HIGH EFFICIENCY Cu2ZnSn(SxSe1-x)4 THIN FILM SOLAR CELLS BY THERMAL CO-
EVAPORATION
Byungha Shin, Kejia Wang, Oki Gunawan, Kathleen B. Reuter, S. Jay Chey, Nestor A. Bojarczuk, Teodor Todorov, David
B. Mitzi, and Supratik Guha
IBM T.J. Watson Research Center, Yorktown Heights, NY, 10598
ABSTRACT
We report on the device results of thermally evaporated
high efficiency Cu2ZnSn(SxSe1-x)4 (CZTSSe) thin film solar
cells with power conversion efficiencies of 7.1% (x=1.0)
and 7.5% (x=0.34). We have carried out extensive
electrical and structural characterization of CZTSSe solar
cells to identify major factors that limit the efficiency. Bias-
dependent quantum efficiency measurements revealed
ineffective collection of charge carriers photo-generated
deep in the absorber layer suggesting a short minority
carrier diffusion length, which was confirmed by time-
resolved photoluminescence measurements.
Temperature-dependence of the series resistance of the
devices is consistent with the presence of a Schottky-type
barrier in the back contact, likely caused by secondary
phases near the CZTS/Mo interface and/or an interfacial
MoSx layer.
INTRODUCTION
The compound Cu2ZnSn(SxSe1-x)4 (CZTSSe) has
emerged as an attractive alternative to conventional
absorber layers of thin film solar cells such as CdTe and
Cu(In,Ga)Se2 (CIGS). Using a hybrid solution-particle
method, Todorov et al.[1] demonstrated a CZTSSe based
thin solar cell with the power conversion efficiency of
9.66%. For pure sulfide CZTS solar cells, the highest
efficiency has been 6.8% as reported by Wang et al.[2]
using thermal co-evaporation of elemental sources and by
Katagiri et al.[3] using co-sputtering. In this work, we
report an improved efficiency of 7.1% for thermally co-
evaporated pure sulfide CZTS solar cells and 7.5%
efficiency for CZTSSe solar cells. We then report and
analyze the results of extensive electrical examination of
these devices to identify the underlying causes that limit
the device performance.
EXPERIMENTS
CZTSSe films were grown on Mo-coated soda lime glass
substrates by thermal evaporation in a vacuum system
equipped with Knudsen-type sources of elemental Cu, Zn,
and Sn. For S and Se, commercially available valved
crackers (from Veeco) were used. Material preparation
procedures have been described in detail in Ref. [2]. The
S: Se ratio was carefully controlled by adjusting the fluxes
from the S and Se crackers and the thicknesses of the
absorber layers were 600 – 650 nm for CZTS and ~ 2300
nm for CZTSSe. The device stack consisted of the
following sequence: ~70 nm thick CdS by chemical bath
deposition / ~80 nm intrinsic ZnO by RF sputtering / either
~450 nm Al doped ZnO or ~180 nm indium tin oxide (ITO)
/ ~100 nm MgF2 anti-reflection coating / Ni-Al (50/2000 nm)
metal fingers. Current-voltage (I-V) measurements were
2
done under simulated AM 1.5G spectrum at 100 mW/cm
(1 sun) illumination. The lifetime of photo-generated
carriers was measured by time-resolved
photoluminescence (TR-PL) using a Hamamatsu single
photon counting system utilizing a 532 nm solid state laser
with a pulse width of less than 1 ns and repetition rate of
15 kHz. The TR-PL measurements were performed on
finished cells.
RESULTS & DISCUSSIONS
Pure sulfide CZTS based solar cells
Figure 1 shows electrical measurements from a 7.1%
efficient CZTS based solar cell: 1(a) Dark and light I-Vs,
1(b) Internal quantum efficiency (IQE) at zero bias and at -
1V (reverse bias), and 1(c) extraction of band gap of
CZTS layer from QE measurements using the following
relations valid for direct band gap materials,
(1)
where  is absorption coefficient and L is approximately
the sum of depletion width and effective diffusion length of
minority carriers.[4] Figure 2 shows the temperature
dependence of (a) the open circuit voltage (Voc) and (b)
the series resistance (Rs). Several observations are
noteworthy. First, while the measured band gap energy
(Eg) of the CZTS film is ~1.45 eV, the open circuit voltage
(Voc) extrapolated at 0K [as shown in Fig. 2(a)] is at ~ 1.1
eV, significantly lower than Eg, indicating a significant
efficiency loss due to a Voc deficit. Secondly, from the
IQE measurement with and without reverse bias (Fig. 1(b)),
we note that the IQE at larger wavelengths (> 550 nm)
was improved at a reverse bias compared to that
measured at zero bias. Among all photo-generated
minority charge carriers (electrons in CZTS) in the
 20
15 (a) Light IV 1.2
Dark IV (a)
10
5
1.0
J (mA/cm )

Voc (V)
0
2

-5
0.8
2
area = 0.45 cm
-10 efficiency = 7.13%
-15 FF = 55.3%
0.6
-20 Voc = 614 mV

-25
Jsc = 21.0 mA/cm
2
0.4
2
Rs = 7.4 cm
-30
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 0 50 100 150 200 250 300 350
V (V) T (K)
1.0 3
10
internal Quantum Efficiency

(b)
14
0.8 (b) 12 B = 127 meV

ln(RsT)
10
2

Rs ( cm )
8
10

2
0.6
6
4
3 4 5 6 7 8
0.4 -3 -1
1 1/T (10 K )
10
0.2
at zero bias
at -1V (reverse) bias
0.0 0
300 400 500 600 700 800 900 1000 10
100 150 200 250 300 350
Wavelength (nm)
6 T (K)
(c)
5 Figure 2: (a) Temperature-dependence of
[hv*ln(1-EQE)] (eV )
2

Voc of 7.1% CZTS device. (b) Temperature-

4 dependence of Rs of 7.1% CZTS device.
2

Extraction of Schottky barrier height (from

3 the slope of ln(RsT) vs 1/T) is shown in the
inset
2 Eg ~ 1.45 eV

0
1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 300 Fitting by
hv (eV) A*exp(-t/)/[1-B*(1-exp(-t/))]
250
PL intensity (a.u.)

 =0.78 +/- 0.06

Figure 1: (a) Dark and light I-V of 7.1% 200
CZTS solar cell. (b) QE measured at -1V
(reverse bias) and at 0V. (c) Extraction of 150
Eg of CZTS from QE measurement.
100

50

absorber layer, only those within a diffusion length’s 0

0 2 4 6 8 10
excursion from the edge of the depletion width will be
Time (ns)
collected, contributing to the photo-current. By applying a
reverse bias, we extend the width of the depletion region; Figure 3: TR-PL (at 960 nm) of 7.1% CZTS
if the minority carrier diffusion length is small, by pushing device. Carrier lifetime was determined
by fitting TR-PL with the formula shown
the depletion region edge deeper into the absorber, we
in the figure.
would collect carriers that would not have been able to
 20
(a) Light IV
10 Dark IV
TCO

J (mA/cm )
0

2
CdS -10 area = 0.45 cm
2

efficiency = 7.51%
FF = 60%
-20
CZTS Voc = 422 mV
2
Jsc = 29.5 mA/cm
-30 Rs = 1.5cm
2

MoSx
-0.2 0.0 0.2 0.4 0.6 0.8
500 nm Mo V (V)
1.0

Internal quantum efficiency

Figure 4: SEM image of 7.1% CZTS device. (b)
0.8

otherwise reach the depletion region. The enhanced QE

0.6
at a reverse bias, therefore, suggests a rather short
diffusion length of electrons in CZTS. TR-PL (Fig. 3)
demonstrates a short carrier lifetime, less than 1 ns – 0.4
much shorter than that of a high quality CIGS device,
which is beyond 50 ns.[5] The minority lifetime model was
0.2
adopted from reference.[5] The bias dependent IQE
results and the TR-PL results indicate that a significant
fraction of the photo-generated carriers, even in a thin 0.0
(~600 nm) absorber layer are not being collected due to a 400 600 800 1000 1200 1400
small carrier diffusion length, resulting is a lower wavelength (nm)
photocurrent. Thirdly, Rs of this device is ~7 cm . In
2
5
comparison, this is about an order of magnitude higher
(c)
[hv*ln(1-EQE)] (eV )

that what is expected in a high quality CIGS device. This,

2

4
in turn, affects fill factor (FF), which is ~ 55%. Previously,
we identified a Schttoky-type barrier formed at the
2

CZTS/Mo back contact as the main contributor to the 3

observed large Rs.[2] The barrier height of the blocking
back contact, which was determined by temperature- 2
dependent Rs measurements, is as high as 0.13 eV, as
shown in Fig. 2(b). Figure 4 presents a scanning electron
microscopy (SEM) image taken from the 7.1% efficiency 1
Eg ~ 1.17 eV
CZTS sample. The CZTS film consists of relative large
grains (500 nm – 1 m) except in the vicinity of CZTS/Mo 0
interface where smaller grains are observed. Additionally, 1.0 1.1 1.2 1.3 1.4 1.5 1.6
a 100 nm thick layer of different contrast between CZTS Energy (eV)
and Mo is apparent, which we identify as a MoS x layer.
Recently, we have performed a TEM study on a similarly Figure 5: (a) Dark and light I-V of 7.5%
prepared CZTS solar cell with 6.6% efficiency,[6] which CZTSSe solar cell. (b) QE measured at 0V.
revealed the presence of phase-separated grains near (c) Extraction of Eg of CZTSSe from QE
measurement.
CZTS/Mo interface. So it is most likely that the smaller
grains seen in the SEM image are phase separated
secondary phases. Considering both electrical and
structural results, it appears that MoSx and/or phase transport. Also, a larger density of grain boundaries near
separated grains near the CZTS/Mo interface are the interface – especially those perpendicular to charge
responsible for the Schottky-type barrier against hole transport direction, i.e. the film thickness direction – would
 1.1 1600
Fitting by
1.0 (a) 1400
A*exp(-t/)/[1-B*(1-exp(-t/))]
0.9 1200

PL intensity (a.u.)
0.8 1000
 =0.50 +/- 0.02
Voc (V)

0.7
800
0.6
0.5 600
0.4 400
0.3 200
0.2
0
0 50 100 150 200 250 300 350 0 2 4 6 8 10

T (K) Time (ns)

3
10 Figure 7: TR-PL (at 1160 nm) of 7.5%
14 CZTSSe device. Carrier lifetime was
(b)
12 B = 99 meV determined by fitting TR-PL with the
ln(RsT)

10
2 formula shown in the figure.
Rs ( cm )

10 8
2

6
4
3 4 5 6
1 -3
10 1/T (10 K )
0
10
100 150 200 250 300
T (K)
Figure 6: (a) Temperature-dependence of Voc
of 7.5% CZTSSe device. (b) Temperature-
dependence of Rs of 7.5% CZTSSe device.
Extraction of Schottky barrier height (from
the slope of ln(RsT) vs 1/T) is shown in the
inset.
make the collection of charge carriers generated close to
the interface more difficult, which is consistent with the
bias-dependent QE results.
CZTSSe based solar cells
By adjusting fluxes of S and Se, one can vary the ratio of
S to Se in the Cu2ZnSn(SxSe1-x)4 absorber, thereby
adjusting the band gap from ~1.45 eV in the pure sulphide
phase (x=1) to ~1.0 eV in the pure selenide phase (x=0).[7]
Figure 5 shows electrical measurements of a CZTSSe
with the absorber layer thickness of 2300 nm and Se to
(S+Se) ratio of 0.66, as measured independently by X-ray
fluorescence spectroscopy and X-ray diffraction. The
device exhibits 7.5% efficiency, higher than that of our
best pure sulphide film. The IQE of the CZTSSe device is
shown in Fig. 5(b). The spectrum extends further into
7 8
-1
infrared region than the CZTS device due to the reduced
band gap of CZTSSe. The band gap energy extracted
from IQE is ~ 1.17 eV as shown in Fig. 5(c). Compared to
350 the CZTS device, the CZTSSe device exhibits lower Voc
(due to the increase in recombination current) and higher
Jsc (due to the extended absorption at longer wavelengths)
as a result of the smaller band gap. Temperature-
dependent Voc and Rs measurements are shown in Fig.
6(a) and 6(b), respectively. Interestingly, Voc of the
CZTSSe device extrapolated at 0K, ~1.0 eV is only 0.1 eV
lower than that of the CZTS device while the difference in
band gap energy is almost 0.3 eV. Therefore, we are not
gaining as much of Voc by going from the lower band gap
CZTSSe to the higher band gap CZTS, which is a
common phenomenon in other chalcogenide systems
such as CIGS.[8] Figure 7 shows TR-PL at 1160 nm
which corresponds to the band gap of the CZTSSe layer.
Similar to the CZTS device, the carrier lifetime of CZTSSe
is also short, ~ 0.5 ns, which must be one of the major
limiting factors in achieving a higher efficiency. The
differences between the CZTS and CZTSSe efficiencies
are not clearly understood. While it is tempting to draw
comparisons to CIGS with varying Eg by changing Ga
concentration, where similar effects are observed and
attributed to unfavorable band alignments with the CdS
emitter layer, this is not understood for CZTS at the
present time.
CONCLUSION
In conclusion, using thermal co-evaporation technique, we
have successfully fabricated high efficiency CZTSSe solar
cells – 7.1% from a pure sulfide CZTS device and 7.5%
from a mixed sulfo-selenide CZTSSe. Electrical
measurements in conjunction with structural studies
suggest that a Schottky-type barrier in the back contact –
which appears to be caused by secondary phases and/or
MoSx interfacial layer between CZTS and Mo – and small
minority carrier diffusion length are among the major
factors limiting conversion efficiency.

ACKNOWLEDGEMENT

We thank Keith Fogel and Richard Ferlita for their help

with the deposition of TCO and Ni/Al metal electrode.

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