Wu et al.

Nanoscale Research Letters (2019) 14:325

https://doi.org/10.1186/s11671-019-3157-x

NANO EXPRESS Open Access

Sb2S3 Thickness-Related Photocurrent and

Optoelectronic Processes in TiO2/Sb2S3/
P3HT Planar Hybrid Solar Cells
Fan Wu1,2* , Rajesh Pathak2, Lan Jiang1, Weimin Chen1, Chong Chen3, Yanhua Tong4, Tiansheng Zhang1,
Ronghua Jian1 and Qiquan Qiao2*

Abstract
In this work, a comprehensive understanding of the relationship of photon absorption, internal electrical field,
transport path, and relative kinetics on Sb2S3 photovoltaic performance has been investigated. The n-i-p planar
structure for TiO2/Sb2S3/P3HT heterojunction hybrid solar cells was conducted, and the photon-to-electron
processes including illumination depth, internal electric field, drift velocity and kinetic energy of charges, photo-
generated electrons and hole concentration-related surface potential in Sb2S3, charge transport time, and interfacial
charge recombination lifetime were studied to reveal the key factors that governed the device photocurrent. Dark
J–V curves, Kelvin probe force microscope, and intensity-modulated photocurrent/photovoltage dynamics indicate
that internal electric field is the main factors that affect the photocurrent when the Sb2S3 thickness is less than the
hole diffusion length. However, when the Sb2S3 thickness is larger than the hole diffusion length, the inferior area
in Sb2S3 for holes that cannot be diffused to P3HT would become a dominant factor affecting the photocurrent.
The inferior area in Sb2S3 layer for hole collection could also affect the Voc of the device. The reduced collection of
holes in P3HT, when the Sb2S3 thickness is larger than the hole diffusion length, would increase the difference
between the quasi-Fermi levels of electrons and holes for a lower Voc.
Keywords: Solar cells, Sb2S3, Photocurrent, Optoelectronic processes

Introduction usually focus on finding the best technology to get better

Sb2S3 has been increasingly utilized for solid thin-film solar optoelectronic performance in solid-state devices [7–10, 13–
cells because of its moderate bandgap of 1.7 eV and an ab- 15]. In this regards, it is imperative to study the photo-
sorption coefficient of 1.8 × 105 cm−1 [1, 2]. Sb2S3 thin films electronic processes in Sb2S3-based solar cells for guiding
can be prepared by various methods, including spray pyroly- the device design and optimization. This includes a compre-
sis [3], electrodeposition [4], chemically deposition [5], and hensive understanding of the balance among absorption, in-
thermal vacuum evaporation technique [6]. In Sb2S3-based ternal electrical field, and transport path, and relative
photovoltaic device, photoelectric conversion efficiency kinetics on Sb2S3 photovoltaic performance, which is im-
(PCE) has reached to 5.7–7.5% by improved technology and portant to guide the optimization of the Sb2S3-based hybrid
device design [1, 2, 7–10]. However, current efficiencies of solar cells. In this work, the conventional TiO2/Sb2S3/
solid-state devices still remain low compared to other poly(3-hexylthiophene-2,5-diyl(P3HT) n-i-p device structure
photovoltaic devices, such as dye-sensitized solar cells [11] was used to study the charge carrier generation and dissoci-
and perovskite solar cells [12]. At present, most of the works ation dynamic processes for different thicknesses of Sb2S3.
It is obvious that the different thickness of Sb2S3 in
* Correspondence: wufanjay@126.com; qiquan.qiao@sdstate.edu
1
TiO2/Sb2S3/P3HT n-i-p solar cells can change (i) the
School of Sciences and Key Lab of Optoelectronic Materials and Devices,
Huzhou University, Huzhou 313000, China
amount of photon harvesting, which influences the
2
Center for Advanced Photovoltaics, Department of Electrical Engineering photon-generated electron/hole concentration; (ii) the
and Computer Sciences, South Dakota State University, Brookings, SD 57007, magnitude of internal electrical field across the Sb2S3
USA
Full list of author information is available at the end of the article
layer, which influences the photon-generated electron/

© The Author(s). 2019 Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0
International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and
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Wu et al. Nanoscale Research Letters (2019) 14:325 Page 2 of 10

hole drift; (iii) electron/hole transport distance to the re- (0.28 M) with stirring in an ice bath (~ 5 °C). The FTO
spective electrode; and (iv) electron/hole recombination substrate was covered with a thin layer of TiO2 and then
[16, 17]. However, the reason for the Sb2S3 thickness- suspended upside-down in the aqueous solution when
dependent performance in n-i-p structure is still am- the color of the solution changed to orange. After 1 h,
biguous, which has been simply attributed to the issues 1.5 h, 2 h, and 3 h of the CBD process, a smooth and
with bulk resistance, photon absorption, generation/re- uniform amorphous Sb2S3 layer was deposited onto the
combination of charge carriers, and internal electric field TiO2-coated FTO substrates, and the sample was thor-
[16–21], but the detailed and quantified analysis for the oughly rinsed with de-ionized water and dried under N2
thickness-dependent photovoltaic parameters is not clear flow. The substrate was further annealed for 30 min in a
yet. To gain insight into the change of Jsc and Voc upon glovebox (O2: 0.1 ppm, H2O: 0.1 ppm) under an N2 at-
the Sb2S3 thickness, TiO2/Sb2S3/P3HT n-i-p solar cells mosphere. The fabrication of n-i-p heterojunction was
were fabricated (Fig. 1), and the thickness of Sb2S3-re- completed by spin casting (1500 rpm for 60 s) of P3HT
lated photon-generated electron and hole transport pro- (15 mg/mL) film on top of Sb2S3 inside a glovebox (O2:
cesses which result in the different photocurrents was 0.1 ppm, H2O: 0.1 ppm) under an N2 atmosphere. Fi-
studied in this work. Moreover, we introduced dynamic nally, the MoO3 (10 nm) and Ag (100 nm) electrode was
intensity-modulated photocurrent/photovoltage spectra deposited by evaporation through a shadow mask.
(IMPS/IMVS) and Kelvin probe force microscope
(KPFM) characterization to study photon-to-electron Instruments and Characterization
processes and investigate the key factors that governed X-ray diffraction (XRD) patterns of the film were recorded
the device performance in different thicknesses of Sb2S3 by an MXP18AHF X-ray diffractometer with Cu Kα irradi-
solar cells. ation (λ = 1.54056 Å). Scanning electron microscopy (SEM)
measurements were performed on a field-emission scan-
Methods ning electron microscope (ZEISS, GeminiSEM 300). The
Reagents absorption spectra were recorded with a Shimadzu UV-
Etched FTO-coated glass substrates were purchased 2600 spectrophotometer. Current density–voltage (J–V)
from Huanan Xiangcheng Co., Ltd., China. SbCl3 (99%), characteristics were measured under AM 1.5 illumination
Na2S2O3 (99%), and titanium diisopropoxide (75% in iso- with an intensity of 100 mW/cm2 using a 94023A Oriel
propyl alcohol) were purchased from Adamas-beta. Sol3A solar simulator (Newport Stratford, Inc.). The light
P3HT was ordered from Xi’an Polymer Company, intensity from a 450 W xenon lamp was calibrated with a
China, and Ag (99.999%) was ordered from Alfa. standard crystalline silicon solar cell. The J–V curves were
collected using an Oriel I–V test station (Keithley 2400
Device Fabrication Source Meter, Newport). External quantum efficiency
The substrates were cleaned via ultrasonication in soap (EQE) spectra of the solar cells were measured by using a
water, acetone, and isopropanol for 60 min each, QE/IPCE measurement kit (Zolix Instruments Co., Ltd.) in
followed by treatment with UV-ozone for 30 min. A thin the spectral range of 300–900 nm. Intensity-modulated
layer of compact TiO2 (0.15 M titanium diisopropoxide photocurrent spectra (IMPS) and intensity-modulated
in ethanol) was spin coated at 4500 rpm for 60 s, photovoltage spectra (IMVS) were measured using an elec-
followed by annealing at 125 °C for 5 min and 450 °C for trochemistry workstation (IviumStat.h, Netherlands) under
30 min. Deposition of Sb2S3 on the top of the TiO2 thin ambient conditions with a background intensity of 28.8
layer was performed by a chemical bath deposition mW/cm2 from a white light-emitting diode, with a small si-
(CBD) method [5, 10, 22]. An acetone solution contain- nusoidal perturbation depth of 10%. Kelvin probe force
ing SbCl3 (0.3 M) was added dropwise into Na2S2O3 microscope (KPFM) was performed by an Agilent SPM
5500 atomic force microscope equipped with a MAC III
controller (comprising three lock-in amplifiers) to map the
surface potential (SP).

Results and Discussion

Deposition and Characterization of Sb2S3/TiO2 Film
FE-SEM images (Fig. 2a) clearly show that different thick-
nesses of Sb2S3 film are deposited on TiO2 layer-coated
glass substrates with the different CBD time t (1.0 h, 1.5 h,
2.0 h, 3.0 h). It can be seen that the uniform Sb2S3 layers
Fig. 1 Illustration of TiO2/Sb2S3/P3HT n-i-p solar cell architecture.h+
were successfully obtained by CBD techniques. The average
denotes the hole and e− denotes the electron
thickness of the Sb2S3 film estimated from the cross-
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 3 of 10

Fig. 2 a Cross-sectional FE-SEM images of Sb2S3 films on TiO2 dense layer-coated glass substrates. b Average Sb2S3 thickness d plotted as a
function of the CBD reaction time t for the Sb2S3 film deposition. The values were estimated by the FE-SEM cross-section images

sectional FE-SEM images is plotted in Fig. 2b as a function Solar Cells

of the CBD time. The average thickness d of Sb2S3 film in- J-V characteristics of solar cells with different thickness
creases linearly with t (Fig. 2b). The average thickness in- d (i.e., CBD t) are compared in Fig. 5a. Table 1 presents
creased almost linearly from 96 to 373 nm by changing the overall photovoltaic performance of these devices.
CBD time from 1 to 3 h. The XRD patterns of Sb2S3 film Increasing thickness d (i.e., CBD time t) significantly af-
with different thickness of Sb2S3 film on FTO glass are fects device performance. The PCE increases as d in-
shown in Fig. 3. The measured XRD spectrum is indexed to creases from 96 to 175 nm (i.e., t increased from 1.0 to
orthorhombic Sb2S3 (JCPDS PCPDFWIN #42-1393) [23]. 1.5 h) and decreases thereafter, especially decreases
As shown in Fig. 4, the TiO2 samples exhibit the ab- largely after d > 280 nm (i.e., t > 2 h). Optimum Sb2S3
sorption onset at 386 nm (3.21 eV) corresponding to the thickness of 175 nm can be determined by comparison
bandgap absorption of TiO2 [24]. All the as-deposited of device efficiencies, at which point a maximum PCE of
TiO2/Sb2S3 layers with different t of CBD exhibit an ab- 1.65%, Jsc of 6.64 mA cm−2, Voc of 0.61 V, and FF of
sorption edge at ca. 750 nm [25]. The absorption inten- 40.81% can be achieved. This result is comparable to the
sity of Sb2S3 on the TiO2 surfaces is clearly in the order other’s reports [16, 26]. Liu et al. studied hybrid ZnO/
3 h > 2 h > 1.5 h > 1 h. This result also indicates that the Sb2S3/P3HT n-i-p cells with Sb2S3 layers of three
Sb2S3 film gradually becomes thicker with a longer CBD different thickness (50, 100, and 350 nm) by thermal
t, which also agrees with the SEM results. evaporation achieving the highest PCE (~ 2%) with the
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 4 of 10

as the d increases (Fig. 5 and Table 1). The device Jsc is

significantly dependent on the Sb2S3 thickness d. The
charge carrier generation and dissociation are key pro-
cesses for photocurrent generation. Firstly, visible light
will pass through the TiO2 layer due to its visible light
window property (Fig. 4) and begin to be absorbed from
TiO2/Sb2S3 interface. Sb2S3 has been proved to be a high
absorption coefficient α around 105 cm−1 in the visible
region [27]. Here, we take α = 105 cm−1 for Sb2S3. The
thickness-dependent illumination depth is depicted in
Fig. 6 according to the Beer-Lambert law I(x) = I0 e-ax, in
which the I0 is the incident photon flux and the I(x) is
the photon flux in Sb2S3. Obviously, the incident pho-
tons cannot be absorbed fully when the Sb2S3 has a
thickness of 100 nm or 200 nm (Fig. 6b). The d-related
Fig. 3 XRD patterns of the as-synthesized Sb2S3 film on FTO with ratio of absorbed photon (Na)/incident photons (Ni) can
different deposition time. Sample 1 is the pure FTO glass substrate,
and samples 2–5 are Sb2S3 films with t of 1 h, 1.5 h, 2 h, and
be calculated by integration of the area of the shaded
3 h, respectively area in coordinate. As shown in Fig. 6b (also refer
Fig. 7b), the Na/Ni is 61% when the d = 96 nm and Na/Ni
is enhanced to 82% when the d = 175 nm. It can be be-
100-nm-thick Sb2S3 [12]. Kamruzzaman et al. studied lieved that the further 21% photons absorbed might
TiO2/Sb2S3/P3HT n-i-p cells with Sb2S3 thicknesses cause the increase in Jsc from 5.50 to 6.64 mA/cm2.
of 45–120 nm by a thermal evaporation method, and When the d increases to 280 nm, the extra 11% photons
the absorber Sb2S3 and hole transporting layer are absorbed and the Na/Ni is further enhanced to 93%,
P3HT were annealed under atmospheric conditions. which shows that more photons could be further
In their studies, the thickness of 100–120 nm absorbed and then might generate more electrons. How-
showed a better power conversion efficiency of 1.8– ever, the device Jsc decreased to 5.06 mA/cm2 which is
1.94% [26]. Obviously, the thickness of Sb2S3 indeed lower than the case of d = 96 nm. When the d increases
strongly affects the device performance, even by to 373 nm, the Na/Ni is close to 100%, and the device Jsc
different deposition strategies of Sb 2S3 film or an- is sharply decreased to 2.64 mA/cm2. Therefore, absorp-
nealing condition. tion is not the sole factor that affects Jsc.
The semilogarithmic plots of the J–V curve of solar
cells in the dark normally exhibit three distinct regimes:
Charge Transport (i) linear increase for leakage dominated current, (ii) ex-
The device Jsc increases remarkably with increasing ponential increase for diffusion dominated current, and
Sb2S3 thickness d from 96 to 175 nm and then decreases (iii) quadratic increase for space-charge-limited current.
The built-in voltage (Vin) normally can be estimated at
the turning point where the dark curve begins to follow
a quadratic behavior (Fig. 7a). Dependences of Vin, Jsc,
Na/Ni, Eke, and Ekh on CBD t are shown in Fig. 7b.
When d increased from 96 to 175 nm, the Na/Ni en-
hanced 34.44%; however, the Jsc only increased by
20.72%, which means that there is another factor limit-
ing the Jsc increment. It has been inferred that this was
might due to the decreased internal electrical field across
the Sb2S3 layer, which weakened the photon-generated
electron/hole drift [16]. Therefore, we calculated the in-
ternal electrical field Ein cross the Sb2S3 based on the re-
lation of Ein = Vin/d (Table 2). Moreover, the drift
velocity of electron ve and hole ve, kinetic energy of elec-
tron Eke, and hole Ekh under internal electric field Ein
were also calculated (Table 2 and Fig. 7b). When the d
Fig. 4 The UV-vis absorption of TiO2 and TiO2/Sb2S3 films with t of
1–3 h, respectively
is 96 nm, the Eke is 296.56 meV, and Ekh is 53.25 meV.
When the d increased to 175 nm, the Eke largely
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 5 of 10

Fig. 5 a J–V curves and b EQE spectra of the solar cells with different CBD t for Sb2S3 film

decreases to 95.29 meV and Ekh decreased to 17.12 meV, Sb2S3 surface becomes lower [28]. This demonstrates
which is lower than the thermal energy at ambient that electrons which could diffuse to the top surface are
temperature (Ekt, 26 meV). This result indicates that the being gradually reduced, indicating that there is an in-
internal electric field has little effects on hole drift when ferior region for photo-generated electrons in thicker
Sb2S3 thickness is or larger than 175 nm. Obviously, the Sb2S3 film as shown in Fig. 6. We also examined the SP
reduced Eke and Ekh with the thicker Sb2S3 should be of P3HT part. The changes of SP of the P3HT are dif-
the reason that limits the increment of Jsc. Further in- ferent from that of Sb2S3. P3HT might be excited by
creasing d from 175 to 280 nm, the Na/Ni enhanced to light to generate excitons and then separate into elec-
13.84%; however, the Jsc get decreased. This might be trons and holes [29, 30], when Sb2S3 is very thin (< 200
due to the decrease in Eke which is close to the Ekt (d = nm). When Sb2S3 becomes thicker, P3HT only acts as
280 nm) but much lower than the Ekh (d = 373 nm), the hole transport layer, because most of the photons
which means the Ein gradually has little effects on elec- are absorbed by Sb2S3 (Fig. 3). Therefore, when the
tron drift when d > 280 nm as observed in this work. thickness of Sb2S3 is less 280 nm, P3HT could be
Therefore, Ein decrement-related electron drift might be photo-excited, resulting in the Fermi level of P3HT
responsible for the Jsc reduction when d increased from gradually decreases as Sb2S3 thickness gradually in-
175 to 280 nm. However, when the d increased to 373 creases (decreased photo-exciton). In the case of 280
nm, the Ein has little effects on electron and hole drift, nm, the SP of P3HT drops rapidly, because there is no
but Jsc still largely decreased, which indicates that Ein is photo-exciton and the P3HT works just as a hole trans-
also not the sole factor that affects the Jsc. port layer to collect holes. As the Sb2S3 thickness in-
We used KPFM to characterize the photo-generated creases to 373 nm which is much larger than the hole
electrons and hole concentration-related surface poten- transport length, the hole collection also drops rapidly,
tial (SP) in Sb2S3/P3HT. The sample for the KPFM causing the Fermi level in P3HT to rise again. More-
measurement was prepared by drop casting the P3HT over, the changes of SP in P3HT is much larger than
precursor solution onto part of the FTO/TiO2/Sb2S3 that in the Sb2S3 in the case of d = 373 nm, which
film surface (Fig. 8). As the Sb2S3 thickness increases means that hole collection is worse than electron col-
from 96 to 373 nm, the SP on the top of Sb2S3 gradually lection and therefore would probably lead to a much
becomes smaller, which means the Fermi level on the decreased Jsc.

Table 1 Device performance of the TiO2/Sb2S3/P3HT n-i-p planar solar cells under AM 1.5 illumination of 100 mW/cm2
CBD time (h) Thickness d (nm) Voc (V) Jsc (mA cm−2) FF (%) PCE (%) τIMPS (μs) τIMVS (ms)
1.0 96 0.59 5.50 43.93 1.44 5.04 1.01
1.5 175 0.61 6.64 40.81 1.65 5.52 1.01
2.0 280 0.60 5.06 40.87 1.25 6.34 1.01
3.0 373 0.46 2.64 37.56 0.45 6.64 1.01
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 6 of 10

Fig. 6 The illustration of the Sb2S3 thickness d-dependent illumination depth x and Ein

Furthermore, IMPS and IMVS, as the powerful lifetime τIMVS related to interfacial charge recombin-
dynamic photoelectrochemical methods in dye- ation under open-circuit condition. According to the
sensitized solar cells [31] and perovskite solar cells relation τ = (2πf)−1 [31–35], τIMPS and τIMVS in the de-
[32], have been applied to study the charge transport vices were calculated (Table 1). The increased τIMPS
dynamics in this work. IMPS/IMVS measures the suggests a longer transport path of charges to collec-
photocurrent/photovoltage response to a small sinus- tion electrode, whereas the unchanged τIMVS infers the
oidal light perturbation superimposed on the same interfacial charge recombination [33]. The inter-
background light intensity under short-circuit/open- facial charge collection efficiency ηc is typical consid-
circuit condition [31–33]. The measured IMPS or ered as ηc = 1-τIMPS/τIMVS [31–35]. Obviously, the
IMVS responses appear in the fourth quadrant of the longer transport time of the τIMPS and the short inter-
complex plane with a shape of the distorted semicircle facial charge recombination lifetime of the τIMVS
(Fig. 10a, b). The time constant τ defined by the fre- would cause a worse charge collection and vice versa.
quency (fmin) of the lowest imaginary component of In this study, the τIMPS increases with the thicker
IMPS or IMVS response is an evaluation of the transit Sb2S3 while the τIMVS is unchanged. Therefore, inter-
time τIMPS for the electrons to reach the collection facial charge collection efficiency ηc decreases with the
electrode under short-circuit condition or the electron thicker Sb2S3, and the changes of Jsc in different

Fig. 7 a Semilogarithmic plots of J–V characteristic in the dark of the solar cells with different CBD t for Sb2S3 film. b Dependences of Vin, Jsc, Na/
Ni, Eke, and Ekh on Sb2S3 thickness d
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 7 of 10

Table 2 Parameters of Vin, internal electric field Ein, drift velocity of the electron (ve) and hole (vh), and kinetic energy of the electron
(Eke) and hole (Ekh) in the dark of the solar cells with different CBD t
d (nm) Vin (V) Ein (× 104 Vcm−1) ve (cm s−1) Eke (meV) vh (cm s−1) Ekh (meV)
96 0.61 6.35 42.55 296.56 16.51 53.25
175 0.63 3.60 24.12 95.29 9.36 17.12
280 0.61 2.18 14.61 34.96 5.67 6.28
373 0.49 1.31 8.78 12.63 3.67 2.26
The mean value of d for a certain Sb2S3 deposition time t is used for calculation of the above parameters Ein,ve,vh, Eke, and Ekh

thickness of Sb2S3 solar cells should be caused by the generated holes from long band could distribute more
transport path and charge collection efficiency, not by uniform in Sb2S3 than that from short band (photo-
charge recombination. generated holes from short band could close to TiO2
The increase in Sb2S3 thickness could absorb more side), resulting in a more efficient collection of the
photons which could enhance the photocurrent. How- hole from long band. Therefore, the EQE in long-
ever, in thicker Sb2S3 layer, most of electrons and wavelength part did not get a large decreased as
holes are generated near the TiO2 side due to expo- much as short-wave part with Sb2S3 thickness of 373
nential photon absorption (Fig. 10c); therefore, the nm (Fig. 5b).
transport path of most of the electrons are almost the As shown in Fig. 10d, it is easily understood that a
same. However, most of the holes need to be diffused smaller τIMPS is accompanied by a thinner Sb2S3 (i.e., a
in a longer path than electrons in the thicker Sb2S3 shorter charge transport path); however, τIMVS mainly
layer, which is demonstrated by longer τIMPS in remains the same when Sb2S3 thickness increased from
Fig. 10d. When the thickness exceeds the hole diffu- 96 to 373 nm in this experiment, which means that there
sion length, the inferior area in Sb2S3 for an ineffi- is no direct dependence of Jsc and Voc on τIMVS (i.e.,
cient hole generation and transport would decrease interfacial recombination) when Sb2S3 thickness
the photocurrent and weaken the Jsc and EQE. The changes. It is well known that the Voc of the TiO2/
hole diffusion length in Sb2S3 is around 180 nm [18]. Sb2S3/P3HT solar cells is normally determined by the
When the thickness of Sb2S3 exceeds hole diffusion difference between the quasi-Fermi levels of the elec-
length, the collection performance of holes is reduced trons in the TiO2 and the holes in the P3HT [36]. As
which is also responded by EQE spectra (Fig. 5b) the collection of holes is reduced in P3HT when the
since the absorption coefficient of the long wave is thickness of Sb2S3 is larger than the hole diffusion
much lower than the short wave, resulting in a longer length, it would increase the difference between the
illumination depth for long wave (Fig. 9) [35]. Photo- quasi-Fermi levels of electrons and holes for a lower Voc.
In addition, a thicker Sb2S3 would increase the higher
series resistance and worse charge collection efficiency;
these unfavorable factors may cause a lower FF in
thicker Sb2S3 device.
Although, the efficiency of planar TiO2/Sb2S3/P3HT
n-i-p solar cells is very low, and how to further im-
prove the device efficiency is a challenge. However,
our results still demonstrated that some further im-
provements could be carried out. For example, enhan-
cing the built-in electric field by employing some
different electron transport layer or hole transport
layer could enhance charge transport and collection.
Moreover, how to improve the hole diffusion ability
should be considered; maybe some conductive addi-
tives is helpful. In addition, interfacial engineer is also
important for improving charge transfer and dissoci-
ation. Last but not least, the method that expressed
in this paper might be offering some helpful reference
Fig. 8 Illustration of SP measurement of Sb2S3/P3HT interface
for other relative high-efficiency solar cells (e.g., or-
by KPFM
ganic solar cells, perovskite solar cells).
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 8 of 10

Fig. 9 KPFM images of Sb2S3 of 1 h (a), 1.5 h (b), 2 h (c), and 3 h (d) and P3HT on Sb2S3 of 1 h (e), 1.5 h (f), 2 h (g), and 3 h (h) under white light
illumination from FTO glass, respectively. i, j The corresponding SP distributions of Sb2S3 and P3HT

Conclusion lead to the reduction in the Jsc when the thickness of

In this paper, the mechanism of photocurrent changes in Sb2S3 is less than the hole transport length. However,
TiO2/Sb2S3/P3HT n-i-p solar cells with different thickness when the thickness of Sb2S3 is larger than the hole
of Sb2S3 was studied. When the thickness is less than the transport length, the internal electric field has little
hole transport length, the absorption and internal electric effects on electron and hole drift, but Jsc still largely
field are the main factors that affect the photocurrent; decreased. KPFM and IMPS/IMVS characterization
when the thickness is larger than the hole transport demonstrated that there is an inferior region for
length, the inferior area in Sb2S3 for an inefficient hole photo-generated electrons in thicker Sb2S3 film. The
generation and transport is the main reason for photocur- inferior area in Sb2S3 for a reduction of holes that
rent decrement. Results showed that device short-circuits’ can diffuse into the P3HT when the Sb2S3 thickness
current density (Jsc) is increased with the enhanced pho- is larger than the hole diffusion length, leading to the
ton absorption when the Sb2S3 thickness is less than the obviously decreased Jsc. Moreover, the reduced collec-
hole transport length; however, when the Sb2S3 thickness tion of holes in P3HT with the increased thickness of
is larger than the hole transport length, device Jsc is Sb2S3 would increase the difference between the
sharply decreased with further increased absorption. In- quasi-Fermi levels of electrons and holes for a lower
ternal electric field decrement-related electron drift could Voc.

Fig. 10 a IMPS and b IMVS characterizations of solar cells with different CBD t for Sb2S3 film. c Illustration of electron and hole diffusion area for
short and long wavelength illumination. d Dependence of τIMPS and τIMVS on CBD t
Wu et al. Nanoscale Research Letters (2019) 14:325 Page 9 of 10

Abbreviations 11. Kweon DH, Baek JB (2019) Edge-functionalized graphene nanoplatelets

CBD: Chemical bath deposition; Ein: Internal electric field; Eke: Kinetic energy as metal-free electrocatalysts for dye-sensitized solar cells. Adv Mater
of the electron; Ekh: Kinetic energy of the hole; Ekt: Thermal energy at 31:1804440
ambient temperature; EQE: External quantum efficiency; FF: Fill factor; 12. Jung EH, Jeon NJ, Park EY, Moon CS, Shin TJ, Yang TY, Noh JH, Seo J (2019)
IMPS: Intensity-modulated photocurrent spectra; IMVS: Intensity-modulated Efficient, stable and scalable perovskite solar cells using poly (3-
photovoltage spectra; J–V: Current density–voltage; Jsc: Short-circuit current; hexylthiophene). Nature 567:511–515
KPFM: Kelvin probe force microscope; Na: Absorbed photon; Ni: Incident 13. Yue W, Wei F, He C, Wu D, Tang N, Qiao Q (2017) L-Cysteine assisted-
photons; P3HT: Poly (3-hexylthiophene-2,5-diyl; PCE: Photoelectric conversion synthesis of 3D In2S3 for 3D CuInS2 and its application in hybrid solar cells.
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This work was supported by the National Natural Science Foundation of solar cells for higher efficiency with polymer-based hybrids for light-
China (21607041, 11747312, 11647306), China Scholarship Council harvesting and straightforward oxide channels for electron transportation.
(201708330103), Science and Technology Planning Project of Zhejiang Sol Energy Mater Sol Cells 114:43–53
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Competing Interests 20. O'Mahony FT, Lutz T, Guijarro N, Gómez R, Haque SA (2012) Electron and
The authors declare that they have no competing interests. hole transfer at metal oxide/Sb2S3/spiro-OMeTAD heterojunctions. Energy
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