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Mater. Res. Express 9 (2022) 055004 https://doi.org/10.1088/2053-1591/ac6b8a
PAPER
Effect of KOH concentration on the properties of ZnO nanoparticles
Saroj Gyawali1, Lipiar Khan Mohammad Osman Goni2, M S Chowdhury1,3 , A Laref4, Saraswati Bajgai1,
Suchada Chantrapromma5 and Kuaanan Techato1,3,∗
1
Faculty of Environmental Management, Prince of Songkla University, HatYai 90110, Songkhla, Thailand
2
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
3
Environmental Assessment and Technology for Hazardous Waste Management Research Center, Faculty of Environmental
Management, Prince of Songkla University, 90110, Songkhla, Thailand
4
Physics Department, College of Science, King Saud University, Riyadh, Saudi Arabia
5
Division of Physical Science, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
∗
Author to whom any correspondence should be addressed.
E-mail: kuaanan.t@psu.ac.th and mdshahariar.c@psu.ac.th
Keywords: solar cells, synthesis, thin film, nanoparticles, perovskite solar cells
Abstract
Of late, ZnO nanoparticles have been regarded as favourable material for designing highly sensitive
and selective gas sensors owing to their striking and multifunctional features. A facile sol–gel process
chemical technique was used in this study for the preparation of undoped ZnO nanoparticles. By
deploying x-ray diffraction (XRD), transmission electron microscopy (TEM), UV–visible near
infrared and photoluminescence spectroscopy (PL), we examined the optical attributes and structural
characterisation of the undoped ZnO nanoparticles through a change in the concentration of the
KOH solution. The typical peaks inspected in the XRD spectrum corroborate the wurtzite hexagonal
arrangement in the undoped ZnO nanoparticles. Moreover, ZnO nanoparticles possess a non-
agglomerated crystalline with spherical morphology, as acquired by TEM. In addition, the vibrational
modes in FTIR spectra vary with the change of concentration of KOH solution in ZnO NPs. The
Raman spectroscopic techniques were used to characterise the ZnO nanoparticles, which revealed
their nanocrystalline nature.
1. Introduction
In recent years, metal oxide nanostructure has drawn considerable attention because of their remarkable
attributes and likely uses in various technologies. Owing to their prominent participation to applied sciences and
their interesting physical properties, metal oxide nanoparticles have appealed to many researchers. As a member
of metal oxide family, ZnO nanoparticles (NPs) are currently drawing significant attention in different domains,
like photovoltaics applications [1, 2], gas sensors [3], thin-film transistor [4], UV photo detector [5],
photocatalyst [6], luminescence, transparent UV protection films, transparent conductors, piezoelectric
nanomaterials, and light emitting diode (LED) [7] due to their excellent structural, high mechanical and thermal
stability, an optical grain about 300 cm−1, and optical and electrical properties along with good chemical
stability. ZnO is a n-type semiconducting material having a broad direct band gap (3.3 eV), greater electron
mobility (166 cm2 Vs−1), low carrier concentration (1.65×1017 cm−3), higher exciton binding energy (60
meV) and favourable to control shape and size [8]. Since the band gap of ZnO is similar to TiO2, ZnO takes in
more light in the UV zone compared to the visible region [9]. Alongside these, various morphologies of ZnO
such as nanotubes, nanorods, nanowires and nanoflowers offer unique possibilities to extend the variety of
applications. Studies on ZnO nanorods and nanowires have been greatly triggered by the use of ZnO nanorods in
developing UV lasers [10] since the controlled morphology has an impact on the functioning of nanoscale-based
optoelectronic devices. In this respect, the researchers have focused a significant amount of attention on the
controlled morphology, growth parameters, and physical properties of such structures. Various chemical and
physical routes have been reported to synthesise ZnO nanoparticle such as sol-gel, direct precipitation, chemical
© 2022 The Author(s). Published by IOP Publishing Ltd
Mater. Res. Express 9 (2022) 055004 S Gyawali et al

vapour deposition (CVD), vapour-liquid-solid (VLS), spray pyrolysis, vapour-electrochemical deposition (ED),
hydrothermal and microwave assisted thermal oxidation, etc [11–15]. Most of the synthesis methods involved
hazardous chemicals, high cost, high temperature and long preparation time which are drawbacks for large-scale
production [12]. CVD and ED require extremely sensitive conditions, involving the demand for single
crystalline substrates [13 ]. Nanorod growth also demands the use of a catalyst and a high temperature about 890
°C for VLS [15] and~500 °C for CVD [16]. While the hydrothermal method is inexpensive and simple, it gives
high yields of zinc oxide on substrate. Hydrothermal synthesis of ZnO nanorods possesses various advantages as
against the ED, VLS, and CVD procedures. However, the nanorods properties produced by hydrothermal
synthesis are not much better than the properties of the nanorods fabricated via the ED, VLS, and CVD
procedures.
Despite the various synthesis techniques for ZnO nanoparticles [10–15], control over their crystalline
structure, stability, and dispersibility remains challenging under the variation of their solution concentration.
Increasing complexity of synthetic reactions necessitates a systematic comprehension of the mechanism of
nanoparticle formation for the undoped ZnO NPs [12, 13]. However, particle structure changes still pose major
obstacles [14]. The different physical properties of NP performance are influenced by particle morphology.
The varying concentrations of KOH solution help to control the PH of the solution which directly related
with the growth ZnO nano partial size. The main functions of ZnO NP in industrial and other real-world uses
include stability, solubility, and structural morphology and shape [17]. This research aims to use KOH solution
conditions to synthesise and characterise effect of KOH on ZnO nanoparticles. The NP growth process is
observed using X-ray powder diffraction (XRD) and high-resolution transmission electron microscopy (HR-
TEM). By changing the concentration of KOH solution, photoluminescence spectroscopy (PL) has been used to
investigate the optical properties of the undoped ZnO nanoparticles.

2. Experimental procedure

2.1. Materials
In this experiment, all the employed reagents and chemicals were of analytical grade. Purchasing of n-Butanol,
Zn (CH3COO)2.2H2O (99.999%), methanol and KOH pellets (…85%) was done from Sigma Aldrich, Malaysia.
All chemicals were employed in pristine condition without any further purification.

2.2. Synthesis
ZnO nanoparticles were synthesized following the sol–gel process method of Beek et al [16]. At first, 125 ml of
0.1(M) Zn (CH3COO)2.2H2O [18] solution was prepared in three separated beaker each and stirred for 10 min
at 70 °C [17]. Three different concentrations, 0.4(M), 0.6(M) and 0.8(M), of KOH solution were prepared,
respectively, in 65 ml CH3OH and stirring for 15 min at 65 °C. KOH solution was added dropwise to the Zn
(CH3COO)2.2H2O solution at 65 °C under vigorous stirring that continued for 15 min. Then the solution was
stirred uninterruptedly for 2 h at the same temperature. ZnO nanoparticles precipitated at the bottom after 24 h.
The nanoparticles formed were separated by decanting the mother liquor. The precipitate of ZnO was washed
twice by CH3OH then finally by n-butanol. The obtained nanoparticles were initially dried by rotary evaporator
and then calcined at 500 °C For 4 H [19].

2.3. Characterization
The structural and crystallographic properties of synthesized ZnO nanoparticles were measured using a
PANALYTICALEMPYREAN diffractometer. X-ray diffraction patterns (XRD) were recorded in the range of
diffraction angles (2θ) from 20° to 80° using Cu Kα radiation with a wavelength of λ=1.5406 Å. Raman spectra
were studied using a BRUKER Raman microscope (Microscope Hyperion 3000) equipped with a charge pair
detector, a spectrometer aperture with a slit of 50 μm and a tuning grating of 900 lines mm−1. In this study, laser
powers with excitation wavelengths of 532 nm and 6 mW, respectively, were used. Agilent spectrometers of ZnO
nanoparticles were obtained in the wavelength range of 350 nm to 550 nm by exciting a xenon lamp laser with a
310 nm line using a Flex One Microscope photoluminescence spectrophotometer at room temperature.
Transmission electron microscope (TEM) JEOL JEM 2010

3. Results and discussions

3.1. XRD
The XRD patterns of ZnO nanoparticle with diffraction angle 20° to 80° at different concentrations (0.4 M, 0.6
M and 0.8 M) of KOH are shown in figure 1. It is observed from the diffraction patterns of ZnO nanoparticles
that all samples exhibit diffraction peaks corresponding to (100), (002), (101), (102), (110), (103) and (112)

2
Mater. Res. Express 9 (2022) 055004 S Gyawali et al

Figure 1. XRD patterns of ZnO NPs prepared in 0.4, 0.6 and 0.8 M KOH.

Figure 2. TEM images of ZnO NPs.

lattice planes at diffraction angles (2θ) 31.7°, 34.4°, 36.1°, 47.5°,56.4°, 62.6° and 67.9°, respectively. The XRD
pattern along with the high intensity peaks at 31.7°, 34.4° and 36.1° from this study is appropriately matched
with the standard XRD spectrum documented in JCPDS card No. 01–070–8070, representing that the grown
ZnO nanoparticles are highly crystalline with hexagonal wurtzite structure (space group: P63mc) [El-Shaer,
2018]. At 0.4(M) KOH, the dominant peak intensity was identified, suggesting a strong orientation and also with
improved crystallinity. The estimation of average crystallite size pertaining to ZnO nanoparticles has been done
based on the half intensity width of the (002), (100), (101) peak by employing Debye–Scherrer’s equation
(equation (1)), in which b defines the FWHM intensity pertaining to the main peak observed at 2θ in radian, l
signifies the X-ray wavelength, k indicates a constant and q signifies the Bragg’s angle of diffraction.
kl
dhkl = (1)
b cos 2q

3.2. TEM
Figure 2 shows TEM images pertaining to NPs with hexagonal shapes, corroborating the ZnO particles’
hexagonal nature. As per TEM results, a spherical morphology is associated with the ZnO NPs, which varies in
crystallite size since the particles are aggregated as well as appear to be non-agglomerated crystalline when there
is a variation in concentration of KOH solution during the step of sample preparation. With regards to ZnO
NPs, formation of various grains and particles formation could be observed (refer figure 2), while the left panel
pertaining to figure 2 demonstrates large particles stemming from adjacent particles that have been merged. A
variation in the concentration of KOH solution used to control PH that will lead to change particle growth as
well as morphology of the particles. Moreover, the size of the nanoparticles was found to be around 20 nm (see
figure 2).

3
Mater. Res. Express 9 (2022) 055004 S Gyawali et al

Figure 3. FTIR spectra of ZnO NPs prepared in 0.4, 0.6 and 0.8 M KOH.

Figure 4. Raman spectra of as-grown ZnO NPs in presence of 0.4, 0.6 and 0.8 M KOH.

3.3. FTIR
The FTIR spectra presented in figure 3 refers to the ZnO nanoparticles synthesised with 0.4, 0.6 and 0.8 M KOH.
The spectra demonstrate vibrational modes pertaining to ZnO NPs, unreacted materials as well as intermediate
species. The OH stretching vibration results in the broad absorption band at 3,369 cm−1. The weak bands
observed at 2,201 and 2,362 cm−1 refer to the vibration modes of CO2 [20]. C–O and C=O stretching vibrations
correspond to the relatively sharp but weak band formed at 1,008 cm−1 as well as the strong bands formed at
1,402 and 1,550 cm−1, respectively, which can be attributed towards the cluster formation of Zn4O(CH3COO)6
tetranuclear oxo zinc acetate [21]. The bands at 667 and 822 cm−1 correspond to Zn–O and Zn–OH stretching
vibrations, respectively.

3.4. Raman
Figure 4 showcases the Raman spectra pertaining to the generated ZnO nanoparticles. The intense absorption
bands observed at 100 and 438 cm−1 refer to E2 (low) and E2 (high) frequency phonons that relate to the
vibration of Zn and oxygen sublattices pertaining to wurtzite crystal structure, respectively. At 100 and 438
cm−1, as per the intense absorption modes, the synthesised ZnO NPs refer to high crystallinity [22]. The low
intensity peak observed at 580 cm−1 corresponds to A1 longitudinal optical (A1 LO) phonon mode, and suggests
structural defects like zinc interstitials, oxygen deficiency or defect complexes with regards to zinc interstitial and
oxygen vacancy in ZnO. The multiphonon scattering process corresponds to broad peak at 653 cm−1 [23]. The
optical and acoustic combinations are shown as peaks at 927 and 1071 cm−1 pertaining to A1 and E2 modes,

4
Mater. Res. Express 9 (2022) 055004 S Gyawali et al

Figure 5. Photoluminescence spectra of ZnO NPs.

respectively [24]. It is quite clear from figure 4 that there is significant red shift (lower energy) in the peaks at 100,
438, 580 and 927 cm−1 with an increase in KOH concentration. However, a contrasting trend of blue shift
(higher energy) was observed in case of the peaks at 653 and 1071 cm−1 with increasing KOH concentration [25].
The presence of deep level defects or surface defects in the sample may have contributed to the observed peak
shifts.

3.5. Photoluminescence
The room temperature photoluminescence spectra of ZnO NPs prepared in presence of different concentrations
of KOH is presented in figure 5. It has been reported that the PL spectrum of ZnO usually contains two emission
bands, with one being in the UV region (370–400 nm) and another being in the visible region (400–700 nm) [26].
However, the PL spectrum of ZnO spherical-shaped NPs and quantum dots with defect levels have been
reported to have showed a broad and weak emission band in the UV region and a collection of emission peaks
covering almost the entire visible region [27]. Therefore, these earlier reports and the PL spectra of ZnO NPs
showed in figure 5 support the experimental findings of XRD and TEM study that the synthesized NPs are
nanometre-sized. In the emission spectra of ZnO NPs, a broad band around 380–390 nm could be seen in the
UV region, which experiences a blue shift with increasing KOH concentration. Whereas, the emission peaks in
the visible region does not show any significant shift in wavelength. However, most of the prominent emission
bands can be seen in the blue and green visible region originating from lattice defects. The origin of different
lattice defects, such as zinc vacancy, zinc interstitial, zinc anti-site, oxygen vacancy, oxygen interstitial, and
oxygen anti-site could be attributed to the increasing concentration of KOH causing compressive strain leading
to intrinsic defects in the material [28, 29].

4. Conclusion

In conclusion, synthesis of various undoped ZnO nanoparticles was carried out, which were characterised by
changing concentration of KOH solution. With this regard, we employed Raman, XRD, TEM and
photoluminescence spectroscopy techniques in order to analyse as well as characterise undoped ZnO
nanoparticles’ optical and structural characteristics. As per the XRD spectra, a hexagonal wurtzite structure was
shown by the ZnO nanoparticles at low concentration solution. As shown by TEM images, the undoped ZnO
nanoparticles were found to be non-agglomerated and demonstrated spherical morphology. In addition, the
FTIR analysis demonstrated the vibrational modes pertaining to variation in ZnO nanoparticles with KOH
solution concentration. By employing Raman spectroscopy, the nanocrystalline characteristics of ZnO
nanoparticles could be determined, which is more distinct at low concentration with regards to KOH solution.
In the PL emission spectra pertaining to ZnO nanoparticles, one emission band was seen in the UV region with
variation in concentration pertaining to KOH solution. Moreover, PL was employed to determine the optical
characteristics pertaining to these nanoparticles and the measured results were in line with the results obtained
by XRD. In this study, a low-cost, simple, chemical method was conducted to prepare ZnO nanoparticles, which
can also be employed for different industrial applications.

5
Mater. Res. Express 9 (2022) 055004 S Gyawali et al

Acknowledgments

This research was supported from Prince of Songkla University and Ministry of Higher Education Science
Research and Innovation Under the Reinventing University Project (Grant Number REV64012), This research
also supported by Prince of Songkhla University under the grant number ENV6505076S.

Data availability statement

No new data were created or analysed in this study.

ORCID iDs

M S Chowdhury https://orcid.org/0000-0003-1321-1176
Kuaanan Techato https://orcid.org/0000-0002-9178-8416

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