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Efficient Antimony-Based Solar Cells by Enhanced

Charge Transfer
Riming Nie and Sang Il Seok*

chemical properties and a variety of com-

The main mechanism of most solar cells is that the light produces positional combinations.[1] They can be
photogenerated electrons and holes, which are transferred to the electron applied in room-temperature radiation
transport layer and the hole transport layer (HTL), respectively. Then, these detection devices, transparent electronic
holes and electrons are transported to the anode and cathode, respectively, to devices, and photovoltaic cells because their
bandgaps cover a large range.[2] One of the
generate electric current. Thus, charge transfer is a crucial process to fabricate
important metal chalcohalides is antimony
efficient solar cells. Here, a fast vapor process is developed to fabricate sulfoiodide (SbSI), which is a ferroelectric
SbSI and SbSI-interlayered Sb2S3 solar cells by annealing an Sb2S3 film and system and has a Curie temperature of
SbI3 powder in an inert gas atmosphere. The charge transfer of the vapor- 22 °C.[3] Furthermore, SbSI exhibits many
processed SbSI solar cells is increased by shortening the path length from interesting properties, including photo-
ferroelectric, piezoelectric, pyroelectric,
SbSI to the HTL. This is achieved by an intimate contact between SbSI and the
pyro-optic, electromechanical, electro-
HTL, which is obtained by optimizing the morphology of SbSI, resulting in a optic, and photorefractive behavior; conse-
record power conversion efficiency (PCE) of 3.62% in pure SbSI-based solar quently, it has become a potential material
cells under standard illumination at 100 mW cm−2. In addition, the charge for use in several applications.[4]
transfer of the SbSI-interlayered Sb2S3 solar cells is enhanced by increasing the Conventional methods that synthesize
external driving force, an energetically favorable driving force provided by the SbSI, including the vertical Bridgman
technique[5] and sintering of antimony
TiO2/Sb2S3/SbSI/HTM structure, and the best-performing SbSI-interlayered
trisulfide (Sb2S3) and antimony triiodide
Sb2S3 solar cell exhibits a PCE of 6.08%. (SbI3),[6] require high temperatures or
pressures. Furthermore, it is difficult to
deposit SbSI films for use in solar cells
owing to the growth rate anisotropy of
Solar cell is a device that converts light energy into electrical SbSI.[7] In our previous work, SbSI films were prepared by the
energy through a series of essential processes. First, the light reaction of Sb2S3 film, deposited by chemical bath deposition
harvester produces photogenerated electron and hole pairs. (CBD), with SbI3 solution in N,N-dimethylformamide (DMF)
Then, these produced electrons and holes are transferred to under an inert gas atmosphere. Subsequently, it was found
the electron transport layer (ETL) and the hole transport layer that the SbSI-based solar cells exhibited a PCE of 3.05% under
(HTL), respectively. Ultimately, the electrons and holes are full air mass 1.5 global (AM 1.5G) illumination.[8] However,
transported to the corresponding electrodes to produce elec- this deposition method requires multiple cycles of spin-
tric current. Although most of the recent works focus on the coating of the SbI3 solution and thermal annealing; therefore,
improvement of the net power conversion efficiencies (PCEs), it is time-consuming and unsuitable for commercial pro-
the work on the correlation between the device performance duction. In addition, the SbSI film prepared by this method
and charge transfer is lacking, especially for the semiconductor was not completely uniform, and it showed considerable
nanocrystal of metal chalcogenide– and metal chalocohalide– aggregation. Therefore, it is important to develop a fast, easy
based solar cells. deposition method to prepare uniform and low-aggregation
Metal chalcohalides have received considerable attention SbSI films.
because of their advantages, such as interesting physical and Sb2S3 inorganic–organic heterojunction solar cells have
attracted much attention because of their high absorption coef-
ficient of ≈1.8 × 105 cm−1 at 450 nm and a suitable bandgap
Dr. R. Nie, Prof. S. I. Seok
Perovtronics Research Center
of ≈1.7 eV.[9] Itzhaik et al. employed CuSCN as a hole trans-
Department of Energy Engineering port material (HTM) to fabricate solid-state Sb2S3-sensitized
School of Energy and Chemical Engineering solar cells, and obtained a PCE of 3.37%.[10] In our previous
Ulsan National Institute of Science and Technology (UNIST) work, we reported inorganic–organic hybrid Sb2S3-based solar
50 UNIST-gil, Eonyang-eup, Ulju-gun, Ulsan 44919, Republic of Korea cells that employed poly(3-hexylthiophene) and poly(2,6-(4,4-
E-mail: seoksi@unist.ac.kr
bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smtd.201900698.
alt4,7(2,1,3-benzothiadiazole)) (PCPDTBT) as effective organic
HTMs.[11] It was observed that the considerable recombina-
DOI: 10.1002/smtd.201900698 tion behavior in Sb2S3 limits the open-circuit voltage (VOC),

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Figure 1.  a,b) Ways to enhance charge transfer.
which directly causes low PCEs. In this regard, the halide
treatment is an effective approach to passivate surface defects
and improve device performance. Tang et al. used mono­
valent halide anions to passivate surface defects in PbS col-
loidal quantum dot (CQD) films; the trap state distribution
was confirmed to be shallower than that of the best organic
ligands by both time-resolved infrared spectroscopy and tran-
sient device characterization.[12] In addition, they introduced
solution-phase passivation using halide anions to reduce the
traps in PbS CQD films, and realized the most efficient all-
inorganic CQD solar cells.[13] Therefore, the halide treatment
of Sb2S3 is expected to be an efficient approach to reduce the
recombination centers in Sb2S3 and improve the device per-
formance of Sb2S3 solar cells. Although many researches have
been carried out on Sb-based solar cells in the recent years,
their PCEs are still lower than 10%. However, investigating the
charge transfer in the devices might be an important approach
to improve the PCEs further.
In this study, pure SbSI and SbSI-interlayered Sb2S3 solar
cells were fabricated by annealing a fluorine-doped SnO2
(FTO)/TiO2 blocking layer (BL)/mesoporous TiO2 (mp-TiO2)/
Sb2S3 film deposited by CBD with SbI3 powder under an
argon or nitrogen atmosphere. The annealing temperature and
time were optimized to obtain a pure and highly crystalline
SbSI film, resulting in a record PCE of 3.62% in pure SbSI-
based solar cells with the cell configuration of FTO/TiO2-BL/
mp-TiO2/SbSI/HTM/Au. To prove that the charge transfer in
the vapor-processed (VP) SbSI solar cells was improved by
shortening the path length from SbSI to the HTL, the physical
properties of VP and solution-processed (SP) SbSI solar cells
were systematically investigated by electrochemical impedance
spectroscopy (EIS), light-intensity-dependent current density–
voltage measurement, field-emission scanning electron micros-
copy (FESEM), atomic force microscopy (AFM), and grazing-
incidence wide-angle X-ray scattering (GIWAXS). The SbSI-
interlayered Sb2S3 solar cells exhibited a PCE of 6.08%, with
a short-circuit current density (JSC) of 14.92 mA cm−2, a VOC
of 0.62 V, and a fill factor (FF) of 0.66. In addition, ultraviolet
photoelectron spectroscopy (UPS) and photoluminescence (PL)
spectroscopy show that the SbSI layer provides an energetically
favorable force to enhance the charge transfer in the SbSI-­
interlayered Sb2S3 solar cells.
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Generally, the light harvester produces photogenerated
carriers (electrons and holes). These electrons are transferred to
the ETL, and the holes are transferred to the HTL. Ultimately,
these holes and electrons are transported to the corresponding
electrodes to generate electric current. Assuming that the
material properties are not changed, the charge transfer can be
enhanced either by shortening the path length from the light
harvester to the ETL or HTL (Figure  1a), or by increasing the
external driving force (Figure 1b). Here, we used these two
ways to improve the PCEs of pure SbSI and SbSI-interlayered
Sb2S3 solar cells, respectively.
Figure  2 illustrates the solution and vapor processes used
to prepare the SbSI layer. First, Sb2S3 is deposited on the
FTO/BL/mp-TiO2 sample by CBD according to our previous
method.[11,14] In the solution process, SbSI is prepared by
multiple cycles of spin-coating of the SbI3 solution onto the
FTO/BL/mp-TiO2/Sb2S3 sample and thermal annealing. In the
vapor process, SbSI is formed by simply annealing the FTO/
BL/mp-TiO2/Sb2S3 sample and SbI3 powder (which vaporizes
under the annealing condition) together. The vapor process has
two advantages over the solution process; it is easy and does not
require multiple cycles of spin-coating and thermal annealing,
and it produces a more uniform SbSI layer.
The effect of the vapor process deposition conditions on the
SbSI film and the resulting photovoltaic characteristics were
investigated. Figure  3a–d shows the X-ray diffraction (XRD)
patterns and UV–vis absorption spectra of FTO/mp-TiO2/
SbSI samples prepared at various annealing temperatures and
times. Two mixed phases, Sb2S3 (JCPDS No. 42–1393) and SbSI
(JCPDS No. 74–2210), are observed after annealing at 125 °C,
and a pure SbSI phase is detected after annealing at 150 °C. As
the annealing temperature increases to 175 °C, only FTO and
TiO2 peaks are detected, indicating that the SbSI film evaporates.
The photographs in the inset show that the color changes from
a mixture of dark brown and dark red (Sb2S3 and SbSI, 125 °C)
to dark red (SbSI, 150 °C) and then to nearly transparent (FTO
and TiO2, 175 °C), in a good agreement with the changes in
the XRD patterns. In addition, the UV–vis absorption spectra
show similar behavior. Further, using a fixed annealing temper-
ature of 150 °C, we optimized the annealing time. Two mixed
phases, Sb2S3 and SbSI, are observed after annealing for 30 s,
and pure SbSI phases are observed after annealing for 45, 60,
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Figure 2.  Schematic illustration of preparation of SbSI layer by a) solution process and b) vapor process.

and 75 s. As the annealing time increases to 90 s, only FTO and
TiO2 peaks are detected. In addition, similar results appear in
the UV–vis absorption spectra. These results demonstrate that
annealing at 150 °C for 45, 60, or 75 s might be suitable for fab-
ricating the SbSI solar cells. The corresponding transmittance
spectra and Tauc plots of these SbSI samples are shown in
Figures S1 and S2 (Supporting Information). The method for
calculating the absorption coefficient (which is used for calcu-
lating the bandgap via the Tauc plot) is shown in Note S1 in the
Supporting Information. The corresponding surface scanning
electron microscopy (SEM) images with different annealing
times were shown in Figure S3 (Supporting Information).
The XRD pattern of SbSI films prepared at 150 °C for 60 s
did not significantly changed after storage for 1 month under

Figure 3.  XRD patterns and UV–vis absorption spectra of FTO/mp-TiO2/SbSI films prepared at a,b) various annealing temperatures and c,d) various
annealing times. e,f) Performance of SbSI solar cells fabricated at 150 °C for 45, 60, or 75 s. The main peaks of FTO and TiO2 in panel (a) and (c) are
labeled “F” and “T,” respectively. The standard Sb2S3 (JCPDS No. 42–1393) and SbSI (JCPDS No. 74–2210) structure files are plotted as black and red
columns, respectively. Insets in panels (a) and (c) are photographs of the corresponding FTO/mp-TiO2/SbSI films.

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ambient conditions, indicating that the SbSI phase is stable in
the atmosphere (Figure S4, Supporting Information). In addi-
tion, a glass/mp-TiO2/SbSI sample was prepared, and it was
found that its XRD pattern matches the reference pattern well
(Figure S5, Supporting Information). Thus, SbSI solar cells
were fabricated under these conditions with a device structure of
FTO/TiO2-BL/mp-TiO2/PCPDTBT/poly(3,4-ethylenedioxythio-
phene) doped with poly(4-styrenesulfonate) (PEDOT:PSS)/Au.
Figure 3e,f shows the device performance of these cells, and
Figure S6 (Supporting Information) shows their corresponding
current density–voltage (J–V) characteristics. The best JSC, VOC,
and FF values were obtained after annealing at 150 °C for 60 s,
and correspond to the highest PCE; the reason may be that the
crystallites formed at 150 °C for 60 s exhibit the best crystal-
linity and largest mean size (Figure S7, Supporting Informa-
tion). The method for calculating the mean size of the crystal-
lites is shown in Note S2 in the Supporting Information.
Figure 4a shows the J–V curves of the best VP and SP SbSI
solar cells. The VP devices show a JSC of 9.26 mA cm−2, a
VOC of 0.60 V, an FF of 65.2, and a PCE of 3.62%. All these
parameters are higher than those of the SP cells, resulting
in a higher PCE and indicating that the VP cells have lower
charge recombination and longer carrier lifetimes.[15] In addi-
tion, the VP devices show a smaller hysteresis (Figure S8,
Supporting Information). The SP and VP solar cells exhibit
stabilized PCEs of 2.90% and 3.50%, respectively (Figure S9,
Supporting Information). Figure 4b shows the corresponding
external quantum efficiency (EQE), which is closely related to
JSC. The EQE spectra of the VP cells show a higher photore-
sponse from 360 to 590 nm, which corresponds to a higher
JSC. The JSC value obtained by integrating the EQE spectrum
with the standard AM 1.5G spectrum is in a very good agree-
ment with that obtained from the J–V curves. To investigate
the dynamics of interfacial charge transfer and recombina-
tion, EIS was performed. The EIS spectra were measured at
various applied biases in a frequency range of 1 MHz to 1 Hz
under solar AM 1.5G irradiation at 100 mW cm−2. Figure 4c,d
presents the Nyquist plots from the impedance spectra results
of the SP and VP solar cells. The simple circuit model pre-
sented in the inset was used to fit these Nyquist curves. The
corresponding parameters are listed in Tables S1 and S2
(Supporting Information). In this circuit, Rs represents the Ohmic

Figure 4. a) J–V curves under standard illumination conditions (100 mW cm−2, AM 1.5G), b) EQE spectra, and c,d) Nyquist plots of SP and VP SbSI
solar cells under illumination. Insets in panels (c) and (d) show the equivalent circuits used to fit the impedance curves. e) Series resistance (Rs),
f) charge-transfer resistance (Rct), and g) one component of constant phase element (CPE-P) extracted from the impedance curves. h) JSC and i) VOC
of SP and VP SbSI solar cells as a function of light intensity.

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series resistance, Rct represents the charge-transfer resistance,
and CPE represents a constant phase element. A CPE is com-
monly characterized by two values, CPE-T and CPE-P. The CPE
is considered to be an ideal capacitor without defects or grain
boundaries when the CPE-P value is 1.[16] Figure 4e–g shows
the Rs, Rct, and CPE-P values of the SP and VP cells under
various applied voltages. The VP cells show lower Rs, higher
Rct, and higher CPE-P values than the SP cells, indicating less
interfacial charge recombination, which is consistent with
the higher VOC and PCE. To clarify the carrier recombination
processes in the SbSI solar cells further, light-intensity-
dependent JSC and VOC measurements were performed.
Figure 4h shows the light-intensity-dependent JSC values of
the SP and VP SbSI solar cells. JSC was fitted by a power-law
dependence (JSC ∝ Iα). Because of the presence of an interfacial
barrier or charge-carrier balance, α is 0.75 for completely space-
charge-limited solar cells; and solar cells without space charge
effects will have an α value of 1.[17] The VP cells have a higher
α value than the SP cells, indicating more efficient extraction
of the photogenerated charges and low charge accumulation in
the VP cells. Figure 4i shows the light-intensity-dependent VOC
values. The semilogarithmic scaling of VOC with I can be used to
evaluate the trap-assisted recombination.[18] Carrier recombina-
tion can be described by the relationship, VOC ∝ n (kBT/q) ln I,
where kB is the Boltzmann constant, T is the temperature,
and q is the elementary charge.[19] Theoretically, the slope of
VOC versus ln(I) should be kBT/q (n = 1) for cells with no trap-
assisted recombination. However, the slope of VOC versus ln(I)
for the VP cells (1.20kBT/q) is smaller than that of the SP cells
(1.41kBT/q), suggesting that trap-assisted charge recombination
was more effectively suppressed in the VP cells.
To determine the cause of the different charge recombination
and device performance of the SP and VP SbSI solar cells, we
investigated the morphology and distribution of SbSI using
FESEM and AFM. Figure  5a,b shows SEM surface images of
glass/mp-TiO2/SbSI samples prepared by the solution process
or vapor process. More clusters of particles appear in the SP
sample; however, the VP sample has a uniform morphology.
The extra clusters of particles in the SP sample might affect
the deposition of HTM and increase its roughness, which will
affect the deposition of Au and increase the possibility of short
circuit. Thus, it is detrimental to the device performance. To
confirm this point, we carried out the AFM measurements. As
shown in Figure 5c,d, after spin-coating of the HTM, the SP
glass/mp-TiO2/SbSI/PCPDTBT sample has a higher roughness
(RMS value of 35.5 nm) than the VP sample (RMS value of
14.2 nm). The corresponding 2D AFM images are shown in
Figure S10 (Supporting Information). Figure 5e,f shows cross-
sectional SEM images of the SP and VP solar cells (FTO/TiO2-
BL/mp-TiO2/SbSI/PCPDTBT/Au). Pores are observed in the

Figure 5.  a,b) Surface SEM images of glass/mp-TiO2/SbSI samples prepared by the solution process or vapor process. c,d) 3D AFM images of glass/
mp-TiO2/SbSI/PCPDTBT samples prepared by the solution process or vapor process. e,f) Cross-sectional SEM images of SP and VP SbSI solar cells.
g,h) Schematic illustration of the operating principles of the SP and VP SbSI solar cells.

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SP solar cells, whereas a compact and uniform morphology is
observed in the VP cells, which also confirms more efficient
infiltration of the HTM into the mp-TiO2 in the VP cells. To
clarify the effect of various degrees of HTM infiltration on
the device performance, we present schematic diagrams of
the operating principles of the SP and VP SbSI solar cells.
As shown in Figure 5g, when the HTM does not infiltrate
the mp-TiO2 adequately (in the SP cell), the photogenerated
carriers separate into electrons and holes. The electrons can
be efficiently transferred to TiO2; however, the holes cannot
be efficiently transferred to the HTM owing to its nonuniform
distribution. Figure 5h shows the operating principle of the VP
SbSI solar cells. Because of the efficient infiltration of the HTM
into the mp-TiO2, electrons and holes can be efficiently trans-
ferred to TiO2 and the HTM, respectively. Thus, more electrons
and holes can be transported to the cathode and anode, respec-
tively, resulting in lower charge recombination and higher
device performance.
To investigate the origin of the differences in charge recom-
bination and device performance further, the crystal properties
of the glass/TiO2-BL/SbSI films prepared by the solution and
vapor processes are compared. GIWAXS not only enables 2D
analysis of the in-plane and out-of-plane crystal orientations, but
also reveals the local crystal phase distribution at various film
depths if the grazing incidence X-ray (GIX) angle is changed.
Figure  6a–f shows the 2D GIWAXS patterns for SP and VP
SbSI. The GIX angle increases from 0.10° to 0.48°, bringing the
GIWAXS patterns on the surface to a deeper position in the
samples. The (200), (210), (220), (121), (211), and (310) crystal
Figure 6. 2D GIWAXS patterns of glass/TiO2-BL/SbSI samples prepared by the a–c) solution process and d–f) vapor process at GIX angles of
a,d) 0.10°, b,e) 0.30°, and c,f) 0.48°. Crystal face indices of SbSI and TiO2 are marked as (hkl) and (hkl)T, respectively. g,h) Formation mechanism of
SP and VP SbSI.
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planes of SbSI and the (110) crystal plane of TiO2 are observed.
Regardless of the depth, both the SP and VP SbSI are prefer-
ably orientated along the (121) direction. However, the crystal-
linity of the VP SbSI is much higher than that of the SP SbSI.
Figure 6g,h shows the SbSI growth mechanism in the solution
and vapor processes to explain the higher crystallinity of the VP
sample. In the solution process, the remaining DMF provides
adhesive and gravitational forces that resist SbSI growth. In
contrast, in the vapor process, SbSI can grow more freely,
resulting in a higher crystallinity.
Commercialization of solar cells requires a large device
area and environmental stability. Here, we focus on the
environmental stability of solar cells, which have moisture
stability, thermal stability, and photostability components. To
determine the moisture stability, cells without any encapsula-
tion were stored under ambient conditions with 60% relative
humidity. Figure 7a shows the moisture stability of the SP and
VP SbSI solar cells. The VP cells retained 92% of the initial
PCE after storage for 1 month, whereas the SP cells retained
only 88% of the initial PCE. The corresponding changes in the
normalized JSC, VOC, and FF values are shown in Figure S11
(Supporting Information). To examine the thermal stability,
un-encapsulated cells were stored at 85 °C in an oven under
ambient atmosphere with 40% relative humidity. Figure 7b
shows the thermal stability of the SP and VP solar cells. After
1 month of storage, the VP and SP cells retained 92% and 87%
of the initial PCE, respectively. To examine the photostability,
un-encapsulated cells were illuminated under AM 1.5G irra-
diation at 100 mW cm−2 without a UV blocking filter at 25 °C.
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Figure 7.  Changes in normalized PCE of un-encapsulated SP and VP SbSI solar cells a) after storage under atmospheric conditions with 60% humidity,
b) measured at 85 °C, and c) under standard AM 1.5G illumination, including UV radiation, from a xenon lamp, as a function of storage time.
d,e) Effects of light, heat, and moisture on the SP and VP cells.

As shown in Figure 7c, the PCE of the SP cells decreased rap-
idly to 30% of the initial value after illumination for 937 min.
In contrast, the VP cells retained 91.8% of the initial PCE after
illumination for 1950 min. These results demonstrate that the
VP cells exhibit excellent overall stability, including resistance to
moisture, heat, and light, when compared with that of the SP
cells. To explain the improved overall stability of the VP cells,
Figure 7d,e shows schematic diagrams of the moisture penetra-
tion, thermal stress, and photostress in the SP and VP cells.
The VP cells exhibit a more compact device structure when
compared with that of the SP cells. This compact structure
prevents humid air and water from entering the device and
reduces the thermally induced and photoinduced stress.
The process of halide treatment of the Sb2S3 surface with
SbI3 vapor in the Sb2S3-based inorganic–organic heterojunction
solar cells is shown in Figure 8a. Before PCPDTBT was depos-
ited, the FTO/TiO2-BL/mp-TiO2/Sb2S3 substrate was annealed
at 150 °C in SbI3 vapor for 10 s to form the FTO/TiO2-BL/
mp-TiO2/Sb2S3/SbSI structure (the effect of the annealing time
in SbI3 vapor was optimized in Figure S12 in the Supporting
Information). The formation of SbSI on the surface of Sb2S3
was confirmed by X-ray photoelectron spectroscopy and Raman
spectroscopy (Figure S13, Supporting Information). Figure 8b
shows the J–V characteristics of the Sb2S3-sensitized solar cells
under illumination at a light intensity of 100 mW cm−2 before
and after the SbSI layer was introduced. The device parameters

Figure 8.  a) Schematic illustration of mp-TiO2/Sb2S3/SbSI nanostructured solar cells. b) Effects of SbI3 surface halide treatment on the J–V character-
istics measured under AM 1.5G solar irradiation (100 mW cm−2), and c) corresponding dark J–V curves.

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Table 1. Photovoltaic performance of solar cells obtained from
Figure 8b.
JSC [mA cm−2] VOC [V] FF [%] PCE [%]
Sb2S3 14.31 0.53 63.0 4.78
Sb2S3–SbSI 14.79 0.55 66.1 5.38
are summarized in Table  1. Before the halide treatment with
SbI3 vapor, the cells showed a PCE of 4.78%, accompanied by
a JSC of 14.31 mA cm−2, a VOC of 0.53 V, and an FF of 63.0%.
After the SbSI interlayer was introduced, the JSC, VOC, and FF
values improved significantly, and the PCE increased to 5.38%.
As shown in Figure 8c, the dark current of the cells was reduced
by the SbSI layer, indicating a decrease in surface defects.
To explain the effect of the SbI3 halide treatment on the
device performance, we measured the EQE of the cells with
and without the SbSI layer. The EQE depends on the light-
harvesting efficiency (LHE), electron injection yield (EIY), and
charge collection efficiency (CCE). As shown in Figure  9a, the
EQE of the cells increased after SbI3 halide treatment. Figure 9b
shows the UV–vis absorption spectra of the FTO/mp-TiO2/
Sb2S3 and FTO/mp-TiO2/Sb2S3-SbSI samples. The SbI3 halide
treatment resulted in a slight increase of the absorption in
the range of 420 and 650 nm; thus, the improvement in the
EQE values can be attributed to the LHE of SbSI without inter-
fering EIY and CCE. To confirm that the charge carriers in light
harvesters could be more efficiently transported to the ETL or
HTL, we obtained the PL spectra of the FTO/mp-TiO2/Sb2S3
Figure 9.  a) EQE spectra, b) UV–vis absorption spectra, c) PL spectra, and d) UPS spectra of Sb2S3 and Sb2S3-SbSI solar cells or films. The inset shows
the energy band diagram of FTO/TiO2-BL/mp-TiO2/Sb2S3-SbSI/ PCPDTBT/Au.
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and FTO/mp-TiO2/Sb2S3-SbSI samples under excitation by
light with a wavelength of 405 nm, as shown in Figure 9c.
After the SbI3 halide treatment, the FTO/mp-TiO2/Sb2S3-SbSI
sample had a lower PL intensity than the FTO/mp-TiO2/Sb2S3
sample, indicating that the generated charge carriers were
more efficiently separated in the FTO/mp-TiO2/Sb2S3/SbSI
sample. To determine the reason for the improved charge-
carrier separation, we measured the energy levels of the FTO/
mp-TiO2/Sb2S3/SbSI sample using UPS. Figure 9d shows
magnified plots of the secondary electron cut-off and highest
occupied molecular orbital regions of the HeI UPS spectra
of SbSI. The Fermi level (EF) of SbSI was determined to be
4.52 eV, and the valence band maximum (VBM) is located
1.10 eV below EF. On the basis of these results and the bandgap
acquired from the Tauc plot (Figure S1b, Supporting Infor-
mation), we determined the energy levels of SbSI (inset in
Figure 9d). The conduction band minimum and VBM of SbSI
were determined to be 3.90 and 5.60 eV, respectively. These
results show that the light-harvesting SbSI interlayer between
TiO2 and PCPDTBT provides an energetically favorable driving
force for transferring photogenerated carriers to TiO2 for an
additional photocurrent.
To improve the device performance further, several experi-
mental parameters such as thickness of mp-TiO2 and time
for CBD reaction were optimized to obtain the best condition
(Figures S14 and S15, Supporting Information). The optimized
condition is as follows: 1 µm thick mp-TiO2, 3 h CBD reaction
time, and 10 mg mL−1 PCPDTBT solution. Figure  10a shows
the J–V characteristics of the best-performing device, which
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www.advancedsciencenews.com
Figure 10. a) J–V curves and b) EQE spectra of the best-performing Sb2S3-SbSI solar cell.
exhibited a JSC of 14.92 mA cm−2, a VOC of 0.62 V, an FF of 0.66,
and a PCE of 6.08% under the 100 mW cm−2 standard AM 1.5G
condition. Figure 10b shows the EQE spectra, and it is evident
that the JSC value integrated from the EQE is in a good agree-
ment with that from the J–V curve.
We demonstrated a vapor process to prepare SbSI solar cells
and SbSI-interlayered Sb2S3 solar cells by annealing Sb2S3 film
(deposited by CBD) and SbI3 powder in an inert gas atmosphere.
In the VP SbSI solar cells, the morphology of the SbSI was opti-
mized, resulting in an intimate contact between the SbSI and
the HTM. This behavior shortened the path length from SbSI to
the HTL and improved the charge transfer, leading to a record
PCE of 3.62% in pure SbSI-based solar cells. In addition, this
intimate contact increased the moisture, thermal, and photo
stability by preventing humid air and water from entering the
device and reducing the thermally induced and photoinduced
stress. In the SbSI-interlayered Sb2S3 solar cells, an energetically
favorable external driving force was provided by forming the
TiO2/Sb2S3/SbSI/HTL structure, which promoted the charge
transfer among TiO2, Sb2S3, SbSI, and HTL, and achieved a
PCE of 6.08%. This work provides several methods to improve
the charge transfer in solar cells that assemble light-harvesting
semiconductor nanostructures on electrode surfaces.
Experimental Section
Preparation of FTO/TiO2-BL/mp-TiO2: A TiO2 BL 100 nm in thickness
was deposited on an FTO substrate (Pilkington, TEC8) by spray
pyrolysis of a 20 × 10−3 m titanium di-isopropoxide bis(acetylacetonate)
solution (Aldrich) at 450 °C. A diluted TiO2 paste (home-made TiO2
nanoparticles; average particle size of ≈50 nm) was spin-coated onto
the FTO/TiO2-BL sample and calcined at 500 °C for 1 h in air to form
1300 nm thick mp-TiO2.
Preparation of FTO/TiO2-BL/mp-TiO2/SbSI or FTO/TiO2-BL/mp-TiO2/
Sb2S3-SbSI: To prepare the FTO/TiO2-BL/mp-TiO2/SbSI samples, Sb2S3
was deposited by CBD according to the previous works. Subsequently,
the FTO/TiO2-BL/Sb2S3 substrate and SbI3 powder (99.9%, Sigma–
Aldrich) were placed on a hot plate and covered by a Petri dish. Next,
the Petri dish was covered by a funnel, which was connected to an argon
gas flow. Then, they were annealed at 125—175 °C for 30–90 s. For the
FTO/TiO2-BL/mp-TiO2/Sb2S3-SbSI samples, the annealing condition
was 150 °C for 10 s. Finally, the samples were ultrasonically cleaned in
DMF to remove the remaining SbI3.
Device Fabrication: A solution of PCPDTBT in dichlorobenzene
(10 mg mL−1) as the HTM was spin-coated onto the FTO/TiO2-BL/
mp-TiO2/light-harvesting material samples at 2000 rpm for 60 s.
Small Methods 2019, 1900698 1900698  (9 of 10)
www.small-methods.com
Subsequently, a diluted solution of PEDOT:PSS in methanol (v/v = 1:2)
as the hole-transport layer was also spin-coated onto the FTO/TiO2-BL/
mp-TiO2/light-harvesting material/PCPDTBT samples at 2000 rpm for
60 s. To complete the device fabrication, a 100 nm thick Au layer was
deposited on the samples in vacuum (1 × 10−7 Torr) as the anode. The
active area of the solar cells was 0.16 cm2.
Material and Device Characterization: XRD patterns were measured
using a Rigaku D/Max 2500 V X-ray diffractometer. The morphology of
the SbSI samples was investigated using FESEM (Hitachi SU-8220).
Cross-sectional images of the devices were obtained using a focused
ion beam (FEI, Helios NanoLab 450). The absorption spectra were
collected on a UV–vis spectrometer (Jasco V-780). The roughness
of the samples was investigated using an atomic force microscope
(MultiMode V, Veeco). GIWAXS measurements were conducted at the
PLS-II 6D UNIST-PAL beamline of the Pohang Accelerator Laboratory
in the Republic of Korea. J–V curves were measured using a metal
mask (area: 0.094 cm2) and a solar simulator (Newport, Oriel Class A,
91195A) with a source meter (Keithley 2400) under 100 mA cm−2 AM
1.5G illumination; a calibrated Si reference cell certified by NREL was
also used. The EQE spectra were measured using an internal quantum
efficiency system (Oriel, IQE 200B). Impedance measurements were
performed using an AUTOLAB (AUT302N) instrument.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korea government (MSIT)
(2018R1A3B1052820). This work was also financially supported by a
project (1.190028.01) of UNIST.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
interlayers, metal chalcohalides, Sb2S3, SbSI, solar cells
Received: October 13, 2019
Revised: November 9, 2019
Published online:
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www.advancedsciencenews.com
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