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Cite this: DOI: 10.1039/d0ce00802h

electronic structure of Cu2ZnSnS4 (CZTS) thin
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films: a DFT study

Andrey A. Kistanov, *a Wei Cao, a Marko Huttula,a Salavat Kh. Khadiullin,b
Elena A. Korznikova,c Aliaksandr Smirnov,d Xinghui Wange and Siarhei Zhukd

New structures made based on Cu2ZnSnS4 (CZTS) by substitutions with Cr, Ti, V, and Mo species were
investigated via density functional theory. The total substitution of Zn by Cr and V leads to the vanishing of
Received 2nd June 2020, the bandgap, while n-type conductivity with a low bandgap of 0.19 eV was predicted in the case Ti. In
Accepted 3rd August 2020
addition, the conduction band minimum and valence band maximum overlapping were observed for the
Mo/Sn ratio of 1/3. Therefore, our study suggests that even the low content of alternative cations in CZTS
DOI: 10.1039/d0ce00802h
allows to control its band alignment. The obtained results can be helpful for designing CZTS-based
rsc.li/crystengcomm intermediate layers to improve the quality of the back interface of the CZTS thin-film solar cells.

Introduction respectively.8 The lack of improvement in the performance of

kesterite solar cells is attributed to the defect intolerant
Cu2ZnSnS4 (CZTS) thin films have attracted considerable nature of the photovoltaic (PV) material.9 The formation of
interest in the last decade due to their high potential for the various anti-site defects and clusters of defects is reported for
application in photovoltaics.1,2 Suitable optical and electronic the complex quaternary compound system.10 These defect
properties make CZTS a promising photovoltaic material for the centers contribute to the recombination and result in low
thin-film solar cells.3 The CZTS thin films are characterized by a open-circuit voltage (Voc) of kesterite solar cells, which is
moderate direct bandgap of 1.5 eV and high absorption known to be a major bottleneck limiting the device
coefficient (>104 cm−1) making them interesting candidates for performance. Moreover, cation-disordering causing the
single-junction solar cells.4 Moreover, CZTS possesses intrinsic recombination is associated with similar size of cations
p-type conductivity due to the presence of Cu vacancies that constituting CZTS.11 Replacing a cation with an isovalent
form shallow acceptor levels.5 In addition, the bandgap of CZTS cation of different size is an effective way to suppress the
can be modulated in the range from 1 to 1.5 eV by tuning S/(Se defect formation and reduce the Voc deficit of kesterite solar
+ S) ratio from 0 to 1.6 Furthermore, CZTS thin films cells.12 Recent progress in the cation substitution is
demonstrate electronic properties comparable to those of Cu(In, systematically reviewed in the work of Li et al.13 The
Ga)Se2 (CIGS) films.1 The latter are widely used in the incorporation of Ag caused an increase in the bandgap and
commercial fabrication of highly efficient thin-film solar cells. decrease of carrier concentration.14 The reduced
In contrast to CIGS, rare-earth elements, In and Ga, are replaced concentration of Ag, in turn, led to an increase in the width
with abundant Zn and Sn in CZTS. The highest reported power of the depletion region.
conversion efficiency (PCE) for CZTSSe solar cells is 12.6%.7 For CZTS, it has been found that the partial substitution
On the other hand, champion CIGS and CdTe thin-film of Zn by Cd causes a decrease in its bandgap and
solar cells demonstrate PCE of 23.35% and 22.2%, enhancement of the minority carrier lifetime.15,16 Moreover,
the Cd substitution allows the fabrication of highly efficient
pure sulfide kesterite solar cells prepared using the
a
Nano and Molecular Systems Research Unit, University of Oulu, 90014 Oulu,
sputtering and solution-based approach.17 However, the
Finland. E-mail: andrey.kistanov@oulu.fi addition of toxic Cd into non-toxic CZTS may limit its
b
Ufa State Aviation Technical University, 450000 Ufa, Russia application perspectives because of the environmental
c
Institute for Metals Superplasticity Problems, Russian Academy of Sciences, concern. Another study by Kumar et al. focused on the review
450001 Ufa, Russia
d
of Zn substitution in CZTS.18 Alternatives to Cd such as Mn,
Belarusian State University of Informatics and Radioelectronics, 220013 Minsk,
Belarus
Fe, Co, Ni and Ba are examined in the study in detail.
e
College of Physics and Information Engineering, Institute of Micro-Nano Devices Obviously, experimental brute force methods of searching
and Solar Cells, Fuzhou University, Fuzhou 350108, China for the best substituents are expensive, requiring significant

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labor inputs, and are time-consuming. To suggest the respectively. The kinetic energy cutoff of 400 eV was adopted.
optimal substituents and speed up the progress in the Periodic boundary conditions were applied in all three
synthesis of high-quality kesterite thin films, atomic directions. The first Brillouin zone was sampled with a 15 ×
simulations are required. The density functional theory (DFT) 15 × 8 k-mesh grid. The Mo/Sn ratio was controlled by the
is the most popular approach in solid-state physics as this substitution of the Sn by Mo atoms.
method is able to predict the electronic properties of a solid The calculated lattice constants a (b) and c of the
with an excellent ratio of accuracy and computational considered pure CZTS unit cell (see Fig. 1a) were found to be
demand.19–21 5.435 Å and 10.843 Å, respectively. Our results are well
In contrast to the above-mentioned studies, which aims to compared with experimental30 and theoretical data.31–33 The
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find suitable cation substitution approaches to fabricate bandgap size (1.38 eV) calculations for pure CZTS (see
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CZTS absorber layers of higher quality, the present study Fig. 1b) show high accuracy and are comparable with the
demonstrates a way to develop the CZTS-based intermediate theoretical and experimental data (1.4–1.5 eV) reported in a
layer. CZTS is known for its instability when in contact with number of works.34–36
Mo at high processing temperatures.22 Detrimental solid-
state reactions at the rear contact lead to the void formation
due to the evaporation of volatile secondary phases.5,22 Results and discussion
Furthermore, the loss of Zn and Sn occurs during
sulfurization.5 In addition, voids are reported to increase the Firstly, the effect of the partial substitution of Zn by Cr, Ti,
series resistance of CZTS solar cells.23 Therefore, ILs are and V is considered. Fig. 2a–c show the band (bottom panel)
deposited to suppress the reaction at the interface between and the atomic (top panel) structures of CZTS with Zn atoms
Mo and CZTS.24 However, the insertion of an IL may lead to substituted by Cr, Ti, and V atoms, respectively. The study
the degradation of CZTS crystallinity as the crystal structures shows the presence of Cr (see Fig. 2a) that leads to the
of the materials are different.25 downward shift of the conduction band minimum (CBM)
In this work, we use first-principles DFT simulations to and the upward shift of valance band maximum (VBM). The
study the effect of Zn substitution by Cr, Ti, and V. These CBM crosses the Fermi level at the point between Γ and X
elements were chosen for the substitution as they are points, and VBM crosses the Fermi level at the point between
characterized by a significantly higher melting temperature nearby the N point, which evidences the closing of the Cu2-
relative to that of Zn with the oxidation state of +2. To the CrSnS4 bandgap. It should be noted that the partial
best of our knowledge, no studies on simulation of Cu2- substitution of Zn by Cr (at the Cr/Zn ratio of 1/1) also leads
CrSnS4, Cu2TiSnS4 and Cu2VSnS4 are reported to date. In to the closing of the bandgap (see Fig. 3a). The modification
addition, in a recent report, we demonstrated a remarkable of the CZTS bandgap with the incorporation of Cr was also
improvement in the PCE of sputtered CZTS solar cells from observed in the experimental study.37 The addition of Cr in
1.6% to 5.5% owing to the Mo incorporation.26 Since CZTS was carried out by the co-sputtering of CZTS and Cr
evidence of Sn substitution by Mo were observed, in this targets. It has been reported that the incorporation of Cr into
study, we also investigate the effect of the partial substitution CZTS performed by the co-sputtering of CZTS and Cr targets
of Sn by Mo on the energy bands distribution using DFT modified the bandgap and structural properties of CZTS thin
simulations to provide insights enabling more efficient films. With the increase of Cr content from 0 to ∼9%, the
designing of CZTS based absorbers. bandgap increased from 1.51 eV to 1.7 eV. On the other hand,
the bandgap decreased to 1.54 eV when measured Cr was
∼15.8%. Note, that in contrast to the study of Sapeli et al.,
Methods
The DFT based first-principles calculations were performed
using the plane-wave Vienna ab initio simulation package
(VASP).27 The Perdew–Burke–Ernzerhof (PBE) exchange–
correlation functional under the generalized gradient
approximation28 (GGA) together with the van der Waals
corrected functional with Becke88 optimization29 were used
for geometry optimization of all structures and band
structure calculations of strained Cu2TiSnS4. The electronic
structure of the structures with the full substitution of Zn/Sn
was considered using the accurate hybrid functional (HSE06).
Due to the high computational cost of hybrid functionals, the
electronic structure of all the remaining structures (with the
partial substitution) was considered using PBE GGA. All the
structures are fully relaxed until the atomic forces and total Fig. 1 Atomic configuration (a) and band structure (HSE06) (b) of
energy values were smaller than 0.01 eV Å−1 and 10−6 eV, CZTS. The red dashed line represents the Fermi level.

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unlike CZTS. It may be expected that by controlling the Zn/Ti

ratio, it is possible to tune not only the bandgap of Cu2TiSnS4
but also band alignment by manipulating CBM and VBM
bands. Indeed, Fig. 3b shows that with an increase in the
concentration of Ti from 0% to 50%, the band alignment
significantly changes, which leads to the shift of CBM and
VBM and the closure of the bandgap. Furthermore, the use
of ultrathin Cu2TiSnS4 instead of the CdS buffer layer may be
useful to passivate the hetero-interface and reduce the
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density of defects, and thus, improve the open-circuit voltage

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deficit.
The simulation study reveals that the substitution of Zn
by V causes strong band mixing, which leads to the vanishing
of the bandgap (see Fig. 2c). This suggests a metallic-like
behavior of Cu2VSnS4. As shown in Fig. 3c, even the partial
substitution of Zn by V leads to the formation of a metallic-
Fig. 2 Atomic configuration and band structure (HSE06) of (a) Cr-, (b) like Cu2VSnS4 structure. Thus, it can be concluded that the
Ti-, and (c) V-doped CZTS. The red dashed lines represent the Fermi full substitution of Zn by alternative cations (Cr, Ti, and V) is
level.
not suitable for the fabrication of thin-film absorbers due to
the low bandgap or its absence. By the interpolation of the
obtained results, the existence of bandgap for a low ratio of
the substituted cations can be expected. Moreover, the cation
substitution with Cr, Ti, and V was found to be effective in
tuning CBM and VBM. Hence, these alternative cations may
be used to provide tools for adjusting band alignment at the
back and front interfaces of the CZTS absorber layer if used
in a relatively small amount.
Owing to the observed metallic-like properties of Cu2-
CrSnS4 and Cu2VSnS4, these materials can be used as IL to
improve the ohmic contact between the CZTS absorber layer
and Mo back contact. Furthermore, as Cu2CrSnS4 and Cu2-
VSnS4 possess the same crystal structure as CZTS, they can
serve as a seed layer to enhance CZTS crystal growth and
reduce the density of defects. Moreover, the deposition of
Cu2CrSnS4 and Cu2VSnS4 IL at the back interface may reduce
the void formation as the loss of volatile elements during
sulfurization is suppressed. Therefore, the series resistance
of the solar cells can be reduced with the reduced voids at
the back interface.
Next, the effect of the partial substitution of Sn by Mo is
investigated. More detailed consideration is addressed to the
substitution of Sn by Mo as in our recent study the positive
effect of Mo incorporation into sputtered CZTS has been
shown.26 To investigate the impact of the Mo content on the
Fig. 3 Band structure (GGA PBE) of (a) Cr-, (b) Ti-, and (c) V-doped
CZTS. From the left to the right the concentration of dopants is 0%, band structure of CZTS some of the Sn atoms are replaced with
50%, and 100%. The black dashed lines represent the Fermi level. Mo atoms. Fig. 4 and 5 show the atomic configurations and
band structures, respectively, of pristine and Mo-doped CZTS.
Surprisingly, at the Mo/Sn ratio of 1/3, the bandgap
the case of the full substitution of Zn by Cr is simulated in shrinks to zero (see Fig. 5b) because the valence and
this report. conduction bands are crossing the Fermi level between the Γ
The substitution of Zn by Ti also induces the shift of CBM and Z points, which supposes the formation of metal-like
towards VBM and a shift of CBM from the Γ point to the CZ(Sn0.75Mo0.25)S. Importantly, there is still an energy gap
point between the X and P points and VBM shifts from the Γ between the X and N points. Further, with an increase in the
point to the N point. As a result, the indirect bandgap of 0.19 Mo content (up to the full substitution of Sn by Mo) in CZTS
eV was observed for Cu2TiSnS4 (see Fig. 2b). It can also be its bandgap vanishes due to the overlapping of valence and
seen that the compound demonstrates n-type conductivity, conduction bands, as shown in Fig. 5c and d.

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Fig. 4 Atomic configuration of Mo-doped CZTS for the Mo/Sn ratio of

(a) 0, (b) 1/3, (c) 1/1 and (d) 3/1. The Cu, Zn, Sn, S, and Mo atoms are
colored in red, violet, gray, yellow and green, respectively.

Fig. 6 LDOS of Mo-doped CZTS for the Mo/Sn ratio of (a) 0, (b) 1/3,
(c) 1/1 and (d) 3/1. The bands corresponding to Cu, Zn, Sn, S, and Mo
atoms are colored in red, violet, gray, yellow and green, respectively.
The vertical black lines represent the Fermi level.
Fig. 5 Band structure (GGA PBE) of Mo-doped CZTS for the Mo/Sn
ratio of (a) 0, (b) 1/3, (c) 1/1 and (d) 3/1. The bands corresponding to
Cu, Zn, Sn, S, and Mo atoms are colored in red, violet, gray, yellow and
green, respectively. The horizontal black line represents the Fermi
level. gap. Importantly, the spin splitting and broadening of Mo
states increase with the increasing concentration (see
Fig. 6c and d). An interesting feature of Mo-doped CZTS is
To deeply understand changes taking place within the that only spin up states (all are Mo states) are occupied below
energy gap of CZTS upon Mo doping, the local density of the Fermi level, which may be responsible for its enhanced
states (LDOS) analysis of pristine and Mo-doped CZTS was light-harvesting ability.
also conducted (see Fig. 6). As shown in Fig. 6b, at the Mo/Sn Using interpolation of the results we may expect the
ratio of 1/3, Mo states are significantly broadened and existence of the bandgap for CZTS with the Mo/Sn ratio in
strongly mixed with the states of the host material. In the range from 0 to 1/3. Formation of metallic-like CZTS
addition, the upward shift of Sn states is observed. An supports observed reduction in resistivity of the CZTS thin
increase of Mo concentration leads to the further shift of Sn films as a result of Mo incorporation in our recent
states and the appearance of Mo states within the energy experimental work.26 In addition, this may also explain the

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enhanced fill factor of Mo-incorporated CZTS solar cells by Acknowledgements

the formation of better ohmic contact at the CZTS/Mo
interface. The authors acknowledge CSC–IT Center for Science, Finland,
The simulation data presented in Fig. 6 provides an for computational resources. A. A. Kistanov, W. Cao, and M.
additional explanation of the phenomena of the increased Huttula acknowledge the financial support provided by the
light absorbance for Mo-incorporated CZTS thin films Academy of Finland (grant No. 311934).
reported in our experimental study.26 Given the short
minority charge carrier diffusion length in CZTS,38 the References
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