Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

Contents lists available at ScienceDirect

Solar Energy Materials & Solar Cells

journal homepage: www.elsevier.com/locate/solmat

The crystal structure of kesterite type compounds: A neutron and X-ray

diffraction study
Susan Schorr
Free University Berlin, Institute of Geological Sciences, Malteserstr. 74-100, Berlin, Germany

a r t i c l e i n f o

Keywords:
Kesterites
Thin lm solar cells
Compound semiconductors
Crystal structure
Structural phase transitions

a b s t r a c t
The atomic structure of the potential photovoltaic materials Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe)
is discussed on the basis of a structural analysis of neutron powder diffraction data rened by the
Rietveld analysis. Both compounds were found to crystallize in the kesterite type structure, but with a
disorder within the CuZn layers at z 1/4 and 3/4. The latter causes CuZn and ZnCu anti-site defects,
whose concentration depends on the sample growth conditions.
The temperature dependent structural phase transition in CZTS was studied by in-situ high
temperature diffraction experiments using high energy synchrotron X-rays. The transition from the
tetragonal kesterite to the cubic sphalerite type structure is discussed by means of the interplay of
increasing and decreasing cationanioncation bond angles in the coordination tetrahedra, reected by
the shift of the anion atomic coordinates to more ideal (x and y) or non-ideal (z) values. This striking
behavior may be connected with frustrations that occur due to the triangular geometry of the
coordination tetrahedra.
& 2011 Elsevier B.V. All rights reserved.

1. Introduction

2. Crystal structure of AI2 BII CIV XVI

4 compounds

Amongst the most promising material options for thin lm

solar cells are compound semiconductors. Chalcopyrite-based
thin lm solar cells, using Cu(In,Ga)Se2 as absorber, show the
highest efciencies in the laboratory (20.1% [1]) as well as in
module production. However, there is a concern over the long
term availability of indium, a major constituent of chalcopyrite
absorbers. Indium is extremely scarce, which means that the price
will continue to rise as it has almost continuously done during the
last ve years. In order to secure the long term development of
compound semiconductor-based thin lm solar cells, the search
for the replacement of indium is advisable.
As some of the chalcopyrite type absorber materials are well
known minerals (RoquesiteCuInS2, GalliteCuGaS2), there is a
variety of stand-by chalcogenide minerals that can used as
reservoirs for the search of new, In-free materials suitable for
solar cell absorbers. Recently it has come to light that the mineral
kesterite (Cu2ZnSnS4) and also the selenium counterpart
Cu2ZnSnSe4 might be suitable to replace the indium-containing
absorber layer in thin lm solar cells. These direct band gap
p-type semiconductors contain only abundant and non-toxic
elements. Initial attempts to fabricate photovoltaic devices with
Cu2ZnSnS4 or Cu2ZnSn(S,Se)4 thin lms led to promising results,
with the AM 1.5 efciencies of up to 6.7% [2] and 9.66% [3],
respectively.

The mineral kesterite belongs to the AI2 BII CIV XVI

4 compound
family (with A Cu, BZn, Fe, CSn and XS, Se). Natural
kesterite often contains iron (Cu2(Zn,Fe)SnS4) but the iron content
varies with the locality.
For AI2 BII CIV XVI
4 compounds two main tetragonal structure types
are known from literature: the kesterite type structure and the
stannite type structure [4]. As for the chalcopyrite type compounds, the mineral, where the structure type was determined
rst, gives the name of the structure. Both structures, the kesterite
type and the stannite type, consist of a ccp array of anions, with
cations occupying one half of the tetrahedral voids. Thus the
structures are closely related, but assigned to different space
groups due to different distributions of the cations A + , B2 + and
C4 + (see Fig. 1). The kesterite type structure is characterized by
alternating cation layers of CuSn, CuZn, CuSn and CuZn at z0, 1/4,
1/2 and 3/4, respectively. Thus one copper occupies the 2a (0,0,0)
position with zinc and the remaining copper ordered at 2c (0,1/2,1/
4) and 2d (0,1/2,3/4) resulting in the space group I4. On the other
hand, in the stannite type structure ZnSn layers alternate with Cu2
layers. The structure is consistent with the symmetry of the space
group I42m, with the divalent cation located at the origin (2a) and
the monovalent cation at the 4d position (0,1/2,1/4). Sn is located
at the 2b site (0,0,1/2) in both structures. The anion lies on the
(1 1 0) mirror plane at 8i (x,x,z) for the stannite type and 8g (x,y,z)
for the kesterite type structure.
Additionally tetragonal structural modications of the kesterite type structure may be considered [5], which belong to the

E-mail address: susan.schorr@helmholtz-berlin.de

0927-0248/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2011.01.002

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002

S. Schorr / Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

Fig. 1. Unit cell representations of the kesterite type structure (a) and stannite type structure (b); as well as for a cation distribution according to the space groups P42c,
P421m and P2. (c)(e) The main difference is the Cu/Zn distribution (Cublue, Znorange, Snred). Big spheres represent the anions. Atomic sphere radii are chosen
arbitrarily. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

space groups P42c, P421c and P2. The modications are restricted
to the exchange of two ions in the cation sublattice. For the rst
(s.g. P42c) Cu and Zn atoms in the layer z 1/4 are exchanged. In
the second modication (s.g. P421m) Cu and Zn atoms are
exchanged between two layers to yield complete Zn and Cu
layers at z 1/4 and 3/4. The last one (s.g. P2) a Cu atom at
z 1/2 is exchanged with the Zn atom at z3/4. This recovers the
stannite type structure at the layers z 1/2 and 3/4, but maintains
the kesterite type structure in the other two layers.
Cu2ZnSnS4 (CZTS) crystallizes in the kesterite type structure.
Hall et al. [4] described an ordered distribution of the cations,
whereas Schorr et al. [6] observed the existence of a Cu/Zn
disorder on the structural sites 2c and 2d. The latter structural
investigations are based on neutron powder diffraction experiments. First-principles calculations for the potential photovoltaic
material CZTS [5] predict the kesterite type structure with I4
symmetry being the most stable one, possibly along with cation
disorder within the CuZn layer.
A disordered distribution of the cations may cause point defects
(vacancies and anti-site defects) and hence inuences the electronic properties of the material. For chalcopyrite type absorber
materials a number of successful studies, especially for CuInSe2,
have been made by absorption and photoluminescence techniques
as well as deep level transient spectroscopy (DLTS) [79] to
characterize the electronic defect levels of intrinsic point defects.
Thus it can be expected that the cation distribution, especially the

Cu/Zn disorder that may cause vacancies and anti-site defects,

plays a crucial role also for the kesterite type compounds.
According to literature Cu2ZnSnSe4 (CZTSe) crystallizes in the
stannite type structure [10], with Zn2 + localized on the 2a (0,0,0)
and Cu + on the 4d position (0,1/2,1/4). But it was proposed by rst
principle calculations [11] that AI2 BII CIV XVI
4 compounds are more
stable in the kesterite type structure, whereas the assumed
stannite structure reported in the literature is most likely due to
partial disorder in the AB (0 0 1) layer of the kesterite structure.
Hence the comparison of experimental and calculated crystal
structures of AI2 BII CIV XVI
4 quaternary chalcogenides [11] show that
there may be a long-standing misunderstanding in the crystal
structure determination. Nevertheless this becomes important for
the accurate characterization of the chemical and physical properties and hence their application in future optoelectronic devices.

3. Neutron diffraction investigation of Cu2ZnSnS4 and

Cu2ZnSnSe4
The cations Cu + and Zn2 + have the identical number of
electrons (28). Since the atomic scattering form factors f are
proportional to the atomic number Z, the positions of the unit cell
atoms of similar atomic number are not easy to be determined.
Hence these cations named above are not distinguishable in the
atomic structure by conventional X-ray diffraction. The problem

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002

S. Schorr / Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

can be solved using neutron diffraction, because of the different

neutron scattering lengths of copper and zinc (bCu 7.718(4) fm,
bZn 5.680(5) fm [12]). Moreover, since atomic nuclei crosssections are very small the destructive interference effects, which
in the case of X-rays lead to a decrease in the scattering amplitude
with increasing diffraction angle 2y, are also small, and neutron
scattering amplitudes do not decrease rapidly with angle. This
gives the advantage that in a neutron diffraction experiment the
Bragg peaks with valuable intensity can be observed also in the
high-Q region. Thus by making use of neutron powder diffraction
and the subsequent Rietveld analysis it is possible to identify the
cation distribution in the crystal structure and extract information about structural point defects in the cation substructure.
A detailed description of the different scattering mechanisms
of X-rays and neutrons by matter can be found elsewhere [13].
Reference powder samples of kesterite type semiconductors
(CZTS and CZTSe) were synthesized by

materials is explained elsewhere [13]. A cation site in the

kesterite type structure may be occupied with different cations
(and vacancies), thus it is insufcient to conne only to the site
occupancy parameters. The mixed site occupancy can be expressed by the average neutron scattering length b. The average
scattering length of the cation site is given by
bj Aj bA Bj bB Vj

The synthesis procedures (i) and (ii) were applied for CZTS and
procedure (iii) for CZTSe. Details about the sample synthesis are
described in Refs. [6,14].
To determine the chemical composition of the powder samples,
wavelength dispersive X-ray measurements (WDX) have been performed using an electron microprobe analysis system. To ensure a
high level of accuracy, the outcome of 20 individual local point
measurements (beam diameter about 1 mm) of the composition
parameters were averaged to an integral chemical composition of
every phase present in the sample. In order to obtain reliable results
from the WDX measurements, the system was calibrated using
elemental standards. The neutron powder diffraction data were
collected at the Berlin Research Reactor BERII at the Helmholtz Center
Berlin for Materials and Energy using the ne resolution powder
In the following the data treatment
diffractometer E9 (l 1.79776 A).
was performed by full pattern Rietveld renement [15] using the
FullProf Suite software package [16]. Both structure models, kesterite
and stannite type, were tested in the analysis. The renement was
done without any chemical constraints. Global prole renement
parameters included a scale factor, a 2y zero-point parameter and
parameters of a peak shape function (U,V,W) using the Caglioti [17]
function for the peak full-width at half-maximum (FWHM). The peak
shape function was a pseudo-Voigt convoluted with an axial divergence asymmetry function [18]. The background was tted using a
ve-parameter polynomial. Renement parameters for the structure
were unit cell parameters, cation site occupancies, anion coordinates
and isotropic displacement parameters.
Because in the Rietveld analysis the thermal parameters are
strongly coupled with the occupancy factors, their rened values
have to be taken into account in particular. Due to the remarkably
stable relative magnitude of the thermal motion of Cu, Zn and S in
stannite group minerals [19], the reasonability of the rened
thermal parameters was judged according to their consistencies
with known values for kesterite [4,20], stannite [4,21] and closely
related minerals [19], like talnakhite, mooihoekite and haycockite, as well as zinc-blende [22,23]. The rened isotropic displacement parameters for CZTS and CZTSe are consistent with values
known from these minerals.
For the determination of cation distribution the method of
the average neutron scattering length was applied. A detailed
introduction to this method applied to thin lm solar cell

Here Aj and Bj describe the fraction (or occupancy) of atom A and

B on site j, whereas Vj is the vacancy fraction. Vacancies (for
instance VCu) as well as anti-site occupancies (for instance CuZn
and ZnCu) will change the neutron scattering length of the
corresponding cation site signicantly. The fraction of the different atoms A and B on a site j have to fulll the condition
X
X
AWDX
Ai and BWDX
Bi
2
i
WDX

(i) solid state reaction of the elements at 750 1C with nal

quenching in ice water,
(ii) solid state reaction of the elements at 750 1C with a nal
1 K/h cooling rate,
(iii) the Bridgman technique [14] with a subsequent annealing
procedure at 650 1C and nal non-controlled cooling.

i
WDX

and B
refer to the chemical composition of the
Here A
sample determined by electron microprobe analysis.
The Eqs. (3a) and (3b) were used for the calculation of the
exp
experimental average neutron scattering lengths bj , here exemplarily shown for the kesterite type structure (Eq. (3a)) with j 2a,
2c, 2d and the stannite type structure (Eq. (3b)) with j 2a, 4d.
The site occupancy values occj resulted from the Rietveld analysis
of the neutron diffraction data.
exp

b2a occ2a bCu

exp

b2c occ2c bZn

exp
b2d

3a

occ2d bCu

exp

b2a occ2a bZn

exp

b4d occ4d bCu

3b

Table 1 gives an overview of the different structural models

used in the renement.
Figs. 24 show the experimental average neutron scattering
lengths of the cation sites for different structural models used in
the renement as determined for CZTS and CTZSe. In case the
rened cation site occupancy differs from their nominal values
according to the structure type, one can conclude that the site is
not only occupied by the initially supposed model cation but by a
mixture of different elements. For example a decrease in the
average neutron scattering length of the 2d site in the kesterite
type structure can be attributed to a partial Zn occupation due to
bCu 4bZn.
Comparing both compounds, a similar cation distribution
concerning copper and zinc arises. Independent of the structure
model used in the Rietveld analysis, the average neutron scattering length of the 2a position (corner and center of the unit cell)
indicates, that this position is occupied by copper only. The
average neutron scattering lengths of the sites 2c and 2d indicate
that the zinc site 2c is partly occupied by copper and the copper
site 2d is partly occupied by zinc, respectively. Thus the existence
of CuZn and ZnCu anti-site defects can be concluded. The defect
concentration depends on cooling rate during sample synthesis.
In the quenched CZTS sample roughly 50% of the zinc site 2c is
occupied by copper and vice versa concerning the copper site 2d.
In the CZTS and CZTSe samples, which have passed through a nal
controlled cooling procedure, nearly 30% of the copper site 2d is
occupied by zinc, whereas  30% of the zinc site 2c is occupied by
copper. There are no indications for the formation of copper
vacancies, which may be due to the near-stoichiometric chemical
composition of the samples. The analysis of intrinsic point defects
in chalcopyrite type CuInSe2 using the same method as described

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002

S. Schorr / Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

Table 1
Cation distribution models used in the Rietveld analysis.
CZTS
Model 1
Kesterite
exp

Model 2
Kesterite

Model 3
Kesterite

exp

exp

Model 4
Stannite
exp

b2a occ2a bCu

b2a occ2a bCu

b2a occ2a bZn

b 2a occ2a bZn

exp
b2c
exp
b2d

exp
b2c
exp
b2d

exp
b2c
exp
b2d

exp
b4d

occ2c bZn
occ2d bCu

occ2c bCu
occ2d bZn

occ2c bCu

occ4d bCu

occ2d bCu

CZTSe
Model 1
Stannite
exp

Model 2
Stannite
exp

b2a occ2a bZn

b2a occ2a bCu

exp
b4d

exp
b4d

occ4d bCu

occ4d bZn

Model 3
Stannite
exp

b2a occ2a bCu

exp
b2c occ2c bZn
exp

b2d occ2d bCu

CZTS: Models 1 and 4 are the kesterite type and stannite type structures.
Models 2 and 3 are the kesterite type structure but with modied cation distribution.
CZTSe: Models 1 and 3 are the stannite type and kesterite type structures.
Model 2 corresponds to the stannite structure, but with modied cation distribution.

Fig. 2. Experimentally determined neutron scattering length in the quenched

CZTS sample (Cu1.99ZnSn1.01S4) using the structural models explained in Table 1.
Both full lines indicate the neutron scattering length for Cu and Zn and the dotted
line indicates an average neutron scattering length of 1/2bCu+ 1/2bZn.

here, has revealed that a signicant amount of copper vacancies

occurs only in non-stoichiometric compounds [24].
Thus we can conclude that contrary to experimental results in
literature [10] CZTSe crystallizes in the kesterite type structure
and not in the stannite type structure.

4. High temperature structural phase transition in

Cu2ZnSnS4a synchrotron X-ray diffraction study
Kesterite compounds belong to the adamantine family; their
structures are based on the diamond type structure [25]. Other
ternary members of the adamantine family are the chalcopyrite
compounds, like CuInS2 and CuInSe2. Both groups, the chalcopyrites
and the kesterites, undergo a temperature dependent structural

Fig. 3. Experimentally determined neutron scattering length in the CZTS sample

(Cu1.99ZnSn1.01S4) using the structural models explained in Table 1. Closed
symbols refer to the quenched sample, open symbols to the sample that was
cooled to room temperature at a rate of 1 K/h. Both full lines indicate the neutron
scattering length for Cu and Zn and the dotted line indicates an average neutron
scattering length of 1/2bCu+ 1/2bZn.

Fig. 4. Experimentally determined neutron scattering length in the CZTSe sample

(Cu2.03Zn1.02Sn0.95Se4) using the structural models explained in Table 1. Both full
lines indicate the neutron scattering length for Cu and Zn and the dotted line
indicates an average neutron scattering length of 1/2bCu+ 1/2bZn.

phase transition to the sphalerite type structure. This phase transition was studied in detail by in-situ high temperature diffraction
experiments using high energy synchrotron X-rays at the beamline
ID15 of the European Synchrotron Radiation Facility (ESRF). Chalcogenide compounds will decompose during heating in air due to the
evaporation of the chalcogen. Thus it is necessary to encapsulate the
sample in a silica tube. High energy synchrotron radiation allows to
measure diffraction pattern with the powder sample and the silica
tube in transmission geometry. On the other hand, a differentiation
between Cu + and Zn2 + is not possible due to the nearly equal
atomic scattering form factor as explained above. Details of the
experimental setup, the measurement strategy and the data treatment by the Rietveld analysis can be found in Refs. [26,28].
The chalcopyrites CuInX2 (XS,Se,Te) and CuGaTe2 show a
sharp orderdisorder structural phase transition that occurs
within a small temperature range of about 10 K [26,27]. The

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002

S. Schorr / Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

Fig. 5. Cation site occupancy resulting from the Rietveld analysis of the synchrotron X-ray data for CuInS2. The Me1 site is the copper site, whereas the Me2 site is
the position of indium. The critical region of the phase transition starts roughly
10 K before the transition temperature.

transition is characterized by a CuIn anti-site occupancy, which

starts in the critical region of the phase transition (see Fig. 5). The
order parameter of the phase transition can be expressed by the
difference between the number of electrons at the cation site in
the disordered phase (cubic) and the ordered phase (tetragonal).
Within the critical region the order parameter goes with (T TC)b
and b 0.35(7) to zero, where TC is the phase transition temperature. The critical exponent obeys universal behavior. A detailed
investigation of the structural phase transition in the chalcopyrite
compound CuInSe2 can be found elsewhere [26].
The character of the structural phase transition in the kesterite
compound CZTS is dominated by a displacement of the anions
starting even at about 150 1C, whereas the phase transitions occurs
at 876 1C [28]. Contrary to the phase transition in the chalcopyrites,
in kesterites the transition is connected with the existence of a
2-phase region. For CZTS this region extends in the temperature
range 863888 1C, where a tetragonal kesterite type and a cubic
sphalerite type phase coexist. The linewidth analysis of the Bragg
shows clearly a broadening in
peak at 2y  5.21 (l 0.141068 A)
this temperature range, which is caused by an overlap of the
sphalerite 111 and the kesterite 112 peak (see Fig. 6).
Taking into account the atomic position parameters of the
anion, a displacive behavior can be obtained over the whole
temperature range. At room temperature the anion occupies a
(x,y,z) position (x0.756, y0.75566, z0.8722 [6]). Due to
different bond lengths of the cationanion bonds (CuS, ZnS,
SnS) the anion is shifted from the middle of the anion tetrahedra
(XA2BC) and thus the tetrahedra is distorted. The distortion can
also be expressed by the cationanioncation bond angles. They
differ substantially from the ideal value (109.471), whereas the Cu
SSn and the ZnSSn angles are smaller and the CuSZn and Cu
SCu angles are larger than the ideal value (see Fig. 7). With
increasing temperature the bond lengths increase anisotropically
causing a change in the bond angles and thus in the anion position.
Due to the trigonal geometry within the tetrahedron frustrations
may occur, because some bond angles increase whereas others
decrease. Only the atomic coordinates x and y approach continuously the ideal value, whereas the anion atomic coordinate z
initially shifts to a more non-ideal position, approaching the ideal
value close to the phase transition temperature (see Fig. 8). This

Fig. 6. Linewidth (FWHM) of the Bragg peak at 2y  2.51 (notice l 0.141068 A)

determined by single peak renement. The linewidth broadening, due to the
overlap of the 112 Bragg peak of the tetragonal phase and the 111 Bragg peak of
the cubic phase is clearly visible.

108.206
108.172

110.712
110.788

Fig. 7. Cationanioncation bond angles in the anion tetrahedron of CZTS in the

kesterite type structure.

striking interplay of increasing and decreasing cationanioncation

bond angles, which may be regarded as frustration in the XA2BC
anion tetrahedron, can be also noticed in the behavior of the lattice
parameters. In the temperature region at 200 1C, where the z
coordinate of the anion starts to shift to increasing non-ideality, a
kink in the lattice parameter c is observed (see Fig. 9). On the other
hand the atomic coordinate x of the sulfur anion decreases linearly
reaching nearly the ideal value xideal 0.25 in the middle of the
2-phase region. Thus the deviation of the anion parameter x from
the ideal value, i.e.

Dx xuxideal

was assumed as a possible order parameter of the phase transition

(with xu x1=2). The order parameter decreases with (T TC)b
and b 0.30(5) to zero, where TC is the phase transition temperature (see Fig. 10).
Thus it can be concluded, that the structural phase transition
from the tetragonal kesterite type to the cubic sphalerite type
structure in Cu2ZnSnS4 is characterized much more by a displacive behavior of the anion substructure than by an anti-site
occupancy within the cation substructure.
5. Summary
Neutron powder diffraction was successfully used to determine
the crystal structure of Cu2ZnSnS4 and Cu2ZnSnSe4 and to identify

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002

S. Schorr / Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

Fig. 8. Ratio of the real/ideal value of the anion atomic coordinates x and z (for better visibility y is not shown). The solid horizontal line marks the ratio real/ideal 1.

Fig. 9. Temperature dependent behavior of the lattice parameter a and c up to

350 1C. For better visibility the values of c/2 are shown. The error bars are within
the symbols.

intrinsic point defects. The results of the neutron diffraction data

analysis showed clearly that Cu2ZnSnSe4 crystallizes in the kesterite type structure, disproving the stannite type structure. Thus
both, CZTS and CZTSe, are kesterite type compounds. The identied
intrinsic point defects are CuZn and ZnCu anti-sites, occurring in the
CuZn (0 0 1) planes at z1/4 and 3/4. Moreover the defect
concentration depends on the cooling rate during sample synthesis. The derived crystal structure and the cation disorder effect are
in agreement with rst-principles calculations [5,11].
In Cu2ZnSnS4 a temperature dependent phase transition from
the kesterite type structure to the cubic sphalerite type structure
occurs at  876 1C, which was shown by in-situ high temperature
diffraction experiments using synchrotron X-rays. Due to the
triangular geometry of the coordination tetrahedra, frustrations
may occur as an interplay of increasing and decreasing cation
anioncation bond angles, even at  200 1C.
It can be concluded, that the combination of both methods can
lead to profound understanding of the correlation between crystal
structure, intrinsic point defect concentration and growth procedure of the compound semiconductors CZTS and CZTSe.

Fig. 10. Order parameter Dx xuxideal of the structural phase transition in CZTS in
dependence on the reduced temperature 9TTC 9. The solid line represents a t
b
corresponding to Dx  9TTC 9 with b 0.30(5). The beginning of the 2-phase
region is marked by the dotted line.

References
[1] M.A. Green, K. Emery, Y. Hishikawa, W. Warta, Solar cells efciency
tables (version 36), Prog. Photovolt: Res. Appl. 18 (2010) 346352.
[2] H. Katagiri, K. Jimbo, S. Yamada, T. Kamimura, W.S. Maw, T. Fukano, T. Ito,
T. Motohiro, Enhanced conversion efciencies of Cu2ZnSnS4-based thin lm
solar cells by using preferential etching technique, Appl. Phys. Express
1 (2008) 041201-1041201-2.
[3] T.K. Todorov, K.B. Reuter, D.B. Mitzi, High-efciency solar cell with earthabundant liquid-processed absorber, Adv. Mater. 22 (2010) E156E159.
[4] S.R. Hall, J.T. Szymanski, J.M. Stewart, Kesterite, Cu2(Zn,Fe)SnS4, and stannite,
Cu2(Fe,Zn)SnS4, structurally similar but distinct minerals, Can. Mineral.
16 (1978) 131137.
[5] J. Paier, R. Asahi, A. Nagoya, G. Kresse1, Cu2ZnSnS4 as a potential photovoltaic
material: a hybrid Hartree-Fock density functional theory study, Phys. Rev. B
79 (2009) 115126-1115126-8.
[6] S. Schorr, H.-J. Hoebler, M. Tovar, A neutron diffraction study of the stannitekesterite solid solution series, Eur. J. Mineral. 19 (2007) 6573.
[7] A.L. Li, I. Shih, Majority and minority carrier traps in monocrystalline CulnSe2,
J. Electron. Mater. 22 (2) (1993) 195199.
[8] A.M. Bakry, A.M. Elnaggar, Study of deep levels in Schottky/CuInSe2 singlecrystal devices by deep-level transient spectroscopy measurements, J. Mater.
Sci. Mater. El. 7 (3) (1996) 191192.

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002

S. Schorr / Solar Energy Materials & Solar Cells ] (]]]]) ]]]]]]

[9] G. Zahn, P. Pauer, Identication of predominant point defects in nonstoichiometric CuInSe2 by X-ray powder diffraction, Cryst. Res. Technol. 23 (4) (1988)
499507.
[10] I.D. Olekseyuk, L.D. Gulay, I.V. Dydchak, L.V. Piskach, O.V. Parasyuk,
O.V. Marchuk, Single crystal preparation and crystal structure of the Cu2Zn/
Cd,Hg/SnSe4 compounds, J. Alloys Compd. 340 (2002) 141145.
[11] S. Chen, X.G. Gong, Electronic structure and stability of quaternary chalcogenide semiconductors derived from cation cross-substitution of IIVI and
IIIIVI2 compounds, Phys. Rev. B 79 (2009) 165211-1165211-10.
[12] V.F. Sears, Neutron scattering lengths and cross sections, Neutron News 3 (3)
(1992) 2637.

[13] S. Schorr, Ch. Stephan, R. Mainz, T. Torndahl,

X-Ray and neutron diffraction
on materials for thin lm solar cells, in: D. Abou-Ras et al. (Ed.), Advanced
Characterization Techniques for Thin Film Solar cells, Wiley VCH, (2011)
347364.
[14] J.N. Lalena, D.A. Clearly, E. Carpenter, N.F. Dean, Inorganic Materials Synthesis
and Fabrication, John Wiley & Sons, Inc., Hoboken, New Jersey, 2008, pp. 3640.
[15] H.M. Rietveld, A prole renement method for nuclear and magnetic
structures, J. Appl. Crystallogr. 2 (1969) 6571.
[16] J. Rodriguez-Carvajal, Recent advances in magnetic structure determination
by neutron powder diffraction, Physica B 192 (1993) 5569.
[17] G. Caglioti, A. Paoletti, F.P. Ricci, Choice of collimator for a crystal spectrometer for neutron diffraction, Nucl. Instrum. 3 (1958) 223228.

[18] J. Rodriguez-Carvajal, FullProf Manual, /www.ill.eu/sites/fullprofS.

[19] S.R. Hall, Crystal structures of the chalcopyrite series, Can. Mineral. 13 (1975)
168172.
[20] A. Lafond, personal communication, 2006.
[21] J. Llanos, M. Tapia, C. Mujica, J. Oro-Sole, P. Gomez-Romero, A new structural
modication of stannite, Bol. Soc. Chil. Quim. 45 (2000) 605609.
[22] B. Moss, R.K. McMullan, T.F.J. Koetzle, Temperature dependence of thermal
vibrations in cubic ZnS: a comparison of anharmonic models, Chem. Phys. 73
(1980) 495508.
[23] M.J. Cooper, K.D. Rouse, H. Fuess, A neutron diffraction study of ZnS and ZnTe,
Acta Cryst. A29 (1973) 4956.
[24] C. Stephan, S. Schorr, M. Tovar, H.-W. Schock, Comprehensive insights
into point defect and defect cluster formation in CuInSe2, Appl. Phys. Lett.,
submitted for publication.
[25] B. Pamplin, A systematic method of deriving new semiconducting compounds by structural analogy, J. Phys. Chem. Solids 25 (1964) 675684.
[26] S. Schorr, G. Geandier, In-situ investigation of the temperature dependent
structural phase transition in CuInSe2 by synchrotron radiation, J. Cryst. Res.
Technol. 41 (2006) 450457.
[27] S. Schorr, G. Geandier, B. Korzun, Cation disorder and anion displacement in
DIIXVI AIBIIIXVI
2 semiconductors, Phys. Status Solidi C 3 (2006) 26142617.
[28] S. Schorr, G. Gonzalez-Aviles, In situ investigation of the structural phase
transition in kesterite, Phys. Status Solidi A 206 (2009) 10541056.

Please cite this article as: S. Schorr, Sol. Energy Mater. Sol. Cells (2011), doi:10.1016/j.solmat.2011.01.002