APPLIED PHYSICS LETTERS 98, 051912 共2011兲

Structural and elemental characterization of high efficiency Cu2ZnSnS4

solar cells
Kejia Wang, Byungha Shin, Kathleen B. Reuter, Teodor Todorov, David B. Mitzi, and
Supratik Guhaa兲
IBM T. J. Watson Research Center, Yorktown Heights, New York 10598, USA
共Received 10 November 2010; accepted 22 December 2010; published online 1 February 2011兲
We have carried out detailed microstructural studies of phase separation and grain boundary
composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal
evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions
between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial
MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4
into ZnS and a Cu–Sn–S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps
as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally
evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such
interfacial compound formation and grain boundary chemistry likely contributes to the lower than
expected open circuit voltages observed for the Cu2ZnSnS4 devices. © 2011 American Institute of
Physics. 关doi:10.1063/1.3543621兴

In recent years the compound Cu2ZnSn共Sx , Se1−x兲4
共CZTSSe兲 has received wide research interest due to its po-
tential as an absorber material for earth abundant and inex-
pensive thin film solar cells using fabrication methods in-
cluding thermal evaporation,1,2 sputtering,3 electroplating,4
and solution processing.5 The highest conversion efficiency
obtained thus far is 9.66% using a Se/ 共Se+ S兲 ratio ⬃0.6 to
0.92.5 For the pure sulfide Cu2ZnSnS4 共CZTS兲, the highest
reported efficiency reported has been 6.8% fabricated by
thermal evaporation1 and sputtering.3
The structural properties of CZTS are important for
achieving high efficiency solar cells, however there have
been limited studies relating the microstructure of CZTS lay-
ers to cell performance.4,6 In our previous work, high effi-
ciency CZTS solar cells with up to 6.8% efficiency were
achieved by thermal evaporation.1 In this letter we used
transmission electron microscopy 共TEM兲, energy-dispersive
x-ray spectroscopy 共EDS兲, and Raman spectroscopy to study
the microstructure of these CZTS absorber layers prepared
by thermal evaporation to understand what is limiting the
efficiency. We demonstrate that phase stability is a key issue
in vacuum deposited materials, and Cu diffusion at the
CZTS/Mo interface may contribute to phase separation of
CuxSnSy and ZnS. We also show that unlike the related, and
better-studied CuInGaSe2 共CIGS兲 materials,7–10 there may be
an accumulation of copper at the grain boundaries in ther-
mally evaporated CZTS.
CZTS thin films were deposited on Mo/soda lime glass
substrates by thermal evaporation in a vacuum system
共10−8 torr background pressure兲. The substrate was heated to
⬃110 ° C during coevaporation of Cu, Zn, Sn, and S. No
excess S was incorporated during deposition and cation:S
ratio is ⬃1 verified by Rutherford backscattering spectrom-
etry 共RBS兲. Then the sample was taken out and annealed in S
vapor at 540 ° C for 5 min on a ceramic hot plate. The pro-
a兲
Author to whom correspondence should be addressed. Electronic mail:
guha@us.ibm.com.
cedures of chemical bath deposition of CdS, sputtered Al–
ZnO layer and evaporation of top metal contact are described
in previous work.1 Solar cell efficiencies have been in the
5%–7.1% range with an absorber layer thickness of 650–750
nm. The composition of Cu/Sn was 1.7–1.9 and Zn/Sn 1.1–
1.5 as measured by x-ray fluorescence. The device fabrica-
tion and electrical characterization have been explicitly dis-
cussed in a previous paper.1
Figure 1共a兲 is a bright field image of a CZTS solar cell.
Several interesting observations can be made as follows: 共i兲
A 150 nm MoSx layer develops at the interface between the
CZTS and Mo as a consequence of inter-reaction; 共ii兲 there
are voids that exist between the CZTS and the MoSx layer;
and 共iii兲 the grain structure in the CZTS layer varies, with
smaller platelet shaped grains at the bottom interface, and
larger, 300–600 nm grains in the rest of the absorber layer.
Raman spectroscopy was used to further characterize the
CZTS absorber layer as shown in Fig. 1共b兲. The laser used
was at 632 nm and illuminated from the top surface. The
Raman spectra revealed only the CZTS peaks at 287, 338,
and 368 cm−1.11 There is no significant indication of phase
separation for Cu2−xS at 475 cm−1,12 ZnS at 355 cm−1,11
Cu2SnS3 at 318 cm−1,12 and Sn2S3 at 304 cm−1.11 The
higher than baseline signal from 220 to 380 cm−1 could be
either due to the broadening peaks of CZTS or small amount
of signals from binary/ternary compounds.
We now turn to the results of the TEM and EDS. Figure
2共a兲 is a bright field TEM image of the lower region of the
CZTS film, showing a distribution of equiaxed and platelet
shaped grains. The CZTS layer and the underlying MoSx
layer are clearly marked. Three EDS scans were taken in
STEM mode across different grains and the scan trajectories
are labeled in Fig. 2共a兲. The round dot indicates the starting
point and the arrow indicate the scanning direction. Scan 1
started in a grain containing Cu, Zn, Sn, and S 共CZTS兲; upon
crossing the grain boundary the Zn signal disappeared indi-
cating a grain with a composition restricted to Cu, Sn, and S.
This grain could be one of the stable Cu–Sn–S compounds
that have been identified such as Cu4SnS4, Cu2SnS3, or

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 051912-2 Wang et al. Appl. Phys. Lett. 98, 051912 共2011兲

MgF2

ZnO

CdS

CZTS

MoSx
300 nm
Mo

(a) (b)

FIG. 1. 共Color online兲 CZTS solar cell: 共a兲 Cross-sectional TEM bright field image. 共b兲 Raman spectroscopy.

Cu2Sn4S9, or any of their combinations. The relative atomic
ratios of the elements as a function of scan position are
shown in Fig. 2共b兲. The results of scan 2 are shown in Fig.
2共c兲. Again, the starting grain was CZTS; however across the
grain boundary the Cu and Sn signals disappeared indicating
that the round grain consists of the binary compound ZnS.
Multiple scans have been taken in other areas, and similar
ZnS and CuxSnSy phase separation has been observed in the
CZTS layer close to the MoSx interface. Scan 3 started in the
ZnS grain and proceeds through the MoSx layer ending in the
underlying Mo layer. The trace in Fig. 2共d兲 clearly shows
diffusion of Cu into the MoSx layer. Similar analyses have
been carried out in solution processed CZTSSe: about 300
nm thick MoSe2 layer was observed and no phase separation
identified from EDS analysis.5
This phase separation is observed in the absorber layer
only near the CZTS/Mo interface and it is tempting to specu-
late that this is caused by the diffusion of Cu into the by
MoSx, triggering a composition change in the CZTS layer
and a resulting phase separation. Note that other factors that
could contribute to the observed ZnS and Cu–Sn–S segrega-
tion are out-diffusion of S into the MoSx layer 共i.e., S avail-
ability during the heat treatment兲. Our results are in qualita-
tive agreement with thermodynamics predicting that Cu2S
and SnS2 can form several stable compounds while there is
no stable compound between ZnS and Cu2S, or between ZnS
and SnS2.13
It should be pointed out that in Raman spectroscopy no
ZnS or Cu2SnS3 peaks were clearly identified implying a
single phase CZTS layer within the absorption depth of the
632 nm laser irradiation used for the measurement. At this
wavelength most of the light is absorbed within the top 100–
200 nm of the CZTS layer, consistent with the TEM obser-
vations that the phase separation appears limited to the back
surface of the absorber layer.

(a) scan 2 (b) scan 1

scan 1 CZTS

voids

scan 3 MoSx

100 nm

FIG. 2. 共Color online兲 共a兲 Bright field image of CZTS/

MoS interface. 关共b兲–共d兲兴 The EDS elements analysis for
three scans at different positions.
(d) scan 3

(c) scan 2

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(a) 50

Atomic % (relative)
CZTS grain 1 40
30
scan 4
20 (b) scan 4
10
0
scan 5 0 5 10 15 20 25 30 35 40 45 50
Cu
Zn Position (nm)
Sn
S
CZTS 50

Atomic % (relative)
grain 2 40
30
CZTS grain 3
20 (c) scan 5
10
0
100 nm 0 5 10 15 20 25 30 35
Position (nm)

FIG. 3. 共Color online兲 EDS analysis of CZTS grain boundaries.

The grain boundary composition in the CZTS absorber
layer is also of interest. In Fig. 3 the elemental analysis
across different CZTS grains, as carried out by EDS analysis
in the STEM mode, are shown. Figure 3共a兲 shows a bright
field image of three adjacent CZTS grains. Scan 4 was car-
ried out between grain 1 and grain 2, and scan 5 was carried
out between grain 1 and grain 3. The grain boundary be-
tween grains 1 and 2 is Cu rich and S poor compared to the
bulk, and a typical result is plotted in Fig. 3共b兲. The grain
boundary between grain 1 and 3 is same composition as the
bulk from scan 5, and a typical result is plotted in Fig. 3共c兲.
This observation has been verified with more than one scan
across each grain boundary. This is different from polycrys-
talline Cu共InGa兲Se2 共CIGS兲 thin films where no change in
Cu composition10 or depletion of Cu 共Ref. 9兲 共almost by a
factor of two兲 in the grain boundaries has been observed.
Phase separation of a lower band gap compound such as
Cu2SnS3 共⬃0.95 eV兲 that is embedded in the absorber layer
near the back contact can result in a lowering of the open
circuit voltage of the device, especially for thin devices. In-
deed, as we have reported earlier,1 temperature dependent
electrical measurements of the open circuit voltage show that
the activation energy for recombination is ⬃1.05 eV, instead
of the expected ⬃1.45 eV that corresponds to the band gap
of CZTS. This inconsistency in the expected value of the
activation energy could be explained by the presence of the
lower band gap phases that separate out in the CZTS layer.
However, the deficit of Voc in large band gap chalcogenide
solar cell has been widely observed even without phase
separation.14 Other likely contributions to the low Voc may
include the observed grain boundary chemistry7–9 and inter-
face recombination at the front CdS–CZTS interface.15
In conclusion, we have carried out a detailed study of the
microstructure in thermally evaporated CZTS absorber layer
based solar cells. We show that inter-reaction between the
underlying Mo electrode and the CZTS layer results in the
formation of a MoSx reaction layer and phase separation of
parts of the CZTS layer adjacent to the Mo electrode into
ZnS and a CuxSnSy compound. Grain boundaries in the
CZTS films appear to have either the same composition as
the bulk, or are copper rich—we do not observe any cases of
Cu deficiency in the grain boundaries. It is likely that the
observed phase separation at the back contact, with the for-
mation of a lower band gap compound such as CuxSnSy, and
the Cu stoichiometry at the grain boundaries, may contrib-
uted to the observed, less than expected values of the open
circuit voltage for CZTS.
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