Physica B 625 (2022) 413535

Contents lists available at ScienceDirect

Physica B: Physics of Condensed Matter

journal homepage: www.elsevier.com/locate/physb

Fabrication and characterization of ZnO/Zn2TiO4/ZnAl2O4 composite films

by using magnetron sputtering with ceramic targets
J.C.A. Queiroz a, M. Naeem b, *, I.A. Sousa a, M.S. Liborio c, E.J.C. Santos d, R.R.M. Sousa e, I.
O. Nascimento a, M.C. Feitor f, T.H.C. Costa a, Javed Iqbal g, h
a
Mechanical Engineering Department, Federal University of Rio Grande do Norte, University Campus, Natal, Brazil
b
Department of Physics, Women University of Azad Jammu and Kashmir, Bagh, Pakistan
c
School of Science and Technology, Federal University of Rio Grande do Norte, University Campus, Natal, RN, Brazil
d
Federal Institute of Technological Education of Rio Grande do Norte, Currais Novos, Brazil
e
Materials Engineering Department, Federal University of Piauí, Campus Minister Reis Velloso, Teresina, PI, Brazil
f
Textile Engineering Department, Federal University of Rio Grande do Norte, University Campus, Natal, RN, Brazil
g
Department of Physics, University of Azad Jammu and Kashmir, Muzaffarabad, Pakistan
h
University of Latvia, Raina bulvaris 19, Riga LV, 1586, Latvia

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

Keywords: Transparent conducting oxides (TCO), including ZnO/Zn2TiO4/ZnAl2O4 composite films, are of considerable
Magnetron sputtering importance in optoelectronic applications. We fabricated composite film assisted with DC magnetron sputtering
Ceramic targets using ceramic target material (ZnO, TiO2, and Al2O3 powders mixture). The influence of processing gases
Transparent conducting oxides
composition (0–50% O2–Ar) on film characteristics, including structural, optical, and electronic properties, is
Bandgap
Optoelectronic properties
assessed. All films contain hexagonal wurtzite ZnO structure and ZnAl2O4, Zn2TiO4 spinel phases, with (002),
(100), and (101) as dominant orientation by increasing oxygen contents. The transmittance of deposited films is
above 81% (except for 50% oxygen), and the bandgap lies between 3.73 and 3.28 eV (reduced by oxygen
addition). The carrier concentration and mobility increase with oxygen addition up to 25%, and resistivity de­
creases by increasing oxygen contents. This study shows that using ceramic targets, the compound film with
variable composition, structural and optoelectronic properties can be obtained by altering the gases admixture.

1. Introduction
The transparent conducting oxide (TCO) thin films are widely used in
several optoelectronic devices, including solar cells, photodetectors,
liquid crystal displays, sensors, active-matrix organic light-emitting di­
odes, and photo-electrochemical water splitting [1]. It is due to their
outstanding electrical and optical properties. Indium tin oxide (ITO) is
one of the extensively used TCO for industrial applications. However,
ITO is not environmentally friendly, expensive and demands alternate
choices to fulfill industrial needs. For this purpose, zinc oxide (ZnO) is an
active choice in TCO films because of its high-temperature stability, low
cost, and eco-friendly due to its non-toxic nature [2]. However, such
films show low electrical conductivity, and thus their practical usage is
quite limited [3].
It is reported that the issue of low electrical conductivity of ZnO films
can be resolved by the addition of numerous impurities such as IIIA
group elements [4,5]. The aluminum-doped ZnO (AZO) films are
extensively reported because aluminum doping can considerably
enhance ZnO film’s electrical conductivity [6]. Furthermore, titanium
doping is also helpful in increasing the electrical properties of ZnO films.
The titanium-based nanocomposites are widely used due to their
promising electrical and antibacterial properties [7–10]. However, the
amount of titanium doping demands optimization. When titanium
doping is higher, it can work as a scattering center and decrease elec­
trical conductivity [11,12]. Thus, to avoid excessive titanium doping,
aluminum and titanium co-doping is used to improve electrical
conductivity.
The deposition of individual ZnO films, aluminum-doped, titanium-
doped, and aluminum-titanium codoped (ATZO) films, can be synthe­
sized by various techniques, with several advantages and disadvantages
in each technique. The synthesis techniques includes chemical vapor
deposition [13], pulsed laser deposition [14], sol-gel method [15],

* Corresponding author.
E-mail addresses: mnaeem@wuajk.edu.pk, naeem.plasma@gmail.com (M. Naeem).

https://doi.org/10.1016/j.physb.2021.413535
Received 5 June 2021; Received in revised form 27 September 2021; Accepted 4 November 2021
Available online 8 November 2021
0921-4526/© 2021 Elsevier B.V. All rights reserved.
J.C.A. Queiroz et al.
Table 1
Samples identification and processing conditions used for films deposition.
Samples labeling Gases mixture (Total flow 20 sccm)
Oxygen (%) Argon (%)
A 0 100
B 15 85
C 25 75
D 50 50
Fig. 1. XRD pattern of magnetron sputtered films deposited samples under various treatment conditions.
atomic layer deposition [16], electrochemical deposition [17], electron
beam evaporation [18] and magnetron sputtering [19,20]. Among
these, chemical vapor deposition, electrochemical deposition, and
sol-gel methods involve various chemicals like zinc acetylacetonate
hydrate and zinc acetate dehydrate, which are hazardous to the envi­
ronment [21–23]. The pulsed laser deposition technique is mainly based
on lasers, which are relatively expensive [24]. The ultimate choice is
sputtering systems, either arc or magnetron sputtering, which can be
used effectively for homogeneous film deposition with dense structure,
and it shows large area deposition [25]. Magnetron sputtering is widely
reported for the deposition of ZnO, AZO, and TZO films by using the
metallic targets of the desired material [26,27]. The deposition of ZnO
film is easily achievable by Zn target and oxygen gas (or oxygen with
Physica B: Physics of Condensed Matter 625 (2022) 413535
Power (W) Pressure (mbar) Time (h) Temperature (oC)
138 0.3 0.5 90
inert gas). However, when doped films are required, sputtering with two
targets is necessary (i.e., co-sputtering) [25]. Unfortunately, the films
obtained by co-sputtering are not homogeneous and exhibit poor elec­
trical properties [25]. On the other hand, it is possible to use segmented
or compound (Zn with doping elements) targets. However, such metallic
targets are quite expensive, and thus the processing cost will be very
high [28]. Furthermore, the doping concentration is fixed (for each
concentration, a separate target is required). Thus this necessary
parameter for the tuning of optoelectronic properties cannot be moni­
tored. It is expected that if laboratory-manufactured ceramic targets
using the powders of desired materials are used, the processing cost and
films composition can be controlled, and multiple doped films can be
obtained.
2
J.C.A. Queiroz et al.
Fig. 2. (a) Rietveld refinement of XRD pattern of sample C, (b) crystallite size of films at various condition.
Besides the AZO and ATZO films, zinc aluminate spinel (ZnAl2O4)
films are of significant interest in several applications [29]. These ma­
terials are widely used in several catalytic reactions, including dehy­
dration, cracking, hydrogenation, and dehydrogenation reaction [30,
31]. Zinc titanate metal oxides (Zn2TiO4) are of significant interest in gas
sensors [32], microwave resonators [33], dielectric [33], catalyst in
liquid phase transformation [34], semiconductor material [35], oxida­
tion of hydrocarbons [36] and as photocatalytic material [37]. Due to
the excellent properties of Zn2TiO4 and ZnAl2O4, several methods have
been used to synthesize such films, including sol-gel [38], solid-state
reaction [39], sputtering [40], a molten salt method [41], and micro­
wave heating [42]. Qin et al. [43] reported ZnO–Zn2TiO4 composite
films’ synthesis by sol-gel process and examined its photocatalytic ac­
tivities. They found that improvement in photocatalytic efficiency by
changing the amount of Zn2TiO4 in composite film. Iaiche et al. [44]
synthesized ZnO– ZnAl2O4 nanocomposite films by ultrasonic spray
pyrolysis and subsequent heat treatment. They confirmed deposited
films’ structure by various techniques, including XRD, XPS, and FTIR
3
Physica B: Physics of Condensed Matter 625 (2022) 413535
spectroscopy. Hou et al. [29] reported the deposition of AZO and
ZnAl2O4 films by atomic layer deposition. They observed that by
annealing these composite films, pure ZnAl2O4 films can be synthesized.
Yue et al. [45] synthesized ZnO–ZnAl2O4 film by squeeze casting
method and investigated the effect of heat treatment on microstructure
and tensile properties. Fan et al. [46] reported the zinc aluminate films
using facile and effective in situ crystallization method, and film was
found to be adherent with aluminum substrate and effective for corro­
sion resistance. Bi et al. [47] synthesized zinc-aluminate spinel film on
aluminum-oxide substrate using pulsed laser deposition system, and
investigated the effect of growth temperature on structural properties.
To the best of authors information as provided in above literature, the
deposition of composite film (ZnO– ZnAl2O4–Zn2TiO4) is not reported so
far, and it is necessary to investigate electrical conductivity and optical
properties of this composite film. Additionally, here instead of conven­
tional metallic targets in magnetron sputtering system, the ceramic
targets are used, which can be manufactured in laboratory in any
dimension and any composition.
J.C.A. Queiroz et al.
Fig. 3. Surface morphology of films deposited samples under various conditions.
Fig. 4. Elemental composition obtained by EDS analysis of films deposited samples under various conditions.
Recently we reported that AZO films could be deposited on the glass
substrate using DC magnetron sputtering equipped with ceramic targets
(by admixing ZnO and Al2O3 powders) and obtained excellent electrical
and optical properties [6]. In this article, we used a mixture of ZnO,
Al2O3, and TiO2 powders to prepare the desired composition targets to
deposit ZnO/Zn2TiO4/ZnAl2O4 composite films on a glass substrate.
Such targets are expected to be of low cost, and the doping amount can
be controlled easily, and thus the films with required doping can be
deposited. The effect of gases admixture (argon-oxygen) on the film’s
quality, film composition, and structural, optical, and electrical prop­
erties are also explored. The effect of argon gas concentration is inves­
tigated here because it mainly contributes to the sputtering of targets. As
a result, the film composition and rate of film deposition can be changed.
Also, argon gas contributes to the dissociation of molecular gases (such
as oxygen). We predict that by changing the gases admixture, the film’s
properties can be modified by changing the atomic oxygen species in the
processing environment.
4
Physica B: Physics of Condensed Matter 625 (2022) 413535
2. Experimental details
Thin films are deposited on a glass substrate (SiO2), in dimension 5 ×
2 cm2, and a thickness of 0.2 cm. Initially, glass substrates were cleaned
with detergent water, washed with running water, cleaned in an ultra­
sonic bath with acetone for 20 min, and dried in air. The sputtering
targets were prepared by admixing zinc oxide (ZnO-ISOFAR with 99.9%
purity), Al2O3, and TiO2 (Aldrich- 98.9% purity) powders. This mixture
of powders was taken to keep 4% aluminum and 2.5% titanium doping
in ZnO. They were mixed using a planetary mill (PUVERISSETE 7),
equipped with a crucible and ball of metal duct, and subsequently
sieved. They were sintered for 2 h, with a temperature of 1300 ◦ C, and
compacted with a 15-ton applied load, such that the final target has 2.5
mm thickness and 60 mm diameter. These targets were installed in DC
magnetron sputtering system, as described elsewhere [48,49]. The
magnetron sputtering system was a cylindrical borosilicate chamber of
40 mm height and 300 mm diameter. The ceramic targets were placed
above the sample holder at 7 cm distance, connected with the upper
flange of the chamber. The targets were pre-sputtered for 5 min using
J.C.A. Queiroz et al.
Fig. 5. Cross-sectional SEM images of films deposited samples under various conditions.
argon gas to remove the surface impurities. The film deposition was
carried out with different argon-oxygen mixtures, and the remaining
parameters were kept fixed, as shown in Table 1.
The phase structure of films was obtained by using X-ray diffraction
(Shimadzu model XRD-6000). It was operated by Cu-Kα radiation
source, the voltage of 40 kV, current 30 mA, and grazing incidence X-ray
diffraction (GIXRD) angle of 0.5◦ . The Debye-Scherrer formula was used
to measure the crystalline size and the Rietveld refinement method to
differentiate the diffraction peaks. The surface morphology and cross-
sectional morphology were observed by scanning electron microscopy
(models Zeiss Auriga 40). Surface topography was examined by atomic
force microscopy (Shimadzu, model SPM 9700). The optical trans­
mittance spectra of films were obtained using a spectrometer (Thermo
fisher scientific, model GENESYS 10S UV–vis). A four-probe method was
used for the measurement of electrical properties. The four probes were
operated by direct current source (0–1 A, 0–50 V), and resistivity was
measured using a current of 0.1 mA.
3. Results and discussion
The XRD pattern of films deposited by magnetron sputtering under
various gases composition is depicted in Fig. 1. The phases are identified
as hexagonal wurtzite ZnO structure (ICSD-067848), along with zinc
titanate Zn2TiO4 (ICSD-080850) and zinc aluminate ZnAl2O4 (ICSD-
026856) spinel phases. The phases present in the film are analogous, but
their intensities are dramatically changed with the change in processing
gases. The film deposited without oxygen gas (sample A) depicts that
peaks are less intense and broad, which indicates that deposited films
exhibit poor crystalline quality [50]. When oxygen contents are added
(sample B-D), the intensities of the ZnO peak (002) are increasing
(25-45◦ ), which indicates the growth of ZnO film along with the c-axis
orientation [51]. However, besides (002) orientation, two more
5
Physica B: Physics of Condensed Matter 625 (2022) 413535
additional dominant peaks (100) and (101) are appearing. As reported
in the literature, the existence of only (002) dominant peaks of ZnO
indicates the nanorods-like morphology [52]. In contrast, the existence
of prominent peaks along (100) and (101) are due to the formation of
ZnO nanoparticles, as reported [53]. Thus, the co-existence of (002) and
(100), (101) peaks collectively suggest the presence of nanorods ori­
ented along the c-axis and decorated with nanoparticles [51]. The
ZnAl2O4 spinel phase’s reaction enthalpy is 0.83 eV; thus, this spinel
phase’s formation is thermodynamically possible due to chemical re­
action in sintering of target material [54]. Also, due to ZnO and TiO2, the
formation of zinc orthotitanate is easily possible [55]. To clearly show
the merged XRD peaks, Rietveld’s refinement of sample C is shown in
Fig. 2a. The crystallite size of films deposited under various conditions is
shown in Fig. 2b. It shows that the crystallite size increases by adding the
oxygen contents in argon gas. It depicts that when films are deposited by
argon gas or argon with low oxygen contents, the films have more
crystallographic faults, and the film’s long-range arrangement is
decreased [56,57]. When a higher amount of oxygen is added, the vol­
ume fraction of crystallized phases increases, which improves crystal­
linity [57]. This can be credited to the change in the film deposition rate
by altering the processing gases environment. As the oxygen is highly
electronegative with more affinity with electrons, oxygen in the cham­
ber reduces the plasma density. Furthermore, positive argon ions are
reduced (due to a smaller amount of argon in gases admixture), and the
processing environment contains higher negative oxygen ions [56].
Also, the glow discharge is weakened due to the higher ionization
threshold of oxygen gas, reducing the film deposition rate. Due to a
decrease in sputtering rate from the target material, the sputtered ions
have adequate time to be arranged regularly on the sample surface.
Thus, the film is more crystalline and has fewer defects [58]. Besides this
constructive impact of oxygen addition, it is still probable that higher
amount of oxygen might form non-conducting clusters (e.g. Al2O3
J.C.A. Queiroz et al. Physica B: Physics of Condensed Matter 625 (2022) 413535

Fig. 6. AFM surface topography of films deposited samples under various conditions.

6
J.C.A. Queiroz et al.
Fig. 7. Surface roughness of films deposited samples under various conditions.
Fig. 8. Transmission as a function of wavelength of films deposited samples
under various conditions.
because of higher affinity between oxygen and aluminum). These clus­
ters can cause a crystalline disorder in the films, and thus instead of
electron donor they will acts as carrier traps [58], which can deteriorate
the electrical properties of film. The film deposited here under all con­
dition shows that no such non-conducting clusters are formed (no such
phases present in XRD), and thus this probability can be rule out.
The surface morphology of film deposited under various conditions is
depicted in Fig. 3. The film deposited using argon gas (sample A) shows
that surface is covered with irregular shape non-uniform distribution of
particles. The surface comprises large-size irregular shape particles/rods
and is decorated with nano-sized particles, as predicted in XRD analysis
[51]. There are several voids between particles, and particle boundaries
are not noticeably visible and are blurred. The sample treated with a
small amount of oxygen admixing (sample B) also displays similar
morphology. On the other hand, when a higher amount of oxygen is
added (sample C, D), the surface contains spherical particles with uni­
form distribution and is closely spaced. Voids between particles are not
apparent. EDS analysis is carried out to quantify elemental composition,
and an average composition obtained by repeating spectra several times
is reported in Fig. 4. As predicted, when a higher amount of oxygen is
7
Physica B: Physics of Condensed Matter 625 (2022) 413535
Fig. 9. Average transmittance of films deposited samples under
various conditions.
added to the chamber, the deposited films’ composition also contains a
higher amount of oxygen. In contrast, the material sputtered from
ceramic targets (i.e., Ti, Al, Zn) is reduced. The composition of the film
and the XRD phase’s are in well-agreement. The cross-sectional SEM
images are shown in Fig. 5. It shows that film thickness is reduced from
354 to 163 nm when oxygen concentration is increased. It can be
justified by decreasing the target’s sputtering at a higher amount of
oxygen, as described above.
The surface topography of films deposited under various conditions
is shown in Fig. 6. It reveals that films deposited by argon gas (sample A)
or with low oxygen contents (sample B) have the inhomogeneous dis­
tribution of particles, and the surface is quite rougher. When a higher
amount of oxygen is added (sample C, D), the particles show a
comparatively homogeneous distribution of particles, and the surface is
reasonably smoother. The resultant surface roughness of various films is
plotted in Fig. 7. It reveals that surface roughness is expressively
decreased when films are deposited with higher oxygen contents. It can
be attributed to the slow growth of films, and particles are distributed in
the periodic arrangement, and a dense structure is formed.
A UV–visible spectrometer is used to compare films’ optical prop­
erties, and transmittance curves are plotted in Fig. 8. The transmission
spectra illustrate the presence of interference fringes. These fringes
endorse that deposited films have outstanding film quality and homo­
geneity, specifically for samples B-D [59]. It indicates that reflections
occur from the film, and no major scattering or absorption occurs from
the film’s bulk region [59]. The average value of transmittance in the
wavelength range 400–900 nm and 420–900 nm is plotted in Fig. 9. This
range is adopted below the infrared region’s edge; the optical trans­
mittance is reduced due to deposited films’ metallic behavior [6]. The
average transmittance of films is greater than 81%, except for the sample
treated using 50% oxygen gas (sample D).
The optical absorption coefficient can be correlated with the
bandgap of the film as follows:
( )n
α(hv) = A hv − Eg
Here n = 12 for direct bandgap semiconductor. To find the optical
bandgap, the graph between (αhv)2 and hv with linear fitting is shown in
Fig. 10. The bandgap’s corresponding value is also shown in Fig. 10,
which shows a decrease in the bandgap with oxygen. This variation in
bandgap energy with oxygen addition can be ascribed to stresses in films
and quantum confinement theory [58].
J.C.A. Queiroz et al.
Fig. 10. Variation of (αhv)2 with photon energy along with the corresponding
bandgap of films deposited samples under various conditions.
π2 ℏ2 1.786 e2
Eg = Ego + − − 0.248 Er
2μR2 εR
Here, Ego represents intrinsic bandgap energy of ZnO at room tem­
perature, ε represents dielectric constant, R is the grain size and Er is
effective Rydberg energy. In the above equation, the second term stands
for blue shift caused by quantum confinement effect due to crystal grain
size, and the third term stands for redshift caused by Columbic inter­
action among electrons and holes. The intrinsic ZnO bandgap is 3.37 eV,
and here deposited film shows a bandgap of 3.73, 3.52, and 3.27, and
3.28 eV for samples A-D, respectively. It clearly shows that a blue shift
occurs for samples A and B, while a redshift for samples C, D. The in­
crease in the bandgap of the film deposited using low oxygen contents
can be ascribed to the quantum size effect [58]. As the bandgap in­
creases when the film’s crystallite size decreases, the bandgap of these
films (small crystallite size, Fig. 2b) is mainly due to the quantum size
effect [58]. However, when the film is deposited using a higher amount
of oxygen, a redshift in the bandgap is observed. The bandgap decreases
with an increase in tensile stresses, whereas the increase with
compressive stresses [60,61]. When the film is deposited with higher
oxygen contents (samples C, D), a higher amount of O2− ions remain on
8
Physica B: Physics of Condensed Matter 625 (2022) 413535
the grain boundaries, which causes tensile stresses in film. Thus, the
redshift in the bandgap at higher oxygen contents can be ascribed to
tensile stresses in the film [58].
The variation of electrical properties of deposited films under various
conditions is depicted in Fig. 11. It shows that film carrier concentration
and mobility increase with oxygen addition up to 25% (sample A to C)
and decreases for sample D. The film’s resistivity reduces with an in­
crease in oxygen contents in gases admixture. The increase in carrier
concentration and mobility with oxygen addition up to 25% can be
ascribed to the generation of adequate oxygen vacancies and improved
film crystallinity [62–64]. When the oxygen contents are increased in
gas mixture, argon contents are decreased; thus, the film growth rate is
reduced (due to a decrease in argon sputtering yield). As a result, enough
time is available for Zn2+ and O2− ions to deposit on samples surface is
an ordered arrangement. Thus, film is crystalline and has fewer defects
[65]. Also, these factors are responsible for decreasing in resistivity of
deposited films [62,63]. Besides the increase in carrier concentration
and mobility with oxygen addition, these parameters are decreased
beyond a certain amount (sample D, 50% oxygen added). It can be
ascribed to a decrease in the film’s thickness, inducing defects in the film
because of increased stresses. Several electrons are probably scattered
by these defects and stuck due to traps produced by these defects; thus,
carrier concentration and mobility are reduced [66,67]. In a previous
report [68], we observed that ZnO/Zn2TiO4/ZnAl2O4 composite films
could be synthesized by hollow-cathode glow discharge. Here, we
observed effective deposition of such composite film by magnetron
sputtering system, which can deposit films uniformly on large scale
samples and the large number of samples, which can be processed
simultaneously.
4. Conclusions and final remarks
In this study, ZnO/Zn2TiO4/ZnAl2O4 composite films are synthesized
assisted with DC magnetron sputtering system. The outcomes of this
work are as follows:
1. As ceramic targets are used to deposit films, specifically designed
metallic targets are not compulsory for film deposition. The film
composition and structural properties of films can be tuned by
changing gases admixture, and thus it is not required to use separate
targets to change the film composition.
2. All deposited films show the hexagonal wurtzite ZnO structure along
with ZnAl2O4 and Zn2TiO4 spinel phases. Besides commonly re­
ported (002) orientation, two more additional dominant peaks (100)
and (101) are observed by increasing oxygen contents. The film’s
crystallinity increases with an increase in oxygen contents due to the
film’s slow growth.
3. The optical transmittance of films is higher than 81%, except for film
deposited using 50% oxygen addition, and bandgap decreases
(3.73–3.28 eV) with an increase in oxygen contents.
4. The carrier concentration and mobility of film increase to 25% ox­
ygen addition, while the film’s resistivity decreases with oxygen
addition.
Our finding shows that film crystallinity, electrical and optical
properties are dependent on the processing gases composition. Good
quality of the film is attained using a mixture of 25% oxygen. The
ceramic targets are low-cost, gases can alter the film’s composition, and
no chemicals are involved (such as conventional chemical routes). Thus,
it can be used effectively for ZnO/Zn2TiO4/ZnAl2O4 composite film
synthesis.
Credit author statement
JCA Queiroz: Investigation, Formal analysis, Methodology, Writing -
review & editing. M. Naeem: Writing - original draft, Investigation,
J.C.A. Queiroz et al. Physica B: Physics of Condensed Matter 625 (2022) 413535

Fig. 11. Variation of electrical properties of films deposited samples under various conditions.

9
J.C.A. Queiroz et al. Physica B: Physics of Condensed Matter 625 (2022) 413535

Formal analysis. I. A. Sousa: Resources, Formal analysis. MS Liborio: [19] E. Sener, O. Bayram, U.C. Hasar, O. Simsek, Structural and optical properties of RF
sputtered ZnO thin films: annealing effect, Phys. B Condens. Matter 605 (2021)
Resources, Formal analysis. EJC Santos: Resources, Formal analysis.
412421.
RRM Sousa: Methodology, Conceptualization. IO Nascimento: Re­ [20] C. Bairam, Y. Yalçın, H.İ. Efkere, E. Çokduygulular, Ç. Çetinkaya, B. Kınacı,
sources, Formal analysis. MC Feitor: Resources, Formal analysis. THC S. Özçelik, Structural, morphological, optical and electrical properties of the Ti
Costa: Methodology, Conceptualization. Javed Iqbal: Writing - review & doped-ZnO (TZO) thin film prepared by RF sputter technique, Phys. B Condens.
Matter (2021) 413126.
editing. [21] A. Davoodi, M. Tajally, O. Mirzaee, A. Eshaghi, The effects of Ti concentration on
the structure, optical, and electrical properties of Al and Ti co-doped ZnO thin
films, Optik 127 (2016) 4645–4649.
[22] K.D.A. Kumar, S. Valanarasu, V. Ganesh, M. Shkir, S. AlFaify, H. Algarni, Effect of
Declaration of competing interest potential voltages on key functional properties of transparent AZO thin films
prepared by electrochemical deposition method for optoelectronic applications,
J. Mater. Res. 33 (2018) 1523.
The authors declare that they have no conflicts of interest.
[23] Z.a.d.R.O. National Center for Biotechnology Information, PubChem Compound
Summary for CID 2724192, 2020, p. 2020, from, https://pubchem.ncbi.nlm.nih.go
Acknowledgements v/compound/Zinc-acetate-dihydrate.
[24] J. Orava, T. Kohoutek, T. Wagner, Deposition techniques for chalcogenide thin
films, in: J.-L. Adam, X. Zhang (Eds.), Chalcogenide Glasses, Woodhead Publishing,
This study was financed in part by the “Coordenação de Aperfei­ 2014, pp. 265–309.
çoamento de Pessoal de Nível Superior (CAPES), Brazil” Finance Code [25] L.-H. Wong, Y.-S. Lai, Characterization of Boron-Doped ZnO Thin Films Prepared
by Magnetron Sputtering with (100− x) ZnO–xB2O3 ceramic targets, Thin Solid
001. Dr Javed Iqbal is thankful to European Regional Development Fund Films 583 (2015) 205–211.
(Project No.1.1.1.5/19/A/003) for the development of quantum optics [26] P. Novák, T. Kozák, P. Šutta, M. Kolega, O. Bláhová, Influence of oxygen on the
and photonics at the university of Latvia. resistivity of Co-sputtered transparent AZO films, Phys. Status Solidi 215 (2018)
1700951.
[27] P. Novák, Possibilities of increasing the usability of sputtered AZO films as a
References transparent electrode, Phys. Status Solidi 216 (2019) 1800814.
[28] Y. Zhou, P.J. Kelly, A. Postill, O. Abu-Zeid, A.A. Alnajjar, The characteristics of
aluminium-doped zinc oxide films prepared by pulsed magnetron sputtering from
[1] T. Hitosugi, N. Yamada, S. Nakao, Y. Hirose, T. Hasegawa, Properties of TiO2-based
powder targets, Thin Solid Films 447 (2004) 33–39.
transparent conducting oxides, Phys. Status Solidi 207 (2010) 1529–1537.
[29] Q. Hou, F. Meng, J. Sun, Electrical and optical properties of Al-doped ZnO and ZnAl
[2] A.M. Hezma, A. Rajeh, M.A. Mannaa, An insight into the effect of zinc oxide
2 O 4 films prepared by atomic layer deposition, Nanoscale research letters 8
nanoparticles on the structural, thermal, mechanical properties and antimicrobial
(2013) 1–8.
activity of Cs/PVA composite, Colloid. Surface. Physicochem. Eng. Aspect. 581
[30] T. El-Nabarawy, A.A. Attia, M.N. Alaya, Effect of thermal treatment on the
(2019), 123821.
structural, textural and catalytic properties of the ZnO-Al2O3 system, Mater. Lett.
[3] K.U. Sim, S.W. Shin, A.V. Moholkar, J.H. Yun, J.H. Moon, J.H. Kim, Effects of
24 (1995) 319–325.
dopant (Al, Ga, and In) on the characteristics of ZnO thin films prepared by RF
[31] J. Wrzyszcz, M. Zawadzki, J. Trawczyński, H. Grabowska, W. Miśta, Some catalytic
magnetron sputtering system, Curr. Appl. Phys. 10 (2010) S463–S467.
properties of hydrothermally synthesised zinc aluminate spinel, Appl. Catal. Gen.
[4] Y. Al-Douri, A.H. Reshak, W.K. Ahmed, A.J. Ghazai, Structural and optical
210 (2001) 263–269.
investigations of in doped ZnO binary compound, Materials Express 4 (2014)
[32] B.C. Yadav, A. Yadav, S. Singh, K. Singh, Nanocrystalline zinc titanate synthesized
159–164.
via physicochemical route and its application as liquefied petroleum gas sensor,
[5] A. Rajeh, H.M. Ragab, M.M. Abutalib, Co doped ZnO reinforced PEMA/PMMA
Sens. Actuators, B 177 (2013) 605–611.
composite: structural, thermal, dielectric and electrical properties for
[33] S.P. Wu, J.H. Luo, S.X. Cao, Microwave dielectric properties of B2O3-doped
electrochemical applications, J. Mol. Struct. 1217 (2020) 128447.
ZnTiO3 ceramics made with sol–gel technique, J. Alloys Compd. 502 (2010)
[6] J.C.A.d. Queiroz, J.B.d.A. Filho, M.C. Feitor, M.S. Libório, E.J.d.C. Santos, U.
147–152.
B. Souto, R.R.M. de Sousa, T.H.d.C. Costa, Structural and optical properties of ZnO:
[34] N. Pal, M. Paul, A. Bhaumik, New mesoporous perovskite ZnTiO3 and its excellent
Al thin films produced by magnetron sputtering with different oxygen flow: an
catalytic activity in liquid phase organic transformations, Appl. Catal. Gen. 393
experimental and ab initio study, Phys. Status Solidi 217 (2020) 2000167.
(2011) 153–160.
[7] M.M. Abutalib, A. Rajeh, Influence of MWCNTs/Li-doped TiO2 nanoparticles on
[35] N. Wang, X. Li, Y. Wang, Y. Hou, X. Zou, G. Chen, Synthesis of ZnO/TiO2 nanotube
the structural, thermal, electrical and mechanical properties of poly (ethylene
composite film by a two-step route, Mater. Lett. 62 (2008) 3691–3693.
oxide)/poly (methylmethacrylate) composite, J. Organomet. Chem. 918 (2020)
[36] H. Obayashi, Y. Sakurai, T. Gejo, Perovskite-type oxides as ethanol sensors, J. Solid
121309.
State Chem. 17 (1976) 299–303.
[8] M.M. Abutalib, A. Rajeh, Preparation and characterization of polyaniline/sodium
[37] S. Janitabar-Darzi, A.R. Mahjoub, Investigation of phase transformations and
alginate-doped TiO 2 nanoparticles with promising mechanical and electrical
photocatalytic properties of sol–gel prepared nanostructured ZnO/TiO2
properties and antimicrobial activity for food packaging applications, J. Mater. Sci.
composites, J. Alloys Compd. 486 (2009) 805–808.
Mater. Electron. 31 (2020) 9430–9442.
[38] J. Mrázek, L. Spanhel, G. Chadeyron, V. Matejec, Evolution and Eu3+ doping of
[9] Q.A. Alsulami, A. Rajeh, Synthesis of the SWCNTs/TiO2 nanostructure and its
Sol− gel derived ternary Zn x Ti y O z-nanocrystals, J. Phys. Chem. C 114 (2010)
effect study on the thermal, optical, and conductivity properties of the CMC/PEO
2843–2852.
blend, Results in Physics 28 (2021) 104675.
[39] P.K. Jain, M. Salim, D. Kaur, Effect of phase transformation on optical and
[10] M.M. Abutalib, A. Rajeh, Enhanced structural, electrical, mechanical properties
dielectric properties of pulsed laser deposited ZnTiO3 thin films, Superlattice.
and antibacterial activity of Cs/PEO doped mixed nanoparticles (Ag/TiO2) for food
Microst. 92 (2016) 308–315.
packaging applications, Polym. Test. 93 (2021) 107013.
[40] L. Budigi, M.R. Nasina, K. Shaik, S. Amaravadi, Structural and optical properties of
[11] J.-L. Chung, J.-C. Chen, C.-J. Tseng, The influence of titanium on the properties of
zinc titanates synthesized by precipitation method, J. Chem. Sci. 127 (2015)
zinc oxide films deposited by radio frequency magnetron sputtering, Appl. Surf.
509–518.
Sci. 254 (2008) 2615–2620.
[41] X. Liu, Molten salt synthesis of ZnTiO3 powders with around 100 nm grain size
[12] J.-C. Lin, M.-C. Huang, T. Wang, J.-N. Wu, Y.-T. Tseng, K.-C. Peng, Structure and
crystalline morphology, Mater. Lett. 80 (2012) 69–71.
characterization of the sputtered ZnO, Al-doped ZnO, Ti-doped ZnO and Ti, Al-co-
[42] A.R. Phani, M. Passacantando, S. Santucci, Synthesis of nanocrystalline ZnTiO3
doped ZnO thin films, Materials Express 5 (2015) 153–158.
perovskite thin films by sol–gel process assisted by microwave irradiation, J. Phys.
[13] S. Saini, P. Mele, T. Oyake, J. Shiomi, J.-P. Niemelä, M. Karppinen, K. Miyazaki,
Chem. Solid. 68 (2007) 317–323.
C. Li, T. Kawaharamura, A. Ichinose, Porosity-tuned thermal conductivity in
[43] X. Qin, L. Cui, G. Shao, Preparation of ZnO-Zn2TiO4 Sol composite films and its
thermoelectric Al-doped ZnO thin films grown by mist-chemical vapor deposition,
photocatalytic activities, J. Nanomater. (2013) 2013.
Thin Solid Films 685 (2019) 180–185.
[44] S. Iaiche, A. Djelloul, ZnO/ZnAl2O4 nanocomposite films studied by X-ray
[14] A.M. Darwish, A. Muhammad, S.S. Sarkisov, P. Mele, S. Saini, J. Liu, J. Shiomi,
diffraction, FTIR, and X-ray photoelectron spectroscopy, Journal of Spectroscopy
Thermoelectric properties of Al-doped ZnO composite films with polymer
(2015) 2015.
nanoparticles prepared by pulsed laser deposition, Compos. B Eng. 167 (2019)
[45] H.Y. Yue, W.D. Fei, L.D. Wang, Effects of heat-treatment on interfacial
406–410.
microstructures and tensile properties of ZnAl2O4 and ZnO coated Al18B4O33w/
[15] L. Xu, W. Kuang, Z. Liu, F. Xian, Improvement of UV emission in ZnO thin film
Al composites, Mater. Sci. Eng. 472 (2008) 231–234.
caused by a transition from polycrystalline to monocrystalline, Phys. B Condens.
[46] G. Fan, F. Li, In Situ crystallization to zinc aluminate films with controlled surface
Matter 583 (2020) 412010.
microstructure and anticorrosion performance, AIChE J. 58 (2012) 2639–2649.
[16] Y. Wu, F. Cao, X. Ji, Optical and electrical properties of Al-doped ZnO thin films by
[47] Z. Bi, R. Zhang, X. Wang, S. Gu, B. Shen, Y. Shi, Z. Liu, Y. Zheng, Synthesis of zinc
atomic layer deposition, J. Mater. Sci. Mater. Electron. (2020) 1–10.
aluminate spinel film through the solid-phase reaction between zinc oxide film and
[17] A. Henni, A. Merrouche, L. Telli, A. Karar, Studies on the structural, morphological,
α-alumina substrate, J. Am. Ceram. Soc. 86 (2003) 2059–2062.
optical and electrical properties of Al-doped ZnO nanorods prepared by
[48] M.S. Libório, G.B. Praxedes, L.L.F. Lima, I.G. Nascimento, R.R.M. Sousa, M. Naeem,
electrochemical deposition, J. Electroanal. Chem. 763 (2016) 149–154.
T.H. Costa, S.M. Alves, J. Iqbal, Surface modification of M2 steel by combination of
[18] A. Kuroyanagi, Properties of aluminum-doped ZnO thin films grown by electron
beam evaporation, Jpn. J. Appl. Phys. 28 (1989) 219.

10
J.C.A. Queiroz et al.
cathodic cage plasma deposition and magnetron sputtered MoS2-TiN multilayer
coatings, Surf. Coating. Technol. 384 (2020) 125327.
[49] L.C. Silva, M.S. Libório, L.L.F. Lima, R.R.M. Sousa, T.H.C. Costa, M. Naeem, D.A.
P. Reis, P.A. Radi, S.M. Alves, Deposition of MoS 2-TiN multilayer films on 1045
steel to improve common rail injection system, J. Mater. Eng. Perform. (2020) 1–8.
[50] S.B. Majumder, M. Jain, P.S. Dobal, R.S. Katiyar, Investigations on solution derived
aluminium doped zinc oxide thin films, Mater. Sci. Eng., B 103 (2003) 16–25.
[51] V.L. Patil, S.A. Vanalakar, A.S. Kamble, S.S. Shendage, J.H. Kim, P.S. Patil, Farming
of maize-like zinc oxide via a modified SILAR technique as a selective and sensitive
nitrogen dioxide gas sensor, RSC Adv. 6 (2016) 90916–90922.
[52] S.A. Vanalakar, S.S. Mali, R.C. Pawar, D.S. Dalavi, A.V. Mohalkar, H.
P. Deshamukh, P.S. Patil, Farming of ZnO nanorod-arrays via aqueous chemical
route for photoelectrochemical solar cell application, Ceram. Int. 38 (2012)
6461–6467.
[53] M.A. Garcia, J.M. Merino, E. Fernández Pinel, A. Quesada, J. De la Venta, M.L. Ruíz
González, G.R. Castro, P. Crespo, J. Llopis, J.M. González-Calbet, Magnetic
properties of ZnO nanoparticles, Nano Lett. 7 (2007) 1489–1494.
[54] H. Dixit, N. Tandon, S. Cottenier, R. Saniz, D. Lamoen, B. Partoens, V. Van
Speybroeck, M. Waroquier, Electronic structure and band gap of zinc spinel oxides
beyond LDA: ZnAl2O4, ZnGa2O4 and ZnIn2O4, New J. Phys. 13 (2011), 063002.
[55] O. Yamaguchi, M. Morimi, H. Kawabata, K. Shimizu, Formation and
Transformation of ZnTiO3 70 (1987) C-97–C-98.
[56] C.-W. Hsu, T.-C. Cheng, C.-H. Yang, Y.-L. Shen, J.-S. Wu, S.-Y. Wu, Effects of
oxygen addition on physical properties of ZnO thin film grown by radio frequency
reactive magnetron sputtering, J. Alloys Compd. 509 (2011) 1774–1776.
[57] E.M. Bachari, G. Baud, S.B. Amor, M. Jacquet, Structural and optical properties of
sputtered ZnO films, Thin Solid Films 348 (1999) 165–172.
[58] H. Zhu, H. Wang, W. Wan, S. Yu, X. Feng, Influence of oxygen and argon flow on
properties of aluminum-doped zinc oxide thin films prepared by magnetron
sputtering, Thin Solid Films 566 (2014) 32–37.
11
Physica B: Physics of Condensed Matter 625 (2022) 413535
[59] Z. Ghorannevis, E. Akbarnejad, A.S. Elahi, M. Ghoranneviss, Application of RF
magnetron sputtering for growth of AZO on glass substrate, J. Cryst. Growth 100
(2016) 62–66.
[60] B.C. Mohanty, Y.H. Jo, D.H. Yeon, I.J. Choi, Y.S. Cho, Stress-induced anomalous
shift of optical band gap in ZnO: Al thin films, Appl. Phys. Lett. 95 (2009), 062103.
[61] R. Kumar, N. Khare, V. Kumar, G.L. Bhalla, Effect of intrinsic stress on the optical
properties of nanostructured ZnO thin films grown by rf magnetron sputtering,
Appl. Surf. Sci. 254 (2008) 6509–6513.
[62] R.A. Ismail, B.G. Rasheed, E.T. Salm, M. Al-Hadethy, Transparent and conducting
ZnO films prepared by reactive pulsed laser deposition, J. Mater. Sci. Mater.
Electron. 18 (2007) 397–400.
[63] D.M. Hofmann, D. Pfisterer, J. Sann, B.K. Meyer, R. Tena-Zaera, V. Munoz-Sanjose,
T. Frank, G. Pensl, Properties of the oxygen vacancy in ZnO, Appl. Phys. A 88
(2007) 147–151.
[64] N. Khemasiri, S. Jessadaluk, N. Kayunkid, S. Rahong, A. Rangkasikorn,
S. Wirunchit, A. Klamchuen, J. Nukeaw, Control the crystal growth of Al-doped
ZnO thin film prepared by pulsed laser deposition and the influences on its optical
and electrical properties, J. Phys. Conf. 901 (2017) 12163–12168, 12163-12168.
[65] J.C.A. Queiroz, M. Naeem, M.S. Libório, E.J.C. Santos, M.C. Feitor, R.R.M. Sousa, T.
H.C. Costa, K.H. Khan, Synthesis of Al-doped ZnO films assisted with hollow-
cathode glow discharge and their characterization, J. Electron. Mater. (2021) 1–12,
https://doi.org/10.1007/s11664-021-08802-1.
[66] S. Choopun, R.D. Vispute, W. Noch, A. Balsamo, R.P. Sharma, T. Venkatesan,
A. Iliadis, D.C. Look, Oxygen pressure-tuned epitaxy and optoelectronic properties
of laser-deposited ZnO films on sapphire, Appl. Phys. Lett. 75 (1999) 3947–3949.
[67] F. Wang, M.Z. Wu, Y.Y. Wang, Y.M. Yu, X.M. Wu, L.J. Zhuge, Influence of thickness
and annealing temperature on the electrical, optical and structural properties of
AZO thin films, Vacuum 89 (2013) 127–131.
[68] J.C.A. de Queiroz, M. Naeem, M.S. Libório, M.G.O. Queiroz, R.R.M. Sousa, E.
B. Melo, M. Feitor, T.H.C. Costa, Synthesis and characterization of ZnO/ZnAl2O4/
Zn2TiO4 composite films by Ar–O2 mixture hollow cathode glow discharge,
Journal of Materials Research and Technology 12 (2021) 2426–2437.