Optik - International Journal for Light and Electron Optics 171 (2018) 453–462

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Optik
journal homepage: www.elsevier.com/locate/ijleo

Original research article

Efficiency enhancement of novel CNTS/ZnS/Zn (O, S) thin film

T
solar cell
⁎
Yousaf Hameed Khattaka,b, , Faisal Baiga,b, Bernabé Marí Soucasea, Saira Begc,
Syed Rizwan Gillanib, Salman Ahmedd
a
ETS de Ingeniería de Diseño, Departament de Física Aplicada, Universitat Politécnica de Valencia, Camí de Vera, Spain
b
Department of Electrical Engineering, Federal Urdu University of Arts, Science and Technology, Islamabad, Pakistan
c
COMSATS Institute of Information Technology, Islamabad, Pakistan
d
Pakistan Engineering Council, Islamabad, Pakistan

A R T IC LE I N F O ABS TRA CT

Keywords: Cu2 NiSnS4 is non-toxic earth abundant material and a promising quaternary semiconductor
SCAPS compound. It is conspicuous and suitable class of material for the manufacturing of high effi-
Solar cell ciency, low cost and sustainable thin film photovoltaic cell. A novel structure
Efficiency enhancement CNTS/ZnS/Zn(O, S)/FTO is proposed in this work for the efficiency enhancement of CNTS based
Numerical analysis
photovoltaic cell. Up till now there has been no model proposed to use Zn(O, S) as electron
Cu2NiSnS4
transport layer for CNTS based device. In this work we proposed for the first time a novel
CNTS
Zn(O,S)
Zn(O, S) electron transport layer for the efficiency enhancement of CNTS thin film photovoltaic
cell. Device modeling is performed on solar cell capacitance simulator (SCAPS) program under
1.5 A M illumination spectrum. Promising optimized functional parameters had been achieved
with the conversion efficiency of 17.06%, open circuit voltage (Voc) of 664mV , short-circuit
current (Jsc) of 31.19 mA/cm2 and fill factor (FF) of 82.37%. The above results will give an
imperative guideline for the feasible fabrication of high efficiency CNTS based photovoltaic cells.

1. Introduction

Recently research established great interest in the designing and fabrication of low cost photovoltaics. Photovoltaic cells are one
of the most auspicious renewable energy generation source [1]. Chalcogenide materials such as CdTe (cadmium telluride), CIS
(copper indium selenide) and CIGS (copper indium gallium selenide) are well familiar materials commercially used for the fabri-
cation of solar cells in the photovoltaic industry [2,3] because of their high conversion efficiency and excellent electrical as well as
optical properties [4–6]. The major drawback of these materials are their toxic nature and rarity of tellurium, gallium and indium in
the earth's crust, which confine the further development of chalcogenide materials solar cells and this also increase the fabrication
cost [4]. So, the commercial production of CIS , CIGS and CdTe based photovoltaic cells are limited. Researchers are currently
working on the earth abundant and nontoxic materials to decrease the overall production cost of solar cell without compromising
optical properties, electronic properties and power conversion efficiency. So, most of the researchers are taken interest on non-toxic
earth abundant materials like CZTSe (copper zinc tin selenide), CZTS (copper zinc tin sulfide), and their alloys based solar cells
[7–11]. These materials are considered as ideal absorbers and the most auspicious replacement for the chalcopyrite absorbers
(CIGS, CIGSe) [12–18]. The rising attention towards quaternary compounds for the production of thin film photovoltaics are due to

⁎
Corresponding author at: Department of Electrical Engineering, Federal Urdu University of Arts, Science and Technology, Islamabad, Pakistan.
E-mail addresses: yousaf.hameedk@gmail.com, yousaf.hameed@fuuastisb.edu.pk (Y.H. Khattak).

https://doi.org/10.1016/j.ijleo.2018.06.001
Received 12 March 2018; Received in revised form 15 May 2018; Accepted 1 June 2018
0030-4026/ © 2018 Elsevier GmbH. All rights reserved.
Y.H. Khattak et al. Optik - International Journal for Light and Electron Optics 171 (2018) 453–462

their potential [19–22]. Currently, Cu2 FeSnS4 (CFTS) , Cu2 NiSnS4 (CNTS) and Cu2 CoSnS4 (CCTS) materials are gaining much attention
in thin film solar cell research because of good electronic and optical properties [14,23]. Till now few studies has been done on
copper nickel tin sulfide Cu2 NiSnS4 (CNTS) . Herein, for the first time we present numerical modeling of CNTS based solar cell. To the
best of our knowledge, no numerical model is presented till now for CNTS based devices. CNTS is earth abundant, nontoxic p-type
semiconductor material having direct optical band gap ranges from 1.45 to 1.74eV [15,24] and large optical absorption coefficient
α > 10 4cm−1 [14,15,25,26]. CNTS consists of inexpensive and earth abundant nickel (Ni) and tin (Sn) that are valuable for the
consciousness of low-cost photovoltaic devices [26,27]. According to Shockley–Queisser efficiency limit, the finest power conversion
efficiency around 33 % [28] (using AM 1.5 G spectrum) is theoretically possible from a CNTS based solar cell by tuning the band gap
from 1.45 to 1.74eV [15,24]. Power conversion efficiency of about 2.71% for CNTS based solar cell is presented in [15]. In [29] the
reported conversion efficiency is 0.09%. Experimentally still it was not possible to reach the conversion efficiency as per Shock-
ley–Queisser limit due to lack of understanding of material characteristics. Here in we report to use Zn (O, S) (ZnO1−xSx with
0 < x ≤ 1) as the electron transport layer (ETL) for CNTS photovoltaic cell. It is the most promising material due its nontoxic nature
and higher optical bandgap, which allows the collection of greater blue photons. By changing the O and S contents in Zn(O,S) ETL
layer, conduction band offset (CBO) value at the junction interface can be tuned [30–32].
Our approach for the efficiency enhancement of CNTS based solar cell performance by means of addressing the following facts:

• Proposing novel Zn(O, S) electron transport layer for CNTS solar cell.
• Proposing new CNTS/ZnS/Zn(O, S)/FTO structure
• Baseline study for CNTS based solar cells
Numerical analysis or numerical modeling is an essential tool for the better understanding of device working parameters. It plays
a significant role in fabrication of an efficient photovoltaic devices. Numerical modeling of CNTS/ZnS/Zn(O, S)/FTO is presented in
this work. Thickness of CNTS absorber layer varies from 1μm to 10μm with bandgap energy is 1.29eV . The bandgaps of ZnS and
Zn(O, S) stacked electron transport layers (ETL) are higher than absorber layer. So, maximum photons are absorbed in CNTS ab-
sorber. Due to this open circuit voltage of a photovoltaic cell increases and overall power conversion efficiency of photovoltaic cell is
improved. The promising results for the proposed device will give beneficial directions for engineers and researchers to fabricate the
efficient CNTS based photovoltaic cell.

2. Modeling

2.1. Solar cell design

Fig. 1 shows our proposed photovoltaic cell structure CNTS/ZnS/Zn(O, S)/FTO, which comprises absorber layer CNTS , stacked
electron transport layers ZnS and Zn(O, S) and window layer FTO. We have investigated the influence of parameters like absorber
layer dopant concentration and thickness, electron transport layer dopant concentration and thickness, compensation ratio and
illumination power of the sun on the performance of our photovoltaic cell model. For optimum values of parameters (absorber layer
thickness 4μm and acceptor carrier concentration 4 × 1018 cm−3 ), we found a conversion efficiency of 17.06%.

2.2. Numerical modeling and material parameters

Solar Cell Capacitance Simulator (SCAPS) one dimensional software developed at the University of Gent Belgium, is used for the
modeling of proposed device. SCAPS software was designed for simulations analysis of J–V characteristics curve, ac characteristics
(C–V and C-f), spectral response(QE) of a device by solving semiconductor basic equations like hole and electron continuity equations
and poisons equations.
For the complete and better understanding of photovoltaic device, the software used for the modeling of a device should be able to
solve the basic semiconductor equations like poisson’s equation relating to the charge electrostatic potential div(ε∇Ψ) = −ρ and
carrier continuity equation for electrons and holes (given in Eqs. (1) and (2)) [33].
∂n 1 →
= div Jn + Gn−Rn
∂t q (1)

Fig. 1. Block diagram of CNTS solar cell.

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Table 1
Simulation parameters used in SCAPS for modeling of CNTS based photovoltaic device [15,24,29,34].
Material parameters p-CNTS n-ZnS n-Zn (O, S) n-FTO
(Absorber) (ETL-1) (ETL-2) (Window)

Thickness, W (μm) 1∼4 0.3 0.1 0.5

Bandgap, Eg (eV) 1.29 3.6 3.2∼3.6 3.5
Electron affinity, χ (eV) 3.28 3.44 3.86 4
Dielectric permittivity, εr 9 9 9 9
CB effective density of state, NC (cm−3) 2.2 × 1018 1.8 × 1019 1.8 × 1019 1 × 1019
VB effective density of state, NV (cm−3) 1.8 × 1019 2.4 × 1019 2.4 × 1019 1 × 1018
Electron/Hole mobilities, μe(cm2/Vs) 11/11 100/25 100/25 20/10
Electron and hole concentration, n, p (cm−3) 4 × 1018 4 × 1016 1 × 1018 1 × 1018

Table 2
Added value of defects [35,36].
Defect properties (p−CNTS/n−ZnS) (p−CNTS/n−ZnS
Interface defect Interface defect

Energy level with respect to Reference (eV) 0.6 0.6

Total Density (1/cm3) Nt 1 × 1013 1 × 1013
Capture Cross section area of electrons (cm²) δe 1 × 10−15 1 × 10−15
Capture Cross section area of holes (cm²) δh 1 × 10−15 1 × 10−15

Fig. 2. Energy band orientation of the CNTS photovoltaic cell.

Fig. 3. J–V characteristics under illumination.

∂p 1 ⎯→
⎯
= − div Jp + Gp−Rp
∂t q (2)

Where n is concentration of electron, p is concentration of holes, Jn is electron current density, Jp is hole current densities, Gn is
electron generation rate, Gp is hole generation rate Rn is electron recombination rate and Gp is hole recombination rate. The

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Fig. 4. Effect of CNTS thickness on the device parameters.

Fig. 5. CNTS thickness effect on J–V characteristics.

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Fig. 6. Acceptor concentrations in the absorber layer.

Fig. 7. Effect of acceptor doping concentration on J–V characteristics.

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Fig. 8. Effect of ZnS ETL thickness on the device parameters.

Fig. 9. Effect of Zn (O, S) ETL thickness on the device parameters.

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Fig. 10. Donor concentration in ZnS ETL layer.

parameters used in SCAPS for numerical analysis are thickness of absorber layer, electron transport layer and window layer and their
electron-hole mobilities, intrinsic carrier concentrations, electron affinities, bandgaps and doping densities. Simulation parameters
required for modeling of proposed device are enlisted in Table 1.
Defects were added at the interface between absorber/ETL1 (p−CNTS/n−ZnS) and ETL1/ETL2 layers (n−ZnS/n−Zn(O, S)) . The
value of added defects are given in Table 2.

3. Results and discussion

Details of material parameters used for the simulation of different layers of photovoltaic cells are given in Table 1. Energy band
diagram of a proposed CNTS/ZnS/Zn(O, S)/FTO solar cell is shown in Fig. 2 and is taken from SCAPS software. Energy band diagram
helps in explaining the properties of solar cell. The deposition of ZnS and Zn(O, S) as electron transport layers provides adjustment of
band gaps between absorber and window layer. The visible light absorption happens throughout the absorber and at heterojunction.
For incident light photons the bandgap value that is optimal for most of light to be absorbed by absorber material for effective power
conversion efficiency is greater or equal to the maximum bandgap of 1.29 eV.
The working of a photovoltaic cell is to convert sunlight energy into electric current. When there is absence of light, the pho-
tovoltaic cell is a large flat diode and gives exponential curve in J−V measurements. Photovoltaic cell starts working under light
illumination condition. Due to absorption of light photon electron hole pairs generated in solar cell and current starts to flow in solar
cell. The J–V characteristic curve under illumination for CNTS/ZnS/Zn(O, S)/FTO photovoltaic cell is shown in Fig. 3. All the
simulations are performed under AM 1.5 illumination spectrum of intensity 100 mW/cm2 .

3.1. Device optimization

3.1.1. Effect of CNTS absorber layer thickness on solar cell

The absorber layer (CNTS) thickness effect on photovoltaic cell performance is shown in Fig. 4. The proposed photovoltaic cell is
analyzed by increasing the absorber thickness from 1μm to 10μm while all other material parameters of different layers kept constant.
CNTS material having absorption coefficient α > 10 4cm−1. With increase in the value of thickness light absorption increases due to
which carrier generation enhances [37]. Initially short circuit current (Jsc) , conversion efficiency (PCE) and open circuit voltage (Voc)
increases and then saturated after reaching to the optimal value of thickness of CNTS layer. The increase in JSC with an increase of VOC
and PCE is principally due to more photons absorption of longer wavelength and this will in turn, affect the ratio of photo-generated

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Fig. 11. Donor concentration in Zn (O, S) ETL layer.

Table 3
Optimized physical parameters of proposed device.
Physical parameters p-CNTS n-ZnS n-Zn (O, S) n-FTO
(Absorber) (ETL-1) (ETL-2) (Window)

Thickness, W (μm) 4 0.3 0.2 0.5

Electron and hole concentration, n, p (cm−3) 4 × 1018 4 × 1016 1 × 1018 1 × 1018

carriers. Voc depends on saturation current (IL) and photocurrent (I0) as given in Eq. (3). The optimal value for absorber thickness
layer is 4μm .

KT ⎞ ⎛ ⎛ IL ⎞
Voc = ⎜⎛ ⎟ ⎜ln⎜ ⎟ + 1⎞⎟
⎝ q ⎠ ⎝ ⎝ I0 ⎠ ⎠ (3)

Effect of absorber thickness on J–V characteristics is shown in Fig. 5. From Fig. 5, with increase in thickness of absorber layer
there is an increase in Jsc up to a value of 4 μm and with further increase in absorber thickness there is a very small change in Jsc . Effect
of thickness on Voc in negligible. The PCE of solar cell with CNTS thickness of 4 μm is 17.06%.

3.1.2. Effect of CNTS absorber layer acceptor concentration on solar cell

The carrier concentration of absorber layer is increased from 5 × 1016cm−3 to 1 × 1019cm−3 and the performance of the solar cell is
shown in Fig. 6. Fig. 6 illustrates that Voc increases with increase in the doping concentration whereas Jsc decreases. The main reason
is that the saturation current of a device rises with the rise of the carrier concentration density and resultantly the Voc increases.
However, the short-circuit current will decrease with increasing carrier densities. This decrease in Jsc is due to the fact that the higher
carrier densities will increase the recombination process and reduce the probability of the collection of the photon-generated elec-
trons. So, the collected conversion efficiency is more dependent on the influence of the concentration density. From Fig. 6 it is clear
that power conversion efficiency and fill factor increase with increase in the carrier concentration in absorber layer material. The
results for J −V characteristics of acceptor doping concertation change is given in Fig. 7. In Fig. 7 with increase in doping concertation
Jsc is almost constant and Voc increases up to optimal value. The optimal value of the concentration of acceptor density of absorber
layer is 4 × 1018 cm−3 .

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3.1.3. Effect of ZnS and Zn(O, S) ETL parameters on solar cell performance
Effect of ZnS and Zn(O, S) electron transport layers thickness on the performance of photovoltaic cell are also explored and shown
in Figs. 8 and 9. For both stacked ETL layers thicknesses are varied from 0.1μm to 1μm . Simulated fallouts show that with an increase
in the ETL thickness there is no major change in functional parameters (PCE , FF, Jsc and Voc ). So, this result is comprehended that
change in thicknesses of ETL layers does not affects the output performance of photovoltaic device. For the designing of
CNTS/ZnS/Zn(O, S)/FTO based photovoltaic device optimum thickness for ZnS and Zn(O, S) taken are 0 .3μm and 0 .2μm respec-
tively.
The effect of ZnS and Zn(O, S) ETL layers donor concentration on the device performance are analyzed by changing the con-
centration densities. With increase in doping concentration in ETL layers, there is a very small change in PCE and Jsc , whereas FF and
Voc are affected by increasing donor doping concentration of stacked ETL layers, effects of the performance of device is illustrated in
Figs. 10 and 11. The optimal values of the concentration of donor densities of ZnS and Zn(O, S) ETL layers are 1 × 1016 cm−3 and
4 × 1018 cm−3 respectively.
The optimized physical parameters of our proposed CNTS/ZnS/Zn(O, S)/FTO device is given in Table 3.

4. Conclusion

In this work, a novel model for CNTS based solar cell is proposed with the aid of numerical modeling for the CNTS based
photovoltaic device. Our approach for the efficiency enhancement of CNTS based solar cell performance by means of proposing new
CNTS/ZnS/Zn(O, S)/FTO structure with ZnS/Zn(O, S) stacked electron transport layers. From numerical analysis it was found that
performance of CNTS based solar cell is highly depended upon absorber layer thickness and absorber doping concentration. Optimal
thickness was found for CNTS absorber layer is 4 μm whereas optimal doping concentration if 4x1018 cm−3 . After detail analysis
promising optimized functional parameters had been achieved with the conversion efficiency of 17.06%, FF 82.37%, Jsc 31.19
mA/cm2 and Voc 664mV . The above results will give imperative guideline for the feasible fabrication of high efficiency CNTS based
photovoltaic cells.

Acknowledgments

This work was supported by Ministerio de Economía y Competitividad (ENE2016-77798-C4-2-R) and Generalitat valenciana
(Prometeus 2014/044).

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