Ultramicroscopy 111 (2011) 552–556

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Ultramicroscopy
journal homepage: www.elsevier.com/locate/ultramic

Atomic-scale distribution of impurities in CuInSe2-based thin-film solar cells

O. Cojocaru-Mirédin a,n, P. Choi a, R. Wuerz b, D. Raabe a
a
Max-Planck-Institut für Eisenforschung, Max-Planck-Straße 1, 40237 Düsseldorf, Germany
b
Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg, Industriestraße 6, 70565 Stuttgart, Germany

a r t i c l e i n f o a b s t r a c t

Available online 11 January 2011 Atom Probe Tomography was employed to investigate the distribution of impurities, in particular
Keywords: sodium and oxygen, in a CuInSe2-based thin-film solar cell. It could be shown that sodium, oxygen, and
Thin-film solar cells silicon diffuse from the soda lime glass substrate into the CuInSe2 film and accumulate at the grain
Photovoltaic boundaries. Highly dilute concentrations of sodium and oxygen were measured in the bulk. Selenium
Cu(In,Ga)Se2 was found to be depleted at the grain boundaries. These observations could be confirmed by
CuInSe2 complementary energy dispersive X-ray spectroscopy studies. Our results support the model proposed
Sodium diffusion by Kronik et al. (1998) [1], which explains the enhanced photovoltaic efficiency of sodium containing
Grain boundary segregation CuInSe2 solar cells by the passivation of selenium vacancies at grain boundaries.
Pulsed laser atom probe
& 2011 Elsevier B.V. All rights reserved.
Transmission electron microscopy

1. Introduction
Copper indium diselenide (CIS), a compound semiconductor
belonging to the I–III–VI2 chalcopyrite family, is one of the most
promising absorber materials for the fabrication of thin-film solar
cells. CIS possesses several beneficial material properties such
as a direct band gap (Eg ¼1.02 eV at room temperature), high
absorption coefficient ( Z105 cm  1), long-term stability, and high
radiation hardness [2].
CIS solar cells are commonly deposited on soda lime glass (SLG)
substrates, which comprise SiO2, Na2O, K2O, and CaO. Several
authors reported diffusion of alkali impurities, in particular sodium,
into the CIS film during the processing of these solar cells [3,4].
Interestingly, sodium impurities were found to significantly enhance
the photovoltaic conversion efficiency (mainly the open circuit
voltage) of CIS solar cells, also known as the ‘‘sodium effect’’ [5,6].
An increase in p-type conductivity [7] and a more pronounced
texture (predominance of uniaxial crystallite orientation) [8] were
suggested as possible reasons for the enhanced efficiency due to
sodium incorporation. However, the ‘‘sodium effect’’ has remained a
subject of controversial discussion.
To develop a comprehensive theory of how sodium improves
the conversion efficiency of CIS solar cells, one needs to study the
elemental distribution at the atomic scale. The concentrations in
bulk and grain boundaries are of particular interest. Some
attempts have been previously made to determine the impurity
concentrations in CIS absorber layers. For instance, Niles et al. [9]
applied Auger Electron Spectroscopy (AES) to detect sodium and
oxygen segregation at the surface and grain boundaries of CIS and
n
Corresponding author.
E-mail address: o.cojocaru-miredin@mpie.de (O. Cojocaru-Mirédin).
to show that solute concentrations inside the grains are highly
dilute. However, the detection limit of AES for both sodium and
oxygen was reported to be only about 0.15 at% [9].
Among the nano-analytical techniques, Atom Probe Tomography
(APT) [10–13] is one of the most promising tools for studying solar
cells, as it allows for spatially resolved chemical analyses with sub-
nanometer resolution [14] and the detection of dilute impurity
concentrations as low as a few tens of ppm [15]. First APT results on
the elemental distribution in Cu(In,Ga)Se2 layers, which are similar
to CIS, were recently published by Cadel et al. [15] and Schlesiger
et al. [16]. Both authors reported significant sodium enrichment at
the grain boundaries. The current paper elucidates the atomic-scale
elemental distribution in an actual CIS solar cell, using pulsed laser
APT. The enhanced energy conversion efficiency due to sodium
incorporation is discussed on the basis of the obtained APT results.
2. Experimental
A CIS solar cell was fabricated at the Zentrum für Sonnen-
energie- und Wasserstoff-Forschung in Stuttgart, Germany. Soda
lime glass (SLG) of 3 mm in thickness was used as a substrate
material. A Mo back contact layer of 500 nm was deposited onto the
SLG substrate by DC sputtering. Subsequently, a polycrystalline
CuInSe2 film of 2 mm in thickness was grown by co-evaporation of
the constituent elements using a high temperature single-stage
inline process [17]. The substrate temperature during film growth
was kept at 600 1C for about 30 min. A CdS buffer layer was
deposited by means of chemical bath deposition at 65 1C followed
by RF sputtering of an intrinsic ZnO layer, DC sputtering of
a ZnO:Al front contact layer, and electron beam evaporation of
Ni/Al contact grids.

0304-3991/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultramic.2010.12.034
 O. Cojocaru-Mirédin et al. / Ultramicroscopy 111 (2011) 552–556
X-ray fluorescence spectrometry (XRF) measurements were
performed to determine the overall composition of the CIS layer,
using an EAGLE XXL system (0.1 mbar, Si(Li) detector and 50 kV
Rh X-ray source). Using the Cu, In, and Se K lines, the accuracy of
the calculated concentrations is better than 0.5 at%.
Structural and compositional analyses of CIS films were done
by scanning transmission electron microscopy (STEM) and atom
probe tomography (APT), respectively. For the STEM investiga-
tions, cross-sectional samples were prepared using a dual-beam
focused-ion-beam (FIB) (FEI Helios Nanolab 600) and the lift-out
technique [18]. STEM was done at a JEOL 2200 FS microscope
operated at 200 kV. APT samples were also prepared by means of
FIB according to the procedure described in [19,20]. In order to
minimize beam damage, a low energy (5 keV) Ga beam was used
at the final ion-milling stage. All APT experiments were carried
out applying laser pulses of 532 nm wavelength, 12 ps pulse
length, and an energy of 0.1 nJ per pulse at a repetition rate of
100 kHz. The specimen base temperature was about 60 K.
3. Results and discussion
3.1. Microstructure of the CIS layer
Fig. 1 shows a cross-sectional STEM bright-field image of the
studied CIS solar cell, where the stacking sequence of the constituent
layers is ZnO:Al/ZnO/CdS/CuInSe2/Mo/SLG. The STEM image reveals
Fig. 1. STEM bright-field image of a CuInSe2-based thin-film solar cell in a cross-
sectional view.
553
a polycrystalline CIS layer, which is not smooth but exhibits
substantial roughness. Top-view scanning electron microscopy
images (not shown here) revealed faceted grains of large size
(between 0.7 and 1.25 mm) and are in agreement with STEM
observations. Besides the large grains in the top CIS region, small
grains of 0.13 to 0.36 mm in size can be recognized at the bottom of
the CIS layer (see Fig. 1). Such a bimodal grain structure is typical
of CIS films grown by elemental co-evaporation in the presence of
sodium [21] and can be discussed in terms of the van der Drift
evolutionary selection mechanism [22]. In this mechanism, the
nucleation stage is characterized by randomly oriented nuclei that
initially grow independently at uniform rate. In the following stage,
the crystals with the direction of fastest growth perpendicular to the
substrate are favored over other crystals and will prevail. For a
tetragonal crystal, the directions of fastest growth are /0 0 1S,
/1 0 0S, and /1 1 0S [22].
Another interesting feature is the presence of a few voids
(about 10 to 100 nm in size) in the CIS layer close to the CIS/Mo
interface (see Fig. 1). These voids probably stem from the deposi-
tion process and are not formed during TEM sample preparation,
as the sample was finally ion-milled at only 5 kV. Such nano-voids
in the CIS layer were also observed by Lei et al. [23] and for CIGS
layers by Rudmann [24].
3.2. Composition of CIS layer (grain and grain boundary)
A typical mass spectrum obtained from an APT analysis of a CIS
layer is given in Fig. 2. While copper and indium were detected as
both single and double charged ions, selenium ions were only
detected in a single charged state. Complex ions, namely CuCO + ,
CuSe + , Cu2Se + , CuSe2+ , Se2+ , and Se3+ were detected as well. Sodium
was detected as Na + . The background noise level in the mass range
close to the Na + peak is extremely low (E40 ppm/a.m.u.) so that
even very low dilute sodium concentrations can be detected. Besides
sodium, oxygen and silicon impurities were detected as O + , O2+ , Si2 + ,
and Si + . A small amount of Ga + was also detected.
Fig. 3 shows three-dimensional maps of all the detected
elements as well as sodium and oxygen only. The analyzed volume
is about 120  120  390 nm3 in size and represents the interior of
a CIS grain. The measured bulk composition is 23.470.06 at% Cu,
29.070.07 at% In, and 47.470.08 at% Se, which is in good agree-
ment with the integral XRF measurement (compare APT-1 and
Fig. 2. Mass spectrum of the complete measurement from Fig. 3 with details
showing the minority elements (Na and O) in the low mass region.
554 O. Cojocaru-Mirédin et al. / Ultramicroscopy 111 (2011) 552–556
XRF in Table 1). In the following, APT-1 and APT-2 denotes the APT
measurements presented in this work. While the sodium concen-
tration detected by APT for the CIS bulk is only about 0.002 at%
(20 ppm), the oxygen concentration is substantially higher and is
about 0.07 at% (700 ppm). The sodium concentration measured in
this work is significantly lower than the value reported by Cadel
et al. [15] for a Cu(In,Ga)Se2 (CIGS) film (85 ppm). Furthermore,
Cadel et al. [15] did not report any oxygen inside CIGS. The
difference in the results between these two works may well be
ascribed to different processing conditions as well as to different
compositions of the absorber layers (CIS and CIGS).
In Fig. 3 neither sodium nor oxygen clusters can be distin-
guished. If such clusters exist they are so tiny that they cannot be
clearly recognized in the elemental maps. Thus, to verify or refute
a possible clustering trend or short range ordering of sodium and/
or oxygen atoms, the cluster identification (maximum separation
method [25]) and the first nearest neighbor (abbreviated as 1NN)
distance distribution method were applied. Neither sodium nor
oxygen clusters were identified by the cluster identification, even
by systematically varying Nmin (minimum number of atoms per
cluster) and dmax (maximum distance between sodium and/or
oxygen atoms) values. The measured 1NN distance distribution
for the oxygen atoms, which is compared to a randomized oxygen
distribution in Fig. 4, should therefore be interpreted as a random
oxygen distribution. The same trend is observed for Na (not
shown here).
Fig. 5a shows another APT data set of the CIS layer. In these
elemental maps, we clearly recognize sodium, oxygen, and silicon
enriched zones, and also a strong correlation between the
distributions of these elements. Rotation and careful inspection
of these enrichment zones reveal that they have a two-
Fig. 3. APT elemental maps of copper (blue), indium (pink), selenium (red),
gallium (yellow), sodium (maroon) and oxygen (sky blue). The volume size shown
in this figure is 120  120  390 nm3. (For interpretation of the references to color
in this figure legend, the reader is referred to the web version of this article.)
Table 1
Chemical composition of single CIS grains measured by APT and of the whole CIS layer (integral) measured by XRF; APT-1: composition of grain shown in Fig. 3 and APT-2:
composition of grain shown in Fig. 5 without GB area.
C(at%) CCu CIn CSe
APT-1 23.4 7 0.06 29.07 0.07 47.4 7 0.08
APT-2 21.0 7 0.06 28.8 70.07 50.0 70.08
XRF 21.3 27.7 50.8
dimensional shape. However, these enrichments are not contin-
uous but are divided into four plate-shaped parts, marked in
Fig. 5a by a dashed-line (for more details see Ref. [26]). Previous
AES studies revealed a correlation between sodium and oxygen
enrichments (in agreement with Fig. 5a) at the CIS grain bound-
aries [9]. Taking these previous results and the two-dimensional
shape of the enrichments into account, we may conclude that the
solute enrichments seen in Fig. 5a are located at or close to a grain
boundary.
The measured bulk composition (excluding the grain boundary
zone) is 21.070.06 at% Cu, 28.8 70.07 at% In, and 50.0 70.08 at%
Se, which is in better agreement with the integral XRF measure-
ment (compare APT-2 and XRF in Table 1) than the APT-1
composition. Our APT measurements indicate compositional
fluctuations within the CIS film. This result is in agreement with
studies done by Eich et al. [29] on lateral inhomogeneities of a
Cu(In,Ga)Se2 absorber film. Slight variations in sodium and oxy-
gen concentrations in the bulk compared to APT-1 can be
measured as well (2675 ppm of sodium and 600 710 ppm of
oxygen, respectively). Although sodium and oxygen atoms are
strongly enriched at the grain boundaries, their concentration
rapidly drops to the bulk values, when moving away from the
segregation zone. In the bulk, sodium and oxygen atoms are
homogeneously distributed over several hundreds of nanometers,
indicating that long range diffusion has taken place. These
observations suggest that the measured bulk concentration values
of sodium and oxygen correspond to their solubility limit in CIS.
In all APT measurements small amounts of gallium were detected
(  0.1 at%). Gallium atoms stem from the deposition process,
as confirmed by secondary ion mass spectrometry (SIMS)
(  0.04 at%). A possible explanation for the relatively high
gallium content measured by APT is the implantation of gallium
Fig. 4. Distribution of the 1NN distances for the oxygen atoms, represented in
Fig. 3. Comparison with the randomised oxygen distribution. The bin size used for
this distribution is 0.2 nm.
CNa CO CGa CSi
0.0027 0.0005 0.077 0.001 0.12 –
0.00267 0.0005 0.067 0.001 0.11 –
– – 0.02 –
 O. Cojocaru-Mirédin et al. / Ultramicroscopy 111 (2011) 552–556
Fig. 5. (a) APT elemental maps of copper (blue), indium (pink), selenium (red),
gallium (yellow), sodium (maroon), oxygen (sky blue) and silicon (black). The
volume size shown is 72  72  260 nm3. (b) Proxigram of species in the sample
with respect to the O 7% isoconcentration surface; the bin size is 0.2 nm. (For
interpretation of the references to color in this figure legend, the reader is referred
to the web version of this article.)
during focused-ion-beam milling. However, we note that the
implantation zone in CIS specimens is restricted to a few nan-
ometers below the surface if 5 keV ions are used in the final ion-
milling step.
Fig. 5b shows a proxigram (for more details see Ref. [30]) of
the elements detected in the sample with respect to the 7 at%
oxygen isoconcentration surface. The proxygram clearly reveals
sodium, oxygen, and silicon accumulations at a CIS grain bound-
ary, where the oxygen concentration is substantially higher
(  18 at%) than the sodium ( 0.6 at%) and silicon (1.4 at%)
concentration (  1 at%). These solute enrichments are most likely
due to out-diffusion from the soda lime glass substrate during the
deposition process (at 600 1C for 30 min), as they were not found
in APT measurements of CIGS layers grown on steel substrates
(not shown here, to be published).
The width of the detected oxygen enrichment is about 7 to
8 nm and therefore much larger than the typical structural width
555
of a grain boundary (  0.5 nm), which can be partly ascribed to a
local magnification effect [27]. This reconstruction artefact results
in a magnified width and lower atomic density of the oxygen rich
grain boundary region, which has a higher evaporation field than
the CIS matrix. Letellier [28] observed for nickel-based super-
alloys that the influence of the local magnification effect increases
continuously as the grain boundary approaches an orientation
parallel to the sample tip axis. Thus, the enlarged width of the
oxygen rich grain boundary zone in Fig. 5a and b is not surprising.
The Gibbsian interfacial excess of solutes G (number of
segregated atoms per unit interfacial area) was determined from
the proxigrams following the procedure described in [29,31]. We
obtain GO ¼4.7  1019 atoms/m2, GNa ¼1.4  1018 atoms/m2, and
GSi ¼2.8  1018 atoms/m2. These values correspond to nearly 10,
0.25, and 0.5 monolayers of oxygen, sodium, and silicon, respec-
tively, with respect to the (1 0 0) CIS plane, where 10 monolayers
of oxygen correspond to  5 nm. Hence, an oxygen containing
compound phase may have been formed at the grain boundary. It
is not possible to determine the exact composition of the oxygen
rich zones because of the strong local magnification effect.
However, a strong depletion of selenium can be clearly detected
in conjunction with the oxygen enrichment, strongly suggesting
that a large number of vacant selenium sites at the grain
boundaries are occupied by oxygen atoms. It should be men-
tioned that similar trends could be measured for several grain
boundaries using EDX (not shown here). APT analyses of other
grain boundaries confirmed sodium and oxygen segregation.
On the other hand, compositional differences at the grain bound-
aries could be detected as well. For instance, the slight
copper enrichment and indium depletion seen in Fig. 5b is not
generally observed. The difference in the measured compositions
of various grain boundaries is not surprising in view of the
variation in solute contents as a function of grain boundary
misorientation [32].
3.3. Correlation between elemental distribution and enhanced
photovoltaic efficiency
Our APT data clearly reveal that sodium, silicon, and oxygen
atoms diffuse from the SLG substrate into the CIS film during film
growth. The enrichment of sodium and oxygen at the grain
boundary indicates that diffusion into the CIS film occurs mainly
along the grain boundaries, where defect density is higher than in
the bulk. Highly dilute concentrations of sodium ( 20 ppm) and
oxygen ( 700 ppm) are detected inside the CIS grains. These
solutes could passivate detrimental lattice defects (e.g., donor like
defects like selenium vacancies, indium atoms at copper sites,
etc.) and contribute to the enhancement of the solar cell effi-
ciency. However, the dilute concentrations of the solutes in the
grains indicate the ‘‘sodium effect’’ cannot be purely regarded as a
bulk effect.
As presented in Fig. 5 grain boundary enrichments of oxygen
and sodium are accompanied by a strong depletion of Se. These
observations are in agreement with the model proposed by
Kronik et al. [1] explaining the ‘‘sodium effect’’ on the basis of
the well-known catalytic effect of alkali metals on surface oxida-
tion of semiconductors [33]. O2  can be formed from physisorbed
O2 by alkali-metal induced polarization of the O–O bond and
lowering of the surface work function. According to Ref. [1], the
formation of grain boundaries in CIS gives rise to a large number
of Se vacancies, which introduce intragap donor levels. These
donors lower the effective p-type conductivity. Neutralizing the
selenium vacancies by chemisorbed O2  according to the reaction
[In0–V+Se
+
] +O2  -[In0–O0Se], the photovoltaic efficiency can be
increased. Once formed, the In–O bonds are stable and can only
556 O. Cojocaru-Mirédin et al. / Ultramicroscopy 111 (2011) 552–556
be broken by significant and deliberate reduction. Furthermore,
this defect chemical model and our APT results suggest that not
only grain boundary passivation is enhanced by the presence and
catalytic effects of sodium but also sodium diffusion can be
assisted by oxygen.
4. Conclusions
In this work, Atom Probe Tomography was employed to
investigate the elemental distribution in the CuInSe2 absorber of
a thin-film solar cell. Sodium and oxygen atoms were found to be
distributed homogeneously in the CuInSe2 grains. The measured
concentrations of sodium (  0.002 at%) and oxygen (  0.07 at%)
may well correspond to the solubility limit of sodium and oxygen
in CuInSe2 at 600 1C. Furthermore, a correlated enrichment of
sodium, oxygen, and silicon atoms was detected, presumably at a
grain boundary. These enrichments are accompanied by selenium
depletion, which is in good agreement with the defect chemical
model proposed by Kronik et al. [1]. The ‘‘sodium effect’’ in our
CIS-based solar cell could be explained by the passivation of
selenium vacancies (detrimental donor defects) by oxygen.
Acknowledgements
The authors thank Wolfram Witte for the CIS-based solar cell
preparation and also Aleksander Kostka and Axel Eicke for their
help in this work.
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