Surfaces and Interfaces 31 (2022) 102026

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Surfaces and Interfaces

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The role of surface defects in the charge transport in organic solar cells
based on oxidized indium thin films
G.I. Omarbekova a, B.R. Ilyassov b, *, A.K. Аimukhanov a, *, D.T. Valiev c, A.K. Zeinidenov a,
V.V. Kudryashov d
a
Buketov University, Scientific Center for Nanotechnology and nanomaterials, Karaganda. Kazakhstan
b
Astana IT University, Nur-Sultan 010000, Mangilik El, EXPO C1, Kazakhstan
c
Tomsk Polytechnic University, Lenin Avenue 30, 634050 Tomsk, Russia
d
Nazarbayev University, School of Engineering and Digital Sciences, Qabanbay Batyr Ave 53, Nur-Sultan 010000, Kazakhstan

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, indium oxide (In2O3) thin films were obtained by the thermal oxidation method of metallic indium
In2O3, Polymer solar cell thin films. The effect of thermal annealing on the morphology, structure, optical properties of In2O3 and also on
Voltage-current characteristics the photovoltaic characteristics of organic solar cells (OSCs) was studied. Annealing of the films was carried out
Impedance spectroscopy
in the temperature range of 200–500 ◦ C. The rise of annealing temperature leads to the increase in the grain size
and to the widening of the In2O3 bandgap. Based on the In2O3 films with various annealing temperatures,
inverted organic solar cells (OSCs) with FTO/In2O3/P3HT:ICMA/MoOx/Ag structure were assembled. OSCs with
In2O3 oxidized at 200 ◦ C generated low power conversion efficiency (PCE) of 0.45%. The increase in the
oxidation temperature up to 300 ◦ C results in a significant improvement in PCE, which has reached 1.38%.
However, a further rise of the annealing temperature deteriorates the photovoltaic performance of OSCs. The
dynamics of charge carrier transfer in OSCs based on In2O3 were investigated by the impedance spectroscopy (IS)
technique. It follows from the IS data that the growth of In2O3 oxidation temperature leads to the improvement in
the In2O3 conductivity, however, it also results in enhanced recombination rate of charge carriers at the In2O3/
P3HT:ICMA interface, which indicates increased surface defects in In2O3 with the rise in the oxidation annealing
temperature.

1. Introduction
The conversion of solar energy into electrical energy is considered to
meet a rapidly growing demand for clean energy in the near future.
Among the various photovoltaic devices existing nowadays, organic
solar cells (OSCs) attract growing interest from scientists, researchers,
and engineers in the field of photovoltaics [1]. The power conversion
efficiency (PCE) of OSCs has exceeded 14% due to the development of
new donor and acceptor materials, the advancement in existing mate­
rials, and the optimization of the morphology of a photoactive layer
[2–7]. The photoactive layer is a mixture of donor and acceptor mate­
rials that form bulk heterojunction (BHJ) morphology. BHJ ensures
effective exciton dissociation. The BHJ layer is sandwiched between an
electron transport layer (ETL) and a hole transport layer (HTL), which
facilitates the extraction of electrons and holes from the BHJ layer,
respectively. The OSC with inverted architecture is widely used because
it provides better stability and improved charge extraction than tradi­
tional OSC [8–10]. The ETL in the inverted structure plays an important
role in charge separation and significantly affect the performance of
OSC. The ETL not only enhances the electron extraction and reduces
charge recombination but also affect the morphology of the photoactive
layer.
Widely used ETL materials for OSC applications are wide-bandgap
metal oxide semiconductors with n-type conductivity, such as ZnO
[11–14], TiO2 [13, 15], SnO2 [16, 17], and In2O3 [18]. They have high
transparency in the visible region, tunable electrical and optical prop­
erties, and suitable energy band structures, which can be adjusted by
deposition conditions [19]. In2O3 is considered as a promising ETL for
OSC due to its high optical transparency (Eg = 3.7 - 3.85 eV) and rela­
tively high electron mobility (14–226 сm2⋅V − 1⋅s − 1) [1].
Oxygen vacancies in the structure of the In2O3 film are oxygen
diffusion channels and thus contribute to the inclusion of oxygen ions in

* Corresponding authors.
E-mail addresses: baurzhan.ilyassov@astanait.edu.kz (B.R. Ilyassov), a_k_aitbek@mail.ru (A.K. Аimukhanov).

https://doi.org/10.1016/j.surfin.2022.102026
Received 6 February 2022; Received in revised form 18 April 2022; Accepted 7 May 2022
Available online 10 May 2022
2468-0230/© 2022 Elsevier B.V. All rights reserved.
G.I. Omarbekova et al.
the material [20]. Oxygen doping of indium oxide plays an important
fundamental role in its physical properties. The unique crystalline
defective structure of indium oxide promotes oxygen segregation at
grain boundaries. As a result, inter-boundary charge states are formed,
which leads to the formation of potential barriers affecting the electron
transport in polycrystalline films [21].
To increase the efficiency of electron extraction from the In2O3 ETL,
it is necessary to obtain films with optimal structure and morphology
facilitating electron transport. Therefore, it is crucial to develop and
choose suitable synthesis methods of In2O3 ETL. Currently, In2O3 films
can be obtained by the following methods: low-temperature solution-
processable techniques [22], ultrasonic spray technique [23], thermal
evaporation [24], ion beam sputtering [25], pulsed laser deposition
[26], and chemical vapor deposition [27]. The structural, optical, and
electrical properties of In2O3 films depend on the deposition methods
and their conditions. Vacuum thermal deposition of indium films with
further oxidation attracts significant attention since by this method films
with high chemical purity and with good adhesion on the substrate are
obtained.
There are several studies on the effect of annealing temperature of
In2O3 thin films on structural, optical and electrical properties to be
worth mentioning. A. Sudha et al. obtained In2O3 thin films by thermal
evaporation of In2O3 and found that with increasing annealing tem­
perature In2O3 conductivity significantly grows. They explain this as a
result of the structural changes taking place in films with increasing
temperature. According to their XRD and SEM studies, the increase of
the annealing temperature leads to the improvement in film crystallinity
and to considerable growth of average grain size and as result to
reduction of both bulk and surface defects. These structural improve­
ments lower the electron scattering phenomenon on grain boundaries
and electron trapping by localized defect states. Consequently, the car­
rier concentration increases with the increase of annealing temperature
resulting in the increase of conductivity of the film [28]. S. Yoon and his
colleagues synthesized In2O3 thin films from indium nitrate hydrate in
anhydrous ethanol as ETL for perovskite and organic solar cells. They
studied the influence of sintering temperature on In2O3 morphology and
conductivity, and also on PCE of the solar devices. They revealed a
considerable increase in the conductivity of In2O3 layers with rising
sintering temperature; however it also leads in a formation of pin-holes,
which renders direct contact between a photoactive layer and ITO and
this causes severe charge recombination. They claim that the trade-off
relationship between the film morphology and conductivity of the
In2O3 ETLs should be considered in order to design high performance
solar cells. Their study indicates that a In2O3 film synthesized from in­
dium nitrate solution and annealed at 300 ◦ C satisfies this trade-off
relationship due to it is pin-hole free and has relatively high conduc­
tivity [29]. Z. Yuan with co-workers deposited In2O3 thin films by a
magnetron sputtering and investigated annealing effect on structural
and electrical properties. They annealed In2O3 thin films at vacuum and
ambient condition, and observed opposite changes in In2O3 conductiv­
ity. When sputtered In2O3 films were annealed at vacuum, a drastic
increase of a carrier concentration and electron mobility is observed.
The rise in carrier concentration was attributed to the increase in the
density of oxygen vacancies due to an oxygen vacancy (Vo) acts as a
doubly ionized donor and contributes at a maximum of two electrons to
the electrical conductivity. Whereas, the increase of electron mobility
was proofed to be due to the decline of probability of electron scattering
at grain boundaries, because with increasing annealing temperature
grain growth occurs [31]. Q. Ma et al. synthesized In2O3 films by
atomic-layer-deposition (ALD) technique and studied the effect of
deposition temperature at relatively low temperature range 160–200 ◦ C.
Despite that In2O3 thin films obtained by ALD requires relatively low
deposition temperature, they used post-annealing treatment of synthe­
sized In2O3 films in air at 300 ◦ C in order to demonstrate
high-performance In2O3 thin-film transistors.
The research works mentioned above thoroughly studied the effect of
2
Surfaces and Interfaces 31 (2022) 102026
Fig. 1. Schematic representation of the synthesis procedure of In2O3 films.
annealing temperature on bulk properties of In2O3 thin films and sub­
sequently on device performance. However, they did not consider the
influence of oxidation temperature on surface structure of the In2O3 thin
films and mechanism of charge recombination at In2O3/photoactive
layer interface involving surface defects. The novelty of this work is
attributed with the understanding of the effect of oxidation temperature
on surface defects in In2O3 and charge transport dynamics at In2O3/
P3HT:ICMA interface by utilizing material characterization techniques
sensitive to surface structure such XPS and impedance spectroscopy.
2. Materials and methods
2.1. Sample preparation procedure
In2O3 films were synthesized on the surface of FTO/glass substrates.
The substrates were cleaned according to a procedure described in our
other work [32]. The synthesis of In2O3 films consisted of two steps. In
the first step, metallic indium (Sigma-Aldrich, powder, 99.99% trace
metals basis) was thermally evaporated on the surface of FTO/glass
substrates in high vacuum. The CY-1700x-spc-2 evaporator (Zhengzhou
CY Scientific Instruments Co., Ltd) was used for the thermal evapora­
tion. In the second step, as-grown indium films were annealed in air
(oxidized) at various temperatures (200 ◦ C − 500 ◦ C) for an hour (Fig. 1).
The fabrication procedure of organic solar cells consisted of the
following steps. Firstly, P3HT:ICMA photoactive layers were spin-coated
on the surface of as-grown In2O3 films at spin-rate of 3000 rpm from
P3HT:ICMA (P3HT 95%, ICMA 98% were purchased from Sigma-
Aldrich) solution in chlorobenzene with a concentration of 1:0.8,
respectively. Next, photoactive layers were annealed in air at a tem­
perature of 140 ◦ C for 10 min. Then, MoOx HTLs (d~30 nm) were
thermally evaporated followed by the evaporation of anodes (Ag,
d~120 nm).
2.2. Characterizations
The surface morphology of films was studied by scanning electron
microscopy (SEM, MIRA 3LMU, TESCAN). Elemental analysis of samples
was carried out using the energy dispersion detector (EDX,
INCAPentaFET-x3, Oxford Instruments, England). The crystal structure
of films was analyzed by an automated multipurpose X-ray diffractom­
eter (XRD, Rigaku SmartLab). XPS spectra were measured using an X-ray
photoelectron spectrometer (XPS, NEXSA, Thermo Scientific). X-ray
source for XPS was monochromatic low power Al Kα (1486.6 eV) and to
compensate for the energy shifting caused due to surface charging, the
flood gun was used.
The absorption spectra of films were measured using an Avantes
spectrometer (AvaSpec-ULS2048CL-EVO) with a combined deuterium-
halogen light source AvaLight-DHC (Avantes) in a spectral range of
200–2500 nm. The impedance spectra were measured using a
potentiostat-galvanostat with an FRA module (P45X, Elins). The
voltage-current characteristics of OSCs were measured by PVIV-1A I-V
Test Station under the standard illumination generated by the Sol3A
Class AAA Solar Simulators (Newport).
G.I. Omarbekova et al.
Fig. 2. XRD patterns of the systensized films.
3. Results and discussion
3.1. XRD, SEM and EDX characterizations
Fig. 2 shows the XRD pattern of as-grown indium films and XRD
patterns of these films after the oxidization at various temperatures. The
position of the XRD reflexes corresponds to the JCPDS map No.
74–1990. The observed diffraction peaks indicate the presence of
polycrystals with a cubic structure in the film [33]. A distinct diffraction
reflex at 32.95◦ is observed in the vacuum-sputtered film, as well as
weakly pronounced maxima at 36.49; 39.32; 54.67◦ related to
Fig. 3. SEM images of the systensized films. (а) - The cross-sectional image of In2O3 film, (b) - In film, (c) - In2O3 film oxidized at Т=200 ◦ C (d) - In2O3 film oxidized
at Т=300 ◦ C, (e) - In2O3 film oxidized at Т=400 ◦ C, (f) - In2O3 film oxidized Т=500 ◦ C.
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Surfaces and Interfaces 31 (2022) 102026
crystalline indium. After thermal annealing of the films at T = 200 ◦ C,
the crystallinity of the film increases, and 4 reflexes are observed at
30.64, 35.53, 51.12, and 60.79◦ indicating the formation of In2O3.
Additionally, diffraction peaks at 36.49; 39.32; 54.67◦ disappear, and
the maximum at 32.95◦ is practically not visible. After annealing of the
films at T = 300 ◦ C and further, the intensity of the reflexes of crystalline
indium oxide increases, which indicates an increase in the degree of
crystallinity of the film as the annealing temperature of In2O3 increases,
while new diffraction maxima are not detected.
Fig. 3 shows SEM image of as-deposited indium film and SEM images
of films oxidized at various temperatures. All In2O3 films were obtained
from indium layers evaporated at the same conditions and as result the
thickness of the synthesized In2O3 films is approximately equal, and
according to the SEM cross-sectional images is around 60 nm (Fig. 3a).
Fig. 4 shows a distribution of grain size in films oxidized at various
temperatures evaluated from SEM images. The indium layer has a
typical polycrystalline structure with an average grain size of d~64 nm.
After annealing at T = 200 ◦ C, an increase in grain size is observed with
the average value of 94 nm. A further increase in the annealing tem­
perature up to 400 ◦ C leads to steady growth of the average grain size.
However, after 400 ◦ C the growth of the average grain size does not
occur.
In the case of EDX analysis, films were systensized on the surface of
the Si substrates. Si was used to make reliable EDX analysis and elimi­
nate EDX signals from the FTO/glass substrate. From EDX data (Table 1),
we observe a change in a quantitative ratio of oxygen/indium (O/In)
elemental composition. As can be seen from Table 1, before annealing,
the film is enriched with indium and, after annealing, the growth in the
share of oxygen is observed, which increases with rising annealing
temperature.
Fig. 5, a represents XPS survey spectra of indium oxide films with
various oxidation states. The main peaks of the spectra are clarified.
G.I. Omarbekova et al. Surfaces and Interfaces 31 (2022) 102026

Fig. 4. The distribution of grain size in films oxidized at various temperatures: (a) - In film, (b) - In2O3 film oxidized at Т=200 ◦ C (c) - In2O3 film oxidized at
Т=300 ◦ C, (d) - In2O3 film oxidized at Т=400 ◦ C, (e) - In2O3 film oxidized Т=500 ◦ C.

annealing temperate of 200 ◦ C, the In2O3 film has a higher concentration

Table 1 of oxygen vacancies on the surface compared with the films annealed at
Elemental composition in the systensized films (Atomic percentages).
the higher temperature. We observe that with increasing annealing
Annealing temperature, ◦ C In,% O,% O/In ratio temperature, the integrated area of Gaussian peak responsible for oxy­
Without annealing 85.4 14.6 0.17 gen vacancies decreases, whereas the area of Gaussian peak from
200 68.4 31.6 0.46 metallic oxide state increases. Therefore, XPS analysis indicates that the
300 60.9 39.1 0.64 density of oxygen vacancies on In2O3 film surface decreases with rising
400 56.3 43.7 0.78
annealing temperature up to 500 ◦ C.
500 53.6 46.4 0.87

3.3. Optical properties

There are three main characteristic peaks for samples annealed in air:
oxygen, indium, and carbon peaks. The XPS technique is very sensitive
and will detect a small amount of contamination on the sample surface.
Usually, it is carbon contamination producing a C 1 s signal [34]. For a
better understanding of the chemical states of elements on the surface of
In2O3, The XPS analysis with the high-resolution spectra of O and In are
carried out, Fig. 5b and 5c, respectively. The oxygen states were
considered in detail.
XPS spectra of oxygen peaks can be divided into two Gaussian peaks
at 531.6 and 529.9 eV (Fig. 6). The peak at 531.6 eV is related to O
vacancies, whereas 529.9 eV is a characteristic of metallic oxide state
(M-O-M) [35]. By comparison ratios of integrated areas of Gaussian
peaks from O vacancies and metallic oxide state (A/B, table 2), the
variation in the density of oxygen vacancies on the film surface with
increasing annealing temperature can be detected. As can be seen from
the XPS spectra in Fig. 6 and the fitted data from table 2, at lower
To determine the effect of the annealing temperature on the optical
properties of In2O3 films, the absorption spectra of films annealed at
different temperatures were measured (Fig. 7). The absorption spectra of
In2O3 films are typical absorption spectra of wide-band semiconductors.
The characteristics of the absorption spectra of In2O3 films at different
annealing temperatures are given in Table 3. As can be seen from Fig. 7,
increasing annealing temperature of In2O3 films from 200 ◦ C to 500 ◦ C
leads to a decrease in absorption intensity in the measured spectral
range.
The insert in Fig. 7 shows Tauc plots from which the bandgap (Eg) of
In2O3 was estimated. Table 3 shows the values of the estimated bandgap
of In2O3 films oxidized at various temperatures. It indicates that the rise
of the annealing temperature from 200 ◦ C to 300 ◦ C leads to the
widening of the Eg from 3.43 eV to 3.45 eV. The increase of Eg can be
associated with a decrease in the oxygen vacancy density, which is

4
G.I. Omarbekova et al.
Fig. 5. XPS data of indium oxide films with various oxidation states: a) XPS Survey b) and c) high resolution XPS spectra for O 1 s and In 3d, respectively.
consistent with XPS data. It is well known that in wide-band metal ox­
ides, at a high oxygen vacancy density, defect energy levels become
delocalized and overlap with the valence band maximum level, which
leads to the narrowing of the Eg [31]. In addition, the improvement of
the crystal structure of In2O3 with the rise of annealing temperature also
affects the bandgap of In2O3. With the increase in the annealing tem­
perature, the grain growth is observed, which in turn leads to a decrease
in the total area of grain boundaries. The defect density at the grain
boundaries is much higher than in the bulk and, consequently, the
decrease in the total grain boundary area leads to the decrease in the
surface defects which are electron traps. This results to an increase in the
concentration of free electrons in the conduction band, which in turn
leads to an increase in Eg due to the Burstein-Moss effect [31]. However,
a further increase in the oxidation temperature may lead to an excess of
oxygen, especially on the surface regions, and to the formation of indium
vacancies, which may lead to the observed narrowing of Eg.
3.4. Photo-electrical properties
One of the important electrical properties of a semiconducting ma­
terial is its conductivity, which depends on carrier mobility. There are
several techniques to measure carrier mobility [36], for example, dark
current injection with space charge limitation (DI-SCLC), carrier
extraction due to a linear increase in voltage (CELIV), but the most
commonly used method is to measure the time of flight of carriers
5
Surfaces and Interfaces 31 (2022) 102026
through a sample (ToF - time of flight). However, the thickness of films
when these techniques are used should be larger 1 μm, which is signif­
icantly greater than the thickness of our films. In this work, we used a
impedance spectroscopy (IS) technique to estimate electron mobility in
oxidized indium films and determine the effect of oxidation
temperature.
Fig. 8 represents measured and fitted impedance spectra of FTO/
In2O3/Al cells with In2O3 films oxidized at different temperature.
Table 4 contains electrical parameters evaluated from fitted IS data.
Electron mobility was estimated by using the following equation [37]:
e⋅Dn
μ= ,
kB ⋅T
where,
Dn =
L2
τD
and, L is film thickness (60 nm), τD=Rt⋅C is transient time of electrons
through In2O3 films.
As can be seen from Fig. 8b, the rise of oxidization temperature leads
to the increase in electron mobility in In2O3 films. This trend is attrib­
uted with the decrease in the probability of electron scattering at the
grain boundaries due to the growth of grain size [31]. The estimated
values of electron mobility in In2O3 films (Fig. 8b) are in good agreement
G.I. Omarbekova et al. Surfaces and Interfaces 31 (2022) 102026

Fig. 6. Graph fitting of high-resolution O1s XPS spectra of indium oxide films with various oxidation states.

Table 2
Comparison of the calculated integrated area from metal oxide (M-O-M) and
oxygen vacancies (Vo) of Gaussian peaks.
# Peaks Area Center Area Area, A/
Intg. Grvty IntgP B

200 ◦ C M-O-M (A) 245,161 529,9 46,3 0,9

O vacancies,Vo 284,560 531,6 53,7
(B)
300 ◦ C M-O-M 272,273 529,9 50,3 1,0
O vacancies,Vo 269,562 531,6 49,7
400 ◦ C M-O-M 278,933 529,9 55,3 1,2
O vacancies, Vo 225,296 531,6 44,7
500 ◦ C M-O-M 296,082 529,8 56,3 1,3
O vacancies, Vo 229,822 531,5 43,7

with data of other works [28–31].

Further, organic solar cells with FTO/In2O3/P3HT:ICMA/MoO3/Ag
architecture were assembled. In this section, we describe the effect of the
annealing temperature of In2O3 films on photovoltaic properties and Fig. 7. Absorption spectra of In2O3 films.
charge transport in OSCs. At photoexcitation, P3HT regions of the
photoactive layer absorb photons and form electron-hole pairs (exci­
tons). Excitons that reach P3HT:ICMA interface before annihilation will Table 3
dissociate into free electrons, which will be injected in ICMA region, and Parameters of optical absorption spectra of In2O3 films at different annealing
holes, which will remain P3HT. Then free charges are separated at temperatures.
In2O3/ICMA and P3HT/MoOx interfaces (Fig. 9). The electrons are N◦ Annealing temperature, ◦ C Absorbance, A.U. (λ= 300 nm) Band gap, eV
injected into the In2O3 ETL layer and the holes into the MoOx HTL layer.
1 200 0.63 3.43
The voltage-current characteristics of the fabricated OSCs are shown 2 300 0.56 3.45
in Fig. 9. Table 5 shows the photovoltaic performance of OSCs evaluated 3 400 0.50 3.43
from the IV curve. As can be seen from Fig. 9 and Table 5, photovoltaic 4 500 0.43 3.40
performance depends on the annealing temperature of In2O3. At the
annealing temperature of T = 200 ◦ C, the efficiency of the device was

6
G.I. Omarbekova et al. Surfaces and Interfaces 31 (2022) 102026

Fig. 8. Impedance spectra of FTO/In2O3/Al cells with In2O3 films oxidized at different temperature (а) and the effect of oxidization temperature on electron mobility
(b) (the inset equivalent circuit of FTO/In2O3/Al cell).

Table 4
Electrical parameters of In2O3 films oxidized at different temperature.
Annealing Rt , Rrec, С, τD, Dn, μ, (сm2‧
temperature, ◦ C (Оhm) (Оhm) (pF) (ps) (сm2‧ V − 1‧
s − 1) s − 1)

200 17.13 15.31 29 496 0.07 2.76

300 10.91 29.12 24 261 0.13 5.13
400 9.05 36.96 22 199 0.17 6.70
500 7.55 86.47 21 158 0.22 8.67

Fig. 10. The impedance spectra of FTO/In2O3/P3HT:ICMA/MoO3/Ag OSCs.

only 0,45%. When the annealing temperature rises to T = 300 ◦ C, we

observe the boost in the short current density (Jsc), open-circuit voltage
(Voc), and efficiency of the device. The further increase in the annealing
temperature of the In2O3 films leads to the deterioration of photovoltaic
performance.
The observed changes in the device performance are associated with
the effect of structural changes in indium oxide films on the charge
transport processes in OSCs. To study in detail the effect of indium oxide
structure on the dynamics of charge transport in OSCs, the impedance
Fig. 9. The voltage-current characteristics of FTO/In2O3/P3HT:ICMA/MoO3/
spectroscopy technique was used.
Ag OSCs. Fig. 10 shows the measured impedance spectra (dashed lines) of
OSCs. The impedance spectra were fitted by the equivalent circuit

Table 5 Table 6
Photovoltaic performance of FTO/In2O3/P3HT:ICMA/MoO3/Ag OSCs. Charge transport properties of FTO/In2O3/P3HT:ICMA/MoO3/Ag OSCs.
Annealing Voc Jsc (mA/ Vmax(V) Jmax FF PCE
Annealing R0, R1, R2 , C2, (F) τ (R2⋅C2),
temperature, ◦ C (V) cm2) (mA/ %
temperature, ◦ C (Оhm) (Оhm) (Оhm) (s)
cm2)
200 58 133 862 3.4548E- 2.98E-05
200 0.37 3.81 0.21 2.19 0.32 0.45
08
300 0.42 8.66 0.26 5.41 0.38 1.38
300 25 136 1801 3.3942E- 6.11E-05
400 0.41 7.76 0.22 4.34 0.31 0.95
08
500 0.39 4.68 0.22 2.69 0.32 0.58
400 19 139 1682 3.8339E- 6.45E-05
08
500 14 133 976 3.4595E- 2.98E-05
08

7
G.I. Omarbekova et al.
shown in the inset of Fig. 10, where R0 is the equivalent resistance of the
external electrodes (RFTO + RIn2O3 + MoOX +Ag), R1C1 characterizes the
photoactive layer/MoOx interface and R2C2 characterizes the photo­
active layer/In2O3 interface. R1 and R2 are resistances characterizing the
recombination channels of holes and electrons, respectively.
Table 6 represents the calculated values of R0, R1 and R2, С2. As can
be seen from Table 6, R0 has the greatest value in the device with In2O3
annealed at 200 ◦ C. R0 represents the total resistance of the external
electrodes and adjacent ETL and HTL layers. Since all functional layers
in OSCs, except In2O3, were fabricated under the same conditions, the
observed changes in R0 are associated with a change in the resistance of
the In2O3 films. R0 has a maximum value for a device with In2O3
annealed at 200 ◦ C. A further increase in the annealing temperature of
In2O3 leads to an decrease in R0, which can be associated with the
decline in oxygen vacancies. As expected, the resistance R1, which
characterizes the hole recombination resistance at the photoactive
layer/MoOx interface, is practically the same in all cases, since the
photoactive layer and MoOX were deposited under the same conditions.
R2, the resistance characterizing electron recombination at the
photoactive layer/In2O3 interface, varies depending on the annealing
temperature of In2O3. The greater R2, the lower the recombination rate
at the phase interface. As can be seen from Table 6, the device with In2O3
annealed at a temperature of 200 ◦ C have the lowest resistance R2,
which indicates about a significant recombination rate at the photo­
active layer/In2O3 interface. Annealing of In2O3 at 300 ◦ C leads to an
increase in recombination resistance by a factor of two. However, a
further increase in the annealing temperature leads to a decrease in R2,
which indicates about the enhancement of recombination processes.
After photoexcitation, electrons from the photoactive layer are
injected into In2O3 and diffuse to the external electrode. However, the
reverse process occurs - the recombination of an electron with a hole in
the photoactive layer (see in the inset in Fig. 10). Usually, recombination
occurs through surface defect levels. Impedance spectroscopy mea­
surement also allows us to calculate the time constant τ = RC, which
characterizes the lifetime of charge carriers in a semiconductor. It fol­
lows from the fitting data of the impedance spectra that τ has a
maximum value for In2O3 films annealed at temperatures of 300 ◦ C and
400 ◦ C.
The impedance analysis data is correlated with the IV-curve. OSCs
based on In2O3 annealed at a temperature of 300 ◦ C has the least value of
R0, the highest value of R2 and a relatively high value of τ, which in­
dicates the formation of an In2O3 film with improved conductivity and
less structural defects. A sharp deterioration of the photovoltaic pa­
rameters of OSCs with In2O3 annealed at temperatures above 400 ◦ C
may be due to an increase in the vacancy density of indium on the
surface of In2O3 or due to an increase in interstitial oxygen density. As
can be seen from the impedance spectroscopy data, the resistance R2,
which characterizes the recombination resistance at the In2O3/PL
interface, is two times lower for a device with In2O3 annealed at 500 ◦ C
compared to the device with In2O3 at 300 ◦ C. The observed increase in
electron recombination at the In2O3/PL interface indicates about in­
crease in the density of surface defects In2O3.
Conclusion
In this work, In2O3 films as electron transport layers for organic solar
cells were obtained by thermal oxidation of indium layers. Indium layers
were deposited on the surface of FTO/glass substrates by vacuum
thermal evaporation of indium powder. The effect of the thermal
oxidation temperature on In2O3 films morphology, structure, and optical
and electrical properties was investigated. XRD study showed at the low
oxidation temperature of 200 ◦ C, the films have XRD peaks of In2O3,
however, it still contains traces of metallic indium associated with a
peak at 32.95 2-theta angle. At higher oxidation temperatures in the
range of 300 – 500 ◦ C, only the In2O3 phase is observed. According to the
SEM study, in comparison with as-grown indium films, oxidized In2O3
8
Surfaces and Interfaces 31 (2022) 102026
films have a larger grain size. In the range of 200 - 400 ◦ C, we observe
growth of the average grain size of In2O3 films. However, at higher
oxidation temperature, at 500 ◦ C, the growth of the average grain size is
not noticeable. XPS analysis indicates that with increasing oxidation
temperature of In2O3 films, the density of oxygen vacancies in films
decreases. Additionally, with increasing oxidation temperature from
200 to 300 ◦ C, we observe the widening of In2O3 bandgap which is
possibly associated with a decrease in the density of oxygen vacancies.
Nevertheless, the further rise in oxidation temperature results in the
narrowing of the bandgap, which can be explained by an increase in
surface defects (indium vacancies or oxygen interstitials) and/or by a
decrease in the grain boundary density (Burstein–Moss shift) due to the
increase in grain size. Inverted OSCs based on the oxidized In2O3 films
were fabricated and the influence of the oxidation temperature on the
photovoltaic properties was studied. OSCs based on In2O3 oxidized at
200 ◦ C showed a very low efficiency (PCE) of 0.45%, which is attributed
to poor optical properties of In2O3 hindering the light absorption by a
photoactive layer. An increase in the oxidation temperature up to 300 ◦ C
has led to a significant improvement in PCE (1.38%). However, a further
increase in the oxidation temperature has resulted in a deterioration of
the photovoltaic characteristics of OSCs. According to an impedance
spectroscopy study, the increase in the oxidation temperature of In2O3
leads to a decrease in the resistance of the In2O3 film, but also leads to an
enhancement of the recombination of charge carriers at the In2O3/
P3HT:ICMA interface, which indicates about an increase in the density
of surface defects in In2O3 films with increasing the temperature of
oxidation.
In sum, this work revealed that despite the improvement in In2O3
conductivity with increasing the oxidation temperature, considerable
recombination processes at In2O3/photoactive layer occur due to the
increase in surface defect density. This work indicates that the main
factor declining performance of OPV with high conductive ETL is
interfacial recombination through defects. Therefore, for the future
development of OPV based on wide bandgap metal oxides such as In2O3,
it is important to develop the strategies to passivate or deactivate surface
defects.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper
Acknowledgments
This research is funded by the Science Committee of the Ministry of
Education and Science of the Republic of Kazakhstan (Grant No.
AP08856176). D. Valiev appreciates the support from Tomsk Poly­
technic University the “Priority 2030′′ development program.
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