Applied Physics A (2022) 128:407

https://doi.org/10.1007/s00339-022-05560-7

Competitive charge transport processes in inverted polymer solar cells

based on ZnO thin films
T. E. Seisembekova1 · A. K. Aimukhanov1 · A. K. Zeinidenov1 · B. R. Ilyassov2

Received: 20 October 2021 / Accepted: 4 April 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2022

Abstract
Polymer solar cells (PSCs) with an inverted architecture are promising photovoltaic devices. The inverted device has clearly
distinguishable electron and hole transport layers (ETL and HTL) compared to traditional PSCs with a direct structure. ETL
and HTL ensure effective charge separation and transport, and their properties significantly affect the photovoltaic perfor-
mance and stability of PSCs. In this research work, we studied the effect of the thickness and quality of zinc oxide (ZnO)
ETL on dynamics of charge transport in FTO/ZnO/P3HT:IC60MA/MoOx/Ag devices and their photovoltaic performance.
We observe that, when ZnO layer thickness is decreased, the power conversion efficiency (PCE) of the device sharply boosts
reaching peak value and then steadily decreases. According to the impedance spectroscopy study, there are two competitive
charge transfer processes in PSCs: electron transport from the photoactive layer to FTO through ZnO and charge recombi-
nation at the ZnO/P3HT:IC60MA interface. The kinetics of these charge transfer processes depends on ZnO thickness and
quality. Our study indicates that there is a balance between charge transport and recombination rate at the thickness of the
ZnO layer of approximately 50 nm. The champion device with ZnO ETL thickness of 54 nm has generated a short-circuit
current of 9.5 mA/cm2, an open-circuit voltage of 0.6 V, and PCE of 3.2% under the light illumination with the intensity of
100 mW/cm2.

Keywords Zinc oxide · Open circuit voltage · Electron transport layer · Indene-C60 monoadduct · Polymer solar cells ·
Photovoltaic performance · Impedance spectroscopy

1 Introduction with the thickness of photoactive materials of only a few

Nowadays, many researchers and scientists in the field of
solar energy study and develop solar cells based on photo-
active organic and polymeric semiconductors [1–3]. These
organic and polymeric semiconducting materials have a high
optical absorption coefficient, high conductivity, and good
mechanical flexibility. Importantly, they can be synthesized
using simple techniques compared to the silicon wafer pro-
duction process [4, 5]. All these unique properties allow
researchers and engineers to develop cost-effective, highly
efficient, environmentally friendly, and flexible solar panels
* B. R. Ilyassov
baurzhan.ilyassov@astanait.edu.kz
1
Center of Nanotechnology and Functional Nanomaterials,
Karaganda Buketov University, University Str., 28,
100028 Karaganda, Kazakhstan
2
Astana IT University, Mangilik El, EXPO C1,
Nur‑Sultan 010000, Kazakhstan
hundred nanometers.
Polymer solar cell consists of a transparent conducting
oxide (TCO) layer, electron and hole transport layers (ETL
and HTL), a photoactive layer, and a thermally evaporated
metallic electrode (Al, Au, or Ag) [6]. The photoactive layer
(PL) is a mixture of donor material (polymer) and acceptor
material (fullerene derivatives), which forms bulk hetero-
junction (BHJ). PSCs can have two architectures, standard
(TCO/HTL/PL/Al) or inverted (TCO/ETL/PL/HTL/Ag or
Au), which depends on the order of ETL and HTL [6].
The typical representative of a standard PSC is a device
with FTO/PEDOT:PSS/P3HT:PCBM/Al architecture [7].
Usually, the first layer deposited on TCO is HTL based on
PEDOT:PSS [8]. Despite regular devices with PEDOT:PSS
have achieved remarkable performance, they have several
drawbacks due to limited properties of PEDOT:PSS [9–11]
and difficulty in the deposition of an additional ETL on bulk
heterojunction layer [12, 13]. PEDOT:PSS is hydrophilic
material and prone to degradation due to moisture [14, 15].

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407 Page 2 of 8
It has poor mechanical resistance, inadequate transparency,
and poor processability in comparison with alternative HTLs
[16–19]. Additionally, microstructural heterogeneity and
nonuniformity in electrical conductivity of the PEDOT:PSS
layer deteriorate charge transport in PSCs [11].
Commonly, PSCs with standard architecture do not have
separate ETL, and therefore only acceptor material (fuller-
ene derivatives) performs its function. However, the inter-
face between fullerene derivatives and metallic cathode (Al)
has high resistance, which negatively affects the device’s
photocurrent [20]. For this reason, various interlayers have
been incorporated to optimize the interface conductivity
[21]. Nevertheless, many reports indicate that PSCs with
clearly defined ETL have improved performance, but it is
difficult to deposit well-known ETL directly on the pho-
toactive layer. PSCs with inverted architecture have been
developed to overcome the mentioned issues of the standard
device architecture. In the inverted device, ETL is deposited
on the TCO electrode (cathode) first, followed by PL, HTL,
and metallic anode [22–24].
Usually, in the inverted PSCs, both ETL and HTL are
inorganic metal oxides. One of the critical components in the
inverted PSCs is a wideband-gap metal oxide semiconductor
with electron conductivity, which serves as ETL. This metal
oxide ETL implements several functions. First, it is a selec-
tive contact, which extracts electrons from the photoactive
layer. Second, it serves as a medium through which electrons
diffuse to the cathode. Additionally, the metal oxide ETL
can be synthesized as a mesoscopic scaffold layer with a
high specific surface area. The mesoscopic scaffold layer
supports more amount of PL, which leads to enhanced light
absorption, and as a result, boosts photocurrent. Besides, it
also serves as a scattering layer, which also contributes to
the increment of photocurrent [22–24].
ZnO is a very promising material used not only in solar
cell applications but also in other important fields, which
include UV photodetectors [25, 26], UV lasers [27], gas sen-
sors [28], and water splitting [29]. Typically, ZnO is intrin-
sically n-doped wide-bandgap semiconductors due to the
presence of shallow donor levels [30]. However, the appli-
cation of ZnO materials can be further extended with the
development of p-doped ZnO, which is a very difficult task
due to the tendency of acceptors in ZnO to form deep impu-
rity levels instead of shallow acceptor levels [25]. Currently,
it is very crucial to develop methods to synthesize p-doped
ZnO films with properties analogous to n-dope counterparts,
which will allow designing advanced optoelectronics devices
based on n-doped and p-doped ZnO heterojunction [25, 31,
32]. For now, due to the lack of suitable p-doped ZnO, the
most common p-type semiconductors used to form the het-
erojunction with n-doped ZnO are p-silicon [26] and C ­ u 2O 3
[29]. The development of p-doped ZnO layers is beyond
the scope of our research, but for more detail regarding the
13
T. E. Seisembekova et al.
advancement in p-doped ZnO, it is worth referring to works
[25, 31, 32].
Nowadays, ZnO, ­TiO2, and ­SnO2 are widely used as ETL
with compact, mesoporous, or nanostructured morphology.
ZnO is considered a suitable ETL for application in PSCs
due to its excellent electrical and optical properties, higher
photostability, and inexpensive and low-temperature syn-
thesis techniques [23]. However, deposition conditions,
morphology, nature and the density of crystal defects,
and thickness of ZnO thin films significantly affect device
performance [23]. Therefore, to develop highly efficient
inverted PSCs based on ZnO thin films, it is necessary: (1)
to optimize morphology, thickness, and structure of ZnO, (2)
to reduce the resistivity of ZnO, and (3) to suppress charge
recombination processes in the ZnO/PL interface.
The study of recombination processes in photovoltaic
and optoelectronic devices is crucial to reveal recombina-
tion channels and to develop strategies to suppress them.
There are various experimental techniques to investigate
charge generation, separation, and transport in photovoltaic
and optoelectronic devices, which include transient absorp-
tion spectroscopy, time-resolved luminescence spectroscopy,
open-circuit voltage decay technique, and impedance spec-
troscopy to name a few. In this study, we used the imped-
ance spectroscopy technique to study charge recombination
in PSCs [33]. However, it is worth mentioning that except
experimental techniques, researchers also use theoretical
methods such as a finite-difference time-domain method
to study the generation of charge carriers in optoelectronic
devices [34, 35].
In addition to ZnO ETL optimization, it is also crucial to
choose suitable acceptor material, which will allow develop-
ing devices with high performance. It is well known that the
open-circuit voltage (Voc) depends on donor–acceptor blend
energetics and theoretically should be equal to the difference
between donor HOMO level and acceptor LUMO level [36].
N. W. Tseng and coworkers used three types of modified
indene-C60 monoadduct fullerene derivatives (IC60MA)
and fabricated PSCs (ITO/ZnO/PTB7: acceptor/MoO3/Al
configuration) with the power conversion efficiency of 6.5%
[37]. IC60MA has a higher LUMO level in comparison with
LUMO levels of typical PC60BM and PC70BM [20], which
boost Voc.
In this work, we concentrated our efforts to develop
highly efficient ITO/ZnO/P3HT: IC60MA/MoO3/Ag devices
and investigated the effect of ZnO properties on photovol-
taic performance. We synthesized compact ZnO layers from
zinc acetate solution using a sol–gel technique. First, we
studied the effect of the spin-coating rotation speed on ZnO
thickness, surface topography, and optical absorption spec-
tra. Then, we investigated the influence of ZnO properties
on charge transfer dynamics in PSCs and their photovol-
taic performance. N. W. Tseng et al. developed ITO/ZnO/
Competitive charge transport processes in inverted polymer solar cells based on ZnO thin films Page 3 of 8
PTB7:IC60MA/MoO3/Al device with a PCE of 6.5% using
PTB7 as a photoactive polymer [37], but in our work, we
developed FTO/ZnO/P3HT:IC60MA/MoOx/Ag device with
PCE as high as 3.2% using more regular photoactive poly-
mer P3HT.
2 Experimental section
ZnO thin films were synthesized on the surface of FTO/
glass substrates (Biotain Hong Kong., Limited, 10–15 Ω/
sq). First, FTO/glass substrates were thoroughly cleaned
according to a cleaning procedure described in the work
[38]. The ZnO precursor solution was prepared by dissolving
98.7 mg of zinc acetate ­(Zn5(OH)8Cl2, pure 99.9%, Sigma
Aldrich) in 1 ml of 2-propanol (pure 99,9% Sigma Aldrich).
To increase the solubility of zinc acetate in 2-propanol, 75 µl
of monoethanolamide was added to the zinc acetate solu-
tion. The final solution was stirred at 60 °C for 2 h and then
had been maintained at room temperature for 24 h. Before
use, zinc acetate solution was filtered through a 45 µm filter.
The ZnO precursor solution was spin-coated on the surface
of cleaned FTO glass substrates at various rotation speeds,
1000, 1500, 3000, 4000, 5000 rpm by SPIN150i spin-coater
(SPS). Finally, coated films were annealed at 200 °C for
15 min and then at 450 °C for 1 h to get ZnO thin films.
Inverted PSCs with FTO/ZnO/P3HT:IC60MA/MoOx/Ag
architecture (Fig. 1b) were fabricated with different ZnO
layer thicknesses. P3HT:IC60MA bulk heterojunction pho-
toactive layers were spin-coated from 1 ml chlorobenzene
solution of P3HT (pure 97% Sigma Aldrich) and Indeno-C60
IC60MA P3HT
а)
b)
Fig. 1  Chemical structuras of BHJ compounds (a) and the architec-
ture of the inverted PSC (b)
407
(IC60MA, pure 98% Solaris Chem.) with a weight ratio of
1:0.8, respectively. After the spin-coating, samples were
annealed at 140 °C for 10 min in a nitrogen atmosphere.
Then, ­MoOx HTL with the thickness of 30 nm was depos-
ited on the surface of PL by thermal vacuum evaporation
technique (via CY-1700x-spc-2, Zhengzhou CY Scientific
Instruments Co., Ltd). Finally, a silver electrode with a
thickness of 120 nm was also thermally evaporated on the
top of ­MoOx HTL.
The surface morphology and the thicknesses of ZnO lay-
ers were measured by scanning electron microscopy (SEM),
MIRA 3 LMU (TESCAN).
The optical absorption spectra of ZnO thin films were
measured by AvaSpec-ULS2048CL-EVO spectrometer
(Avantes) in the range of 200–500 nm. The impedance spec-
tra of PSCs were measured by potentiostat P45X (Elins)
with the FRA module. Current–voltage characteristics of
PSCs were measured by PVIV-1A I-V Test Station under
the light illumination from xenon lamp with an output power
of 100 mW/cm2, which was calibrated by reference silicon
solar cell (Newport).
3 Results and discussion
Figure 2 illustrates SEM images of surfaces of synthesized
ZnO thin films. Overall, the ZnO thin films are dense and
uniform, but they contain cracks. The crack density and size
depend on film thickness, which is regulated by the spin-
coating rate. The film deposited at 1500 rpm is practically
cracks free. With increasing spin-coating rate, cracks appear
in the films, and their sizes become larger. It is well known
that cracks negatively affect device performance by render-
ing direct contact between the cathode (ITO or FTO) and
HTL [39].
Table 1 contains values of ZnO film thicknesses for the
different spin-coating rotation speeds evaluated from SEM
images. As was expected, ZnO film thickness decreases with
increasing the rotation speed.
It is well known that the film thickness affects the inten-
sity of the optical absorption spectrum and semiconductor
bandgap. We measured absorption spectra of ZnO layers
with different thicknesses shown in Fig. 3. The measured
absorption spectra of ZnO thin films are similar to absorp-
tion spectra of wide-bandgap metal oxide semiconductors
[40].
From Fig. 3, it is noticeable a shift in the fundamental
absorption edge of ZnO with the reduction of film thick-
ness. Additionally, the film thickness reduction leads to a
decrease in the absorption intensity. ZnO optical bandgap
was evaluated from Tauc plots represented in the inset of
Fig. 3 [40]. The dependence of absorbance at 380 nm and
optical bandgap on film thickness is shown in Table 2. First,
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407 Page 4 of 8 T. E. Seisembekova et al.

Fig. 2  SEM images of surfaces

of synthesized ZnO thin films.
a 1500 rpm, b 3000 rpm,
c 4000 rpm, d 5000 rpm, e
6000 rpm

Table 1  The dependence of ZnO film thickness on the spin-coating Table 2  The dependence of the absorbance at 380 nm and optical
rotation speed bandgap of ZnO on film thickness

Spin-coating rotation speed, rpm Film thickness № Film thickness Absorbance [A.U], Optical
ZnO, nm ZnO, nm (λ = 360 nm) band gap (eV)

1000 86 ± 5 1 86 ± 5 1,20 3.03

1500 68 ± 5 2 68 ± 5 1,07 3.01
3000 54 ± 5 3 54 ± 5 1,05 3.02
4000 42 ± 5 4 42 ± 5 1,02 3.04
5000 26 ± 5 5 26 ± 5 0,94 3.05

the reduction in film thickness results in the narrowing of the

Fig. 3  Absorption spectra and Tauc plots (the inset) of ZnO films
with different thicknesses
bandgap, which is possibly due to quantum size restriction
phenomena. However, further thickness reduction results in
the widening of the ZnO bandgap, which according to the
references [41, 42] can be related to the deterioration of ZnO
crystallinity.
Furthermore, we fabricated polymer solar cells based on
the synthesized ZnO films and studied the influence of ZnO
thickness and quality on photovoltaic performance. SEM
cross-section image of the device is shown in Fig. 4. The
thickness of the photoactive layer (P3HT:ICMA) was inten-
tionally made thicker by reducing the spin-coating rate to
obtain a distinguishable multilayered structure image. The
energy band diagram of the FTO/ZnO/P3HT:IC60MA/
MoOx/Ag device is presented in Fig. 5a. The energy band
diagram was drawn based on data presented in the differ-
ent reports [20, 23, 36]. Except for ZnO ETL, other func-
tional PSC layers were deposited at the same conditions. The

13
Competitive charge transport processes in inverted polymer solar cells based on ZnO thin films Page 5 of 8 407

of ZnO ETL. When the ETL thickness is 86 ± 5 nm, the

Fig. 4  SEM cross-section image of FTO/ZnO:P3HT:IC60MA/MoOx/
Ag device
measured current–voltage characteristics (IV curve) of PSCs
with different ZnO thicknesses are shown in Fig. 5b and their
photovoltaic performance is presented in Table 3. As can be
seen from Fig. 5b, the IV curve depends on the properties
efficiency of PCS is only 1%. However, when the thick-
ness decreases, the efficiency sharply increases and reaches
the maximum value of 3.2% at the ZnO ETL thickness of
54 ± 5 nm. With further thickness reduction, the efficiency
steadily decreases.
As can be seen from Table 3, at ZnO ETL thickness of
54 ± 5, both open-circuit voltage (Voc) and short-circuit
current density (Jsc) have maximum values of 0.6 V and
9.5 mA/cm2, respectively, which contributes to the overall
boosted efficiency of 3.2%. This result shows that ZnO ETL
thickness significantly affects the photovoltaic performance
of PSCs. Therefore, there is optimal ETL thickness at which
there is a balance between the competitive charge transfer
processes.
Theoretically, Voc can be as high as effective bandgap
energy of donor–acceptor blend of BHJ divided on the
elementary charge (the effective bandgap energy is a differ-
ence of donor HOMO level and acceptor LUMO level) [36].
However, there are energy losses in PSCs and experimental
Voc is far less than the theoretically predictable value [36].
The difference of quasi-Fermi level of electrons and holes in

Fig. 5  Energy band diagram (a) and current–voltage characteristics of FTO/ZnO:P3HT:IC60MA/MoOx/Ag devices (b)

Table 3  Photovoltaic ZnO film thick- Voc (V) Jsc (mA/cm2) Vmax(V) Jmax (mA/cm2) FF PCE %
characteristics of polymer solar ness, nm
cells
86 ± 5 0.39 5.9 0.26 3.9 0.44 1.0
68 ± 5 0.45 8.3 0.30 5.9 0.47 1.8
54 ± 5 0.60 9.5 0.42 7.6 0.56 3.2
42 ± 5 0.41 7.9 0.28 5.1 0.44 1.4
26 ± 5 0.30 4.3 0.20 2.5 0.38 0.4

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407 Page 6 of 8 T. E. Seisembekova et al.

ETL and HTL restricts the photovoltage of inverted polymer
solar cells [36]. For this reason, it is crucial to optimize ETL
and HTL properties to achieve high Voc. In this study, the
molybdenum oxide and the photoactive layer were deposited
under the same conditions, therefore, the observed changes
in the Voc are solely due to the properties of the zinc oxide.
The position of the quasi-Fermi level of electrons in ZnO
under device operation depends on the density of injected
electrons in the conduction band and also is affected by the
density and types of ZnO defects [38, 43]. The higher the
positions of the quasi-Fermi level of the electrons to the bot-
tom of the conduction band, the higher the generated pho-
tovoltage is. Defects forming shallow donor levels in the
bandgap shift the Fermi level of electrons up, close to the
bottom of the conduction band [38]. Thus, the observed vari-
ation in the Voc of PSCs is due to the variation of the ZnO
film thickness and as well can be associated with a change
of the defect density in ZnO [38, 43].
The reduction of ZnO thickness should contribute
to fast electron transport to the cathode (FTO) due to
decreasing film resistance [43]. However, it also enhances
the recombination rate of injected electrons at the ZnO/
PL/FTO interface due to the increase in the number of
pinholes, cracks, and crystal defects [44, 45]. As a result,
these two charge transfer processes oppositely affect the
photovoltaic performance of PSCs. To quantitatively ana-
lyze the charge transfer processes in PSCs, we used the
impedance spectroscopy (IS) technique and measured
impedance spectra of PSCs with different ZnO ETL thick-
nesses. Figure 6 (the inset) shows an equivalent circuit
used to fit the measured impedance spectra, where R1 is
an in-plane resistance of ZnO ETL, R 2C represents the
ZnO/PL interface, where R2 is a recombination resistance
determining recombination rate. In Fig. 6, the measured
impedance spectra (square dots) of PSCs with various ZnO
ETL thicknesses are shown.
The measured impedance spectra were fitted (solid
lines in Fig. 6), and values of R1, R2, C, and other charge
transport parameters were estimated. These parameters
are shown in Table 4, where τ eff is an effective lifetime
of injected electrons in ZnO ETL and k eff is a parameter
characterizing the recombination rate of injected electrons.
The effective lifetime of charge carriers is equal to the
time constant of R2C circuit (the inset in Fig. 6), which
was estimated from IS fitting data. The recombination rate
parameter ­keff can be calculated according to the following
equation [33]:
1
kef f = . (1)
𝜏ef f
As can be seen from Table 4, the ZnO ETL thickness
reduction leads to the decrease in ETL resistance (R1),
which facilitates electron transport to FTO. However, it
is clear from Table 4 that the reduction of the ZnO ETL
thickness also results in a decrease in the recombination
resistance (R2), which facilitates the recombination rate of
injected electrons. Therefore, on one hand, with decreas-
ing R1, faster electron transport occurs, but on the other
hand, the competing recombination process through R2
also speeds up due to decreasing R2 (see Fig. 7).
Impedance spectroscopy analysis confirmed that there
is an optimal thickness of ZnO ETL at which there is a bal-
ance between the rate of electron transport to the cathode
and the rate of backward recombination of charge carriers.
When ZnO ETL has an optimal thickness, the electron
lifetime (τeff) has the maximum value, whereas the recom-
bination rate (keff) of charge carriers does the lowest value.
Indeed, our IV and IS studies indicate that the optimal
thickness of ZnO ETL synthesized at conditions specified
in the experimental section is 54 ± 5 nm. In our PSC with
that optimal thickness, τeff has the highest value of 2.8 ms,
while keff has the lowest value of 350 ­s−1.

Table 4  Charge transfer parameters of PSCs

Film thickness R1, R 2, R2/R1 τeff, keff,

ZnO, nm (ohm) (ohm) (ms) (s−1)

86 ± 5 480 1274 1.8 1.2 830

68 ± 5 365 1022 2.8 2.3 435
54 ± 5 169 637 3.7 2.8 350
Fig. 6  Impedance spectra of PSCs with different ZnO film thick- 42 ± 5 140 289 2.1 0.4 2500
nesses. (The inset shows an equivalent electrical circuit, which was 26 ± 5 109 250 1.3 0.5 2000
used to fit impedance data)

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Competitive charge transport processes in inverted polymer solar cells based on ZnO thin films Page 7 of 8
Fig. 7  Representative diagram of generation and transfer of charge
carriers in FTO/ZnO/P3HT:IC60MA/MoOx/Ag polymer solar cells:
1—photon absorption and exciton formation; 2—dissociation of exci-
ton to free charges; 3—electron injection into ZnO; 4—recombina-
tion of an electron with a hole at ZnO/P3HT interface
4 Conclusion
In this study, we fabricated inverted polymer solar cells
with FTO/ZnO/P3HT:IC60MA/MoO x/Ag architecture.
We investigated the effect of the thickness and quality of
ZnO layers on the photovoltaic performance of polymer
solar cells. ZnO films were deposited from a zinc acetate
solution by a spin-coating technique. The thickness of the
ZnO layer was regulated by tuning spin-coating rotation
speed. It was revealed that decreasing ZnO film thickness
results in poor film quality with increased crack density
and size. After the injection of electrons from the photoac-
tive layer into the ZnO layer, two competitive charge trans-
fer processes occur inversely affecting photovoltaic perfor-
mance. As ZnO layer thickness decreases, its resistance
also decreases, which facilitates electron transport to the
cathode (FTO). However, the deterioration of film qual-
ity contributes to the reduction of recombination resist-
ance due to the increase in crack density and sizes, which
enhances the recombination rate of charge carriers. It gives
a clue that there is an optimal thickness of ZnO ETL, at
which should exist a balance between these two competing
charge transfer processes. We found that, at our ZnO depo-
sition conditions, the optimal thickness of ETL should be
around 50 nm to obtain PSCs with the high short-circuit
current density and with the high open-circuit voltage.
The champion device with ETL thickness of 54 ± 5 nm
revealed Jsc, Voc, and power conversion efficiency as high
as 9.5 mA/cm2, 0.6 V, and 3.2%, respectively. Impedance
spectroscopy analysis showed that, at the optimal ETL
thickness, the effective lifetime of electrons in ZnO has
the maximum value, and recombination rate at the ZnO/
photoactive layer interface has a minimum value in com-
parison to the ZnO layer with different thicknesses.
407
Funding This research was funded by the Science Committee of the
Ministry of Education and Science of the Republic of Kazakhstan
(Grant No. AP09561879).
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