Facile synthesis of spray pyrolyzed ZnO/NiO nanocomposites thin films

Article abstract of DOI:10.1080/10426507.2020.1804144

This study reviews ZnO, NiO, and ZnO/NiO nanocomposites thin films deposition using the Spray Pyrolysis Technique (S.P.T). The thin films were deposited onto ordinary glass substrates heated at 500 °C from aqueous solutions of zinc chloride and nickel chl

Full text of DOI:10.1080/10426507.2020.1804144

Phosphorus, Sulfur, and Silicon and the Related Elements
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Facile synthesis of spray pyrolyzed ZnO/NiO
nanocomposites thin films
Bouhank Antar & Bellal Youcef
To cite this article: Bouhank Antar & Bellal Youcef (2020) Facile synthesis of spray pyrolyzed
ZnO/NiO nanocomposites thin films, Phosphorus, Sulfur, and Silicon and the Related Elements,
195:11, 895-900, DOI: 10.1080/10426507.2020.1804144
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
2020, VOL. 195, NO. 11, 895–900
https://doi.org/10.1080/10426507.2020.1804144
Facile synthesis of spray pyrolyzed ZnO/NiO nanocomposites thin films
Bouhank Antara,b and Bellal Youcefa,c
b
aResearch Center in Industrial Technologies CRTI, Cheraga, Algiers, Algeria; Laboratory of Chemical Process Engineering (LCPE), Faculty of
c
Technology, Ferhat ABBAS Setif-1 University, Setif, Algeria; Faculty of Technology, Department of Engineering Process, Laboratory of
Electrochemistry, Molecular Engineering and Redox Catalysis (LEIMCR), Ferhat ABBAS Setif-1 University, Setif, Algeria
ABSTRACT
ARTICLE HISTORY
This study reviews ZnO, NiO, and ZnO/NiO nanocomposites thin films deposition using the Spray
Pyrolysis Technique (S.P.T). The thin films were deposited onto ordinary glass substrates heated at
500ꢀC from aqueous solutions of zinc chloride and nickel chloride precursors dissolved in distilled
water. The structural, morphological, and optical properties of the ZnO, NiO, and ZnO/NiO thin
films have been studied by X-ray diffraction, scanning electron microscopy, Raman spectroscopies,
and so on. The optical band gaps are 3.3 and 3.5 eV for ZnO and NiO thin films, respectively
obtained by UV–Vis spectroscopy. However, the optical band gaps of ZnO/NiO nanocomposites
thin films, are noticeable out of the range (3.4–3.64 eV).
KEYWORDS
Thin films; nanocomposites;
spray pyrolysis;
characterizations
GRAPHICAL ABSTRACT
Introduction
two semiconductors materials have been recognized as an
excellent material notably for photocatalytic processes due to
their high catalytic activity, wide bandgap, low cost, and
environmental friendliness.[7–11] Many deposition techniques
have been widely used to produce ZnO/NiO thin films. The
most studied techniques include, sol–gel method,[12] spray
pyrolysis,[13,14] chemical vapor deposition (CVD),[15] and RF
magnetron sputtering,[16] we have chosen the spray pyrolysis
method for the ZnO/NiO deposition because this latter
presents an advantage to be efficient, fast, wide surfaces
deposition with low cost.
Nanocomposites are multiphase solid materials, at least two
phases, which one of them or all phases is in the nanometer
scale. The improvement of the physical/chemical properties of
nanocomposite thin films compared to the study of separate
phases, has been the subject of many experimental research-
ers.[1,2] Nanocomposites are widely used in many applications
such as photovoltaic devices,[3] photocatalysis,[4] gas sen-
sors,[5] UV detectors,[6] and so on. The aim of this paper is
the synthesis of a nanocomposite thin films using some metal
oxides. Among of them, the combination of zinc oxide and
Nickel oxide (ZnO/NiO) nanocomposite with different per-
centage. The first one is n-type semiconductor (ZnO) and the
second one is p-type semiconductor (NiO). The combination
Experimental setup
Spray pyrolysis technique was used to deposit ZnO, NiO,
of them results a new application in material sciences. These and the combination ZnO/NiO thin films on ordinary glass
CONTACT Bouhank Antar
a.bouhank@crti.dz; antarbouhank@yahoo.fr
Research Center in Industrial Technologies CRTI, P.O. Box 64, Cheraga, 16014
Algiers, Algeria.
ß 2020 Taylor & Francis Group, LLC

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B. ANTAR AND B. YOUCEF
Figure 1. XRD patterns of ZnO, NiO and ZnO, NiO nanocomposites thin films.
substrates. These latter were ultrasonically cleaned by using of ZnCl2 was dissolved in 50 ml of distilled water and stirred
isopropanol, acetone, and distilled water for 15 min at about for 15 min to prepare 0.1 M of precursor solution for ZnO.
50 ꢀC and subsequently dried in hot air oven. The clean sub- Similarly, 1.188 g M of NiCl2ꢁ6H2O was dissolved in 50 ml
strates were carefully located on the substrate heater. for the of distilled water and stirred for 15 min too to prepare NiO
preparation of Zno, NiO and ZnO/NiO thin films we need source solution. To prepare the nanocomposites ZnO/NiO
the precursors of Zinc chloride (ZnCl2) (Sigma Aldrich, thin films, the two solutions (Zno and NiO) were mixed
Purity 97%) and Nickel chloride hexahydrate NiCl2ꢁ6H2O together with different percentage and stirred for 15 min to
(Sigma Aldrich, Purity 99.98%) as starting materials. 0.702 g obtain homogeneous solution.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
897
Figure 2. AFM and SEM images of ZnO, NiO and ZnO, NiO nanocomposites thin films.
The growth was performed by spraying the solution rate (100, 002, 101) reduces with the presence of the NiO as
of about 5 ml/min when the temperature of spray pyrolysis with inverse case (NiO with presence of ZnO).
machine reaches 500 ꢀC. The samples remain on the system
for cooling gradually. Meanwhile these latter were calcined
spontaneously.
Morphological characterization
The morphology of the prepared thin films of ZnO, NiO
and their combinations have been investigated by using
SEM and AFM. The SEM images are showed in the figures
Materials characterization
The morphological study was showed by using an atomic below (Figure 2).
force microscope (A.F.M.) (BRUKER—ICON DIMENSION
The investigations obtained by AFM images revealed a
(United States)) and Scanning Electron Microscopy (S.E.M.) panoramic view of the ZnO/NiO nanoparticles grown on a
(ZEISS Gemini-SEM300 (France)). The results allow the glass substrate covering the whole area with overall uniform
nanostructure study and determination of the surface rough- density, roughness of the surface mostly at the equi percent-
ness and the average grain size. Then the optical study age of ZnO and NiO which is confirmed by SEM image.
absorption Domain was conducted using UV–Vis
Spectrophotometer (UV-1800 Shimadzu (Japan)) to study
the thin films reflectivity, transmission and for calculation of
Raman spectroscopy characterization
the optical band gap. The phase’s identification examined by
Raman spectroscopy (Renishaw inVia Raman spectroscope
(United Kingdom)) and the structural study was investigated
by X-ray diffractometer (XRD) (Bruker D2 Phaser 2G
United States). Note that all measurements were carried out
at room temperature.
Raman spectroscopy characterization technique is a nondes-
tructive method of characterizing the molecular composition
of a material and the external structure, which makes it pos-
sible to study the vibrational modes of existing bonds in
materials. The figure below shows that the Raman spectrum
of thin-film ZnO shows several bands, the active modes
Raman spectroscopy for hexagonal ZnO are presented by
peaks A1, 2E2, and E1. The polar modes A1 and E1 can be
divided into Transverse Optical (TO) and Longitudinal
Optical (LO) modes observed at the 377 cmꢂ1 position. The
Experimental results and discussion
XRD characterization
We use the XRD as a characterization technique to identifi- important peak E2 (high) ¼ 433 cmꢂ1 corresponding to the
cation material’s phases especially in thin films, we can also vibrations of Zn-O.[17] The spectra of pure NiO thin film
have information on the crystallinity and structure of the shows several characteristic bands, as we see in the Raman
elaborated thin films. The Figure 1 shows the XRD patterns spectra of NiO a large peak at 540 cmꢂ1 corresponding to
of ZnO, NiO thin films and the combination of ZnO/NiO the vibrations of Ni-O (a phonon modes TO and LO),[18] at
with different percentages deposited at 500 ꢀC.
about 700 cmꢂ1 two phonon 2TO modes, the last peak
It can be noted, from the results shown in the figures powerful appears at ꢃ 1100 cmꢂ1 corresponds to 2LO
above, that the intensity of the characteristic peaks of ZnO modes. Part of the phonon-bound Raman spectra indicated

898
B. ANTAR AND B. YOUCEF
Figure 4. Absorbance of ZnO/NiO nanocomposites thin films.
Figure 3. Raman spectra of ZnO, NiO and ZnO, NiO nanocomposites thin films.
Figure 5. Graph of transmittance spectra of ZnO/NiO nanocomposites
thin films.
with (LO and 2TO modes) of the figure below in a nano-
scale NiO thin film is quite similar to that of the single crys-
tal (a.u). The Raman spectra of ZnO/NiO nanocomposites
showed also in below with different percentages of
combination.
From the figure of Raman spectra of ZnO/NiO nanocom-
posites, we can see the presence of all characteristic bands of
the both (ZnO and NiO) with the increasing intensities
(Figure 3).
observed around 382 nm for pure ZnO thin film, this value
decrease with increasing of NiO percentages (379 nm for
ZnO 75% and 378.4 for 50% of ZnO).
The transmission measurements were given below
(Figure 5) for the prepared ZnO, NiO, and ZnO/NiO
(75%–25%, 50%–50%, and 25%–70%) thin films, A region of
high transparency located between 300 and 600 nm, the
value of the transmission is almost in the range of 20–80%
which gives the ZnO/NiO thin films transparency character
in the ultra violet and low adsorption in the visible. This
result indicates that the thin films prepared with our condi-
tions are homogeneous and have smooth surfaces. Which
confirms the optimal deposition temperatures enabling
Optical properties
Figure 4 shows the absorbance spectrum of ZnO/NiO with
different percentage (25–50–75%), this figure indicates that
the thin films have a high UV absorbance property that
wavelengths are about 400 nm. The absorption edge transparent ZnO, NiO, and ZnO/NiO films to be obtained,

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
899
surface investigation by AFM characterization of our thin
films revealed nanoparticles grown on a glass substrate cov-
ering the whole area with overall uniform density, roughness
of the surface. The characteristic bands of ZnO, NiO, and
the combination ZnO/NiO are revealed with Raman investi-
gation. The add of NiO to ZnO led the Eg of ZnO to
improve and increase.
Acknowledgments
Authors gratefully acknowledge the financial support of the Directorate
General for Scientific Research and Technological Development
(DGRSDT), authors also would like to thank Nechadi Meriem of
Energetic and Solid-State Electrochemistry Laboratory (Setif-1
University), and Yacine BOUACHIBA of Thin Film and Interfaces
Laboratory (Constantine-1) for the characterization equipment
and help.
Figure 6. Optical gap Eg determination of ZnO/NiO nanocomposites thin films.
Table 1. Values of Eg of ZnO/NiO nanocomposites thin films.
References
NiO/ZnO
75%–25%
NiO/ZnO
50%–50%
NiO/ZnO
25%–75%
Material
Eg(eV)
NiO
ZnO
3.4
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3.64
3.58
3.60
3.66
uniform and stoichiometric are in the vicinity of 500 ꢀC. We
can calculate the band gap energy Eg from the transmittance
spectra using the following relation:
T ¼ exp ½ꢂaðkÞdꢄ
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ꢀ ꢁ
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d
1
T
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optical transmittance, respectively.
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:
n
ð
Þ
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ð
Þ
1
2
n ¼ for allowed direct transition, and equal to 2 for indir-
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