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Inorganic lead-free antimony-based perovskite-

Cite this: J. Mater. Chem. C, 2021,
9, 15301
inspired solar cells with a carbon electrode and
green anti-solvent regulation†
Jun Zhou, Fei Zhao, Junhao Shen, Yang Zhou, Yuyao Wu, Yixin Guo,*
Jinchun Jiang * and Junhao Chu

The emergence of inorganic antimony (Sb)-based perovskite-inspired solar cells simultaneously

Received 17th August 2021,
Accepted 9th October 2021
DOI: 10.1039/d1tc03885k
rsc.li/materials-c
overcomes the poor stability and toxicity of lead (Pb)-based perovskite solar cells. However, in addition
to reducing the toxicity of the device itself, further reducing the toxicity in the preparation process is
also a necessary condition for commercialization. Herein, different anti-solvents have been used to
precisely regulate the nucleation process and improve the quality of the films. Among them, the film
with green anisole as a novel anti-solvent shows a dense surface morphology with good crystallinity and
presents better light absorption. As a reward, the power conversion efficiency (PCE) of the champion
device can reach 2.07% with low-cost carbon electrodes, which is improved by 470% in comparison
with 0.44% for the control device without anti-solvent, and it is one of the top values for inorganic
antimony (Sb)-based perovskite-inspired solar cells. In addition, the device exhibits good thermal and air
stability without humidity control. This work will provide a new way to prepare highly efficient lead-free
antimony-based perovskite-inspired solar cells.

Introduction
In recent years, perovskite solar cells have received widespread
attention due to their low cost, simple fabrication process and
excellent performance. The champion PCE has increased from
3.8% to more than 25.2% now.1–3 However, most high-efficient
perovskite solar cells have organic cations, which will result in
relatively poor thermal stability. In addition, the toxicity of Pb
in perovskite solar cells can cause environmental pollution and
hinder the commercialization process of perovskite solar
cells.4–8 Therefore, research on inorganic lead-free perovskite
solar cells is very urgently required.
Some lead-free perovskite materials have already been stu-
died. The divalent tin cation (Sn2+) has similarity with the
divalent lead cation (Pb2+) in terms of size and valence shell,9
so Sn can be used to fabricate perovskite films instead of Pb.
But Sn2+ can be easily oxidized to Sn4+ in an atmospheric
environment. This will result in increased film defects and
decreased device efficiency.10 Except for metastable Sn2+,
School of Physics and Electronic Science, East China Normal University, Shanghai
200241, China. E-mail: yxguo@ee.ecnu.edu.cn, jcjiang@ee.ecnu.edu.cn
† Electronic supplementary information (ESI) available: Reaction of anti-solvents
and precursor solutions; cross-sectional SEM image of Sb-based perovskite-
inspired solar cells; J–V curves, champion and statistical performance parameters
of Sb-based perovskite-inspired solar cells using different solvents; plot of dJ/dV
vs. V; and thermal stability. See DOI: 10.1039/d1tc03885k
trivalent antimony and bismuth cations (Sb3+ and Bi3+) also
have similar electronic configurations to Pb2+ and are not easily
oxidized in an atmospheric environment.11,12 Therefore, sub-
stitution of Pb-based perovskites with inorganic Sb-based or Bi-
based perovskite-inspired materials may be a better choice to
overcome the poor stability and toxicity of Pb-based perovskite
solar cells.
It is known that Sb-based perovskite derivatives will form
two different structures (0D and 2D structures) under different
preparation conditions.13,14 Regarding the A–Sb–XS structure,
the perovskite-inspired materials formed by combining Sb2X93
and Cs+ will form a 2D structure through treatment at a
temperature of Z230 1C.15 Compared to 0D structural inor-
ganic perovskite-inspired materials, the 2D structure of the
perovskite-inspired materials has a smaller optical band gap
and a lower exciton binding energy, and the photovoltaic
performance of the corresponding device is better.14,15
Peng et al.16 explored the comparative experiment of 2D-
Cs3Sb2ClxI9x and 0D-Cs3Sb2I9, and found that 2D-
Cs3Sb2ClxI9x has a smaller direct optical band gap (2.05 eV).
Besides, chloride incorporation promotes larger grain growth,
and passivates deep level electronic defects within the grains.17
After 2D-Cs3Sb2ClxI9x is integrated into the device, the photo-
voltaic performance is also greatly increased. Mei et al.11
explored the comparative experiment of 2D-Cs3Sb2ClxI9x and
2D-Rb3Sb2I9. The direct optical band gap of 2D-Rb3Sb2I9 was

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obtained as 2.24 eV, which is closer to the direct optical band
gap14 of 0D-Cs3Sb2I9. In addition, the inorganic structure has
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thermodynamic advantages compared to 2D-MA3Sb2ClxI9x.19
At present, the performance of Sb-based perovskite-inspired
solar cells is relatively limited.20 It is well known that the
preparation of high-quality perovskite films is important to
achieve high-performance perovskite solar cells. The anti-
solvent assisted crystallization method is one of the methods
that improve the quality of the film. The anti-solvent crystal-
lization technology was originally widely used in the pharma-
ceutical industry.21 The solute in the original solvent becomes
relatively insoluble by adding an anti-solvent, thereby precipi-
tating the drug. Similarly, when the anti-solvent is added to the
perovskite layer, the solubility of the precursor solution is
reduced, so that the solute is quickly separated from the
solution to form a high coverage and a smooth dense film.
Therefore, the anti-solvent-assisted crystallization method is
explored to prepare high-quality films.22–25 The suitable choice
of anti-solvent is very important to determine whether a highly
uniform, pinhole-free perovskite film can be produced. So far,
anti-solvent engineering has been widely used in the prepara-
tion of Pb-based perovskite solar cells. For instance, Zheng
et al.26 used toluene as an anti-solvent to fabricate Pb-based
perovskite solar cells with a PCE of 8.29%. Jin et al.27 used a
mixed anti-solvent of phthalocyanine nickel and chlorobenzene
to prepare Pb-based perovskite solar cells and achieved a PCE of
19.18%. Liu et al.28 used o-dichlorobenzene (o-PhCl2) as an anti-
solvent to prepare Pb-based perovskite solar cells with a PCE of
20.72%.
Several attempts have also been made towards anti-solvents
in inorganic antimony-based perovskite-inspired solar cells and
some achievements have been achieved. Umar et al.29 used
isopropyl alcohol as an anti-solvent to prepare Sb-based inor-
ganic perovskite-inspired solar cells with a structure of FTO/
TiO2/Cs3Sb2I9/Au and achieved a PCE of 1.21%. Peng et al.15
used toluene as an anti-solvent to fabricate antimony-based
inorganic perovskite-inspired solar cells with a structure of
FTO/TiO2/Cs3Sb2ClxI9x/LZ-HTL-1-1/Au, and achieved a PCE of
2.15%. However, some anti-solvents such as toluene and chlor-
obenzene have certain toxicity, especially chlorobenzene, which
does serious harm to the soil, atmosphere and drinking
water.30–34 Besides, Sb-based perovskite derivatives already
Fig. 1 Process flow of Cs3Sb2ClxI9x film fabrication with anti-solvent regulation.
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offer a concrete opportunity for commercialization as absorbers
for indoor photovoltaics, and this situation requires the
research community to urgently address the toxicity issues
associated with their preparation processing.16 With the appli-
cation of green anti-solvents, the impact of the preparation
method on the environmental pollution will be minimized.35,36
Here, we report a facile strategy to improve the quality of
Cs3Sb2ClxI9x perovskite-inspired films using a green anti-
solvent assisted method. And given the remaining toxicity in
the precursor solution, such as dimethylformamide, further
work is still underway to completely solve the toxicity in the
whole solution preparation process. Compared to the film with
chlorobenzene or isopropyl alcohol as an anti-solvent, the film
with green anisole as an anti-solvent shows a denser surface
morphology with better crystallinity and presents better light
absorption. In order to decrease the consumption of the whole
device preparation process, low-cost carbon-based devices were
assembled with a structure of FTO/Nb2O5/Cs3Sb2ClxI9x/P3HT/
carbon. The champion device with anisole as a green anti-
solvent has a relatively high PCE of 2.07%. This is much
superior to Sb-based perovskite-inspired solar cells prepared
with chlorobenzene or isopropyl alcohol as an anti-solvent.
This inorganic Sb-based device also shows good stability under
long-term storage and heating conditions.
Results and discussion
As shown in Fig. S1 (ESI†), the situation about adding the anti-
solvent at different times has been taken into account and the
optimized drop-time has been obtained. The process of fabri-
cating an Sb-based perovskite-inspired film with an anti-solvent
is shown in Fig. 1. The anti-solvent assisted method can
efficiently improve the nuclear process and heighten the final
film surface. The method of High Temperature Vapor Anneal-
ing (HTVA) is introduced in the annealing step.18 The melting
point of SbI3 is relatively low (170 1C at atmospheric pressure),
and its gas pressure is considerable at temperatures above
200 1C.37,38 Therefore, SbI3 in the gas phase (Z200 1C) can
prevent the Cs3Sb2ClxI9x film from losing SbI3.18,39 In order to
further explore the effects of the various anti-solvents on the
morphologies of the perovskite-inspired films, the surface
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Fig. 2 SEM images of Cs3Sb2ClxI9x films using (a) anisole, (b) isopropyl alcohol, and (c) chlorobenzene as anti-solvents and (d) without an anti-solvent
before annealing. SEM images of Cs3Sb2ClxI9x films using (e) anisole, (f) isopropyl alcohol, and (g) chlorobenzene as anti-solvents and (h) without an anti-
solvent after annealing on Nb2O5/FTO.
morphologies of Cs3Sb2ClxI9x perovskite-inspired films with
anisole, isopropyl alcohol and chlorobenzene as anti-solvents
were studied. SEM images of the corresponding films before
annealing are shown in Fig. 2(a–c). Except for the film made by
anisole, the films made by other anti-solvents have shown
various degrees of voids before annealing. After annealing,
the same phenomenon can also be observed, and the film
prepared using anisole shows the best film quality with better
crystallinity and compact surface (as shown in Fig. 2(e–g)).40,41
Micron-sized voids are formed on the surface of the film
without adding an anti-solvent, which severely reduces the
carrier transport ability (as shown in Fig. 2(d) and (h)).
XRD patterns were measured to study the crystal structures
of Cs3Sb2ClxI9x films prepared using different anti-solvents.
The main peaks of the films fabricated with several different
anti-solvents were at around 25.81, 30.01 and 42.71 (as shown in
Fig. 3(a)), which correspond to the (201), (022) and (220) planes
of the 2D Cs3Sb2ClxI9x perovskite-inspired structure.15 The
XRD peak of the (201) plane in the Cs3Sb2ClxI9x film with
anisole is much greater than that of isopropyl alcohol or
chlorobenzene. This result suggests that the use of anisole
can effectively increase the crystalline of the Cs3Sb2ClxI9x film
and offer more efficient charge collection in the final device. PL
spectra were further recorded to study the photogenerated
carrier recombination process in Cs3Sb2ClxI9x films with
different anti-solvents. The Cs3Sb2ClxI9x film fabricated using
anisole shows the best PL intensity, which indicates that the
film has the least non-radiative recombination and the best
film quality (as shown in Fig. 3(b)).11,42 The PL spectrum of
Cs3Sb2ClxI9x prepared using anisole is deconvolved into three
Gaussian bands (as shown in Fig. 3(c)). The three emission
peaks are respectively at 1.40 eV, 1.72 eV and 1.99 eV. The three
peaks respectively correspond to defect-assisted emission, STE
Emission and band edge emission. STE emission dominates
the PL spectra. The band edge emission and defect-assisted
emission are auxiliary pathways. Different recombination path-
ways for excitons are shown in Fig. 3(d).43,44 The absorption
spectra of perovskite-inspired films prepared using different
anti-solvents are also presented in Fig. 3(e). It can be observed
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that the Cs3Sb2ClxI9x film with anisole as the anti-solvent has
the highest absorption intensity, which can improve the light
utilization rate. Therefore, the short current density ( JSC) of the
devices made using anisole will also increase. In addition, the
initial absorption wavelength of all films is about 600 nm with a
calculated bandgap of 2.07 eV (as seen in Fig. 3(f)). The band
gap value is close to the value reported by the relevant literature
(2.05 eV).15 The slight difference in band gap values may be
attributed to the different contents of chlorine in the
Cs3Sb2I9xClx film, as reported by Paul et al.17 Moreover, the
best bandgap of semiconductor materials suitable for indoor
light collection is around 1.9 eV, which indicates the potential
of Sb-based perovskite-inspired materials in indoor photovol-
taic applications.16,45
The schematic structure and cross-sectional SEM image of
perovskite-inspired solar cells are respectively shown in
Fig. 4(a) and Fig. S2 (ESI†). The champion J–V curves and
characteristics of perovskite-inspired solar cells prepared using
different anti-solvents are presented in Table 1 and Fig. 4(b).
The Cs3Sb2ClxI9x solar cell without an anti-solvent has a
relatively low PCE of 0.44% with an open circuit voltage (VOC)
of 0.77 V, a JSC of 1.14 mA cm2 and a fill factor (FF) of 0.51 (as
shown in Table 1). When a Cs3Sb2ClxI9x film was fabricated
using chlorobenzene as the anti-solvent, the JSC of the device
significantly increases to 3.18 mA cm2 and the PCE increases
to 0.44%. When the anti-solvent is replaced with isopropyl
alcohol, the JSC and PCE can increase to 3.92 mA cm2 and
1.48%, respectively. Furthermore, the device with anisole as an
anti-solvent could result in the highest VOC value of 0.84 and
the FF has also increased to 0.55, presumably due to the
enhanced film quality of the anisole treated Cs3Sb2ClxI9x film.
In addition, a comparative experiment with DMF and DMSO as
solvents was also carried out, and the measurement results are
shown in Table S1 (ESI†). The results have proved that the
performance of the devices prepared using DMF as the solvent
is better. The J–V curves and statistical characteristics are
respectively shown in Fig. S3 and S4 (ESI†). Therefore, a
relatively high PCE of 2.07% can be achieved. Compared with
a champion PCE of Cs3Sb2ClxI9x solar cells reported by
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Fig. 3 (a) X-Ray diffraction patterns of Cs3Sb2ClxI9x films fabricated using different anti-solvents. (b) PL spectra of Cs3Sb2ClxI9x films prepared with
different anti-solvents on Nb2O5/FTO. (c) Deconvolved band representation of Cs3Sb2ClxI9x prepared by anisole. (d) Recombination pathways.11 FE: free
exciton; GS: ground state; IBE: impurity-bound exciton; STE: self-trapped exciton; A: photo-excitation; B: band edge emission; C: phonon-assisted
indirect transition; D: STE emission; and E: defect-assisted emission; (e) UV-vis absorption spectra of the Cs3Sb2ClxI9x films prepared using different
anti-solvents. (f) Band gap of the Cs3Sb2ClxI9x film.

Peng et al.16 (2.15%) and Paul et al.17 (2.2%), our result shows a
little PCE loss due to the minimum JSC, as seen in Table 2. The
JSC loss can be mainly attributed to the decreased optical
reflection when a low-cost carbon electrode was used to replace
the metal electrode. Thus, further work still needs to be carried
out to improve the PCE of carbon based Cs3Sb2ClxI9x solar
cells by increasing the optical reflection between the light-
absorber layer and the carbon electrode.
Shunt conductance (G) is an important parameter for mea-
suring the absorber layer film quality in solar cells. The
corresponding G can be calculated according to the
relationship between the output current (J) and output voltage
(V) of thin-film solar cells:46
h q i
J ¼ J0 exp ðV  JRÞ þ GV  JL
AkT
where the leakage current density and diode ideal factor are
respectively represented by J0 and A; JL represents the photo-
current density; the series resistance and parallel resistance are
represented by R and 1/G, respectively; q represents the amount
of charge of the electron; k and T are respectively represented by
a Boltzmann constant and thermodynamic temperature. Fig. S5

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Fig. 4 (a) Schematic representation of the device structure. (b) J–V curves of perovskite-like solar cells fabricated using different anti-solvents. (c) EQE
spectra of the perovskite-like solar cells with different anti-solvents. (d) Statistical photovoltaic parameters of perovskite-like solar cells with different
anti-solvents.

Table 1 Performance parameters of Cs3Sb2ClxI9x solar cells with different anti-solvents

Sample VOC (V) JSC (mA cm2) FF (%) PCE (%)

a
Anisole 0.84(0.84  0.02) 4.47(4.20  0.27) 55.20(54.45  1.33) 2.07(1.91  0.13)
Isopropyl alcohol 0.79(0.77  0.03) 3.92(3.59  0.31) 47.70(46.48  2.61) 1.48(1.28  0.12)
Chlorobenzene 0.78(0.77  0.02) 3.18(2.81  0.20) 41.15(42.18  1.41) 1.03(0.91  0.07)
Without an anti-solvent 0.77(0.73  0.03) 1.14(1.05  0.18) 51.39(45.63  6.40) 0.44(0.35  0.07)
a
Statistical performance from 10 individual devices.

(ESI†) shows the value of G and the device with anisole as an fabricated using anisole exhibits a higher integrated current
anti-solvent shows the lowest G value, indicating superior density than devices prepared using other anti-solvents, which
device performance. The IPCE spectra of the devices with is in accordance with J–V results. In order to evaluate the
different anti-solvents are shown in Fig. 4(c). The device reproducibility, the statistical characteristics of the devices of

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Table 2 A summary of the performance parameters of Cs3Sb2ClxI9x
solar cells
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VOC JSC PCE
Structure (V) (mA cm2) (%) Ref.
FTO/TiO2/Cs3Sb2ClxI9x/LZ-HTL-1-1/Au 0.60 6.46 2.15 16
ITO/PEDOT:PSS/Cs3Sb2ClxI9x/PCBM/Al 0.72 6.39 2.2 17
FTO/Nb2O5/Cs3Sb2ClxI9x/P3HT/C 0.84 4.47 2.07 Our work
the perovskite-inspired absorber layer prepared using different
anti-solvents were measured and are shown in Table 1 and
Fig. 4(d). The devices using anisole as the anti-solvent film
showed significantly improved J–V parameters with an average
PCE of 1.91%, which is much higher than the devices fabri-
cated using other anti-solvents. J–V curves of forward and
reverse scans are shown in Fig. S6 (ESI†). The device exhibits
a measure of hysteresis, which may be due to the unbalanced
carrier extraction in a planar device structure.
The Nyquist spectrum of the device is shown in Fig. 5(a). The
semi-circular shape shown in the figure is reported as a typical p–n
junction.45 It can be seen from Table 3 that the Rrec value of the
device prepared with anisole is the highest, followed by isopropyl
alcohol, and that of chlorobenzene is the lowest. A higher Rrec value
indicates less recombination across the circuit. The use of anisole
greatly reduces the carrier recombination ability, and therefore the
PCE of the device was greatly improved. Fig. 5(b) shows the long-
term stability measured at room temperature without controlling
the environmental humidity. The PCE of the device fabricated
without anti-solvents decreased quickly while the PCE of the device
fabricated with anisole only decreased by 25% in the past 240 hours,
which showed good air stability on the contrary. The thermal
stability of the corresponding device has also been tested by heating
for 7 hours at 100 1C continuously. As shown in Fig. S7 (ESI†), the
efficiency of the device prepared using anisole can be maintained
above 93%, which also shows good thermal stability.
Conclusions
In summary, we have conducted a detailed strategy to control
the fabrication process of a Cs3Sb2ClxI9x film and improve the
Fig. 5 (a) Impedance spectra of Sb-based perovskite-like solar cells prepared with different kinds of anti-solvents under dark conditions. (b) Long-term
stability of the corresponding devices.
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Table 3 The value of series resistance (Rs) and recombination resistance
(Rrec) obtained by equivalent circuit fitting
Anisole Isopropyl alcohol Chlorobenzene
Rs (O) 67.84 66.21 58.91
Rrec (O) 1683.0 748.1 637.3
corresponding device performance. In order to improve the
quality of the film, the influence of different anti-solvents on
film formation was explored. Compared with other commonly
used anti-solvents, the film prepared using anisole has better
crystalline quality, denser surface morphology and inhibited
recombination possibility, which improve the carrier transport
ability and the final PCE of the perovskite-inspired solar cell.
With low-cost carbon as the electrode, a champion PCE of
2.07% can be obtained with good device air/thermal stability. In
conclusion, this work proposed a simple, green and repeatable
method for the fabrication of Pb-free perovskite or perovskite-
inspired films, and their photovoltaic devices.
Experimental
Materials
All chemicals were used as received without further purifica-
tion. CsI (99.9%), SbI3 (98%) and SbCl3 (99.95%) were bought
from Sigma-Aldrich. N,N-Dimethylformamide (DMF) (99.8%)
was purchased from Alfa Aesar. Anisole (99%), isopropyl alco-
hol (IPA) (99.5%) and chlorobenzene (99%) were purchased
from MACKLIN. P3HT (Mw 100 000) and carbon paste (MTW-
CE-C-003) were respectively brought from Sigma-Aldrich and
Shanghai MaterWin New Materials Co., Ltd.
Cs3Sb2ClxI9x film deposition
Firstly, CsI (0.75 M), SbI3 (0.25 M) and SbCl3 (0.3125 M) were
mixed in DMF and stirred at 70 1C for 3 hours then filtered.
Next, the precursor solution was dripped onto a substrate and
spin-coated for 30 s at 3000 rpm. About 8 seconds after the start
of spin coating, 65 mL of chlorobenzene, isopropyl alcohol and
anisole were dispensed on the substrates. Then, the samples
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were moved to a closed glass jar containing 10 mL of SbI3 DMF
solution and annealed for 10 minutes at 240 1C.
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Solar cell device fabrication
Firstly, a glass substrate with FTO was sonicated in deionized
water, acetone, isopropyl alcohol, ethanol and deionized water
for 15 minutes. Then, the substrate was treated with UV-ozone
for 10 minutes. Next, Nb2O5 films were sputtered from a Nb2O5
ceramic target (Jiangxi Ketai Advanced Materials, 99%) with
5  104 Pa base pressure. A radio frequency magnetron
sputtering system (Beijing Technol Science, JCP-450) was used
for deposition with 150 W RF power and 0.2 Pa work pressure.47
Next, the prepared substrates were annealed at 500 1C for
30 min. After the substrates were cooled down, the substrates
were treated with UV-ozone for 10 minutes. The substrates were
transferred to a nitrogen-filled glove box to deposit perovskite-
inspired films. Then, the hole transport layer was prepared by
using the configured P3HT solution (6 mg mL1 chlorobenzene
solution) on the sample at 3000 rpm for 60 s. Finally, carbon
paste was screen printed and annealed on a heating stage at
120 1C for 15 min. The active area of the fabricated device is
0.09 cm2.
Characterization
The X-ray diffraction (XRD) patterns of the perovskite-inspired
films fabricated using different anti-solvents were recorded
with CuKa radiation using an X-ray diffractometer (Bruker D8
Advance). The optical properties of the films in the wavelength
range of 300–800 nm were measured using an ultraviolet-
visible-near infrared spectrophotometer (Cary5000). The photo-
luminescence (PL) spectrum of the films was recorded using a
fluorescence spectrophotometer (LabRAM HR 800 UV) with an
excitation source of 532 nm. The electron microscopy image of
the films was obtained using a field emission scanning electron
microscope (Hitachi S-4800). The current density–voltage ( J–V)
characteristics of photovoltaic devices were measured under
AM 1.5G simulated solar illumination (100 mW cm2) using a
Keithley 2400 digital source meter. The J–V measurement speed
is 100 mV s1, and the scanning direction is reverse. Consider-
ing the uncertainty of the experimental apparatus, the mea-
sured VOC, JSC, and PCE values may have a certain error.
Therefore, performance parameters from the calibrated solar
cells are given in Table S2 (ESI†) to reflect the possible uncer-
tainty. The incident photon-to-current conversion efficiency
(IPCE) system (TLS1509, Zolix) was used to acquire the external
quantum efficiency (EQE) of various perovskite-inspired solar
cells in AC mode. The electrochemical impedance spectra were
recorded using an electrochemical workstation (EC-lab, Bio-
Logic VMP3) with AC perturbation at 0.8 V under dark
conditions.
Conflicts of interest
There are no conflicts to declare.
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Acknowledgements
This work was supported by the Major State Basic Research
Development Program of China (No. 2013C B922300).
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