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org Research Article

Understanding the Mechanism between Antisolvent Dripping and

Additive Doping Strategies on the Passivation Effects in Perovskite
Solar Cells
Juan Long,∥ Wangping Sheng,∥ Runying Dai, Zengqi Huang, Jia Yang, Jiaqi Zhang, Xiang Li,
Licheng Tan,* and Yiwang Chen*
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sı Supporting Information

ABSTRACT: Perovskite polycrystalline films contain numerous

intrinsic and interfacial defects ascribed to the solution preparation
process, which are harmful to both the photovoltaic performance
and the stability of perovskite solar cells (PVSCs). Although
various passivators have been proved to be promising materials for
passivating perovskite films, there is still a lack of deeper
understanding of the effectiveness of the different passivation
methods. Here, the mechanism between antisolvent dripping and
additive doping strategies on the passivation effects in PVSCs is
systematically investigated with a nonfullerene small molecule
(F8IC). Such a passivated effect of F8IC is realized via
coordination interactions between the carbonyl (CO) and
nitrile (C−N) groups of F8IC with Pb2+ ion of MAPbI3.
Interestingly, F8IC antisolvent dripping can effectively passivate the surface defects and thus inhibit the nonradiative charge
recombination on the upper part of the perovskite layer, whereas F8IC additive doping significantly reduces the surface and bulk
defects and produces a compact perovskite film with denser crystal grains, thus facilitating charge transmission and extraction.
Therefore, these benefits are translated into significant improvements in the short-circuit current density (Jsc) to 21.86 mA cm−2 and
a champion power conversion efficiency of 18.40%. The selection of an optimal passivation strategy should also be considered
according to the energy level matching between the passivators and the perovskite. The large energetic disparity is unsuitable for
additive doping, whereas it is expected in antisolvent dripping.
KEYWORDS: defects, passivation, antisolvent dripping, additive doping, perovskite solar cells

■ INTRODUCTION
Perovskite solar cells (PVSCs) are regarded as one of the most
promising photovoltaic technologies owing to their low cost
and high efficiency.1 Until now, the highest authenticated
power conversion efficiency (PCE) of PVSCs has reached
25.2%.2 The high PCE is attributed to the fascinating
optoelectronic properties of perovskite materials, such as the
strong light-harvesting capacity,3 unique defect tolerant
property,4 fast charge carrier mobility,5 low exciton binding
energy,6 and tunable bandgap.7 Inevitably, the perovskite
polycrystalline films contain numerous defects ascribed to the
solution preparation process, including interstitials, vacancies
and impurities, as well as noncoordinated ions at their grain
boundaries (GBs) and surfaces.8 All these defects lead to
charge recombination and ion migration.9,10 On a device
efficiency level, such defects can undesirably influence the
carrier transport via the formation of nonradiative recombina-
tion centers, thus hindering the further enhancement of the
device efficieny.11 On a device stability level, the migration of
halide ions and organic cations through the point defects has
been considered as the main reason for the inherent thermal
instability. Moreover, because of the GB defects, moisture and
oxygen can penetrate into perovskites, which will damage the
stability of the device.12,13
To address these issues, various passivation strategies have
been used to suppress the intrinsic and surface defects in
perovskite devices, which are proposed to enhance the
optoelectronic performance and prolong the durability of
PVSCs.14 Particularly, additive engineering has shown
potential in the fabrication of high-efficiency PVSCs.15−17
Moreover, numerous passivators such as metal halide salts,
Received: August 21, 2020
Accepted: November 19, 2020
Published: December 2, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.0c15042

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Figure 1. Schematic illustration of the F8IC-passivated PVSCs via antisolvent dripping and additive doping methods.
organic halide salts, organic semiconductors, inorganic acids,
ionic liquids, and nanoparticles have been proved to be
efficient for passivating the perovskite films.18−24 Among them,
nonfullerene n-type organic semiconductors have attracted
much attention due to their distinct properties, which is
beneficial for obtaining high-performance PVSCs. These
molecules with various functional groups and excellent
conductivity can significantly fill in the GBs of perovskites
via electrostatic interactions, thereby realizing grain boundary
passivation and improving the charge transfer efficiency
between the grains.25 Moreover, the energy level of non-
fullerene n-type organic semiconductor molecules can be
adjusted to match well with the perovskite materials, which
further improves the exciton transmission efficiency.26 For
instance, Liu et al. have proved that the introduction of
conjugated molecules that functionalize with Lewis acid or
base groups in the perovskite films via additive doping can
facilitate heterogeneous nucleation and growth of the
crystalline solvate during solution-casting, resulting in
passivation of trap states at GBs.25 Han et al. have employed
an organic dye (AQ310) as a passivator by antisolvent dripping
and suggested that the trap states have been reduced due to the
coordination between the existing −COOH groups in AQ310
and the uncoordinated Pb2+ ions.27 It has been proved that
many passivation molecules can effectively reduce the defect
density, and the passivation mechanisms of various functional
groups have been clarified.28 Moreover, it has also been
confirmed that the molecular configuration will affect the
passivation effectiveness.29 However, there is still a lack of
deeper understanding of the effectiveness of PVSCs using
different passivation methods because of the complexity and
diversity of the introduced methods. Therefore, a scientific
consensus should be put forward to understand the differences
of adding passivators via various methods on the passivation
effects in the perovskite films.
In this work, the mechanism between antisolvent dripping
and additive doping strategies on the passivation effects in
PVSCs is systematically investigated with a nonfullerene small
molecule (F8IC). Here, a planar p-i-n device configuration of
ITO/NiOx/MAPbI3 (without and with F8IC)/PCBM/BCP/
Ag has been adopted in which F8IC is added into the
perovskite via antisolvent dripping and additive doping
strategies, respectively, due to its good solubility in
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chlorobenzene (CB) and dimethylformamide (DMF) (Figure
1). F8IC as a Lewis base, which has different functional groups
with a lone electron pair, can suppress the defects by
coordinating with uncoordinated Pb2+ ions in the perovskite
films. Furthermore, this nonfullerene n-type organic semi-
conductor molecule can promote charge transmission and
extraction, resulting in the improvement of the device
performance. Our findings indicate that the same passivator
added via various methods results in different degrees of
passivation for perovskite defects. The F8IC added via
antisolvent dripping can effectively passivate the surface
defects and thus inhibit the nonradiative charge recombination
on the upper part of the perovskite layer, which results in
improvements in the open-circuit voltage and fill factor (FF).
The cross-sectional scanning electron microscopy (SEM)
image shows that an ultrathin molecule layer is formed on
the perovskite film with clear GBs. More importantly, the F8IC
added via the additive doping method can effectively reduce
the defects distributed on the surface and inside the bulk film,
and homogenous and compact perovskite films with denser
and uniform crystal grains can be obtained. Thus, the charge
transfer efficiency of F8IC-passivated PVSCs via additive
doping is significantly enhanced. These benefits are translated
into significant improvements in Jsc to 21.86 mA cm−2 and a
champion PCE of 18.40%, which are both superior to the
relatively low photovoltaic parameters (Jsc of 20.70 mA cm−2
and average PCE of 17.05%) of F8IC-passivated PVSCs via
antisolvent dripping. However, additive doping is not the
optimal passivation method for all nonfullerene n-type organic
semiconductor passivators. The small energetic disparity
between passivators and the perovskite is expected to serve
as an efficient bridge for carrier transport when the passivators
are added via the additive doping method, whereas the large
energetic disparity will form a barrier to reduce the charge
injection.
■
EXPERIMENTAL SECTION
Materials. The synthetic methods of nickel oxide (NiOx)
nanocomposites (NPs) followed the standard process described in a
previous report.30 Lead(II) iodide (PbI2, 99.999% purity) and [6, 6]-
phenyl-C61-butyric acid methyl ester (PC61BM) were purchased from
Xi’an Polymer Light Technology Corp. Methylamine iodide (MAI, >
99% purity), silver (Ag), and gold (Au) were obtained from TCI Inc.
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Figure 2. (a) UV−vis absorption spectra, (b) XRD patterns, (c) steady-state PL spectra, and (d) TRPL spectra of the perovskite films without
F8IC and with F8IC via antisolvent dripping and additive doping methods, respectively.
F8IC and IT-4F were purchased from Derthon OPV Co., Ltd.
Bathocuproine (BCP, 96.0%), anhydrous chlorobenzene (CB), N, N-
dimethylformamide (DMF, anhydrous, 99.8%), and anhydrous
dimethyl sulfoxide (DMSO, anhydrous, 99.9%) were purchased
from Sigma-Aldrich Inc. Ethanol absolute was purchased from
Aladdin.
Device Preparation. The patterned indium tin oxide (ITO) glass
substrate was unceasingly cleaned with detergents, acetone, distilled
water, and isopropanol alcohol by ultrasonication for 20 min and then
dried under a nitrogen stream. The precleaned ITO glass substrates
were exposed to oxygen plasma for 3 min before spin-coating NiOx
compact films. The NiOx NPs were acquired by dispersing 20 mg of
NiOx powder in 1 mL of deionized water. Then, NiOx NPs were
deposited on ITO glass substrates at 2000 rpm for 30 s followed by
thermal annealing at 120 °C for 30 min. After cooling down to room
temperature, the samples were transferred into a N2 glovebox. The
precursor solution was obtained by dissolving 1.3 M PbI2 and 1.3 M
MAI into an anhydrous DMF and DMSO (9:1, v/v) mixed solvent,
and then different volumes of F8IC or IT-4F stock solution (1 M in
DMF) were added to the perovskite precursor solution. The
precursor solution was spin-coated on ITO/NiOx at 4000 rpm for
30 s followed by dropping of CB, F8IC/CB, or IT-4F/CB solutions
during the last 10 s of the spinning process. After spin-coating the
perovskite film, the substrate was annealed at 100 °C for 10 min. After
cooling down to room temperature, PC61BM solution (20 mg mL−1
in anhydrous CB) was spin-coated at 2000 rpm for 30 s on top as an
electron transport layer. Subsequently, BCP (0.5 mg mL−1 in
anhydrous ethanol) was then spin-coated on the PC61BM film at
4500 rpm for 1 min. Lastly, a 100 nm-thick Ag anode (thermal
deposition rate of 1.0 Å/s) was deposited on the substrate under a
vacuum level of 3 × 10−4 Pa.
Characterization. The ultraviolet−visible (UV−vis) spectra were
recorded using a UV visible spectrophotometer (SHIMADZU, UV-
2600). The X-ray diffraction (XRD) patterns were measured using a
Rigaku D/Max-B X-ray diffractometer with the Bragg−Brentano
parafocusing geometry. The steady-state photoluminescence (PL) and
time-resolved photoluminescence (TRPL) measurements were
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carried out using a photoluminescence spectrometer (FLS920,
Edinburgh Instruments Ltd.). The SEM images of perovskite films
were recorded using a SU8020 scanning electron microscope in which
an acceleration voltage of 8 kV was used. The X-ray photoelectron
spectroscopy (XPS) measurements were carried out using a Thermo-
VG scientific ESCALAB 250 photoelectron spectrometer with a
monochromatic Al (Kα) (1486.6 eV) X-ray source. Time-of-flight
secondary ion mass spectroscopy (TOF-SIMS) measurements were
carried out using a TOF-SIMS 5, ION-TOF GmbH. Sputter depth
profiling was performed with the pulsed primary ions from a Cs+ (2
keV) liquid metal ion gun, and analysis was accomplished using a 3-
lens 30 kV BiMn primary ion gun. The water contact angle was
measured using a Krüss DSA100s drop shape analyzer. Fourier-
transform infrared (FTIR) spectra were measured using a Shimadzu
IRPrestige-21 spectrometer. The illuminated current density−voltage
(J−V) curves of photovoltaic devices were measured using a Keithley
2400 under 100 mW·cm−2 simulated AM 1.5 G irradiation (Enlitech
Co., Ltd), and the light intensity was calibrated using a standard
single-crystal Si photovoltaic cell. The external quantum efficiency
(EQE) spectrum was recorded using a Solar Cell Spectral Response
Measurement System QE-R3011 (Enlitech Co., Ltd). The electrical
impedance spectroscopy (EIS) measurement was performed using a
Zahner electrochemical workstation. The hole and electron mobilities
were obtained with a space-charge limited current (SCLC) model
using the Mott−Gurney law.
■
RESULTS AND DISCUSSION
The Impact of Passivation Strategies on the Optical
and Structural Properties of Perovskite Films. The UV−
vis absorption spectra of both F8IC-passivated perovskite films
exhibit enhanced absorption intensity as shown in Figure 2a.
We speculate that this is due to the improvement in the
perovskite film quality rather than the superposition of the
F8IC absorption (Figure S1) or the varied thicknesses of the
different films (Figure 1). The XRD patterns of perovskite
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Figure 3. (a−c) Top-view SEM images of the perovskite films without F8IC and with F8IC via antisolvent dripping and additive doping methods,
respectively. (d−f) Contact angle changes of the corresponding perovskite films. (g) PL spectra of perovskite films with F8IC via antisolvent
dripping and additive doping, which were recorded under an excitation light from either FS or GS. (h) TOF-SIMS elemental depth profiles of F−,
which was used as an indicator of F8IC in the perovskite films. (i) XPS spectra of Pb 4f of the corresponding perovskite films.

films illustrated in Figure 2b exhibit the same diffraction peaks
corresponding to the (110) and (220) phases, indicating that
the introduction of F8IC has not resulted in the formation of
impure phases in the perovskite. The relative intensities of the
(110) lattice planes of perovskite with F8IC antisolvent and
F8IC additive become stronger and sharper with a full width at
half maximum (FWHM) value of 0.28 and 0.27° (compared
with the reference value of 0.31°), which verifies the enhanced
crystallinity. This result is in agreement with the enhancement
absorption in the UV−vis spectra, suggesting that F8IC can
influence the perovskite crystallization kinetics, thus leading to
the formation of high-quality perovskite films. The fine
adjustment of the concentration of F8IC in CB or a precursor
has a significant impact on the crystalline structural properties
of perovskite films (Figure S2). To further investigate the
influence between antisolvent dripping and additive doping
methods on the charge transport properties of perovskite films,
the steady-state PL and TRPL spectra of glass/perovskite were
measured. As shown in Figure 2c, a slight blue shift in the PL
peak was observed in both F8IC-passivated perovskite films,
which is ascribed to the reduction of spontaneous radiative
recombination caused by the trap states on the GBs and
surfaces.31 In addition, the exciton lifetime of the perovskite
films can be extracted by fitting the TRPL spectra to a single-
exponential function (Figure 2d). The perovskite film without
F8IC shows a τave value of 31.52 ns, which decreases to 25.89
and 10.77 ns for the perovskite films with incorporated F8IC
by antisolvent dripping and additive doping methods,
respectively. The shorter PL decay for the F8IC-passivated
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perovskite films implies possible Förster resonance energy
transfer.32 Compared with the exciton lifetime of perovskite
films obtained by F8IC antisolvent dripping, the perovskite
film with incorporated F8IC via additive doping exhibits a
drastic fast decay lifetime, which indicates that a uniform
distribution of F8IC in the perovskite film may result in an
effective near-field interaction.33 Owing to the weak absorption
at a short wavelength, the F8IC molecule cannot be directly
photoexcited. As a result, the emission from this blend must
stem from its near-field interactions with MAPbI3.
The Impact of Passivation Strategies on the Degree
of Defect Passivation for Perovskite Films. The top-view
and cross-sectional SEM measurement is adopted to under-
stand the effect of passivation strategies on the morphologies
of perovskite films (Figures 3 and 1). The GBs between
perovskite grains can be clearly observed in the perovskite film
without F8IC (Figure 3a). Upon the addition of F8IC with
antisolvent dripping, a few exotic substances with different
contrasts appear at the GBs and the surface of the perovskite
film (Figure 3b). This phenomenon is more obvious on
increasing the concentration (∼0.4 mg mL−1) of F8IC (Figure
S3a), and even an ultrathin molecule layer is formed above the
perovskite (Figure 1). Interestingly, a homogenous and
compact surface morphology with denser and uniform crystal
grains is seen in F8IC-passivated perovskite films via additive
doping (Figure 3c, Figure S3b). It has been reported that the
introduction of nonfullerene molecules in the perovskite
precursor can effectively promote the nucleation and growth
of the solvates.18 Therefore, we speculate that the precursor
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Figure 4. Device performance of PVSCs without F8IC and with F8IC via antisolvent dripping and additive doping methods, respectively. (a)
Current density−voltage (J−V) curves of the champion devices measured in different scan directions under standard AM 1.5 G illumination (100
mW cm−2). (b) Steady-state photocurrent and output PCE at the maximum power point. (c) Dark J−V curves. (d) Light intensity-dependent Voc
for PVSCs. (e) J−V curves of the electron-only (ITO/SnOx/MAPbI3/PCBM/BCP/Ag) devices. (f) Stability of the unencapsulated PVSCs in an
ambient environment with a relative humidity of 60% and a temperature of 25 °C.

with F8IC can form large crystalline solvates preferentially
when the solvent is removed, and then these solvates act as
templates for further growth of perovskites, resulting in a
compact surface morphology. All these results suggest that the
F8IC incorporated via the additive doping strategy can
efficiently passivate the defects of the perovskite for obtaining
high-quality polycrystalline films with denser and uniform
crystal grains.
Nevertheless, the F8IC molecules may be excluded from
perovskite crystals to GBs or interfaces via antisolvent
dripping, and passivation can be achieved by rationally
modifying the adsorption and desorption properties of
passivation molecules without affecting the grain size. The
distribution of F8IC molecules in the perovskite film is
important to reveal the impact of passivation strategies on the
degree of defect passivation. The different distributions of
F8IC molecules can be proved by contact angle measurements.
As shown in Figure 3d−f, with the addition of F8IC, the
derived contact angles increase from 71.9 to 81.1° and 76.4°
via antisolvent dripping and additive doping methods,
respectively. Moreover, the PL spectra of glass/perovski-
te:F8IC with different passivation strategies are recorded under
an excitation light from the film side (FS) or glass side (GS),
respectively (Figure 3g). The spontaneous radiative recombi-
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nation through trap states usually results in red shift of the PL
emission compared to that from the band-edge transition. The
PL peak will blue shift after passivating the trap states.34 The
perovskite film with F8IC antisolvent dripping exhibits an
intense PL peak at 770 nm at the FS, while the PL emission
peak at the GS displays a red shift to 772 nm with lower
intensity. This indicates that F8IC added via the antisolvent
dripping method can effectively passivate the surface defects
and inhibit the nonradiative charge recombination only on the
upper part of the perovskite layer. However, the PL peaks are
irrelevant to the excitation light directions for the films
modified via the additive doping strategy. Similar optical
properties have been observed from the top and bottom
surfaces, which illustrates that the F8IC introduced by this
method can not only reduce the surface defects but also result
in a lower defect concentration inside the bulk film. The TOF-
SIMS measurement is employed to investigate the depth
profile of F8IC molecules in the perovskite layer, and the
elemental F is used as an indicator of F8IC. Figure 3h displays
the gradient distribution of F− in the F8IC-passivated
perovskite film obtained by antisolvent dripping, while F−
has a relatively homogenous distribution in the perovskite film
incorporated with the F8IC additive. This uniform distribution
of F8IC in the perovskite layer will lead to a more effective
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near-field interaction between the perovskite and passivators,
which is consistent with the PL results. These results imply
that the different distributions of F8IC molecules in the
perovskite film will affect the degree of defect passivation. In
order to obtain more insight into the passivation mechanism,
high-resolution XPS spectra of the corresponding perovskite
films are shown in Figure 3i. For the reference perovskite film,
two main peaks located at 137.79 and 142.67 eV correspond to
Pb 4f 7/2 and Pb 4f 5/2, respectively. The Pb 4f peaks shift to
lower binding energies in the F8IC-passivated films via
antisolvent dripping (137.67 and 142.58 eV, respectively)
and additive doping (137.58 and 142.39 eV, respectively). The
binding energy shifts of Pb 4f 7/2 and Pb 4f 5/2 after F8IC
doping indicate a decrease in cationic charges of Pb2+ ions,
which can be attributed to the donation of the lone electron
pair of F8IC to the empty 6p orbital of Pb2+ through
complexation. Meanwhile, the results from FTIR measurement
can further prove the interaction between F8IC and the
perovskite (Figure S4).
The Impact of Passivation Strategies on the PVSC
Device Performance. The impact of passivation strategies on
the photovoltaic performance is explored by fabricating an
invert planar heterojunction device with the structure of ITO/
NiOx/MAPbI3 (with or without F8IC)/PCBM/BCP/Ag
(Figure 1). The concentration of F8IC has a great influence
on the device performance (Table S1), where an appropriate
concentration (0.30 mg/mL for antisolvent dripping and 0.10
mg/mL for additive doping) can yield the champion PCE. The
current density−voltage (J−V) curves of the champion
reference device (without F8IC) and F8IC-passivated devices
(with F8IC via antisolvent dripping and additive doping
methods, respectively) are measured in different scan
directions under standard AM 1.5 G illumination (100 mW
cm−2) and are shown in Figure 4a. The corresponding detailed
photovoltaic parameters are summarized in Table 1. The
Table 1. Photovoltaic Parameters of PVSCs Based on the
Reference and F8IC-Incorporated Devices Measured in
Different Scan Directions under Standard AM 1.5 G
Illumination (100 mW cm−2)
Voc Jsc PCE
device scan (V) (mA cm−2) FF (%) (%)
w/o F8IC reverse 1.05 20.59 74.92 16.19
forward 1.05 20.45 73.18 15.71
F8IC antisolvent reverse 1.06 20.70 77.61 17.05
forward 1.06 20.33 77.37 16.67
F8IC additive reverse 1.07 21.86 78.36 18.40
forward 1.07 21.81 78.16 18.19
device without F8IC gives a PCE of 16.19% with a Voc of 1.05
V, a Jsc of 20.59 mA cm−2, and a FF of 74.92%, which is
comparable to that of PVSCs with similar structures.35 The
F8IC-passivated device treated via antisolvent dripping exhibits
a PCE of 17.05% with a Voc of 1.06 V, a Jsc of 20.70 mA cm−2,
and a FF of 77.61%. By contrast, the PCE of the device
fabricated using the F8IC additive doping strategy yields a
significant improvement to 18.40%, with a Voc of 1.07 V, a Jsc
of 21.86 mA cm−2, and a FF of 78.36%. Furthermore, no
significant hysteresis can be observed in all devices. It is
obvious that the F8IC-passivated device reveals a significantly
enhanced efficiency, primarily owing to the increase of Voc and
FF. The significantly enhanced Voc and FF are attributed to the
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reduction of bulk defect-related recombination via F8IC
passivation. Interestingly, the fabricated device using the
additive doping strategy displays an outstanding Jsc of 21.86
mA cm−2 compared to that of the device fabricated via
antisolvent dripping (20.70 mA cm−2), which is attributed to
the efficient charge transfer. Moreover, the statistical data of
the photovoltaic parameters for over 20 devices are shown in
Figure S5 and Tables S2−4, which verifies the good
reproducibility of the enhancement of device performance.
The integrated (Jsc) values from the EQE spectra (Figure S6a)
match well with the Jsc values obtained from the J−V curves.
The steady-state photocurrent and stabilized PCE output
measurements are carried out under a constant voltage bias
near the maximum power point. The results confirm that a
higher and much swifter photocurrent can be obtained using
the F8IC additive doping strategy (Figure 4b).
In addition, we conducted dark current measurements to
explore the charge carrier recombination. As shown in Figure
4c, the F8IC-passivated devices exhibit a lower leakage current
density compared with the reference, which suggests the
suppressed charge carrier recombination and increased shunt
resistance. Additionally, the increased injection current for the
F8IC-passivated device via the additive doping strategy
indicates a faster electron extraction. This efficient electron
extraction can avoid the carrier accumulation at the interface.
To further investigate the trap-assisted recombination details,
the dependence of voltage and device current is measured at
various illumination intensities. As shown in Figure 4d, the Voc
versus illumination intensity produces a slope of unity for kT/
q, where k is the Boltzmann constant, T is the absolute
temperature, and q is the elementary charge. The slope of the
reference device is 1.84, and it decreases to 1.69 and 1.51 for
the F8IC-passivated devices via antisolvent dripping and
additive doping, respectively. The decrease of the slope
demonstrates inhibition of trap-assisted carrier recombination,
which agrees well with the decreasing of trap states. Moreover,
the Jsc versus illumination intensity can be identified using the
relation Jsc ∝ Iα, where I is the light intensity and α is the
exponential factor. As shown in Figure S6b, the value of α for
the reference device is 0.923, which increases to 0.960 and
0.983 for F8IC-passivated devices via antisolvent dripping and
additive doping, respectively. This result suggests the reduction
of bimolecular recombination under a short-circuit state.36 EIS
is another strategy to understand the carrier transport and
recombination. The Nyquist plots (Figure S6c) exhibit only a
single characteristic arc, as reported in the literature,37 which
probably represents the charge recombination resistance (Rrec).
After introducing F8IC into the active layer via solvent-
dripping or direct incorporation, the Rrec extracted from the
Nyquist plots increases from 28 to 47 and 49 kΩ, respectively,
which can be attributed to the more efficient passivation of
trap states and suppressed charge carrier recombination.
Overall, these consistent results confirm that the addition of
F8IC can effectively passivate the defects and restrain charge
recombination, thereby accelerating the enhancement of
photoelectric performance.
We then contrive to investigate the influence of F8IC doping
on the trap-state density with different passivation strategies,
which is obtained using the SCLC method. The linear J−V
relationship shown in Figure 4e confirms that the Ohmic
region starts at a low voltage. With the increase in voltage bias,
it transforms into the trap-filled limited region (red region),
which can be recognized by the rapid nonlinear rise (set in at
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Figure 5. SCLC model for (a) the hole-only devices with the device structure of ITO/NiOx/MAPbI3 (without and with F8IC)/Au and (b) hole-
only devices with the device structure of ITO/NiOx/MAPbI3 (without and with IT-4F)/Au. (c, d) Energy level diagrams of p-i-n planar
heterojunction PVSCs with F8IC additive and IT-4F additive, displaying the charge carrier extraction pathways. (e) Energy level diagram of typical
nonfullerene n-type organic semiconductor molecules and their passivation methods from previous studies.

VTFL) of injected current.38 The trap-state density can be
calculated using the following equation39
ent L2
VTFL =
2εε0
where L is the thickness of the perovskite film, ε (=32) is the
relative dielectric constant of the perovskite, and ε0 is the
vacuum permittivity. Unsurprisingly, the measured trap-state
density (nt) declines from 1.69 × 1016 cm−3 (w/o F8IC) to
1.41 × 1016 cm−3 (F8IC antisolvent) and 1.21 × 1016 cm−3
(F8IC additive). The lower nt in the F8IC-passivated film
confirms that F8IC can effectively passivate the trap states via
additive doping. The stability of the devices is investigated
under ambient conditions without any encapsulation (relative
humidity ∼60%, temperature ∼25 °C) for 30 days, as shown in
Figure 4f. The devices experience a rapid decay and retain 50,
75, and 80% of the initial PCEs in the PVSCs without F8IC
and with F8IC via antisolvent dripping and additive doping
methods, respectively. Moreover, we carry out stability tests
under continuous one-sun illumination in a nitrogen
atmosphere (Figure S6d). The evolution of normalized PCEs
for the devices with and without F8IC passivation indicates
that the F8IC-passivated devices show enhanced illumination
stabilities owing to the reduced surface defects. It has been
reported that the trap site in the perovskite film will serve as a
channel through which moisture can permeate and thus
(1) accelerate the decomposition of the perovskite crystal.12,13
Thus, additive doping is more effective than the antisolvent
dripping method in defect passivation by F8IC molecules.
Universality of Optimal Passivation Strategies. To
investigate whether all nonfullerene n-type organic semi-
conductor molecules have this passivation phenomenon, IT-4F
(3,9-bis(2-methylene-((3-(1,1-dicyanomethylene)-6,7-di-
fluoro)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno-
[2,3-d:2′,3′-d’]-s-indaceno[1,2-b:5,6-b’]dithiophene) has been
applied as a representative passivator for fabricating PVSCs via
these two different methods. As shown in Figure S7a, it
contains the same functional groups as F8IC such as CO,
nitrile (C−N), and thiophene groups. At the same time, IT-4F
has a lower highest occupied molecular orbital (HOMO)
energy level (−5.7 eV) than F8IC (−5.4 eV).40,41 Figure S7b
shows the J−V characteristic curves of the best-performance
devices, and the corresponding detailed photovoltaic param-
eters are summarized in Table S5. Surprisingly, the PCE of the
56157 https://dx.doi.org/10.1021/acsami.0c15042
ACS Appl. Mater. Interfaces 2020, 12, 56151−56160
ACS Applied Materials & Interfaces
IT-4F-passivated device treated via antisolvent dripping
increases to 17.05% with a slight increase of Voc, Jsc, and FF.
In comparison, the IT-4F-passivated device treated via additive
doping exhibits overall degraded photovoltaic parameters. We
have used the SCLC model to measure and compare the
charge carrier mobility in F8IC- and IT-4F-incorporated
perovskite films. The dark current of the hole-only devices
(ITO/NiOx/MAPbI3 (without and with F8IC or IT-4F)/Au)
is well fitted (Figure 5a,b) using the Mott−Gurney law42
9 V2
J= εε0μ 3
8 L (2)
The hole mobility of 6.94 × 10−3 cm2 V−1 s−1 is obtained
from the curve fitting for the F8IC-passivated perovskite film
via additive doping, which is even higher in contrast to the
reference film (3.19 × 10−3 cm2 V−1 s−1). However, the hole
mobility of the IT-4F passivated perovskite film via additive
doping is relatively slower (1.15 × 10−4 cm2 V−1 s−1) than the
reference film. These results are most likely owing to the
mismatch of energy levels between MAPbI3 and semi-
conductor molecules, which plays a vital part in carrier
transport by the additive doping method. It is reported that the
F8IC and IT-4F molecules have HOMO values of −5.4 and −
5.7 eV, respectively. By contrast, the HOMO of F8IC has the
same value with the conduction band minimum (CBM) of
MAPbI3 (−5.4 eV) (Figure 5c), and the HOMO of IT-4F
exhibits a disparity of 0.3 eV with the CBM of perovskites
(Figure 5d). The small energetic disparities can result in
effective hole injection from the perovskite to NiOx, whereas
the large energetic disparities will form a barrier to reduce the
charge injection. So far, a large number of nonfullerene n-type
organic semiconductor molecules with various functional
groups have been used to passivate the defects. Figure 5e
shows the energy levels of representative molecules, and the
photovoltaic parameters of the devices are listed in Table S6. It
is observed that the semiconductor molecules incorporated via
the antisolvent dripping method have large energetic
disparities with the perovskite. These small molecules, for
instance, IDIC (indacenodithiophene end-capped with 1,1-
dicyanomethylene-3-indanone), ITIC-Th [(3,9-bis(2-methyl-
ene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis-
(5-hexylthienyl)-dithieno[2,3-d:2′,3′-d’]-s-indaceno[1,2-b:5,6-
b’]dithiophene)], IT-4F, and ITIC (3,9-bis(2-methylene-(3-
(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexyl-
phenyl)-dithieno[2,3-d:2′,3′-d’]-s-indaceno[1,2-b:5,6-b’]-di-
thiophene), can effectively suppress the defects and enhance
the photoelectric performance.25,43−45 Nevertheless, some
molecules with small energetic disparities (such as ITIC and
INIC) exhibit improved optoelectronic performance using the
additive doping method.46,47 Hence, additive doping is not the
optimal passivation method for all nonfullerene n-type organic
semiconductor passivators. The selection of an optimal
passivation strategy should also be considered according to
the energy level matching between the passivators and
perovskite. The small energetic disparity is expected to serve
as an efficient bridge for carrier transport when the passivators
are added via the additive doping method, whereas the large
energetic disparity will form a barrier to reduce the charge
injection.
56158
■
www.acsami.org Research Article
CONCLUSIONS
In conclusion, we realize that the same passivator added via
various methods result in different degrees of passivation for
perovskite defects. The mechanism between antisolvent
dripping and additive doping strategies on the passivation
effects in PVSCs is demonstrated by adding a nonfullerene
organic semiconductor molecule F8IC into the perovskite. In
result, only the surface defects of the perovskite film have been
passivated through the antisolvent dripping method, which
result in an improvement in Voc and FF. More importantly, the
F8IC added via additive doping effectively decreases the
defects distributed on the surface and inside the bulk film, and
homogenous and compact perovskite films with denser and
uniform crystal grains can be obtained, which lead to a
significant promotion of charge carrier transfer. Additionally, it
has been proved that additive doping is not the optimal
passivation method for all nonfullerene n-type organic
semiconductor passivators. IT-4F is applied to confirm that
the selection of optimal passivation strategies should also be
considered according to the energy level matching between the
passivators and perovskite. The small energetic disparities are
expected to serve as an efficient bridge for carrier transport
when the passivators are added via the additive doping
method, whereas the large energetic disparities will form a
barrier to reduce the charge injection. Provided that the
performance of PVSCs is desired to be further enhanced, more
effort should be paid on the passivation of defects, such as the
selection of passivators with an optimal binding configuration
and the passivation method.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c15042.
UV−vis absorption spectra, XRD patterns, top-view
SEM images, FTIR spectra, J−V metrics, EQE spectra,
Jsc dependence, EIS, J−V curves, and photovoltaic
parameters of the PVSCs under different conditions
(PDF).
■
AUTHOR INFORMATION
Corresponding Authors
Licheng Tan − College of Chemistry and Institute of Polymers
and Energy Chemistry, Nanchang University, Nanchang
330031, China; orcid.org/0000-0001-7208-7297;
Email: tanlicheng@ncu.edu.cn
Yiwang Chen − College of Chemistry and Institute of Polymers
and Energy Chemistry, Nanchang University, Nanchang
330031, China; Institute of Advanced Scientific Research
(iASR), Jiangxi Normal University, Nanchang 330022,
China; orcid.org/0000-0003-4709-7623;
Email: ywchen@ncu.edu.cn
Authors
Juan Long − College of Chemistry and Institute of Polymers
and Energy Chemistry, Nanchang University, Nanchang
330031, China
Wangping Sheng − College of Chemistry and Institute of
Polymers and Energy Chemistry, Nanchang University,
Nanchang 330031, China
https://dx.doi.org/10.1021/acsami.0c15042
ACS Appl. Mater. Interfaces 2020, 12, 56151−56160
ACS Applied Materials & Interfaces
Runying Dai − Institute of Advanced Scientific Research
(iASR), Jiangxi Normal University, Nanchang 330022,
China
Zengqi Huang − College of Chemistry and Institute of
Polymers and Energy Chemistry, Nanchang University,
Nanchang 330031, China
Jia Yang − College of Chemistry and Institute of Polymers and
Energy Chemistry, Nanchang University, Nanchang 330031,
China
Jiaqi Zhang − College of Chemistry and Institute of Polymers
and Energy Chemistry, Nanchang University, Nanchang
330031, China
Xiang Li − College of Chemistry and Institute of Polymers and
Energy Chemistry, Nanchang University, Nanchang 330031,
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c15042
Author Contributions
∥ (17) Jiang, Q.; Zhao, Y.; Zhang, X.; Yang, X.; Chen, Y.; Chu, Z.; Ye,
J.L. and W.S. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
L.T. acknowledges the support from the National Natural
Science Foundation of China (NSFC) (51973088, 51663015,
and 51672121). Y.C. acknowledges the support from the
National Natural Science Foundation of China (NSFC)
(51833004).
■
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