Inorganic Chemistry Communications 149 (2023) 110391

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Inorganic Chemistry Communications

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Short communication

Structural, optical and mechanical investigations on pure and Co-doped

SnO2 thin films samples
S. Chayoukhi a, *, B. Gassoumi b, H. Dhifelaoui c, N. Boucherou d, A. Boukhachem e, M. Amlouk b,
A. Zghal a
a
laboratoire mécanique, productique et énergétique (LMPE). Ecole Nationale Supérieure d’ingénieurs de Tunis, Université de Tunis, B.P. 56, Bab Menara 1008, Tunis,
Tunisia
b
laboratoire nanomatériaux, nanotechnologie et énergie (L2NE), Faculté des sciences de Tunis, Université de Tunis El Manar, 2092 Tunis, Tunisia
c
laboratoire de Mécanique Matériaux et Procédés (LMMP), Ecole Nationale Supérieure d’ingénieurs de Tunis, Université de Tunis, B.P. 56, Bab Menara 1008, Tunis,
Tunisia
d
Research center in Industrial Technologies (CRTI), P.O. Box 64, Cheraga 16014, Algiers, Algeria
e
Laboratoire Nanomatériaux et Systèmes pour Les Energies Renouvelables (LANSER), Centre de Recherches et des Technologies de L’Energie Technopole Borj Cedria, Bp
95, Hammam Lif 2050, Tunisia

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

Keywords: Cobalt-doped tin oxide (SnO2:Co) thin films were successfully deposited on ordinary glass substrate by using a
Cobalt doping simple spray pyrolysis technique at the temperature of 450 ◦ C. XRD analysis shows that the prepared films
Finite element crystallize in a tetragonal structure with (1 1 1) preferred orientation. Lattice parameters, crystallite size, strain
Nanoindentation
and dislocations densities were calculated. Optical investigations by the meaning of reflectance and trans­
SnO2
Urbach energy
mittance measurements show a large optical band gap with a significant increase with Cobalt doping ratio.
Mechanical proprieties in terms of microhardness, Young modulus and yield strength were investigated through
nanoindentation measurements. Numerical study via Abaqus finite element proves the validity of the numerical
model and shows the effect of cobalt doping on the mechanical properties of the SnO2 binary compound.

1. Introduction:
Tin oxides are utilized in many industrial applications, such as
conductive and transparent electrodes used in thin film solar cells [1,2],
biomarkers [3], catalysts [4], therapeutics [5], structural re­
inforcements [5] and photovoltaic applications [2].
Several researches have been conducted to improve some properties
of this binary compound under many doping elements. For example, Mo
and F are used by Turgut et al. [6] to improve electro-optical properties,
Cr is used by Subramanyam et al. [7] to study structural, optical and
magnetic properties, Mn and Co are also used in other researches
[8,9,10] to obtain better magnetic and optical performance of tin oxide
thin films.
In terms of electronic structure, it is found that SnO2 is a large band
gap material [11,12] with a good chemical thermal stability [7,13]. In
terms of doping, SnO2 was the subject of many works: Fang et al. [13]
were doped SnO2 by fluorine to improve the nanomechanical properties.
They found that the friction coefficient decreases with increasing Freon
flow. Basyooni et al. [11] studied undoped and Cobalt-doped tin oxide
thin films. They found that SnO2:Co can detect CO2 in the atmosphere at
room temperature, while the undoped SnO2 has a weak detection. Rahal
et al. [11] reported that crystalline quality is improving by Sb doping
with a high dependency of both optical gap and the electrical
conductivity.
Several methods have been used to prepare SnO2 thin films, for
example, pulsed laser deposition (PLD), reactive sputtering, chemical
vapor deposition (CVD), electron cyclotron resonance sputtering and
spray pyrolysis [13,14,15].
Among these techniques, spray-pyrolysis has several advantages,
such its simplicity, low cost of equipment and offers the possibility to
produce a large area. In addition, this technique gives crystallized thin
films without resorting to post heat treatment [14,16,17].
Many works were investigated to study some physical properties of
SnO2 under many doping elements, but few have focused on the nano­
mechnical properties doped with a magnetic element [14,15].
The present study seeks to present some physical properties of

* Corresponding author.
E-mail address: slah.chayoukhi@yahoo.fr (S. Chayoukhi).

https://doi.org/10.1016/j.inoche.2023.110391
Received 2 August 2022; Received in revised form 22 November 2022; Accepted 1 January 2023
Available online 3 January 2023
1387-7003/© 2023 Elsevier B.V. All rights reserved.
S. Chayoukhi et al.
Fig. 1. Process of the pyrolysis spraying technique.
Fig. 2. XRD patterns of SnO2:Co sprayed thin films.
cobalt-doped tin oxide (SnO2:Co) sprayed thin films with (Co)/ (Sn)
atomic ratio ranges from 0 to 6% with a 2% doping level step. A detailed
studies were carried out to reveal the effects of cobalt doping on the
structural, optical, morphological and mechanical properties of SnO2
thin films by meaning of some appropriates investigation methods. First,
the structural properties were studied by X-ray diffraction (XRD). Sec­
ond, optical properties are obtained by analyzing optical transmission
and reflectance spectra. The morphological properties were examined
by using a scanning electron microscope (SEM). Particular attention was
made to studying some mechanical parameters such as microhardness,
Young modulus and yield strength by the meaning of the nano­
indentation measurements. Finally, a numerical confirmation of me­
chanical properties was carried out.
2. Materials and methods
2.1. Preparation of films
The pure and Co-doped SnO2 thin films were successfully synthesized
using an aqueous solution of SnCl2, 2H2O (0.01 M) with the addition of
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Inorganic Chemistry Communications 149 (2023) 110391
some acetic acid droplet as a catalyst. Cobalt chloride hexahydrate
(CoCl2, 6H2O) was used as a doping agent with the (Co) to (Sn) ratio of
0 %, 2 %, 4 % and 6 %. The solution was kept under stirring for 15 min.
During the solution stirring time, ordinary glass substrates with a size of
(2Cm × 1Cm) were placed on the heating plate. As reported previously
[18,19], the heating of the plate was done progressively to avoid ther­
mal shock of the substrates. When the desired synthesis temperature is
reached (450 ◦ C), a pump was used to push the solution toward the
sputtering device whose start is fixed at 4 ml/min. Nitrogen gas was used
as carrier gas whose pressure is about 0.35 bars. The distance between
the sputtering bus (spaying device) and the glass substrates is about 27
cm [17]. Then, the prepared films were naturally cooled for three hours
in order to reach room temperature (see Fig. 1).
2.2. Characterization techniques
The structural properties of Co-doped SnO2 thin films have been
obtained by X-ray diffraction pattern analysis in the range of 5–80◦ using
Cu monochromatic source radiation (λKα = 1.5406 Å) with a step of
0.02◦ during 30 min. The optical properties of Co-doped SnO2 thin films
S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

Fig. 3. XRD pattern (a) and Rietveld refinement plot (b) of undoped SnO2 spray thin film.

Table 4
Crystallite size values of SnO2:Co films.
D(110) (nm) D(111)(nm) D(211) (nm) D(130) (nm)

SnO2 9.83 49.78 50.45 11.34

SnO2: Co 2% 9.14 36.49 24.59 10.75
SnO2: Co 4% 4.34 5.11 7.97 –
SnO2: Co 6% 3.65 21.9 – –

Table 5
Dislocation density values of SnO2:Co films.
δ(110) (1016 δ(111)(1016 lines/ δ(211) (1016 δ(130)
lines/m2) m2) lines/m2) (1016 lines/
m 2)

SnO2 1.034 0.040 0.039 0.777

Fig. 4. atomic position in SnO2 material. SnO2: Co 1.197 0.075 0.165 0.865
2%
SnO2: Co 5.309 3.829 1.574 –
Table 1 4%
Lattice’s parameters of Co-doped and undoped SnO2 sprayed thin films. SnO2: Co 7.50 0.208 – –
6%
a b c Unit-cell volume (Å3)

SnO2 4.722 4.722 3.224 71.922

SnO2: Co 2% 4.724 4.724 3.219 71.875
SnO2: Co 4% 4.723 4.723 3.178 70.905 Table 6
SnO2: Co 6% 4.672 4.672 3.265 71.279 Values of < ε>, <D > and < δ > of SnO2:Co sprayed films.
JCPDS card no◦ :088–0287 4.737 4.737 3.186 71.51 <ε> (10− 3) <D>(nm) <δ> (1016 line/m2)

SnO2 7.54 30.35 0.47

SnO2: Co 2% 7.2 20.24 0.57
Table 2 SnO2: Co 4% 11.65 5.8 3.57
Texture coefficient values of SnO2 thin films. SnO2: Co 6% 10.77 12.77 3.85

TC(110) TC(111) TC(211) TC(130)

SnO2 0.08 3.66 0.05 0.20 were recorded using a Perkin-Elmer Lambda 950 spectrophotometer by
SnO2: Co 2% 0.08 3.69 0.04 0.17 analyzing the optical transmission and reflectivity spectra in the wave­
SnO2: Co 4% 0.22 3.67 0.10 – length range of 300–2000 nm. For optical treatment, thin film thick­
SnO2: Co 6% 0.09 3.90
nesses were measured by using profilometer Bruker (DektaK XT).
– –

Scanning electron microscope (SEM) was used to study the

morphological properties of SnO2:Co thin films. The mechanical prop­
Table 3 erties were measured by nanoindentation. Tests were performed using
Microstrain values of SnO2 for different Co doping levels.
nanoindenter type NHT2 (Anton Paar, Switzerland) equipped with a
ε(110) (10− 3) ε(111) (10− 3) ε(211) (10− 3) ε(130) (10− 3) diamond Berkovich tip with a nominal angle equal to 65.3◦ and a
SnO2 14.37 4.96 5.18 5.67 nominal radius curvature of 20 nm. During the nanoindentation tests a
SnO2: Co 2% 13 5.1 5.24 5.46 maximum load of 10 mN was applied to all SnO2:Co thin films with a
SnO2: Co 4% 18 8.84 8.12 – constant loading and unloading rate of 20 mN/min.
SnO2: Co 6% 14.09 7.46 – –

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S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

Fig. 5. SEM images of the SnO2 (a), SnO2:Co 2% (b), SnO2:Co 4% (c) and SnO2:Co 6%(d).

Fig. 6. transmittance (a) and reflectance (b) spectra of SnO2:Co sprayed thin films.

3. Results and discussion
3.1. Structural analysis
Fig. 2 shows the X-Ray diagram of undoped and Co-doped SnO2 thin
films. These patterns show the existence of two intense peaks related to
(1 1 0) and (1 1 1) directions and two less intense peaks corresponding to
the miller index (2 1 1) and (1 3 0) respectively. These diffraction peaks
show that the prepared films crystallize in tetragonal structure accord­
ing to 00-088-0287JCPDS card which belongs to P42/mnm space group.
On the other hand, it is found that the crystallites of all the prepared
films are preferentially oriented along the (1 1 1) plane with a direction
peak located around 38.75◦ of 2θ position peak. In order to reinforce this
finding, Rietveld’s refinement of undoped SnO2 was carried out (Fig. 3).

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S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

Fig. 7. Plot of (αhν)2vs hν of Co-doped SnO2 sprayed thin films: (a) eV unit and (b) cm− 1
unit.

related to interplanar spacing and Miller index h, k and l by the

Table 7 following relation [12,21,22].
Values of Eg and EU of Co-doped SnO2 sprayed thin films.
1 h2 + k2 l2
Eg EU 2
= + 2 (2)
dhkl a2 c
− 1 − 1
/eV /cm /meV /cm
Calculated values of SnO2:Co lattice parameters are listed in Table 1,
SnO2 4.018 32371.16 171 1360
SnO2: Co 2% 3.948 31804.56 194 1551 from these results, it is observed the particularity of Co 4% doping level
SnO2: Co 4% 3.937 31714.20 250 2000 with its minimum value of lattice parameters and therefore the mini­
SnO2: Co 6% 3.892 31356.03 254 2081 mum values of the unit cells volume. This effect can induce the
maximum compactness.
In addition to the lattice parameters, several other structural pa­
This study shows the absence of secondary phases and also verifies
rameters were interpreted from the X-ray diffraction analysis, such as
the structure of the deposited material. As a matter of fact, in the
texture coefficients, crystallite size, microstrain, dislocation density.
tetragonal structure, the Sn4+ ions co-occupy the octahedral sites and
The preferential orientation of crystallites has been calculated from
the O2– ions occupy the octahedron vertices (Fig. 4). Also, this suggests
the values of the texture coefficient. In this regard, the texture coeffi­
that this doping consists in substituting tin by cobalt.
cient (TC(hkl)), can be estimated using the following formula [17,23]:
In the XRD measurements, it is found a Bragg position shift with Co
doping; this effect is related to a variation of lattice parameters which I0(hkl)

(3)
I0(hkl)
are deduced from the interplanar spacing dhkl by using Bragg relation TC = ∑ I0(hkl)
N− 1
[16,17,20]. I0(hkl)

2dhkl sinθ = nλ
where n is the diffraction order (n = 1) and λ is the X-ray wavelength.
In the tetragonal structure, the lattice parameters (a and c) are
(1) where, I(hkl) is the measured intensity related to the Miller (hkl) indices,
I0 is the reference intensity from JCPDS card N◦ : 00-088-0287. The re­
sults of the TC calculations are listed in Table 2.

1
Fig. 8. Plot of Ln(α) vs the photon energy of SnO2:Co thin films: (a) eV unit and (b) cm− unit.

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S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

the doping rate. This can affect the physical properties of this doped
oxide binary such as the band gap energy, the transparency and the
mechanical properties.
It is known that the ideal crystal X-ray diffraction pattern is usually
characterized by a very low FHWM which indicates the sparseness of the
defects in the crystal structure. Indeed, from the analysis of X-ray
diffraction pattern of pure and Co-doped SnO2, we can see that in all the
different patterns, the FHWM is not null which indicates the presence of
defects in the structure of doped and undoped SnO2. These structural
defects are studied in terms of calculation of micro-strain (ε) [17,24],
Crystallite size (D) [25] and Dislocation density [26] which are repre­
sented by the following relationships.
β
ε= (4)
4tanθ

kλ
D= (5)
βcosθ
Fig. 9. variation of both dislocation density and Urbach energy vs Co
doping level. 1
δ= (6)
D2

where k = 0.9 is the Scherrer constant, β is the width at half maximum

(FWHM) and λ is the X-ray wavelength. The values of these parameters
are shown in Tables 3, 4 and 5 respectively.
From the obtained values of microstrain and dislocation density, we
can say that the incorporation of cobalt in the SnO2 matrix has an effect
of increasing the structural defects, this seen at the level of the value of
dislocation density which corresponds to the doping level 6% Co.
To better explain the effect of Co doping on the structural properties
of the binary oxide SnO2, the average value of the crystallite size, the
microstrain and the dislocationdensity can be calculated by the
following relations [6,27]:
⎧ ∑
⎪ TC(hkl) .D(hkl)
⎪
⎪ < D >= ∑ (7)
⎪
⎪ TC(hkl)
⎪
⎪
⎪
⎪ ∑
⎨ TC(hkl) .ξ(hkl)
< ε >= ∑ (8)
⎪
⎪ TC(hkl)
⎪
⎪
⎪
⎪ ∑
⎪
⎪ TC .δ
⎪
⎩ < δ >= ∑ (hkl) (hkl) (9)
TC(hkl)
Fig. 10. Experimental load-depth curves of SnO2:Co thin films.
The values of average crystallite size, microstrain and dislocation
density are shown in Table6.
These results clearly show that the structural defects increase with
Table 8
Experimental mechanical parameters.
the increase of the Co content in the SnO2 structure, the rate of defects in
the structure is explained by the decrease of the crystallite size and the
SnO2 SnO2:Co 2% SnO2:Co 4% SnO2:Co 6%
increase of dislocation densities. Actually, the increase in structural
H (GPa) 5.9 6.2 6.8 8 defects as a function of Co doping rate can directly affect the physical
E (GPa) 78 80 85 86
properties of the material, such as optical properties and mechanical
Er (GPa) 78.39 79.22 84.74 86.08
S (mN/µm) 112.85 115.80 127.86 128.10
properties of this doped binary compound.
ν 0.315 0.31 0.315 0.32
hmax (µm) 0.27 0.26 0.25 0.24 3.2. Morphological properties
hf (µm) 0.15 0.14 0.12 0.11
R(%) 44.4 46.15 52 54.6
The morphology of undoped and Co doped SnO2 spayed thin films
was verified by scanning electron microscopy (SEM). Fig. 5 shows SEM
micrographs of undoped SnO2 and Co–doped SnO2 thin films. It can be
Table 9 seen that SEM observations depict a clearly disturbed surface with
Plastic deformation energy. randomly oriented islets-like (with various sizes) showing a rough sur­
SnO2 SnO2:Co SnO2:Co SnO2:Co face morphology. Regarding the difference between the SEM images
2% 4% 6% (Fig. 5), it is found that the SnO2 surface state depends on cobalt doping.
Plastic deformation energy 0.52 0.43 0.42 0.38
(10-9 J) 3.3. Optical properties

From this texture coefficients study, it is possible to find that cobalt The optical properties of Co-doped SnO2 sprayed thin films were
doping ensures the good organization of the lattice. Effectively, the investigated through the UV–Vis spectro-photometric measurements
texture coefficient for the preferential orientation (1 1 1) increases with using unpolarized radiation at normal incidence in the wavelength
range of 300–2000 nm.

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S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

Fig. 11. Process meshing (a) and mesh zones (b) used in the FE calculations.

Fig. 12. Numerical and experimental load-depth curves of the SnO2:Co films.

have the highest transmission of about 85%. This effect is consistent

Table 10 with the structural studies described above. Thus, it can be concluded
SnO2:Co material properties used for simulation. that cobalt doping has a considerable effect on the optical properties of
SnO2 SnO2:Co 2% SnO2:Co 4% SnO2:Co 6% SnO2. On the other hand, the fundamental absorption edge of the films
Poisson’s ratio ν 0.37 0.36 0.37 0.38 corresponds to transitions of electrons from the valence band to the
Yield strength σy(GPa) 3.9 4 4.3 4.7 conduction band edge and this can be used to calculatethe difference in
the optical band gap of the films using the following relation [28,29]:
[ ]
Fig. 6 shows both reflectance and transmittance spectra. From these 1 (1 − R)2 + ((1 − R)4 + (2RT)2 )0.5
optical results for all prepared films, it is found that the transmission α = Ln (10)
d 2T
drops very sharply near the UV region due to the onset of fundamental
absorption. However, in the infrared region the films with 4% Co doping As SnO2 is the direct transition semiconductor, the absorption

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S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

Fig. 13. Von-Mises constraint of the SnO2:Co thin films.

coefficient can be expressed by [19]:

1 d[α(hν)]
= (13)
(11)
1
αhν = [A(hν − Eg )]2 EU d[hν]
Fig. 8 shows the plot of Ln(α) vs the photon energy of SnO2:Co pre­
where A is a constant, hν is the photon energy and Eg is the optical band
pared films.
gap.
The calculated Urbach energies are listed in Table 7. It is clear that
Fig. 7 shows the plot of [α.(hν)]2 versus the photon energy hν which
the Urbach energy increases with increasing Co-doping rate. This result
yields in the sharp absorption edge for the high quality films by a linear
is consistent with the structural studies. Indeed, as shown in Fig. 9,
fit.
Urbach energy and dislocation density varies in the same way as the
The calculated values of optical band gap Eg of Co-doped SnO2 are
doping ratio. This effect reinforces the observations on the structural
summarized in Table7. It is clear that the value of the gap energy de­
studies especially in terms of dislocation density and the finding
creases with increasing Co-doping rate. Complementary to this calcu­
mentioned by M. Karyaoui et al. [35] And B. Gharbi et al. [36].
lation, correlation with the structural defects was taken account.
Actually, in all material impurities and structural defects can induce
3.4. Nanoindentation and finite element simulation
some localized states.
As reported by A. Loukil et al. [30] and H. Arifa et al. [31], the ab­
Mechanical properties of the sprayed SnO2:Co thin films were stud­
sorption coefficient can have non-zero values even for energies lower
ied by nanoindentation experiments. The load-displacement curves
than the optical band gap.
were obtained by the Oliver and Pharr method under a load of 10 mN.
This phenomenon can be interpreted as a spreading effect of the
Fig. 10 shows the evolution of penetration depth as a function of applied
densities of state in the band gap with characteristic width energy called
load for undoped and Co-doped SnO2 thin films.
Urbach energy. According to the empirical Urbach law, around the band
The load-depth curves, Young’s modulus (E) and nanohardness (H)
gap energy, the absorption coefficient obeys the following relation
were studied. The measured values of Young’s modulus (E) and nano­
[32,33]:
hardness (H), the reduced elastic modulus (Er), Poisson coefficient (ν)
hν
α = α 0 e EU (12) and stiffness parameter (S) as well as the maximum displacement (hmax)
and the residual impression depth are measured using integrated soft­
The values of the Urbach’s energy (EU) are calculated by taking the ware, and their values are gathered in Table 8.
reciprocal of the slopes of the linear portion in the lower photon energy The elastic recovery rate (R) is given by equation (14), which
region of these curves through the equation’s system [34]: calculated values are also listed in Table 8.

8
S. Chayoukhi et al.
Fig. 14. Equivalent plastic deformation of SnO2:Co thin films.
hmax − hf
R(%) = 100 (14)
hmax
At a first glance, it is found that measured values of the hardness and
Young’s modulus results for pure SnO2 are in agreement with those
found by Villegas et al. [14].
On the other hand, from these measurements, it can be seen the effect
of cobalt doping. All these mechanical parameters depend on the Co
doping level. The Young’s modulus, nanohardness and stiffness, increase
with Co doping, while the maximum displacement decreases. Therefore,
the tin dioxide films become increasingly rigid with increasing Co
doping (Table 8). This result is consistent with the structural
investigation.
In addition, it is found that the load-depth curves have a hysteresis
effect which is related to the nonlinearity character of this phenomenon
and consequently the plastic behavior. The plastic deformation energy
was obtained by calculating the area between loading and unloading
curves; their values are listed in Table 9.
From this rapid calculation, it is found that the plastic deformation
energy decreases with cobalt ratio. This is consistent with the hardness
and Young modulus values (Table 8).
In order to confirm the results obtained from the experimental study,
a numerical study based on the finite element method (FE) was per­
formed with a commercial code ABAQUS/CAE. Fig. 11a shows the
process meshing used which is an eight-node linear brick element with
reduced integration type (C3D8R). In order to improve the accuracy of
the indentation modeling, a finer mesh with a higher element density
was used in the contact area and a larger mesh was applied to the rest of
the sample and to the indenter (Fig. 11b).
In this study, the specimen was modeled by a disc of 15 µm radius,
and assumed to be isotropic and homogeneous. In the case of the
9
Inorganic Chemistry Communications 149 (2023) 110391
Berkovich indenter type used in these measurements with center-to-face
angle is equal to 65.3◦ , the indenter considered as a rigid solid so as not
to deform during the simulation. Based on the SEM observation, three
assumptions have been taken into consideration in this study; firstly, the
applied interaction is considered as a standard surface-to-surface contact
where the surfaces are assumed to be perfectly flat and secondly the
influence of the surface roughness is negligible and thirdly, the friction
coefficient between the specimen and the indenter is assumed to be zero.
In accordance with the experimental measurements, in the numeri­
cal study, the indentation was performed using only vertical displace­
ment of the indenter.
In this numerical investigation, maximum displacements (hmax) and
Young’s modulus values are deduced from experimental measurements
(Table 8) also, the speed of loading and unloading are fixed at the same
value of 2 µm/min. The Poisson’s ratio and yield strength were identi­
fied by minimizing the average relative error ξF between numerical and
experimental load-depth curves using the following equation [37]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
)2̅
√ m ( i
1√ ∑ Fexp − Finum
ξF = √ (15)
m i=1 Fiexp
where Fiexp and Finum are the applied experimental force and the calcu­
lated force corresponding to the same displacement for a set of m points.
The force displacement responses from the simulation are repre­
sented and compared to experiment results as shown in Fig. 12. The
comparison indicates a satisfactory correlation of the model and the
tests. The small discrepancy found is due to various parameters related
to the experimental process and the accuracy of the material properties
introduced in the model.
It is observed that the numerical values of Poisson’s ratio are close to
S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

Fig. 15. Residual impression depth of SnO2:Co thin films.

thin films were studied through XRD analysis, SEM observations and
Table 11 optical investigations. The effect of cobalt doping on the mechanical
Residual parameters of indentation. properties of such binary was also investigated by means of the nano­
SnO2 SnO2:Co 2% SnO2:Co 4% SnO2:Co 6% indentation measurements. X-ray diffraction shows that SnO2:Co thin
S-Mises(GPa) 2.75 2.77 3.22 3.34 films crystallize in tetragonal structure with (1 1 1) preferred orienta­
PEEQ 0.32 0.315 0.30 0.29 tion. Some structural parameters are calculated and discussed with co­
U (µm) 0.165 0.161 0.154 0.150 balt doping ratio particularly, the crystallinity of SnO2 thin films
decreases with increasing Co doping rate. Through nanoindentation
investigations, Young modulus, hardness and yield strength are
the experimental data which confirms the numerical study (Tables 8 and
measured. This mechanical study shows that these parameters increase
10). Likewise, the yield strength increases with the level of cobalt doping
with Co atomic content. The simulation by ABAQUS confirms the effect
(Table 10). This result is consistent with the finding described above in
of cobalt doping. The residual stress, residual strain, and residual
terms of hardness and stiffness parameters and confirms that SnO2 films
displacement are calculated and seem depending on Co doping. Further
become increasingly rigid with increasing Co doping.
studies are planned to test such doped films in interesting applications
Complementary to this numerical study, another one based on the
like gas and biosensors as well as the opto-mechanical linkage.
morphology of residual impression was carried out. Figs. 13, 14 and 15
stand for the finite element simulation of the residual indentation for
CRediT authorship contribution statement
SnO2:Co thin films in terms of Von-Mises stress (S-Mises), equivalent
plastic strain (PEEQ) and residual displacement (U) respectively. Their
S. Chayoukhi: Conceptualization, Data curation, Writing – original
values are determined and given in Table 11. In all these studies, it is
draft. A. Boukhachem: Formal analysis, Methodology. M. Amlouk:
observed that the stresses and strains are high below the tip of the
Investigation, Writing – review & editing. A. Zghal: Project adminis­
indentation while in the surrounding area they become progressively
tration, Validation.
smaller and zero in the boundary of the plastic zone. The S-Mises in­
creases while the PEEQ and U decrease with increasing Co doping. As for
the other mechanical parameters, these values are in good agreement Declaration of Competing Interest
with the structural study and confirm that the substitution of tin by
cobalt affects the microscopic properties as well as the macroscopic The authors declare that they have no known competing financial
properties. interests or personal relationships that could have appeared to influence
the work reported in this paper.
4. Conclusion
Data availability
Co-doped SnO2 thin films deposited on glass substrates by the spray
No data was used for the research described in the article.

10
S. Chayoukhi et al. Inorganic Chemistry Communications 149 (2023) 110391

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