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Phys. Status Solidi C, 1– 3 (2013) / DOI 10.1002/pssc.201200843

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current topics in solid state physics
Photoluminescence characterization
of Cu2ZnGeS4 single crystals
S. Levcenko*,1, M. Guc2, C. Merschjann1, G. Gurieva1, S. Schorr1,3, M. Lux-Steiner1, and E. Arushanov1,2
1
Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner Platz 1, 14109 Berlin, Germany
2
Institute of Applied Physics, Academy of Sciences of Moldova, Academiei Str. 5, 2028 Chisinau, Moldova
3
Freie Universitaet Berlin, Institute of Geological Sciences, Malteser Str. 74-100, 12249 Berlin, Germany

Received 11 October 2012, revised 15 January 2013, accepted 1 February 2013

Published online 16 May 2013

Keywords Cu2ZnGeS4, photoluminescence, single crystals

* Corresponding author: e-mail sergiu.levcenco@helmholtz-berlin.de, Phone: +49 30 8062 42830, Fax: +49 30 8062 43173

Optical properties of the Cu2ZnGeS4 bulk single crystals were
characterized by using Raman spectroscopy and photolumi-
nescence spectroscopy technique. The strongest lattice vibra-
tion mode of this compound observed at 359 cm-1 and less in-
tensive modes at 273, 291, 332, 370, 383, 405 and 414 cm-1.
PL spectra of the Cu2ZnGeS4 consist of dominant broad emis-
sion band located at about 1.40 eV and a less intensive near
2.00 eV at 4.5 K. The observed PL bands were attributed to
the donor acceptor pair transitions, with activation energy of
37 (140) meV for dominant and less intensive band, respec-
tively.

© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Cu2ZnGeS4 (CZGeS) alloyed with
manganese has drawn attention for its potential application
in magnetoelectronics [1]. More recently, CZGeS was
found to be a photofunctional material for hydrogen evolu-
tion from an aqueous solution under visible-light irradia-
tion [2] as well as suitable absorber in thin solar cell appli-
cation [3]. Also it was suggested to use CZGeS films as a
p- type substrate for a high-intensity light emission device
in which a light emitting material represented by ZnS
doped with Cu or Ga [4]. Although there are a number of
studies discussing the possible application of CZGeS semi-
conductor, there are only a few reports concerning the ba-
sic material properties of CZGeS. So far structure [5, 6],
magneto-optic [1], optical absorption [6, 7], electrolyte
electroreflectance [8], ellipsometry [9] and far infrared ab-
sorption studies [10] were carried out on this material.
However reports on electrically and optically active defects,
which would be of primary importance for the applications,
are still rather limited [11].
Here we present the results Raman and photolumines-
cence (PL) study of Cu2ZnGeS4 crystals grown by chemi-
cal vapor transport using iodine as a transport agent. PL
properties of the Cu2ZnGeS4 crystals were studied in terms
of the temperature (4.5-300 K) and excitation intensity.
2 Experimental details Single crystals were grown
byvapour transport of stoichiometric amounts of the ele-
ments using iodine as a transport agent. The concentration
of iodine was about 5 mg iodine/cm3. Optimum crystal
growth was achieved with the charge zone maintained at
850 °C and the growth zone at 800 °C. As-grown crystals
had plates shape up to 5 mm x 3 mm in area and were red
in transparent light. The energy dispersive X-ray micro-
analysis (EDAX) measurements show some variations be-
tween the ratio of Zn and Ge among the examined samples.
However, the average atomic ratio of Cu:Zn:Ge:S was
found to be 23.9:12.1:11.9:52.1 close to stoichiometry in
studied samples. Hot probe measurements revealed that
grown crystals are p- type semiconductors.
PL spectra were excited using 8 mW He:Cd laser (325
nm). The luminescence signals were analyzed by using a
Czerny-Turner spectrograph equipped with a silicon
charge coupled device (CCD) camera and an InGaAs pho-
todetector. Raman measurements were performed in the
back-scattering configuration on a DILOR LabRam Micro-
Raman system. A He-Ne (632.8 nm) laser was used for ex-
citation. The studied samples were probed at several arbi-
trarily chosen spots and the measured spectra were cor-
rected by a Si-wafer reference.

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2 S. Levcenko et al.: Photoluminescence characterization of Cu2ZnGeS4

3 Results and discussion Figure 1 displays the

Raman spectra of Cu2ZnGeS4 single crystal at room tem-
perature in the range 160-450 cm-1. All the observed modes
can be attributed to Cu2ZnGeS4 compound, while modes at
274, 291 and dominant 359 cm-1 are characteristic modes
of Cu2ZnGeS4 orthorhombic structure [12]. Note also that
less intensive modes at 332 and 383 cm-1 observed in our
Raman spectra are in agreement with IR modes at 338 and
385 cm-1 reported in Ref. [10].

(a)

Figure 1 Raman spectra of Cu2ZnGeS4 crystal at 300 K.

PL spectrum of Cu2ZnGeS4 measured at 4.5 K consists

of dominated broad emission (#1) at about 1.4 eV with
full width at half maximum of 0.5 eV and less intensive
band (#2) near 2.0 eV (Fig. 2a). Based on available ex-
perimental data on band gap energy (Eg) of the CZGeS
compound [7-9], the observed emission attributed to defect
related recombination. In Fig. 2a is shown the variation of
the PL spectra of CZGeS versus the excitation laser inten-
sity at 4.5 K. It was found that the PL intensity at the emis-
sion band maximum increases with respect to the excita-
tion intensity. A blue shift of about 20 (10) meV per dec-
ade of excitation power for #1(#2) PL bands was observed,
respectively. For an excitation laser photon (IEX) with an
energy exceeding the band gap energy Eg the PL intensity
(IPL) follows the power low (IPL ~ IEX γ); the coefficient γ is
generally 1< γ <2 for the free- and bound-exciton emission,
and γ <1 for free-to-bound (FB) and donor-acceptor pair
(DAP) recombination [13]. The IPL of #1 band was sublin-
ear to the excitation intensity IEX as shown in Fig. 2b. For
the better analysis of #2 band, we subtracted the contribu-
tion of #1 band by a Gaussian approximation. The IPL be-
havior of #2 band was determined to be slightly superlinear,
which might be due to its low intensity. Thus, the found
blue shift of PL maxima indicates that the observed PL
bands of CZGeS can be attributed to DAP recombination,
while obtained values of γ point to different origin of the
defect involved in the PL emission.
(b)
Figure 2 Excitation power dependence of the (a) PL spectra and
(b) integrated PL intensity of Cu2ZnGeS4 crystal measured at 4.5
K. The peak positions of the PL bands at the highest and the low-
est intensity are indicated by the solid and broken lines, respec-
tively, in (a).
The evolution of the PL spectra with temperature rise
from 20 to 300 K is shown in Fig. 3a and Fig. 3b. PL bands
were found to be red shifted and quenched with increasing
temperature.
The temperature behavior of DAP emission intensity
was described by model based on temperature dependence
of the capture cross section at the recombination centers
and thermally activated process with well-defined energy
[14]:
I DAP = 1+α T 3 / 2 +α T 3 /I20 exp( − E
1 2 act / k BT ) (1)
where α1 and α2 are the process rate parameters, I0 is the in-
tensity at the lowest temperature and Eact is the activation
energy.

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Phys. Status Solidi C (2013)
(a)
(b)
Figure 3 Temperature dependence of (a) (#1)-band and (b) (#2)-
band of Cu2ZnGeS4 crystal measured in the range 20-300 K.
Figure 4 Temperature dependence of the integrated PL intensity
spectra of (#1) and (#2)-band of Cu2ZnGeS4 crystal.
From the results presented on Fig. 4 one can obtain activa-
tion energy of about 37 (140) meV for #1(#2) bands, re-
spectively. These values may correspond to the ionization
energy of the shallow level involved in DAP. Taking into
account that our samples were p-type semiconductors, we
attributed these determined levels to acceptor intrinsic de-
fects of CZGeS. It is interesting to note that our shallower
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3
level correlates well with value of activation energy (0.03
eV) determined from electrical resistivity of CZGeS [11].
However, we would like to point out, that the defect levels
are not known yet and further study is necessary to verify
origins of the observed PL bands of Cu2ZnGeS4.
4 Conclusions Raman spectra of Cu2ZnGeS4 bulk
single crystals consists of a dominant mode at approxi-
mately 359 cm-1 and less pronounced modes at 274, 291,
332, 370, 383, 405 and and 415 cm-1. Low-temperature PL
measurements on Cu2ZnGeS4 showed bands located at
1.40 eV, and 2.00 eV at 4.5 K. Based on the temperature
and excitation power analysis the PL emissions were at-
tributed to the donor acceptor pair transitions. The activa-
tion energy of the 1.40 (2.00) eV band was estimated to be
37(140) meV from thermal quenching of the PL spectra,
respectively.
Acknowledgements Financial supports from IRSES PVI-
COKEST 269167, BMBF MDA11\002 and STCU 5402 projects
are acknowledged. S. L. thanks the Alexander von Humboldt
Stiftung for support.
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