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Molecular doping of CuSCN for hole transporting

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Cite this: DOI: 10.1039/c9qi00557a

layers in inverted-type planar perovskite solar
cells†
In Su Jin, Ju Ho Lee, Young Wook Noh, Sang Hyun Park and Jae Woong Jung *

Received 16th May 2019,
Accepted 5th July 2019
DOI: 10.1039/c9qi00557a
rsc.li/frontiers-inorganic
Among many strategies to develop high-performance perovskite solar cells, interface engineering is con-
sidered as a promising approach for achieving high power conversion efficiency. Specifically, high optical
transparency and excellent electrical properties are essential for optimized hole transport materials in
inverted-type planar perovskite solar cells. In this study, we demonstrate that the molecular doping of
copper thiocyanate (CuSCN) by 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) signifi-
cantly enhances the photovoltaic performance of perovskite solar cells. The incorporation of F4TCNQ
into CuSCN leads to successful electron transfer from CuSCN to F4TCNQ, which affords more balanced
energy level alignment at the interface of the perovskite layer for hole conduction. Device analyses reveal
faster charge transport and less carrier recombination in the F4TCNQ-doped CuSCN-based devices, con-
tributing to not only the improved efficiency but also the hysteresis elimination. At the optimized doping
concentration, the doped CuSCN exhibited an ∼35% increased efficiency as high as 15.01% in the
inverted-type planar perovskite solar cells.

1. Introduction voltaic performance.11 There are several prerequisites for excel-

In the last decade, organo-lead trihalide perovskite-based solar
cells (PSCs) have received enormous interest as a next-gene-
ration photovoltaic technology due to their low material cost,
superior efficiency, and low-temperature solution
processability.1–4 The state-of-the-art power conversion efficien-
cies (PCEs) of PSCs have been achieved as high as 24% via suc-
cessful engineering in materials and devices.5 So far, high-per-
formance PSCs have usually been fabricated with a typical
device configuration of n–i–p, in which mesoscopic TiO2 and
organic semiconductors were used at the interfaces in the
devices as electron-transporting materials (ETMs) and hole-
transporting materials (HTMs), respectively.5–10 In contrast,
the inverted-type devices in a configuration of p–i–n have also
been investigated because of their much simpler device struc-
ture together with a more facile procedure for device fabrica-
tion. For the inverted-type devices, HTMs play a key role in
extracting and collecting the photo-generated holes from the
perovskite absorber, thus circumventing undesired recombina-
tion losses at the interfaces and enhancing the overall photo-
Department of Advanced Materials Engineering for Information & Electronics,
Kyung Hee University, 1732 Deogyeong-daero, Giheung-gu, Yongin-si,
Gyeonggi-do 446-701, Republic of Korea. E-mail: wodndwjd@khu.ac.kr
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c9qi00557a
lent candidates for HTMs in the inverted-type planar PSCs
such as high optical transparency and well-matched energy
levels. Highly transparent HTMs enable maximized photon
harvesting of the perovskite absorber, and the balanced
valence band maximum (VBM) levels of HTMs to the perovs-
kite ensure minimized undesired energy losses of hole carrier
transportation.19–21 For these criteria, a variety of p-type semi-
conductors including both organic and inorganic materials
have been utilized as HTMs in the inverted PSCs, which have
achieved comparable PCEs to the typical n–i–p devices in
recent years.12–15 Copper thiocyanate (CuSCN) is another inter-
esting p-type semiconductor that has been demonstrated as an
attractive candidate for solution-processed HTMs in opto-
electronic devices.16–18 Very recently, solution processed
CuSCN films have also been demonstrated as excellent HTMs
in PSCs because of their high optical transparency in the
visible region as well as sufficient energy levels (VBM =
−5.4 eV) to function as outstanding HTMs in PSCs.19–21
However, there are still some issues in CuSCN-based devices
that remain to be resolved such as unsatisfactory photovoltaic
performance and severe hysteresis. To further boost the photo-
voltaic performance, the ideal HTMs should possess high hole
mobility because the accumulated hole carriers in HTMs will
lead to undesirable energy level alignment at the interfaces,
which results in weak built-in field strength in each layer of
the device and a large energy level offset to the perovskite

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layer.22 Derived from that, relatively low hole mobility (conduc-
tivity) of CuSCN would lead to limited hole transfer to the per-
ovskite layer, which accelerates hole accumulation at the inter-
face and thus results in electron–hole recombination.20,25–27 For
this concern, considerable effort has been made to improve the
electronic properties of HTMs and hence to improve band align-
ment at the HTM/perovskite interface by p-type doping of
HTMs.23,24 For example, p-type doping of nickel oxide has been
explored to improve the electronic properties of the HTMs in
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the planar PSCs, and considerable PCE improvements have
been demonstrated.25–28 Thus, exploring the impact of p-type
doping of CuSCN on the photovoltaic performance of planar
PSCs is an important aspect of their optimization.
Here, we demonstrated the improved photovoltaic perform-
ance of inverted-type planar PSCs by employing the doped
CuSCN as a HTM for the first time. 2,3,5,6-Tetrafluoro-7,7,8,8-
tetracyanoquinodimethane (F4-TCNQ), a strong electron-
accepting molecule with the very low lowest unoccupied mole-
cular orbital (LUMO, −5.2 eV) energy levels, has been widely
used in organic electronics as a dopant to enhance photocon-
ductivity in conjugated polymers and to reduce the hole injec-
tion barrier in the devices29–31 (Fig. 1a). As F4TCNQ was mixed
with CuSCN, the electron transfer from CuSCN to F4TCNQ
occurs and then both the VBM and the Fermi level of CuSCN
become closer to the VBM of the perovskite, which resulted in
the reduction of the energy level offset between at the interface
of HTM/perovskites. As a result, F4TCNQ doping remarkably
enhanced hole extraction capability and reduced the resistance
for hole transport at the CuSCN/perovskite interface, boosting
Fig. 1 Schematic illustration of the device structure of PSCs studied in this work with electron transfer between CuSCN and F4TCNQ (a) and AFM
height images of CuSCN thin films with different concentrations of F4TCNQ (b).
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the PCE for the planar PSCs up to 15.01%. The systematic
device analyses further revealed that the doped CuSCN
enabled faster charge transport and less carrier recombina-
tion, which contributes to PCE enhancement and hysteresis
elimination.
2. Experimental
2.1 Materials
Copper thiocyanate (reagent grade) was purchased from
Duksan pure chemicals. Diethyl sulfide (98%), isopropyl
alcohol (99%), dimethyl sulfoxide (DMSO, 99%), and N,N-di-
methylformamide (DMF, 99%) were purchased from Sigma
Aldrich. Methylammonium iodide (MAI) was purchased from
Dyesol. Lead(II) iodide (99.9985%) was purchased from Alfa
Aesar. F4TCNQ and [6,6]-phenyl C61 butyric acid methyl ester
(PCBM) were purchased from TCI chemical and Nano-C,
respectively.
2.2 Device fabrication and measurements
The pre-cleaned ITO-coated glass substrates were treated with
UV-O3 for 15 min. The CuSCN solution in diethyl sulfide
(30 mg ml−1) with or without F4TNCQ was spin-coated on ITO-
coated glass substrates at 4000 rpm for 30 s and then annealed
at 100 °C for 10 min in the ambient atmosphere. The perovs-
kite precursor solution in which MAI (159 mg), PbI2 (461 mg)
and DMSO (78 mg) (1 : 1 : 1 molar ratio) were dissolved in
600 mg of DMF was spin-coated at 5000 rpm for 25 s onto the
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CuSCN/ITO substrates. At 7 s after the spin-coating proceeded,
400 μL of chlorobenzene was added dropwise onto the rotating
substrate. After the substrates were annealed at 100 °C for
10 min, the PC61BM solution (15 mg ml−1 in chlorobenzene)
and bis-C60 (2 mg ml−1 in isopropyl alcohol) were sub-
sequently spin-coated. Finally, the 100 nm thickness of the Ag
electrode was evaporated by using a thermal evaporator under
<5 × 10−6 Torr at an evaporation rate of 0.4 Å s−1 to complete
the device fabrication. The J–V curves of devices were
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measured using a solar simulator (AM 1.5G, 100 mW cm−2)
with a parameter analyzer (4200-SCS, Keithley). The aperture
area for the devices was 10 mm2, and the irradiation intensity
was calibrated with an NREL-calibrated reference cell (Abet
Technologies). More than 20 devices were fabricated in each
condition for statistical analysis of photovoltaic performance.
2.3 Characterization
X-ray photoelectron spectroscopy (XPS) measurements and UV
photoelectron spectroscopy (UPS) measurements were carried
out using an AXIS ultra-delay line detector (DLD) (Kratos, UK)
equipped with monochromatic Al Kα (1486.6 eV) as an X-ray
source (or He I gas (21.22 eV) as a UV source). The transmit-
tance and absorption properties were measured using a UV-Vis
spectrophotometer (Cary 100, Agilent). The surface mor-
phologies of thin films were confirmed by field-emission scan-
ning electron microscopy (FE-SEM, S-4800, Hitachi) and
atomic force microscopy (AFM, CoreAFM, Nanosurf ). The
photoluminescence spectra of the perovskite layers were
characterized using fluorescence spectrometers (FS5 spectro-
fluorometer, Edinburgh Instrument) with an excitation wave-
length of 450 nm. The photoluminescence decay was moni-
tored using a time-correlated single photon counting system
with a picosecond pulsed laser (Edinburgh Instrument) with
an excitation at 405 nm. X-ray diffraction (XRD) analysis was
carried out to obtain X-ray diffractograms of CuSCN and per-
ovskite films using a Bruker XRD (D8 Advance, Bruker
Corporation). The modulated spectroscopy and the electro-
chemical impedance spectra (EIS) of the devices were recorded
using a potentiostat (Compactstat, IVIUM) under illumination
of white light emitting diodes.
3. Results and discussion
The doped CuSCN thin films were prepared by mixing
F4TCNQ with different concentrations in diethyl sulfide (DES).
Both CuSCN and F4TCNQ are well soluble in DES with a good
solubility at room temperature (>10 mg ml−1), and the solution
is stable up to several weeks without the formation of any
aggregate (Fig. S1a†). The yellowish color for the solution of
CuSCN doped with F4TCNQ comes from the native absorption
for F4TCNQ in the range of 350–450 nm (Fig. S1b†). The
CuSCN thin films were deposited from a simple spin-coating
process under ambient conditions, and the films were dried
under mild conditions (100 °C for 10 min). The CuSCN thin
films were smooth and flat with small root-mean-square (RMS)
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roughness values regardless of F4TCNQ doping (Fig. 1b).
Because a primary advantage for CuSCN as a hole transport
layer is excellent transparency in the UV-Vis region, the optical
properties of CuSCN thin films were investigated by varying
the doping concentration of F4TCNQ. As seen in Fig. 2a, the
CuSCN thin films exhibited an optical transparency of >88% in
the wavelength range of 350–900 nm regardless of doping with
F4TCNQ, which corresponds to low absorptivity of CuSCN in
the UV-Vis-NIR range (Fig. S1b†). The exceptional transparency
in CuSCN is essential for avoiding the overlap with the para-
sitical absorption of CH3NH3PbI3, thus allowing maximized
photon harvesting of inverted-type planar heterojunction
PSCs.17 The inset of Fig. 2a depicts the Tauc analysis to deter-
mine the optical bandgap (Eg) of the CuSCN thin films from
UV-Vis absorption spectra. Here, the value of (αhν)2 was calcu-
lated for the direct bandgap transition of photons as a func-
tion of photon energy (hν), where α is the absorption coeffi-
cient, h is Planck’s constant, and ν is the radiation frequency.
For the CuSCN thin films the intercept of a linear fit of the
spectra yielded a direct Eg value of 3.92 eV for both pristine
and doped CuSCN which have an excellent agreement with the
previous reports.32 It is also noted that the crystal structure for
CuSCN thin films deposited from spin-coating was confirmed
as a rhombohedral β-phase as three diffraction peaks corres-
ponding to the (003), (101) and (006) crystallographic planes
were identified in XRD investigations (Fig. S2†).
To figure out the doping principle for CuSCN with
F4TCNQ, electronic structures of CuSCN thin films were
probed using ultraviolet photoelectron spectroscopy (UPS),
which is widely used to study the density of states below the
Fermi level (EF) of a material and its surface.33–36 From the sec-
ondary cut-off region, the work functions (φ) of the pristine
and doped CuSCN thin films were determined to be 4.88 and
5.04 eV, respectively, while the valence band maximum (VBM)
levels of the pristine and doped CuSCN were calculated to be
−5.30 and −5.38 eV, respectively (Fig. 2b). Along with the Eg
value of CuSCN thin films derived from the Tauc plots, it is
evident that the energy level offset for the valence band
maximum (ΔEVBM) at the interface of ITO and CuSCN becomes
narrow from 0.42 to 0.34 eV with F4TCNQ doping. This result
could be derived by the successful electron transfer from
CuSCN to F4TCNQ, which is consistent with some previous
reports of F4TCNQ and related p-type semiconductors.32 The
UPS spectra of the perovskite (CH3NH3PbI3) layers on both
CuSCN thin films were also obtained as shown in Fig. 2b, and
the corresponding energy levels for EF, EVBM, and ECBM are
shown in Fig. 2c. Despite the relatively large thickness (hun-
dreds of nm) of the perovskite layer compared to that of
CuSCN, it is clear that EVBM − EF for the interface of CuSCN
and the perovskite layer effectively decreases after doping with
F4TCNQ, indicating that the ΔEVBM value for charge transfer
between CuSCN and the perovskite is reduced, which
approaches more well-matched and balanced hole-transport
pathway at the interfaces between the layer in the devices. All
these results derived from UPS measurements could be
ascribed to the effective electron transfer between CuSCN and
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Fig. 2 Transmittance spectra of CuSCN thin films with different concentrations of F4TCNQ (Inset: Tauc plot for CuSCN/F4TCNQ thin films) (a), UPS
spectra of CH3NH3PbI3 and CuSCN thin films with and without F4TCNQ (0.03 wt%) on ITO-coated glass (arrow: onset) (b), and the comparison of
energy level alignment of perovskite/CuSCN/ITO with and without F4TCNQ doping (c).

F4TCNQ, which definitely accelerates the p-type doping effect
in the CuSCN thin films.
To further confirm electron transfer from CuSCN to
F4TCNQ, core-level peaks for CuSCN thin films were analyzed
by XPS (Fig. 3). For Cu, S, C, and N, the core-level binding
energy has an unambiguous shift of 0.5–0.9 eV with the
doping of F4TCNQ, which is another evidence for effective
electron transfer from CuSCN to F4TCNQ. The shift toward
high binding energy demonstrates electron transfer from
CuSCN to F4TCNQ, which agrees well with the phenomena of
a shift with p-type doping of semiconductors.35,36 The obvious
signal for fluorine was also detected in the doped CuSCN thin
film, indicating the successful p-type doping of CuSCN by
F4TCNQ (Fig. S3a†). Elemental mapping for the doped CuSCN
thin film also suggests that F4TCNQ is well-distributed in the
compact CuSCN grains (Fig. S3b†).
To evaluate the effectiveness of the doping of CuSCN as a
HTL in PSCs, the inverted-type planar heterojunction devices

Fig. 3 XPS spectra of CuSCN with and without F4TCNQ for the core level of Cu 2p (a), S 2p (b), C 1s (c), and N 1s (d).

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were fabricated with a device architecture as follows: ITO/
CuSCN/perovskite/PC61BM/bis-C60/Ag.37 It is noted that the
perovskite films formed on CuSCN were composed of compact
grains, and the film morphology, crystallinity and absorption
properties were comparable regardless of F4TCNQ doping
(Fig. S4†). The current density ( J)–voltage (V) curves for the
devices incorporating pristine and doped CuSCN as HTLs
under irradiation are shown in Fig. 3, and the corresponding
photovoltaic parameters are listed in Table 1. The details of
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12.79% and 10.46% for 0.06 wt% and 0.09 wt% of F4TCNQ,
showing a similar variation trend of VOC, JSC and FF, and thus
the optimized doping concentration for F4TCNQ was found to
be 0.03 wt% (Fig. 4b). The integrated values from EQE curves
for the devices with un-doped and doped CuSCN were consist-
ent with the stabilized JSC values measured under continuous
illumination at 100 mW cm−2 for 600 s, which verifies the
improved photoelectric conversion properties of the doped
CuSCN with F4TCNQ (Fig. 4c and d). Hysteresis upon the scan

device fabrication are described in the Experimental section.
The reference devices using the un-doped CuSCN as a HTL
exhibited PCEs up to 11.07% under AM 1.5G illumination
(100 mW cm−2) with an open-circuit voltage (VOC) of 0.92 V, a
short-circuit current density ( JSC) of 19.00 mA cm−2 and a FF
of 0.62 (Fig. 4a). We acquired the cross-sectional SEM image
(Fig. 4a) of the devices, which use F4TCNQ-doped CuSCN, the
perovskite, PCBM, bis-C60, and a silver layer. It can be shown
that very thin F4TNCQ-doped CuSCN (∼20 nm), perovskite
(∼300 nm), thin PCBM and bis-C60 (∼20 nm), and silver layer
(∼100 nm). In the devices with the doped CuSCN films, the
PCEs increased to 15.01% with 0.03 wt% of F4TCNQ owing to
the remarkably enhanced VOC (1.00 V) and FF (0.73). As the
doping concentration was further increased, the PCEs drop to
direction for J–V measurements is another critical issue for
PSCs with a planar heterojunction and is more serious in the
CuSCN-based devices.38 In order to compare the impact of
F4TCNQ doping of CuSCN on the hysteresis behaviors of the
devices, the hysteresis effect index (HI) was quantified using
the following equation:
Ð OC
ðJRS ðVÞ  JFS ðVÞÞdV
HI ¼ SC
Ð OC ð1Þ
SC JRS ðVÞdV
Despite the fact that the hysteresis was negligible with
small HI values for both devices employing the un-doped
(0.029) and doped CuSCN (0.003), the significantly lower HI
value for the device with the doped CuSCN clearly indicates

Table 1 The photovoltaic performance of PSCs with different doping ratios of F4TCNQ

Doping JSC* RS RSh

ratio (wt%) VOC (V) JSC (mA cm−2) (mA cm−2) FF PCE (%) (Ω cm2) (Ω cm2)

0 0.92 (0.91 ± 0.07) 19.45 (18.17 ± 1.56) 19.00 0.62 (0.63 ± 0.06) 11.07 (10.41 ± 1.20) 6.42 1.69 × 103
0.03 0.99 (0.98 ± 0.03) 21.01 (20.85 ± 1.03) 20.44 0.72 (0.70 ± 0.03) 15.01 (14.10 ± 0.84) 4.05 2.80 × 103
0.06 0.93 (0.94 ± 0.02) 20.77 (20.27 ± 1.70) 19.51 0.66 (0.64 ± 0.05) 12.79 (12.07 ± 0.85) 5.84 2.26 × 103
0.09 0.91 (0.89 ± 0.07) 18.54 (18.52 ± 2.10) 17.69 0.62 (0.60 ± 0.06) 10.46 (9.89 ± 0.90) 9.30 0.87 × 103

Fig. 4 J–V curves of the PSCs (a) and variation of PCEs with CuSCN with different concentrations of F4TCNQ (b), EQE spectra (c), steady-state
photocurrent generations under 100 mW cm−2 illumination (d), hysteresis characteristics (e), and statistics of PCE for the optimal devices with un-
doped and doped CuSCN (f ). Inset of (a): cross-sectional SEM image of the device employing the doped CuSCN (thicknesses for doped-CuSCN, the
perovskite, PC60BM, and Ag are ∼15 nm, 420 nm, ∼20 nm, and 120 nm, respectively).

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that the charge accumulation and charge traps were much sup-
pressed and thus efficient hole extraction from the perovskite
layer to the HTL was achieved in the device using F4TCNQ-
doped CuSCN.37,38 All these beneficial prospects of the
F4TCNQ doping for the charge transport/collection efficiency
at the interface of CuSCN/perovskite led to substantial
enhancement in PCEs for the planar inverted-type PSCs, as
seen in statistical analysis (Fig. 4f ).
To understand the kinetics regarding the charge transport/
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extraction of the CuSCN films with regard to F4TCNQ doping,
photoluminescence (PL) of the perovskite layer was compared
with individual HTLs. Fig. 5a shows that the PL of the perovs-
kite film is significantly quenched with the doped CuSCN thin
films as compared to the un-doped CuSCN, which suggests
enhanced selective extraction of hole carriers in the doped
CuSCN. We further investigated the hole extraction capability
of CuSCN thin films by monitoring PL decay by using a time-
correlated single photon counting system (Fig. 5b). The PL
decay curves were fitted using a biexponential decay function
in which the PL decay takes place through two relaxation path-
ways in the perovskite layer.39 The fast decay (τ1) and the slow
decay (τ2) are considered to correlate with effective hole extrac-
tion by the HTL and the radiative decay within the perovskite
Fig. 5 Photoluminescence spectra of the perovskite layer (a) and its
decay (b) on the CuSCN thin films with and without F4TCNQ.
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layer, respectively. The bare perovskite layer on the glass sub-
strate showed the average lifetime (τave) of photogenerated exci-
tons of 123.32 ns, while the perovskite layer deposited on the
un-doped and the doped CuSCN films exhibited τave values of
115.54 and 60.76 ns, respectively. The fast decay of PL is evi-
dence of effective hole extraction at the interface between the
perovskite and the HTL, which is consistent with the steady-
state PL result. Thus it is concluded that the F4TCNQ doping
effectively enhances the hole transport/extraction capabilities
for efficient charge transfer and transport to the corresponding
electrodes with regard to the perovskite layer, which is critical
in preventing electron–hole pair recombination and in increas-
ing PCE of the solar cell.
Because intensity-modulated spectroscopy gives important
information for charge transfer and recombination kinetics at
the interfaces of PSCs, intensity-modulated measurements of
the devices with different HTLs were investigated to further
understand the influence of F4TCNQ doping of CuSCN on the
PCE discrepancy. The electron transport time constant (τc) and
the electron diffusion coefficient (Dn) were calculated from the
equation of τc = 1/2πfc and Dn = ω2/(2.35τc), where ω and fc are
the thickness of perovskite films (∼450 nm in this work) and
the characteristic frequency minimum from intensity-modu-
lated photocurrent spectroscopy (IMPS) curves, respectively. As
shown in Fig. 5a, the plots of τc for the devices with varying
short circuit currents (ISC) indicate that electron transport
becomes much faster at the interface with the doped CuSCN
as compared to that of un-doped CuSCN, and thus the Dn
value for the doped CuSCN-based device was more extended as
compared to the un-doped CuSCN-based device, which would
be correlated with the suppressed backward recombination in
the device as evident to improved FF and JSC. For the intensity-
modulated photovoltage spectroscopy (IMVS) analysis, the
recombination time constant (τr) was calculated using the
equation of τr = 1/2πfr, where fr is the characteristic frequency
minimum of IMVS curves with different ISC values (Fig. 6b).
The un-doped CuSCN afforded shorter τr and thus the absolute
time for bimolecular recombination is very short, while
F4TCNQ doping effectively prolonged the τr value for recombi-
nation in the device. This result is another evidence for
improved electronic properties for the interface between the
perovskite layer and the doped CuSCN, which resulted in
quick hole extraction and the suppressed charge recombina-
tion in the device employing the doped CuSCN.40–42
Electrochemical impedance spectroscopy (EIS) of the
devices was also performed to examine the efficacy of F4TCNQ
doping for charge transporting behavior at the interfaces of
the PSCs. Fig. 6c shows the Nyquist plots for the devices with
different HTLs measured in the dark with a 0.75 V bias in the
frequency range of 1 MHz to 10 mHz, and their fitting results
of the equivalent circuit are listed in Fig. 6c. The high-fre-
quency intercept to the Z′ axis which represents the series re-
sistance (Rs) is mainly associated with the serial resistance of
ITO, the HTL and the perovskite layer. Specifically, the semi-
circle in the high-frequency range is correlated with the inter-
facial resistance (Rtrans) occurring at the perovskite layer with
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Fig. 6 Device analyses for IMPS (a), IMVS (b), and EIS (c) for planar PSCs
with CuSCN with and without F4TCNQ.
its interface with the HTL, while the semicircle in the low-fre-
quency range corresponds to the recombination resistance
(Rrec) at the interface of perovskite/HTL. From the fitting
results of the equivalent circuit, the charge-transfer resistance
(RTrans) values were found to be 203 and 125 Ω for the devices
with the un-doped and the doped CuSCN, respectively. The
low RTrans value denotes the improved interfacial contact
between doped-CuSCN and the perovskite film, where the
photo-generated hole carriers are efficiently extracted from the
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perovskite layer. Therefore, device analyses using IMPS, IMVS,
and EIS analysis further confirmed that the F4TCNQ-doped
CuSCN led to improved charge transport and reduced charge
recombination at the interfaces in the devices to afford
enhanced photovoltaic performance of inverted-type planar
PSCs.
Finally, the stabilities of the devices with different HTLs
were examined. First, for analysis of the operational stability
under 1 sun illumination, stabilized power output of the
devices was measured up to 600 s (Fig. S5†). The devices
exhibited stabilized PCE values of 14.70% and 11.20% with
the doped and the un-doped CuSCN, respectively, which meet
the PCEs obtained from J–V curves. The plateau of the steady-
state PCEs for the both devices indicates high operational
stability of the devices with CuSCN regardless of the molecular
doping. We then measured the long-term stability of the
devices (Fig. S6†). The device with the F4TCNQ doping showed
much better long-term stability under the same conditions as
compared to the device with the pristine CuSCN. Furthermore,
the PCE of the device with F4TCNQ is very stable, where the
PCE maintains 94.0% of the initial value after 100 h in a glove
box. Although the underlying mechanism for the different PCE
decay of two devices is not clear yet, better device stability is
another favourable property of molecular doping in CuSCN for
practical applications of the perovskite solar cells.
4. Conclusions
In summary, this work proposes a strategy to optimize the elec-
tronic properties of CuSCN as a HTM for inverted-type planar
PSCs via molecular doping using F4TCNQ. The sufficient elec-
tron transfer from F4TCNQ to CuSCN enabled much better
energy level alignment, which led to efficient hole carrier
transport and relatively reduced charge recombination as
demonstrated by UPS and XPS investigations. Further device
analyses also demonstrated the much-reduced charge trans-
port resistance and elongated charge lifetime in the doped
CuSCN-based devices. With the optimized doping concen-
tration, the inverted-type planar PSCs achieved a PCE up to
15.01% which is enhanced by ∼35% as compared to the
devices with a pristine CuSCN. It thus sheds light on under-
standing the intrinsic properties of molecular doping of
CuSCN, which guides further investigation and improvement
of photovoltaic performance of planar PSCs.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by Korea Electric Power
Corporation (Grant number: R17XA05-11). This work was also
supported by the Basic Science Research Program through the
Inorg. Chem. Front.

Research Article
National Research Foundation of Korea (NRF) funded by the
Ministry of Science, ICT & Future Planning (Grant number:
2017R1C1B2009691).
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