Optik

Potential Strategies to boost the efficiency of CZTS solar cells - A theoretical

investigation
--Manuscript Draft--

Manuscript Number: IJLEO-D-23-01614

Article Type: Full length article

Section/Category: Photovoltaic and photo catalysis

Keywords: SCAPS, Kesterites, CZTS

Corresponding Author: Kannan P.K., Ph.D.

Thiagarajar College of Engineering
Madurai, Tamil Nadu INDIA

First Author: Kannan P.K., Ph.D.

Order of Authors: Kannan P.K., Ph.D.

Mariappan Anandkumar, Ph.D.

Abstract: CZTS is predicted to be an efficient absorber than CIGS due to its cost effective, earth
inabundant constituents. But, it reached a maximum experimental efficiency of 12.6%
in 2013 and it remains the same for the past decade. This is due to the various
crystallographic factors that limits the performance of CZTS like antisite defect
formation, unfavourable band alignment with n type CdS etc. This article addresses
some of the potential strategies through which CZTS research can be pursued further
using SCAPS 1D simulator. First, it deals with understanding the difference among
CZTS and its derivatives CZTSe and CZTSSe. Later, bandgap graded structures using
exponential and linear gradient laws are constructed and the performance of such
structures are evaluated. Later, the performance of CZTSSe devices using various n
type semiconductors are studied. Cation substituted CZTS structures like ACZTS and
CCZTS are discussed and the performance characteristics of such devices are also
studied.

Suggested Reviewers: Suhash Ranjan Dey, Ph.D.

Professor, Indian Institute of Technology Hyderabad
suhash@msme.iith.ac.in

Sushmita Chaudhari, Ph.D.

Assistant Professor, Madhav Institute of Technology and Science
sushmitac@mitsgwalior.in

Praveen Eliyas, Ph.D.

Assistant Professor, Government Polytechnic College, Theni, Tamil Nadu
eptony.physics@gmail.com

Brijesh Singh Yadav, PhD

Materials Specialist, Saule Technologies Inc
bybrijeshsingh01@gmail.com

Subramanian A.L., Ph.D.

Assistant Professor, Thiagarajar College of Engineering
alsphy@tce.edu

Opposed Reviewers:

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
Author Agreement

Original Article Statement

The above manuscript is the author’s original work and has neither been published nor
been submitted simultaneously to elsewhere. All authors have verified the contents of the
manuscript and have agreed to the submission.

With kind regards,

Yours Sincerely,

Dr. P.K. Kannan

Assistant Professor
Thiagarajar College of Engineering
Madurai-TamilNadu
India
Impact Statement

1. Some Potential strategies to enhance the kesterite solar cells are analysed through SCAPS 1-
D.
2. Cation modified structures in CZTS like Ag doped CZTSSe and Cd doped CZTSSe are simulated
for the first time.
3. Cd1-xZnxS is found to be most optimum n-type semiconductor for CZTSSe solar cells
4. Bandgap grading in CZTSSe structures are simulated using linear and exponential bandgap
variance.
Cover Letter

Madurai, Tamil Nadu, INDIA

10th April 2023

Dear Esteemed Editor and Referees,

Greetings,

We would be grateful to submit the manuscript titled “Potential Strategies to boost the efficiency
of CZTS solar cells - A theoretical investigation” in your esteemed journal.

Herewith we want to highlight some of the crucial aspects of our work.

This article addresses some of the key issues that limits the performance of Cu2ZnSnS4 (CZTS) as
a photovoltaic absorber material such as antisite defects formation, unfavorable band alignment
with the n type semiconductor etc. through Solar Cell Capacitance Simulator (SCAPS 1D). In this
article, potential strategies such as finding a suitable n type semiconductor and cation substitution
in CZTS are investigated through SCAPS. This is one of the first attempt in simulating structures
such as Ag doped CZTSSe and Cd doped CZTSSe in SCAPS, which are experimentally proven to
reduce the antisite defects in CZTS. In such structures, the decrement in antisite defect density
yielded an efficiency enhancement in CZTS.
This article addresses some of the key limiting factors that are present in CZTS and discusses some
of the potential strategies in elimination of such limiting factors.
We hope this manuscript will be of special interest to the broad readership of Optik. Hence, we
would like to get this manuscript reviewed and considered for publication in your esteemed
journal.

We thank you, in advance, for your attention to this manuscript.

Best regards,

Dr. P.K. Kannan

Assistant Professor
Department of Physics
Thiagarajar College of Engineering
Madurai – 625 015
Tamil Nadu, India.
Mobile: +91-8106353593
Mail: pkkphy@tce.edu
Manuscript Click here to view linked References

1
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5 Potential Strategies to boost the efficiency of CZTS solar cells - A theoretical
6 investigation
7
8 Kannan P.K. 1*, Mariappan Anandkumar2
9
10 1
Department of Physics, Thiagarajar College of Engineering, Madurai – 625 015, Tamil Nadu,
11
12
India.
13 2
14
High-Entropy Materials Research Laboratory, South Ural State University, Russia, Chelyabinsk
15 Oblast, 454080
16
17 Abstract
18
19 CZTS is predicted to be an efficient absorber than CIGS due to its cost effective, earth inabundant
20
21 constituents. But, it reached a maximum experimental efficiency of 12.6% in 2013 and it remains
22
23
24 the same for the past decade. This is due to the various crystallographic factors that limits the
25
26 performance of CZTS like antisite defect formation, unfavourable band alignment with n type CdS
27
28
29 etc. This article addresses some of the potential strategies through which CZTS research can be
30
31 pursued further using SCAPS 1D simulator. First, it deals with understanding the difference among
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34
CZTS and its derivatives CZTSe and CZTSSe. Later, bandgap graded structures using exponential
35
36 and linear gradient laws are constructed and the performance of such structures are evaluated.
37
38 Later, the performance of CZTSSe devices using various n type semiconductors are studied. Cation
39
40
41 substituted CZTS structures like ACZTS and CCZTS are discussed and the performance
42
43 characteristics of such devices are also studied.
44
45
46 Introduction
47
48 Copper Zinc Tin Sulfide (CZTS), is proposed to be an efficient alternative to the current
49
50
51 commercially active CIGS technology due to its non-toxic and earth-abundant constituents[1,2].
52
53 Despite its advantages like having a direct bandgap of 1.5 eV and a high absorption coefficient
54
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56 (>104cm-1), the maximum efficiency achieved with CZTS solar cells is 10% [3]. Other deriving
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 1
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4 materials, such as CZTSSe, with a tailorable bandgap of 1.0 to 1.5 eV, also resulted in a maximum
5
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7 efficiency of 12.6 % in 2013[4].
8
9
10 Even after extensive studies on CZTS manufacturing via multiple techniques since 2013, no
11
12 efficiency improvement in the case of CZTSSe has been discovered. As a result, finding an
13
14
15 effective way to address the existing drawbacks of CZTS technology is crucial. Although many
16
17 experimental parameters limit the performance of CZTS absorbers, several crystallographic factors
18
19
20 stand out. In CZTS solar cells, the following are the major unfavorable factors that limit the Voc of
21
22 the solar cell.
23
24
25 (a) Narrow CZTS phase formation regime that eases secondary phase formation [5,6].
26
27
28 (b) Unfavorable cliff-like conduction band offset with n-type CdS, which leads to interfacial
29
30 recombination[7].
31
32
33 (c) It has a very low antisite defect formation energy, which leads to the formation of band
34
35 tails, which leads to an increase in the recombination in CZTS[5,8,9].
36
37
38 Among various factors, the phase purity of CZTS can be ensured by optimizing the correct
39
40
41 synthesis techniques and through advanced characterization techniques [1]. Also, some other
42
43 strategies like post-deposition annealing [10,11] and alkali treatments like Na, K, etc., have shown
44
45
46
promising enhancement owing to enhancement in the grain size of the absorbers [12]. However,
47
48 because these processes are difficult to regulate, achieving the same outcomes with experimental
49
50 repeatability is extremely difficult, making these strategies unsuitable for the long term.
51
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53 Nevertheless, searching potential alternatives for n-CdS which has a favorable band alignment
54
55 with CZTS [13] and cation substitution in CZTS [14] with other elements that can reduce the
56
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58 antisite defect formation in CZTS are promising routes through which CZTS research can be
59
60 pursued further.
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4 As a result, using SCAPS - 1D (Solar Cell Capacitance Simulator) software, such prospective
5
6
7 concepts for increasing the efficiency of CZTS solar cells are theoretically studied, and the existing
8
9 technological prospects for implementing these techniques are discussed.
10
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12 Numerical Simulation Using SCAPS-1D
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15
16
SCAPS-1D is a renowned simulator designed at the Department of Electronics and Information
17
18 Systems, Gents University, Belgium, which is used to simulate the device characteristics of
19
20 polycrystalline thin film solar cells [15]. This is used to determine the electrical characteristics of
21
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23 the solar cell under various illuminations at different operating temperatures. In addition, it
24
25 generates theoretical Quantum Efficiency plots and the estimated band structures of the solar cell
26
27
28 structures using various absorption models, which is crucial in understanding the effect of various
29
30 layers and their impact on the device parameters. Simulating possible device architectures prior to
31
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33 experimental trials limits the redundancies and is crucial in the proper choice of the various layers
34
35 in the cell.
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38 Until now, numerous modeling studies on determining the optimal thickness of each layer, defect
39
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41 density, temperature, and work function of electrodes are studied in detail using SCAPS software
42
43 [9,13,16–19]. Nevertheless, a collaborative study that may explain prospective solutions for
44
45
46
increasing the efficiency of CZTS solar cells is required to effectively conduct CZTS research.
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48
49 SCAPS simulator functions are based on solving the one-dimensional semiconductor Poisson
50
51 equation and the electron-hole continuity equations. The bulk form of these equations is given
52
53
54
below.
55
56
𝜕 𝜕Ψ 𝜌𝑑𝑒𝑓
57 (𝜀0 𝜀𝑟 ) = 𝑞 (𝑝 − 𝑛 + 𝑁𝐷+ − 𝑁𝐴− + )
58 𝜕𝑥 𝜕𝑥 𝑞
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 1
2
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4 𝜕𝐽𝑛 𝜕𝑛
5 − − 𝑈𝑛 + 𝐺 =
6 𝜕𝑥 𝜕𝑡
7
8
9 𝜕𝐽𝑝 𝜕𝑝
− − 𝑈𝑝 + 𝐺 =
10 𝜕𝑥 𝜕𝑡
11
12
13 The charge carrier transport through drift and diffusion of the carriers are expressed as
14
15
16 𝜇𝑛 𝑛 𝜕𝐸𝐹𝑛
17 𝐽𝑛 = −
18 𝑞 𝜕𝑥
19
20
21 𝜇𝑝 𝑝 𝜕𝐸𝐹𝑝
22 𝐽𝑝 = +
23
𝑞 𝜕𝑥
24
25
26 Where Ψ is the electrostatic potential, ε0,εr is the permittivity of vacuum and semiconductor, n and
27
28 p are the free carrier concentrations of electrons and holes, 𝑁𝐷+ and 𝑁𝐴− are the density of ionized
29
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31 donors and acceptors, 𝜌𝑑𝑒𝑓 is the charge density of defects, G is the generation rate, 𝐽𝑛 , 𝐽𝑝 are the
32
33 electron-hole current density. The Poisson and continuity equations, at boundaries such as contacts
34
35
36 and interfaces altogether lead to a cluster of coupled differential equations in (Ψ, n, p) and (Ψ, 𝐸𝐹𝑛 ,
37
38 𝐸𝐹𝑝 ). SCAPS cracks to calculate a signal solution and a steady state with these equations.
39
40
41
42 Device structure and simulation parameters
43
44
45 Figure 1 depicts the thin film solar cell device construction employed in this study. Throughout
46
47 this study, the same thicknesses were used for all the layers. However, modifications in the
48
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50 characteristics of the absorber layer, buffer layer, and so on are made, and the effect of various
51
52 absorbers and buffers on the ultimate performance of CZTS-based solar cells is investigated.
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24 Figure 1. Device structure used in the current study
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27
The device structure is made up of an absorber material (CZTS and its derivates), an n-type
28
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30 semiconductor, ZnO, and AZO as a window layer sandwiched between the top and bottom contact
31
32 electrodes. Every solar cell device has a series and shunt resistance associated with it. In this work,
33
34
35 all the simulations are performed with a series resistance of 1 Ω cm2 and shunt resistance of 106 Ω
36
37 cm2[16]. The front and back electrode electrical properties are defined in Table 1. The simulation
38
39
40 parameters used in this work are summarized in Table 2.
41
42
43 Table 1: Electrode properties used in the work
44
45
46 Property Front electrode Back electrode
47
48
Surface Recombination Velocity (cm/s)
49
50
51 Electrons 105 107
52
53 Holes 107 105
54
55
56 Metal work function (eV) 5.0 Flat bands
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 1
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4 Table 2: Simulation parameters used in the work
5
6
7 Property CZTS CZTSe CZTSSe CdS ZnO AZO
8
9
10
Thickness 2 2 2 0.05 0.08 0.06
11
12 Bandgap (Eg) 1.5 0.95 1.3 2.4 3.3 3.37
13
14 Electron Affinity χ 4.5 4.35 4.2 4.5 4.6 4.45
15
16
17 Dielectric permittivity ε 10 13.6 13.6 10 9.0 9
18
19 CB density of state 2.2E18 2.2E18 2.2E18 2.2E18 2.2E18 2.2E18
20
21
22 VB density of state 1.8E19 1.8E19 1.8E19 1.8E19 1.8E19 1.8E19
23
24 Electron thermal velocity 1.0E7 1.0E7 1.0E7 1.0E7 1.0E7 1.0E7
25
26
27
Hole thermal velocity 1.0E7 1.0E7 1.0E7 1.0E7 1.0E7 1.0E7
28
29 Electron mobility 1.0E2 1.0E2 1.0E2 1.0E2 1.0E2 1.0E2
30
31 Hole mobility 2.5E1 2.5E1 2.5E1 2.5E1 2.5E1 2.5E1
32
33
34 Donor density 1.0E1 1.0E1 1.0E1 1.0E18 1.0E18 1.0E20
35
36 Acceptor density 1.0E18 5.0E16 1.0E15 0 1.0E1 0
37
38
39
40
41
42 The absorber layers are further made realistic by the addition of defects in order to be comparable
43
44 with the experimental reported results. For this investigation, multivalent defects with charge state
45
46
47 (3+/2+, 2+/+,+/0) in the conduction band corresponding to a defect energy level of Et=1.4eV with
48
49 0.5 eV characteristic energy has been assumed [16]. Also, charged acceptor defects (0/-,-/2-,2-/3-
50
51
52 ) are located in the valence band. The defect parameters used in this work are summarized in Table
53
54 3.
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 1
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4 Table 3: Defect parameters used in the work
5
6
7
8
9
10 Defect Electron hole
11 Charge state:
Defects density Nt capture cross section Level
12 Type
13 (cm-3) (σe,σh) (cm2)
14
15
16
17 Multivalent defect 5E14 (0/-) acceptor 10-13,10-13 0.1 eV above VBM
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19 VCu, CuZn VB tail
20
21
22 Multivalent defect 5E14 (-2/-)acceptor 10-14,10-14 0.2 eV above VBM
23
24 ZnSn, CuSn VB tail
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27 Multivalent defect 5E14 (-2/-3)acceptor 10-14,10-14 0.5 eV above VBM
28
29 VSn, ZnSn, CuSn VB tail
30
31
32
33
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35 All the simulations were performed with a temperature of 300 K and AM 1.5G spectrum is used
36
37 in all the studies. Even with varied absorber and buffer layers, the thickness of all the layers
38
39
40
employed in this study stays constant.
41
42
43 Results and Discussion
44
45
46 i) CZTS vs CZTSe vs CZTSSe devices - a comparison
47
48
49 In this work, several strategies to enhance the efficiency of CZTS solar cells are tested. For
50
51 understanding all these structures, it is quintessential to know how the various derivative structures
52
53
54 of CZTS have a band alignment with the n-CdS layer. Hence, 3 separate simulations with CZTS,
55
56 CZTSe, and CZTSSe absorber structures are chosen and the corresponding J-V plots of the 3
57
58
59 structures with all the device parameters are shown in figure 2 and 3 respectively.
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5 -10
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8
9
10 -20
11 J (mA/cm2)
12
13
14 -30
15
16
17
18
19 -40 CZTS
20 CZTSe
21 CZTSSe
22
23 -50
24 0.0 0.2 0.4 0.6 0.8
25
26 V
27
28
29 Figure 2: I-V curve of CZTS, CZTSe, CZTSSe
30
31
32
33 50 18
34 0.70 71
35 17
36 45
37 0.65 70 16
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39 40 15
40 69
0.60
41 14
42 35
68
43 0.55 13
44
45 30
67 12
46 0.50 Voc (V)
47 Jsc (mA/cm2) 11
48 25 66
FF
49 0.45
50
Efficiency 10
51 20 65
52 CZTS CZTSe CZTSSe
53 Absorber
54
55
56
57 Figure 3: Device parameters of CZTS, CZTSe and CZTSSe
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4 These results clearly indicate that the efficiency of the absorbers decreases in the following order
5
6
7 CZTSSe>CZTSe>CZTS, which agrees with the maximum efficiency achieved with either of these
8
9 materials [19]. The band alignment of these structures with the n-CdS layer is the defining
10
11
12 characteristic that is responsible for the significant efficiency decrease. The simulated band
13
14 diagrams corresponding to all three absorbers are shown in figure 4.
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26
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28
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30
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32 Figure 4: Simulated band diagrams for CZTS, CZTSe and CZTSSe solar cells
33
34
35 The conduction band of the absorber and buffer can align into two distinct configurations such as
36
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38 spike and cliff-like band alignments. For the cliff-like band alignment, it will restrict the flow of
39
40 injection electrons which leads to high interfacial recombination of the defects in forward bias,
41
42
43 which can lead to a reduction in Voc and FF [7]. In the case of spike-like configuration, the CBO
44
45 is crucial and the devices' Voc and FF will be unaffected. However, a high CBO prevents
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47
48
photogenerated carriers from crossing over the spike resulting in a reduction in JSC of the devices.
49
50 For high-performance devices, an optimal CBO of 0 to 0.4 eV is very desirable [20]. Still, a huge
51
52 debate is going on regarding the band alignment in the case of CZTS and CZTSe absorbers,
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54
55 because it is immensely dependent on the defects present in the material. In the literature, spike
56
57 and cliff-like CBO for CZTS and CZTSe absorbers have been reported using different
58
59
60 photoelectron spectroscopies such as UPS, XPS, and HEXAPS. However, in the case of sulfo-
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4 selenide absorbers, Haight et al. investigate the variation in CBO and VBO of CZTSSe films
5
6
7 experimentally. They found that the Valence band minimum moves down on increasing S/S+Se
8
9 ratio and the conduction band minimum is weakly dependent on S concentration. As a result, the
10
11
12 VBO decreases on increasing the S/S+Se ratio. Although very minor variation in the CBO is
13
14 observed in this simulation work, the VBOCZTSe>VBOCZTSSe>VBOCZTS matches exactly with the
15
16
17 experimentally observed results [7].
18
19
20 As a result, we can conclude that variations in the S/S+Se ratio have a significant influence on the
21
22 band alignment and the optoelectronic properties of CZTSSe devices.
23
24
25 ii) Bandgap gradience in CZTSSe solar cells
26
27
28 As tuning the S/S+Se ratio plays a crucial role in enhancing the efficiency of CZTSSe solar cells,
29
30
31 by varying the bandgap of the semiconductor using standard distribution functions like
32
33 exponential, uniform distribution in SCAPS, the bandgap graded CZTSSe absorber layers can be
34
35
36 simulated [21]. Although experimentally, production of such structures over a large area is still
37
38 questionable, but with nanoparticles route having precise composition and by depositing
39
40
41 nanoparticulate thin films with varying composition and having crucial control on the annealing
42
43 and diffusion of the precursors, the growth of such composition gradient CZTSSe absorbers may
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45
46
be possible [22].
47
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49 In SCAPS, there are various laws based on which the composition grading on the absorber along
50
51 the y direction and corresponding variation in the physical properties can be studied. The
52
53
54
composition is varied such that the composition of the layer is A1-yBy while the properties of pure
55
56 compounds A (Cu2ZnSnSe4) and B (Cu2ZnSnS4) are determined by the composition at both the
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 1
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4 ends of the absorber along y direction and the gradient model chosen. Two gradient models such
5
6
7 as linear grading and exponential grading models are used in this study.
8
9
10 The linear and exponential grading laws are expressed in the equations below.
11
12
13 𝑃𝐴 (𝑦𝐵 −𝑦)+𝑃𝐵 (𝑦−𝑦𝐴 )
Linear grading law:
14 𝑦𝐵 −𝑦𝐴
15
16
𝑦 −𝑦 𝑦−𝑦𝐴
17 sinh[ 𝐵 ] sinh[ ]
𝐿𝐴 𝐿𝐵
18 Exponential grading law: 𝑃0 + (𝑃𝐴 − 𝑃0 ) 𝑦 −𝑦 + (𝑃𝐵 − 𝑃0 ) 𝑦𝐵 −𝑦𝐴
19 sinh[ 𝐵 𝐴 ] sinh[ ]
𝐿𝐴 𝐿𝐵
20
21
22
Where LA and LB are the characteristic lengths, yA and yB are the composition parameters and P0
23
24
25 is the background value [23]. So, in the case of linear grading, compositions at y(x=0), y(x=d) are
26
27 defined while in the case of exponential grading along with those, the background value and
28
29
30 characteristic lengths are defined. In the present case, the characteristic length of 0.1 μm is used
31
32 and a background value of 0.5 is used in all the simulations, while the compositions at left (y(x=0))
33
34
35 and right (y(x=d)) are varied. These values are fixed because at this length the efficiency of the
36
37 cells is maximum and the calculations ended up correctly without convergence failure. The
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39
40
composition gradience panel used in the simulation work is shown in figure 5.
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29 Figure 5: Compositional gradience absorber layer definition in SCAPS 1D
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32
33
Using exponential grading law, the device parameters with varying compositions chosen at the left
34
35 and right are summarized in figure 6. A maximum device efficiency of 19.3% is achieved for a
36
37 Se/S+Se ratio of 0.4, which corresponds to the device having 0.4 Se composition at x=0 and 0.6
38
39
40 Se composition at x=2 and it is significantly higher than the efficiency of CZTSSe solar cell
41
42 calculated in the previous section.
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5 Composition at right (x=2 mm)
6 1.0 0.8 0.6 0.4 0.2 0.0
7 45 1.6
8 20
9 80
40 1.4
10 18
11
12 35 1.2 70 16
13
14 30 14
15 1.0
16 60
25 12
17 0.8
18
19 20 10
0.6 50
20 Voc (V)
21 8
15 Jsc (mA/cm2)
22 0.4
23 FF 40 6
24 10 Efficiency
25 0.2 4
26 0.0 0.2 0.4 0.6 0.8 1.0
27
28
Composition at left (x=0 mm)
29
30
31 Figure 6: Device characteristics for bandgap gradience structures using exponential law
32
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34 Similarly, various composition modifications are applied using linear gradient law, and the related
35
36
37 cell efficiencies are reported in figure 7. The composition of the films is varied using linear
38
39 gradient law, and the corresponding compositions that yielded results without convergence failure
40
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42
are shown in Table 4 listed below.
43
44
45 Table 4: Composition of the films simulated using linear gradient law
46
47
48 Sl.No. Se Composition at left Se Composition at right Se/(S+Se)
49
50 1 0.7 0.3 0.7
51
52
53 2 0.6 0.4 0.6
54
55 3 0.4 0.6 0.4
56
57
58 4 0.3 0.7 0.3
59
60
61
62
63
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 1
2
3
4
5
6 Composition at right (x=2 mm)
7
0.7 0.6 0.5 0.4 0.3
8
9 19.0
80
10 40 1.0
11 78 18.5
12
13 0.9 18.0
35 76
14
17.5
15 74
16 0.8
17.0
30
17 72
18 16.5
19 0.7
Voc (V) 70
25 16.0
20
Jsc (mA/cm2)
21 FF 68 15.5
0.6
22 Efficiency
23 20 66 15.0
24 0.3 0.4 0.5 0.6 0.7
25 Composition at left (x=0 mm)
26
27
28
29 Figure 7: Device characteristics for bandgap gradience structures using linear gradient law
30
31
32 For the device having 0.6 Se composition at x=0 and 0.4 Se composition at x=2 μm, a maximum
33
34
35 efficiency of 18.8% is achieved which is significantly higher than the maximum efficiency
36
37 determined for the ungraded CZTSSe system reported in this work.
38
39
40
(iii) Searching for alternative n-type semiconductors
41
42
43
44 CdS were employed as an n-type semiconductor in the most efficient lab-size device made using
45
46 CZTSSe. As discussed in the earlier section, both spike and cliff-like CBO are observed for CZTS
47
48
and CZTSe absorbers with that of n-CdS. So, it is crucial to develop an n-type semiconductor that
49
50
51 has a favorable band alignment with that of CZTS and its derivatives [13,17]. Although studies
52
53 employing semiconductors such as ZnS and In2S3 are currently underway, further research using
54
55
56 additional binary and ternary sulfides is required. As a result, various innovative n-type
57
58 semiconductors are employed in this study, and the photovoltaic performance of optimized
59
60
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 1
2
3
4 CZTSSe devices is reported. The experimental parameters used for the simulation is listed in Table
5
6
7 5.
8
9
10 Table 5: n-type semiconductors material properties used in the work
11
12
13 Property CZTSSe CdS ZnS Cd1-xZnxS ZnSe In2S3
14
15 Thickness 2 0.05 0.05 0.05 0.05 0.05
16
Bandgap (Eg) 1.3 2.4 3.3 2.98 2.9 2.82
17
18 Electron Affinity χ 4.2 4.5 4.1 4.2 4.02 4.5
19
20 Dielectric permittivity ε 13.6 10 10 9.4 10 13.5
21
22 CB density of state 2.2E18 2.2E18 2.2E18 2.2E18 2.2E18 2.2E17
23
24 VB density of state 1.8E19 1.8E19 1.8E19 1.8E19 1.8E19 1.8E19
25
26 Electron thermal 1.0E7 1.0E7
1.0E7 1.0E7 1.0E7 1.0E7
27
velocity
28
29 Hole thermal velocity 1.0E7 1.0E7 1.0E7 1.0E7 1.0E7 1.0E7
30
31 Electron mobility 1.0E2 1.0E2 1.0E2 2.7E2 2.5E1 1.0E2
32
33 Hole mobility 2.5E1 2.5E1 2.5E1 2.7E1 1.0E2 2.5E1
34
35 Donor density 1.0E1 1.0E18 1.0E18 1.0E17 1.0E17 1.0E13
36
37 Acceptor density 1.0E15 0 0 0 0 1.0E1
38
39
40
41
42 80 18
43 35.2 0.95
75
44 17
45 0.90 70
46 35.0
47 0.85 65 16
48 34.8 Voc (V)
49 0.80 60
Jsc (mA/cm2) 15
50
51 FF 55
34.6 0.75
52 Efficiency
50 14
53
34.4 0.70
54 45
55 13
0.65 40
56 34.2
57
58 0.60 35 12
59 CdS CdZnS In2S3 ZnSe ZnS
60 Figure 8: Device characteristics for the CZTSSe devices using various n-type semiconductors
61
62
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 1
2
3
4 The device performance of the solar cells with various n-type semiconductor layers is shown in
5
6
7 figure 8. It is clear from the results that CdS, ZnS, and the solid solution of Cd1-xZn1-xS yielded
8
9 almost similar efficiency when compared to other semiconductors. This finding supports reducing
10
11
12 the use of hazardous Cd in CZTS solar cells by replacing Zn in CdS without impacting cell
13
14 performance.
15
16
17 iii) Cation Substitution in CZTSSe
18
19
20 One of the key factors that limit the CZTS solar cell performance is the inevitable formation of
21
22
23 Cu-Zn antisite defects in it [14]. Such defects in CZTS have a low formation energy and these
24
25 defects lead to the formation of deep energy levels in CZTS. The major reason for such antisite
26
27
28 defect formation is the similar ionic radii of the cations (ionic radius of Cu+ and Zn2+ is ~0.74Å).
29
30 One of the most efficient approaches to minimize such antisite defect formation is to substitute Cu
31
32
33 or Zn in the lattice with isovalent cations, which have a very large ionic radius. Elements such as
34
35 Ag (Ag+ ionic radius ~1.14 Å) and Cd (ionic radius ~0.92 Å) are the perfect candidates for
36
37
replacing Cu and Zn in CZTSSe respectively [24]. However, such substitutions significantly can
38
39
40 alter the band structure and density of states of the material, thus the bandgap and carrier
41
42 concentration of such cation-substituted structures are found in the literature.
43
44
45
46
1. Ag substitution for Cu in CZTSSe (ACZTSSe)
47
48
49 The creation of CuZn antisite defects in CZTSSe is feasible when Ag is replaced with Cu in the
50
51 CZTSSe structure. Although such structures already exist, one of the major factors is that the career
52
53
54
concentration of ACZTSSe falls rapidly on increasing the Ag concentration in CZTSSe [24–28].
55
56 There is a scarcity of accurate information on the defect density and bandgap of such systems.
57
58
59
60
61
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 1
2
3
4 Hence, in this study, the device parameters used and the information on defect density used are
5
6
7 listed in Table 6.
8
9
10 Table 6: Material properties of cation substituted structures used in the simulation
11
12
13 Property ACZTSSe CCZTSSe
14
15
16 Thickness 2 2
17
18 Bandgap (Eg) 1.5 0.95
19
20
21
Electron Affinity χ 4.5 4.35
22
23 Dielectric permittivity ε 10 13.6
24
25 CB density of state 2.2E18 2.2E18
26
27
28 VB density of state 1.8E19 1.8E19
29
30 Electron thermal
31
1.0E7 1.0E7
32
33 velocity
34
35 Hole thermal velocity 1.0E7 1.0E7
36
37
38
Electron mobility 1.0E2 1.0E2
39
40 Hole mobility 2.5E1 2.5E1
41
42 Donor density 1.0E1 1.0E1
43
44
45 Acceptor density 1.0E18 5.0E16
46
47
48
49
50 With the expectation that the antisite defect CuZn will vary greatly as the Ag alloying increases,
51
52 the defect density of the ACZTSSe structure is altered from 5E14 to 5E13 in this study. As
53
54
55 expected, the efficiency of the cells shows an increment from 10.69 to 11.38%.
56
57
58
59
60
61
62
63
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65
 1
2
3
4
5 37.6 0.535
6 11.4
7 Voc (V) 60
8
37.5 0.530 Jsc (mA/cm2) 11.3
9 59
10
FF
11 Efficiency 11.2
12 37.4 0.525 58
13 11.1
14
15 37.3 0.520 57
16 11.0
17
18
37.2 0.515 56 10.9
19
20
55 10.8
21
22 37.1 0.510
23 10.7
24 54
25 37.0 0.505 10.6
26 1.00E+14 2.00E+14 3.00E+14 4.00E+14 5.00E+14
27
28 CuZn Antisite Defect Density
29
30
31
32 Figure 9: Device characteristics of ACZTSSe cells fabricated with various defect density
33
34
35 Although, these small reductions in antisite defect density through Ag alloying are more
36
37
38 promising. However, some experimental studies found that Ag alloying at higher concentrations
39
40 leads to the conversion of the CZTSSe from p-type to n-type. Therefore, Ag alloying at higher
41
42
43 concentrations significantly can hamper the carrier concentration.
44
45
46 2. Cd substitution for Zn in CZTSSe (CCZTS)
47
48
49 Another potential cation substituted structure in CZTSSe that can potentially minimize the antisite
50
51 defects is the substitution of Cd in place of Zn in CZTS. However, these structures lead to the
52
53
54 conversion of the kesterite CZTSSe into its stannite polymorph at higher Cd concentrations. This
55
56 leads to the reduction of SnZn antisite defects when compared to that of CZTSSe. Like the previous
57
58
59
60
61
62
63
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 1
2
3
4 case, the concentration of SnZn antisite defect concentration is varied from 5E14 to 5E13 to
5
6
7 understand how the defect concentration affects the performance of these absorbers[14,24].
8
9
10
37.5 72 11.8
11
12 0.48 Voc (V)
13 37.4 Jsc (mA/cm2)
14 70 11.6
15 FF
16 37.3 0.47 Efficiency
17 68 11.4
18
19 37.2 0.46
20
21 66 11.2
37.1
22 0.45
23
24 37.0 64 11.0
25
26 0.44
27 36.9
62 10.8
28
29 36.8 0.43
30
31 60 10.6
32 1.00E+14 2.00E+14 3.00E+14 4.00E+14 5.00E+14
33
34 CuSn Antisite defect density
35
36
37 Figure 10: Device characteristics of CCZTSSe cells fabricated with various defect density
38
39
40
41
When the antisite defect density is reduced, a maximum efficiency of 11.6% is obtained. Thus, by
42
43 substituting Cd for Zn, the bandgap of CZTSSe may be enhanced through the reduction of antisite
44
45 defect density.
46
47
48
49
3. Other cation substituted CZTSSe derivatives
50
51
52 Other structures such as CZTGSSe (Cu2Zn(Sn,Ge)(S,Se)4), CZBTSSe (Cu2(Zn,Ba)Sn(S,Se)4) and
53
54 some other transition metal elements such as Mn, Fe, Co, and Ni are also tried as a substitution for
55
56
57
Zn in CZTSSe already been fabricated experimentally and devices fabricated with these materials
58
59
60
61
62
63
64
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 1
2
3
4 showing promising results [14]. Higher performance can be expected with a more in-depth
5
6
7 understanding of this family of materials and further device optimization.
8
9
10 4. Other promising strategies
11
12
13 There are some other strategies such as post-deposition annealing of the precursors, grain boundary
14
15
16
passivation by alloying with Na, K, etc., and finding alternative device structures such as utilizing
17
18 CZTS as a p+ layer in addition to the ACZTS structure already exist. But, analyzing those
19
20 structures through SCAPS is not feasible and hence these strategies are beyond the scope of this
21
22
23 article.
24
25
26 Conclusions
27
28
29 In this work, various strategies for increasing the efficiency of kesterite CZTS solar cells are
30
31
32 investigated and analyzed in detail using a SCAPS – 1D simulator. Based on this research, Cd1-
33
34 xZnxS is identified as the most suitable buffer layer for the CZTSSe absorber. This paper also
35
36 investigates other cation substitution structures in CZTS, such as ACZTSSe and CCZTSSe, as well
37
38
39 as the device performance of such structures. Ultimately, this work discusses the currently
40
41 researched efficiency enhancement strategies applicable to kesterite CZTS and investigates the
42
43
44 significance of each route through the SCAPS 1-D tool.
45
46
47 References:
48
49
50 1. Yoo H, Kim J. Comparative study of Cu2ZnSnS4 film growth. Sol Energy Mater Sol
51 Cells. 2011;95(1):239–44.
52
53 2. Kannan P.K., Sushmita Chaudhary, SR Dey, M Ramadan. Progress in Development of
54
55 CZTS for Solar Photovoltaics Applications.Encyclopedia of Smart Materials. 2022;(2):681-698.
56
57 3. Cui X, Sun K, Huang J, Yun JS, Lee CY, Yan C, et al. Cd-Free Cu2ZnSnS4 solar cell
58 with an efficiency greater than 10% enabled by Al2O3 passivation layers. Energy Env Sci.
59 2019;12(9):2751–64.
60
61
62
63
64
65
 1
2
3
4 4. Wang W, Winkler MT, Gunawan O, Gokmen T, Todorov TK, Zhu Y, et al. Device
5
6 Characteristics of CZTSSe Thin-Film Solar Cells with 12.6% Efficiency. Adv Energy Mater.
7 2014;4(7):1301465.
8
9 5. Yu K, Carter EA. Elucidating Structural Disorder and the Effects of Cu Vacancies on the
10 Electronic Properties of Cu2ZnSnS4. Chem Mater. 2016;28(3):864–9.
11
12 6. Davydova A, Rudisch K, Scragg JJS. The Single Phase Region in Cu2ZnSnS4 Thin Films
13
14 from Theory and Combinatorial Experiments. Chem Mater. 2018;30(14):4624–38.
15
16 7. Siebentritt S. Why are kesterite solar cells not 20% efficient?. Thin Solid Films.
17 2013;(535):1–4.
18
19 8. Yu K, Carter EA. A Strategy to Stabilize Kesterite CZTS for High-Performance Solar
20 Cells. Chem Mater. 2015;27(8):2920–7.
21
22 9. Hempel H, Eichberger R, Repins I, Unold T. The effect of Cu-Zn disorder on charge
23
24 carrier mobility and lifetime in Cu2ZnSnSe4. Thin Solid Films. 2018;(666):40–3.
25
26 10. Sanchez MF, Sanchez TG, Courel M, Reyes-Vallejo O, Sanchez Y, Saucedo E, et al.
27 Effect of post annealing thermal heating on Cu2ZnSnS4 solar cells processed by sputtering
28 technique. Sol Energy. 2022;(237):196–202.
29
30 11. Chamekh S, Khemiri N, Kanzari M. Effect of annealing under different atmospheres of
31
32 CZTS thin films as absorber layer for solar cell application. SN Appl Sci. 2020;2(9):1507.
33
34 12. Bin Liu, Jie Guo, Ruiting Hao, Lu Wang, Kang Gu, Shuaihui Sun, Abuduwayiti Aierken.
35 Effect of Na doping on the performance and the band alignment of CZTS/CdS thin film solar
36 cell. Sol. Energy. 2020;(201):219-226.
37
38 13. Abd El Halim B, Mahfoud A, Mohammed Elamine D. Numerical analysis of potential
39
40 buffer layer for Cu2ZnSnS4 (CZTS) solar cells. Optik. 2020;(204):164155.
41
42 14. Jianjun Li, Dongxiao Wang, Xiuling Li, Yu Zeng,Yi Zhang. Cation Substitution in
43 Earth‐ Abundant Kesterite Photovoltaic Materials. Adv. Sci. 2018;(5):1700744.
44
45 15. Burgelman M, Nollet P, Degrave S. Modelling polycrystalline semiconductor solar cells.
46 Thin Solid Films. 2000;527(32):361–362.
47
48 16. Sadanand, Dwivedi DK. Theoretical investigation on enhancement of output performance
49
50 of CZTSSe based solar cell. Sol Energy. 2019;(193):442–51.
51
52 17. Hood SN, Walsh A, Persson C, Iordanidou K, Huang D, Kumar M, et al. Status of
53 materials and device modelling for kesterite solar cells. J Phys Energy. 2019;1(4):042004.
54
55 18. Jhuma FA, Shaily MZ, Rashid MJ. Towards high-efficiency CZTS solar cell through
56 buffer layer optimization. Mater Renew Sustain Energy. 2019;8(1):6.
57
58
59
60
61
62
63
64
65
 1
2
3
4 19. Ashraf MA, Alam I. Numerical simulation of CIGS, CISSe and CZTS-based solar cells
5
6 with In2S3 as buffer layer and Au as back contact using SCAPS 1D. Eng Res Express.
7 2020;2(3):035015.
8
9 20. Mitzi DB, Gunawan O, Todorov TK, Wang K, Guha S. The path towards a high-
10 performance solution-processed kesterite solar cell. Sol Energy Mater Sol Cells.
11
12 2011;95(6):1421–36.
13
14 21. Burgelman M, Marlein J. Analysis Of Graded Band Gap Solar Cells With SCAPS. 23rd
15 European Photovoltaic Solar Energy Conference and Exhibition.2008; 2151 - 2155.
16
17 22. Andrade-Arvizu J, Izquierdo-Roca V, Becerril-Romero I, Vidal-Fuentes P, Fonoll-Rubio
18 R, Sánchez Y, et al. Is It Possible To Develop Complex S–Se Graded Band Gap Profiles in
19
20 Kesterite-Based Solar Cells?. ACS Appl Mater Interfaces. 2019;11(36):32945–56.
21
22 23. Simya OK, Mahaboobbatcha A, Balachander K. Compositional grading of CZTSSe alloy
23 using exponential and uniform grading laws in SCAPS-ID simulation. Superlattices Microstruct.
24 2016;(92):285–93.
25
26 24. Sai Gautam G, Senftle TP, Carter EA. Understanding the Effects of Cd and Ag Doping in
27
28 Cu2ZnSnS4 Solar Cells. Chem Mater. 2018;30(14):4543–55.
29
30 25. Saha U, Alam MdK. Boosting the efficiency of single junction kesterite solar cell using
31 Ag mixed Cu2ZnSnS4 active layer. RSC Adv. 2018; 8(9):4905–13.
32
33 26. Wang D, Wu J, Liu X, Wu L, Ao J, Liu W, et al. Formation of the front-gradient bandgap
34 in the Ag doped CZTSe thin films and solar cells. J Energy Chem.2019;(35):188–96.
35
36 27. Giraldo S, Jehl Z, Placidi M, Izquierdo‐ Roca V, Pérez‐ Rodríguez A, Saucedo E.
37
38 Progress and Perspectives of Thin Film Kesterite Photovoltaic Technology: A Critical Review.
39 Adv Mater. 2019(16):1806692.
40
41 28. Nguyen TH, Kawaguchi T, Chantana J, Minemoto T, Harada T, Nakanishi S, et al.
42 Structural and Solar Cell Properties of a Ag-Containing Cu2ZnSnS4 Thin Film Derived from
43
44 Spray Pyrolysis. ACS Appl Mater Interfaces. 2018;10(6):5455–63.
45
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53
54
55
56
57
58
59
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Declaration of Interest Statement

Declaration of interests

☒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.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: