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Thin film solar cell with 8.4% power conversion efficiency using an Earth-
abundant Cu2ZnSnS4 absorber

Article in Progress in Photovoltaics Research and Applications · January 2013

DOI: 10.1002/pip.1174

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 PROGRESS IN PHOTOVOLTAICS: RESEARCH & APPLICATIONS
Prog. Photovolt: Res. Appl. (2011)
Published online in Wiley Online Library (wileyonlinelibrary.com). DOI: 10.1002/pip.1174

SHORT COMMUNICATION

Thin film solar cell with 8.4% power conversion

efficiency using an earth-abundant Cu2ZnSnS4 absorber
Byungha Shin, Oki Gunawan, Yu Zhu, Nestor A. Bojarczuk, S. Jay Chey and Supratik Guha*
IBM T. J. Watson Research Center, Yorktown Heights, NY 10598, USA

ABSTRACT
Using vacuum process, we fabricated Cu2ZnSnS4 solar cells with 8.4% efficiency, a number independently certified by an
external, accredited laboratory. This is the highest efficiency reported for pure sulfide Cu2ZnSnS4 prepared by any method.
Consistent with literature, the optimal composition is Cu-poor and Zn-rich despite the precipitation of secondary
phases (e.g., ZnS). Despite a very thin absorber thickness (~600 nm), a reasonably good short-circuit current was
obtained. Time-resolved photoluminescence measurements suggest a minority carrier-diffusion length on the order
of several hundreds of nanometers and relatively good collection of photo-carriers across the entire absorber thickness.
Copyright © 2011 John Wiley & Sons, Ltd.

KEYWORDS
Cu2ZnSnS4; earth-abundant absorber; co-evaporation; photoluminescence

*Correspondence
Supratik Guha, IBM T. J. Watson Research Center, Yorktown Heights, New York 10598, USA.
E-mail: guha@us.ibm.com

Received 13 May 2011; Revised 24 June 2011

1. INTRODUCTION benefits of a 1.5 eV absorber are detailed in [13]), to retain

There has been much renewed interest in the earth-abundant
compound Cu2ZnSnS4 (band gap = 1.45–1.5 eV) as a po-
tential candidate for a light absorbing layer in thin film so-
lar cell devices to replace conventional absorber layers
such as CdTe and Cu(In,Ga)Se2 (CIGS) [1]. We call a com-
pound used for photovoltaic applications as earth abundant if
there is enough material supply of the elemental constituents
of this compound available to support the current annual
worldwide electricity consumption of 17 000 TWh using solar
cells that are made using this compound. The details of annual
electricity production potential for different photovoltaic mate-
rials are provided in [2]. Various approaches have been
reported to fabricate Cu2ZnSnS4 (CZTS) layers including
thermal co-evaporation [3–5], sputtering [6,7], pulsed laser
deposition [8], electroplating [9,10], and solution process
[11,12]. Notably, using a hybrid solution-particle method
and by substituting some of the sulfur with selenium, Todorov
et al. [11] demonstrated the power conversion efficiency of
9.66% using a mixed sulfo-selenide CZTSSe absorber
whose [S]/([S] + [Se]) and estimated bandgap is ~0.4 and
~1.2 eV, respectively. It may be preferable, however, both
from an environmental compatibility perspective as well as
the desire for a higher bandgap absorber (the technical
a selenium-free CZTS composition. The best efficiencies
reported for the pure sulfide CZTS solar cells so far have been
6.8% using either thermal co-evaporation of elemental sources
[4] or co-sputtering [6]. In this work, we show that very thin
CZTS absorber layers (~600 nm) can be deposited using a
150 C vacuum thermal evaporation process and subsequent
short (5 min) high-temperature (570 C) atmospheric pressure
anneal and report a solar cell efficiency of 8.4%. These mea-
surements have been independently confirmed and certified
by an external, accredited laboratory—The Newport Tech-
nology and Applications Center’s Photovoltaic (TAC-PV)
Lab.a These are the highest efficiencies reported for the
pure sulfide CZTS absorber using any technique.
2. EXPERIMENTAL
Cu2ZnSnS4 films were grown on Mo-coated soda lime
glass substrates by thermal evaporation in a vacuum sys-
tem equipped with Knudsen-type sources of elemental
a
Newport is accredited by the American Association for Labora-
tory Accreditation (A2LA) to ISO/IEC 17025. Measurements
were done according to the American Society for Testing Mate-
rials (ASTM) standards E948 and ASTM E1021.

Copyright © 2011 John Wiley & Sons, Ltd.

Cu2ZnSnS4 solar cell with 8.4% efficiency B. Shin et al.

Cu, Zn, and Sn. For S, a commercially available valved (a) MgF2
cracker (from Veeco, Plainview, NY, USA) was used.
TCO (i-ZnO/Al:ZnO)
The substrate temperature during growth was kept rela-
tively low (~150 C) to minimize the possibility of forming CdS
secondary phases at the CZTS/Mo interface due to high
volatility of SnS [5]. After evaporation, a short (5 min) at-
CZTS
mospheric pressure anneal was performed at 570 C using a
process described earlier [3,4]. The rest of the device struc-
MoSx
ture consists of 90–100-nm-thick CdS by chemical bath
deposition, ~80 nm intrinsic ZnO, ~450 nm Al-doped 0.2 m Mo
ZnO by sputtering, Ni–Al metal fingers, and ~100 nm
MgF2 anti-reflection coating. Transmission electron mi-
croscopy (TEM) samples were prepared using an FEI HE- (b) TCO
LIOS 4000 DualBeam (FEI, Hillsboro, OR, USA) focused
ion beam, with the thinned specimen lifted off and placed CdS
on a carbon supporting film. A JEOL 3000F (JEOL Ltd,
Tokyo, Japan) machine operating at 300 kV was used for CZTS
the TEM analysis. Current–voltage (I–V) measurements
were performed under simulated AM 1.5 Global spectrum
and 100 mW/cm2 (1 sun) illumination by ourselves as well ZnS
as by the external, accredited laboratory at Newport Inc., as MoSx
described earlier. The lifetime of photo-generated carriers Mo 0.2 m
was measured on fully processed cells by time-resolved
photoluminescence (TR-PL) using a Hamamatsu single
photon counting system utilizing a 532-nm solid-state laser (c)
with the pulse width less than 1 ns and the repetition rate of 100
Mo Cu Zn
15 kHz. The average power density of the excitation laser Mo ZnO
Relative atomic %

80 Sn S Cd
in TR-PL is ~15 mW/cm2 (0.15 sun).
MoS
60 ZnS CZTS CdS

3. RESULTS AND DISCUSSION
Figure 1(a) presents a cross-sectional bright field TEM
image of our best CZTS solar cell (8.4% efficiency). An in-
terfacial layer (~110-nm-thick), which is identified as
MoSx by the compositional data shown in Figure 1(c), is
observed at the CZTS/Mo interface as a result of the
post-deposition annealing at 570 C. The equiaxed grains
in the CZTS layer exhibit a bimodal size distribution: big-
ger grains as large as the film thickness plus smaller grains
localized in the immediate vicinity of the CZTS/Mo inter-
face. Figure 1(b) shows a dark field scanning transmission
electron microscopy image of the 8.4% CZTS solar cell.
The red arrow, which extends from Mo to ZnO, marks
the direction of an energy-dispersive X-ray spectroscopy
(EDX) line scan. Elemental profiles determined from the
EDX scan are shown in Figure 1(c), which demonstrates
the presence of a ZnS-rich grain near the MoSx layer.
On the basis of EDX profiling such as the ones shown in
Figure 1(c), we learn that the larger grains are CZTS and
the smaller grains near the CZTS/Mo interface are ZnS,
which is phase-separated out of the initially Zn-rich
columnar grains. As far as avoiding phase separation is
concerned, therefore, growing CZTS close to its stoichi-
ometry would be beneficial. Literature reports indicate
however that the optimal elemental ratios for higher quality
solar cells are in the range of Cu/Sn = 1.7–1.8 and Zn/
Sn = 1.2–1.3 [1], a finding that we find our results
40
20
0
0 200 400 600 800
Position (nm)
Figure 1. (a) Bright field TEM image of 8.4% Cu2ZnSnS4 (CZTS)
solar cell, illustrating bimodal distribution of grain structure of
CZTS. (b) Dark field scanning transmission electron microscopy
image of 8.4% CZTS solar cell. The red arrow, which extends from
Mo to ZnO, marks the direction of X-ray spectroscopy (EDX) line
scan. We rotated the raw transmission electron microscopy images
used in Figure 1(a) and (b) so that the layer stacking direction is
aligned along the vertical direction of the page, which we believe
makes the figures more easily comprehensible. As a result, we
trimmed the corners that do not provide any further information.
(c) Elemental profiles determined by EDX scan [the red arrow in
Figure 1(b)], which demonstrates the presence of ZnS near the
CZTS/MoSx interface.
consistent with. A speculative reason for this is as follows.
First principle calculations suggest that defects with the
lowest formation energy in CZTS are CuZn antisites
[14,15]. Nucleating and growing CZTS grains out of initially
Zn-rich environments such as the case in our best CZTS device
would suppress the formation of CuZn defects in the final
CZTS grains and ZnS phases that segregated out may simply
act as a “dark” space without doing significant harm to the
device except reducing the effective volume of the absorber.

Prog. Photovolt: Res. Appl. (2011) © 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
B. Shin et al. Cu2ZnSnS4 solar cell with 8.4% efficiency

10
The explanation is based upon the assumption that such point
(a)
defects are electrically active and detrimental to the device. =8.4%; FF=65.8%; Voc=661 mV
5
I–V characteristics of a finished solar cell under dark Jsc=19.5 mA/cm2; Rs=4.5 cm2

Current density (mA/cm2)

and under 1-sun illumination are shown in Figure 2(a). 0
The light I–V curve in Figure 2(a) was measured by the ex-
ternal accredited laboratory at Newport Inc. and is very -5 0.41eV
similar to our own measurement. Despite a very thin ab- CZTS
sorber thickness (~600 nm), short-circuit current (Jsc) is CdS
-10 1.45eV 0.41eV
reasonably good. The maximum Jsc attainable (assuming
100% collection efficiency of photo-generated carriers) -15
0.29 eV
with a 600-nm-thick absorber, bandgap energy (Eg) of
0.54 eV
which is 1.45 eV, is ~30.1 mA/cm2.b If we take into ac- -20
count of the anticipated losses in Jsc from transparent con- 0.0 0.2 0.4 0.6 0.8
ducting oxide (ZnO) and CdS, as estimated by the Voltage (V)
measured quantum efficiency for wavelengths <520 nm
(Eg of CdS), the maximum Jsc reduces to 23.4 mA/cm2. 1.0
Our CZTS solar cell collects ~83% of this maximum Jsc at- 0.9 (b)
tainable from a solar cell consisting of ZnO/CdS/600 nm 0.8
CZTS, suggesting reasonably good collection of the
0.7
photo-generated carriers. Although the open-circuit volt-
0.6
age (Voc) is the highest (661 mV) among reported CZTSSe

solar cells, as previously addressed [16], achieving a
higher efficiency appears to be limited by a Voc deficit in
addition to a rather high series resistance of 4.5 Ω cm2.
Figure 2(b) shows the external quantum efficiency (EQE)
measured at zero bias as well as at a reverse bias ( 1 V).
Improved EQEs are observed at longer wavelengths at the re-
verse bias, which indicates some difficulty in collecting photo-
carriers created deep in the absorber (i.e., those generated by
incident photons of longer wavelengths). The application of a
reverse bias extends the depletion layer into the absorber layer
so that a larger fraction of the minority photo-carriers are swept
by the field, with a resultant increase in photo-current.
Figure 3 presents TR-PL spectrum at emission wave-
length of 960 nm, which is the peak position of a broad
PL spectrum collected as a function of wavelength at room
temperature (see the inset of Figure 3). This peak position
corresponds to ~1.3 eV, which is smaller than the esti-
mated bandgap of 1.45 eV by the EQE measurement. How-
ever, TR-PL spectrum measured at 860 nm (~1.45 eV) is
almost identical to the TR-PL at 960 nm except for a higher
level of noise due to the weaker luminescence signal at
860 nm. Because of the pulsed nature of excitation source
(15 kHz), the initial excess carrier concentration created by
each pulse of laser is approximately 5000 times as large as
the steady-state excess carrier concentration during continu-
ous illumination at the same power density. Therefore, the
number of carriers generated by a single pulse of laser in our
measurements is approximately equal to the number of steady-
state excess carriers under ~750 sun illumination, that is, a high
injection regime, which explains the initially fast decay of the
b
We estimated the maximum Jsc from the total number of
photons in AM 1.5 Global solar spectrum between 300 and
860 nm (corresponding to the Eg of CZTS, 1.45 eV) absorbed
by a 600-nm-thick CZTS, assuming 100% collection efficiency
of photo-generated carriers.
EQE
0.5
0.4
0.3
0.2
at 0V
0.1
at -1V (reverse bias)
0.0
300 400 500 600 700 800 900 1000
Wavelength (nm)
Figure 2. (a) I–V characteristics under dark (blue) and under 1-
sun illumination (red). Light I–V was measured by an external,
accredited laboratory (The Newport Technology and Applications
Center’s Photovoltaic Lab), and it is very similar to our own measure-
ment (not shown here). Band alignment between CdS and
Cu2ZnSnS4 (CZTS) (adapted from [18]) is shown in the inset. (b)
External quantum efficiencies (EQEs) measured at zero (blue) and
at a reverse bias ( 1 V, red).
spectrum. For the determination of a carrier lifetime, a portion
of the spectrum (15–25 ns) avoiding the initial fast decay was fit-
ted by a single exponent. The lifetime (t) of 7.8 ns is extracted.
With this value of the lifetime and with a conservative as-
sumption of electron mobility (mn) of >5 cm2/V s,c we es-
timate the lower bound of the diffusion length (Ln) of
electrons in CZTS, Ln ~ (Dnt)1/2 = [mn(kT/q)t]1/2 ~ 350 nm,
where Dn is diffusivity of electrons in CZTS. We also
estimated the depletion width, Wd, using the equation
c
The reported hole mobility in CZTS ranges in 6–30 cm2/V s
(references for the reported hole mobility are Tanaka et al., Jour-
nal of Physics and Chemistry of Solids, 2005; 66: 1978–1981;
Liu et al., Solar Energy Materials and Solar Cells, 2010; 94:
2042–2045). Recent first principle calculations suggest a lighter
electron effective mass in CZTS and, hence, a higher electron
mobility is expected (see Persson, Journal of Applied Physics,
2010; 107: 053710-1-8).

Prog. Photovolt: Res. Appl. (2011) © 2011 John Wiley & Sons, Ltd.
DOI: 10.1002/pip
Cu2ZnSnS4 solar cell with 8.4% efficiency
Figure 3. Time-resolved photoluminescence (TR-PL) spectrum
at the emission wavelength of 960 nm. Carrier lifetime of
7.8 ns was determined by a single exponent fit to the spectrum
(15–25 ns). Plot of PL versus wavelength is shown in the inset.
Wd = (2e0esVbi/qNA)1/2 ~ 180 nm [17]. Here, Vbi is the band
bending of CZTS at the CdS/CZTS interface, e0 is the vac-
uum permittivity, es is the dielectric constant of CZTS, and
NA is the p-type carrier density of CZTS. We use a value of
Vbi of ~0.41 eV obtained from ultraviolet photoelectron
spectroscopy measurements [18], a value of es of 7 from
first principle calculations [19], and a value of NA of
~1  1016/cm3 from drive-level capacitance profiling (not
shown here). The sum of the estimated depletion width
(~180 nm) and the minority carrier diffusion length
(>350 nm) is close to the CZTS absorber thickness
(~600 nm), suggesting good collection of carriers across
the entire absorber thickness.
4. SUMMARY
In summary, using a vacuum thermal evaporation method,
we have fabricated CZTS solar cells with thin absorber
(~600 nm) layers and with power conversion efficiencies
of up to 8.4%. The TR-PL measurements in conjunction
with the estimated depletion width suggest (i) a minority
carrier diffusion length on the order of several hundreds
of nanometers and (ii) reasonably good collection of
photo-carriers across the entire CZTS absorber.
ACKNOWLEDGEMENTS
We acknowledge Keith Fogel and Richard Ferlita for their
help with the deposition of Al : ZnO and Ni/Al metal
contacts.
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