Influence of manganese on magnetic and electronic properties of ZnCr 2Se4

Article abstract of DOI:10.1016/j.materresbull.2012.04.029

The Zn_1-xMn_xCr₂Se₄ crystals were prepared by chemical vapor transport in closed silica tubes using ZnSe and MnSe with CrCl₃ as the transport agent. Four crystals with different Mn content (x = 0.12, 0.13, 0.18 and 0.24) were studied by X-ray photoelectron spectroscopy (XPS) and magnetic measurements in order to determine influence of manganese on their magnetic and electronic properties. The XPS revealed no change of chemical shifts of Cr core lines indicating a Cr³⁺ (3d ³) electronic configuration. Magnetization measurements revealed a systematic increase in saturation magnetic moments from 6.32 μ_B/mol for x = 0.12 to 7.63 μ_B/mol for x = 0.24, as well as effective paramagnetic Bohr magneton numbers from 4.87 μ_B/mol for x = 0.12 to 6.91 μ_B/mol for x = 0.24.

Full text of DOI:10.1016/j.materresbull.2012.04.029

Materials Research Bulletin 47 (2012) 1881–1886
Contents lists available at SciVerse ScienceDirect
Materials Research Bulletin
journal homepage: www.elsevier.com/locate/matresbu
Influence of manganese on magnetic and electronic properties of ZnCr2Se4
b
b
b
Izabela Jendrzejewska a, , Paweł Zajdel , Jan Heimann , Jozef Krok-Kowalski ,
*
´
Tadeusz Mydlarz c, Janusz Mrzigod a
a University of Silesia, Institute of Chemistry, Szkolna 9, 40-006 Katowice, Poland
b University of Silesia, Institute of Physics, Uniwersytecka 4, 40-007 Katowice, Poland
c International Laboratory of High Magnetic Fields and Low Temperatures, Gajowicka 95, 53-529 Wrocław, Poland
A R T I C L E I N F O
A B S T R A C T
Article history:
The Zn1ꢁxMnxCr2Se4 crystals were prepared by chemical vapor transport in closed silica tubes using ZnSe
and MnSe with CrCl3 as the transport agent. Four crystals with different Mn content (x = 0.12, 0.13, 0.18
and 0.24) were studied by X-ray photoelectron spectroscopy (XPS) and magnetic measurements in order
to determine influence of manganese on their magnetic and electronic properties. The XPS revealed no
change of chemical shifts of Cr core lines indicating a Cr3+ (3d3) electronic configuration. Magnetization
Received 2 August 2011
Received in revised form 10 March 2012
Accepted 17 April 2012
Available online 24 April 2012
measurements revealed a systematic increase in saturation magnetic moments from 6.32
x = 0.12 to 7.63 B/mol for x = 0.24, as well as effective paramagnetic Bohr magneton numbers from
4.87 B/mol for x = 0.12 to 6.91 B/mol for x = 0.24.
mB/mol for
Keywords:
m
A. Inorganic compounds
A. Magnetic materials
B. Crystal growth
m
m
ß 2012 Elsevier Ltd. All rights reserved.
C. Photoelectron spectroscopy
D. Magnetic properties
1. Introduction
was estimated using scanning electron microprobe and verified
later by XRD refinement, which also proved the cubic structure and
tetrahedral position of Mn. The results have already been reported
in Ref. [11].
In this paper, we present details of single crystal growth
together with the thermodynamical computations of equilibrium
constants for the chemical transport reactions, the results of
magnetic and XPS studies in order to show the effect of magnetic
manganese ions on magnetic and electronic properties of these
spinels.
ZnCr2Se4 is a normal cubic spinel with nonmagnetic Zn2+ ions
occupying the A sites. At room temperature, ZnCr2Se4 is an
electrical semiconductor with a magnetic spiral structure (spiral
angle
f
= 42 ꢀ 18), and its paramagnetic Curie–Weiss temperature
u is 115 K [1–6]. It shows a spontaneous helical spin ordering
below TN = 20 K [7]. Due to the positive value of u, the nearest-
neighbor exchange interaction can be considered to be
a
ferromagnetic one. Magnetic properties of this compound may
be appreciably altered by a cationic substitution both of magnetic
and nonmagnetic types, especially when doped with another 3d
metal [8,9].
2. Experimental procedure
The influence of Mn located on tetrahedral site on magnetic
properties of the matrix has been investigated earlier using
neutron diffraction by Siratori [10]. They concluded that chromium
does not change its valence state remaining as a 3+ ion and that the
manganese slightly boosts the ferromagnetic character of the
system.
2.1. Computation of equilibrium constants for the chemical transport
reactions
A necessary condition to be met in chemical transport reactions
is creation of chemical potential difference
D
ui, which can be
pi/pi), forming
expressed in terms of partial pressure pi ( ui = RTD
D
D
However, up till now, there are no studies conducted on single
crystalline materials with larger Mn content. We present here a
family of single crystals with general formula Zn1ꢁxMnxCr2Se4 with
various concentrations of manganese. The chemical composition
between melting and crystallization zones. The equilibrium values
of partial pressure for the individual components pi depend on the
value of equilibrium constant Ka for the transport reaction. The
highest values of
Ka ꢂ 1 (log Ka ꢂ 0). In such a case, a high transport ability of the
reaction is to be expected, even at small temperature difference
Dpi at small Ka changes may be obtained when
D
T
[12,13]. In order to select proper reaction conditions, a thermody-
namic model of chemical transport for ZnSe–MnSe–CrCl3 system
was developed.
* Corresponding author at: Division of Crystallography, University of Silesia,
Szkolna 9, 40-006 Katowice, Poland. Tel.: +48 32 3591503; fax: +48 32 3591545.
E-mail addresses: izajen@ich.us.edu.pl, izajen@wp.pl (I. Jendrzejewska).
0025-5408/$ – see front matter ß 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2012.04.029

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I. Jendrzejewska et al. / Materials Research Bulletin 47 (2012) 1881–1886
The chosen transporting agent CrCl3 dissociates to CrCl2, CrCl4
and Cl2 above 773 K [14,15].
ZnSe and MnSe pass to vapor phase as a result of the following
reactions:
ZnSe þ 2CrCl3ðgÞ ¼ ZnCl2ðgÞ þ 2CrCl2ðgÞ þ 1=2Se2ðgÞ
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
ZnSe þ 2CrCl3ðgÞ ¼ 1=2Zn2Cl4ðgÞ þ 2CrCl2ðgÞ þ 1=2Se2ðgÞ
MnSe þ 2CrCl3ðgÞ ¼ MnCl2ðgÞ þ 2CrCl2ðgÞ þ 1=2Se2ðgÞ
ZnSe þ CrCl4ðgÞ ¼ ZnCl2ðgÞ þ 2CrCl2ðgÞ þ 1=2Se2ðgÞ
ZnSe þ CrCl4ðgÞ ¼ 1=2Zn2Cl4ðgÞ þ 2CrCl2ðgÞ þ 1=2Se2ðgÞ
MnSe þ CrCl4ðgÞ ¼ MnCl2ðgÞ þ 2CrCl2ðgÞ þ 1=2Se2ðgÞ
ZnSe þ Cl2ðgÞ ¼ ZnCl2ðgÞ þ 1=2Se2ðgÞ
Fig. 1. Dependence of the equilibrium constant Ka on the reaction temperature T for
transport with CrCl3 (reactions (1)–(3)), CrCl4 (reactions (4)–(6)) and Cl2 (reactions
(7)–(9)).
ZnSe þ Cl2ðgÞ ¼ 1=2Zn2Cl4ðgÞ þ 1=2Se2ðgÞ
were placed in a horizontal furnace, where a melting zone
temperature of 1073–1173 K and crystallization zone temperature
MnSe þ Cl2ðgÞ ¼ MnCl2ðgÞ þ 1=2Se2ðgÞ
of 1043–1143 K were used with a gradient of
DT = 20–40 K. The
Therefore, the transporting reactions, with CrCl3, CrCl4 and Cl2
as transporting agents, were used to calculate the equilibrium
constants in a heterogeneous system (a gas phase and some solid
phases) using the H.S.C. Chemistry computer program ver. 6.01.
The detailed description of computation of the equilibrium
constants for the chemical transport reactions was reported in
Ref. [16].
furnace was cooled during one day after 14 days of heating.
Conditions of growth and chemical compositions are presented in
Table 1. The obtained crystals are shown in Fig. 2.
4. Magnetic measurements
Magnetic susceptibility of the single crystals was studied in the
temperature range of 4.2–300 K and in magnetic fields up to 1 T.
Magnetization was measured at liquid helium temperature in
fields up to 14 T using an induction magnetometer. The magnetic
parameters for the investigated single crystals of Zn1ꢁxMnxCr2Se4,
calculated per molecule vs. concentration of manganese are shown
in Table 2. The magnetic characteristics of Zn1ꢁxMnxCr2Se4 single
crystals are summarized in Figs. 3 and 4.
To sum up, the ZnSe–MnSe–CrCl3 system fulfils conditions for
the simultaneous transport of ZnSe and MnSe (the same sign of
enthalpy and the same value of volatility) and the crystallization of
Zn1ꢁxMnxCr2Se4 single crystals. The plots for the dependence of the
equilibrium constant vs. temperature for the transport reactions
(1)–(9) are shown in Fig. 1.
3. Sample preparation
5. XPS measurements
Synthesis of single crystals of Zn1ꢁxMnxCr2Se4 was carried out
according to the reaction:
X-ray photoelectron spectra were obtained with a Physical
Electronics PHI 5700/660 XPS spectrometer using monochroma-
tized Al K radiation. Its hemispherical analyzer ensures resolution
a
4ð1 ꢁ xÞZnSe þ 4xMnSe þ 2CrCl3 ¼ Zn1ꢁxMnxCr2Se4
of about 0.3 eV of kinetic energy of photoelectrons. The binding
energies scale was calibrated using the Fermi level of Ag, peaks: 4f
of Au, 3d of Ag and 2p of Cu. Just prior to measurement, the samples
were cleaved under high-vacuum conditions (about 10ꢁ10 h Pa) in
order to obtain a fresh surface, free of contaminants.
For all samples, the following spectra were measured: (1) an
overview in the binding energy range of ꢁ2 to 1400 eV, (2) the
valence band region ꢁ2 to 20 eV, and (3) the characteristic peaks
(for Se: 3d; for Cr, Zn and Mn: 2p). The background was subtracted
þ 3ð1ꢁxÞZnCl2 þ 3xMnCl2
forx ¼ 0:1ꢁ0:3
(10)
As starting materials for the crystal growth, binary selenides
ZnSe and MnSe were used with anhydrous CrCl3. The binary
selenides were synthesized from elemental Zn, Mn and Se. All
reactants were of 5 N purity. The exact quantities of the binary
selenides, according with stoichiometry of the chemical transport-
ing reaction, were sealed in quartz ampoules evacuated to a
pressure of 10ꢁ4 Pa. The ampoules containing powdered substrates
Table 1
Conditions of growth and chemical composition of Zn1ꢁxMnxCr2Se4 crystals.
Assumed composition xa
Amounts of substrates
(mmol)
Tv (K)
Tc c(K)
D
Td (K)
Chemical formula [14]
b
No.
nZnSe
nMnSe
1.
2.
3.
4.
0.10
0.20
0.30
0.30
14.4
12.8
11.2
11.2
1.6
3.2
4.8
4.8
1173
1073
1073
1073
1133
1043
1043
1053
40
30
30
20
Zn0.88Mn0.12Cr2Se4.0
Zn0.87Mn0.13Cr2Se4.0
Zn0.82Mn0.18Cr2Se4.0
Zn0.76Mn0.24Cr2Se4.0
a
Composition x assumed from the relation of the starting materials.
Temperature of the dissolution zone.
b
c
Temperature of the crystallization zone.
d
Difference of temperatures between the dissolution and the crystallization zones.

I. Jendrzejewska et al. / Materials Research Bulletin 47 (2012) 1881–1886
1883
Fig. 2. Single crystals of the Zn1ꢁxMnxCr2Se4-system obtained by chemical vapor transport.
using Tougaard’s approximation. To compare qualitatively the
intensities of the valence band spectra, it was useful to do some
rough scaling. From the overviews, we took the proportion of the
maximum intensity near the Fermi level (between 2 and 3 eV) to
the intensity of the selenium 3d peak. As the selenium content is
the same for all single crystals, it was reasonable to normalize the
overviews by these peaks and valence band spectra by the
mentioned proportion. The spectra of the elements were normal-
ized by the intensity of the characteristic peaks.
close to zero in the temperature range of 1000–1200 K, in which
the growth of the single crystals was carried out). The calculated
log Ka values for transport reactions with chlorine (reactions (7)–
(9)) have values far from zero, indicating that chlorine does not
participate in the transport process (see Fig. 1).
Equilibrium constants for ZnSe transport reaction have values
and course similar to the ones for MnSe transport reaction
(reactions (1)–(6)). Therefore, the conditions for simultaneous
ZnSe and MnSe transport and for single crystals growth are met.
Based on the calculated values of equilibrium enthalpies for the
reactions, it results that reactions (1)–(6) are endothermic
6. Results and discussion
(D
H2ꢃ98 < 0). The transport proceeds from the melting zone (having
higher temperature) to the crystallization zone (having lower
temperature).
Single crystals with well developed walls and edges were
obtained. Based on the reactions (1)–(9), one may assume that in
the ZnSe–MnSe–CrCl3 system, volatile compounds of zinc and
manganese may form, e.g. ZnCl2, Zn2Cl4, MnCl2, and selenium as
Se2 or in the form of polymerized Se4, Se6, Se8 molecules [17,18].
From reactions (1)–(3) and (4)–(6), it results that chemical
transport proceeds using CrCl3 and CrCl4 (the log Ka values are
Chemical composition of four single crystals of Zn–Mn–Cr–Se
system with different concentration of manganese was analyzed
and confirmed by X-ray diffraction study. The structure refine-
ments, taking into account site occupancy factors, indicated that
Mn ion shared tetrahedral sites with Zn ion. Thus, the formula
Table 2
Values of the paramagnetic effective Bohr magneton number and saturation magnetization per formula unit, asymptotic Curie temperature, Ne´el temperature and Curie
constant per mol for Zn1ꢁxMnxCr2Se4 and the ZnCr2Se4.
Chemical compound
meff
(m
B/f.u.)
msat
(
m
B/f.u.)
QCW (K)
CM (K/mol)
TN (K)
Zn0.88Mn0.12Cr2Se4.0
Zn0.87Mn0.13Cr2Se4.0
Zn0.82Mn0.18Cr2Se4.0
Zn0.76Mn0.24Cr2Se4.0
ZnCr2Se4 [1–6]
4.87
5.47
6.38
6.91
5.47
3.87
5.92
6.32
6.75
7.34
7.63
5.90
3.0
103
105
107
108
115
2.96
3.84
5.09
5.97
3.74
28
33
28
28
22
Free Cr3+ ion
Free Mn2+ ion
5.0

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I. Jendrzejewska et al. / Materials Research Bulletin 47 (2012) 1881–1886
Mn content refined from the single crystal XRD is much larger than
the reported, (3) the crystal possesses defects and regions of higher
inhomogenity, which are not seen by surface sensitive
a
microprobe. Here, we incline to the later two, which are
intermittently coupled.
Because in all compounds under study the magnetic coupling of
the moments localized on both Mn2+ and Cr3+ cations is realized via
superexchange magnetic interactions, one can distinguish the
following paths of magnetic interactions: Cr–Se–Cr, Cr–Se–Se–Cr
and Cr–Se–Mn–Se–Cr. The magnetic interactions along these paths
are connected with the overlap of wave functions of both p orbitals
of anions and 3d orbitals of cations. Different overlaps occur, which
can cause either ferromagnetic or antiferromagnetic coupling. The
detailed discussion of the character of the couplings, taking into
account the very specific helical structure of the materials, has
been performed by Plumier [5] using 3 exchange integrals and later
on Dwight and Menyuk [6] with 5 parameters. In both cases, the
proper analysis of the interactions required at least 3 different
integrals and the knowledge of either the spiral pitch or the critical
field.
Fig. 3. Magnetization isotherms for Zn1ꢁxMnxCr2Se4 crystals.
Fig. 3 presents the magnetization isotherms at liquid helium
temperature for various manganese concentrations x. The satura-
tion effect was observed at higher fields, above 60 kOe.
The susceptibility curves exhibit maxima at the range of 18–
30 K, indicating the presence of the magnetic ordering. As it may be
seen in inset of Fig. 4, the magnetic phase transition is very sharp,
characteristic for first-order-type. Generally, the Zn1ꢁxMnxCr2Se4
crystals show a linear 1/
xmol = f (T) behavior in the 150–300 K
range (Fig. 4).
The value of paramagnetic Curie–Weiss temperature does not
change much with Mn content, however it is slightly lower than
the one reported for pure ZnCr2Se4. This small lowering can be
explained by the formation of the chemical disorder which
disturbs the internal Weiss field or differences in the temperature
range from it was calculated. However, the increase of QCW with
increasing Mn-content may indicate a boost of the ferromagnetic
interactions, which is consistent with the appearance of small
ferromagnetic component in neutron diffraction [10] and the
decrease of the spiral pitch. As it was pointed out [10] the increase
of the lattice parameter due to a larger radius of Mn compared to
Zn has a similar impact on the magnetism as for example
substitution of Cd. In other words, larger distances between Cr ions
decrease antiferromagnetic NNN exchange pathways.
Fig. 4. Temperature dependence of inverse magnetic susceptibility for
Zn1ꢁxMnxCr2Se4 single crystals.
The calculated saturation and effective magnetic moments have
larger values than the ones for pure ZnCr2Se4-spinel. Substitution
of nonmagnetic Zn2+ ion by magnetic Mn2+ may considerably affect
the Cr–Se–Cr and Cr–Se–Se–Cr magnetic superexchange interac-
tion.
describing cation distribution in the system is: Zn1ꢁxMnxCr2Se4.
the observed symmetry was cubic, space group Fd3m [11].
¯
From the magnetization isotherms shown in Fig. 3, it results
that all studied crystals magnetize with large difficulties, and that
magnetic transitions of spin flop type occur in them. However, in
the field stronger than 6 T, all samples reach magnetic saturation.
As it results from Fig. 3 and Table 2, the value of magnetic moment
of saturation is significantly higher than the value for ZnCr2Se4
matrix, so this ‘‘surplus’’ must originate from manganese ions. The
theoretical values of saturation magnetic moments calculated
The valence band spectra of investigated Zn1ꢁxMnxCr2Se4 single
crystals are presented in Fig. 5 (ZnCr2Se4 [19] is used for
comparison).
In Fig. 5, also a Zn 3d peak of zinc metal measured by us and the
valence band of elemental selenium are shown. The peak of Zn 3d
levels is the most noticeable feature in the spectrum. Although the
peak lies in the valence band area, it is core-like and appears as
unresolved localized doublet. Nevertheless, some weak hybridiza-
tion of states: 3d of Zn and 4 s of Se exists (similar to 4d peak of Cd
in CdCr2Se4 [20]). The Zn 3d levels in Zn1ꢁxMnxCr2Se4 spinels differ
from those of the metallic Zn element. In pure metal, they are much
more resolved (due to smaller distances between Zn atoms in
metal than in spinels) and the maximum of 3d5/2 peak in metal is a
little closer to the Fermi level (at 10 eV). With the increase of Mn
concentration in Zn1ꢁxMnxCr2Se4 spinels, the binding energy of
Zn3d peak decreases a little comparing with that of ZnCr2Se4,
meanwhile the Se 4s peak shifts to higher binding energy and is
more flattened. A similar shift and flattening of the Se 4s peak with
assuming refined Mn content, 5
Cr and Mn, increase from 6.32
m
B/ion and parallel polarization of
m
B/molecule for x = 0.12 to 7.63 mB
/
molecule for x = 0.24, therefore exceed the experimental ones for
higher contents. We have to note that reversing the procedure, i.e.
calculating the expected Mn content on the basis of saturation
moment gives xMn = 0.08, 0.17, 0.29 and 0.35.
There are three possible causes of such behavior. (1) Ion
different than Cr3+ or Mn2+ contributes to the magnetization. Here
a possible candidate is Cr2+ with moment of 4
m
B/ion but there it is
not corroborated by the XPS. (2) The systematic uncertainty of the

I. Jendrzejewska et al. / Materials Research Bulletin 47 (2012) 1881–1886
1885
Fig. 7. XPS spectrum of Zn 2p core-levels in Zn1ꢁxMnxCr2Se4 crystals (‘‘1’’ –
Zn0.88Mn0.12Cr2Se4.0, ‘‘2’’ – Zn0.87Mn0.13Cr2Se4.0, ‘‘4’’ – Zn0.76Mn0.24Cr2Se4.0).
Fig. 5. XPS valence band spectra of Zn1ꢁxMnxCr2Se4 crystals (‘‘1’’
Zn0.88Mn0.12Cr2Se4.0, ‘‘2’’ – Zn0.87Mn0.13Cr2Se4.0, ‘‘4’’ – Zn0.76Mn0.24Cr2Se4.0).
–
Sb concentration was observed for (Zn1ꢁxSbx)[Cr2ꢁx/3]Se4 system
[19] but the shift of the Zn3d peak had opposite direction.
The strict valence band region extents from the Fermi level (i.e.
0 eV) up to 8 eV and has a flat maximum at 3.5 eV. No changes were
observed with Mn substitution for the part from 0 eV up to 3.5 eV
(it consists mainly of the Cr 3d and Se 4p states [19]). For area from
4 eV up to 8 eV, the electron states of Zn1ꢁxMnxCr2Se4 spinels
compared with ZnCr2Se4 are shifted toward Fermi level.
The spectrum of Cr 2p chromium core levels (i.e. doublet Cr 2p3/
and Cr 2p1/2) is shown in Fig. 6.
2
The Cr 2p3/2 peak is split into a clearly resolved doublet.
Distance between the components of the doublet is 1 eV. The same
value was obtained in the (Zn1ꢁxSbx)[Cr2ꢁx/3]Se4 system [19] and
for other chromium chalcogenide spinels [21]. It is a typical value
for 3d transition metals in the electronic state 3d3 [22]. It confirms
that in all Zn1ꢁxMnxCr2Se4 single crystals investigated by us,
chromium is in the 3d3 electronic state. There is a shift by about
0.1 eV towards lower energy of both components of the Cr 2p3/2
peak in Zn1ꢁxMnxCr2Se4 spinels comparing to ZnCr2Se4, so the
distance 1 eV is preserved. But the peaks of Cr 2p1/2 levels are not
shifted. A similar shift exists for Zn 2p3/2 peaks (Fig. 7).
It is worth to mention that Zn 2p peaks in chalcogenide spinels
have binding energy close to the value of the one for elemental zinc
(121.8 eV) [23].
Fig. 8. XPS spectrum of Se 3d core-levels in Zn1ꢁxMnxCr2Se4 crystals (‘‘1’’ –
Zn0.88Mn0.12Cr2Se4.0, ‘‘2’’ – Zn0.87Mn0.13Cr2Se4.0, ‘‘4’’ – Zn0.76Mn0.24Cr2Se4.0).
The spectra of the 3d peaks of selenium measured in
Zn1ꢁxMnxCr2Se4 single crystals are compared with 3d Se levels
of ZnCr2Se4 single crystal in Fig. 8. The 3d peaks are resolved into
3d5/2 and 3d3/2 levels. There is a visible shift of the peaks with
manganese concentration towards lower energies.
7. Conclusions
This study was undertaken in order to cover the process of
crystal growth and to select conditions for obtaining single crystals
of Zn1ꢁxMnxCr2Se4. Application of CrCl3 as a transport agent in the
chemical vapor transport method, based on the thermodynamic
calculations, was found to be successful and was experimentally
confirmed. The chemical transport proceeded from hot to cool
zone. This phenomenon confirmed that the reaction was endo-
thermic.
For the Zn1ꢁxMnxCr2Se4 system, values of log Ka for the
transport reactions are similar to equilibrium state values
(log Ka ꢂ 0). For temperatures above T > 500 K, CrCl3 and CrCl4
are present in the transporting ampoule and they are a better
transporting agent than Cl2 because their value of log Ka is closer to
zero (Fig. 3, reactions (1)–(6)).
Calculated values of log Ka for Cl2 are higher than zero (Fig. 1,
reactions (7)–(9)). So we conclude that the transport of ZnSe and
Fig. 6. XPS spectrum of Cr 2p core-levels in Zn1ꢁxMnxCr2Se4 crystals (‘‘1’’ –
Zn0.88Mn0.12Cr2Se4.0, ‘‘2’’ – Zn0.87Mn0.13Cr2Se4.0, ‘‘4’’ – Zn0.76Mn0.24Cr2Se4.0).

1886
I. Jendrzejewska et al. / Materials Research Bulletin 47 (2012) 1881–1886
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Acknowledgement
This paper is funded from science resources for years 2008–
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