equally to this work.
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solution-processed photovoltaic devices due to their low-cost
fabrication and rapidly increasing power conversion efficiency
(PCE) exceeding 23%.1–4 However, 3D perovskite solar cells
commonly suffer from inherent instabilities with respect to
humidity, illumination and heat, which signicantly hinders
the realization of commercial applications.5–7 In order to search
for novel intrinsically stable perovskite materials, Ruddlesden–
Popper layered quasi-two-dimensional (Q-2D) perovskites with
a general formula of (RNH3)2An!1MnX3n+1 are developed, where
RNH3 represents the bulky organic spacer and the perovskite
frame consists of a small cation (A), divalent metal (M) and
halide anion (X).8–10 Compared with their 3D counterparts, Q-2D
perovskites exhibit better ambient stability owing to the
stronger interaction between the organic spacer and the
perovskite frame and the more hydrophobic property of the
organic spacer,11–13 but much lower PCEs are obtained in Q-2D
perovskite devices because of the poor charge transport and
large exciton binding energy.10,14,15 The intrinsic insulating
organic spacer layer of Q-2D perovskites is considered to mainly
block the vertical charge carrier transport, and thus signi-
cantly decreases the PCE of Q-2D perovskite devices.12,16
Promoting the vertical orientation of Q-2D perovskite lms on
substrates can effectively reduce the hindering effect of the
organic spacer and achieve efficient charge transport, and
therefore becomes an effective strategy to boost the PCE of Q-2D
perovskite devices.
Currently, several approaches including the hot-casting
method,13,17 the mixed-cation strategy,18,19 additive assis-
tance12,20,21 and organic spacer design22,23 are reported to effec-
tively improve the vertical alignment of Q-2D perovskite lms (n
# 5) on substrates. Mohite and co-workers introduced a hot-
casting technique to realize the preparation of vertically
oriented BA2MA3Pb4I13 (BA+ ¼ CH3CH2CH2CH2NH3+) lms,
giving a high PCE of 12.51%.13 On this basis, a higher PCE of
13.7% was achieved by designing a novel mixed-cation compo-
sition of BA2(MA0.95Cs0.05)3Pb4I13.17 Moreover, a combination of
NH4SCN and NH4Cl additives was employed to fabricate vertically
ordered PEA2MA4Pb5I16 (PEA+ ¼ C6H5CH2CH2NH3+) lms,
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delivering an average PCE of 12.9%.21 Despite these signicant
advances toward highly efficient Q-2D perovskite devices, current
studies merely focus on the optimization of unary organic spacer
(mostly either BA or PEA) Q-2D perovskite materials. So far, there
is still no report about the vertically oriented growth of binary
organic spacer Q-2D perovskites. Inspired by the compositional
engineering of three-dimensional perovskites, binary organic
spacer Q-2D perovskites are promising to achieve more efficient
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charge transport and better device performance compared with
their unary spacer counterparts. However, the realization of the
vertical orientation of binary spacer Q-2D perovskites still
remains challenging since each type of unary spacer Q-2D
perovskite has obviously different fabrication conditions. There-
fore, developing binary spacer Q-2D perovskites requires enor-
mous work to explore the effects of a binary spacer on the crystal
orientation, charge transport and device performance, which
eventually promotes the development of Q-2D perovskite
optoelectronics.
Compared to their 3D counterparts, Q-2D perovskite devices
usually suffer from a much lower short-circuit current density
(Jsc) due to the existence of an insulating organic spacer, and
thus the corresponding PCE is severely limited.13,18,24 At present,
this limiting factor can be greatly overcome by the realization of
the vertical orientation of perovskite crystals, which is well
supported by a high Jsc of #20 mA cm!2 in BA2MA3Pb4I13 solar
cells.17,25 Naturally, a high open-circuit voltage (Voc) of Q-2D
perovskite devices will play a dominant role in further
improvements of device efficiency. So far, most of the reported
Voc values of Q-2D perovskite (n ¼ 4 and 5 with a bandgap of
#1.60 eV) devices are much smaller than 1.20 V.12,19,25 Therefore,
a higher Voc close to 1.2 V is urgently required in Q-2D perov-
skite devices in order to further boost the PCE.
In this work, we have prepared vertically oriented (PEA1!x-
BAx)2MA3Pb4I13 (x # 0.3) binary spacer Q-2D perovskite lms for
the rst time, and the effects of binary spacer PEA–BA on the
lm phase, lm morphology and crystal orientation as well as
optical properties are investigated in detail. Furthermore, we
systematically compare the optoelectronic properties of unary
(PEA) and binary (PEA–BA) spacer perovskite lms, such as
charge transfer dynamics, trap density and hole mobility. We
have found that the introduction of a binary spacer causes
improved lm surface quality, preferable vertical orientation of
crystals and enhanced optoelectronic properties. Accordingly,
the (PEA0.8BA0.2)2MA3Pb4I13 binary spacer device yields a peak
PCE of 15.7%, and more importantly, a maximum Voc of 1.21 V
is also achieved due to an extremely small non-radiative
recombination loss of #100 mV.
2 Results and discussion
For the sake of simplicity, we utilize BA0, BA0.1, BA0.2, BA0.3 and
BA1 to represent the chemical formula (PEA1!xBAx)2MA3Pb4I13
with x ¼ 0, x ¼ 0.1, x ¼ 0.2, x ¼ 0.3 and x ¼ 1, respectively. The
crystal phase of (PEA1!xBAx)2MA3Pb4I13 binary spacer perov-
skite lms is investigated using X-ray diffraction (XRD) patterns
(Fig. S1†). Obviously, two dominant diffraction peaks are
located at the 2q of 14.21$ and 28.52$ for the BA0 unary spacer
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lm, corresponding to the (111) and (202) lattice planes.13 No
additional diffraction peaks appear when the BA organic spacer
is incorporated into PEA2MA3Pb4I13 structure. With the increase
of the BA spacer concentration from 0% to 30%, the main
diffraction peak (111) experiences a slight shi from 14.21$ to
14.35$ in the magnied XRD region (Fig. S1b†). This gradual
shi in the main peak could be ascribed to the smaller spacer
size of BA than that of PEA. In order to further verify the BA
spacer concentration in the nal lms, perovskite lms
deposited on indium tin oxide (ITO) substrates are dissolved in
the solvent of dimethyl sulfoxide-d6 (DMSO-d6) and the result-
ing solution is examined via proton nuclear magnetic resonance
(1H NMR). It is found that the experimentally measured BA
spacer concentrations are quite close to BA ratios in the starting
materials (Fig. S3†).
Then, the effects of BA contents on the morphology of
(PEA1!xBAx)2MA3Pb4I13 binary spacer lms are studied by
scanning electron microscopy (SEM) and atomic force micros-
copy (AFM). As shown in Fig. 1, uniform morphologies along
with full coverage are observed for all perovskite lms. Without
a BA spacer, the BA0 unary spacer lm exhibits a comparably
bumpy surface with a root-mean-square (RMS) roughness of
26.9 nm as well as a considerably vertical orientation tendency
of perovskite crystals. Interestingly, the introduction of 10% BA
spacer enables small dents on the lm surface to become much
smaller and greatly promotes the formation of a smooth lm,
yielding a signicantly decreased RMS roughness of 11.2 nm.
When substituting PEA with 20% BA spacer, further fusion and
disappearance of small dents on the lm surface generate a very
smooth lm with a minimum RMS roughness of 8.07 nm.
However, a further increase to 30% BA spacer causes a deterio-
rated surface with evident cracks and convexities, correspond-
ing to an increased RMS roughness of 14.0 nm. It is clear that
the binary spacer perovskite lm with 20% BA displays the best
surface quality among all samples. In addition, the comparison
of cross-sectional SEM images suggests that the vertical orien-
tation of perovskite crystals is notably strengthened with the
addition of a BA organic spacer, which is favourable for charge
transport along the vertical direction.
In order to further probe the crystal orientation of unary
(PEA) and binary (PEA–BA) spacer Q-2D perovskite lms, two-
dimensional X-ray diffraction (2D-XRD) measurements are
implemented. The BA0 unary spacer lm exhibits two sharp and
discrete Bragg spots corresponding to the lattice planes of (111)
and (202) rather than diffraction rings (Fig. 2a), indicating the
formation of highly oriented crystal grains.12,13,26 Strikingly, this
oriented alignment of crystal domains is further strengthened
in the BA0.2 binary spacer lm, where the two Bragg spots are
more focused (Fig. 2b), consistent with the enhanced vertical
alignment of crystals as observed in the cross-sectional SEM
images (Fig. 1a). Moreover, we employ grazing-incidence wide-
angle X-ray scattering (GIWAXS) measurements to further
verify the enhanced vertical orientation of Q-2D perovskite lms
with BA spacer addition. Both the lms without and with a BA
spacer show discrete Bragg spots (Fig. S4†), indicative of the
highly oriented crystal grains.12,18,27 However, the Bragg spots
become more focused in the BA0.2 binary spacer lm compared
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Fig. 1(a) Top view and cross-sectional (insets) scanning electron microscopy (SEM) images and (b) atomic force microscopy images (size: 5 mm
% 5 mm) of (PEA1!xBAx)2MA3Pb4I13 (n ¼ 4) binary organic spacer perovskite films coated on PTAA substrates, x ¼ 0, 0.1, 0.2, 0.3, respectively.

Fig. 2 Two-dimensional XRD images of (PEA1!xBAx)2MA3Pb4I13 binary spacer films coated on PTAA substrates with x ¼ 0 (a) and 0.2 (b),
respectively. (c) Schematic illustration of the vertical orientation of a (PEA0.8BA0.2)2MA3Pb4I13 frame on the substrate.

to the BA0 unary spacer lm, indicating that the addition of a BA
spacer can further strengthen the vertical alignment of crystals.
Such a vertical orientation enables the perovskite inorganic
layers to be perpendicular to the substrate (Fig. 2c) and there-
fore ensures the formation of efficient charge transport path-
ways in Q-2D perovskite lms.
Absorbance and photoluminescence (PL) spectroscopy
measurements are performed to examine the absorption and
emission properties of Q-2D perovskite lms. Apparently,
except the absorption onset (#800 nm), additional absorbance
peaks at around 524, 570, 612 and 642 nm exist in all samples,
which can be ascribed to the excitonic absorption of Q-2D
perovskite phases with n ¼ 1, 2, 3 and 4, respectively (Fig. 3a).
This result indicates that Q-2D perovskite lms (nominally
prepared with“n ¼ 4”) consist of multiple perovskite phases
with different n values, which is highly consistent with previous
reports.12,18,28–30 In order to further conrm the mixed phases of
our samples, we compare the PL signal of the BA0.2 lm excited
from both the front side (perovskite lm) and back side (glass
substrate). Both excitations exhibit a dominant emission peak
at 774 nm, which is ascribed to the emission from the large-n
(close to N) phases (Fig. S8a†); however additional weak
multiple peaks at higher energy (attributed to small-n phases)
appear when excited from the back side (Fig. S8b†). Such
a difference in PL spectra between front and back excitations
suggests that the large-n (close to N) phases locate at the upper
surface of the lm whereas the small-n phases are situated at
the bottom of the lm near the substrate, which is also reported
in previous studies.12,28,30,31 This analysis further supports the
notion that Q-2D perovskite lms are a mixture of multiple
phases with different n values. The absorbance onset of these
lms is located at #800 nm and undergoes a blue shi at
a higher BA spacer concentration (Fig. S9a†). Similarly, the BA0
unary spacer lm shows a PL peak at 779 nm, and the PL peak
gradually shis to 773 nm when the BA spacer content is
increased to 30% (Fig. 3b). This blue shi can be possibly
attributed to a slightly larger bandgap of the BA2MA3Pb4I13 lm
than that of its PEA counterpart (Fig. S9b†). In the steady-state
PL spectra, the BA0 unary spacer lm presents the strongest PL
signal among all samples and the introduction of a BA spacer
signicantly lowers PL intensities, indicating a BA-doping-
induced more efficient charge transfer process from Q-2D

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Fig. 3 Absorbance spectra (a), steady-state photoluminescence (PL) spectra excited from the front side (b) and time-resolved PL spectra (c) of
(PEA1!xBAx)2MA3Pb4I13 binary spacer films coated on PTAA substrates. (d) Trap density and hole mobility of (PEA1!xBAx)2MA3Pb4I13 binary spacer
films.
perovskites to poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine)
(PTAA). In order to further quantitatively compare the charge
transfer dynamics, the time-resolved PL spectra of these lms
are recorded and tted to a bi-exponential function in Fig. 3c,
and the corresponding tting parameters are summarized in
Table S1.† A fast decay lifetime (s1 ¼ 7.29 ns) and a slow one (s2
¼ 432 ns) are obtained in the case of the BA0 unary spacer lm,
yielding an average lifetime (save) of 283 ns. As expected, the
incorporation of a BA spacer from 0% to 30% leads to
a continuous decrease of save from 283 to 50.4 ns, further
underpinning the notion that the addition of a BA spacer
facilitates the transfer of photo-induce carriers from Q-2D
perovskites into PTAA. Such a faster charge-transfer process is
helpful for suppression of charge recombination at the
perovskite/PTAA interface.
According to the space charge-limited current (SCLC)
model,32,33 the trap density and hole mobility of (PEA1!xBAx)2-
MA3Pb4I13 binary spacer lms with the structure of ITO/PTAA/
Q-2D perovskite/Au are calculated (details in the ESI†) from
the dark current–voltage characteristics in Fig. S10,† where we
observe an ohmic response (red line) and a SCLC response
(green line) as well as a trap-lled limited region in between.
With the addition of the BA spacer, the trap density undergoes
a slight decrease from 3.25 % 1015 to 2.90 % 1015 cm!3 with the
lowest value at x ¼ 0.2 (Fig. 3d), which is comparable to the
excellent reported values of 1.31 to 2.78 % 1015 cm!3 in unary
BA counterparts.17 Furthermore, the incorporation of a BA
spacer enables the hole mobility to increase to a peak value of
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4.15 % 10!3 cm2 V!1 s!1 at x ¼ 0.2 from 3.15 % 10!3 cm2 V!1 s!1
at x ¼ 0. Evidently, the binary spacer lm with 20% BA displays
the lowest trap density and highest hole mobility among all
samples, which is ascribed to the superior surface morphology
and preferable vertical orientation of crystals.
The photovoltaic performance of these binary spacer Q-2D
perovskite lms is investigated in the following architecture
ITO/PTAA/perovskite/[6,6]-phenyl-C61-butyric acid methyl ester
(PCBM)/bathocuproine (BCP)/Ag (Fig. S11†), and the current
density–voltage (J–V) curves of the most representative devices
(close to average results) measured under AM 1.5 illumination
conditions are depicted in Fig. 4a. Photovoltaic parameters and
the corresponding statistical distributions are summarized in
Table 1 and Fig. S12,† respectively. BA0 based unary spacer devices
exhibit a Jsc of 13.7 mA cm!2, a Voc of 1.13 V, and a ll factor (FF) of
60.5%, yielding a PCE of 9.37%. Obviously, the introduction of
a BA spacer signicantly improves the device performance
parameters, and a peak PCE of 15.1% along with a Jsc of 18.5 mA
cm!2, a Voc of 1.19 V and an FF of 68.8% is achieved in BA0.2 based
binary spacer cells. Further increasing the BA spacer concentra-
tion to 30% results in reduced performance parameters (Jsc ¼ 15.2
mA cm!2, Voc ¼ 1.14 V, FF ¼ 62.1% and PCE ¼ 10.8%), which still
outperform those of BA0 based unary spacer cells. The signicant
enhancement in BA-containing binary spacer device performance
parameters can be attributed to the superior lm surface quality
and preferable vertical orientation of crystals as well as improved
optoelectronic properties with regard to charge transfer dynamics,
trap density and hole mobility.
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Fig. 4 (a) J–V characteristics of Q-2D perovskite devices with different active layers under AM 1.5G solar irradiation. (b) External quantum
efficiency (EQE) spectra and integrated Jsc of devices with different active layers. (c) J–V curve of the (PEA0.8BA0.2)2MA3Pb4I13 based champion
device under AM 1.5G solar irradiation. (d) Steady measurement at the maximum power output point.

The external quantum efficiency (EQE) curves and integrated
Jsc of solar cells with different active layers are illustrated in
Fig. 4b. The integrated Jsc is determined to be 13.4, 15.4, 18.3
and 15.1 mA cm!2 for BA0, BA0.1, BA0.2 and BA0.3 based devices,
respectively, in good accordance with that obtained from J–V
curves. According to statistical analysis of PCE (Fig. S12d†), the
BA0.2 binary spacer champion device yields a Jsc of 18.7 mA
cm!2, a Voc of 1.20 V, an FF of 70.0% and a PCE of 15.7%, which
are extracted from Fig. 4c. This efficiency value signicantly
outperforms the PCE record (12–14%) for unary spacer (PEA or
BA) Q-2D perovskite (n # 5) devices.17,21,34 It is also notable that
no evident hysteresis of J–V characteristics is viewed for the
BA0.2 device in the forward and reverse scan directions
(Fig. S13†). In addition, we also record the stabilized photo-
current and efficiency at the maximum power output point
(Fig. 4d), and the photocurrent maintains constant under
continuous illumination, producing a stable PCE of 15.2%.
Moreover, BA0.2 based binary spacer devices demonstrate
a high Voc with an average value of 1.19 V as shown in Fig.-
S12b,† and the peak value approaches 1.21 V as extracted from
the J–V curve in Fig. 5a. This value is among the highest re-
ported Voc obtained for Q-2D perovskite solar cells21,23 and is
comparable to the 1.21–1.24 V record for 3D perovskite (with
a bandgap of #1.6 eV) devices.35–37 Surprisingly, the loss-in-
potential (difference between the bandgap and Voc) is merely
0.39 V, implying extremely small non-radiative recombination
losses in BA0.2 binary spacer cells. The non-radiative recombi-
nation losses (DVoc) can be related to the EQE of a light-emitting
diode (LED) employing the following equation DVoc ¼ !kT %
ln(EQE)/q, where k is the Boltzmann constant, T denotes the
temperature, and q represents the elementary charge.36,38 When
the BA0.2 based binary spacer device is operated as an LED at an
input bias of 2 V, the corresponding bright red emission is
observed (inset of Fig. 5a). Moreover, we achieve an EQE value of
2.4% at an injected current density equal to Jsc (Fig. S14b†),
leading to a DVoc of #100 mV, which is the smallest reported
DVoc for Q-2D perovskite cells.35,36
In order to better comprehend the charge recombination
process of devices with unary or binary spacers, we chose BA0
and BA0.2 based devices for comparison and then carried out

Table 1 Summary of photovoltaic parameters of Q-2D perovskite solar cells. Each value stands for the average of 20 cells

Active layer Jsc [mA cm!2] Voc [V] FF [%] PCE [%]

PEA2MA3Pb4I13 13.7 & 0.3 1.13 & 0.02 60.5 & 1.5 9.37 & 0.8
(PEA0.9BA0.1)2MA3Pb4I13 15.6 & 0.4 1.16 & 0.02 66.2 & 2.0 12.0 & 0.7
(PEA0.8BA0.2)2MA3Pb4I13 18.5 & 0.3 1.19 & 0.02 68.8 & 2.0 15.1 & 0.6
(PEA0.7BA0.3)2MA3Pb4I13 15.2 & 0.3 1.14 & 0.02 62.1 & 1.5 10.8 & 0.8

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Fig. 5 (a) J–V curve of the (PEA0.8BA0.2)2MA3Pb4I13 based device with the maximum Voc, and the device works as an LED at a bias of 2 V and emits
bright red light (inset). (b) Jsc and (c) Voc of devices without and with a BA spacer as a function of light intensity. (d) Normalized transient
photovoltage decay and (e) Nyquist plots of devices without and with a BA spacer. (f) Stability test of Q-2D perovskite solar cells stored in ambient
air with 40–50% relative humidity.
several kinds of characterization including light dependent Voc
and Jsc measurements, transient photovoltage measurement
(TPV) and electrochemical impedance spectroscopy (EIS).
Fig. 5b depicts a power-law relationship between Jsc and light
intensity (Jsc f Ia), where a close to 1 expresses a solar cell
without space charge limit effects, whereas a ¼ 0.75 implies
that the device is space charge limited owing to a carrier
imbalance.39,40 A similar a value of 0.958 and 0.970 is acquired
for BA0 and BA0.2 based devices, respectively, manifesting that
both devices suffer from negligible space charge limit effects.
Furthermore, light dependent Voc can provide important
information on the recombination mechanism of devices. The
dominant occurrence of trap-assisted recombination predicts
that the natural logarithmic relationship between light intensity
and Voc has a slope of 2kT/q, while a trap-free relationship
delivers a slope of kT/q.41,42 Clearly, the slope of Voc versus the
natural logarithm of light intensity decreases from 1.63kT/q to
1.33kT/q when 20% BA organic spacer is introduced into the
PEA2MA3Pb4I13 structure (Fig. 5c). This result indicates that
trap-assisted charge recombination can be more effectively
suppressed with the addition of a BA spacer, in good agreement
with the lower trap density of the BA0.2 binary spacer lm as
observed in Fig. 3d.
Besides, the charge recombination lifetime can be extracted
from the transient photovoltage decay curves,40,43 and the
comparison of photovoltage transients of BA0 and BA0.2 based
devices is shown in Fig. 5d. The BA0 unary spacer device
demonstrates a charge recombination lifetime of 363 ms, which
increases #4 fold in the BA0.2 based binary spacer cell, sug-
gesting lower charge recombination losses in binary spacer
devices. To further evaluate the charge recombination
dynamics, we compare the EIS results of unary and binary
spacer devices. Fig. 5e presents the Nyquist plots of devices
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measured in the frequency range from 1 MHz to 1 Hz in the
dark. Generally, the small arc in the high-frequency region is
mainly attributed to the charge transfer process between
perovskites and select contacts with two typical impedance
parameters of charge contact resistance (Rcon) and capacitance
(C1), while the large arc in the low-frequency range corresponds
to the recombination process described by the recombination
resistance (Rrec) and chemical capacitance (C2).40,44,45 Obviously,
the BA0.2 binary spacer device has a larger Rrec than the BA0
unary spacer cell, manifesting that a stronger recombination
process exists in the BA0 based device. Overall, we observe
signicantly decreased charge recombination losses in BA-
containing binary spacer devices according to the light depen-
dent Voc, TPV and EIS results, and such low charge recombi-
nation losses can certainly contribute to signicant
improvements of BA-containing binary spacer device
performance.
Additionally, we investigate the stability of BA0 and BA0.2
based devices in ambient air with 40–50% relative humidity,
and the corresponding normalized PCEs are shown in Fig. 5f.
Aer storing for 30 days, both unsealed BA0 and BA0.2 based
cells show excellent ambient stability, retaining 81% and 88%
of their initial efficiency, respectively. These results are close to
the recent stability measurements reported in Q-2D perovskite
solar cells,12,17,18 supporting the excellent environmental toler-
ance of Q-2D perovskite devices.
3 Conclusion
In summary, for the rst time, we have successfully designed
and fabricated vertically oriented (PEA1!xBAx)2MA3Pb4I13 (x #
0.3) binary organic spacer Q-2D perovskite thin lms, and we
nd that both the surface quality of the perovskite lm and the
J. Mater. Chem. A, 2019, 7, 9542–9549 | 9547

Journal of Materials Chemistry A
vertical orientation of crystals are signicantly enhanced by the
incorporation of binary organic spacer PEA–BA. Meanwhile, the
binary spacer perovskite lms exhibit remarkable improve-
ments of optoelectronic properties with respect to charge
transfer dynamics, trap density and hole mobility. The excellent
lm quality and optoelectronic properties lead to an average
PCE of 15.1% in (PEA0.8BA0.2)2MA3Pb4I13 binary spacer devices
with a maximum value of 15.7%. This value exceeds the effi-
Published on 27 March 2019. Downloaded by National University of Kaohsiung on 8/2/2022 3:12:31 AM.
ciency record (12–14%) for unary spacer (PEA or BA) Q-2D
perovskite devices. More importantly, a peak Voc of 1.21 V cor-
responding to a loss-in-potential of 0.39 V is also obtained,
yielding a non-radiative recombination loss of #100 mV, which
is the smallest reported loss value for Q-2D perovskite devices.
In addition, the introduction of binary spacer PEA–BA effec-
tively decreases the device recombination losses, further sup-
porting signicant enhancements of binary spacer device
performance. Our ndings provide an effective organic spacer
design strategy which is promising to develop stable and effi-
cient Q-2D perovskite materials and devices.
Conflicts of interest
The authors declare no competing nancial interest.
Acknowledgements
This work was nancially supported by the National Key
Research and Development Project funding from the Ministry
of Science and Technology of China (Grants No.
2016YFA0202400 and 2016YFA0202404), the Peacock Team
Project funding from the Shenzhen Science and Technology
Innovation Committee (Grant No. KQTD2015033110182370),
and the Fundamental Research Project funding from the
Shenzhen Science and Technology Innovation Committee
(Grant No. JCYJ20170412154554048).
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