Nano Energy 63 (2019) 103867

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Adduct phases induced controlled crystallization for mixed-cation T

perovskite solar cells with efficiency over 21%
Min Wang, Fengren Cao, Kaimo Deng*, Liang Li*
School of Physical Science and Technology, Jiangsu Key Laboratory of Thin Films, Center for Energy Conversion Materials & Physics (CECMP), Soochow University,
Suzhou, 215006, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Organic-inorganic perovskite solar cells have attracted extensive attentions due to the advantages such as high
Perovskite solar cells power conversion efficiency and easy fabrication over other counterparts. Mixed-cation perovskite is considered
Adduct phase as one of the most efficient light absorbers for perovskite solar cells and the device performance has a close
Solvent engineering connection to the quality of the perovskite thin film. Herein, we systematically investigate the influence of
Crystallization
adduct phase in the mixed-cation perovskite precursor film on the crystallization of the perovskite. By tuning the
adduct phase through solvent engineering, we successfully optimize the morphology and optoelectronic prop-
erties of the perovskite film and the planar-type perovskite solar cells with a power conversion efficiency over
21% can be achieved. Our work provides an effective method to control the growth of the mixed-cation per-
ovskite film and thus boost the device performance with enhanced efficiency and stability.

1. Introduction
Organic-inorganic hybrid perovskite solar cells (PSCs) have been
considered as one of the most promising photovoltaic devices and
commercial products with a large-scale production are expected. PSCs
have achieved a huge development in less than a decade and its power
conversion efficiency (PCE) has risen from 3.8% to 23.7% since the first
report by Kojima et al., in 2009 [1,2]. Among the functional layers in
PSCs, the perovskite film plays the most important role in affecting the
device performance, and thus the fabrication of high-quality perovskite
thin film is a necessary precondition for obtaining efficient PSCs [3].
Methylammonium lead trihalide (MAPbX3) and formamidinium lead
trihalide (FAPbX3) (X = Cl, Br, I) are the most commonly used active
materials with an appropriate band gap for PSCs. The FAPbI3 based
PSCs have a better stability than those with MAPbI3 [4]. However,
FAPbI3 can be formed with photoinactive δ-phase or photoactive α-
phase, which can easily convert to δ-phase at room temperature [5]. To
solve these problems, mixed-cation perovskite with FA and MA as the
A-site cation is studied and it is reported that introducing a small
amount of MA+ into FAPbI3 favors the crystallization of α-phase.
Adding Cs+ into the A-site position can further suppress the formation
of δ-phase [6]. To date, mixed-cation perovskite is one of the most ef-
ficient light absorbers for high-performance PSCs [7]. The widely em-
ployed methods for fabricating perovskite films are one-step anti-
solvent and two-step deposition. The two-step deposition can offer
perovskite films with a large grain size and a high reproducibility, but it
is hard to exactly control the composition of perovskite [8]. The one-
step anti-solvent method using chlorobenzene or toluene as washing
solvent can lead to perovskite with a more precise stoichiometric ratio
[9]. However, the perovskite film fabricated by the latter usually has a
small grain size compared to the former. The small grain size accom-
panies a large quantity of grain boundaries and defects, which hamper
the charge transport and increase charge recombination [10,11].
Therefore, it is desirable to develop facile methods to enlarge the grain
size and reduce the defects in the perovskite film through the one-step
anti-solvent method.
The solvent engineering is considered as an effective strategy to
improve the quality of perovskite films [12]. Park et al. introduced N,N-
dimethyl sulfoxide (DMSO) into perovskite precursor solution to form
the adduct of PbI2•MAI•DMSO due to the interaction between Lewis
base (DMSO and iodide in MAI) and Lewis acid PbI2, which improves
the quality of perovskite by the slow evaporation of DMSO during an-
nealing, and a PCE up to 19.7% was achieved [13]. Seok et al. obtained
a PCE of 20.3% by manipulating the formation of Lewis base adduct
through intramolecular exchange between DMSO and formamidinium
lead iodide (FAI) [14]. The Lewis base adduct with a structure of
MA2Pb3I8(DMSO)2 that was identified by Zheng et al. through experi-
ments and calculations has a positive effect on the crystallization of the

*
Corresponding authors.
E-mail addresses: dkm@suda.edu.cn (K. Deng), lli@suda.edu.cn (L. Li).

https://doi.org/10.1016/j.nanoen.2019.103867
Received 19 April 2019; Received in revised form 30 June 2019; Accepted 30 June 2019
Available online 02 July 2019
2211-2855/ © 2019 Elsevier Ltd. All rights reserved.
M. Wang, et al.
perovskite thin film [15]. However, previous works studied the influ-
ence of Lewis base adduct on the pure-cation perovskite, for which the
precursor contains only PbI2 and MAI (or FAI), and the involved me-
chanism how the Lewis base adduct affects the morphology and op-
toelectronic properties of the perovskite film has not been deeply in-
vestigated. In a typical process to fabricate mixed-cation perovskite
through the anti-solvent method, DMSO is introduced into the pre-
cursor solution [16]. However, the mixed-cation perovskite system is
more complicated because other Lewis acid including PbBr2, MABr and
FAI may form a stable adduct phase with DMSO as well [17]. Due to the
different precursors, the formation of the Lewis base adducts and the
role of DMSO in the precursor solution may be different from pure-
cation perovskite system, and the influence of Lewis base adduct on the
growth of mixed-cation perovskite remains to be understood.
Herein, we for the first time study the formation of the intermediate
adduct phase in the precursor of mixed-cation perovskite, and its in-
fluence on the properties of the perovskite film and the performance of
PSCs. We find that the Lewis base adduct in the mixed-cation perovskite
system still exists in the form of PbI2•MAI•DMSO despite the different
composition from the pure-cation perovskite precursor that contains
PbI2 and MAI. In addition, the formation of the Lewis base adduct in
mixed-cation perovskite precursor is an indirect process that is derived
from the internal solute ionization and ion exchange. By changing the
amount of DMSO in the precursor, the precursor film with different
amounts of Lewis base adducts can be obtained, which has a great effect
on the crystallization and optoelectronic properties of the perovskite
film. Compared to the precursor solution lack of DMSO, N,N-di-
methylformamide (DMF) and DMSO mixed solvent with a volume ratio
of 3:5 can produce compact perovskite films with an increased grain
size and reduced defects, which are beneficial to efficient carrier
transport and suppressed recombination. Based on this high-quality
mixed-cation perovskite film, an average PCE approaching to 20% can
be realized for PSCs with a champion value of 21.2%.
2. Results and discussion
We prepared the precursor solutions of mixed-cation perovskite
using DMF/DMSO mixed solvent with different volume ratios and the
corresponding precursor films were obtained by the one-step anti-
solvent method. The X-ray diffraction (XRD) patterns of the precursor
films and annealed films were measured to identify the structural in-
formation. When the solvent volume ratio is 3:1, the XRD patterns of
the precursor film contains the characteristic peaks of the cubic phase
and delta perovskite structure [18], which represent the photoactive
and photoinactive phase, respectively (Fig. 1a). As the volume ratio
increases, a new diffraction peak at 9.2° appears. A further increase of
the volume ratio leads to the appearance of more diffraction peaks (6.6°
and 7.3°). For the volume ratio of 3:7, an extra diffraction peak turns
out at 9.7° with a strong intensity, which is attributed to the adduct
phase of PbI2•DMSO (Fig. S1a) [19]. All the diffraction peaks in the
small angle range disappear after annealing, as it is apparent from the
XRD patterns in Fig. 1b. We conclude that the diffraction peaks below
10° correspond to the Lewis adduct phase. To understand the compo-
sition of the adduct phase, we conducted control experiments by
measuring the XRD patterns of precursor films with different compo-
sitions dissolved in DMSO. The precursor film that contains PbI2 and
FAI only shows characteristic peaks of δ-FAPbI3 (Fig. S1b). It is noted
that FAI molecular has a similar size to DMSO molecular. However,
PbI2 has a stronger interaction with FAI than DMSO, and FAI can re-
place DMSO in the PbI2•DMSO adduct phase [14]. No diffraction peaks
can be found in the small angle range, indicating that the adduct phase
of PbI2•FAI•DMSO cannot form. In the same way, we exclude the ex-
istence of the adduct phase of PbBr2•MABr•DMSO (Fig. S1c). Interest-
ingly, when the precursor film contains only PbI2 and MABr, the dif-
fraction peaks can be found at 6.6°, 7.3° and 9.2° (Fig. S1d), which
coincide with the XRD patterns in Fig. 1a.
2
Nano Energy 63 (2019) 103867
To further identify the Lewis adduct phase in the mixed-cation
perovskite precursor, Fourier transform infrared spectroscopy (FT-IR)
was measured. Fig. 1c shows FT-IR spectroscopy of the precursor films
with different DMF/DMSO volume ratios. All the precursor films show a
significant stretching vibration of S]O at 1047 cm−1, which is attrib-
uted to the residual DMSO in the perovskite [20]. It is reported that an
extra stretching vibration of S]O from DMSO will appear at a lower
frequency when the adduct phase forms [13]. For the perovskite pre-
cursor film with a DMF/DMSO volume ratio of 3:1, the stretching vi-
bration of S]O at a lower frequency cannot be observed, which means
that no adduct phase forms. This result is consistent with the above-
mentioned XRD patterns. The perovskite precursor films with more
DMSO content in the mixed solvent exhibit a new stretching vibration
of S]O at 1015 cm−1, which suggests that the absorption bands arise
from the same adduct phase. Another stretching vibration of S]O ap-
pears at 980 cm−1 due to the formation of PbI2•DMSO adduct phase for
the volume ratio of 3:7 (Fig. S2a) [21]. There is no significant shift of
the stretching vibration of S]O for PbI2-FAI-DMSO and PbBr2-MABr-
DMSO precursor films, which is in accordance with the above conclu-
sion that no adduct phase is formed in the two precursor films (Fig.
S2b). As expected, there appears a stretching vibration of S]O at
1015 cm−1 for PbI2-MABr-DMSO precursor film. The XRD patterns and
FT-IR spectroscopy of the PbI2-MABr-DMSO precursor film suggest the
existence of adduct phase in the mixed perovskite film (Fig. S2c).
We notice that the adduct phase in the PbI2-MABr-DMSO precursor
film shares the same structural and FTIR properties as the PbI2-MAI-
DMSO precursor film, as shown in Fig. S3 and Fig. S4. We interpret that
the ion exchange between I− and Br− occurs in the PbI2-MABr-DMSO
precursor that favors the formation of PbI2•MAI•DMSO adduct phase.
To confirm this process, we studied the precursor that contains PbBr2
and MAI. The XRD patterns and FT-IR spectra of the corresponding
precursor film are also consistent with the results of PbI2-MAI-DMSO
precursor film, which further proves the formation of PbI2•MAI•DMSO
adduct phase through ion exchange (Fig. S1e and Fig. S2c). Therefore,
we can safely conclude that the adduct phase in the mixed-cation
perovskite precursor film is PbI2•MAI•DMSO. According to a previous
report, the diffraction peak at 9.2° is attributed to the (022) crystal
plane of the PbI2-rich PbI2•MAI•DMSO adduct phase [22], while the
diffraction peak at 6.6° corresponds to the (002) crystal plane of the
organic-molecule-rich adduct phase [15,23]. As the DMF/DMSO vo-
lume ratio increases, more diffraction peaks appear for the precursor
films of the mixed-cation perovskite, indicating that the amount of
DMSO in the mixed solvent is important for the property of adduct
phase. The excessive DMSO will lead to the formation of the PbI2•DMSO
adduct phase and should be responsible for the increased amount of
PbI2 in the final mixed-cation perovskite film as shown in Fig. 1b.
It is widely accepted that the growth process of the perovskite film is
closely related to the crystal nucleation [24]. To understand how the
adduct phase affects the nucleation process, we traced the crystal-
lization process of mixed-cation perovskite by using a metallographic
microscope [16]. Fig. 2 shows the nucleation process of perovskite films
with different DMF/DMSO volume ratios without antisolvent proces-
sing and the corresponding video is provided in the supporting in-
formation. The black area in the optical images of precursor films re-
presents the nucleation centers, and the amounts of the nucleation
centers decrease with the increased DMSO content in the mixed solvent,
due to the strong chelating ability between DMSO with PbI2 [16]. The
nucleation centers of perovskite will appear gradually because of the
breakage of the PbI2•MAI•DMSO or PbI2•DMSO adduct phase during
annealing, which can slow the crystallization process of the perovskite.
For the DMF/DMSO volume ratio of 3:1, a fast nucleation and crys-
tallization process can be observed during annealing. The optimal
DMSO content in the mixed solvent results in a moderate amount of
adduce phase in the perovskite precursor film, which induced a slower
nucleation especially for the volume ratio of 3:5. Scanning electron
microscope (SEM) images of the corresponding annealed mixed-cation
M. Wang, et al.
Fig. 1. XRD patterns of perovskite films with different DMF/DMSO volume ratios (a) before and (b) after annealing. (c) FT-IR of different perovskite precursor films.
perovskite films are presented in Fig. 3. The average grain size of the
perovskite film with a solvent volume ratio of 3:1 is around 200 nm.
The small grain size in the perovskite film is mainly ascribed to the fast
nucleation and crystallization process. As the increase of DMSO content
in the mixed solvent, the grain size gradually increases. With a solvent
volume ratio of 3:5, the average grain size increases to around 600 nm
and the perovskite film is compact and smooth. The grain size dis-
tribution of perovskite films with different DMF/DMSO solvent ratios is
presented in Fig. S5. The increased grain size results from a proper
amount of adduce phase in perovskite precursor film and a slower
nucleation during annealing. Meanwhile, the white phase in the SEM
images shows the formation of PbI2 at the grain boundaries. The re-
sidual PbI2 may be related to the influence of adduct phase during the
crystallization process of the perovskite. A large number of studies have
confirmed that PbI2 can passivate the defects in the perovskite film
[25–27]. However, the grain size of the perovskite film decreases with a
solvent volume ratio of 3:7 and too much PbI2 appears at the grain
boundaries. Atomic force microscopy (AFM) were measured to further
characterize the morphology of the perovskite films and the AFM
images in Fig. S6 show that the perovskite film prepared with a solvent
volume ratio of 3:5 has the lowest roughness. The photoluminescence
(PL) spectra of the perovskite films deposited on ITO substrate indicate
that the solvent volume ratio of 3:5 leads to the strongest PL intensity
(Fig. S7a), which means that the perovskite film has a better ability of
carrier separation than perovskite films with other solvent ratios. The
absorption spectra also indicate that the perovskite based on the solvent
volume ratio of 3:5 has the strongest absorption (Fig. S7b). These re-
sults can be explained by the large crystal grain size, less defects and
reduced charge recombination.
The planar-type PSCs were fabricated based on the mixed-cation
perovskite films using SnO2 and Spiro-OMeTAD as the electron trans-
port layer and hole transport layer, respectively. Table 1 summarizes
the statistics of photovoltaic parameters for devices with different
3
Nano Energy 63 (2019) 103867
solvent volume ratios. The short-current density (Jsc) has a low de-
pendence on the solvent volume ratio, but it largely affects the open
circuit voltage (Voc) and fill factor (FF). The devices with a DMF/DMSO
volume ratio of 3:1 exhibit an average Voc of 1.11 V and FF of 0.69,
while those with an optimal volume ratio (3:5) show an increased value
of 1.15 V and 0.75. The improved Voc and FF finally lead to an average
PCE as high as 19.8% for the optimized devices. The photocurrent
density-voltage (J-V) curve of the champion device based on a DMF/
DMSO volume ratio of 3:5 is presented in Fig. 4a with a Jsc of
23.13 mA/cm2, Voc of 1.16 V, FF of 0.79 and PCE of 21.2%. Fig. S8
presents the J-V curve of the best device based on other solvent volume
ratios, with a PCE of 18.99%, 20.06%, 19.77% for a DMF/DMSO vo-
lume ratio of 3:1, 3:3 and 3:7, respectively. The marked increase in PCE
shows the positive effect of the optimized perovskite film to the device
performance. The monochromatic incident photon-to-electron conver-
sion efficiency (IPCE) and integrated short-circuit current density of the
champion device are presented in Fig. 4b. The high quantum efficiency
over 90% in the visible light range leads to an integrated current
density of 22.19 mA/cm2, which is in good agreement with the Jsc in
the J-V curve. The reverse and forward scan J-V of a typical device with
the optimal solvent volume ratio is presented in Fig. 4c, showing a
negligible hysteresis effect. Fig. S9 shows the maximum power point
tracking (MPP) in an ambient condition with a humidity up to 75%.
Under environments with such a high humidity, the device can main-
tain an output current density of 21.36 mA/cm2 for 7 h, which shows a
high stability of the device. To further study the device stability, we
measured the PCE of our devices stored in an ambient condition with a
humidity up to 20%, and the normalized PCE in Fig. 4d shows that
more than 80% of the initial PCE can be remained after 500 h.
We also measure Voc and Jsc under various light intensities to study
the recombination kinetics of PSCs with different solvent volume ratios.
The ideality factor n of the device is obtained through the formula FX,
where k, T, q and I are Boltzmann constant, temperature, charge
M. Wang, et al. Nano Energy 63 (2019) 103867

Fig. 2. The optical images show the nucleation process of perovskite films during annealing with different DMF/DMSO volume ratios: (a) 3:1, (b) 3:3, (c) 3:5, (d) 3:7.

Fig. 3. SEM images of perovskite films based on different DMF/DMSO volume ratios: (a) 3:1, (b) 3:3, (c) 3:5, (d) 3:7.

constant and light intensity, respectively [28]. The slopes shown in bimolecular process [29]. A larger slope means more defects and thus a
Fig. 5a are 3.84 kT/q, 2.80 kT/q, 2.30 kT/q and 3.34 kT/q for the DMF/ more severe recombination in the devices. The larger slope for the
DMSO volume ratio of 3:1, 3:3, 3:5 and 3:7, respectively. The charge device with a DMF/DMSO volume ratio of 3:1 is consistent with the
recombination at open circuit is a combination of monomolecular and small grain size of the perovskite film and more defects [30]. It is

4
M. Wang, et al. Nano Energy 63 (2019) 103867

Table 1 which suggests that there has the lowest trap density in the perovskite
The statistical distribution of photovoltaic parameters for PSCs with different film. We measured electrochemical impedance spectroscopy (EIS) to
solvent volume ratios. further investigate the charge dynamics in the different devices [33].
DMF:DMSO Voc (V) Jsc (mA/cm2) FF PCE (%) There are two semicircles which represent the high-frequency and low-
frequency component, respectively. The high-frequency component is
3:1 1.11 ± 0.05 22.91 ± 0.75 0.69 ± 0.02 18.3 ± 0.80 associated with the charge transport resistance (Rct), and the low-fre-
3:3 1.13 ± 0.04 23.30 ± 0.69 0.72 ± 0.04 19.0 ± 0.70
quency one corresponds to the charge recombination resistance (Rrec).
3:5 1.15 ± 0.03 23.20 ± 0.73 0.75 ± 0.03 19.8 ± 0.69
3:7 1.12 ± 0.03 23.10 ± 0.71 0.70 ± 0.04 18.8 ± 0.77 Fig. 5d shows that the Rct of the different devices are almost identical,
suggesting that the charge transfer capabilities are similar. However,
there is a remarkable difference in Rrec for different devices. The device
believed that a larger grain size can reduce the amounts of defects in the based on a DMF/DMSO volume ratio of 3:5 has the highest Rrec, sug-
perovskite film, which can suppress the charge recombination and gesting the lowest charge recombination. The above results confirm the
improve the device performance [31]. Fig. 5b shows the Jsc vs light reduced defects in the perovskite film when the solvent volume ratio is
intensity curves of devices with different solvent volume ratios. All the 3:5, which further demonstrates the significance of manipulating the
slopes of the devices are around 0.9. The similar slopes indicate that adduct phase in the precursor film.
almost all the carriers are swept out prior to the charge recombination
under the short-circuit condition [29]. Space charge limiting current
(SCLC) is an effective method to study the trap density in the devices 3. Conclusions
[32]. We fabricate the electron-only devices with a structure of FTO/
Perovskite/PCBM/Ag using perovskite films prepared with different In summary, we systematically study the adduct phase in the mixed-
solvent volume ratios. At the low bias voltage region, it is identified as cation perovskite system and find that the adduce phase of
the Ohmic-type response with a linear relationship between the voltage PbI2•MAI•DMSO in the mixed-cation system has a great impact on the
and current. At the intermediate region, the current increases rapidly as crystal nucleation for the perovskite film. By adjusting the amount of
the increase of the voltage, which represents the trap filling region. The DMSO in the precursor, the formation of adduce phase can be modu-
kink point between the two regions defines the trap-filling limit voltage lated to an optimal level, which can improve the quality of the per-
(VTFL). There has a formula between VTFL and trap density (Nd): ovskite film with a large grain size, smooth surface and reduced defects.
The optimized perovskite film improves the performance of PSCs with a
2ε0 ε
Nd = VTFL, boosted PCE over 21%. The successful control of the crystal nucleation
qL2
through tuning the adduct phase provides an extra method in opti-
where q, L, ε and εo are the elementary charge, the thickness of per- mizing the properties of the perovskite film, which may be applied in
ovskite, the relative dielectric and the vacuum permittivity, respec- other perovskite systems and contribute to the further development of
tively [16]. Fig. 5c shows the J-V curves of electron-only devices with PSCs.
different solvent volume ratios. It is marked that a solvent volume ratio
of 3:5 results in the smallest VTFL among the four types of devices,

Fig. 4. (a) J-V curve and (b) IPCE spectra of the champion device with a DMF/DMSO volume ratio of 3:5. (c) Reverse and forward scan of a typical device. (d) The
normalized PCE for the device that is stored in an ambient condition.

5
M. Wang, et al.
4. Experimental details
4.1. Materials
Lead iodide (PbI2), lead bromine (PbBr2), DMF and SnO2 colloidal
dispersion (tin (IV) oxide, 15% in H2O colloidal dispersion) were pur-
chased from Alfa Aesar. DMSO was purchased from Sigma-Aldrich.
Formamidinium iodide (FAI) was purchased from Lumtec Technology
Corp, Taiwan. Methylammonium bromine (MABr) and Spiro-OMeTAD
were purchased from Xi'an Polymer Light Technology Corp.
4.2. Device fabrication
The as-received SnO2 colloidal dispersion was diluted by deionized
water (1:1 by volume ratio), and then spin-coated onto the UV-treated
ITO substrates at 5000 rpm for 20 s, and then annealed at 60 °C for
10 min. The mixed-cation perovskite precursor was prepared by dis-
solving 1.15 M PbI2, 1.1 M FAI, 0.2 M PbBr2 and 0.2 M MABr in the
mixed solvent of DMF/DMSO (3:1, 3:3, 3:5 and 3:7 by volume ratio).
Then 40 μL CsI/DMSO solution (1.5 M) was added into the perovskite
precursor and the mixed solution was stirred at 70 °C for 15–20 min
before use. The mixed perovskite precursor was spin-coated onto SnO2
substrate with a two-step spin coating program: first at 1000 rpm with
accelerated speed of 400 rpm for 10 s and second at 4000 rpm with
accelerated speed of 1000 rpm for 35s. 100 μL chlorobenzene was
added as anti-solvent 25s before the end of spin-coating and the per-
ovskite film was annealed at 100 °C for 10 min. The Spiro-OMeTAD
solution was prepared by dissolving 72.3 mg Spiro-OMeTAD in 1 mL
chlorobenzene. After that, 29 μL 4-tert-butylpyridine and 18 μL Li-TFSI
(520 mg/mL in acetonitrile) were added. Then the mixed solution was
stirred for 3 h before use. 50 μL Spiro-OMeTAD solution was spin-
coated onto the perovskite film at 2000 rpm for 30 s. Finally, a metal
electrode of 90-nm-thick Ag was deposited using thermal evaporation.
6
Nano Energy 63 (2019) 103867
Fig. 5. Optoelectronic properties of devices
based on different DMF/DMSO volume ra-
tios. (a) Voc and (b) Jsc of PSCs plotted
against light intensity (dots), together with
linear fits (solid lines). (c) Dark I–V char-
acteristics of electron-only devices. The
inset shows the structure of the corre-
sponding electron-only device. (d) EIS of
PSCs.
4.3. Characterizations
The XRD patterns of samples were characterized using X-ray dif-
fractometer (X-pert PRO). The powder of perovskite was characterized
using Fourier infrared spectrometer (NICOLET 6700). The morphology
of samples was checked by field-emission scanning electron microscope
(FE-SEM, SU8010, Hitachi) and Atomic Force Microscope (Multiomode
8). The J-V curves of these PSCs were measured using a Keithley 2400
source meter at room temperature in ambient conditions. The device for
the aging test was kept in a sealed container with a controlled humidity
of 20%. For the maximum power point tracking, a bias voltage was
applied to the solar cell and the device was operated under an ambient
condition with a relative humidity of 75%. The PL spectrum was re-
corded by a spectrofluorometer (Horiba, Fluoromax-4) with a 520 nm
excitation wavelength under room temperature. The absorption spectra
were recorded by a UV–vis spectrophotometer (Shimadzu, UV-3600).
The monochromatic incident photon-to-electron conversion efficiency
curves were tested with a Newport QE 200 system. The electrochemical
impedance spectroscopy was measured by an electrochemical work-
station (Autolab, PGSTAT 302 N) under white light illumination at 0 V
bias voltage with an alternative signal amplitude of 5 mV in the fre-
quency range of 800–0.001 kHz.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (51772197, 51422206, 51372159), 1000 Youth
Talents Plan, Key University Science Research Project of Jiangsu
Province (17KJA430013), Six Talents Peak Project of Jiangsu Province,
333 High-level Talents Cultivation Project of Jiangsu Province, and was
funded by the Priority Academic Program Development (PAPD) of
Jiangsu Higher Education Institutions.
M. Wang, et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.nanoen.2019.103867.
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