BACHELOR OF SCIENCE (HONS.

) INDUSTRIAL PHYSICS (AS251)

FACULTY OF APPLIED SCIENCE
SOLID STATE PHYSICS (PHY592)
JOURNAL SUMMARY
EVALUATION OF STRUCTURAL, MORPHOLOGICAL, OPTICAL,
AND ELECTRICAL PROPERTIES OF ZINC OXIDE
SEMICONDUCTOR NANOPARTICLES WITH MICROWAVE
PLASMA TREATMENT FOR ELECTRONIC DEVICE APPLICATIONS

NUR IRYANI 2021480394 AS2514D

EMYLIA BINTI
ZAINOL
DATE OF 16 JUNE 2023
SUBMISSION
DATE OF JOURNAL 3 MAY 2023
APPROVED
LECTURER’S NAME DR NURUL IZRINI BINTI IKHSAN
TABLE OF CONTENT

1. Research Objective……………………………………………………………….……….1
2. Problem Statement………………………………………………………………….……..1
3. Physics Principle…………………………………………………………………….……..1
i) X-ray diffraction (XRD) analysis………………………………………….………1
ii) Scanning Electron Microscope (SEM)………………………………….……….1
iii) Raman spectroscopy…………………………………………………….………..2
iv) Electrical resistivity……………………………………………………….………..2
4. Scientific Finding……………………………………………………………………………2
 1. RESEARCH OBJECTIVE
The main objectives of this research were to create untreated and plasma-treated ZnO
nanoparticles (ZnO NPs) using a sol-gel method and to analyse them using XRD, Raman
spectroscopy, UV-Vis spectroscopy, and I-V characteristic methods. The research focused on
the impact of plasma treatment on the optical, vibrational mode, structural, and electrical
characteristics of ZnO nanoparticles. XRD and Raman spectroscopy were used to establish
the crystalline nature and purity of the generated samples, as well as to determine the average
crystalline size, lattice constant, unit cell volume, and porosity. The study also sought to
explore changes in Raman band intensity, bandgap reduction obtained by plasma treatment,
and electrical property enhancement without producing structural deformities. The study's
overall goal was to determine the appropriateness of the generated ZnO NPs with enhanced
characteristics for future uses in electrical devices.

2. PROBLEM STATEMENT
This study addresses the demand for low-cost, environmentally friendly optoelectronic
devices. Current optoelectronic devices based on inorganic materials, notably metal oxides,
have attracted interest, although they are still limited. Because of its outstanding properties,
zinc oxide (ZnO) is a potential material for electronic devices, however there is little literature
on its detailed investigation for electronic applications. Furthermore, flaws in ZnO
nanoparticles (NPs), such as high particle size and its influence on the bandgap, limit their
performance at lower temperatures and longer wavelengths. Size, shape, and synthesis
method all have an impact on the production procedures and qualities of ZnO NPs.

3. PHYSICS PRINCIPLE

i) X-ray diffraction (XRD) analysis

The XRD inspection revealed structural characteristics, crystalline phases, and

microstructures of ZnO nanoparticles. The peaks in the XRD patterns revealed that both
samples were crystalline, and the peaks moved to higher angles with greater intensity
following plasma treatment. This investigation was based on X-ray diffraction physics
principles, which allow for the identification of crystal structure and phase composition of
materials.

ii) Scanning Electron Microscope (SEM)

The particle size and shape of both samples were revealed by SEM micrographs. The results
showed that following plasma treatment, the particle size of the nanoparticles increased, which
was compatible with the findings of the XRD spectra. The as-synthesized nanoparticles
exhibited an uneven form with no distinct grain boundaries, but following plasma treatment,

1
agglomeration and porosity were reduced somewhat. When compared to the untreated
sample, the surface of the plasma-treated sample seemed smoother. The reduction in porosity
following plasma treatment increased the properties of the nanoparticles.

iii) Raman spectroscopy

It offers information on the material's vibrational properties. The research supports ZnO's
hexagonal structure and the participation of optical phonons at the Brillouin zone point. The
occurrence of quiet modes, which are inactive in Raman spectra, is explained by the Raman
selection rule. The observed phenomena are explained by variations in nanoparticle volume
and inter-atomic spacing, as well as the effect of vibrational amplitudes and grain size on the
force constants. The Raman study results agree with the XRD analysis results, verifying the
purity of the specimens.

iv) Electrical resistivity

It focuses on zinc oxide nanoparticles to investigate the link between electrical resistivity and
crystal structure/composition of materials. It emphasises that following plasma treatment, the
resistance of zinc oxide nanoparticles reduces while the conductivity improves, which is
related to changes in the bandgap and better electrical characteristics. The relevance of
electrical qualities in optoelectronic device performance is emphasised, notably the
requirement for low leakage current and the usage of ultra-wide bandgap materials to ensure
stable operation at higher temperatures.

4. SCIENTIFIC FINDING
Untreated and plasma-treated zinc oxide nanoparticles (ZnO NPs) were investigated in this
work to determine the impact of plasma treatment on their optical, structural, and electrical
properties. The crystalline structure of ZnO NPs was verified by XRD measurement, and
plasma treatment increased lattice characteristics and decreased porosity. The increase in
grain size caused by plasma treatment resulted in increased Raman band intensity and a
decrease in the bandgap, which improved electron transport. Electrical studies revealed that
plasma treated ZnO NPs had higher conductivity and decreased resistance, which was
ascribed to a reduction in acceptor defects and local oxygen vacancies. These findings
demonstrate the ability of microwave plasma treatment to improve the characteristics of ZnO
NPs for use in electronic devices.

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Available online at www.sciencedirect.com

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

Original Article

Evaluation of structural, morphological, optical,

and electrical properties of zinc oxide
semiconductor nanoparticles with microwave
plasma treatment for electronic device applications

Shahroz Saleem a, Muhammad Hasnain Jameel b,c,*, Azka Rehman c,

Muhammad Bilal Tahir c, Muhammad Imran Irshad c, Zhen-Yi Jiang b,
R.Q. Malik d, Abdul Ahad Hussain e, Ateeq ur Rehman e,
Abdullah Hasan Jabbar f, Abdullah Y. Alzahrani g, Mohamed A. Salem g,h,
M.M. Hessien i
a
Shaanxi Key Laboratory for Advanced Energy Devices and Shaanxi Engineering Lab for Advanced Energy
Technology, Xi'an 710119, China
b
Shaanxi Key Laboratory for Theoretical Physics Frontiers, Institute of Modern Physics, Northwest University, Xi'an
710069, China
c
Department of Physics, Khwaja Fareed University of Engineering & Information Technology Rahim Yar Khan,
Pakistan
d
Department of Medical Instrumentation Techniques Engineering, Al-Mustaqbal University College, Babylon, Iraq
e
Department of Physics, University of Agriculture Faisalabad, Pakistan
f
Optical Department, College of Medical and Health Technology, Sawa University, Ministry of Higher Education and
Scientific Research, Al-Muthanaa, Samawah, Iraq
g
Department of Chemistry, Faculty of Science & Arts, King Khalid University, Mohail, Assir, Saudi Arabia
h
Department of Chemistry, Faculty of Science, Al-Azhar University, Nasr City 11884, Cairo, Egypt
i
Department of Chemistry, College of Science, Taif University, P.O Box 11099, Taif, 21944, Saudi Arabia

article info abstract

Article history: ZnO is an important II-IV n-type direct bandgap semiconductor material that has exhibited
Received 19 March 2022 wide consideration due to its applications in optoelectronic devices. In the present
Accepted 31 May 2022 investigation, untreated and plasma-treated ZnO NPs were fabricated by a sol-gel route
Available online 6 June 2022 and analyzed with XRD, Raman, UV-Vis spectra, and IeV characteristic techniques. To be
used in electronic applications, the ZnO nanoparticles were subjected to a plasma treat-
Keywords: ment process to tune their optical, vibrational mode, structural and electrical properties.
Plasma treatment XRD confirmed the pure Wurtzite tetragonal phase crystalline nature of produced samples.
ZnO Semiconductor The average crystalline size, lattice constant, unit cell volume, and porosity were found in
XRD the range of 3.81e4.68 nm, a ¼ 3.217e3.323  A and c ¼ 2.032e2.178  A, 5.662e11.274 
A3 and
SEM 7.09e5.03%, respectively. The Raman spectra revealed that the intensity of Raman bands
Raman was increased due to the increase in the vibrational amplitude and increase in force

* Corresponding author.
E-mail address: mhasnainjamil@gmail.com (M.H. Jameel).
https://doi.org/10.1016/j.jmrt.2022.05.190
2238-7854/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 2 1 2 6 e2 1 3 4 2127

UV constants with the enhancement in grain size, these spectra results are in good agreement
IV with XRD and reveal the purity of samples. The bandgap found reduced from 3.56 eV to
Device applications 3.39 eV by plasma treatment. The electrical studies revealed that plasma treatment im-
proves the electrical properties of ZnO NPs without producing any structural distortions. I
eV characteristic curves confirmed that the conductivity was increased from 8.3 X 106 to
5.5 X 104 [ cm1 on plasma treatment which caused an increase in leakage current. The
improved structural, vibrational mode, optical and electrical properties of prepared ZnO
NPs make them a suitable candidate for application in electronic devices.
© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

studied from its morphology, there is limited literature on the

1. Introduction
Emerging low-cost environmentally friendly optoelectronic
devices is a major issue to meet recent problems. For this
purpose, various optoelectronic devices such as light-emitting
devices, solar cells, and catalytic systems are used [1e3].
These devices are made based on several inorganic materials,
particularly metal oxides, and activated an area of present
attention for such a large number of optoelectronic devices.
This devotion is because of the variety of exceptional char-
acteristics, that can be simply altered by changing the content
of used materials, composition, structure, and nanoparticles
size to match the device requirements [4e6]. The optoelec-
tronic industry requires materials with the property of wide
energy bandgap (Eg) since this property enhances the working
ability of optoelectronic devices including sensors, light-
emitting diodes (LED), touch screens liquid crystal displays,
and solar cells [7e9]. In addition, structural and optical char-
acteristics of metal oxides are modified by the plasma treat-
ment effect.
Semiconductor NPs have achieved great attention in fresh
years due to their exceptional characteristics such as special
optical characteristics, larger surface-to-volume ratio, and
unique electronic characteristics as compared to their bulk
counterparts. The larger surface-to-volume ratio can be linked
to a few of the exceptional characteristics of NPs. An impor-
tant class of semiconductors is the transition metals oxides
[10e12]. Some wide bandgap semiconductors, such as TiO2,
GaN, ZnO, SiC, etc., have achieved widespread interest for
material researchers because of their numerous applications
in the area of optoelectronic devices [12,13]. Out of these
semiconductor materials, Zinc oxide (ZnO), which exhibits a
hexagonal structure, is an important inorganic material with a
direct wider bandgap of about 3.36 eV and a larger bandgap of
60 meV at room temperature, is the best candidate for several
electronic devices including sensors, diodes, light-emitting
devices (LED), nanolasers, field emission, photodetectors, flat
display devices, electroluminescence devices, nano-
generators, as electrode material in supercapacitors and solar
cells because of its pyroelectric, semiconducting, piezoelec-
tric, electronic and optoelectronic characteristics, high elec-
trochemical activity, low cost, ease of synthesis, high
electrochemical activity, desirable morphological features
and nontoxicity [14e17]. Though physical characteristics of
Zinc oxide have been extensively deliberated which can be
ZnO that has been widely studied for electronic devices.
Because of its inexpensiveness, eco-friendly nature, and
electrochemical activity, materials scientists have started to
deeply study zinc oxide as prospective electrode material for
electronic devices.
In the past, several researchers have described the prepa-
ration and various features of ZnO NPs by several procedures
including co-precipitation, hydrothermal method, sol-gel
method, green synthesis utilizing natural products, capped
precipitation, chemical vapor deposition, laser ablation, etc. It
is a well-known fact that the size, nanoparticles morphology,
stoichiometric parameters, and preparation method can be
altered the properties of nanoparticles. Similar to other
nanoparticles, ZnO nanoparticles also have size, shape, and
synthesis method-dependent characteristics. Thus, the se-
lection of preparation techniques shows a significant role in
obtaining the characteristics of nanoparticles. A sol-gel tech-
nique is the best useful technique for the preparation of ZnO
as it exhibited several benefits as compared to the other
method with their better control ratio, simplicity, more ho-
mogeneous composition, and higher purity [18].
However, there existed a few defects for ZnO. As the
quantum confinement cause the large particle size which in
turn becomes a cause to effect the bandgap of ZnO NPS, in this
case, the optoelectronic device showed the best response only
at higher temperature and shorter wavelength, which limited
its applications. Saleem et al. found that the ZnO NPs with
large particle sizes prepared by co-precipitation showed a
bandgap between 5.05 eV and 5.23 eV and the device showed
good photoresponse only at higher temperatures [19]. Pandey
et al. described that the zinc oxide nanoparticles prepared via
the chemical precipitation technique exhibited the increasing
bandgap with decreasing particle size, which suggested that
such semiconductor-based devices can only be useful in ultra-
wideband gap semiconductor spintronics applications [20].
Rusdi et al. described the sol-gel fabrication of zinc oxide NPs
which exhibited an increase in band gap due to strong internal
forces between valance and conduction band caused by a
decrease in lattice spacing [21].
In current literature, zinc oxide nanomaterials were pro-
duced by a sol-gel process. The Sodium hydroxide (NaOH) and
zinc acetate dehydrate (Zn(CH3COO)2.2H2O) as initial re-
actants, while deionized water as solvent material and poly-
ethylene glycol is taken as a surfactant was employed in the
sol-gel method. Raman spectroscopy, X-ray diffraction
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(XRD), IeV characteristic, and Ultraviolet-visible (UV-Vis)
characterization analysis were performed for the analysis of
the fabricated NPs. This literature aimed to analyze the impact
of plasma treatment on the optical, structural, vibrational
mode, and electrical parameters of synthesized untreated and
plasma-treated ZnO nanoparticles. The consequences ach-
ieved from this literature will be applied as a basis to enhance
the applications of electronic devices.
2. Materials and methods
2.1. Materials
Zinc acetate dehydrates (Zn(CH3COO)2.2H2O) and sodium hy-
droxide were initial reactants, while deionized water was
utilized as solvent and polyethylene glycol was taken as sur-
factant. All these chemicals were analytic grade purchased
from scientific store Faisalabad.
2.2. Methods
A sol-gel process was employed for the fabrication of zinc
oxide NPs by sodium hydroxide and zinc acetate dehydrate as
initial chemical reactants. The stoichiometric amount of zinc
acetate dehydrate was dissolved into deionized water and
started stirring of this chemical solution until the chemical
was completely dissolved. 0.8 M of NaOH was completely
dissolved into deionized water on continuous stirring at room
temperature. 0.6% Polyethylene glycol was used as a surfac-
tant which was added to Zinc acetate dehydrate solution.
Sodium hydroxide (NaOH) was added to this combined solu-
tion to maintain pH during a chemical reaction between 7 and
8. This joined solution was heated on the magnetic stirrer for
3 h. Until this suspension solution becomes milky white color
after a chemical reaction. After that 3 times were washed with
deionized and 2 times with ethanol after make centrifuging at
5000 rpm for 15 min. The prepared sample was kept at 80  C in
the oven for 2 h to remove water content. This dry sample was
put into a furnace at 500  C for its calcination. After grinding,
the sample was obtained in powder form and was ready for
characterization. The plasma treatment was performed after
characterization for comparatively analyzing their structural
and optical features in comparison with untreated sample
results.
3. Measurement techniques
3.1. Characterizations of ZnO NPs
XRD analysis was carried out by PANalytical X'Pert Pro target
Cu-Ka with secondary monochromator radiation
Table 1 e XRD calculated values of treated and untreated zin oxide nanoparticles (ZnO-NPs).
Samples Crystallite d-spacing
Size(nm)
Untreated 3.81 2.4522 3.217
Plasma Treated 4.68 4.6801 3.323
(l¼0.1540 nm, the tube worked at 45 kV, scans were collected
over a 2q range of 20e60 ). UV spectra were measured in the
range of 300e800 nm by JASCOV- 630 spectrophotometers.
Scanning Electron Microscope (SEM) was performed at the
National University of science and technology (NUST) by SEM
Model Quanta 250 FEG, Raman spectra, and IeV characteristic
technique was performed at the University of Agriculture
Faisalabad.
3.2. Phase analysis
XRD patterns were attained in the 2 qrange of 20e60 utilizing
X-ray diffraction spectrometers (Bruker make (Model D8)
operate at 45 kV and 40 mA using Cu Ka radiation (1.54  A) at
a scan rate of 1 2q/s. The results show typical diffraction
peaks at 2q ¼ 32.09 , 33.56 , 36.61 , 42.78 , 46.74 , and 57.72
for an untreated sample and 2q ¼ 32.96 , 33.74 , 36.75 ,
42.94 , 46.79 , and 57.79 for plasma treated. The micro-
structures of as-prepared ZnO nanoparticles, such as struc-
tural parameters and crystalline phases were analyzed with
XRD. The consequences of the XRD analysis are calculated in
Table 1. XRD peaks revealed that ZnO nanoparticles of un-
treated and after plasma-treated are single phase. After
plasma treatment, the peaks were shifted towards a higher
angle which increase the intensity of all peaks. It can be seen
from the XRD patterns that both samples revealed crystal-
line nature.
As shown in Fig. 1, the width at half diffraction (FWHM) of
ZnO NPs before and after plasma treatment is 0.38262 and
0.31247, respectively and the characteristic peak was moved
towards a high angle after plasma treatment, suggesting that
the plasma treatment enhanced the crystallite size of zinc
oxide NPs from 3.81 nm up to 4.68 nm, and the plasma
modification process did not just act on the surface. The
nanoparticle crystallite size was assessed through
DebyeeScherrer formula [22].
Kl
D¼ (1)
bCosQ
where the values of ‘K’ and ‘l’ are 0.94 and 1.54, respectively,
‘b’ is full width at half maximum (FWHM) of the diffraction
peaks, and ‘q’ is the diffraction angle for that peak.
The interplanar spacing between atoms was determined
with the help of Brass's law which is given as:
l
d¼ (2)
2 sin q
where'd’ is the interplanner or d-spacing between atoms, ‘q’ is
the diffraction angle for that peak and ‘l’ is the wavelength of
the incident X-ray. The d-spacing was directly related to peak
position which was shifted towards a higher angle after
plasma treatment of the sample, consequently d-spacing
increased.
Lattice Lattice X-ray Bulk Prosity (%)
Constant Volume density g/cm3 densityg/cm3
2.032 5.662 19.791 18.331 7.09
2.178 11.274 9.9404 9.44 5.03
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Fig. 1 e XRD patterns of treated and untreated zinc oxide
nanoparticles (ZnO-NPs).
The unit cell constant of the untreated sample was
a ¼ b ¼ 3.2179 
A and c ¼ 2.0321 
A, after plasma treatment, the
unit cell constant was increased up to a ¼ b ¼ 3.3239 
A and
c ¼ 2.1784 A. The movement of the characteristic peak to-
wards a higher angle corresponds to an enhancement in lat-
tice constant ‘a’ and ‘c’. These obtained consequences
revealed that new atoms/ions are introduced to the crystal
plane through microwave plasma treatment, and the lattice
united in the crystal grain block is deformed and stressed. At
the same time, it can also be proved that plasma acts not only
on the surface but also on the bulk crystalline structure. With
the expansion in unit cell constant, lattice volume was also
increased from 5.6628 A3 to 11.2747 A3. An increase in volume
exhibits an increase in optical transparency and a decrease in
density, which means that plasma treatment enhances the
optical transparency. The increase in lattice parameters
shows the conformity of Vegard,s rule prediction. The lattice
parameters and volume were calculated from the following
Eqs. (3) and (4), respectively [23]:
1 4 h2 þ hk þ k2 l2
¼ þ 2
d2hkl 3 a2 c of the linear fit provides the lattice strain (ε) and the y-inter-
pffiffiffi
3 2
V¼ a c
2 the microstrain show that produced nanoparticles are under
The higher X-ray density was exhibited by untreated ZnO
NPs while plasma treated ZnO NPs exhibited lower X-ray
density as given in Table 1. The bulk density was decreased
with the reduction of X-ray density. It can be illustrated from
Table 1 that after plasma treatment, X-ray density and bulk
density were decreased. The X-ray and bulk densities of an
untreated and plasma-treated sample have been calculated
from the following equation:
n Mw
rx ¼
NA V
Where ‘n’ shows the atomic number consisting of a unit cell
(n ¼ 8), ‘Mw’ shows the atomic weight of the compound, ‘NA’ is
the Avogadro's number and ‘V’ is the unit cell volume.
2129
m
rB ¼ (6)
V
where ‘v’ is the volume of a sample while ‘m’ is the mass of the
tablet.
The porosity of the samples was decreased from 7.09% to
5.03% on plasma treatment. The reduction in porosity on
plasma treatment enhances the features of nanoparticles. The
porosity is calculated from Eq. (7) by putting the values of X-
ray density and bulk density from Eqs. (5) and (6), respectively.
 
rB
Porosity ¼ 1   100% (7)
rx
The dislocation density and micro-strain produced in un-
treated and plasma-treated samples can be calculated by
using the following formula [24]:

dhkl ¼ 1 D2 (8)
ε ¼ bCotq=4 (9)
Dislocations are the anomaly in a crystal that occurs
because of the lattice mismatch from one part of the crystal to
another part of that crystal. The dislocation density gives in-
formation about crystallographic defects present in any
crystal. In this case, dislocation densities are obtained to
change with micro-strain. It can be seen from the calculated
data that the dislocation density (dhkl) values decreases after
plasma treatment from 0.068889 to 0.045657. The decrease in
dislocation density found that ZnO NPs on plasma treatment
has the least crystallographic defects. On the basis of obtained
XRD patterns, WeH exploration was performed by following
relation [25]:
Κl
bhkl cos q ¼ þ 4εSinq (10)
D
Where ‘D’ is denoted for crystalline size, ‘l’ is incident falling
wavelength; ‘q’ is peak position, ‘b’ is FWHM, ‘ε’ is micro-strain
and ‘K’ has a constant value of 0.94. The microstrain is
considered constant in each crystallographic direction and
then, in this case, the crystal is probable to be isotropic. A plot
with 4sinq values on the x-axis vs bhklcosq values on the y-axis
has been plotted for each analyzed diffraction peak. The slope
(3)
cept of the plot provides the crystalline size (D) is represented
in Fig. 2(a-b) for the synthesized specimens. All the values of
(4)
tensile strain. The crystallite size (TDS) calculated by the
Scherrer formula analogous to the (101) peak was chosen to
match the crystallite size calculated from the WeH plot (to-H).
It can be noted that the magnitude of microstrain is answer-
able to the alteration between the TDS and tW-H. For the un-
treated sample, both the values of tDS and tw-H show a large
difference and the microstrain is large. After plasma treat-
ment of the sample, the difference between tW-H and tD-S
slightly reduces and the microstrain also slightly reduces as
shown in Table 2. As we ignore numerous factors in the WeH
(5)
plot such as domain shape or size distribution, profile size
(Gaussian or Lorentzian), and the elastic anisotropy for the
micro-strain, therefore the utilization of the WeH plot is
problematical for quantitative peak profile analysis.
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Fig. 2 e Microstrain graph of treated and untreated ZnO nanoparticles (ZnO-NPs).
Table 2 e The dislocation density of untreated and plasma-treated ZnO NPs.
Samples Crystallite
Size (to-H) (nm)
Untreated 3.81
Plasma Treated 4.68
Consequently, it turns out to be necessary to remark that the
WeH analysis can be taken in the qualitative sense, instead of
a numerical demonstrative of linked parameters.
3.3. Morphology analysis
The morphology of untreated and plasma treated sample
were studied by scanning electron microscope (SEM). Fig.3
indicates the SEM micrographs of untreated and plasma
treated samples in low and high magnification, supporting the
corresponding particle size histograms. As expected, the
particle size of nanoparticles was increased after plasma
treatment, being consistent with XRD spectra results.
Furthermore, it is noticed that the morphology of the as-
synthesized nanoparticles was irregular and no clear grain
boundaries. After plasma treatment, agglomeration and
porosity were a minor decreased which can be seen from
following SEM micrographs. The porosity was calculated from
XRD analyzed data which can be seen from Table 1 which was
but after plasma treated was 7.09%e5.03%. The size of treated
nanoparticles was about 12 nm, after plasma treatment it was
increased up to 13 nm. The surface of plasma treated sample
was less as compared to that of untreated sample. Reduction
of porosity after plasma treatment enhanced the features of
nanoparticles’ features.
3.4. Raman spectra
The Raman spectrum is a versatile and essential analytical
technique that is used for studying the disorders, structural
defects, and crystallization of nano and microstructures. This
characterization technique performs a vital role in infrared
spectroscopy to provide a fingerprint by which molecules can
be detected, which is of excessive advantage in electronics,
optoelectronics, spintronics, and photo-catalysis applications.
Crystallite Density Williamson-Hall
Size (tW-H) (nm) Dislocation (d) Analysis (ε) (103)
13.1 0.068889 4.51
11.9 0.045657 2.47
Vibrational characteristics of ZnO NPs are investigated by
Raman spectra. This semiconductor material with a hexago-
nal structural fit into the space group of P63mc which was
confirmed by the factor-group analysis. For the best ZnO
crystal, first-order Raman scattering involves only the optical
phonons at the G point of the Brillouin zone. According to the
group theory, optical modes should be present in a wurtzite
zinc oxide are present below [27,28].
Lopt ¼ A1 þ 2B2 þ E1 þ 2E2 (11)
where E1 and A1 modes are two polar branches, which are
split into transversal optical and longitudinal optical compo-
nents due to macroscopic electric fields is attributed to lon-
gitudinal optical phonons. The A1, E1, and E2 modes are first-
order Raman-active modes.
Fig.4 exhibits the Raman spectra for pure and plasma-
treated ZnO samples in the range of 200e700 cm1. The B1
modes are in general inactive in Raman spectra according to
the Raman selection rule and are known as silent modes. The
multiphonon scattering modes have been found at 327, 434
and 544 cm1 for untreated ZnO NPs and 331, 439 and 547 cm1
for plasma-treated ZnO NPs, which are assigned to E1 and E2
modes. The optical phonon bands obtained at 434 and
439 cm1 for these two specimens, respectively, are a sharp
and stronger bands that have been attributed to one 2E2 mode
including primarily a Zn motion that is a characteristic band
of the wurtzite phase [29], these bands are practically not
dependent on particle size. This consequence is matched with
the before described data in the literature [30]. The probable
cause for this is the specifics of the E2 high band, which in-
dicates an unusually stronger anharmonicity and, conse-
quently, well-pronounced asymmetric even for the bulk zinc
oxide crystal [31]. The zone boundary phonons 3E2H-E2L give a
second-order Raman spectrum which is attributed to the
bands found at 327 and 331 cm1. The bands at 544 and
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Fig. 3 e The surface morphological images of untreated and plasma treated ZnO NPs.
547 cm1 are very weak bands from the E1 (OL) mode of zinc
oxide linked to oxygen deficiency [32]. Its intensity is depen-
dent on the fabrication technique, crystal orientation, and
crystallinity. The asymmetric bands at 382 and 384 cm1 (A1T
mode) associated with the structural order and disorder in the
crystal lattice and ascribed to the A1 (transverse optical) polar
phonon mode of pure and plasma-treated ZnO [33] are
enclosed by broadband property an of a ZneO bond at 434 and
439 cm1 for these specimens, respectively. Hense these
consequences obtained by Raman analysis are matched with
XRD analysis and revealed the pureness of specimens.
Comparing two Raman spectra of these specimens, it is can
seen from the figure that the Raman bands move towards a
high number after plasma treatment and exhibited that in-
tensities increase which the enhancement in particle size.
Though, the band broadening is insignificant, and thus it is
not supposed further in current investigation. Thus, the
increasing particle size influenced the other characteristics of
the nanoparticles became a cause of the observed shift. When
the grain size increases, two influences on the vibrational
characteristics of ZnO NPs might take place. Firstly, a volume
expansion take place in the nanoparticles which is caused by
plasma treatment, consequently, force constants increase due
to increasing the inter-atomic spaces. In vibrational
Fig. 4 e Raman spectra of untreated and plasma-treated
zinc oxide nanoparticles (ZnO-NPs).
2131
transitions, the change in wavenumber is proportional to k1/2,
where k is known as the force constant. Therefore, the high
force constants became a cause to shift the Raman bands shift
towards a high wavenumber. There is another influence that
the expansion influence induces increases in the vibrational
amplitudes of the close neighbor bonds as a result of the
decrease of the MSRD, which can be deduced as a thermal
vibrational disorder measure and static disorder measure of
the material. The intensity of the Raman bands is affected by
the vibrational amplitude enhancement with increasing grain
size. In this study, We achieved that the change in Raman
spectra of ZnO NPs is a result of the influence of vibrational
amplitudes of the close neighbor bonds and larger grain size
on the force constants.
3.5. Optical study
Generally, the oxygen deficiency, impurities, and bandgap
perform a significant part in detecting the absorbance of the
samples. Fig. 5 exhibits that absorption spectra were recorded
of untreated and plasma-treated zinc oxide nanoparticles
between 300 and 800 nm. From Fig. 5, it has been seen that
maximum absorption has occurred at 479 nm and 451 nm for
the untreated and plasma-treated nanoparticles, respectively,
which lie in the red shift region. This type of redshift in the
absorption spectra has been detected in the present research
work and can be explained by well-known quantum confine-
ment effects on ZnO NPs in comparison with bulk ZnO. The
bandgap was estimated from the Tauc plot by graph plotted of
the wavelength Vs absorption that is given as:
2
ðahnÞ ¼ BðhaEa Þ (12)
Where a is the absorbance coefficient, Ea is the energy
bandgap, hn is photon energy in eV, n ¼ 2 is for direct detec-
tion and B is the constant associated with the material. Ac-
cording to the Tauc equation, the energy bandgap of prepared
untreated and plasma-treated zinc oxide nanoparticles are
3.56 eV and 3.39 eV, respectively. These band gaps were higher
than bulk zinc oxide (3.37 eV). It may be due to an increase in
particle size and quantum confinement effect. The energy
band gap studies revealed that plasma treatment of ZnO NPs
reduces the energy bandgap with the enhancement in grain
size. In the case of untreated ZnO specimen, the optical band
gap was lightly higher which cause to reduction in the
2132 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 2 1 2 6 e2 1 3 4

Fig. 5 e UV vis spectra of untreated and plasma-treated ZnO nanoparticles (ZnO-NPs).

electron transfer between the valence and conduction band
due to the minor high forces of attraction between these
bands. Contrary to this, the optical band gap was reduced after
plasma treatment which caused to increase in the electron
transfer between the valance and conduction band due to a
reduction in forces between the valance and conduction band.
From this optical study, it is concluded that the high photo-
response will be shown by microwave plasma treated ZnO
nanoparticles with a band gap of 3.39 eV for optoelectronic
devices than untreated ZnO NPs. To increase the photo-
response of high bandgap (3.56 eV) untreated ZnO NPs for
optoelectronic devices, the electronic devices must be oper-
ated at higher temperature and power switching, electron
transfer between valance and conduction band will be
increased which results in high photoresponse showed by
ZnO NPs for optoelectronic devices.
3.6. Electrical measurement
The IeV characteristics of the specimens were measured to
discover the effect of plasma treatment on the electrical
characteristics of zinc oxide nanoparticles (ZnO-NPs), which
show in Fig. 6. These curves demonstrate the relation between
the current passing through the electronic device and the
voltage employed across its terminals. The calculated values
from IeV characteristic curves have listed in Table 3. Fig. 6 (a-
b) shows an ohmic and nonohmic relation at a low applied
voltage (V < 1V) given in Eq. (1).
I ¼ KVa (13)
Where I is the current, V is known as applied voltage, K is
constant and a is the nonlinearity coefficient which defines
the ohmic and non-ohmic nature of any material [34]: For
ohmic materials a ¼ 1 and in the case of nonohmic materials
a > 1. In the present study, the obtained IeV curves showed a
curved behavior employing the non-ohmic nature and a linear
behavior implying the ohmic nature of the untreated and
plasma-treated zinc oxide nanoparticles, respectively. The
resistivity of the material was calculated by Eq. (14) given as;
RA
r¼ (14)
L
where ‘r’ is the resistivity, ‘A’ is the area (A ¼ pr2) of the pellet,
‘L’ is the length of electrodes and ‘R’ is the resistance of the
specimen. The inverse resistivity gives conductivity
to these nanoparticles. The values of electrical resistivity
and conductivity of synthesized samples are summarized
in Table 3.

Fig. 6 e Plot of IeV characteristics of untreated and plasma-treated ZnO NPs at room temperature.
 j o u r n a l o f m a t e r i a l s r e s e a r c h a n d t e c h n o l o g y 2 0 2 2 ; 1 9 : 2 1 2 6 e2 1 3 4
Table 3 e Electrical characteristics of untreated and
plasma-treated ZnO NPs.
Samples Resistivity (r) Conductivity(s)
(U cm) ([ cm1)
Untreated ZnO 1.2  105 8.3 X 106
Plasma treated ZnO 1.8  103 5.5 X 104
The electrical resistivity of ZnO NPs is dependent on the
crystal structure and composition of the material. The results
show that the resistivity of ZnO NPs decreases on plasma
treatment from 1.2  105 to 1.8  103 U cm while the dc con-
ductivity increases from 8.3 X 106 to 5.5 X 104 [ cm1. The
decrement in band gap is also ascribed to the reduction in
resistivity and increase in conductivity of the fabricated
nanoparticles. Therefore, the plasma treatment on ZnO NPs
offers high electrical properties for ZnO-based optoelectronic
devices. The optoelectronic device requires a low leakage
current to escape from over heating or burning during its use.
The reason is that heating affects the working of the device
due to the movement of Zn2þ towards the boundary of grain,
also deletion layer produced on the boundary of grain. On the
other hand, those devices which are constructed on the base
of ultra-wide bandgap materials can operate ats higher tem-
peratures and cannot heat or burn during their use. Such de-
vices are mostly solar cells.
4. Conclusion
In conclusion, Untreated and plasma-treated ZnO NPs were
produced using a sol-gel procedure to study the impact of
plasma treatment on the optical, structural and morpholog-
ical characteristics of ZnO NPs. XRD analysis was utilized to
reveal the phase identification and purity of synthesized ZnO
NPs. The wurtzite hexagonal phase and crystalline structure
of ZnO NPs having an average crystalline size in the
3.81e4.68 nm range was confirmed without impurity phases.
Lattice parameters of ZnO NPs were increased while porosity
decreased when subjected to plasma treatment. A small
decrease in dislocation density and microstrain was found to
decrease due to the increase in crystallite size on plasma
treatment, which exhibits structural improvements. The
reduction in porosity on plasma treatment enhances the
features of nanoparticles. Raman spectra studies revealed
that the intensity of Raman bands increases due to an in-
crease in vibrational amplitude and an increase in force con-
stant caused by the increase in grain size on microwave
plasma treatment. UV-Vis spectra studies revealed that
plasma treated ZnO NPs showed the best performance due to
reduction in bandgap caused by increasing particle size,
consequently, electrons can easily transport from valance to
conduction band due to weak attractive forces between them.
IeV characteristic curves confirmed that the conductivity was
increased from 8.3 X 106 to 5.5 X 104 mho cm1 on plasma
treatment which caused an increase in leakage current, on the
other hand, resistance significantly decreased from 1.2  105
to 1.8  103 [ cm1 due to the reduction in acceptors defects
caused by the Zn2þ cations resulted in local oxygen vacancies.
Additionally, electrical consequences revealed that non-
2133
ohmic and non-ohmic behavior of untreated and plasma
treated ZnO NPs, respectively. Therefore, the conductivity of
the material increased after plasma treatment. These findings
suggested the possibility of evaluating of structural, vibra-
tional mode, optical, and electrical properties of ZnO NPs with
microwave plasma treatment and have a large potential for
the development of electronic devices.
Declaration of Competing Interest
The authors declare the following financial interests/personal
relationships which may be considered as potential
competing interests: Muhammad Hasnain Jameel reports
financial support was provided by National Natural Science
Foundation of China under Grants (No.51872227, 51572219).
Zhen-Yi Jiang reports a relationship with National Natural
Science Foundation of China under Grants (No.51872227,
51572219). that includes: board membership and funding
grants. Zhen-Yi Jiang has patent pending to Zhen-Yi Jiang. The
authors declare that there is no conflict of interest.
Acknowledgment
The authors extend their appreciation to the deanship of sci-
ence research at King Khalid for funding this work through
under grant number (RGP.2/191/43). This work was supported
by the National Natural Science Foundation of China under
Grants (No.51872227, 51572219).
Data availability statement
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
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