Spectroscopic diagnostic and structural characterization for (Selenium, Zinc oxide and Manganese oxide) prepared by laser induce plasma

Abstract

.In this paper, the plasma parameters of the three materials (selenium, zinc oxide, and manganese oxide) were calculated using laser induced breakdown spectroscopy, where the plasma is generated by this technique through the interaction of the laser with the solid target and the calculation of the electron temperature and electron density. Also, the structural properties of the prepared thin films were studied. It was found from the standards that the crystal size (XRD) of the three materials decreases with increasing energy, and this corresponds to measurements of (AFM) where the average diameter decreases with increasing energy

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Journal of Physics: Conference Series
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Spectroscopic diagnostic and structural characterization for (Selenium,
Zinc oxide and Manganese oxide) prepared by laser induce plasma
To cite this article: K A Aadim and R H Jassim 2021 J. Phys.: Conf. Ser. 1963 012023
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2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
1
Spectroscopic diagnostic and structural characterization
for (Selenium, Zinc oxide and Manganese oxide)
prepared by laser induce plasma
K A Aadim1 and R H Jassim2
1Department of Physics, College of Science, University of Baghdad, Iraq
2Department of Physics, College of Science for women, University of
Baghdad, Iraq
kadhim_adem@scbaghdad.edu.iq
mail: -e
ABSTRACT .In this paper, the plasma parameters of the three materials (selenium,
zinc oxide, and manganese oxide) were calculated using laser induced breakdown
spectroscopy, where the plasma is generated by this technique through the interaction
of the laser with the solid target and the calculation of the electron temperature and
electron density. Also, the structural properties of the prepared thin films were
studied. It was found from the standards that the crystal size (XRD) of the three
materials decreases with increasing energy, and this corresponds to measurements of
(AFM) where the average diameter decreases with increasing energy
1- Introduction
Due to its versatile and complex nature, laser-induced plasma (LIP) formation is a rapid
process which has been under investigation for several decades. For a very short period of
time, the intense laser pulse delivers energy to the target surface, which excites, ionizes and
vaporizes the material immediately into an extremely hot vapor plume, also known as a
'plasma plume'[1]. LIBS is an atomic emission spectroscopy technique that causes optical
sample excitation using highly energetic laser pulses [2]. The interaction between focused
laser pulses and the sample produces plasma made of ionized matter. 'Spectral signatures' of
chemical composition of many different material types in solid, liquid or gas state [3,4] may
be supplied with plasma light emissions. The ablation process is divided into three stages
using lasers with long pulse durations (> 1 ns). In the first stage, the laser light interacts with
the solid, resulting in quick ionization of the target surface into plasma on a short time scale
relative to the duration of the pulse. The laser light is absorbed effectively by the plasma that
isothermally expands in the second phase. The resulting plasma plume expands quasi-
adiabatically in the third stage after the end of the laser pulse, in a medium that can include
vacuum or a background gas [5]. In the emission spectrum, visible lines that are useful for
plasma parameters such as electron temperature, electron number density, debye length and
plasma frequency estimation are shown. If the plasma is in local thermodynamic equilibrium
(LTE), by calculating the electron temperature, the relative strength of two lines originating
from the same species form and the same ionization phase can be achieved [6]. In LTE, The
plasma temperature is calculated from the equation [7]:

2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
2
Te = 
󰇛
󰇜
………………………………………..….. (1)
The number of free electrons per unit volume describes the electron density (ne). For
determining electron density, there are several credible methods used, including plasma
spectroscopy, microwave and laser interferometry, and Thomson scattering. Electron density
determination by linear Stark expansion of plasma spectral lines results from the resulting
collisions in line expansion and peak wavelength shift of charged species.
2. Experimental Setup
Optical atomic emission spectra of zinc, manganese, and selenium plasma were calculated
using the laser induced breakdown spectroscopy technique as shown in Fig. 1.
This system consists of a laser device (Nd:YAG) with a wavelength of 1064 nm and a pulse
duration of 9 nanoseconds with a repetition frequency of 6 hertz, where it is at an angle of 45
with the solid target and the focal length is 10 cm, so the process of contrasting is easier and
faster and focusing the laser on a smaller area where the size of the laser spot is The depth and
concentration is small and thus the strong breakdown and production of the plasma are shown
in the above figure. The optical emission spectroscopy (OES) method was used to determine
electron temperatures, plasma frequency densities as well, mathematically determining the
length of Debye and Debye number.
3. RESULTS AND DISCUSSIONS
3.1 Plasma spectrum of (Zinc, Manganese and Selenium).
Laser induced (zinc, selenium and manganese) plasma optical emission spectrum of 300 nm
to 900 nm plume in ambient air with laser pulse energies of (650, 750, 850 and 950) mJ. The
plasma spectrum consists of a number of neutral lines and the assignment of these lines was
done using NIST database. Figures (2,3 and 4) shows the highest intensity lines in the plasma
spectrum (Zn, Mn and Se) spectral lines in the air ambient. Transitions are identified using the
National Institute of Standards and Technology's spectral data base (NIST). Increases in
plasma height and plasma emission are the result of the increase in target ablation. The
Figure 1. Show the conventional LIBS system configuration

2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
3
plasma shielding effect is observed at higher laser peak power values, i.e. the plasma becomes
opaque to the laser beam that shields the target so that the intensity of the lines drops. Due to
the variation in their statistical weight, probability of transition and excited energy level, the
peak intensities vary from peak to peak. Which according to Boltzmann, designates the
number of excited atoms at this level In addition, it can be noted that the difference in the
percentage increase in the intensity of the peaks by increasing the laser energy used is due to
the difference in plasma temperature that affects the distribution of excited atoms according to
Boltzmann[8]. Figures show the variation of electron temperature (Te) and electron density
(ne) with laser energy (a, b and c). The electron temperature and electron density increased by
increasing laser pulse energy due to the laser peak energy that increased the likelihood of
ionization collisions with increasing electron energy in all metals. The electron temperature is
heavily dependent on the laser's peak power as the latter is the source of evaporation,
atomization, and concentrated ionization of the target [8].
Figure 2. Plasma emission spectroscopic pattern for pure target Zn at different laser energy
sources.
Figure 3. Plasma emission
spectroscopic pattern for pure target Mn
at different laser energy
Figure 4. Plasma emission
spectroscopic pattern for pure target Se
at different laser energy sources

2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
4
Tables (1, 2and 3) show the calculated electron temperature, electron density and plasma
frequency for the target of zinc, manganese and selenium at different laser energies. All
calculated plasma parameters correspond to the plasma conditions and criteria. Plasma was
achieved through the results of the plasma parameters ( 
). This result is in agreement
with [9].
Table (1). Plasma parameters with different laser energies for a pure (Zn) target.
Laser energy (mJ)
FWHM (nm)
 (eV)
ne (cm-3)
 (Hz)
 (cm)
ND
650
2.70
0.021
7.08E+17
7.6E+12
1.3E-07
6.0E-03
750
3.00
0.021
7.87E+17
8.0E+12
1.2E-07
5.9E-03
850
3.10
0.022
8.13E+17
8.1E+12
1.2E-07
6.3E-03
Figure (b). Variation of  and 

plasma emitted from pure Se target
using laser with different energy.
Figure (c). Variation of  and 

plasma emitted from pure Mn target
using laser with different energy
Figure (a). Variation of  and 
 plasma
emitted from pure Zn target using laser with
different energy

2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
5
Table (2): - Plasma parameters with different laser energies for a pure (Se) target.
Laser energy (mJ)
FWHM (nm)
(eV)
ne (cm-3)
(Hz)
(cm)
ND
650
2.60
0.736
6.82E+17
7.4E+12
7.7E-07
1.3E+00
750
2.70
0.777
7.08E+17
7.6E+12
7.8E-07
1.4E+00
850
2.80
0.797
7.34E+17
7.7E+12
7.7E-07
1.4E+00
950
2.80
0.821
7.34E+17
7.7E+12
7.9E-07
1.5E+00
Table (3). Plasma parameters with different laser energies for a pure (Mn) target.
3. 2 Structural characteristics
3.2.1X-Ray Diffraction
The Diffraction of X-rays results of the figures below (5) were shown for thin films of pure
zinc oxide deposited on glass bases at room temperature and by the effect of laser energy (950
mJ). It was observed that it is polycrystalline and has a hexagonal crystal system for Zinc
oxide and the preferred growth trend is (002) for which is in good in agreement with [10,11].
X-ray diffraction pattern for Mn powder is polycrystalline cubic system and MnO thin film
shows an amorphous structure. Whereas the results of pure selenium thin films prepared after
the one-hour annealing process were also polycrystalline with a hexagonal crystal system and
the preferred growth direction (011) as shown figure (6) and this result is consistent with [12]
950
3.30
0.024
8.65E+17
8.4E+12
1.2E-07
6.7E-03
Laser energy (mJ)
FWHM (nm)
 (eV)
ne (cm-3)
 (Hz)
 (cm)
ND
650
3.20
0.214
8.9E+18
2.7E+13
1.15E-06
5.4E+00
750
3.30
0.219
9.2E+18
2.7E+13
1.14E-06
5.3E+00
850
3.50
0.225
9.7E+18
2.8E+13
1.12E-06
5.08E+00
950
3.50
0.231
1.1E+19
2.9E+13
1.1E-06
4.7E+00
Figure (5). XRD patterns of the (ZnO)
thin film using prepared PLD technique
with number of pulse =100 shots
Figure (6):- XRD patterns of the Se thin film
prepared using PLD technique and annealed
at 373k with number of pulse =100 shots.

2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
6
3.2.2 Morphological properties
3D AFM images and granularity accumulation distribution chart of (ZnO, MnO and Se) thin
films deposited on glass substrate were synthesized with different laser energy and number of
shots shown in Fig (7). These figures show that the particle sizes for all atoms are located in
the nanometric scale. These Shapes illustrates that the average diameter decreases with
increasing number of energies laser this result is in agreement with [13].
E=950mJ, ZnO, G.S=34.16nm E=950mJ, G.S=46.91nm,MnO
E=950 mJ, Se, G.S=45.23nm
Figure (7). 3D AFM and their granularity accumulation distribution thin film prepared by
PLD with laser energy and annealed T=373 K for Se and at R.T for ZnO and MnO.
Conclusions
1- Laser-induced plasma emission spectral line intensity showed a strong dependence on
pulsed laser energy.
2- The XRD characterization indicates that with a hexagonal system, ZnO and Se have
wurtzite type polycrystalline thin film, while with a cubic system, MnO has wurtzite
type polycrystalline thin film.
3- AFM investigation shows that the average roughness and RMS increase with
increasing of the energy, while the average diameter decreases with increasing of the
energy

2nd International Conference on Physics and Applied Sciences (ICPAS 2021)
Journal of Physics: Conference Series 1963 (2021) 012023
IOP Publishing
doi:10.1088/1742-6596/1963/1/012023
7
ACKNOWLEDGEMENTS
We thank University of Baghdad, College of Science, Department of Physics, Plasma Physics
Lab. for supporting this work
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