Alexandria Engineering Journal (2017) 56, 225–229

H O S T E D BY
Alexandria University

Alexandria Engineering Journal

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ORIGINAL ARTICLE

Cadmium free high efficiency Cu2ZnSn(S,Se)4 solar

cell with Zn1
xSnxOy buffer layer
Md. Asaduzzaman a,*, Ali Newaz Bahar a, Md. Mohiuddin Masum a,
Md. Mahmodul Hasan b

a
Department of Information and Communication Technology (ICT), Mawlana Bhashani Science and Technology
University (MBSTU), Santosh, Tangail 1902, Bangladesh
b
Department of Computer Science and Engineering (CSE), Mawlana Bhashani Science and Technology University
(MBSTU), Santosh, Tangail 1902, Bangladesh

Received 30 September 2016; revised 2 December 2016; accepted 21 December 2016

Available online 9 January 2017

KEYWORDS Abstract We have investigated the simulation approach of a one-dimensional online simulator
CZTSSe solar cell; named A Device Emulation Program and Tool ðADEPT 2:1Þ and the device performances of a thin
Cd free; film solar cell based on Cu2 ZnSnðS; SeÞ4 ðCZTSSeÞ absorber have been measured. Initiating with a
ZTO buffer; thin film photovoltaic device structure consisting of n-ZnO : Al=i-ZnO=Zn1
x Snx Oy
Efficiency; ðZTOÞ=CZTSSe=Mo=SLG stack, a graded space charge region ðSCRÞ and an inverted surface layer
Conduction band offset ðISLÞ were inserted between the buffer and the absorber. The cadmium ðCdÞ free ZTO buffer, a
competitive substitute to the CdS buffer, significantly contributes to improve the open-circuit volt-
age, Voc without deteriorating the short-circuit current density, Jsc . The optimized solar cell perfor-
mance parameters including Voc , Jsc , fill factor ðFFÞ, and efficiency ðgÞ were calculated from the
current density-voltage curve, also known as J–V characteristic curve. The FF was determined as
73:17%, which in turns, yields a higher energy conversion efficiency of 14:09%.
Ó 2016 Faculty of Engineering, Alexandria University. Production and hosting by Elsevier B.V. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction And in recent years the Cu2 ZnSnS4 ðCZTSÞ and the
CZTSSe, the promising absorber layer materials, have drawn
The use of photovoltaic device has been growing so rapidly to much attention to the photovoltaic researchers for highly effi-
utilize the world’s amplest energy source, incident sunlight. cient and low-cost thin film solar cells [1–4]. Besides, the
CZTSSe absorber-based solar cells expose more radiation
* Corresponding author.
severity, excellent stability and higher energy conversion effi-
ciency of 12:6% [2]. Despite having lower energy conversion
E-mail addresses: asaduzzaman.mbstu@gmail.com (Md. Asaduzza-
man), bahar_mitdu@yahoo.com (A.N. Bahar), masum.mbstu@gmail. efficiency than the most common absorbers, CIGS and CdTe
com (M.M. Masum), hasan.cse.mbstu@gmail.com (M.M. Hasan). based thin-film solar cells having the recorded efficiencies of
Peer review under responsibility of Faculty of Engineering, Alexandria 22:3% and 22:1% respectively [5], the CZTSSe solar cell has
University. become an emerged photovoltaic absorber to the researchers
http://dx.doi.org/10.1016/j.aej.2016.12.017
1110-0168 Ó 2016 Faculty of Engineering, Alexandria University. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
226
because of its p-type conductivity and tunable direct band gap
of 1:50 eV with a higher absorption coefficient of 104 cm
1 [6–
10]. Moreover, comparing to the expensive and scarce indium
ðInÞ, the global annual production of Zn and Sn is about 20
and 340 times more, and the availability is 500 times and 14
times higher [11]. And therefore, the mixed chalcogenide,
CZTSSe has become a more emergent choice and a potential
alternative to the CIGS and CdTe absorbers. However, an
environment-friendly non-toxic zinc-tin-oxide ðZTOÞ material
was also introduced as an alternative buffer layer to the con-
ventional toxic CdS buffer layer material [12]. Another reason
beyond using ZTO buffer in CZTSSe thin film solar cell is
that it has a wider energy band gap ranges from 3:20 to
3:74 eV [13,14], permitting the photons having a lower wave-
length into the absorber and thus increasing the conversion
efficiency.
The theoretic knowledge of solar cells anticipates that for
all voltages the light current density ought to be fixed. But
CZTSSe photovoltaic devices often show deviances from this
ideal behavior. It will be shown by using numerical simulation
that this effect can be demonstrated introducing a conduction
band offset ðCBOÞ at the ZnO=ZTO and ZTO=CZTSSe inter-
faces. Besides this, the effects of CBO on Voc , Jsc , FF, and g
have also been analyzed. Photovoltaic cell having conduction
band offsets around 0:3 eV provides a better device perfor-
mance [15].
2. Solar cell device modeling
The numerical analysis needed for the solar cell device model-
ing is performed by using the simulator ADEPT 2:1 [16]. The
steady-state band gap profile, hole and electron carrier trans-
port, recombination profile are estimated by using the Pois-
son’s equation and the electron and hole continuity
equations given by the followings [17]:
Figure 1 Schematic diagram of CZTSSe thin film solar cell
structure.
Md. Asaduzzaman et al.
 
d dW  

eðxÞ ¼ q pðxÞ
nðxÞ þ Nþ

D ðxÞ
NA ðxÞ þ Pt ðxÞ
Nt ðxÞ
dx dx
ð1Þ
dnp np
np0 dn dnp d2 np
¼ Gn
þ np ln þ ln n þ Dn 2 ð2Þ
dt sn dx dx dx
dpn pn
pn0 dn dpn d2 pn
¼ Gp
þ pn lp þ lp n þ Dp 2 ð3Þ
dt sp dx dx dx
where e is the permittivity, W the electrostatic potential, q the
charge of electron, p the free hole, n the free electron, NþD the
donor concentration, N
A the acceptor concentration, n the
electric field, Pt the trapped hole, Nt the trapped electron, Gn
the generation rate for electrons, Gp the generation rate for
holes, ln the electron mobility, lp the hole mobility, Dn the dif-
fusion coefficient for electrons, and Dp the diffusion coefficient
for holes, and all the parameters are a function of coordinate
position x.
For bulk defects, the recombination current density is
determined by the Shockley-Read-Hall ðSRHÞ modeling
approach and for interface defects, an extension of the SRH
modeling approach is used. The SRH model for interface
defects permits carriers from both the valence and the conduc-
tion bands to take part in the recombination process for
interfaces.
3. Solar cell structure and numerical simulation
The CZTSSe solar cell structure is considered to consist of the
material layers including n-type Al-doped ZnO, intrinsic-ZnO,
n-type ZTO buffer, p-type CZTSSe absorber, and Mo on
soda-lime glass substrate. Between the ZTO buffer and
CZTSSe absorber, an inverted surface layer ðISLÞ, CuIn3 Se5
is inserted which is commonly known as an ordered vacancy
compound ðOVCÞ layer [18]. The inverted surface layer
reduces the recombination rate and hence improves the cell
performances by shifting away the electrical junction from
the higher-recombination interface to the ZTO=CZTSSe inter-
faces. The CZTSSe solar cell structure is shown in Fig. 1.
A simulation was conducted in order to interpret the mea-
sured current density versus voltage relationship referred to as
J–V characteristic curve. An OVC layer with a thickness of
60 nm, a band gap of 1:37 eV, an electron mobility of
10 cm2 V
1 s
1 , a hole mobility of 40 cm2 V
1 s
1 and a carrier
density of 2  1016 cm
3 have been used [15,18–20]. The indi-
rect band gap of the ZTO buffer decreases from 3:74 eV at
90  C deposition temperature to 3:23 eV at 180  C deposition
temperature [13,14]. The main reasons behind differing the
deposition temperature are to change the conduction band
energy level and to affect the size of the grain of crystalized
materials which in turn contribute to improve the performance
of the photovoltaic cells [12]. It is proven that the higher
atomic layer deposition ðALDÞ temperature of ZTO buffer
causes lower open circuit voltage and at lower deposition tem-
perature the efficiency of the solar cell is limited by the lower
fill factor [12]. So, the lower deposition temperature is more
preferable as the band gap becomes narrower with the increas-
ing deposition temperature. At 90  C deposition temperature
the ZTO buffer with a ½Sn=ð½Sn þ ½ZnÞ composition of 0:18
results in a band gap of 3:74 eV with a critical thickness of
around 50 nm [12]. For modeling an effective recombination
rate, a deep level defect with an interface defect concentration
Cadmium free high efficiency Cu2ZnSn(S,Se)4 solar cell 227

of 1  1010 cm
2 is placed in the midway of the band gap of the

ZTO, the OVC and the space charge region ðSCRÞ of the
CZTSSe absorber. The most important material properties
used to simulate the CZTSSe solar cell by the ADEPT 2:1 tool
are summarized in Table 1 [2,12,15,18–20].

4. Results and discussions

4.1. Effect of ZTO buffer layer on the cell performance

The light J–V characteristic curve obtained after conducting

the simulation of CZTSSe solar cell with ZTO buffer under
the global AM1:5G illumination condition is shown in
Fig. 2. In this case, the cell performance was estimated without
using the CuIn3 Se5 ISL. And the FF and the efficiency of
CZTSSe solar cell were calculated as 70:23% and 12:98%
respectively.

4.2. Effect of CuIn3 Se5 ISL on the cell performance

Figure 2 Current density versus voltage curve of CZTSSe based
solar cell.
While using CuIn3 Se5 as an inverted surface layer between the
ZTO buffer and CZTSSe absorber layer, the performance var-
ies. This layer is used to inhibit the interface recombination
processes and to reduce the defect density at the interface
[21]. However, the short-circuit current density, Jsc reduces
owing to the spike barrier for recombination at the
ZTO=CZTSSe interface and photo-generated electrons in com-
parison with the cell with CdS buffer layer. The careful control
of using CuIn3 Se5 between the ZTO buffer and the CZTSSe
absorber is necessary as the cell performance is greatly affected
by the thickness of this inverted surface layer [22]. It is
observed that the use of 60 nm thick ISL at the
ZTO=CZTSSe interface in CZTSSe solar cell yields a higher
energy conversion efficiency of 14:09% with Jsc , Voc , and FF
of 33:74 mA cm
2 , 731:26 mV, and 73:17% respectively.
Fig. 3 represents the J–V characteristic curve for CZTSSe solar
cell with CuIn3 Se5 ISL.
The comparison of performance parameters between the
device structures with ZTO buffer and with CdS buffer is illus-
trated in Table 2. From the observation, it is clear that the
ZTO should be a promising option as a substitute buffer layer
Figure 3 J–V characteristic curve of CZTSSe solar cell with
to CdS. The shunt resistance has been computed from the
CuIn3 Se5 ISL.
slope close to V ¼ Voc whereas the serial resistance has been
calculated from the slope nearby V ¼ 0.
Fig. 4 shows the energy band diagram with a band gap ated because of the difference of electron affinities. The CBO
grading. At the ZTO=CZTSSe interface, a barrier was gener- generates a barrier that acts as a secondary diode similar to

Table 1 Material parameters used in ADEPT 2:1 for CZTSSe solar cell simulation.
Properties Cu2 ZnSn ðS; SeÞ4 Zn1
x Snx Oy i-ZnO ZnO : Al
Thickness, s ½nm 1600 50 20 350
Band gap, Eg ½eV 1:50 3:74 3:30 3:40
Electron affinity, ve ½eV 4:63 4:06 4:60 4:60
Donor concentration, Nd ½cm
3  – 1  1017 3  1016 2  1017
Acceptor concentration, Na ½cm
3  2  1016 – 3  1016 –
Hole mobility, lp ½cm2 V
1 s
1  25 40 20 20
Electron mobility, ln ½cm2 V
1 s
1  100 160 80 80
228
Table 2 Performance parameters of Cu2 ZnSnðS; SeÞ4 thin film solar cell.
Description
CZTSSe cell with CdS buffer [1]
CZTSSe cell with ZTO buffer
CZTSSe cell with ZTO buffer and CuIn3 Se5 ISL
Figure 4 Energy band diagram with a band gap grading.
the main diode. The CZTSSe absorber absorbs photons
nearby the junction where the band bending produces a well.
This well amasses electrons and recombines at the
ZTO=CZTSSe interface or defeat the barrier. The barrier can
halt the current flow if this barrier is bigger than we supposed.
The electric field response and the recombination rate cor-
responding to the thickness of the cell are also shown in
Fig. 5a and b respectively.
Figure 5 (a) Electric field response; (b) recombination profile.
Md. Asaduzzaman et al.
Voc ðmVÞ Jsc ðmA cm
2 Þ FF ð%Þ g ð%Þ
513:40 35:21 69:80 12:60
656:31 36:04 70:23 12:98
731:26 33:74 73:17 14:09
5. Conclusions
The ADEPT 2:1 device simulator has been used to conduct a
numerical simulation of a thin film solar cell having a device
structure n-ZnO : Al/i-ZnO/n-ZTO/p-CZTSSe with an
ordered vacancy compound OVC layer, also known as
inverted surface layer, sandwiched between the ZTO buffer
and the CZTSSe absorber. The recombination rate in the space
charge region ðSCRÞ controls the open circuit voltage ðVoc Þ
generated by the cell. The Voc can be decreased by enhancing
the SCR band gap followed by the increase in the barrier
height. By using the ZTO buffer in the CZTSSe solar cell, a
14:09% power conversion efficiency ðPCEÞ was achieved under
the global illumination condition AM1:5G with an operating
temperature of 300:15K and a shadowing factor of 0:10. It
can be concluded that the Zn1
x Snx Oy ðZTOÞ material can be
used as a buffer layer substitute to the toxic and carcinogenic
CdS material as the photovoltaic parameters of the cell with
ZTO buffer substantiate a better performance than the existing
cell with conventional CdS buffer. And thus it supports
strongly to fabricate an environment-friendly, cost-effective
and highly efficient CZTSSe thin film solar cell with ZTO buf-
fer layer in the laboratory.
Authors’ contributions
MA conducted the device modeling, led the simulation, pre-
pared and drafted the manuscript. MMM and MMH helped
to analyze the results and to prepare the manuscript. ANB
supervised the research and aided to submit the manuscript.
All authors read and approved the final manuscript.
Cadmium free high efficiency Cu2ZnSn(S,Se)4 solar cell
Acknowledgment
The authors would like to express their gratitude for the use of
ADEPT 2:1, an online based one-dimensional simulation tool
developed by the research group of Purdue University, USA.
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