Inorganic Chemistry Communications 155 (2023) 111037

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Inorganic Chemistry Communications

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Short communication

Effects of 60Co γ-radiation on the structural, morphological, optical,

tribological and mechanical properties of SnO2 sprayed thin films
S. Chayoukhi a, *, B. Gassoumi b, H. Dhiflaoui c, A. Mejri d, A. Boukhachem e, M. Amlouk b
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 Ssciences 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
Laboratoire de Dosimétrie, Centre National des Sciences et Technologies Nucléaires (CNSTN), Pôle Technologique, 2020, Sidi Thabet BP 72, Tunisia
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: Tin oxide (SnO2) thin films have been used, in the last decades, in a variety of devices and applications exposed
SnO2 to high-energy radiation that affects their physical properties. In this manuscript, the influence of 60Co γ-radi­
Gamma-ray irradiation ation (with doses of 30, 45, 60, 75 and 90 kGy) on the characteristics of SnO2 thin films is studied thoroughly.
Microhardness
The produced films were deposited on ordinary glass, preheated at 450 ◦ C, using the spray pyrolysis method. The
Scratch tests
Wear resistance
effects of the different doses of gamma-ray on the properties of SnO2 thin films were characterized by X-ray
Urbach energy diffraction, scanning electron microscopy, UV–vis spectroscopy and mechanical tests. The experimental results
show that irradiation led to considerable modifications in the structural, morphological, optical, tribological and
mechanical characteristics of the studied films. These changes occurred regularly when radiation doses were
below 60 kGy and randomly when doses were above that value. XRD results reveal that by increasing the
irradiation dose up to 60 kGy, crystallite size increased from 46.22 to 56.39 nm. However, dislocation density
and microstrain showed an opposite trend to crystallite size with absorbed doses. This behavior can be explained
by the crystallite rearrangement due to the increase of the temperature under the effect of irradiation. The
γ-irradiation led to a decrease in the optical gap energy from 4.0 to 3.9 eV as the γ-dose increased from 0 to 60
kGy because of the modification of the structural defect. The γ-irradiation affected significantly the mechanical
properties of the deposited SnO2 thin films. It was observed that the parameters of hardness, wear resistance and
substrate adhesion decreased while the friction coefficient increased (from 0.07 to 0.09) with increasing the
γ-radiation dose. In addition, the surface of SnO2 thin films became smoother with the increase of the irradiation
dose. However, the surface was not damaged with the change of the film morphology. Despite the different
changes undergone by SnO2 films when irradiated with gamma rays, they are still efficiently employed in a
variety of applications.

1. Introduction
Metal oxide thin films are used extensively in industry thanks to their
relevance to a variety of applications [1–4]. They are utilized in devices
and applications exposed to radiation such as nuclear reactors, satellites,
space shuttles, military equipment and biomedical applications [5–7].
High-energy radiation can alter the physical and mechanical properties
of metal oxide thin films, which influences remarkably their
performance [8–10]. These effects are correlated with the radiation dose
which has proven to be a suitable physical modification tool [11,12].
Several researches were carried out to study the changes in the
properties of the metal oxide thin films after radiation. For instance,
Maged et al. [6] studied the structural, optical and electrical behavior of
SnO2 thin films irradiated with gamma rays. They found that the re­
sistivity of the thin films decreased, while the mobility and carrier
concentration increased with the rise of the gamma ray dose. A similar

* Corresponding author.
E-mail address: slah.chayoukhi@fst.utm.tn (S. Chayoukhi).

https://doi.org/10.1016/j.inoche.2023.111037
Received 1 May 2023; Received in revised form 27 June 2023; Accepted 6 July 2023
Available online 7 July 2023
1387-7003/© 2023 Elsevier B.V. All rights reserved.
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

study was carried out by Sen et al. [13] on h-MoO3 thin films deposited
by spray pyrolysis. The authors reported that γ-irradiation led to a
decrease in the degree of crystallinity. However, dislocation density and
lattice strain increased oppositely to crystallite size with absorbed doses.
Sen et al. [14] also examined the effects induced by 60Co gamma radi­
ation on the properties of the nano-structured α-MoO3 for use in opto-
electronic and photonic devices. They demonstrated that the crystal­
linity deteriorated at low doses (10 kGy) and improved at high doses
(120 kGy). On the other hand, lattice strain and dislocation density were
modified in inverse order to crystallite size. Furthermore, Sudha et al.
[5] found that the structural, optical and electrical properties of
annealed SnO2 films changed significantly for gamma irradiation at
moderate doses, but for high doses these properties varied slightly. In
the same line, Wang et al. [15] demonstrated that irradiation of tin-zinc
oxide thin films with gamma rays leads to reliable and stable electrical
characteristics, at moderate doses and minor degradation at higher
doses. Likewise, Al-Ghamdi et al. [16] investigated the properties of
SnO2-F samples before and after γ-irradiation. They reported that the
dislocation density, the microstrain, the optical band gap and the elec­
trical resistance decreased with the rise of the irradiation dose. Kaya
et al. [17] proved that gamma irradiation improved the crystallographic
structure and the surface roughness of n-SnO2/p-Si films used as het­
erojunction diodes. Kozlovskiy et al. [18] demonstrated that irradiation
of TiN-based thin films with low-energy Kr14+ ions resulted in the
changes of the structure and the morphology of these films. These
Fig. 1. Schematic diagram of SnO2 film preparation.
modifications caused a significant decrease in the hardness of the film. It
was also reported that metal oxide thin films can be used in biomedical
applications such as implant coatings due to their mechanical properties 2.2. Techniques
[7,19–20]. As already-mentioned, these mechanical properties were
modified by γ-irradiation. First, the structural characteristics of the non-irritated and irradiated
In the present work, the changes of the structural, morphological, samples were studied by X-ray diffraction (XRD) using the mono­
optical and tribological properties of SnO2 thin films exposed to 60Co chromatic source radiation of Cu (λKα = 1.5406 Å) in the range of 20◦ to
gamma irradiation are studied. The structural characteristics are 80◦ with a step of 0.02◦ during 30 min. Second, the scanning electron
examined using X-ray diffraction analysis (XRD). Optical properties are microscopy (SEM) was employed to evaluate the surface morphology of
determined from transmission and reflectance spectra. In addition, the SnO2 thin films taken before and after irradiation. A Perkin-Elmer
morphological characteristics are investigated using scanning electron Lambda 950 spectrophotometer was employed to measure the optical
microscopy (SEM). The changes in the structural properties of SnO2 characteristics of the irradiated and non-irritated samples by examining
films may, therefore, play an important role in modulating these films’ the optical transmission and the reflectivity spectra in the range of
mechanical properties. Based on these modifications, appropriate ap­ wavelengths 300–2000 nm. The mechanical characterization of non-
plications can be envisaged. Thus, particular attention was given to irritated and irradiated SnO2 thin films includes microhardness, tribo­
changes in SnO2 mechanical properties, which are investigated in terms logical behavior and adhesion. The micro-hardness tests were performed
of microhardness, adhesion behavior, friction and wear resistance using by means of a Microvickers-DM2A microdurometer equipped with a
microhardness, scratch and wear tests. square-based pyramidal diamond indenter. Adhesion was determined
using an MST type scratch tester, equipped with a Rockwell diamond
2. Experimental setups spherical tip with a radius of 100 nm, by applying a progressive load
varying from 0.03 N to 7 N over a 3 mm track length using a loading
2.1. Preparation and irradiation of SnO2 thin films speed of 1 N/s. The tribological behavior was studied by wear tests over
a 3 mm stroke using a constant load scratch to determine the friction and
SnO2 were prepared by the spray pyrolysis process. The aqueous wear resistance. To attain this objective, several tests were performed
solution was made in 50 ml of SnCl2 and 2H2O using an acetic acid with normal loads ranging from 0.5 to 2 N and sliding speed of 10 mm/
catalyst. The samples were prepared and the conditions for the deposi­ min.
tion operation were defined as shown in the diagram presented in Fig. 1.
The solution was stirred during 15 min and, then, sprayed onto the glass 3. Results and discussion
substrate with a flow rate of 4 ml/min. The substrate was separated from
the nozzle by a distance of 27 cm. It was preheated progressively to a 3.1. Effect of the radiation on the structural properties
temperature of 450 ◦ C in order to prevent any thermal shock damage.
Nitrogen was utilized as the gas carrier to deposit the films under a To investigate the effect of gamma irradiation on the structural
pressure of 0.35 bar. characteristics, X-ray diffraction study was performed. The X-ray dif­
The obtained SnO2 thin films were irradiated by 60Co gamma rays fractograms of the non-irradiated and irradiated SnO2 films are pre­
with its 1.25 MeV photon energy in the National Centre for Nuclear sented in Fig. 2. Six peaks appear with relatively high intensities at
Sciences and Technologies (CNSTN), Technopole of Sidi Thabet, Tunisia 26.71◦ , 33.89◦ , 38.27, 51.74◦ , 62.17◦ and 66.01◦ assigned respectively
[22]. The used gamma doses were adjusted to 0 kGy, 30 kGy, 45 kGy, 60 to (1 1 0), (1 0 1), (1 1 1), (2 1 1), (3 1 0) and (3 0 1) planes of the tetrag­
kGy, 75 kGy and 90 kGy at room temperature with 60 Gy/min dose rate. onal crystal structure of SnO2 according to JCPDS N◦ : 00-088-0287 card.
The diffractogram analyses of the non-irritated and irradiated SnO2
demonstrate that the intensity belonging to (1 1 1) plane had low value
at 60 kGy dose. On the other hand, the full-width half maximum

2
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

Fig. 2. XRD patterns of SnO2 thin films γ-irradiated at different doses.

(FWHM) for the (1 1 1) peak decreases from 0.4 to 0.38 with increasing coefficient values are summarized in Table 1.
gamma doses from 0 kGy to 60 kGy. Subsequently, it increases to attain a To study the effect of gamma radiation on the structural character­
maximum of 0.48 at 75 kGy. Then, it decreases till 0.344 for a gamma istics, the lattice parameters of the synthesized thin films were calcu­
dose of 90 kGy). From this analysis, it may be deduced that the range lated before and after irradiation using the following formula for the
irradiation affected considerably the intensity of the peaks as well as the tetragonal structure [24,25].
width at half height, which influenced the crystallite size of the syn­
1 h2 + k2 l2
thesized thin films. 2
= + 2 (2)
dhkl a2 c
It can be seen that the synthesized films had a preferred orientation
along (1 1 1) plan. To explain the effect of gamma irradiation on the where a and c are the lattice parameters and dhkl is the interplanar
preferred orientation of the crystallites, the texture coefficient (TC) was distance calculated using Bragg equation.
computed in each gamma dose. The values of this parameter was esti­
mated applying the flowing relation [23,24]: 2dhkl sinθ = nλ (3)

I(hkl) where n is the order of diffraction (n = 1) and λ denotes the X-ray

TC(hkl) =
I0(hkl)
(1) wavelength.
∑ I(hkl)
N− 1
I0(hkl)
The lattice parameters are listed in Table 2.
The X-ray diffractograms reveal that the diffraction peaks are rela­
where I0 represents the reference intensity from JCPDS card N◦ : 00- tively broad, suggesting the presence of the structural defects in the
088-0287, I(hkl) is the measured intensity related to the Miller (hkl) synthesized thin film. These structural defects were expressed in terms
indices and N number of the considered peaks. The calculated texture of the average crystallite size D, microstrain ε and dislocation density δ.

Table 1
Table 2
texture coefficient TC (hkl) values for different γ-irradiation doses.
Lattice’s parameters unirradiated and irradiated SnO2 sprayed thin films.
TC (h k l)
a (Å) c (Å)
Sample TC (110) TC (111) TC (211) TC (310) TC (301)
0 kGy 4.722 3.224
0 kGy 0.2 3.84 0.12 0.51 0.3 30 kGy 4.739 3.186
30 kGy 0.29 3.48 0.17 0.64 0.45 45 kGy 4.721 3.181
45 kGy 0.17 4.02 0.09 0.46 0.23 60 kGy 4.737 3.185
60 kGy 0.46 2.51 0.37 0.82 0.79 75 kGy 4.751 3.198
75 kGy 0.55 2.53 0.3 0.86 0.68 90 kGy 4.743 3.192
90 kGy 0.34 3.09 0.27 0.63 0.61 00–088-0287 4.75 3.198

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S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

These parameters were calculated using the following formulas [26,27]: Table 4
⎧ Average values of crystallite size, dislocation density and microstrain of unir­
⎪ kλ radiated and irradiated SnO2 sprayed thin films.
⎪
⎪ D(hkl) = (a)
⎪
⎪ βcosθ
⎪
⎪ samples <D> (nm) <δ> (1014 lines/m2) <ε> (10− 4)
⎪
⎨ β
ε(hkl) = (b) (4) 0 kGy 39,1 12,29 59,9
⎪
⎪ 4tanθ 30 kGy 39,2 11,36 59,3
⎪
⎪
⎪
⎪ 1 45 kGy 39,4 8,57 28,9
⎪
⎩ δ(hkl) = D2
⎪ (c)
60 kGy 46,0 6,68 23,9
(hkl)
75 kGy 25,2 18,04 39,2
where k = 0.90 is the Scherrer constant, λ represents the X-ray 90 kGy 40,1 18,69 30,0

wavelength, θ is the Bragg diffraction angle and β designates the full-

width at the half-maximum (FWHM) of the (1 1 1) peak. parameters was noticed for high gamma doses (between 60 and 90 kGy).
The results of the crystallite size, microstrain, dislocation density and This behavior can be explained by the crystallite rearrangement due to
texture coefficient of the peak (1 1 1) are presented in Table 3. It can be the increase of the temperature under the effect of irradiation [3,17,32].
seen that the dislocation density gradually decreases with the increase of In addition, γ-radiation was highly energetic and, therefore, highly
the gamma irradiation dose in the range (0 kGy- 60 kGy), while the penetrative of matter. Thus, the interaction of gamma radiation with
crystallite size rises with the augmentation of the irradiation dose until SnO2 thin films led to the destruction of bonds and the formation of new
reaching a maximum of 56.4 nm for 60 kGy. Then, it decreases to a ones. Moreover, localized defects were created, particles detached and
minimum of 31.09 nm for 75 kGy and, subsequently, rises to the value of structural damage (Frenkel defects) occurred [13]. This effect resulted
46.48 nm at 90 kGy. The irregular variation of the crystallite size at high in the formation of defects, such as oxygen vacancies, atomic displace­
doses of gamma rays (between 60 and 90 kGy) was due to the increase in ments or changes to crystal structures through the increase or decrease
the local temperature under the effect of irradiation [28,29]. The evo­ of defects [14].
lution of crystallite size as a function of gamma irradiation dose can be
explained by the fact that, for doses between 0 kGy and 60 kGy, there
was coalescence between crystallites, leading to an increase in crystallite 3.2. Morphological properties
size. However, for a dose of 75 kGy, the decrease in crystallite size
resulted from the fact that, when gamma photons interacted with the The change of the morphological properties of SnO2 films after
targeted nanomaterials, the atoms moved and broke the molecules, gamma irradiation was investigated by the scanning electron micro­
leading to the formation of smaller crystallites. Nevertheless, at a dose of scopy images (Fig. 3). The films exhibited a distinctly disrupted surface
90 kGy, the crystallite size further increased due to the fact that high- with different randomly-oriented islets showing a rough surface
dose of γ-irradiation induced the fusion of small crystallites and led to morphology. However, the surface roughness became smoother with the
the defects in the structure of thin films [12,14]. We note the particu­ increase of the irradiation dose. Comparable observations were also
larity of the 75 kGy dose that caused crystallite fragmentation. In fact, obtained by other researchers [17,33]. The radiation generated local
the size of the crystallite was reduced to 2/3 of that of the unirradiated heating resulted in the mobility of the surface atoms. This mobility can
sample. Indeed, according to Tables 2 and 3, the D/c (crystallite size/ be at the origin of the modification of the surface morphology of the
lattice parameter) ratio decreases from 14.5 to 9.75. Beyond this dose, films [33]. Despite the changes in the film morphology, the surface was
crystalite size increases again because of the fusion of the SnO2 meshes. not damaged, which shows that the surface stresses produced by the
To clarify the impact of gamma irradiation on the structural prop­ radiation were not significant.
erties of SnO2 thin films, the average value of the crystallite size < D>,
the microstrain < ε > and the dislocation density < δ > were determined
applying the following system [30,31]: 3.3. Optical properties
⎧ ∑
⎪ TC .D
⎪ < D >= ∑ (hkl) (hkl) (a)
⎪ 3.3.1. Transmission and reflectance spectra
⎪
⎪
⎪
⎪
TC(hkl) The optical properties of the synthetized thin films were studied
⎪
⎪
⎨ ∑
TC(hkl) .ε(hkl) using transmittance and the reflectance spectra at room temperature.
< ε >= ∑ (b) (5) Fig. 4 depicts the optical transmittance and the reflectance spectra of the
⎪
⎪ TC(hkl)
⎪
⎪
⎪ ∑ as-deposited and the irradiated SnO2 films, respectively. It demonstrates
⎪
⎪
⎪
⎪
⎩ < δ >= ∑
TC(hkl) .δ(hkl)
(c) that the optical transmission of all samples varies between 55% and 90%
TC(hkl) and a reflectance lower than 25%, which reflects the transparent char­
acter of the irradiated and non-irradiated thin films. It is also obvious
The calculated values of these parameters are gathered in Table 4. In
that the transmission decreases for 0, 30, 45 and 75 kGy. Furthermore,
fact, the defect in the structure was justified by the increase in the
this parameter increases for the irradiation doses γ of 60 and 90 kGy.
crystallite size and the decrease in the dislocation densities and micro­
This phenomenon was probably due to the change in the lattice
strain. This phenomenon was observed in the gamma irradiation range
parameter as a function of γ-irradiation dose and the increase of the rate
between 0 kGy and 60 kGy. However, an irregular evolution of these
of defaults in the structure.

Table 3 3.3.2. Optical energy gap

crystallite size, microstrain and dislocation density values of the peak (1 1 1) for The absorption coefficient of the synthesized layers was calculated
different irradiation doses. from the optical transmittance using the following relationship [24,34]:
SnO2 D(nm)(111) δ(111) (1014 lines/m2) ε (111) (10− 3) TC (111) [ ]
1 (1 − R)2 + ((1 − R)4 + (2RT)2 )0.5
α = Ln (6)
0 kGy 46.22 4.68 4.7 3.84 d 2T
30 kGy 46.31 4.66 2.56 3.68
45 kGy 46.83 4.55 2.3 4.02 where d is the thickness of the synthesized thin film, T denotes the
60 kGy 56.39 3.14 1.89 2.51 transmission and R corresponds to the reflectance. According to Tauc’s
75 kGy 31.09 10.34 3.43 2.53 law, the relationship between the absorption coefficient and the band
90 kGy 46.48 4.62 2.82 3.09
gap energy is given by [35,36]:

4
S. Chayoukhi et al.
Fig. 3. SEM images of irradiated samples with different doses: Virgin sample, (b) 30 kGy, (c) 45 kGy, (d) 60 kGy, (e) 75 kGy, (f) 90 kGy.
Fig. 4. Transmittance (a) and reflectance (b) spectra of SnO2 thin films at different doses.
( )n
αhv = A hv − Eg (7)
where A is a constant, α refers to the optical absorption coefficient, hν
designates the photon energy, Eg denotes the gap energy and n corre­
sponds to an exponent depending on the type of the transition (n = 1/2
for a direct transition, n = 3/2 for an indirect transition).
The band gap energy values for the different γ-irradiation doses can
be obtained by extrapolating the linear part of the curve of the variation
of (αhv)2 in function of hv (Fig. 5). The obtained values of the gap energy
for the various γ doses are listed in Table 5. It is obvious that the value of
this parameter varies regularly up to 60 kGy (Eg = 3.9 eV), whereas it
varies randomly at higher doses. Thus, the evolution of the gap energy is
in agreement with the structural study. Indeed, the band structure is
generally linked to the crystal potential, which in turn is linked to the
crystal structure and the nature of the atoms making up the elementary
unit. In fact, this band structure is deduced from the solution of the
Schrödinger equation, taking into account the pseudopotential and the
5
Inorganic Chemistry Communications 155 (2023) 111037
symmetry of the crystal. In this work, as shown in Fig. 7a, the gap energy
(Eg) and the lattice parameter c show similar variations as a function of
gamma radiation dose. On the other hand, as gamma radiation has an
effect on crystallinity in terms of TC(111) value Fig. 7b, the gap energy
and texture coefficient have virtually the same correlation as Eg and c.
Finally, the presence of defects has been studied in the structural part in
terms of dislocation and in the optical part in terms of Urbach energy.
Fig. 7c illustrates well this effect.
Furthermore, the absorption coefficient as a function of hv photon
energies was not null for energy values lower than the gap energy, which
explains the presence of the defects in the irradiated SnO2 thin films. The
effect of such defects on the optical properties of these films was
described by the Urbach energy (EU) that depends on the formation of a
band tail in the band gap due to the creation of localized states. The
Urbach energy was used to determine the width of the localized states
applying the following expression [23,37]:
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

dose. It is about 168 meV, for 0 kGy, and 241 meV for 45 kGy. Then, it
decreases and reaches a value of the order of 204 meV for 90 kGy. This
behavior may be due to the variation of the rate of the defects in the
structure of the synthesized thin films according to the irradiation doses.
This result is coherent with the findings obtained in the structural study.

3.3.3. Refractive index and the extinction coefficient

The refractive index and the extinction coefficient are fundamental
optical properties. Indeed, the dispersion of the irradiated and non-
irradiated films was studied using these two parameters. The refrac­
tive index was determined employing the formula written below [29]:
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
(1 + R) 4R
n= + - k2 (10)
(1 − R) (1 − R)2

where R is the optical reflectance, n denotes the refractive index and

k is the extinction coefficient calculated by applying the following
formula:
αλ
Fig. 5. Plot of (αhν)2 vs hν of unirradiated and irradiated SnO2 sprayed k= (11)
thin films. 4π
where α is the absorption coefficient and λ denotes the wavelength.
The refractive index as well as the extinction coefficient is presented
Table 5 in Fig. 8. It can be seen that the refractive index increases slightly with
Values of Eg and EU of unirradiated and irradiated SnO2 sprayed thin films.
the rise of gamma irradiation dose from 0 kGy to 45 kGy. Afterwards,
Sample Eg (eV) EU (meV) this index decreases for 90 kGy of gamma dose in the visible domain. It is
0 kGy 4.012 168 also noted that there is an abnormal dispersion of this parameter for 30
30 kGy 3.952 199 kGy and 90 kGy doses in the wavelength range from 550 nm to 750 nm.
45 kGy 3.93 241 In this range, it is observed that this parameter increases because of the
60 kGy 3.9 218
use a multi-oscillator model [29]. In addition, it is observed that the
75 kGy 3.967 223
90 kGy 3.959 204 extinction coefficient has relatively low values in the visible domain,
which is explained by the low absorption of the thin films in this
( ) wavelength range. The increase of this coefficient in the infrared range
hv indicates the metallic character of the synthesized samples.
α = α0 exp (8)
EU
3.4. Mechanical properties
hv
Ln(α) = Ln(α0 )+ (9)
EU 3.4.1. Microhardness behavior
where α is the absorption coefficient, hν denotes the photon energy, As reported in our previously-published paper [21], the hardness
α0 is a constant and EU represents the Urbach energy. study by nanoindentation method shows the elastoplastic behavior of
Fig. 6 shows the Ln (α) variation versus the photon energy hν. The the tin oxide thin films with a hardness value of 5.9 GPA (601.6 Hv). In
value of the Urbach energy was determined from the inverse of the slope this work, the effect of radiation on the hardness of these films is
of this curve. The obtained values of EU are listed in Table 5. As seen in investigated.
the latter, the Urbach energy increases with the rise in γ-irradiation The Vickers microhardness was measured in two steps: loading for a
few seconds (50 mgf load) and unloading. The permanent indentation
left by the indentation allowed determining the HV hardness using the
following equation [38]:
◦
2.F.sin 1362 F
HV = ≈ 1.854 2 (12)
d2 d
where F is the applied load and d is the diagonal of the footprint.
The measured hardness values for gamma irradiated SnO2 films are
shown in Fig. 9 including the error bars for the standard deviation values
of Vickers hardness. It was noticed that the measured values are lower,
compared to those found by other researches [39–41]. However, they
decrease steadily with the increase of the irradiation dose up to 60 kGy,
whereas they vary randomly for high doses. This variation in hardness as
a function of gamma-ray dose can be explained by the fact that the
moderate doses of gamma radiation led to a rise in the film grain size and
a decrease in the dislocation density and strain, as discussed in the
structural section. It was due to the formation of the nanocrystallite
zones whose size varied with the change in the irradiation dose [5,42].
These results are consistent with those obtained by other research works
[5,16,18].

Fig. 6. Plot of Ln (α) vs hν of unirradiated and irradiated SnO2 thin films.

6
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

Fig. 7. Eg, <D> and <ε> vs gamma irradiation doses.

Fig. 8. Plot of refractive index (a) and Extinction coefficient (b) as a function of wavelength.

7
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

Fig. 9. Microhardness values at different radiation doses.

3.5. Tribological properties

3.5.1. Friction coefficient

To examine the effect of gamma radiation on the friction coefficient
of SnO2 thin films, wear tests were performed on pristine and irradiated
samples. A low load of 1.5 N was used to avoid plastic deformation. The
coefficient of friction is the ratio of the measured frictional force to the
applied normal load. Fig. 10a represents the variation of the friction
coefficients with time for the films before and after irradiation. These
coefficients are stable over time, indicating the homogeneity of the films
along the surface.
The curve of the average friction coefficients versus the radiation
dose is shown in Fig. 10b. It was found that sprayed SnO2 thin films had
lower coefficient of friction compared to other metal oxides [7,19,41].
The measured values increase progressively up to a dose of 60 kGy,
while they vary randomly for high doses. The average friction coefficient
of the unirradiated sample is about 0.06, while it is equal to 0.07, 0.08,
0.09, 0.075 and 0.08 for samples irradiated with 30, 45, 60, 75 and 90
kGy, respectively. Indeed, the evolution of the friction coefficient was
related to the hardness properties of the samples. In fact, it increased Fig. 10. Effect of irradiation on the friction coefficient: evolution as a function
when the hardness decreased and vice versa, as shown above. of time (a) and γ-dose (b).

3.5.2. Wear resistance

In the conducted experiments, the wear tests were performed with
loads varying between 0.5 and 2 N. The wear resistance of films was
evaluated by studying the evolution of the following three parameters:
the wear volume, the energy dissipated by friction and the wear rate.
The film wear volume was determined by measuring the surface
profile on the wear track. Fig. 11 displays the variation of this parameter
as a function of gamma radiation dose under different normal loads. The
energy dissipated during a scratch test was produced by the tangential
forces. It was determined by the following equation [43]:
∑
E = v.t Ft (13)

where v, t and Ft are the sliding speed, time and tangential force,
respectively.
The evolution of the energy dissipated by friction with the radiation
dose and normal load is shown in Fig. 12. The curves representing the
variation of the wear volume versus the dissipated energy are linear for
all samples (Fig. 13). The associated slopes are the wear rates whose
values are given in Table 6. They represent the ability of the surfaces to
resist frictional wear [44].
The Figs. 11, 12 and 13 show that the wear volume, the dissipated Fig. 11. Wear volume as a function of radiation doses at various normal loads.
energy and the wear rates increase with gamma irradiation up to a dose

8
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

the scratch test, the normal load increased progressively from 0.03 N to
7 N, the load speed was fixed at 16 N/min and the scratching length was
equal to 3 mm.
Critical charges (LC) were identified by combining SEM image of the
scratch track and the graph of the friction force versus normal load
(Figs. 14 and 15). The LC1 load corresponds to an initial part of the
plastic deformation and the appearance of the first cracks on the surface.
However, LC2 is the highest critical load that represents the first failure
symptoms of the adhesive. On the other hand, LC3 was taken into ac­
count when the deterioration of the film was more than 50% [45].
During the scratch test, spalling increased with normal loading along the
scratch track. When the interfacial shear stresses accumulated and suf­
ficiently exceeded the bond forces, the delamination of the film occurred
[44]. The adhesion strength was determined by the following equation
[45]:
( )[ ]
2LC (4 + ν)3πμ
σc = − (1 − 2ν) (14)
π wc
2 8

where σc, LC, wc, μ and ν are the adhesion strength, critical spalling
load, critical scratch width, coefficient of friction and Poisson’s ratio,
Fig. 12. Dissipated energy as a function of radiation doses at various
respectively.
normal loads.
The critical loads (LC1, LC2 and LC3) and adhesion strength obtained
before and after irradiation at a dose of 90 kGy are shown in Table 7. The
latter reveals that irradiation decreases the critical loads and adhesion
strength. As a result, it may be deduced that: i) the irradiated thin film
had higher scratch damage than the pristine film, and ii). Irradiation
reduced the adhesion or scratch-resistance properties of SnO2 thin films.
However, despite this reduction, these films still adhered better to the
substrate than other metal oxides [7,19,41].

4. Conclusion

In this study, SnO2 thin films were prepared, by the spray pyrolysis
technique, on an ordinary glass substrate preheated at 450 ◦ C before
being irradiated with 60Co gamma rays at different irradiation doses.
The effect of irradiation on the physical properties of the films was also
examined. The structural analysis and the morphological observations
showed that, with rising the irradiation dose up to 60 kGy, grain size
increased while dislocation density decreased. These results are

Fig. 13. Variation of the wear volume as a function of dissipated energy at

different radiation doses.

Table 6
Wear rates and associated correlation parameter (R2) values for SnO2 thin films
before and after irradiation.
Gamma dose (kGy) 00 30 45 60 75 90

wear rate (μm3/J) 2.0 2.5 2.6 3.8 2.7 3.3

Correlation parameter: R2 0.99 0.99 0.99 0.99 0.98 0.99

of 60 kGy, regardless of the normal applied load levels. However, for

high doses (between 60 and 90 kGy), an irregular evolution of these
parameters is observed. These results reveal that irradiation degraded
the wear performance of SnO2 thin films because of the changes in the
crystal structure of the films after gamma irradiation due to local
heating.

3.5.3. Adhesion behavior

To investigate the effect of gamma radiation on the adhesion
behavior of SnO2 thin films, a scratch test was performed on two sam­
Fig. 14. Scratch measurements under progressive loading and SEM observa­
ples, one virgin and the other irradiated with a dose of 90 kGy. During tions of pristine SnO2 thin film (a): LC1, (b): LC2, (c): LC3.

9
S. Chayoukhi et al. Inorganic Chemistry Communications 155 (2023) 111037

References

Fig. 15. Scratch measurements under progressive loading and SEM observa­
tions of a sample irradiated at 90 kGy (a): LC1, (b): LC2, (c): LC3.
Table 7
Critical loads and adhesion strength of the SnO2 thin films before and after
irradiation.
SnO2 thin film LC1 (N) LC2 (N) LC3 (N) σC (MPa)
Pristine 1.1 3.35 5.55 20
Irradiated (90 kGy) 0.92 2.0 4.31 19
consistent with those related to the mechanical findings which showed
degradation in terms of hardness, friction, wear resistance and adhesion
behavior. The optical study demonstrated that the gap energy was
minimal at the dose of 60 kGy while the Urbach energy increased with
the rise of the γ-irradiation dose. Nevertheless, an improvement in the
surface roughness was observed. It became smoother with the increase
of the irradiation dose. It was also revealed that the characteristic pa­
rameters of the structure, morphology, optical and mechanical proper­
ties evolved with the rise of the irradiation dose. It was also obvious that,
despite the reduction in the mechanical properties of SnO2 thin films
when irradiated with gamma rays, these films exhibited good adhesion
to the substrate with lower coefficient of friction and more satisfactory
hardness, compared to those of other metal oxides.
CRediT authorship contribution statement
S. Chayoukhi: Conceptualization, Writing – original draft. B. Gas­
soumi: Formal analysis. H. Dhiflaoui: Data curation. A. Mejri: Inves­
tigation. A. Boukhachem: Methodology, Validation. M. Amlouk:
Supervision.
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.
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