Journal of Cluster Science

https://doi.org/10.1007/s10876-022-02368-6

ORIGINAL PAPER

Solution Processed ­WO3 and PEDOT:PSS Composite for Hole Transport

Layer in ITO‑Free Organic Solar Cells
P. Gurudevi1 · P. Venkateswari2 · T. Sivakumar2 · C. Ramesh3 · P. Vanitha4

Received: 27 June 2022 / Accepted: 10 October 2022

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2022

Abstract
We developed PEDOT:PSS [poly (styrenesulfonate)-doped poly(3,4-ethylenedioxythiophene] and tungsten oxide ­(WO3)
based hybrid thin films by facile hydrothermal method. The solution processed W ­ O3–PEDOT:PSS hybrid thin films are fully
characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV–Vis (UV), Raman, X-ray photoelectron
spectra (XPS) and Brunauer–Emmett–Teller (BET) surface area analysis. XRD and SEM results suggest that ­WO3 has crys-
talline structure with monoclinic phase and spherical shaped nanoparticles (20–25 nm), which is uniformly decorated on the
surface of PEDOT:PSS sheets. The value of E ­ g [calculated by linear extrapolating of (F(R ∞) hν)2 and hν] was evaluated to
be 3.11 and 2.85 eV for pure ­WO3 and ­WO3/PEDOT:PSS, respectively. The PL intensity of ­WO3/PEDOT:PSS is maximum
lower than the pristine ­WO3 and PEDOT:PSS, implying an improved interfacial contact quality at the ­WO3/PEDOT:PSS.
Photovoltaic performance of ­WO3–PEDOT:PSS devices were measured under AM 1.5 G 1 sun light intensity of 100 mW/
cm2. Organic solar cell devices with W ­ O3–PEDOT:PSS layer give rise to a significant increase in J­ SC from 9.35 ± 0.03 to
16.2 ± 0.01 mA/cm2 respectively and in ­VOC from 0.28 V to 0.72 V respectively, resulting in a remarkable PCE increase from
0.592 ± 0.03 to 0.714 ± 0.02%. The ­WO3/PEDOT:PSS composite deliver a PCE of 7.81 ± 0.01%. The superior performance
of ­WO3/PEDOT:PSS composite was attributed to the reduced current leakage, enhanced hole extraction characteristics, and
less trap-assisted interfacial recombination via current density–voltage.

Keywords WO3–PEDOT:PSS · Composite thin films · Spin coating · Solar light · Organic solar cells · Photo conversion
efficiency

Introduction well as the simplicity of the printing-based processes used

Organic solar cells (OSCs) based on polymer–fullerene com-
posite active layers have been considered as next generation
photovoltaic devices following Si-based photovoltaics due
to their low fabrication cost, light weight, and flexibility, as
* P. Gurudevi
gurudevi.mphil@gmail.com
1
Department of Electronic Science, A.V.C. College
(Autonomous), Mannampandal, Mayiladuthurai,
Tamil Nadu 609305, India
2
Department of Electronics, Rathnavel Subramaniam College
of Arts and Science (Autonomous), Sulur, Coimbatore,
Tamil Nadu 641402, India
3
Department of Mechanical Engineering, M. Kumarasamy
College of Engineering, Karur, Tamil Nadu 639006, India
4
Department of Management Studies, M. Kumarasamy
College of Engineering, Karur, Tamil Nadu 639006, India
to manufacture the cells [1–3]. In academic and industrial
research, power conversion efficiencies (PCEs) of 3–5%
have been easily obtained from bulk heterojunction OSCs
with poly 3-hexylthiophene (P3HT) and [6, 6]-phenyl ­C61
butyric acid methyl ester (PCBM) active layers due to the
simplicity of both their structure and the fabrication pro-
cess. In particular, a recent important report on OSCs with
a high PCE of 9.2% suggests that cost-efficient and high-
performance OSCs may be mass-produced in the near future
[4]. Wide bandgap polymer donor PM6 and narrow band-
gap polymer acceptor PY-IT were selected to construct all-
polymer solar cells (all-PSCs) with a layer-by-layer (LbL)
or bulk heterojunction (BHJ) structure. The solvent additive
1-chloronaphthalene (CN) plays a vital role in improving
the performance of all-PSCs. The PCE of LbL all-PSCs is
improved to 15.81% from 13.67% by incorporating 1 vol%
CN in PY-IT solution, benefiting from the simultaneously
enhanced short circuit current density (­ JSC) of 22.61 mA/cm2

13
Vol.:(0123456789)

and fill factor (FF) of 73.62% [5]. At present, the majority
of research into OSCs has been devoted to the development
of new organic active materials or device structures (e.g.,
tandem or inverted OSCs) to improve the performance of
photovoltaics [6].
Although the choice of organic active materials and
device structure is critical to the performance of an OSC,
the importance of a stable transparent anode cannot be
ignored because exciton formation and carrier extraction is
significantly affected by the transmittance and resistivity of
the transparent anode. One of the major challenges to be
overcome for the commercialization of OSs is the develop-
ment of transparent electrodes that are inexpensive, solution-
processable, and suitable for OPV devices [7–10]. Indium
tin oxide (ITO) is widely used as a transparent conductive
electrode because of its high transparency (~ 90%) and low
sheet resistance (~ 10 Ω/sq). However, the application of
ITO in flexible electronics is challenging owing to its poor
mechanical properties and high-temperature manufacturing
processes, as well as the limited supply sources of indium.
Although various materials, such as carbon nanotubes, gra-
phene, metallic nanowires, and conductive polymers, have
been proposed to replace ITO, many of them are expensive
within the framework of commercialization [11]. Transpar-
ent electrodes for flexible electronics require a high electri-
cal conductivity, a high transmittance for visible light, and
simple processability [12–19]. Conductive polymers, such
poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)
(PEDOT:PSS) complexes, have great potential for large-
area deposition through solution-based processes with an
aqueous dispersion as well as cost reduction via mass pro-
duction [20–22]. PEDOT:PSS has been widely used as the
flexible transparent electrode because of the advantage of
high mechanical flexibility, high conductivity, high trans-
parency in the visible range and excellent thermal stability.
PEDOT:PSS films are typically fabricated by spin coating
onto substrates. The film coats on the entire substrate. When
used as the bottom electrode, patterning of the PEDOT:PSS
is needed to avoid or reduce the shunt current to improve the
device performance. PEDOT:PSS has exhibited good stabil-
ity under ambient conditions and a direct-current (DC) con-
ductivity over a wide range from 0.01 S/cm to the order of
­103 S/cm [23]. However, it is known that the acidic nature of
the PEDOT:PSS layer leads to severe etching of the ITO and
the diffusion of indium into the organic active layer, which
in turn causes degradation of the OSC [24]. To solve the
problems associated with acidic PEDOT:PSS, metal oxides
such as NiO, ­V2O5, ­MoO3, and ­WO3 have been introduced as
a hole injection layer (HIL) between the organic active layer
and ITO anode in order to improve the reliability of OSCs
[25–28]. These oxide HILs could assist in hole extraction at
the ITO anode and improve OSC performance. In particular,
­WO3 has been reported as an effective and stable HIL for
13
P. Gurudevi et al.
OSCs. Choi et al. reported on the merits of an W ­ O3 HIL,
specifically citing its high optical transmittance over a wide
solar spectral range and proper energy level alignment for
hole-extraction from P3HT [29]. Tao et al. also suggested
­WO3 with a high work function of 4.80 eV to efficiently
extract holes and suppress electrons from the active layer
[30]. Although W-doped indium oxide has been suggested as
an alternative to ITO anode for OSCs, a new electrode con-
cept combining a buffer layer and anode for PEDOT:PSS-
free OSCs has not yet been reported [31]. In this study, we
design and fabricate OSCs of ­WO3–PEDOT:PSS hybrid
thin films with high PCE and stability for the first time. The
PEDOT:PSS acts as an conductive binder to connect the
­WO3 nanoparticles leading to reduced impedance and bet-
ter electrochemical properties. The improved photovoltaic
mechanism of the proposed materials was also discussed.
Experimental Section
Materials
The conducting polymer (PEDOT:PSS) was used for the
synthesis of hybrid material and purchased from Agfa-
Gevart, Group Belgium. W ­ O3 prepared by hydrothermal
method, the main precursor i.e. sodium tungstate dehydrate
­(Na2WO4·2H2O ≥ 99.09%) was used in synthesis process
that was purchased from Sigma Aldrich. The chemical struc-
ture and energy level of PEDOT:PSS was displayed in Fig.
S1a, b.
Fabrication Process of ­WO3 and ­WO3/PEDOT:PSS
Thin Films
Solution A was made by dissolving ammonium molybdate
­Na2WO4·2H2O in water to make a 0.01 mol/L solution. Solu-
tion B was a 2 mol/L hydrochloric acid (HCl) water solution.
The pH of the solution was measured by using digital pH
meter. The pH of the mixed solution was changed between 1
and 1.5 by dropping solution B into solution A. After 30 min
in an ultrasonic bath, glass substrates were cleaned with
distilled (DI) water, acetone, and alcohol. The final solvent
solution was then added to the treated and dried glass sub-
strate using spin deposition techniques at 3000 rpm for 60 s
and dried for 30 min on a hot plate at 100 °C. In the prepa-
ration of W­ O3/PEDOT:PSS composite films, PEDOT:PSS
aqueous solution was mixed with ­WO3 aqueous solution
with the ratio of 1:1. The final aqueous solution was applied
to the washed and dried glass substrate using a spin coat-
ing process at 3000 rpm for 60 s and dried for 30 min on
a hot plate at 100 °C. A pure PEDOT:PSS film was also
made without the addition of ­WO3 aqueous solution as a
comparative. In the preparation process of pristine ­WO3,
Solution Processed ­WO3 and PEDOT:PSS Composite for Hole Transport Layer in ITO‑Free Organic…

ammonium molybdate (1.2 g) was diluted with 50 mL of DI Results and Discussion

water. After that HCl solution was added drop by drop under
strong magnetic stirring until the pH value reaches to 8. The Structural Analysis
final solvent solution was then added to the treated and dried
glass substrate using spin coating techniques at 3000 rpm for To confirm the formation of W ­ O3/PEDOT:PSS compos-
60 s and dried for 30 min on a hot plate at 100 °C. ites, XRD patterns was conducted. Figure 1 shows the
XRD pattern of PEDOT:PSS, W ­ O3 and W­ O3/PEDOT:PSS
composite samples. In XRD spectra of bare PEDOT:PSS,
Characterization Techniques there was no diffraction peak observed for commercially
available PEDOT:PSS conducting polymer due to amor-
To identify the crystal structure, X-ray diffraction (XRD) phous nature [32]. The XRD pattern of pristine ­WO3 thin
studies were carried out using PANalytical X-ray diffrac- film sample, there are series of significant peaks were
tometer with nickel-filtered Cu Ka (30 kV, 30 mA). The observed at 2θ = 23.45°, 23.88°, 24.64°, 26.85°, 29.28°,
surface morphology of the samples was studied using scan- 33.60°, 33.89°, 34.46°, 42.23°, 47.52°, 55.11°, 60.19°
ning electron microscopy (SEM; S-4100, Hitachi). The and 75.16° ICDD-20-1324 [33, 34]. Since there were no
functional group present in the nanocomposite was con- peaks of conducting polymer PEDOT: PSS in the XRD
firmed by Raman spectroscopy RA400, Mettler Toledo. The pattern of ­WO3/PEDOT:PSS composite, which signify the
X-ray photoelectron spectroscopy spectra (XPS) of ­WO3/ amorphous nature of conducting polymer. After the incor-
PEDOT:PSS nanocomposite were recorded via Thermo poration of ­WO3 in to PEDOT:PSS, the peak intensity is
ESCALAB 250 at room temperature. Photoadsorption spec- increased indicating that increase in crystalline nature of
tra of catalysts were tested by UV–Vis diffuse reflectance composite materials. The average grain size was calculated
spectroscopy (DRS Hitachi UV-3600). Photoluminescence from Debye–Scherrer’s formula.
spectra (PL) of CdS-DETA-based samples were tested with
FLS920 fluorescence lifetime and steady state spectrom- K𝜆
d= ,
eter. Specific surface area values ­(SBET) were tested with 𝛽 cos 𝜃
ASAP2020 instrument. where d is the mean crystallite size, K is the shape factor
taken as 0.89, λ is the wavelength of the incident beam, β
is the full width at half maximum and θ is the Bragg angle.
Construction of Organic Solar Cell Setup The average crystalline size of was found as 21.8  nm,
34.1 nm, and 41.6 nm for pure ­WO3, PEDOT:PSS, and ­WO3/
A thin ­WO3–PEDOT:PSS composite film was deposited by PEDOT:PSS composite films, respectively.
using spin coated technique (3000 rpm for 60 s). The pre-
pared glass was sintered at 100 °C for 30 min while sheltered
with a glass Petri dish. Spin-coating P3HT [poly(3-hex-
ylthiophene)] and PCBM (1-(3-methoxycarbonyl)-propyl-
1-phenyl-[6,6]C61) (Sigma Aldrich) in o-dichlorobenzene
(ODCB) at 600 rpm for 60 min resulted in the active layer.
Thermal evaporation was used to deposit a LiF (0.3 nm)
and aluminium (150 nm) cathode through a shadow mask
at a base pressure of 2 × ­10−7 Torr created a device with a 6
­mm2 active area. The gadget was covered with a glass Petri
dish and thermally annealed at 150 °C for 15 min. Five cells
were prepared for each material. Photocurrent–photovoltage
(J–V) curves were recorded under white light irradiation
of 100 mW/cm2 (AM 1.5 G) by a xenon arc lamp (CHF-
XM500, Trusttech Co., Ltd., China) in the air and at room
temperature. All the tests were measured five times in the
same environment and the average data were taken. The
long-term stability of the performance of the DSSCs was
measured with an AM 1.5 G solar simulator (Bunkoh-keiki
Co., Ltd., OTENTO-SUN5) with and without a UV cut-off
filter (< 420 nm). The test was carried out at RT with relative Fig. 1  XRD pattern of the PEDOT:PSS, ­WO3, and ­WO3/PEDOT:PSS
humidity of 71%. composite thin film samples

13

Morphological Studies
The surface morphology of the PEDOT:PSS, W ­ O3 and
hybrid film are also investigated by SEM and AFM analy-
sis. The PEDOT:PSS film reveals a smooth and featureless
morphology as shown in Fig. 2a. On the other hand, the
­WO3 film shows a coarse and rough surface owing to the
stacked nanoparticles (Fig. 2b). The stacked nanoparticles
form much aggregation with grain size within 30–40 nm
well-distributed on the surface. In the hybrid film, it can be
seen that the W ­ O3 nanoparticles are well-dispersed in the
PEDOT:PSS matrix. AFM can provide detailed informa-
tion about surface morphology, topography and homogene-
ity of the films. The AFM micrographs in Fig. 2d–f show the
surface features of the PEDOT:PSS, ­WO3-NPs and hybrid
films, respectively. From Fig. 2d, it is obvious that in the
pristine PEDOT:PSS, the thickness and roughness of the
PEDOT:PSS films gradually increase. By contrast, the ­WO3
Fig. 2  SEM images of a PEDOT:PSS, b ­WO3, c ­WO3/PEDOT:PSS, AFM 2D images of d PEDOT:PSS, e ­WO3, f ­WO3/PEDOT:PSS, and g EDS
image of ­WO3/PEDOT:PSS
13
P. Gurudevi et al.
NPs are adsorbed homogeneously (Fig. 2e). In addition,
more ­WO3 NPs are observed in the AFM height images,
implying that the W ­ O3 NPs adsorbed on top layer may be
interdigitated with the ones adsorbed in the underneath lay-
ers owing to the much smaller thickness of the PEDOT:PSS
than the size of the ­WO3 NPs. Similar trend is also observed
for the hybrid films (Fig. 2f) because the thickness of a
PEDOT:PSS layer is also much smaller than the size of W ­ O3
NPs. The room mean square roughness of the PEDOT:PSS,
­WO3 and hybrid films obtained from the AFM analysis is
0.824, 5.64 and 2.23 nm, respectively. Therefore, both the
SEM and AFM images of the hybrid film show a smoother
morphology compared with that of ­WO3 film. In addition,
the PEDOT:PSS acts as a conductive binder to connect the
­WO3 nanoparticle which cab reduce the electrical resistance
of the resultant film. The chemical compositions were fur-
ther characterized by EDX, which is suitable for element
analysis of thin films. As shown in Fig. 2g, the films consist
Solution Processed ­WO3 and PEDOT:PSS Composite for Hole Transport Layer in ITO‑Free Organic…
of W, O and S elements. This suggest that PEDOT:PSS was
successfully incorporated in the ­WO3 framework.
Raman Spectra Analysis
The better understanding of structural analyses and configu-
ration of pure PEDOT:PSS polymer and ­WO3/PEDOT:PSS
hybrid composite films were studied at excitation wave-
length 532 nm as presented in Fig. 3. The band assigned at
frequency 285 ­cm−1, 333 ­cm−1, 735 ­cm−1 and 821 ­cm−1 are
identified as the pure monoclinic phase of crystalline nature
of ­WO3 nanomaterial [35]. The peaks at 735  ­cm−1 and
821 ­cm−1 are attributed to the stretching modes (W–O–W)
Fig. 3  Raman spectra of (a) PEDOT:PSS, (b) W
­ O3, and (c) W
­ O 3/
PEDOT:PSS composite thin film samples
Fig. 4  a UV–Vis absorption spectra and b band gap plot of PEDOT:PSS, W
­ O3, and ­WO3/PEDOT:PSS thin films
and peaks centered at frequency 285 ­cm−1 and 333 ­cm−1 rep-
resents the binding modes linkages of oxygen molecules in
­WO3. The Raman impressions of PEDOT:PSS are described
in the following references [36, 37]. The different modes
of vibration for PSS are centered at 995 ­cm−1, 1137 ­cm−1,
1571 ­cm−1. The peaks at frequency 1272 ­cm−1, 1374 ­cm−1,
1447  ­cm−1 and 1544 ­cm−1 are identified as the inter-ring
stretching C–C, stretching of C–C, symmetrical C=C, and
antisymmetrical C=C vibration modes, respectively. The
obtained Raman results confirm that prepared hybrid com-
posite films properties do not depend on the mixing of indi-
vidual ­WO3 material but also on the process of bond sharing
between ­WO3 nanoparticles and PEDOT:PSS conducting
polymer.
Optical Characteristic Studies
The UV–Vis absorption spectra of pure conducting poly-
mer and hybrid composites films exhibit four absorption
bands  (Fig.  4). The conducting polymer PEDOT: PSS
spectra exhibit absorption bands at 473  nm, while the
­WO3/PEDOT:PSS hybrid composite films the absorption
bands are found to be at position 525 nm. The peaks cen-
tered nearby absorption wavelength 473 nm were due to the
π–π*, π–polaron and polaron–π* transition, respectively. The
localized polaron band between 400 and 600 nm confirmed
that bonds chain of PEDOT:PSS conducting polymer were
compressed. Absorption spectra also indicate the shift in
absorption peaks towards longer wavelength region depict-
ing that the energy band gap of nanocomposites decreased.
From these spectra optical band-gap energy (­ Eg) was calcu-
lated using Kubelka–Munk model, which is described by
13

F(R∞) = K/S = (1 − ­R∞)2/2R∞, where ­R∞ = ­Rsample/Rstandard
is the reflectance of an infinitely thick specimen, while K
and S are the absorption and scattering coefficients, respec-
tively. F(R∞). hν)2 = A (hν − ­Eg). The variation of F(R∞).
hν)2 versus hν was plotted and the straight line range of these
plots is extended on the x-axis (hν) to obtain the values of
optical band gap (­ Eg). The value of E­ g (calculated by lin-
ear extrapolating of (F(R ∞) hν)2 and hν) was evaluated to
be 2.95 eV, pure conducting polymer. Whereas, the band
gap energy of pure ­WO3 and ­WO3/PEDOT:PSS were 3.11
and 2.85 eV, respectively. The PL behaviors of the pure
PEDOT:PSS, ­WO3 and ­WO3/PEDOT:PSS composites were
Fig. 5  Photoluminescence spectra of PEDOT:PSS, W
­ O3, and W
­ O 3/
PEDOT:PSS composite thin film samples
­ O3, and ­WO3/PEDOT:PSS and b pore size curve
Fig. 6  a ­N2 adsorption and desorption analysis of W
13
P. Gurudevi et al.
measured for analyzing the charge-transfer processes at the
­WO3/PEDOT:PSS interfaces. As shown in Fig. 5, the inten-
sity of the PL spectra obtained for the ­WO3/PEDOT:PSS is
maximum lower than the pristine ­WO3 and PEDOT:PSS,
implying an improved interfacial contact quality at the ­WO3/
PEDOT:PSS. The improved interfacial contact quality is
favourable for an enhanced charge transfer to take place at
the ­WO3 and PEDOT:PSS interface.
Surface Area and Elemental Composition Analysis
Brunauer–Emmett–Teller (BET) characterization dem-
onstrated the mesoporous nature of W ­ O 3 and W
­ O 3/
PEDOT:PSS (Fig. 6). The nitrogen adsorption/desorption
isotherms were similar in shape. However, ­WO3 and ­WO3/
PEDOT:PSS showed a more distinct hysteresis loop in the
P/P0 range of 0.5 to 1.0 than that of W ­ O3 (Fig. 6a). This
finding can be attributed to the porosity of PEDOT:PSS and
the presence of ultrafine ­WO3 nanoparticles deposited on
PEDOT:PSS nanosheets. The mesoporous feature can be
further studied using the pore size distribution curves. The
pore size range of ­WO3 and ­WO3/PEDOT:PSS was 4 nm
to 12 nm (Fig. 6b). The surface area of W ­ O3/PEDOT:PSS
was calculated to be 135.8 ­m2/g, which was higher than
­ O3 (60.9 ­m2/g). This mesoporous structure with
that of W
high surface area of composites can play an important role
in providing rapid electrolyte transport, shorter diffusion
paths, and more active sites for photochemical reactions
on the electrode surface. XPS is a surface technique that is
able to provide information on the chemical and electronic
structure of molecules. The survey spectrum of the ­WO3/
PEDOT–PSS consists of W 4f, O 1s, C 1s, and S 2p, which
Solution Processed ­WO3 and PEDOT:PSS Composite for Hole Transport Layer in ITO‑Free Organic…
is shown in Fig. 7a. The XPS core level spectra of W 4f, O
1s, C 1s, and S 2p of the W ­ O3/PEDOT–PSS are shown in
Fig. 7b–e. In Fig. 7b, there are two peaks at approximate
34.6 eV and 36.8 eV corresponding to W 4­ f7/2 and W 4­ f5/2,
respectively [38], which is in good agreement with the exist-
ence of W­ 6+ in W
­ O3/PEDOT:PSS. The peak at 532.5 eV can
be attributed to the binding energy of C=O, which was most
likely to be partly caused by the water molecule attached to
the surface of composites. The C 1s core level spectrum,
which can be curve-fitted into four peaks at 284.7, 284.8,
286.3, and 289.2 eV, corresponding to s­ p2 hybridized car-
bon, ­sp3 hybridized carbon, C–O, and C=O, respectively
[39]. Regarding the S 2p spectra in Fig. 7e, the two strong
peaks at 162.5 and 163.9 eV are assigned to those of S 2­ p3/2
and S ­2p1/2, respectively.
Photovoltaic Studies
The constructed solar device was shown schematically in
Fig. 8a. The illuminated current–voltage (J–V) character-
istics of solar cells under 1.5 G irradiation (100 mW/cm2)
using PEDOT:PSS, ­WO3 and ­WO3/PEDOT:PSS compos-
ites layers are shown in Fig. 8b. The photovoltaic param-
eters of all the devices are summarized in Table  1. As
Fig. 7  XPS spectra of ­WO3/PEDOT:PSS composite a survey, b W 4f, c O 1s, d C 1s and e S 2p
shown in Table 1, the device with the W ­ O3/PEDOT:PSS
composite layer shows the highest PCE of 7.81 ± 0.01%,
with an open-circuit voltage (­ VOC) of 0.714 ± 0.02% V, a
short-circuit current (­ JSC) of 16.2 ± 0.01%, mA/cm2 and a
FF of 58.1 ± 0.03%. while the ­WO3 exhibited the lowest
­JSC, FF, and PCE of (10.5 ± 0.02 mA/cm2, 56.0 ± 0.06, and
3.12% ± 0.01%). The low photovoltaic parameter values of
the latter can be attributed to its low charge-collection effi-
ciency (due to its high thickness), which in turn increases
charge recombination. The improved PCE of the ­WO3/
PEDOT:PSS composite is attributed to the high electrical
conductivity of the PEDOT:PSS. The external quantum effi-
ciency (EQE) of each sample cell was measured, as shown
in Fig. 8c. As expected, the cells with the ­WO3/PEDOT:PSS
layer displayed a higher EQE value in the visible and near
infrared regions in comparison with the bare W ­ O3 (which
is consistent with the increase of J­ SC), benefiting from
increased intensity of the incident light to the p–n junction.
In the ultraviolet band, the unexpected lower EQE value was
caused by parasitic absorption of ­WO3 material. This can
be largely attributed to the recombination that occurred on
the surface or in the bulk, which reduced the carrier den-
sity and thus caused the decrease of short-circuit current
density (Fig. 8b). Unlike W ­ O3/PEDOT:PSS displayed a
13
 P. Gurudevi et al.

Fig. 8  a Schematic representation of the organic solar cell device bility test of PEDOT:PSS, ­WO3, and ­WO3/PEDOT:PSS composite
set up, b J–V characteristics curve of PEDOT:PSS, W­ O3, and ­WO3/ thin film samples
PEDOT:PSS composite thin film samples, c ECE spectra and d sta-

Table 1  Photovoltaic parameters of PEDOT:PSS, W

­ O3, and W
­ O 3/ of the DSSCs was measured with an AM 1.5 G solar simu-
PEDOT:PSS lator (Bunkoh-keiki Co., Ltd., OTENTO-SUN5) with and
Samples JSC (mA/cm2) VOC (V) FF η (%) without a UV cut-off filter (< 420 nm). The test was carried
out at RT with relative humidity of 71%.
PEDOT:PSS 9.35 ± 0.03 0.592 ± 0.03 35 ± 0.05 1.32 ± 0.03 After 500 h continuous testing, the device loss only 2.1%
WO3 10.5 ± 0.02 0.631 ± 0.02 56 ± 0.06 3.12 ± 0.02 of PCE from its initial value, which suggest that fabricated
WO3/ 16.2 ± 0.01 0.714 ± 0.02 58 ± 0.03 7.81 ± 0.01 device showed ultra stability. In order to further study the
PEDOT:PSS
performance of the cells, the dark current density versus
Data for each cell are based on five individual samples with standard voltage characteristic of the hybrid solar cells was meas-
deviation ured, and the results were plotted (Fig. 9a). The dark J–V
curves were simulated according to the thermionic emis-
high-extinction coefficient and parasitic absorption in this sion model [40]. By combining the thermionic emission
ultraviolet wavelength region. In order to explore the stabil- model and the curve we tested, the n, J­ s, and Φbi of the
ity of the prepared OSC in the practical devices, the device solar cells were extracted (see Table 2). The device with
was further tested the J–V parameters in multiple experi- ­WO3/PEDOT:PSS layers exhibited a J­ s value of 1.59 × ­10−7
ments (Fig. 8d). The long-term stability of the performance A/cm2, approximately a half of that of the W ­ O3 device

13
Solution Processed ­WO3 and PEDOT:PSS Composite for Hole Transport Layer in ITO‑Free Organic…

Fig. 9  a Dark J–V curve of electrode sample, b dynamic photocurrent response, c EIS Nyquist plots of PEDOT:PSS, W
­ O3 and ­
WO3/
PEDOT:PSS, and d transient PL spectra

Table 2  Diode ideality factor (n), reverse saturation current density to the improved contact ability of the PEDOT:PSS layer.
­(Js), and Schottky barrier height (Φbi) values of PEDOT:PSS, W ­ O3, Moreover, the PCE obtained in the present work is higher
and ­WO3/PEDOT:PSS
than previous published works [41–44] and the results are
Samples Js (A/cm2) n Φbi (eV) summarized in Table 3.
WO3 2.91 × ­10−7 2.65 0.815
Electrochemical and Photodynamic Response
WO3/PEDOT:PSS 1.59 × ­10−7 2.27 0.836

Electrical impedance spectroscopy (EIS) was performed

(which was 2.97 × ­10−7 A/cm2). The smaller n value of the
PEDOT:PSS incorporated device implied a suppressed
recombination rate. Moreover, the improved J­ 0 and n param-
eters are also a compelling evidence that the charge carriers
were collected by the electrode with higher efficiency thanks
to investigate the charge transport dynamics of the OSCs
fabricated with PEDOT:PSS, ­WO3 and ­WO3/PEDOT:PSS
(Fig. 9b). This analysis allowed us to observe the current
response by applying alternating current voltage as a func-
tion of frequency; the OSCs with W ­ O3/PEDOT:PSS dem-
onstrated slightly lower charge transfer resistance, revealing

13
 P. Gurudevi et al.

Table 3  Comparison results of Device name Type Solar power PCE (%) References
PCE between present work and
already reported works MoO3/Au/MoO3–PEDOT:PSS OSC 1.5 G (100 mW/cm ) 2
3.03 [41]
PEDOT:PSS OSC 1.5 G (100 mW/cm2) 4.41 [42]
MoO3 OSC 1.5 G (100 mW/cm2) 2.96 [42]
TiO2/MWCNT/PEDOT:PSS DSSC 1.5 G (100 mW/cm2) 0.34 [43]
MoS2 in α-MoO3 OSC 1.5 G (100 mW/cm2) 1.34 [44]
MoO3/PEDOT:PSS OSC 1.5 G (100 mW/cm2) 7.81 This work

that the holes were effectively transported from the active
layer to the anode. The corresponding R ­ S value of cells
employing ­WO3/PEDOT:PSS as HTL was 14.8 Ω∙cm2,
while the reference showed 21.7 Ω∙cm2. Lower ­RS indicates
that better interfacial contact and charge collection efficiency
were obtained due to the addition of the conducting ­WO3/
PEDOT:PSS layer. To further investigate the separation
and transfer efficiency of the photo-generated electrons and
holes, photocurrents of ­WO3/PEDOT:PSS nanocompos-
ites under visible light irradiation were detected for four
on–off cycles. The transient photocurrent measurement was
performed under the illumination of 380 nm and 520 nm
LEDs driven by a pulse generator (AVTECH, AV-1011-B).
The duration and frequency were 400 μs and 50 Hz respec-
tively. The rise time and fall time of the light pulse are less
than 0.5 μs. Photocurrent was measured by connecting the
device to a digitizing oscilloscope (TEK, TDS540D) with
the input impedance of 50 Ω. The devices were kept in the
dark until the measurement was carried out. Figure 9c shows
the photocurrent responses of PEDOT:PSS, W ­ O3 and W ­ O 3/
PEDOT:PSS under visible light irradiation for four on–off
cycles. From Fig. 9c, the current intensity rises to a steady
value when the light on, and rapidly decreases to the dark
current value when the light off. At the moment of both light
on and light off, the changes of currents are almost vertical,
indicting the charge transport rates in the fabricated sam-
ples are very fast. Among all of these materials, the ­WO3/
PEDOT:PSS nanocomposite exhibits the highest photocur-
rent response, suggesting the highest separation efficiency
and longest lifetime of the photo-generated electrons and
holes in ­WO3/PEDOT:PSS nanocomposite. The result fur-
ther provides valid evidence that the homogeneous disper-
sion of ­WO3 on PEDOT:PSS can accelerate the separation
and transfer of charge carriers in the interfacial surface of
­WO3/PEDOT:PSS nanocomposites, which is considered to
the contribution to the enhancement of the photoconversion
efficiency. The charge transfer could be further affirmed
by transient PL spectra, as displays in Fig. 9d. The ­WO3/
PEDOT:PSS shows a shorter decay time τ value 8.01 ns
than ­WO3 (11.52 ns), related to a nonradiative pathway and
rapid interfacial electron injection efficiency at the W ­ O 3/
PEDOT:PSS layer composite. The improved photocurrent
and life time of W ­ O3/PEDOT:PSS compared with bare
­ O3 is due to boost the efficiency of charge transfer and
W
separation.
Conclusions
In summary, hybrid nanocomposite material was prepared
by mixing of ­WO3 nanoparticles in PEDOT:PSS conduct-
ing polymer and film of ­WO3/PEDOT:PSS composite suc-
cessfully developed by cost-effective spin coating method.
The PL intensity was lower for W ­ O3/PEDOT:PSS compos-
ite layer than compared with ­WO3, indicating that greater
PL quenching due to exciton dissociation occurred in the
active layer of the ­WO3/PEDOT:PSS composite. The OSCs
using ­WO3/PEDOT:PSS as anodes showed a considerable
improvement in PCE of 7.81 ± 0.1%, with an open-circuit
voltage ­(VOC) of 0.714 ± 0.2%, V, a short-circuit current
­(JSC) of 16.2 ± 0.1%, mA/cm2 and a FF of 58.1 ± 0.3%. Addi-
tionally, the ­WO3/PEDOT:PSS composite anode exhibited
a lower charge-transport r and shorter decay than the ­WO3
film, as indicated by impedance spectroscopy and transient
PL spectra analysis. Our results suggest that high-quality
­WO3/PEDOT:PSS hole transparent electrodes can be fab-
ricated via the combination of a conductive polymer com-
posite and the novel processing protocol, yielding high-
performance OSCs.
Supplementary Information  The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10876-0​ 22-0​ 2368-6.
Acknowledgements  The manuscript should not be submitted to more
than one publication for simultaneous consideration. The submitted
work should be original and should not have been published elsewhere
in any form or language.
Author Contributions  PG and PV, study conceptualization and writ-
ing (original draft) the manuscript. TS, data curation, formal analysis
and writing (review and editing), and funding acquisition and project
administration.
Data Availability  The data that support the findings of this study are
available from the corresponding author, upon reasonable request.
Declarations 
Conflict of interest  The authors declare they have no competing of in-
terest.

13
Solution Processed ­WO3 and PEDOT:PSS Composite for Hole Transport Layer in ITO‑Free Organic…

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