Letter

http://pubs.acs.org/journal/aelccp

Interfacial Defect Passivation and Charge

Carrier Management for Efficient Perovskite
Solar Cells via a Highly Crystalline Small
Molecule
Rongmei Zhao, Lin Xie,* Rongshan Zhuang, Tai Wu, Rongjun Zhao, Linqin Wang, Licheng Sun,
and Yong Hua*
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sı Supporting Information

ABSTRACT: Minimizing the interfacial defects and improving the charge transferability of charge-transfer layers
have become the most important strategies to boost the efficiency and stability of perovskite solar cells. However,
most molecular passivators currently employed to alleviate interfacial defects generate poorly conductive aggregates
at the interfaces, hindering the extraction of charge carriers. Here, a holistic interface engineering strategy
employing a highly crystalline small molecule of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) is
reported. We reveal that C8-BTBT bridges the perovskite film to the hole-transporting layer with reduced interfacial
defects and improved charge carrier management. Moreover, such interfacial modification with air-stable C8-BTBT
achieves a desirable and robust morphology of Spiro-OMeTAD by reducing the aggregates. Accordingly, C8-BTBT-
treated devices exhibit a great enhancement to all photovoltaic performance characteristics with an absolute
efficiency improvement exceeding 2%. The C8-BTBT-modified Spiro-OMeTAD enables decent thermal tolerance,
which paves the way for enhancing the performance of Spiro-OMeTAD-based perovskite optoelectronics.

H ybrid organic−inorganic all-solid perovskite solar

cells (PSCs) have demonstrated remarkable progress
in photovoltaic power conversion efficiency (PCE)
from 9.7%1 to a certified value of 25.6%2 within the past
decade, showing great potential for next-generation photo-
titanium dioxide (TiO2) and tin dioxide (SnO2) are the most
successful ETLs for the mesoscopic and planar structured
PSCs because of their outstanding electron transferability and
suitable band alignment.8−10 The most successful HTL in
highly efficient PSCs is lithium bis(trifluoromethanesulfonyl)-
voltaic technology. The high-efficiency output of PSCs lies in
their low-cost solution processing3,4 and impressive optoelec-
tronic properties, including a high absorption coefficient, direct Received: September 4, 2021
photocarrier generation, tunable bandgap, and long carrier Accepted: October 28, 2021
diffusion length.5−7 The state-of-the-art PSCs consist of a Published: November 4, 2021
polycrystalline perovskite layer that is sandwiched between
electron- and hole-transporting layers (ETL and HTL) that are
for the charge carrier extraction and transport. To date,

© 2021 American Chemical Society https://doi.org/10.1021/acsenergylett.1c01898

4209 ACS Energy Lett. 2021, 6, 4209−4219
ACS Energy Letters http://pubs.acs.org/journal/aelccp Letter

Figure 1. (a) Chemical structure of C8-BTBT. (b) UV−vis absorption spectra of C8-BTBT and Sprio-OMeTAD solution in CH2Cl2. (c)
Energy level diagram of the perovskite, C8-BTBT, and Spiro-OMeTAD. (d) XRD patterns of C8-BTBT prepared on a glass substrate. (e)
GIWAXS pattern of C8-BTBT prepared on Silica wafer. (f) SCLC measurement of the hole-only devices based on C8-BTBT. (g) Schematic
illustration depicting process of interfacial engineering based on C8-BTBT.

imide (LiTFSI) doped Spiro-OMeTAD. Although LiTFSI
enables the oxidation of Spiro-OMeTAD to improve its hole
mobility, the phase accumulation of hygroscopic LiTFSI results
in severe morphology degradation of Spiro-OMeTAD film
through formation of pinholes, which can be further aggravated
by heating.11−14 The inferior morphology is the main reason
for the poor thermal stability in Spiro-OMeTAD-based
PSCs.15−17
Moreover, the carrier lifetime of polycrystalline perovskite
films is still shorter than that of its single crystal, and the
massive presence of the nonradiative recombination sites at the
interface is the dominant loss mechanism of the photovoltage
(VOC),18−20 suggesting that the defect passivation at the
surfaces and grain boundaries (GBs) have yet to be
optimized.21−23 Recently, employing interfacial defect passiva-
tion strategy via organic molecules has been considered as one
of the most effective approaches to improve the efficiency of
PSCs, including Lewis bases24 and acids25 and other molecule
derivatives of alkylammonium,26−28 pyridine, and thio-
phene.29−31 However, most organic molecules used in
interfacial defect passivation are insulators with an amorphous
state, implying that there is a possibility of charge carrier loss
during the extraction/transport before contributing the current
to the PSCs. According to the literature, most molecular
4210
passivators have been meticulously modulated into ultrathin
layers (or ultralow concentrations) to minimize the charge
carrier’s loss, which increases the difficulty and the repeatability
of the process.32−34 In addition, the imbalanced charge carrier
transferability of the ETL and HTL is another important issue
for interface recombination. 35,36 This is due to the
accumulation of charge carriers at the interface, which may
lead to the losses of fill factor (FF) and short-circuit current
density (JSC). Although the engineering of individual functional
layers has been well-established and exploited in separated
works, holistic engineering strategies in terms of defect
passivation and charge carrier management have not been
widely considered and systematically investigated in the
development of PSCs, especially for the perovskite/HTL
interface.37−40 Furthermore, the effect of molecular passivators
on manipulating morphology for HTLs has rarely been
studied.
Herein, we introduce a feasible interfacial engineering
strategy that involves the synergic engineering of interfacial
defect passivation, charge carrier management, and morpho-
logical manipulation of Spiro-OMeTAD by employing the
highly crystalline C8-BTBT. To the best of our knowledge,
highly crystalline small molecules with high hole mobility have
not yet been demonstrated in PSCs as multifunctional and
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ACS Energy Letters http://pubs.acs.org/journal/aelccp
versatile interlayers. The rationale for selection of C8-BTBT as
interfacial layer is as follows: (1) C8-BTBT offers considerably
high hole mobility (hole mobility up to 43 cm2 V−1 s−1).41 (2)
The [1]benzothieno[3,2-b]benzo-thiophene (BTBT) is a
promising core structure for air-stable semiconductors.42 (3)
The sulfur atoms in the BTBT π-backbone supply the
possibility of defect passivation effect. Through a systematic
study, we uncover the key role of highly crystalline C8-BTBT
in reducing interfacial defects of perovskite film, constructing
efficient charge extraction bridges for the holes and improving
the transferability of Spiro-OMeTAD. Our findings not only
offer a feasible strategy to enhance the device performance but
also highlight the importance of a highly crystalline small
molecule with outstanding hole mobility in reconstructing the
morphology of the Spiro-OMeTAD film to improve thermal
stability. Consequently, our strategy yields significant enhance-
ment in all photovoltaic characteristics, enabling us to fabricate
PSCs with a PCE over 21% with improved thermal and
ambient stability.
We began our investigations with a study of understanding
the photophysical and electrochemical properties in highly
crystalline C8-BTBT (Figure 1 and Table 1). Figure 1a
Table 1. Optical and Photoelectrical Properties of C8-
BTBT and Spiro-OMeTAD
material λmaxa (nm) EHOMOb (eV) ELUMOc (eV) Eg (eV)
C8-BTBT 308 −5.23 1.61 3.62
Spiro-OMeTAD 385 −5.22 −2.29 2.93
a
Measured in CH2Cl2 solution. bHOMO level is calculated from the
onset of the first oxidation potential in differential pulse voltammetry,
according to the equation: EHOMO = −5.1 − (E1/2 − E1/2Fc), E1/2Fc =
0.2 eV. cELUMO = EHOMO + Eg.
presents the chemical structure of C8-BTBT employed in this
work, in which the identical alkyl tails are symmetrically
substituted in the molecular long-axis direction of the
benzothienobenzothiophene (BTBT) core to improve the
solubility and facilitate lateral intermolecular interaction.43,44
The optical absorption of C8-BTBT and Spiro-OMeTAD
solution in dichloromethane (CH2Cl2) is shown in Figure 1b;
we derived a bandgap of 3.62 and 2.93 eV for the C8-BTBT
and Spiro-OMeTAD, respectively, using the Tauc plot (Figure
S1). The highest occupied molecular orbital (HOMO) energy
levels of C8-BTBT and Spiro-OMeTAD were determined by
differential pulse voltammetry (DPV) measurement (Figure
S2). Accordingly, the HOMO levels of C8-BTBT and Spiro-
OMeTAD are calculated to be −5.23 and −5.22 eV,
respectively, indicating the HOMO of C8-BTBT is matched
well between the valence band (VB) edge of perovskite and the
HOMO level of Spiro-OMeTAD. The energy level diagram of
perovskite, C8-BTBT, and Spiro-OMeTAD is illustrated in
Figure 1c. It can be seen that the insertion of C8-BTBT leads
to an optimized energy band alignment. To explore the
thermal stability of C8-BTBT, differential scanning calorimetry
(DSC) and polarized optical microscopy (POM) were
performed (Figure S3). It is shown that C8-BTBT undergoes
a phase transition from solid crystal to liquid crystal at 110.2
°C, and from liquid crystal to isotropic liquid at 124.7 °C. The
DSC result indicates that C8-BTBT shows stable solid crystal
phases below 110 °C. To investigate the ordering and
crystallinity of the C8-BTBT, we performed X-ray diffraction
(XRD) and grazing incidence wide-angle X-ray scattering
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Letter
(GIWAXS) experiments, as shown in Figure 1d,e. The XRD
pattern of the C8-BTBT film exhibits three dominant
characteristic peaks at 2θ of 3.2°, 6.2°, and 9.2° (Figure 1d),
which can be assigned to (100), (200), and (300) planes of
crystalline C8-BTBT as previously reported.45 The strong
diffraction (100) peak with a small full width at half-maximum
(fwhm) of 0.094 shown in the C8-BTBT XRD pattern suggests
the high crystallinity due to the strong π−π stacking of the
BTBT core in the C8-BTBT film. To gain insight into the
orientation of C8-BTBT, GIWAXS measurements were
conducted. As revealed in Figure 1e, uniform intensities
along the Debye−Scherrer rings are observed, indicating that
the C8-BTBT crystallites are isotopically oriented on top of the
perovskite film.46,47 Furthermore, the hole mobility of the C8-
BTBT was calculated to be 8.22 × 10−4 cm2 V−1 s−1 through
the space charge-limited current (SCLC) measurement with a
hole-only device (Figure 1). Details of the sample preparation
procedure and SCLC measurements are provided in the
Supporting Information.
An illustration of the interfacial engineering of PSCs
modified with C8-BTBT is shown in Figure 1g. We fabricated
C8-BTBT-based devices in a mesoporous architecture
consisting of the following layers: fluorine-doped tin oxide
(FTO)/compact titanium oxide (c-TiO2)/mesoporous TiO2
(mp-TiO2)/perovskite/C8-BTBT/Spiro-OMeTAD/Au. To
modify the perovskite film and Spiro-OMeTAD film at the
same time, we employed a simple double-coating method as in
the following: First, a typical perovskite film with a
composition of (FAP-
bI3)0.875(MAPbBr3)0.075(CsPbI3)0.05(PbI2)0.03 was prepared by
a one-step spin-coating method followed by dripping of
chlorobenzene (CB). Then, a solution of 1−40 mg mL−1 of
C8-BTBT dissolved in CB was spin-coated onto the perovskite
surface without annealing treatment. The hole-transport layer
was subsequently deposited on top of the perovskite/C8-
BTBT by spin-coating a Spiro-OMeTAD/CB solution. It is
noteworthy that C8-BTBT will not be utterly removed from
the perovskite surface by the deposition of Spiro-OMeTAD/
CB owing to the coordination interaction with the perovskite
surface, as we discuss later.
To investigate the influence of C8-BTBT on perovskite film,
various characterizations were carried out on the bare
perovskite films modified without and with C8-BTBT. We
first conducted UV−vis absorption measurement on perovskite
film with and without C8-BTBT modification. Figures 2a and
S4 show that C8-BTBT has a negligible effect on optical
bandgap and light absorption. Subsequently, XRD measure-
ment is performed to study the effect of C8-BTBT on the
crystal structure and crystallinity of perovskite film. As shown
in Figure 2b, the bare perovskite film and C8-BTBT-modified
perovskite film present the identical diffraction peaks of a
typical perovskite film at 2θ of 14.1°, 28.3°, and 34.9°,
suggesting the modification of C8-BTBT will not change the
perovskite crystal structure. However, two strong additional
peaks located at 6.2° and 9.2° evident in the XRD pattern of
C8-BTBT-modified perovskite film indicate the existence of
the highly crystalline C8-BTBT phase. The result is well
consistent with the atomic force microscopy (AFM) (Figure
2c) and scanning electron microscopy (SEM) images (Figure
S5a). Notably, the C8-BTBT clusters irregularly accumulate on
the perovskite film surface, instead of a continuous thin layer
over the perovskite film. The root mean square (RMS) of
perovskite film increases from 28.8 to 35.9 nm after
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Figure 2. (a) UV−vis absorption spectra of perovskite film modified with and without C8-BTBT. (b) XRD patterns of perovskite film and
C8-BTBT-modified perovskite film prepared on FTO/TiO2 substrates. (c) Top-view AFM image of C8-BTBT-modified perovskite film. (d)
Pb 4f XPS spectra for perovskite and C8-BTBT-modified perovskite film. (e) S 2p XPS spectra for bare C8-BTBT film and C8-BTBT-
modified perovskite film. (f) TRPL spectra of perovskite film and C8-BTBT-modified perovskite film prepared on glasses.

modification with C8-BTBT (Figure S5b). The morphology of
C8-BTBT clusters presents a hexagonal crystal morphology,
which is consistent with the theoretical prediction by using the
material studio software,48 further confirming the high
crystallinity of C8-BTBT prepared on the perovskite film.
Nevertheless, it was difficult to specify the chemical
interaction based on these analyses; if any inclusions exist
inside or outside the perovskite crystal, the chemical binding
energy of perovskite can vary slightly. Therefore, X-ray
photoelectron spectroscopy (XPS) was carried out to under-
stand the perovskite interface with C8-BTBT (Figure S6). XPS
spectra of the Pb 4f for the bare perovskite film showed two
peaks located at 143.08 and 138.28 eV, corresponding to the
Pb 4f 5/2 and Pb 4f 7/2, respectively (Figure 2d), whereas the
corresponding binding energy shifted to lower values of 142.88
and 137.98 eV for the C8-BTBT-modified film. In the
meantime, the binding energy at 164.68 and 163.48 eV was
related to the S 2p 1/2 and S 2p 3/2 of the bare C8-BTBT film
shift to higher bind energy in the C8-BTBT-modified
perovskite film (Figures 2e and S7). The complementary
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peak shift of Pb 4f and S 2p in the perovskite film with C8-
BTBT treatment evidenced the correlation interaction between
the C8-BTBT and the Pb on the perovskite surface.49,50 Thus,
we presumed that the introduction of C8-BTBT at the
perovskite surface can passivate the interfacial defect effectively
caused by the uncoordinated lead of perovskite film and serve
as a bridge between Spiro-OMeTAD film and perovskite film
to improve interfacial contact and charge carrier extraction. To
verify our assumption, time-resolved photoluminescence
(TRPL) measurement was conducted (Figure 2f). The result
shows that the C8-BTBT-modified perovskite film prepared on
glass exhibits a longer carrier lifetime lengthening than that of
the control film, implying the suppressed nonradiative charge
recombination sites from defects. The fitting details and values
for the TRPL are summarized in Table S1. To confirm the
passivation effect of C8-BTBT in polycrystalline perovskite
film, we fabricated the PSCs with C8-BTBT through the
antisolvent dripping process to mix the C8-BTBT in bulk
perovskite film. We carefully modulated the concentration of
the C8-BTBT in antisolvent (CB) as shown in Figure S8 and
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Figure 3. (a) Steady-state PL and (b) TRPL of perovskite film and perovskite/HTLs on FTO/TiO2 substrates, respectively. (c and d) AFM
images of Spiro-OMeTAD and Spiro-C8 prepared on perovskite films. (e) SCLC measurements of the hole-only devices based on Spiro-
OMeTAD and Spiro-C8. (f) Illustration of hole collection and transportation in Spiro-C8 film.

Table S2. The best performance is given by the C8-BTBT with
a concentration of 1 mg mL−1, which is higher than the control
device. The trap states of the control and C8-BTBT-modified
samples were calculated to be 6.35 × 1016 and 2.56 × 1016
cm−3 with the SCLC measurements (Figure S9). A lower trap
density is observed in C8-BTBT-treated devices, indicating the
passivation effect of C8-BTBT in polycrystalline perovskite
film, which could be assign to the chemical interaction between
the C8-BTBT and perovskite film. When considering the fact
of the high solubility of C8-BTBT in CB, we examined the
XPS spectra of S 2p of C8-BTBT-modified film after washing
with pure CB solvent to probe the presence of C8-BTBT on
perovskite surface even after the Spiro-OMeTAD deposition.
As revealed in Figure S10, a weak S 2p peak is still able to be
detected in the washed film by the XPS measurement. This
observation reveals that Spiro-OMeTAD deposition will not
utterly remove the C8-BTBT from the perovskite surface
because of the strong chemical interaction between them. On
4213
the other side, the weak intensity of S 2p peak in washed C8-
BTBT-modified film implies that most of the C8-BTBT
dissolved into the Spiro-OMeTAD solution, thereafter forming
a mixture with Spiro-OMeTAD in the HTL.
The high solubility of C8-BTBT in CB solvent enables the
C8-BTBT to integrate into Spiro-OMeTAD film during the
spin-coating process, thereby changing the performance of
Spiro-OMeTAD. To understand whether the Spiro-OMeTAD
deposition affects its properties, the steady-state PL (SSPL)
and TRPL measurements were first performed to characterize
the charge-transfer behavior at the interface between the
perovskite and Spiro-OMeTAD, as shown in Figure 3a,b. The
SSPL and TRPL spectra were recorded by preparing samples
on FTO/TiO2 substrates. Lower SSPL intensity was noted for
Spiro-OMeTAD modified with C8-BTBT film (hereafter
termed “Spiro-C8”) as compared with the Spiro-OMeTAD
film, indicating faster charge carriers transfer at the interface
because of the efficient hole extraction by the Spiro-C8. Carrier
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Figure 4. (a) J−V curves of control and C8-BTBT PSCs. (b) PCE distribution of control and C8-BTBT devices. (c) EQE and integrated JSC
of control and C8-BTBT-modified devices. (d) Steady-state power output for the best-performing C8-BTBT-modified device. TA spectra of
(e) bare perovskite film, (f) perovskite/Spiro-OMeTAD film, and (g) perovskite/Spiro-C8 film. (h) Normalized fs-TA kinetics at 680 nm of
the pristine perovskite film, perovskite/Spiro-OMeTAD, and perovskite/Spiro-C8 in response to a 475 nm excitation with a fixed pump
fluence of 14 μJ cm−2. (i) Dark J−V curves of control and C8-BTBT-modified hole-only devices.

lifetime lengthening, with the HTL and ETL extraction layer, is
confirmed through TRPL studies, where the average lifetimes
of the perovskite, Spiro-OMeTAD, and Spiro-C8 films are
120.9, 31.9, and 28.7 ns, respectively. The carrier lifetime
lengthening decreased noticeably in Spiro-C8-treated perov-
skite film, which offers confirmation of the reduction in
nonradiative recombination sites at the interface. The fitting
details and values for the TRPL are summarized in Table S3.
For a more comprehensive characterization of electronic
properties and morphology of Spiro-OMeTAD film modified
with C8-BTBT, we also performed the SCLC and AFM
measurements. The hole mobility (μh) of Spiro-C8 was
calculated to be 5.62 × 10−4 cm2 V−1 s−1 (Figure 3e), whereas
that of Spiro-OMeTAD with LiTFSI dopants displays hole
mobility of 1.89 × 10−4 cm2 V−1 s−1. Hole mobility of Spiro-C8
that is about three times higher than that of Spiro-OMeTAD
should benefit from the incorporation of highly crystalline C8-
BTBT with a high hole mobility of 8.22 × 10−4 cm2 V−1 s−1. It
is known that the morphology of Spiro-OMeTAD is critically
important to the performance of PSCs. AFM measurements
were carried out to evaluate the effect of the C8-BTBT on the
Spiro-OMeTAD’s morphology (Figure 3c,d). Notably, many
4214
isolated and scattered large domains of over 1 μm diameter
(RMS = 6.15 nm) are observed in the as-cast Spiro-OMeTAD
film, which is assigned to the self-assemble of Spiro-
OMeTAD.11 In contrast, after modification of C8-BTBT, the
morphology of Spiro-C8 shows uniform small domains with a
smoother surface (RMS = 3.59 nm) across the entire scanning
area. Park et al. recently reported a new hole-transporting
material (named HL38), which can capture the mobile Li+ and
reduce the aggregation of Li+ because of the strong
complexation between the Li+ and HL 38.51 In our study, to
study the chemical interaction between LiTFSI and C8-BTBT,
Fourier-transform infrared spectroscopy (FTIR) and Raman
measurements were carried out as shown in Figure S11.
However, the characteristic chemical bonding peaks shift, such
as S−N−S, C−S, and S=O stretching in LiTFSI and C−S and
C=C stretching in C8-BTBT, were not observed in FTIR and
Raman spectra. These results indicate that there is no strong
chemical interaction between the Li+ and C8-BTBT. To gain
deep insight into the behavior of highly crystalline C8-BTBT
in the Spiro-OMeTAD film, we conducted the AFM
measurements of Spiro-OMeTAD film doping with C8-
BTBT and washed the modified Spiro-OMeTAD film with
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Table 2. Summary of Photovoltaic Parameters (Reverse Scan) for the Control and C8-BTBT-Modified Devices, Measured
under AM 1.5 Illumination
Device JSC (mA cm−2)
control best 23.80
average 24.33 ± 0.41
C8-BTBT best 24.70
average 24.69 ± 0.31
CB solvent. Interestingly, C8-BTBT crystals exhibit large
domains with a diameter over 1 μm (Figure S12a). This
indicates that C8-BTBT shows strong self-assembled capability
within the Spiro-OMeTAD film, suggesting C8-BTBT presents
a huge difference in crystalline speed and process compare to
Spiro-OMeTAD. Upon CB post washing, the nanosize C8-
BTBT crystals can be observed in the highlighted areas
resulting in the formation of a mottled top-view morphology
(Figure S12b,c). Considering the different crystallization
processes of C8-BTBT and Spiro-OMeTAD, we propose
that C8-BTBT crystals on top of the perovskite film
experienced redissolve and recrystalline processes during the
deposition of Spiro-OMeTAD. The proposed behavior and
working mechanism of C8-BTBT in Spiro-OMeTAD are
depicted in Figure 3f. The independent highly crystalline C8-
BTBT phase within the bulk film of Spiro-OMeTAD can
hinder the aggregation of LiTFSI and crystallinity of Spiro-
OMeTAD owing to forming continuous and compact hole-
transfer channels. Furthermore, the favorable morphology of
Spiro-OMeTAD enables improving the hole collection and
transport, resulting in a reduction of nonradiative recombina-
tion at the interface.
Considering these findings, we carefully modulate the
concentration (1−40 mg mL−1) of C8-BTBT employed as
an interfacial layer to fabricate PSCs. The statistical photo-
voltaic parameters of C8-BTBT-modified devices are shown in
Figure S13 and Table S4. The optimal concentration of C8-
BTBT as the interfacial layer is achieved at 5 mg mL−1.
Notably, the C8-BTBT-modified device, even a C8-BTBT/CB
solution with the ultrahigh concentration of 40 mg mL−1, still
shows better performance than that of the control device. This
indicates that the less-concentration sensitive C8-BTBT
provides a wide processing window in interfacial engineering
for enhancing the performance of PSCs. Figure 4a presents the
current density−voltage (J−V) curves of the control and C8-
BTBT-based PSCs measured under standard AM 1.5G
illumination in ambient conditions. The photovoltaic charac-
teristics are summarized in Table 2. The champion control
device prepared without C8-BTBT shows JSC, VOC, FF, and
PCE values of 23.80 mA cm−2, 1.09 V, 74.23% and 19.17%,
respectively. The best-performing C8-BTBT-modified device
presents an increase across all photovoltaic parameters,
resulting in a best PCE value of 21.94%. The statistical
distribution of PCE values from over 20 devices each for the
control and C8-BTBT-modified devices (Figure 4b) confirms
that the enhancement to photovoltaic performance arises
because of the introduction of C8-BTBT. The external
quantum efficiency (EQE) of the fabricated devices is depicted
in Figure 4c. The integrated JSC values for the control and C8-
BTBT-modified PSCs are found to be 23.03 and 23.73 mA
cm−2, respectively, consistent with the JSC values obtained from
the J−V curves. Maximum power point tracking is performed
to evaluate the stable steady-state power output (Figure 4d).
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Letter
VOC (V) FF (%) PCE (%)
1.09 74.23 19.17
1.07 ± 0.024 71.46 ± 2.12 18.68 ± 0.29
1.11 80.13 21.94
1.11 ± 0.004 77.95 ± 1.46 21.32 ± 0.34
The C8-BTBT-modified device yielded stabilized PCE of
20.76% at the bias of 0.86 V.
It is now required to unravel the reasons for the improved
VOC, JSC, and FF. Femtosecond transient absorption (fs-TA)
was carried out to investigate ultrafast hot carrier dynamics in
perovskite films. The films were excited at 475 nm. The TA
spectra show a negative (ΔA < 0) characteristic feature that is
known as photobleaching (PB). The normalized fs-TA spectra
of perovskite film, perovskite/Spiro-OMeTAD film, and
perovskite/Spiro-C8 in a short time scale (from 10 fs to 100
ps after excitation) are plotted in Figure 4e−g. When the
excitation is higher than the bandgap energy, the hot carriers in
the original perovskite film show a nonequilibrium distribution
as shown in Figure 4e. Under the same experimental
conditions, the broadening of the high-energy tail of the fs-
TA spectra is reduced in the presence of Spiro-OMeTAD
(Figure 4f). The broadening of the high-energy tail of the TA
spectra further slightly shrinks in the presence of C8-BTBT
(Figure 4g). This suggests that the hot hole carriers can be
efficiently extracted by using the C8-BTBT as the interfacial
layer.52 In order to compare the hot carrier extraction across
the Spiro-OMeTAD and Spiro-C8 film, we have plotted the
normalized kinetics of all systems at 680 nm in Figure 4h. In
the presence of Spiro-C8, the bleach recovers within less than
the 10 ps time scale, while for the bare perovskite film and the
perovskite/Spiro-OMeTAD film, they recover within tens of
picoseconds. This indicates that the hot holes could be easily
extracted from the deep energy levels of the perovskite surface
and transferred to the Spiro-C8. We also performed the SCLC
measurements to characterize the trap states in the control and
C8-BTBT-modified devices (the details are provided in the
Supporting Information). As displayed in Figure 4i, the VTFL of
control and C8-BTBT-modified devices are 0.69 and 1.12 V,
respectively. The corresponding trap density (Ntrap) of the
control and C8-BTBT-modified devices are calculated to be
3.82 × 1016 and 2.35 × 1016 cm−3, respectively. Thus, the first
conclusion drawn from these data is that the synergistic
reduction in interfacial defects of the perovskite film and the
reduction in nonradiative recombination at the interface are
the main reasons for increased VOC.
As revealed in the EQE spectra, the EQE value of the C8-
BTBT-modified device is higher than that of the control device
for the entire wavelength range. It is well-recognized that EQE
is defined as the product of absorption efficiency and charge
extraction efficiency.53,54 The same absorption intensity in
absorption spectra indicates that C8-BTBT modification is
unable to increase the film’s light absorption efficiency.
Therefore, the improved JSC in C8-BTBT-modified device
should be ascribed to the improved charge collection
efficiency. To address the improved charge collection efficiency
supplied by C8-BTBT, we designed an experiment that
fabricated the devices by directly doping the various
concentrations of C8-BTBT in the Spiro-OMeTAD film
(without LiTFSI dopants). The results are shown in Figure
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ACS Energy Lett. 2021, 6, 4209−4219
ACS Energy Letters http://pubs.acs.org/journal/aelccp
Figure 5. (a) Thermal stability and (b) Long-term stability of control and C8-BTBT-based PSCs. Top-view AFM images of (c) Spiro-C8 and
(d) Spiro-OMeTAD on perovskite substrates. (e) Proposed working mechanism of C8-BTBT in Spiro-OMeTAD under the heating stress.
S14 and Table S5. The device made from the bare Spiro-
OMeTAD shows poor performance with a PCE value of
3.78%. Interestingly, the device performance was improved
while we incorporated the proper amount of C8-BTBT into
the Spiro-OMeTAD. The most obvious improvements of
photovoltaic parameters are JSC and FF, whereas, when C8-
BTBT is employed as the dopant in the Spiro-OMeTAD film,
it cannot increase the VOC. As a result, the improved charge
collection efficiency should be attributed to the increased hole
mobility and fine-tuning morphology of Spiro-OMeTAD,
leading to the enhancement of JSC and FF in C8-BTBT-
modified devices. The enhancement to all the photovoltaic
parameters highlights the advantage of C8-BTBT serving as an
interfacial modification rather than a dopant in the Spiro-
OMeTAD film.
Thermal instability is a great challenge for the commerci-
alization of Spiro-OMeTAD-based PSCs.55−57 To evaluate the
effect of C8-BTBT modification on device thermal stability, we
subjected our control and C8-BTBT-modified devices to an
elevated temperature of 65 °C (Figure 5a). The thermal
stability was monitored by periodically measuring the PCE of
devices that were kept in a thermal oven with a relative
humidity of 5% ± 5%. After 125 h storage at 65 °C, the C8-
BTBT-modified device kept 88% of its initial PCE, whereas the
control device shows a rapid degradation to 56% of its initial in
PCE under the same testing conditions. In addition, the
ambient stability was evaluated by storing these devices in the
dark, at room temperature and relative humidity of 40% ± 10%
(Figure 5b). The control device lost 32% of its initial PCE
upon storing over 1500 h, while the C8-BTBT-modified device
kept over 90% of its initial PCE. To understand the origins that
accounted for the improved thermal stability of the C8-BTBT-
modified device at evaluated temperature, we carefully tracked
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Letter
the morphological changes of Spiro-OMeTAD film over time.
A clear degradation pathway of the Spiro-OMeTAD film is
revealed in Figure S15. The appearance of numerous pinholes
and the increased surface roughness (up to 9.27 nm) present in
the control films aging at 65 °C after 125 h indicate the
aggregation of LiTFSI and crystallinity of Spiro-OMeTAD
were aggravated under the thermal stress (Figure 5c,d). In
contrast, the morphology of the C8-BTBT-modified film
remains stable, which is assigned to the stable crystalline phase
of C8-BTBT in Spiro-OMeTAD. This further confirms that
C8-BTBT can efficiently prevent the aggregation of LiTFSI
and crystallinity of Spiro-OMeTAD even under heating stress.
The proposed mechanism of C8-BTBT is shown in Figure 5e.
The water contact angle (WCA) measurement was conducted
to assess the hydrophobicity of C8-BTBT-modified films
(Figure S16). The WCA was further increased from 84.5° to
93.7° owing to the hydrophobic nature of the C8-BTBT-
modified film surface, exemplifying its moisture tolerance. On
the basis of the detailed morphology characterization above,
we gained a clear understanding that such inferior morpho-
logical changes of Spiro-OMeTAD are responsible for the
device degradation under heating stress.
In summary, we have successfully demonstrated an effective
interfacial engineering strategy to fabricate efficient and stable
PSCs. It features superior interfacial passivation owing to its
chemical interactions with the perovskite surface and efficient
charge carrier management due to the high hole mobility of the
highly crystalline C8-BTBT. We have also rationalized the
importance of C8-BTBT in HTLs in further improving hole
mobility as the third dopant. By employing this strategy, the
C8-BTBT-modified device exhibits an increase of PCE from
19.17% to 21.94%, which is attributed to the reduced
nonradiative recombination at the surface and improved
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ACS Energy Lett. 2021, 6, 4209−4219
ACS Energy Letters http://pubs.acs.org/journal/aelccp
charge carrier collection and transport. More importantly, it
reduces the aggregations of LiTFSI and Spiro-OMeTAD,
forming a stabilized morphology and hydrophobic surface for
Spiro-OMeTAD film. Therefore, the C8-BTBT-treated device
shows improved thermal and ambient stability. This work
provides important insights into interfacial engineering in
Spiro-OMeTAD-based PSCs to achieve both high efficiency
and thermal stability.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsenergylett.1c01898.
Materials and device fabrication procedures; statistical
photovoltaic parameters of PSCs with different C8-
BTBT concentrations; Tauc plots of UV−vis spectra for
perovskite, C8-BTBT-treated perovskite film, Spiro-
OMeTAD film, and C8-BTBT-modified Spiro-OMe-
TAD film; DPV spectra of C8-BTBT; POM texture of
liquid crystal of C8-BTBT; SEM and AFM images of
perovskite film and C8-BTBT-modified perovskite film;
XPS spectra of perovskite film, C8-BTBT-modified
perovskite film, and C8-BTBT film; FTIR and Raman
spectra of LiTFSI, C8-BTBT, and mixture of LiTFSI and
C8-BTBT; AFM images of C8-BTBT-doped Spiro-
OMeTAD film with and without CB post-treatment;
tables of TRPL data and electronic parameters (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Lin Xie − Yunnan Key Laboratory for Micro/Nano Materials
& Technology, School of Materials and Energy, Yunnan
University, Kunming 650091, China; orcid.org/0000-
0002-8496-0548; Email: l.xie@ynu.edu.cn
Yong Hua − Yunnan Key Laboratory for Micro/Nano
Materials & Technology, School of Materials and Energy,
Yunnan University, Kunming 650091, China; orcid.org/
0000-0003-4799-2871; Email: huayong@ynu.edu.cn
Authors
Rongmei Zhao − Yunnan Key Laboratory for Micro/Nano
Materials & Technology, School of Materials and Energy,
Yunnan University, Kunming 650091, China
Rongshan Zhuang − Yunnan Key Laboratory for Micro/Nano
Materials & Technology, School of Materials and Energy,
Yunnan University, Kunming 650091, China
Tai Wu − Yunnan Key Laboratory for Micro/Nano Materials
& Technology, School of Materials and Energy, Yunnan
University, Kunming 650091, China
Rongjun Zhao − Yunnan Key Laboratory for Micro/Nano
Materials & Technology, School of Materials and Energy,
Yunnan University, Kunming 650091, China
Linqin Wang − Center of Artificial Photosynthesis for Solar
Fuels, School of Science, Westlake University, Hangzhou
310024, China; orcid.org/0000-0001-6293-6742
Licheng Sun − Center of Artificial Photosynthesis for Solar
Fuels, School of Science, Westlake University, Hangzhou
310024, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsenergylett.1c01898
4217
Letter
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
L.X. thanks High-Level Talents of Yunnan University
(CZ21623201). Y.H. thanks the National Natural Science
Foundation of China (22065038), the Key Project of Natural
Science Foundation of Yunnan (KC10110419), High-Level
Talents Introduction in Yunnan Province (C619300A010), the
Fund for Excellent Young Scholars of Yunnan
(K264202006820), the Program for Excellent Young Talents
of Yunnan University and Major Science (C176220200),
International Joint Research Center for Advanced Energy
Materials of Yunnan Province (202003AE140001), and
Technology Project of Precious Metal Materials Genetic
Engineering in Yunnan Province (No. 2019Z E001-1,
202002AB080001) for financial support. The authors thank
Dr. Xiaohe Miao and instrumentation and service center for
physical sciences at Westlake University for facility support and
technical assistance.
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■ NOTE ADDED AFTER ASAP PUBLICATION

This article originally published with an inaccurate description
for C8-BTBT. Polymer was changed to small molecule in the
title and several places throughout the text. The corrected
article published November 8, 2021.

4219 https://doi.org/10.1021/acsenergylett.1c01898
ACS Energy Lett. 2021, 6, 4209−4219