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Effect of Li doping on structure and optical properties of NiO nano thin-films by

SPT Effect of Li Doping on Structure and Optical Properties of NiO Nano Thin-
Films by SPT

Article  in  AIP Conference Proceedings · March 2020

DOI: 10.1063/5.0000136

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Effect of Li doping on structure and optical
properties of NiO nano thin-films by SPT
Cite as: AIP Conference Proceedings 2213, 020102 (2020); https://doi.org/10.1063/5.0000136
Published Online: 25 March 2020

M. O. Dawood, S. S. Chiad, A. J. Ghazai, N. F. Habubi, and O. M. Abdulmunem

AIP Conference Proceedings 2213, 020102 (2020); https://doi.org/10.1063/5.0000136 2213, 020102

© 2020 Author(s).
 Effect of Li Doping on Structure and Optical Properties of
NiO Nano Thin-Films by SPT
M. O. Dawood1), S.S. Chiad 2), A. J. Ghazai3), N. F. Habubi 2) and O. M.
Abdulmunem1a)
1
Department of Physics, College of Science, Mustansiriyah University, Iraq.
2
Department of Physics, College of Education, Mustansiriyah University, Iraq.
3
Department of Physics, College of Science, Al-Nahrain University, Iraq.

a)
Author for correspondence: E-mail: munem@uomustansiriyah.edu.iq.

Abstract. Structural and optical properties of undoped NiO and Li doped NiO thin films at a volumetric content of (1%
and 3%) by spray pyrolysis (SPT) were thoughtful. X-ray diffraction patterns indicate that deposited films are cubic
polycrystalline with a dominant peak at (101) plane. The study assure that Li doping did not affect the structure or
dominant peak. Average crystallite size was set to be in the range of 11.08– 21.76 nm with an average roughness of (0.33-
0.59) nm was evaluated by atomic force microscopy. Transmittance values of undoped NiO and Li doped films reaches
85% in Vis- NIR regions. Optical energy gap values for undoped NiO and Li were equal to 2.94, 3 and 3.06 eV
respectively.

INTRODUCTION
Nickel Oxide semiconductor with wide band gap of 4.0 eV [1,2] and can exist in various oxidation states [3].
NiO has stellar strength and electrochemical constancy [4, 5]. low electrical resistance, when film growth conditions
lead to generating nickel vacancies and/or forming interstitial oxygen atoms in NiO crystallites[5]. Many
applications that are used NiO thin films like, electrochromic display and thermoelectric devices [6,7] gas and
magnetoresistance sensors [8,9], transparent conducting electrodes [10]. NiO films was prepared by different
processes, like sputtering [11], reactive-pulsed laser deposition [12], electron beam evaporation [13,14],spray
pyrolysis [15,16], electrochemical deposition [17]. In present paper, SPT was adopted to study structural
,topographical,and optical of the prepared films.

MATERIALS AND METHODS

Undoped NiO and Li doped NiO films were prepared on a cleaning glass substrate utilizing SPT. 0.1 M of nickel
chloride was disbanded in 100 mL of redistilled water. To maintain the doping agent, 0.1 M of LiCl was used in the
volumetric percentage range 2 and 4. Table1 illustrates the optimum conditions that were used during the preparation
for NiO and Li-doped NiO. The gravimetric method was used to obtain the desired thickness, of 300 ± 30 nm.
Absorbance and transmittance spectra were obtained using Schimadzu spectrophotometer. Structural parameters
were obtained by X-ray diffractometer (Shimadzu, model: XRD-6000, Japan) using CuKα radiation. AFM (AA 3000
Scanning Probe Microscope) was utilized to study deposited thin films surface.

2nd International Conference on Materials Engineering & Science (IConMEAS 2019)

AIP Conf. Proc. 2213, 020102-1–020102-5; https://doi.org/10.1063/5.0000136
Published by AIP Publishing. 978-0-7354-1964-3/$30.00

020102-1
 TABLE 1. Preparation conditions for the prepared thin films.
Substrate temperature (°C) 450°C
Distance between Nozzle to substrate 28cm
Spraying rate 4 mL/min
Sprayer time 10 S
The time interval between to sprayer to avoid 1.5 min
cracking

RESULTS AND DISCUSSION

Transmittance (T) spectra of the prepared films were dispayed in Fig. 1. T of Li:NiO films decreases of nearly
90% to 80% as Li increases. It can be first attributed to observing crystallization and grain size of Li:NiO films
increase with Li content , and scattering effect happened at higher doping content. Secondly, presence of Ni+3ions
results in brown or black colorations [18]. Spectral absorption coefficient α can be calculated by using Eq. 1 as
shown in Fig.2.
Inset of Fig. 3 presents plots of (αhν)2 against photon energy (h𝑣) for Li:NiO films. Optical energy gap was
calculated by Eq. (1) [19]. Optical energy gap of Li:NiO films progressively decreases from 2.9 to 3.06 eV for Li
doping, results a decrease in carrier mobility. This could be attributed to dopant phenomena, which act as a scattering
center.
𝛼ℎ𝑣 = 𝐴(ℎ𝑣 − 𝐸𝑔 )𝑛 (1)
𝛼 = ln⁡(1⁄𝑇𝑑) (2)
Where A constant, and n is equal to 0.5 or 2 for direct and indirect transitions.

FIGURE 1. Transmittance versus λ for deposited films.

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 FIGURE 2. Absorption coefficient versus λ for deposited films.

FIGURE 3. Illustration of the energy bandgap for the deposited films.

Figure 4 display patterns of prepared films. The peaks correspond to (010), (012) and (110) peaks of standard
PDF card (JCPDS card no.04.0835) indicating that all the samples are polycrystalline. Preferential orientation of NiO
thin films increasing with increasing doping 0.1 % Li and 0.3 % Li. This indicates the combination of more Li 3+ ions
on the film during the preparation process [20]. Crystallite size D was estimated by Scherrer’s formula [21].
0.9𝜆
𝐷= (3)
𝛽𝑐𝑜𝑠𝜃
Where β (FWHM) and λ is the X-ray wavelength (1.54056Å). Cystallite size was 33nm see Table 2. The
dislocation density δ and the strain Ԑ for preferential reflection (101) are calculated using the Eq. (4) and (5) [22].
𝛿 = 1⁄𝐷 2 (4)

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 𝜀 = 𝛽𝑐𝑜𝑠𝜃 ⁄4 (5)

FIGURE 4. XRD patterns of prepared films.

TABLE 2. Structural parameters for deposited films.

Li % (hkl) 2ϴ Lattice constants (Å) FWHM(Deg.) D (nm) (ε) x10-4
zero (101) 37.25 a2.955 c7.227 0.7566 11.08
1 (101) 37.25 a2.955 c7.227 0.6843 12.25
3 (101) 37.25 a2.955 c7.227 0.3851 21.76

Surface morphology of prepared films was studied by AFM. Surface morphology of NiO and Li:NiO thin films
as observed from AFM micrographs (see Fig. 5) proves that the spherical shape grains are uniformly distributed with
the average diameter of about (100) nm, rms roughness of the surface is about (0.4) nm. Also, as the doping
increase, the grains less in size. The roughness also follows the same behavior. The Data in Table 3 indicate a high
smooth surface.

FIGURE 5. AFM parameters versus dopants (a, b and c), AFM images of (d) 0%, (e) 1% and (f) 3%.

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 TABLE 3. AFM morphology deposited films.
Li: Doping (%) Avg. Diameter (nm) Average roughness (nm) R. M. S. (nm)
0% 106.71 0.59 0.686
1% 100.82 0.359 0.419
3% 99.39 0.337 0.399

CONCLUSIONS
SPT was successful technique in preparing high of the deposit films. T of Li:NiO films decreases from 90% to
80% as Li content increases from 1 to 3 at%. Preferential orientation of NiO thin films was increase with increasing
doping content. This indicates the combination of more Li3+ ions on the film.

ACKNOWLEDGMENTS
The author would thank Mustansiriyah University for their support in this paper.

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