Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980

https://doi.org/10.1007/s10854-020-03336-4

Effect of UV exposure of ITO/PEDOT:PSS substrates

on the performance of inverted‑type perovskite solar cells
Hamed Moeini Alishah1 · Mehmet Kazici1,2 · Fatih Ongül3 · Sinem Bozar1 · Macide Cantürk Rodop1 ·
Cihangir Kahveci1 · Melih Besir Arvas4 · Yücel Sahin4 · Metin Gencten5 · Murat Kaleli6 · Salih Akyürekli6 ·
Hüseyin Utku Yilmaz6 · Ahmet Bugrahan Bayram6 · Serap Günes1

Received: 6 January 2020 / Accepted: 27 March 2020 / Published online: 16 April 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
We have fabricated inverted-type perovskite solar cells employing ­CH3NH3PbI3−xClx perovskite in the form of ITO/
PEDOT:PSS/Perovskite/PCBM/Al. The effects of UV radiation on ITO/PEDOT:PSS substrates have been investigated for
perovskite solar cells. ITO/PEDOT:PSS substrates were exposed to UV radiation for 5 to 15 min. The perovskite solar cells
fabricated on UV-irradiated ITO/PEDOT:PSS substrates exhibited better performance as compared to those fabricated on
substrates employing non-treated PEDOT:PSS. We used photovoltaic characterization, UV–VIS absorption, sheet resistance,
X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), and external
quantum efficiency (EQE) characterization techniques to investigate the effect of UV irradiation of ITO/PEDOT:PSS sub-
strates on the performance of perovskite solar cells. The devices fabricated on ITO/PEDOT:PSS (UV irradiated for 10 min)
exhibited the best device performance of all. We achieved a 9% increase in the overall power conversion efficiency for the
devices fabricated on substrates exposed to UV radiation.

1 Introduction

Currently, silicon solar cells dominate the photovoltaic (PV)

market [1]. However, due to high manufacturing costs and
* Serap Günes energy-intensive fabrication routes, wide use of silicon solar
sgunes@yildiz.edu.tr cells is rather limited. Recently, perovskite solar cells have
Fatih Ongül been the most popular among the third generation solar cells
fatihongul@gmail.com due to a rapid increase in their power conversion efficiencies
(PCE)s in a very short time interval of almost 10 years [2–6].
1
Department of Physics, Faculty of Arts and Science, Methylammonium lead iodide (­ CH3NH3PbI3) perovskite
Yildiz Technical University, Davutpaşa Campus, Esenler,
34210 Istanbul, Turkey nanocrystals have attracted attention as a new class of light
2
harvesters for mesoscopic solar cells. Initial devices were
Department of Physics, Faculty of Arts and Science, Siirt
University, Siirt, Turkey similar to electrolyte-based dye-sensitized solar cells except
3
the replacement of dye with a perovskite C­ H3NH3PbI3. Such
Department of Electricity and Energy, Ardahan Vocational
School of Technical Sciences, Ardahan University, Ardahan, cells exhibited PCEs of 6.5% [7]. PCE was further increased
Turkey to 11% for the devices consisting of perovskite absorber of
4
Department of Chemistry, Faculty of Arts and Science, ­CH3NH3PbI3–xClx, which possess a near infrared absorp-
Yildiz Technical University, Davutpaşa Campus, Esenler, tion [8]. Later, PCE of 17% was achieved by employing
34210 Istanbul, Turkey chemically tailored novel conjugated polymers [9]. Inverted-
5
Department of Metallurgy and Materials Engineering, type perovskite solar cells were fabricated on conductive
Faculty of Chemistry and Metallurgy, Yildiz Technical poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)
University, Davutpasa Campus, Esenler, 34210 Istanbul, (PEDOT:PSS) substrates. Adam et  al. reported PCE of
Turkey
12% for inverted-type perovskite solar cells in which addi-
6
Department of Physics, Faculty of Arts and Science, tives such as dimethyl sulfoxide (DMSO) and Zonyl in
Süleyman Demirel University, Isparta, Turkey

13
Vol:.(1234567890)
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980 7969
PEDOT:PSS were employed and [6]-phenyl-C61-butyric
acid methylester (PCBM) was used as electron transport
layer. Devices exhibited low hysteresis and excellent opera-
tional stability [10]. Currently, PCEs exceeded 20% by
replacing the perovskite of M ­ APbI3 with formamidinium
lead iodide ­(FAPbI3) [11].
Until recently, two different types of device structures
have been used in perovskite-based solar cells one of which
is in the form of thin conducting oxide (TCO) electrode/
titaniumdioxide ­(TiO2) (other electron transporting layer
(ETL))/perovskite/Spiro-OMeTAD (or other hole trans-
porting layer (HTL))/metal electrode and the other is TCO/
PEDOT:PSS/perovskite/PCBM/Al. The former device struc-
ture is standard (non-inverted) perovskite solar cell structure,
whereas the latter is inverted-type perovskite solar cells. The
latter has several advantages such as low-temperature film
formation, low-cost fabrication, and small hysteresis as com-
pared to those of the former [12].
Since the fabrication of first inverted perovskite solar
cells [13], various methods such as morphology control
of the perovskite layers [14–17], interface engineering [4,
18, 19], use of different ETLs [19–21] and HTLs [22, 23],
and structural optimization [24, 25] have been employed
to improve the PCE of inverted-type perovskite solar cells.
However, the PCE of inverted-type perovskite solar cells
is still lower than that of traditional perovskite solar cells.
PEDOT:PSS was initially employed in organic solar cells
as a hole transporter and a buffer layer to prevent the electron
leakage from the active layer to the indium tin oxide (ITO),
to enhance hole extraction, and to planarize the ITO surface
[26]. However, although PEDOT:PSS is one of the mostly
used HTLs in the solar cell research, it has not yet satisfied
the performance of solar cells. Therefore, PEDOT:PSS with
better morphology, stability, and electrical conductivity is of
great interest. Various strategies have been followed to meet
these goals such as adding an additive into PEDOT:PSS [27,
28], treating the PEDOT:PSS films with solvents [29–31],
and thermal annealing [32, 33]. It has been demonstrated in
the literature that PEDOT:PSS treatment has a significant
role on the device performance of both organic and inverted-
type perovskite solar cells [27–34].
The aim of this study is to use an easy method to investi-
gate the effect of modification of PEDOT:PSS by UV treat-
ment on the performance of perovskite solar cells. We have
irradiated the surface of PEDOT:PSS-coated ITO substrates
with UV radiation, separately for 5 to 15 min, and investi-
gated its effect on the device performance. We observed that
the device performance is improved upon UV irradiation on
PEDOT:PSS surface. We achieved a PCE of 11.3%.
2 Experimental
Initially, all ITO-coated glass substrates were patterned by
etching with an acid mixture of HCl:HNO3:H2O (4.6:0.4:5)
for 40 min. After etching, glass substrates were cleaned in
ultrasonic bath with acetone and isopropanol at each stage
for 20 min, respectively. Initially, all of the ITO substrates
were exposed to UV irradiation for 30 min. An aqueous
solution of PEDOT:PSS (Clevios PH1000), used as hole
transport layer, was deposited on ITO-coated glass substrates
by spin coating at 1000 rpm for 45 s and thermally annealed
at 120 °C for 30 min at ambient conditions to remove any
residual moisture. After spin coating and thermal annealing
of PEDOT:PSS layers, PEDOT:PSS films were exposed to
UV radiation for 5 to 15 min separately. As reference sam-
ples we have also used PEDOT:PSS samples which were
not UV treated. C ­ H3NH3PbI3−xClx perovskite films were
prepared as described in literature [10]. ­CH3NH3PbI3−xClx
mixed halide perovskite precursor solutions were prepared
with molar ratios of 1­ PbI2, ­1PbCl2, and 4.4CH3NH3I by
dissolving in DMF. The perovskite precursor solution was
stirred overnight at 50 °C to and then was filtered through
a PTFE filter (0.45  μm) prior to use. ­CH3NH3PbI3−xClx
mixed halide solution was spin cast at 1500 rpm for 20 s
and 2000 rpm for 5 s at ambient conditions and then was
annealed at 110 °C for 45 min in air. PCBM solution was
prepared by dissolving 2% of PCBM in a mixture of 0.5 ml
chlorobenzene and 0.5 ml chloroform and later it was spin
cast at 1500 rpm for 15 s and 2000 rpm for 15 s on top of
the perovskite films at ambient conditions. For the top elec-
trode, 100 nm of Aluminum (Al) was thermally evaporated
in vacuum system (2 × 10−6 mbar) in a dry glovebox.
All current–voltage (I–V) measurements of OPV devices
were carried out using Keithley 2400-LV source meter with
LabVIEW software under nitrogen in a dry glovebox right
after production. For simulating AM 1.5 conditions, a LOT-
Quantum Design solar simulator with 150W xenon arc lamp
was used as the excitation source with an input power of 100
mW/cm2 white-light illumination calibrated using a refer-
ence silicon diode. The photovoltaic parameters of devices
such as Voc, Jsc, FF, and PCE and parasitic resistances
including the series resistance (Rs) and the shunt resistance
(Rsh) were received by LabVIEW program calculated auto-
matically from the current density–voltage curves. The shunt
resistance (Rsh) of device can be calculated from the inverse
slop of the current density–voltage curve at the near point
of short circuit current density (Rsh = dV/dJ(V=0)). The series
resistance (Rs) of device can be calculated from the inverse
slop of the current density–voltage curve at the near point
of open circuit voltage (Rs = dV/dJ(V=Voc)).
Current density–voltage (J–V) measurements were per-
formed both in the forward and reverse scans from 1.5
13

7970
to − 1.5 V and − 1.5 V to 1.5 V at a rate of 0.05 V/s under
illumination to determine the hysteresis factor (HF) of per-
ovskite solar cells.
Hysteresis factor (HF) is calculated using the following
formula:
PCEForward − PCEReverse
HF =
PCEForward
FF is calculated using the following formula:
Vm ∗ I m
FF =
Voc ∗ Isc
PCE is calculated using the following formula:
(
Pout
)
FFxVoc xJsc
𝜂AM1.5 (%) = x100 = x100
Pin Pin
External quantum efficiency (EQE) was performed with
optical system consisting of a xenon lamp, a filter wheel,
mechanical chopper, and a monochromator (Acton SP150)
and recorded by using a lock-in amplifier (EG&G 7260).
The incident monochromatic light intensity at each wave-
length was recorded as a reference with calibrated silicon
diode. External quantum efficiency (EQE) of photovoltaic
devices was measured in the wavelength range from 300 nm
to 900 nm at 5 nm internals under short circuit conditions.
The sheet resistances of the PEDOT:PSS films were meas-
ured with a two-point probe technique. Resistances of non-
treated and UV-treated PEDOT:PSS films were determined
by the ohmic behavior of the I–V curves in the dark at room
temperature. Sheet resistances of PEDOT:PSS films were
calculated from following equation:
Rsheet =
R×W
L obtained from AFM measurement is similar to the rough-
where R is the resistance, W is the width, and L is the length.
The optical absorption spectra of the PEDOT:PSS films
were measured using a UV–VIS spectrometer (Perkin
Elmer).
The surface morphologies of the PEDOT:PSS films and
the perovskite films were examined by using FEI Quanta
FEG 250 scanning electron microscope (SEM). The crys-
talline structures of ­CH3NH3PbI3-xClx perovskite film and
non-treated and UV-treated PEDOT:PSS films were charac-
terized using X-ray diffraction method (XRD) by Bruker D8
Advance Twin-Twin with Cu ­Kα radiation (λ = 1.5418 Å).
Electrochemical impedance spectroscopic (EIS) analysis
was carried out by using classical three electrodes system
including electrochemical cell with Gamry Reference 3000
model equipment. Working electrodes were UV-treated
PEDOT:PSS electrodes for different time intervals (non-
treated (0 min), 5 min., 10 min. and 15 min.) on UV-treated
13
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980
ITO substrates for 30 min, which were exactly the same as
used in the device configuration. Platinum wire and satu-
rated calomel electrode (SCE) were the counter and refer-
ence electrodes, respectively. 0.1 m of L­ iClO4 was used as
an electrolyte. Each spectrum was fitted an equivalent circuit
model and error rate was lower than 5% for each fitting pro-
cess. EIS spectra were obtained between 0.01 and 1­ 05 Hz at
open circuit potential. Electrochemical active surface areas
of the PEDOT:PSS/ITO with and without UV treatment
were calculated by cyclic voltammetric analysis carried out
in 1 mM ­K4Fe(CN)6 and 1 M KCl solution between − 0.5 V
and 1.0 V versus SCE with 50 mV s−1 scanning rate.
AFM and KPFM analyzes were performed with Shi-
madzu SPM-9600 device. Dynamic mode is used for AFM
analysis. In KPFM analysis, firstly, Highly Oriented Pyro-
lytic Graphite reference measurement was done. Then, the
surface potential of the samples was measured. Pyramidal
silicon-etched AFM probe (40 N/m, 325 kHz) was used in
AFM analysis. Pt/Ir-coated KPFM probe (2.8 N/m, 75 kHz)
was used for surface potential measurement in KPFM
analysis.
3 Results and discussion
Figure 1 shows the SEM images of non-treated and UV-
treated PEDOT:PSS samples for 5 to 15 min. As can be seen
from the figure, all films exhibited a smooth morphology.
We also performed atomic force microscope (AFM)
measurements to better understand and evaluate the changes
in the morphology of the PEDOT:PSS films. Figure 2a–d
shows the AFM images of non-treated and UV-treated
PEDOT:PSS films for different time intervals.
Root mean square (RMS) roughness (Rq) of a surface
ness average, with the only difference being the mean-
squared absolute values of the surface roughness profile.
The Rq is more sensitive to peaks and valleys than the
average roughness due to squaring of the amplitude in
its calculation [35]. The rms roughness values were as
1.434 nm, 2.31 nm, 1.250 nm, and 1.240 nm for non-treated
and UV-treated PEDOT:PSS films for 5, 10, and 15 min,
respectively. All surfaces were smooth. Maximum height
scale on the right sides of the figures is expressed as the
vertical distance between the deepest valley and the high-
est peaks on the film profiles. The maximum height scales
were 21.42 nm, 26.64 nm, 12.46 nm, and 16.42 nm for non-
treated and UV-treated PEDOT:PSS films for 5, 10, and
15 min, respectively. Although there are slight changes in
the height scale profiles, the height scales are comparable.
However, the features of the films were slightly different.
The non-treated PEDOT:PSS films exhibited rather a com-
pact film morphology, whereas UV-treated PEDOT:PSS
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980 7971
Fig. 1  SEM images of a PEDOT:PSS, b PEDOT:PSS (UV: 5 min.), c PEDOT:PSS (UV: 10 min.), and d PEDOT:PSS (UV: 15 min.)
films exhibited different sizes of shiny grains on the sur-
face of the UV-irradiated PEDOT:PSS films. It has been
observed in the literature that the applied electric field has
an effect on the morphology of the PEDOT:PSS films [36].
Lim et  al. also observed irregular shaped grains on the
surface of PEDOT:PSS films on which an electric field is
applied [36]. The structure of the grains was almost similar
to the grains we have observed in this study (see Fig. 2).
We performed electrochemical impedance spectroscopy to
understand the nature of the surface of non-treated and UV-
treated PEDOT:PSS films and we have observed that the
electrochemically active surface area of the PEDOT:PSS
films increased upon UV treatment, which will be discussed
in detail below.
Figure 3 shows the SEM images of perovskite films on
non-treated and UV-treated PEDOT:PSS films for time inter-
vals of 5 to 15 min with scales of 500 nm and 1 μm for each
films. When UV exposure time of the PEDOT:PSS films is
increased to 15 min the perovskite films tend to form larger
grains. It has been reported in the literature that the surface
of PEDOT:PSS is improved to become hydrophobic when
exposed to UV radiation [26]. Therefore, the wettability of
the surface is improved. Surface energy plays an important
role in the control of the growth of perovskite and thereby
the performance of the perovskite solar cells [37]. Perovskite
films deposited on a hydrophilic surface contain small grain
size, leading to a reduction in PV performance [37]. It is
difficult to achieve continuous pinhole-free hydrophilic
organolead triiodide perovskite films on the hydrophobic
surfaces of non-wetting hole transport layers although aver-
age grain sizes are much larger on hydrophobic surfaces
[38]. Forming a smooth and uniform perovskite layer is criti-
cal for high-performance perovskite solar cells. Therefore,
the control of the grain size and the contact between the
grains are important. The factor, which determines the grain
size, is the mechanism by which the perovskite is formed on
the substrate. The theoretical studies reveal that large grain
size with a homogeneous grain distribution can produce high
current values [39]. In this study, SEM images show that
the grain size is increased upon UV irradiation. However,
the grain size distribution is not homogenous. Also, there
are voids between the grains, especially for the samples
exposed to UV irradiation for 15 min. The increase of the
voids between the grains leads to a poor contact between
the grains.
To confirm the successful formation of perovskite films
on the PEDOT:PSS-coated ITO surface, we have per-
formed XRD analysis. Figure  4 shows the XRD image
of a ­CH3NH3PbI3-xClx perovskite films. The diffraction
peaks corresponding to (110), (220), and (314) confirm
13

7972
Fig. 2  AFM images of
PEDOT:PSS films a non-treated
b UV-treated for 5 min c UV-
treated for 10 min d UV-treated
for 15 min
the perovskite structure, which is consistent with the litera-
ture [40]. Full width half maximum (FWHM) values were
recorded as 0.0738 for (110) at 14.22° and (200) planes at
28.37°, which confirms a crystalline perovskite structure
[40].
Figure  5 shows the sheet resistance graph of
PEDOT:PSS films for different time intervals of UV
exposure time. It has been observed that the sheet resist-
ance decreased for 5 to 10  min of UV irradiation and
then increased after 15 min. PEDOT:PSS films consist of
highly conductive hydrophobic PEDOT rich core and a
hydrophilic insulating PSS-rich shell [41]. It is the hydro-
gen bonds of the PSS chains of the shell, which provide
coherence to the material [41]. The external effects such as
electric field may cause phase separation of PEDOT:PSS
[36]. Here, we have external effect as the application of a
UV irradiation. It might be possible that the UV irradia-
tion leads to a phase separation between PEDOT and PSS
in which either PEDOT or PSS phase is dominant and
also leads to the migration of one of these phases to the
surface from the deeper parts of the PEDOT:PSS films,
which have been already observed upon application of
an electric field in the literature [37]. Since PEDOT and
PSS have different electrical properties, sheet resistances
can be affected. We have exactly observed that the sheet
13
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980
resistances are influenced by the application of the UV
irradiation. It decreased initially for 5 to 10 min of UV
irradiation and then increased again for 15 min of irradia-
tion. PSS is insulating, whereas PEDOT is the conducting
part in PEDOT:PSS [41]. A possible excess of PSS-rich
domains close to the surface in time by the effect of UV
irradiation may explain the increase in the sheet resistance
for the samples exposed to UV irradiation for 15 min.
We have performed XRD studies on differently treated
PEDOT:PSS substrates to investigate whether UV treatment
has an effect on the crystallinity of PEDOT:PSS films. Fig-
ure 6 shows the XRD spectra of non-treated and UV-treated
PEDOT:PSS films. A broad peak is observed at about 25
degrees which belongs to the (020) plane of the backbone of
the PEDOT:PSS. Although there is a small difference in the
peak intensities, the amorphous nature of the PEDOT:PSS
is retained [42].
Figure  7 shows the FTIR spectra of non-treated and
UV treated PEDOT:PSS films in the range of 500 cm −1
to 2500 cm−1. The IR band at 818 cm−1 is mainly attrib-
uted to C–S stretching bond. The IR bands at 1010 cm−1
and 1164 cm−1 are attributed to C–O–C band stretching in
the ethylene dioxy units. The IR bands of 1369 cm−1 and
1529 cm−1 are mainly due to C–C and C=C stretching of
thiophene rings and the sulfonic acid groups of PSS [43].
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980 7973

Fig. 3  SEM images of perovskite films coated on top of a, b PEDOT:PSS, c, d PEDOT:PSS (UV: 5 min.), e, f PEDOT:PSS (UV: 10 min.), and
g, h PEDOT:PSS (UV: 15 min) in 500 nm and 1 μm scales, respectively

13

7974 Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980

10000 calculated which led to a PCE of 11.3%. After exposing the

PEDOT:PSS films to UV light for 15 min Jsc of 15.5 mA/
(110) cm2, a Voc of 0.89 V, and a FF of 0.76 were calculated which
8000
led to a PCE of 10.5%. As can be seen, the PCEs of the
devices increased upon exposure of PEDOT:PSS films up
Intensity [au]

6000 to 10 min. After 15 min of UV exposure of PEDOT:PSS

films to UV light, the device performance was almost the
(200)
4000
same with the reference device consisting of non-treated PV
films. The photovoltaic parameters including the hysteresis
factor are summarized in Table 1. It is seen that the UV
2000 irradiation time of the PEDOT:PSS has a profound effect
on the device performance. There are several mechanisms
(314)
0
reported in the literature on the physical and chemical
20 40 60 80 changes of PEDOT:PSS upon UV irradiation, which can
2 [Degrees] be summarized as the decrease of charge trapping-related
defects [44], increase in work function [45], transformation
of PEDOT:PSS chains from benzoid to quinoid after UV
Fig. 4  XRD graph of perovskite ­(CH3NH3PbI3−xClx) film
radiation, which prevents the formation of a hole extrac-
tion barrier between the PEDOT:PSS and the active layer
3 [46]. All these effects increase the extraction efficiency and
thereby eliminate the recombination probability of the elec-
trons and the holes, which, in turn, leads to a better device
performance. In our study, lowest PCE was achieved for the
devices employing PEDOT:PSS exposed to 15 min of UV
2 irradiation and the main loss was due to low Jsc. It has been
R sheet(kΩ/□)

previously mentioned that forming a smooth and uniform

1
0 ments in this study that the morphology of the PEDOT:PSS
0 5 10
UV illumination time (min.)
Fig. 5  Sheet resistances of non-treated and UV-treated PEDOT:PSS
films
Figure  8 shows the current density–voltage (J–V)
curves of devices employing non-treated and UV-treated
PEDOT:PSS films between 5 to15 min. Reference device in
which PEDOT:PSS was non-treated exhibited a short cir-
cuit current density Jsc of 16.4 mA/cm2 and an open circuit
voltage Voc of 0.88 V. A fill factor of 0.72 was calculated
which led to a PCE of 10.4. For the devices employing
PEDOT:PSS film which was exposed to UV light for 5 min
exhibited a Jsc of 16.6 mA/cm2 and a Voc of 0.89 V and a FF
of 0.75 was calculated which led to a PCE of 11.1%. Increas-
ing the UV exposure of PEDOT:PSS films to 10 min led to a
Jsc of 17.2 mA/cm2 and a Voc of 0.89 V and a FF of 0.74 was
perovskite layer is critical for high performance perovskite
solar cells. Bad contact between the grains and also poor
connection to the back contact may lower the Jscs. Therefore,
the control of the grain size and the contact between the
grains affect Jsc. The factor, which determines the grain size,
is the mechanism by which the perovskite is formed on the
substrate. It has been demonstrated by the AFM measure-
15 films is affected by the UV irradiation which leads to a
different film formation behavior of perovskite on differ-
ently treated PEDOT:PSS substrates. The theoretical stud-
ies reveal that large grain size with a homogeneous grain
distribution can produce high current values [42]. In this
study, SEM images show that the grain size is increased
upon UV irradiation. However, the grain size distribution is
not homogenous. Also, there are voids between the grains,
especially for the samples exposed to UV irradiation for
15 min. The increase of the voids between the grains leads
to a poor contact between the grains and causes a decrease
in the short circuit current density.
Figure 9 shows the external quantum efficiency (EQE)
of the devices employing non-treated and UV-treated
PEDOT:PSS films for different time intervals (left scale)
and also the absorption of non-treated and UV-treated
PEDOT:PSS films for different time intervals (right scale).
EQE is defined as the number of photo generated charge
carriers contributing to the photocurrent per incident photon

13
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980 7975

Fig. 6  XRD Spectra of a non-

treated b PEDOT:PSS (5 min
UV treated) c PEDOT:PSS
(10 min UV treated) films
d PEDOT:PSS (15 min UV
treated) films

75 observed about 484 nm in the EQE spectrum. Same kind of

shoulder is observed about 526 nm in absorption profile of
70 715 PEDOT:PSS films which is in accordance with the literature
818
1164
1122 1010 [41, 48, 49]. The characteristic shoulder at 484 at EQE spec-
65
trum is similar to the absorption profile of PEDOT:PSS films
Transmission [%]

1271 1033
1369
60
1529 1412 1056 on ITO substrates. The shift in wavelength is attributed to
the contribution of perovskite and PCBM to the photocurrent
55 1412 715 generation, which are employed in the device configuration.
1014 846
Through the comparison of the EQE and absorption, we can
50 1122 1056 1042 conclude that all the components in the device configuration
1164
contribute to the photocurrent generation mechanism. How-
ITO/PEDOT:PSS (5 min)
45
1529 1262 ITO /PEDOT:PSS (10 min) ever, we have observed a change in the absorption profile at
ITO /PEDOT:PSS (15 min)
1369 ITO/PEDOT:PSS (Non-treated) longer wavelengths between 500 and 700 nm. it is known
40
2000 1500 1000 500
in the literature that the absorption profile of PEDOT:PSS
Wavenumber [cm-1]
may vary in the NIR region when the oxidation state of
PEDOT:PSS changes [50]. Although the wavelength region
of 550 to 750 nm is not within NIR region, it is close to NIR
Fig. 7  FTIR spectra of non-treated and UV treated ITO/PEDOT:PSS
films for different time intervals and since the experiments were done in air, the PEDOT:PSS
surface may be oxidized and the change in the absorption of
differently treated PEDOT:PSS films may be attributed to
and is used to get information on the energy of photons that the oxidized states of the PEDOT:PSS [50, 51].
contribute to current generation in solar cell [47]. Compari- Electrochemical impedance spectroscopy was used to
son of EQE and absorption spectra of individual components determine resistance characteristics of the non-treated and
employed in the device configuration provides information UV-treated ITO/PEDOT:PSS electrodes. Figure 10 shows
on which components contribute to the charge carrier gen- the fitted (to an equivalent circuit model given inset of
eration. EQE spans between 350 and 800 nm. A shoulder is Fig. 10) EIS spectra of the electrodes. Here, Rs, Rct, Cdl,

13

7976 Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980

103 103

102 UV 0 min. UV 5 min.

102
1
10
101
100
J [mA/cm2]

J [mA/cm2]
10-1 100

10-2 10-1
10-3
0 0

Dark -5 10-2 Dark -5

10-4 Forward Forward

-10 -10
Reverse Reverse
-5 -15 10-3 -15
10
-20 -20
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
10-6 10-4
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
V [Volt] V [Volt]

104 103

103 UV 10 min. 102 UV 15 min.

2 1
10 10

10 1
100

J [mA/cm2]
J [mA/cm2]

100 10-1

10-1 10-2

10-2 0
10-3 0

-5 -5

10-3 Dark -10

10-4 Dark -10
Forward Forward
-4 -5
10 Reverse
-15
10 Reverse
-15

-20 -20
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
10-5 10-6
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
V [Volt] V [Volt]

0
UV 0 min.
UV 5 min.
-5 UV 10 min.
UV 15 min.
J [mA/cm2]

-10

-15

-20
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
V [Volt]

Fig. 8  Semi-logarithmic J-V curves of devices employing non-treated, 5 min, 10 min, and 15 min UV-treated PEDOT:PSS films. The graph at
the bottom is the comparison of J-V curves in linear scale. Inset is the J-V curve of perovskite solar cells under reverse and forward bias

and W represent the solution resistance, charge transfer composition, these values were comparable for each type
resistance, double layer capacitance, and Warburg imped- of the electrodes (Table 2). However, a decreasing ten-
ance values, respectively [52–54]. Rs value is mainly dency was observed for the UV-treated ITO/PEDOT:PSS
related with the resistance of solution and resistance of electrodes due to increasing conductivity of electrode
electrical connections of the electrodes [52, 53]. Since surface by this treatment process (Table 2) [54]. R ct is
each EIS analysis was carried out in the same electrolyte

13
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980 7977

Table 1  Photovoltaic parameters of fabricated devices PEDOT:PSS electrodes after UV treatment with formed
UV 0 min UV 5 min UV 10 min UV 15 min active sides [54]. Cdl and Warburg impedance values cor-
respond to the formed double layer capacitance on the
Voc (V) 0.88 0.89 0.89 0.89 electrode surface and diffusion rate of the ions to the elec-
Jsc (mA/cm2) 16.4 16.6 17.2 15.5 trode surface, respectively [52–54]. Certain increases were
FF 0.72 0.75 0.74 0.76 also obtained for C dl and Warburg impedance after UV
Rs (Ω) 20 20 22 23 treatment. The increase in these values were associated
Rsh(Ω) 6261 37077 159953 16875 with the formation of electrochemically active sites on
PCE (%) 10.4 11.1 11.3 10.5 the electrode surface as a result of UV treatment [54].
HF 0.07 0.10 0.12 0.15 The rate of normalized surface areas was calculated using
Randles–Sevcik equation (Table 2) [55, 56]. The increase
on the electrochemically active surface areas of the UV-
0.5 treated ITO/PEDOT:PSS electrodes was also supported by
70
the AFM analysis (see Fig. 2). It has been observed that
60 0.4 the active surface areas of the electrode systems increased
as a result of UV treatment.
50 Figure  11 shows the surface potential images of
Absorption [au]
0.3
EQE [%]

40
PEDOT:PSS films on ITO surfaces obtained from Kel-
vin Probe Microscopy (KPFM) measurements. KPFM
30 Non-Treated 0.2 is used to determine the surface electric potential differ-
UV_5min ence. This method is widely used due to its extremely
20 UV_10min
UV_15min 0.1 high surface sensitivity [57]. This method is used to
10 study energy-level alignment of conjugated polymers on
different electrodes [57]. We have measured the contact
0 0.0
400 500 600 700 800 potential difference (V CPD) between the KPFM tip and
Wavelength [nm] non-treated PEDOT:PSS as − 0.43  V ,whereas V CPD(s)
were − 0.19  V, − 0.24  V, and − 0.135  V,for UV-treated
Fig. 9  Comparison of external quantum efficiency of devices and PEDOT:PSS for 5, 10, and 15  min, respectively. Con-
absorption of non-treated and UV-treated PEDOT:PSS films (bold tact potential difference is proportional to the difference
lines are absorption) between the work functions of the sample and the KPFM
tip [58]. Since the tip was the same during all the measure-
correlated with the resistance of rate-controlled electro- ments, we can state that the work function of PEDOT:PSS
chemical reaction and electron transfer [52, 53]. is increased upon UV irradiation. The increase in work
R ct values decreased for the UV-treated ITO/ function is crucial for the performance of solar cells since
PEDOT:PSS electrodes (see Table 2), which indicates it governs the hole extraction barrier between the active
increased electrocatalytic activity of the surfaces of ITO/ layer and the PEDOT:PSS. Our results are in agreement

Fig. 10  Fitted EIS spectra of

ITO/PEDOT:PSS electrodes
without UV treatment of
PEDOT:PSS film and ITO/
PEDOT:PSS electrodes with
5, 10, and 15 min UV-treated
PEDOT:PSS films

13

7978 Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980

Table 2  Electrochemically active surface areas and fitted impedance values of UV-treated and non-treated PEDOT:PSS electrodes at different
time intervals of 5 min., 10 min, and 15 min
Electrode Electrochemically active Normalized Rs Normalized Rct Normalized W Normalized
surface area ­(cm2) (Ω cm−2) (Ω cm−2) Cdl (F cm−2)

Non-treated PEDOT:PSS 3.06 25.96 7.81 0.00103 1.017 × 10−7

ITO/PEDOT:PSS UV-treated for 5 min 3.47 18.53 7.33 0.00106 1.210 × 10−7
ITO/PEDOT:PSS UV-treated for 10 min 3.44 23.03 7.20 0.00107 1.211 × 10−7
ITO/PEDOT:PSS UV-treated for 15 min 3.39 20.93 7.19 0.00110 1.352 × 10−7

Fig. 11  KPFM surface potential

images of PEDOT:PSS films
a non-treated, b UV treated
for 5 min, c UV treated for
10 min d UV treated for 15 min.
(Insets are the surface potential
histograms)

with the reports in the literature stating that the work func-
tion of PEDOT:PSS is increased upon UV-irradiation [44,
51].
4 Conclusion
We investigated the effect of UV treatment on ITO/
PEDOT:PSS substrates in inverted-type perovskite solar
cells. We observed that UV treatment on PEDOT:PSS for
certain time (up to 10 min) causes an improvement in the
PCEs of herein investigated perovskite solar cells. We per-
formed SEM, XRD, I-V, absorption, resistivity, and external
quantum efficiency measurements to understand the effect
of UV radiation on the device performance.
15 min of exposure to UV irradiation worsens the PV
performance. The PCE of solar cells are directly propor-
tional to the Jsc, Voc, and FF of solar cells. The main loss
for the devices employing UV-treated PEDOT:PSS films for
15 min was the decrease in Jsc. One of the reasons for low
Jscs in perovskite solar cells is the difficulty of the control of
morphology of the perovskite films. EIS studies showed that
electrochemically active surface areas of the PEDOT:PSS
films increased upon UV irradiation, which is in agreement
with the AFM studies. It is known from the literature that
the substrate, on which the perovskite film is formed, has an

13
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980 7979
effect on the film formation properties of the perovskites.
We have confirmed also in this study that the perovskite film
formation, thereby the morphology of perovskite films, is
affected by the UV treatment of ITO/PEDOT:PSS substrates.
The effect of UV radiation on PEDOT:PSS on the perfor-
mance of organic solar cells has already been studied in the
literature. However, its effect on perovskite solar cells has
not been studied in the literature before, to our best knowl-
edge. In the study by Lee et al. [46], they observed a higher
PCE for the devices employing UV-treated PEDOT:PSS
films and this higher efficiency was attributed to the lower
device series resistance and the work function change after
UV irradiation, which we have observed the same. However,
they have observed a negligible change in the surface mor-
phology. In our case, we have shown that the UV irradia-
tion affects PEDOT:PSS morphology and this change affects
the film formation properties of perovskites on differently
treated PEDOT:PSS substrates. And also as an important
advantage, in our study, we have observed that we do not
need long UV irradiation times to observe the effect of UV
irradiation on the device performance. In another study by
Xing et al. [59], they have observed UV irradiation-induced
conductivity improvement in PEDOT:PSS films. However,
they needed high UV irradiation times (25 h) to achieve the
highest conductivity. In our case, we were able to achieve
high PCEs for perovskite solar cells with shorter UV irra-
diation times.
In conclusion, modification of PEDOT:PSS layer to over-
come its disadvantages for its use in solar cell research has
been widely studied in the literature. The aim of this study
was to investigate the modification of PEDOT:PSS layer
by UV irradiation and to study the effect of this modifica-
tion on the performance of perovskite solar cells. Unlike
the literature, we have observed that this treatment has an
effect on the morphology of the PEDOT:PSS films and as an
advantage we do not need long irradiation times for improve-
ment of device performance. Further investigations will be
performed to understand the effect of UV source intensity
on the performance of the devices.
Acknowledgements  We gratefully acknowledge Prof. Sariciftci for
accepting Fatih Ongül as visiting scientist and providing the experi-
mental facilities of Linz Institute for Organic Solar Cells (LIOS). Fatih
Ongül acknowledges the Scientific and Technological Research Coun-
cil of Turkey-TÜBİTAK (2219 BİDEB-1059B191601931) for financial
support.
References
1. M.A. Green, Y. Hishikawa, E.D. Dunlop, D.H. Levi, J. Hohl-
Ebinger, A.W.Y. Ho-Baillie, Prog. Photovolt. Res. Appl. 26, 427
(2018)
2. T. Miyasaka, A. Kojima, K. Teshima, Y. Shirai, J. Am. Chem. Soc.
131, 6050 (2009)
3. W.S. Yang, J.H. Noh, N.J. Jeon, Y.C. Kim, S. Ryu, J. Seo, S.I.
Seok, Science 348, 1234 (2015)
4. Z.H.H. Zhou, Q. Chen, G. Li, S. Luo, T.B. Song, H.S. Duan, Z.
Hong, J. You, Y. Liu, Y. Yang, Science 345, 542 (2014)
5. J. Burschka, N. Pellet, S.-J. Moon, R. Humphry-Baker, P. Gao,
M.K. Nazeeruddin, M. Grätzel, Nature 499, 316 (2013)
6. M.A. Green, A. Ho-Baillie, ACS Energy Lett. 2, 822 (2017)
7. J.-H. Im, C.-R. Lee, J.-W. Lee, S.-W. Park, N.-G. Park,
Nanoscale 3, 4088 (2011)
8. H.J. Snaith, M.M. Lee, J. Teuscher, T. Miyasaka, T.N.
Murakami, Science 338, 643 (2012)
9. Q. Xue, G. Chen, M. Liu, J. Xiao, Z. Chen, Z. Hu, X.F. Jiang,
B. Zhang, F. Huang, W. Yang, H.L. Yip, Y. Cao, Adv. Energy
Mater. 6, 1 (2016)
10. G. Adam, M. Kaltenbrunner, E.D. Głowacki, D.H. Apaydin,
M.S. White, H. Heilbrunner, S. Tombe, P. Stadler, B. Ernecker,
C.W. Klampfl, N.S. Sariciftci, M.C. Scharber, Sol. Energy
Mater. Sol. Cells 157, 318 (2016)
11. S.S.W.S. Yang, J.H. Noh, N.J. Jeon, Y.C. Kim, S. Ryu, J. Seo,
S. Seok, Science 348, 1234 (2015)
12. T. Liu, K. Chen, Q. Hu, R. Zhu, Q. Gong, Adv. Energy Mater.
6, 1600457 (2016)
13. J.Y. Jeng, Y.F. Chiang, M.H. Lee, S.R. Peng, T.F. Guo, P. Chen,
T.C. Wen, Adv. Mater. 25, 3727 (2013)
14. L. Zheng, D. Zhang, Y. Ma, Z. Lu, Z. Chen, S. Wang, L. Xiao,
Q. Gong, Dalton Trans. 44, 10582 (2015)
15. Z. Yuan, Y. Yang, Z. Wu, S. Bai, W. Xu, T. Song, X. Gao, F.
Gao, B. Sun, A.C.S. Appl, Mater. Interfaces 8, 34446 (2016)
16. J.F. Wang, L. Zhu, B.G. Zhao, Y.L. Zhao, J. Song, X.Q. Gu,
Y.H. Qiang, Sci. Rep. 7, 1 (2017)
17. B. El Cohen, L. Etgar, Front. Optoelectron. 9, 44 (2016)
18. G. Yang, C. Wang, H. Lei, X. Zheng, P. Qin, L. Xiong, X. Zhao,
Y. Yan, G. Fang, J. Mater. Chem. A 5, 1658 (2017)
19. W. Zhang, X. Zhang, T. Wu, W. Sun, J. Wu, Z. Lan, Electro-
chim. Acta 293, 211 (2019)
20. K. Mahmood, S. Sarwar, M.T. Mehran, RSC Adv. 7, 17044
(2017)
21. M.F. Noh, C.H. Teh, R. Daik, E.L. Lim, C.C. Yap, M.A. Ibra-
him, N.A. Ludin, A.R. Bin Mohd Yusoff, J. Jang, M.A. Teridi,
J. Mater. Chem. 6, 682 (2018)
22. Y. Guo, H. Lei, L. Xiong, B. Li, G. Fang, J. Mater. Chem. A 6,
2157 (2018)
23. J. Zhang, Q. Daniel, T. Zhang, X. Wen, B. Xu, L. Sun, U. Bach,
Y.B. Cheng, ACS Nano 12, 10452 (2018)
24. Y. Zhang, G. Grancini, Y. Feng, A.M. Asiri, M.K. Nazeeruddin,
ACS Energy Lett. 2, 802 (2017)
25. D. Zhou, T. Zhou, Y. Tian, X. Zhu, Y. Tu, J. Nanomater.
8148072, 1 (2018)
26. X.J. Xu, L.Y. Yang, H. Tian, W.J. Qin, S.G. Yin, F. Zhang, Chin.
Phys. Lett. 30, 077201 (2013)
27. O.P. Dimitriev, D.A. Grinko, Y.V. Noskov, N.A. Ogurtsov, A.A.
Pud, Synth. Met. 159, 2237 (2009)
28. D.A. Mengistie, P.C. Wang, C.W. Chu, J. Mater. Chem. A 1,
9907 (2013)
29. C. Song, Z. Zhong, Z. Hu, Y. Luo, L. Wang, J. Wang, Y. Cao,
Org. Electron. 43, 9 (2017)
30. J.S. Yeo, J.M. Yun, D.Y. Kim, S.S. Kim, S.I. Na, Sol. Energy
Mater. Sol. Cells 114, 104 (2013)
31. Z. Hu, J. Zhang, Y. Zhu, Renew. Energy 62, 100 (2014)
32. Y. Kim, A.M. Ballantyne, J. Nelson, D.D.C. Bradley, Org. Elec-
tron. Phys. Mater. Appl. 10, 205 (2009)
33. J. Zhou, D.H. Anjum, L. Chen, X. Xu, I.A. Ventura, L. Jiang,
G. Lubineau, J. Mater. Chem. C 2, 9903 (2014)
34. M. Yu, X. Huang, S. Wang, B. Chen, Y. Zhang, B. Chen, M.
Liu, W. Zhang, J. Xiong, RSC Adv. 7, 17398 (2017)
13

7980
35. R.R.L. De, D.A.C. Albuquerque, T.G.S. Cruz, F.M. Yamaji,, F.L.
Leite, At. Force Microsc. - Imaging, Meas. Manip. Surfaces At.
Scale, In Tech (2012)
36. K. Lim, J. Kang, S. Jung, S. Lee, J. Park, D.G. Kim, Y.C. Kang,
Bull. Korean Chem. Soc. 39, 469 (2018)
37. H. Kim, J. Hong, C. Kim, E.Y. Shin, M. Lee, Y.Y. Noh, B. Park,
I. Hwang, J. Phys. Chem. C 122, 16630 (2018)
38. C. Bi, Q. Wang, Y. Shao, Y. Yuan, Z. Xiao, J. Huang, Nat. Com-
mun. 6, 7747 (2015)
39. M. Ameri, E. Mohajerani, M. Ghafarkani, N. Safari, S.A. Alavi,
J. Phys. D. Appl. Phys. 52, 125501 (2019)
40. H. Choi, C.K. Mai, H.B. Kim, J. Jeong, S. Song, G.C. Bazan, J.Y.
Kim, A.J. Heeger, Nat. Commun. 6, 7348 (2015)
41. U. Lang, E. Muller, N. Naujoks, J. Dual, Adv. Funct. Mater. 19,
1215 (2009)
42. V. Singh, S. Arora, M. Arora, V. Sharma, R.P. Tandon, Semicond.
Sci. Technol. 29, 045020 (2014)
43. D. Yoo, J. Kim, S.H. Lee, W. Cho, H.H. Choi, F.S. Kim, J.H. Kim,
J. Mater. Chem. A 3, 6526 (2015)
44. Y.J. Lin, F.M. Yang, C.Y. Huang, W.Y. Chou, J. Chang, Y.C. Lien,
Appl. Phys. Lett. 91, 092127 (2007)
45. C. Tengstedt, A. Kanciurzewska, M.P. de Jong, S. Braun, W.R.
Salaneck, M. Fahlman, Thin Solid Films 515, 2085 (2006)
46. H.K. Lee, J.K. Kim, O.O. Park, Org. Electron. Phys. Mater. Appl.
10, 1641 (2009)
47. L.M. Campos, A.J. Mozer, S. Günes, C. Winder, H. Neugebauer,
N.S. Sariciftci, B.C. Thompson, B.D. Reeves, C.R.G. Grenier, J.R.
Reynolds, Sol. Energy Mater. Sol. Cells 90, 3531 (2006)
48. J.F. Li, C. Zhao, H. Zhang, J.F. Tong, P. Zhang, C.Y. Yang, Y.J.
Xia, D.W. Fan, Chin. Phys. B 25, 028402 (2015)
13
Journal of Materials Science: Materials in Electronics (2020) 31:7968–7980
49. A.P. Wanninayake, S. Li, B.C. Church, N. Abu-Zahra, AIMS
Mater Sci. 3, 35 (2016)
50. T. Park, C. Park, B. Kim, H. Shin, E. Kim, Energy Environ. Sci.
6, 788 (2013)
51. Y.J. Xing, M.F. Qian, D.Z. Guo, G.M. Zhang, Chin. Phys. B 57,
44 (2014)
52. M. Gençten, K.B. Dönmez, Y. Şahin, K. Pekmez, E. SuvacI, J.
Solid State Electrochem. 18, 2469 (2014)
53. S. Sarker, A.J.S. Ahammad, H.W. Seo, D.M. Kim, Int. J. Photo-
energy 851705, 1 (2014)
54. S.K. Swami, N. Chaturvedi, A. Kumar, N. Chander, V. Dutta, D.K.
Kumar, A. Ivaturi, S. Senthilarasu, H.M. Upadhyaya, Phys. Chem.
Chem. Phys. 16, 23993 (2014)
55. P. Zhu and Y. Zhao, Mater. Chem. Phys. (2019).
56. H. Gürsu, M. Gençten, Y. Şahin, Electrochim. Acta 243, 239
(2017)
57. C. Kim, B. Lee, H.J. Yang, H.M. Lee, J.G. Lee, H. Shin, J. Korean
Phys. Soc. 47, S417 (2005)
58. M. Salerno, S. Dante, Materials (Basel). 11, 951 (2018)
59. Y. Xing, M. Qian, G. Wang, G. Zhang, D. Guo, J. Wu, Sci. China
Technol. Sci. 57, 44 (2014)
Publisher’s Note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.