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Energy Reports 6 (2020) 447–458

www.elsevier.com/locate/egyr

Tmrees, EURACA, 13 to 16 April 2020, Athens, Greece

The effect of ZnSe Core/shell on the properties of the window layer of

the solar cell and its applications in solar energy
Dr. Nisreen Kh. Abdalameera , Dr. Sabah N. Mazhir (Prof.)a ,∗,
Dr. Kadhim A. Aadim (Prof.)b
a Department of Physics, College of Science for Women, University of Baghdad, Baghdad, Iraq
b Department of Physics, College of Science, University of Baghdad, Baghdad, Iraq

Received 5 August 2020; received in revised form 4 September 2020; accepted 26 September 2020

Abstract
In this paper, ZnSe nanoparticles (ZnSe NPs) were prepared by selenium nitrate and zinc metal sheets to improve the
absorption coefficient that affects the solar cell. Also, core–shell structured ZnSe was prepared by atmospheric pressure
plasma jet system. The structure properties and optical were described by X-ray (XRD) diffraction, and ZnSe NP absorbance
measurements. Finally, with support from structural and optical studies, the current density–voltage (J–V) properties of n-
ZnSe/p-Si solar films found that conversion efficiency strongly depends on strongly porous silicone time. fill factor (F.F)
increase from (0.40 to 0.56) with increasing porous time and efficiency (η) increasing from 0.89 to 2 with increase porous
time from 5min to 20 min.
⃝c 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
Peer-review under responsibility of the scientific committee of the Tmrees, EURACA, 2020.

Keywords: Plasma jet; ZnSe NPs; Solar energy; Core–shell

1. Introductions
ZnSe is an important technical optoelectronic semiconductor with a large 2.7 eV bandgap. ZnSe can be substituted
in solar photovoltaic cells. Due to its potential applications in several optical and electronic devices and as a
buffer/window material for thin film-heterojunction solar cells it is seen as an important technological material.
In several of these applications, the energy bandgap, thickness of the film and the wavelength of the film absorption
or transmission are of concern. Specific ZnSe thin films deposition methods have been used, including thermal
evaporation, electrochemical deposition and chemical deposition in baths [1]. Nanotechnology is a multidisciplinary
field of science and technology research. Synthesis, structures and use of materials and equipment below 100 nm
made a major contribution to a wide variety of biomedical fields such as imaging, pharmaceutical goods, diagnostic
∗ Corresponding author.
E-mail addresses: physical2017@yahoo.com (Dr. N.K. Abdalameer), sabahnm_phys@csw.uobaghdad.edu.iq (Dr. S.N. Mazhir),
kadhim_adem@yahoo.com (Dr. K.A. Aadim).

https://doi.org/10.1016/j.egyr.2020.09.023
2352-4847/⃝ c 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.
org/licenses/by/4.0/).
Peer-review under responsibility of the scientific committee of the Tmrees, EURACA, 2020.
Dr. N.K. Abdalameer, Dr. S.N. Mazhir and Dr. K.A. Aadim Energy Reports 6 (2020) 447–458

devices and other areas [2]. The smaller and larger ratio of volume of NPs are the main features that make biomedical
applications useful, which leads to many new properties such as easy operation, biomolecular conjugation, etc. In
order to save people’s lives, different illnesses such as cancer, diabetes, strokes, Alzheimer’s early diagnosis, etc. was
the main priority in the biomedical sector [3]. There are very few studies of ZnSe-NPs nanostructures among Specific
semi-conductive forms (i.e. CdSe, CdTe, CdS). The N-type semiconductor ZnSe is 2.7 eV in width at 25 ◦ C [4].
ZnSe-NPs can be used for many areas in the family of selenide nanoparticles (e.g. CdSe, FeSe etc.) for example
flat screens, light emitting diodes, biomedical sensors and applications photo detectors [5–7].
A broader analysis was carried out of methods of synthesis of ZnSe–NP including wet chemistry, Hydrothermal
sol–gel, solvothermal, microemulsion, reverse micellum and pyrolysis. However, these processes suffer from many
disadvantages, such as the use of high-pressure and temperature additives, as well as hazardous materials/chemicals
as well as the pureness of the final product [8–10]. Therefore, the preparation of ZnSe-NPs was needed with cold
plasma and (core–shell) methods to reduce toxicity in an easy, green, economic and environmental manner. There
is growing interest in the use of plasma for biomedical applications, especially under the so-called ‘plasma drug’
to take advantage of the action of low-power, air-pressure plasmas for therapeutic purposes [11,12].
Core-nanoparticles have a core composed of a substance which is covered with a different substance. For
biological applications, nanoparticles’ core shell has significant advantages over basic nanoparticles, for example:
(i) Cytototoxicity lower [13] (ii) Enhanced bio- and cytocompatibility, disbursement (iii) improved conjugation with
other bioactive molecules (iv) Enhanced thermal and chemical stability. Shell coating not only serves as a non-toxic
barrier, but also enhances the core nature of the content. (i) The coating of other materials increases optical properties
and photostability for core/coating semiconductor nanoparticles. (ii) the hydrophilicity of nanoparticles is very
critical for dispersal in biological (aqueous) environments. Can biodispersibility and biological and cytocompatibility
make It is a valuable alternative to typical stocks of medicines. Synthesis simplicity is also an important factor in
drawing attention to this type of content. If the core material becomes hydrophobic, it addresses the problems of
Distribution and cyto-compatibility in form of core/shell nano-particles on a core surface to cover the hydrophilic
material. (iii) For many bio-use applications, the conjugation of biomolecules on the particle surface is very
necessary. In certain cases it may be difficult to combine the related material with a specific form of biomolecules;
in this case it is easier to overcome this problem by covering an suitable bio-compatible product. (iv) Although a
core material during environmental exposure is vulnerable to chemical and/or heat alteration, the coating of inert
material typically enhances core particle stability. In such cases, nanoparticles in core/shell are more promising than
single nanoparticles for biological applications [14,15].
Milk thistle (MT)/Silybum marianum (L.), is an annual or semi-annual plant occurring worldwide. The medicinal
sections are the mature seeds. which are highly rich in antioxidants. They have been used as a medication for the
treatment of diseases of the kidneys, liver, and they biliary tract for decades. Based on its interactions with different
receptors, MT’s cytoprotective function is likely mediated by its antioxidant properties [16].
Plasma usually is an ionized gas which incorporates particles of charge (electrons, ions, and molecules). The
word ionized refers to the life of a free-electron or more but does not refer to an atom or molecule. Plasma has
free charging particles that store positive and negative charges in the macroscopic stage [17,18].
One of the main goals of the present paper is to apply the plasma jet technique to prepare ZnSe-NPs.

2. Materials and methods

2.1. Plasma jet system

Argon gas was used in the regular atmospheric pressure jet plasma system to produce cold plasma to prepare
the ZnSe nanoparticle. The plasma system consists of the following parts: Fig. 1.

• High voltage power supply of 15 kV, and 23 kHz.

• A metal hollow tube made of stainless steel, 3 cm in length and 1 mm in diameter, which connects to the
anode of the power supply.
• Metal strip of conductive stainless steel, 6 cm length and 5 mm width, which ends with a flat piece (1 × 1)
that connects to the cathode of the power supply (cathode).
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Dr. N.K. Abdalameer, Dr. S.N. Mazhir and Dr. K.A. Aadim Energy Reports 6 (2020) 447–458

Fig. 1. Scheme of plasma jet system (cold plasma).

2.2. Preparation of selenium salt solution

The saline solution of selenium (SeO (NO3 )2 ) Prepared at 0.1 M concentration through a reaction of selenium
dioxide (SeO2 Avonchem, UK) with nitric acid (HNO3 ) (CDH, India) in 100 ml of deionized water only as in the
following equation:
SeO2 + 2HNO3 = SeO(NO3 )2 + H2 O (1)
2 ml of the prepared substance and diluted with 500 ml of deionized water, where the molecular weight was
218.96 g/mol so that the salt solution concentration was 0.0004 M.

2.2.1. Preparation of selenium N.P.s and ZnSe N.P.S (Core–Shell)

This preparation method involved the exposure of the 10 ml of selenium nitrate at a concentration of 0.0004
molar in a 25 ml glass beaker to cold plasma or 3 min at gas flow rate of 2 L/min. It is observed that the solution
color was changed as an indication of obtaining the nanoparticles.
Then, we changed the flat electrode with a zinc metal sheet on the pre-prepared selenium nanoparticle and
exposed them to the plasma with the same conditions of time and gas flow rate. We observed the color change of
the solution as an indication of obtaining the nanoparticles, where selenium NPs were the core, while zinc (shell)
coated them to reduce toxicity (see Fig. 2).

2.3. Preparation the extract of milk thistle plant seeds (MT)

The extract contains the metabolites of cells in addition to their components. The components are usually of
anti-oxidant properties [19], i.e. they act as substances with a reducing ability that converts selenium ions into
nano selenium and changes color after exposure to plasma. Impurities were first removed from seeds which were
then washed several times with deionized water. Five grams of the seeds were added to 100 ml of deionized water
magnetically starred for 20 min at 60 ◦ C. The extract was placed in the centrifuge tubes and the material was
reduced to the liquid and filtered with filter paper, as shown in Fig. 3.

2.4. Preparation of ZnSe NPs with MT

The green solution was prepared by adding 2% of the extract to 8% of the solution of selenium nitrate, with a
ratio is (2: 8) (10 ml), and the plasma is exposed at the gas flow rate 2 L /min and for time of 3 min, observed the
color change indicating the obtaining of nanoselenium in the green environment friendly way.
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Fig. 2. (a) Se NPs , (b) Se with Zn sheet, (c) ZnSe NPS . . (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)

Fig. 3. The extract of milk thistle (MT) plant seeds. . (For interpretation of the references to color in this figure legend, the reader is
referred to the web version of this article.)

The electrode of the system was changed by a zinc metal sheet under the same conditions of gas flow rate and
time. Thus, the zinc metal enveloped the green nanoselenium and changed the color, leading to the obtaining of the
zinc selenide compound in the green way (core–shell), as demonstrated in Fig. 4.

2.5. Optical and structural measurements

A UV wavelength range of 300 to 1100 nm (UV-1800 spectroscopy) was used with a double-optical spectrometer
(PD-303 UV) to detect Surface Plasmon Resonance (SPR) at room temperature for ZnSe NPs.
The structural evolution of the synthesized ZnSe NPs was carried out using an X-ray [XRD-6000, AS (3k.
NOPC)], with a Cu-Kα-radiation wavelength of λ = 0.15418 nm operating at 40 kV and 30 mA in a configuration
of θ – 2θ. The following Debye–Scherrer equation was used [20].
0.9λ
D= (2)
β cos θ
(D) is the crystalline dimension, (λ) is wavelength (1.5406 Å) of the X-ray, (θ ) is the degree of the peak of
diffraction, and (β) is the complete maximum peak width (FWHM).
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Fig. 4. ZnSe NPS with MT. . (For interpretation of the references to color in this figure legend, the reader is referred to the web version
of this article.)

Fig. 5. Porous silicon system.

2.6. Porous silicon preparation

A (p-type) silicon wafer with a resistance of 0.01–0.02  cm was prepared cut it to the required size and
rinse with ethanol to clean the surface from any contamination and then rinse With (Hf) concentration (5%) to
remove the oxide and dry it in the air. As for the etching system. The electrochemical shown in Fig. 5 consists
of a power supply to supply the system with voltage Fitting, current density meter, digital clock, Teflon hollow
cylinder Diameter (1 cm) inside solution: Ethanol: HF (in ml) 2 from HF solution and (1 ml) From the solution
of ethanol to reduce the bubbles of hydrogen emitted during the reaction, which leads to obstruction The etching
process continues, as two electrodes were used to apply current through the first electrode cell A cathode made of
platinum is immersed in a solution (HF) and the anode second electrode is a disk Stainless steel placed under the
silicon slide from the bottom, as demonstrated in Fig. 5.
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Fig. 6. (a) Absorption and (b) absorption coefficient as a function of wavelength for ZnSe NPs.

Fig. 7. Calculation of photon energy for ZnSe direct method.

3. Result and discussion

3.1. UV – Visible absorption spectrum analysis for ZnSe NPs

UV–Visible absorption spectroscopy was used for the calculation of the band energy. The optical absorbance was
measured at room temperature as a function of wavelength (300–1100 nm) for ZnSe NPs with an average thickness
of 200 nm, where the absorption spectrum was declined as previously described [21], as shown in Fig. 6a, b.
In the following formula, the bandgap energy of films outside the absorption range was calculated using the
Tauce method [22]:
)1/2
αhυ = A hυ − E g
(
(3)
where α is the linear coefficient of absorption, A is a constant, hα is photon energy and eg is the band-lap energy
for direct and indirect NPs [23]. Eg of the film can be determined by plots (αhυ)2 versus hυ and the straight lines
can be extrapolated to the photon energy axis. Eg is higher than the ZnSe bulk optical bandgap (2,7 eV) due to the
quantity containment of ZnSe nano crystallite. The energy gap is Eg = 3.4 eV in ZnSe nano this increase in the
energy gap in nanoscale solutions may arise from the effect of quantum volume, agree with [24] shown in Fig. 7a,b

3.2. UV – Visible absorption spectrum analysis for ZnSe-green NPs

Fig. 8a,b illustrates the optical absorbance as a function of wavelength in the range of 300–1100 nm at room
temperature for ZnSe green with an average thickness of 200 nm. the absorption spectrum declined indicates that
surface plasmon resonance peak of ZnSe green NPs at 600 nm, this characteristic is evident in the visible light
area and is responsible for the color change when the material reaches the nanoscale. This property causes the
temperature around the nanoparticle to rise when the light falls on it. Thus, this feature was employed in many
applications, including: the inhibition of growth of cancer cells [25].
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Fig. 8. (a) Absorption and (b) absorption coefficient as a function of wavelength for ZnSe NPs.

Fig. 9. Calculation of photon energy for ZnSe green direct method.

Table 1. 2θ , crystalline size, d-value, FWHM and crystalline size of ZnSe thin film of prepared
under 12 kV voltage, 23 kHz frequency and gas flow rate 2 L/min.
Sample 2θ FWHM d-value size of crystalline (nm) Avg
(deg) (deg) (A◦ )
ZnSe NPs 27.3 1.31 3.3077 6.256178 13.0955
45.4 0.68 1.99 12.69116
54.4 0.44 1.67.76 20.33917

In the same way, the energy gap of ZnSe NPs was calculated and found to be close to that known for these NPs,
as shown in Fig. 9.

3.3. Structural properties using XRD diffraction

ZnSe NPs synthesized in cold plasma showed Bragg’s X-ray (XRD) patterns reflecting ZnSe NPs fcc structure.
Fig. 10 illustrates the X-ray diffraction patterns for ZnSe NPs prepared where a maximum of two peaks is observed,
equivalent to 27.3◦ , 45.4◦ , and 54.4◦ , corresponding to the (111), (220) and (311). This applies to the ZnSe NPs in
line with ZnSe’s regular X-ray diffraction model (JCPDS no. 01-088-2345). The above pattern demonstrates that
no other materials can replicate the diffraction pattern of any peak that indicates the purity of the prepared sample
and the absence of external contamination that matches findings from other studies [26].
The crystalline size of (ZnSe NPs) indicates that the sizes of samples prepared were below the nanoscale, as
appear in Table 1.
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Fig. 10. X-ray patterns of ZnSe NPs.

Fig. 11. Cross section of a solar cell [27].

3.4. Solar cell and structure

A solar cell is an electronic system that turns sunlight Electricity directly. Light on the solar cell generates both
electricity and voltage. Firstly, a substance in which light absorption lifts the electron to a more energy level, and
secondly, the movement from the solar cell to an outer circuit of that higher energy electron. The electron dumps its
energy into the external circuit and returns to the solar cell. Photovoltaic transmission of electricity requirements can
meet a variety of materials and processes, but in practice almost all photovoltaic energy conversions use p-junctive
semiconductor material, as shown in Fig. 11.
The efficiency of solar was calculated using the following formula [28]
η = (Voc xIsc /Pin ) F.F (4)
where Voc is open circuit voltage (V) and Isc is short circuit current (mA/cm2 ) and F.F is fill factor
F.F = Vm x Im /Voc x Isc (5)
where Vmax and Imax are voltage and current at the point of maximum power output of the cell.
The I–V characteristics of the n-ZnSe/p-PSi solar cell were seen in under illumination utilizing power densities
equivalent to 100 mW/cm2 with the forward and reverse bias applied. The forward current usually is higher than
the reverse current. From our figures we can see clearly that the pattern of photocurrent density increases by the
bias voltage. The current–voltage characteristics of the n-ZnSe/p-PSi solar cells as shown in Figs. 12 to 15. It is
clear that with increase porous time from 5 min to 20 min, Open circuit voltage increase VOC and Present ISC short
circuit.
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Fig. 12. I–V characteristics for n-ZnSe/p-Porous Si at porous time at 5 min.

Fig. 13. I-V characteristics for n-ZnSe/p-Porous Si at porous time at 10 min.

Fig. 14. I-V characteristics for n-ZnSe/p-Porous Si at porous time at 15 min.

Fill factors (F.F) increase from (0.40 to 0.56) with increasing porous time and efficiency (η) increasing from
0.89 to 2 with increase porous time from 5 min to 20 min as shown in Fig. 16. Table 2 summarizes the relevant
photovoltaic parameters.
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Table 2. Solar cells performance of ZnSe thin films based on p-PSi.

Porous time Voc Jsc Fill factor Efficiency (η)
(V) (mA/cm2 ) (F.F)
5 min 0.36 5.60 3.3077 6.256178
10 min 0.32 6.32 0.44 1.10
15 min 0.42 7.00 0.54 1.75
20 min 0.46 8.10 0.56 2.00

Fig. 15. I-V characteristics for n-ZnSe/p-Porous Si at porous time at 20 min.

Fig. 16. Efficiency and fill factor as a function porous time for n-ZnSe/p-Porous Si.

4. Conclusions
In summary, we have prepared ZnSe core–shell NPs by cold plasma using zinc sheet and selenium nitrate. We
prepared ZnSe NPs using a green method by the milk thistle seed at room temperature. In order to improve the
absorption coefficient that affects the solar cell efficiency, we have tuned optical properties to the desired particle
size for ZnSe-NPs. Owing to their quantum confinement effects on their optical spectra, all nanoparticles showed
their absorption peak. In terms of cost, speed of reproducibility and meeting all “green” preparation requirements
for ZnSe-NPs, this method offers several advantages. Work also focused on effect of porous time for silicon on
conversion efficiency for solar cells.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could
have appeared to influence the work reported in this paper.
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Acknowledgment
The authors gratefully acknowledge for University of Baghdad, College of Science, Department of Physics,
Plasma Physics Lab, Iraq for supporting this work.

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