Numerical Analysis of Graded Band Gap CZT (S, Se) Solar Cells Using AMPS-1D

IPASJ International Journal of Electrical Engineering (IIJEE)
Web Site: http://www.ipasj.org/IIJEE/IIJEE.htm

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ISSN 2321-600X
A Publisher for Research Motivation........
Volume 4, Issue 10, October 2016
Numerical analysis of graded band gap

CZT(S,Se) solar cells using AMPS-1D
Abdulkader Jaleel Muhammad1, Ali Ismail Salih2, Ginan Fadel3
Assistant Professor/University of Kirkuk
Assistant Professor /University of Kirkuk
B. Sc. / Dept. of Physics, College of Science, University of Kirkuk, Kirkuk, Iraq.
ABSTRACT
The one-dimensional simulation program called Analysis of Microelectronic and Photonic Structures (AMPS-1D), was used to
simulate the performance of some novel solar cell structures. The cells based on Copper-zinc-tin-sulphide (selenide),
Cu2ZnSn(S,Se)4 as absorber layer, cadmium sulfide (CdS) as a buffer layer , un-doped ZnO (i-ZnO) and F-doped SnO2 (FTO)
as a window layer. The effect of grading the band gap through changing the value of x in the composition CZTSX, Se1-X is
investigated. Improved performance, in terms of efficiency was observed. An efficiency of about 30% for a graded-band cell is
reported relative to non-graded cells where the efficiencies are around 20%.
Keywords: Solar cell, CZT(S,Se) thin film, graded band gap, AMPS-1D.
1. INTRODUCTION
Copper-zinc-tin-sulphide (selenide), Cu2ZnSn(S,Se)4 , composition is usually obtained by replacing the indium (In) in
chalcopyrite CuInS2 with zinc (Zn) and tin (Sn) [1]. It is one of the most promising materials for the newer generation
of solar cells, because it depends on materials which are abundant and inexpensive (compared with CIGS and CdTe).
CZTS(Se) is a quaternary semiconductor which can form crystal structures that are classified as kesterite type and
stannite type. The difference between these two types is in the order of cation layers. In kesterite type the cation layers
of CuSn, CuZn, CuSn, and CuZn alternating at z=0, 1/4, 1/2, and 3/4, planes respectively (z=fractional coordinate along
the long c-axis of the structure), while in the stannite type the ZnSn layers alternate with Cu2 layers. Chen et al. [2]
using first-principle calculations showed that the kesterite structure has a lower energy than the stannite structure for
CZTS(Se), so that most CZTS(Se) crystals crystallize in kesterite structure.
CZTS(Se) is a semiconductor that have optimal direct band gap in the range 1.45 - 1.6 eV for CZTS (0.9eV -1eV for
CZTSe), and absorption coefficient larger than 104 cm-1[3,4], so that it can be highly promising absorber layer in solar
cell applications.
CZTS(Se) is self-doping through the formation of intrinsic defects that include the vacancies (Vcu, Vzn, Vsn, Vs),
interstitials (Cui, Zni, Sni, Si), and the antisites (CuZn, ZnCu, ZnSn, SnZn, CuSn, etc.) [5]. Existence of point defects lead to
the self-doping and intrinsic p-type conductivity of CZTS(Se), Chen and co-workers have thoroughly studied the defect
characteristics of CZTS(Se) [6] and calculated the defect formation energies of various isolated point defects (vacancies,
interstitials and antisites) as a function of Fermi energy, All investigations converge to the general agreement that the
acceptor defects such as CuZn or CuSn antisites and the Cu vacancy (VCu) have lower energy of formation with the lowest
formation energy for CuZn antisite defect then donor defects , Such low formation energies of the acceptor defect levels,
particularly CuZn antisite, make p-type conductivity is more possible of Cu2ZnSnS4 [5,7,8] and Cu2ZnSnSe4 [9].
CZT(S,Se) thin film based solar cells has achieved great interest during the past period [10]. The performance of the
solar cell can improve by incorporating graded band gap which helps to absorb a larger amount of radiation of different
wavelengths. In this paper we study the improvement which might result from using graded band gap by changing x in
the composition; CZT(SX, Se1-X) ; where x represents the ratio {[S]/( [S] + [Se])}. Through changing x from 0 to 1, the
band gap of CZTSSe is tuned from 0.9eV for Cu2ZnSnSe4 (CZTSe) to 1.5eV for Cu2ZnSnS4 (CZTS).
We will use AMPS-1D (Analysis of Microelectronic and Photonic Structures) [11] to perform the numerical simulation.
Figure 1 shows the schematic of the geometrical structure of the solar cell design studied in this work. The aim of this
study is to improve upon the performance of CZT(S,Se) thin film solar cells.
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ISSN 2321-600X
Figure 1 CZT(Sx, Se1-x) solar cell structures used in the simulation, a single absorber-layer (non-graded
band) on the left and a 3-absorber-layer (graded band) on the right.
2. DESCRIPTION OF AMPS-1D
AMPS is a software that has been developed by Stephen Fonash [12] and his collaborators at the Pennsylvania state
university to solve the system of highly complex and nonlinear equations that characterize a photovoltaic device under
different operation conditions (thermodynamic equilibrium, voltage bias, etc.). The AMPS-1D program can operate in
two different modes: the density of state (DOS) mode or the lifetime mode, the details can be found in the AMPS
manual [11]. In this study we used the DOS mode.
To model the charge transport processes in the solar cell device shown in the figure 1 the three nonlinear equations (the
Poisson's equation, continuity equation for free electrons, and continuity equation for free holes) must be solved, the
Poisson's equation [13] is:
Where is dielectric permittivity of semiconductor, is electrostatic potential, q is electron charge, n, p are the
+
concentrations of free electron and free hole respectively,

,
are the concentrations of ionized donors and
acceptors, .
are the concentrations of trapped holes and electrons.
While the continuity equations in steady state conditions are:
Where Jn, Jp are electron and hole current density, Rn, RP are electrons and holes recombination velocities of direct bandto-band and indirect transitions, G is the optical generation rate which can be expressed by:
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where,
.
are , respectively, the photon flux of the incident light and the light reflected from the back surface
at wavelength, of i at some point x, depending on the light absorption coefficient, and the light reflectance in the
forward and reverse direction.
The three governing equations (1), (2), and (3) must hold at all point in the solar cell, and the solution to these
equations includes determining the state variables (x) and the electron quasi-Fermi level EFn, and the hole quasi-Fermi
level EFp or, equivalently, (x), n(x), and p(x), which are known as a function of depth. There must be boundary
conditions imposed on the set of equations. The solution to equations (1), (2), and (3) must satisfy the following
boundary conditions.
Where
,
,
are effective interface recombination speeds for holes and electrons at x=0 and x=L.
Newton-Raphson technique is used in AMPS-1D. Solving these equations we can get the carrier concentrations, electric
fields and currents, and device parameters like the short circuit current (Jsc), the open circuit voltage (Voc), the fill
factor (FF) and efficiency which defines the performance of the solar cell.
3. MODELING AND SIMULATION

To simulate the solar cell model that seen in the figure 1 by AMPS-1D and obtain the results, we must enter the
parameters for each layer in the structure. Figure 2 displays the user interface of AMPS-1D. In this study we
investigated four different cases (solar cell structures). The first case consists of 4-layers plus the contacts; that is:
TCO/i-ZnO/n-CdS/pCZTS with no selenium (x=1 in the general formula CZTSXSe1-X). The second case consists of
5layers plus the contacts; that is: TCO/i-ZnO/n-CdS/p-CZTSe/p-CZTS. In this structure the ptype material is made of
two layers (x=0) and (x=1). This introduces a gradient in the energy gap from (0.9 eV) to (1.5 eV). In the third case we
add a layer with x=0.5 between the x=0 and the x=1 layers so that the cell consists from 6-layers plus the contacts; that
is: TCO/iZnO/n-CdS/p-CZTSe/p-CZTS0.5Se0.5/p-CZTS. The final case consists of a 4-layer cell plus the contacts, that
is: TCO/i-ZnO/n-CdS/p-CZTSe with no Sulphur (x=0 in the general formula CZTSXSe1-X).
TCO layer is transparent conductive oxide in this study we take it F-doped SnO2 (FTO). the thickness of the p-layer
(the absorber layer) are kept constant even when using gradient structures.
The parameters and the band gap for CZTSXSe1-X were calculated using the known parameters of (CZTS), (CZTSe) plus
the following equations:
Eg(x) =x Eg(CZTS) + (1-x) Eg(CZTSe) b x (1-x)
(6)
K(x) = x K(CZTS) + (1-x) K(CZTSe)
(7)
Where Eg(CZTS) is the band gap energy for CZTS, Eg(CZTSe) is the band gap energy for CZTSe, and b is a band
bowing parameter and it is equal to 0.07 for CZTSSe [14], K in eq.7 represents any parameter we want to calculate, e.g.
absorption coefficient.
Table 1 show the description of the parameters required in the simulation together with the values which are used in this
study. While table 2 shows the thickness of the layers. The total absorber layer thickness is kept 3000nm for all the
cases. Table 3 is the parameters needed for the front and back contacts in the AMPS-1D program, the contacts are
ohmic contacts.
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Figure 2 AMPS-1D simulation front panel contains the device and general layer parameters.
Table 1: Material parameters needed for the layers that used in this study [15,16]
Layers
FTO
i-ZnO
CdS
CZTS
CZTSe
CZTS0.5 Se 0.5
Dielectric constant,
10
10
10
13.6
11.8
Conductivity type
Electron mobility, n (cm2/V s)
20
25
25
100
100
100
Hole mobility, p (cm2/V s)
100
100
100
20
25
22.5
Free Carrier concentration, NA or

ND (cm-3)
(D)
1e+20
(D) 1e+18 (D) 1.1e+18 (A) 4e+16 (A) 5e+16 (A) 4.5e+16
Band gap, Eg (eV)
4.2
3.35
2.4
1.56
0.95
1.24
density of state, Nc (cm-3)
1.2e+20
2.2e+18
2.2e+18
2.2e+18
2.2e+18
2.2e+18
density of state, Nv (cm-3)
7e+20
1.8e+19
1.8e+19
1.8e+19
1.8e+19
1.8e+19
Electron affinity, ( eV)
4.5
4.35
4.1
4.35
4.22
parameters
Table 2: Thickness of each layer in the cases used in this study. The thickness of FTO, i-ZnO and CdS layers are kept
constant at 130, 80, and 60 nm respectively.
Layer thickness
Case 1
Case 2
Case 3
Case 4
CZTS
3000 (nm)
2950(nm)
1950(nm)
CZTS0.5 Se0.5
1000(nm)
CZTSe
50 (nm)
50(nm)
3000 (nm)
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Table 3: Parameters used for the front and back contacts (note: the back contact work function in the case4 equal to 0.7)
parameters
Front contact
(O)
Back contact
(L)
Work function, PHIBO, or PHIBL (eV)
Surface recombination speed for electrons, SNO, or SNL (cm/sec)
1e+7
1e+7
Surface recombination speed for holes, SPO, or SPL (cm/sec)
1e+7
1e+7
Reflection coefficient, RF, or RB
0.1
0.9
4. RESULTS AND DISCUSSION

4.1 Effect of graded band gap
Table 4 summarizes the results of calculating the important parameters of the solar cell that is Voc, Jsc, FF and the
efficiency. Figure 3 shows the J-V characteristics and Figure 4 displays the energy band diagrams in the graded band
gap in case 3. The cases are as follows: case 1 is TCO/i-ZnO/n-CdS/p-CZTS, case2 is TCO/i-ZnO/n-CdS/p-CZTSe/pCZTS, case3 is TCO/i-ZnO/n-CdS/p-CZTSe/p-CZTS0.5Se0.5/p-CZTS, and case 4 is TCO/i-ZnO/n-CdS/pCZTSe. By
taking different cases for CZTSX, S1-X thin film solar cell with graded absorber layer (cases 2 and 3) we can observe
from the results of the numerical simulation a notable increase in the efficiency of solar cell of structure of case 3. The
efficiency of case 3 is about 30% meanwhile that of the cases 1 and 2 is about 20% and 22% and that of case 4 is about
17.2%. The increase of the efficiency of case 3 can be attributed to a noticeable increase in Jsc.
The increase in Jsc observed in case 3 which is a graded band gap structure; (Eg varies from 0.9 to 1.2 to 1.56 eV in
three consecutive layers), may be due to an effective electric field introduced due to the variation in Eg. This field will
cause the drift of electrons which are minority carrier in a p-type material toward the n-type material and increase the
collection, which result in an increase in the observed current density.
Table 4: Performances parameters of different solar cell cases, the shaded area represents graded-band cells.
FF
Eff %
Case1
cases
1
No. of absorber layers
1.018
Voc
22.725
Jsc (mA/cm^2)
0.874
20.227
Case2
1.018
22.214
0.765
22.214
Case3
1.008
35.594
0.837
30.036
Case4
0.507
42.609
0.799
17.274
Figure 3 JV- curve for graded band gap solar cells (case-3) obtained using AMPS-1D.
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Figure 4 The energy band diagram for graded band gap solar sell (case 3; 3-absorber-layers).
4.2Effect of CZTS0.5 Se0.5 layer thickness
As it was shown in the previous paragraphs, the cell structure called case-3, that is the 6layer plus the contacts structure:
TCO/i-ZnO/n-CdS/p-CZTSe/p-CZTS0.5Se0.5/p-CZTS, exhibit the highest efficiency of about 30%, therefore it was
desirable to investigate the effect of the thickness of the intervening layer (CZTS0.5 Se0.5) on the efficiency and on the
overall performance of the cell. For this purpose, we simulated the characteristics of cells with various (CZTS0.5 Se0.5)thickness, ranging from 50 nm to 2000 nm. Figure 5 displays the efficiency-versus- thickness characteristic of these
cells. We can distinguish two regions of CZTS0.5Se0.5 thickness which influence the electrical parameters (especially Jsc
& Eff). The first region where the thickness is > 1000 nm; in this region the short circuit current density Jsc and the
efficiency Eff increase with thickness, while the second region where the thickness is < 1000 nm, we observe that Jsc
and Eff are almost constant. This tendency towards a saturation value may be explained on the basis that as the
thickness increases, more and more incident photons are absorbed, hence Jsc and Eff increase till where almost all the
incident photons are absorbed, then any further increase in the thickness is an economic loss because it does not improve
the efficiency. The optimum thickness is something about 1000 nm.
For the sake of comparison, we investigated the effect of thickness of (CZTS0.5Se0.5) absorber layer on the performance
of cells consisted from 4-layers plus the contacts, e.g.: TCO/i-ZnO/n-CdS/p-CZTS0.5Se0.5, the absorber layer thickness
is varied from 50 to 4000 nm, while keeping everything else constant. Figure 6 shows the result of the simulation, only
curves of efficiency are shown due to space limitations. Voc increases from about 0.38 V to about 0.79 V, Jsc increases
from about 17.6 to about 32.9 mA/cm2, while the efficiency increases from about 5% to about 22%. Note Eff for this
structure at a thickness of 1000 nm is about 19%, while its value for the same thickness for case-3 cell (TCO/i-ZnO/nCdS/pCZTSe/p-CZTS0.5Se0.5/p-CZTS) is about 30%. This result indicates the advantage of the gradedband structure
over the single-layer structure. The increase in Voc in the single-layer structure with the increase of thickness may be
due to increase of the depletion region thickness available for charge redistribution. In comparison Voc in the gradedband cell was almost constant at about 1.008 V.
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ISSN 2321-600X
Figure 5 Effect of the thickness of CZTS0.5 Se0.5 layer on the graded-band cell efficiency.
25
20
Eff (%)
15
10
0
0
500
1000
1500
2000
2500
3000
3500
4000
4500
thickness(nm)
Figure 6 Effect of CZTS0.5Se0.5 absorber thickness on the efficiency of a single-layer cell.
5. CONCLUSIONS
We have used AMPS-1D to study the performance of CZT (SX, Se1-X) thin film solar cells. It was observed that the
efficiency will increase by using graded band gap. The band gap can be changed through the change of the composition
parameter x {x= [S]/([S]+[Se])}. A triple ptype absorber layer of 1950nm thick CZTS (Eg=1.56), 1000nm thick CZT
(S0.5, Se0.5) (Eg=1.2 eV) and a 50nm thick CZTSe (Eg=0.96 eV) layers exhibit an efficiency of about 30% relative to
non-graded structures where the efficiencies are around 20%. This simulation shows that grading the energy gap could
have a remarkable impact on the increase in the photogenerated current and reduce the recombination in the back
contact resulting in a significantly improved efficiency.
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ISSN 2321-600X
Acknowledgements
We would like to acknowledge the use of AMPS-1D program that was developed by Dr. Fonash's group at Pennsylvania
State University (PSU). We also would like to express our thanks to University of Kirkuk, and one of us (G. F.) would
like to thank university of Kirkuk, college of Science for the study grant.
References
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AUTHOR
Abdulkader Jaleel Muhammad was born in Kirkuk, Iraq, in 1950. He received the B.S. and
M.S. degrees in physics from University of Baghdad, Iraq, in 1971, and 1978, respectively. He
obtained the Ph.D. degree in Electronic Materials and Devices, from Department of Electrical &
Electronic Engineering, University of Leeds, UK, in 1984. He worked as a staff member in
University of Salahaddin-Hawler in Arbil, Kurdistan Region-Iraq. From 1985-1990 he worked as
a senior scientist in a Scientific Research Center in Baghdad, Iraq. From 1995-2005 he was an
Assistant professor in Department of Electrical and Electronic Engineering, University of
Garyounis, Benghazi, Libya. From 2007-2010 he held the post of Head of the Department of physics, College of
science, University of Kirkuk, Kirkuk, Iraq. His current interest includes electronic device physics especially
MOSFETs, electrical and optical properties of electronic materials, high temperature superconductivity, solar cells,
photovoltaics, and power electronics. He recently retired from University of Kirkuk.
Ali Ismail Salih has been awarded the degree of B.Sc. in Applied Physics from University of
Technology in academic year (1992-1993). M. Sc. degree in Applied physics (Material science)
from University of Technology in 1998 Title of Thesis: decolourization of Iraqi glass. Ph. D.
degree in Applied physics (Material techniques) from University of Technology in 2008 Title of
Thesis: Preparation of metal matrix composites- MMCs by different techniques and comparison
between them). He has been a Member of Iraqi physics and Mathematics Society in 1993.
Between years (2000-2003) worked as anengineering inspector in Iraqi North oil company
(NOC). In years (2003-2008) worked as Assistant lecturer at Kirkuk University-College of
Science-Physics Department. In (2012) as a Lecturer at Kirkuk University-College of Science-Physics Department.
From 20-12-2012 as Assistant professor till this date.He has published more than ten papers research in Applied
physics.
Ginan Fadel Muhammad Ali has been awarded the degree of B.Sc. in physics from University of Kirkuk in academic
year (2013-2014), She prepares her MSc. thesis in physics in college of science university of Kirkuk
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IPASJ International Journal of Electrical Engineering (IIJEE)

Web Site: http://www.ipasj.org/IIJEE/IIJEE.htm

A Publisher for Research Motivation........

Volume 4, Issue 10, October 2016