Materials Chemistry and Physics 149-150 (2015) 467e472

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

ssbauer properties of double-doping LaFeO3

Magnetic, Raman and Mo
perovskite oxides
A. Benali a, M. Bejar a, *, E. Dhahri a, M. Sajieddine b, M.P.F. Graa c, M.A. Valente c
Laboratoire de Physique Appliqu
ee, Facult
e des Sciences, B.P. 1171, 3000 Sfax, Universit
e de Sfax, Tunisia
Laboratoire de Physique des Mat
eriaux, Facult
e des Sciences et Techniques, BP 523, 23000 B
eni-Mellal, Universit
e Sultan Moulay Slimane, Morocco
c
I3N and Physics Department, University of Aveiro, 3810-193 Aveiro, Portugal
a

h i g h l i g h t s

La0.8Ca0.2xPbxFeO3 compounds were synthesized by the solegel method.
ssbauer study: presence of Fe3 tetrahedral site and a doublet for x 0 sample.

Mo
ssbauer results revealed the presence of Fe3O4 phase.

For x > 0 samples, the Mo

The substitution of Ca2 by Pb2 introduces a change on the magnetization.

Competition between tetrahedral FM and octahedral AFM interactions.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 16 May 2014
Received in revised form
17 October 2014
Accepted 26 October 2014
Available online 4 November 2014

The La0.8Ca0.2xPbxFeO3 (x 0.00, 0.05, 0.10, 0.15 and 0.20) compounds were prepared by the solegel
method using the citric acid route. The structural study revealed that all samples crystallized in the Pnma
orthorhombic structure with the apparition of Ca2Fe2O5 and Fe3O4 secondary phases for samples with
x  0.05, conrmed by the Raman spectroscopy study.
ssbauer spectra exposed, for x 0.00 sample, the presence of a one sextuplet, related to
The tted Mo
the Fe3 ion in the tetrahedral site, and a doublet. However, for x > 0.00 samples, the t results showed
the apparition of other sextuplets related to the Fe3O4 phase. The percentage of this latest phase was
found to increase and to reach a maximum for the x 0.10 sample and to decrease after for x 0.15 and
0.20 samples.
The variation of the magnetization (M) as a function of the temperature (T), under an applied magnetic
eld of 0.05 T, showed the presence of a ferromagneticeparamagnetic transition. The magnetic study
exposed that the magnetization decreases rst for x  0.10 samples and then increases for the two other
samples. This behavior was related to the competition between the Fe3eFe3 tetrahedral ferromagnetic
interactions and the octahedral antiferromagnetic ones between Fe3 and Fe2 ions.
2014 Elsevier B.V. All rights reserved.

Keywords:
Magnetic materials
Raman spectroscopy and scattering
ssbauer effect
Mo
Powder diffraction

1. Introduction
There has been much interest in perovskite-structured compounds (of general formula ABO3) because of their unique catalytic
action [1], colossal magnetoresistance effects [2,3], and gas-sensing
properties [4e13].
Many materials of technological and scientic interest have
structures which derive from, or are related to, the parent ABO3

* Corresponding author.
E-mail address: bejar_moez@yahoo.fr (M. Bejar).
http://dx.doi.org/10.1016/j.matchemphys.2014.10.047
0254-0584/ 2014 Elsevier B.V. All rights reserved.

perovskite structure. One such class of materials is the rare-earth

calcium ferrites with the general formula Ln1xCaxFeIII1x
FeIVxO3d (Ln lanthanide ion), with Ln3 and Ca2 occupying the
A-site and Fe occupies the B-site. The structural characteristics of
these compounds can lead to a range of useful physical properties,
such as mixed electric and ionic conductivity and ordered magnetism at elevated temperatures. While at present, most of the studies
of the technological applications of the Ln1xCaxFeO3d family have
been focused on their catalytic ability for carbon monoxide and
methane oxidation. Similar classes of perovskite-related oxide
materials, such as the rare-earth strontium cobaltates, have been
investigated for use as cathode materials for Solid Oxide Fuel Cells

468

A. Benali et al. / Materials Chemistry and Physics 149-150 (2015) 467e472

(SOFC) [14], ceramic membranes for high temperature oxygen

separation [15,16] and magnetic sensors [17]. For signicant Cadoping, charge balance is maintained by a combination of Fe4
and oxygen vacancies (d > 0) [18]. At low temperatures,
Ln1xCaxFeO3d compounds are reported to undergo a Charge
Disproportionation (CD) transition, in which the Fe4 disproportionate into Fe3 and Fe5 [19]. This CD transition is thought to be
related to the observation of glass behavior [5]. The mixed oxidation state of Fe ion of the B-site and oxygen-site vacancies are both
important structural characteristics of these materials, with
oxygen-site vacancies being necessary for good oxygen conductivity [2] and the magnetic behavior being dependent on the Fe3/
Fe4 (and reportedly Fe5) distribution and ratio [18e20]. Based on
el
what appear to be impure samples, some works suggest a Ne
temperature (TN) for samples with x 0.25 of 693 K [21]. Interpolation of other results [18,19] suggests a lower TN for
La0.8Ca0.2FeO3d samples in the region of 500e550 K. This lower
temperature suggests, in a room temperature measurement (T/
TN ~ 0.6), that a moment reduction of about 15e20 % should be
observed. The lowest moment on Fe4 has a small effect with the
existence of any canting of the antiferromagnetism resulting in a
ferromagnetic moment.
In this work, the lead doping effects on the structural, Raman,
ssbauer and magnetic properties of La0.8Ca0.2xPbxFeO3
Mo
(x 0.00, 0.05, 0.10, 0.15 and 0.20) compounds are discussed.

2. Experimental details
The nanosize crystalline La0.8Ca0.2xPbxFeO3 (x 0.00, 0.05, 0.10,
0.15 and 0.20) compounds [22] were synthesized by the solegel
method [23,24]. This method was chosen because it is known to
give a high degree of homogeneity and the particle size can be
controlled up to the nanosize level. Stoichiometric amounts of
lanthanum nitrate, lead nitrate, calcium nitrate, ferric nitrate and
citrate acid (all analytically pure) powders were weighted.
The phase purity, the homogeneity, lattice structure and cell
parameters of our compounds were checked by X-ray diffraction
(XRD) analysis (Siemens D5000 X-ray diffractometer, with monochromator CueKa radiation (lCu 1.5406 )). The XRD data were
also used for rening the lattice parameters by means of Rietveld
analysis [25], by using the FULLPROOF program software.
Room temperature (RT) Raman spectroscopy was performed
under backscattering geometry, using a Jobin Yvon HR 800 system
and an excitation wavelength of 473 nm. For the RT absorption
experiments, a Shimadzu UV 2100 spectrometer was used in
transmission mode in a wavelength range from 200 to 900 nm. The
Raman spectra were recorded with a modular double grating
excitation spectrouorimeter with a TRIAX 320 emission monochromator (Fluorolog-3, Horiba Scientic) coupled to an HR 980
Hamamatsu photomultiplier, using a front face acquisition mode.
As an excitation source a 450 W X arc lamp was used [26].
ssbauer spectra were collected at
The transmission 57Fe Mo
room temperature using a constant acceleration spectrometer and
a 25 mCi 57Co source in Rh matrix in a constant acceleration mode
ssbauer spectrometer (Weissel).
using standard conguration of Mo
The velocity scale was calibrated using an a-Fe foil. Estimated isomer shifts (IS) are given relative to this standard. The tting of the
spectra was carried out with a set of Lorentzian lines, determined
by least squares tting programme NORMOS.
The magnetic measurements were made using a cryogen free
Vibrating Sample Magnetometer (VSM) that allows measurements
as a function of temperature (between 200 and 750 K), with a
maximum value of magnetic eld of 10 T.

3. Results and discussion

3.1. X-ray diffraction
Phase identication and structural analysis were carried out by
the X-Ray Diffraction (XRD) technique with Cu-Ka radiation at room
temperature. The data were analyzed by the Rietveld method using
the FULLPROOF program [27]. Fig. 1 shows examples of the
renement results of XRD patterns for x 0.00 and 0.10 samples. In
fact, samples with x < 0.10 crystallized in the orthorhombic structure with Pnma space group. However, for samples with x  0.10,
beside the orthorhombic phase, spectra revealed other peaks
ascribed to the Ca2Fe2O5 and Fe3O4 secondary phases identied
with X0 Pert High Score Plus program.
3.2. Raman spectroscopy
Fig. 2 shows the RT Raman spectra of La0.8Ca0.2xPbxFeO3
(x 0.00, 0.05, 0.10, 0.15 and 0.20) compounds. Some peaks related
to the La0.8Ca0.2xPbxFeO3 main phase can be noticed in all samples.
The Raman bands, for x 0.00, observed at 145, 170, 255, 285, 400,
430 and 640 cm1 are similar to those reported by M. Popa et al.
[28] and Y. Wang et al. [29] specic of the LaFeO3 oxide (Fig. 3(a)).
However, with the increase of Pb-content (x s 0.0), other bands
appeared and their intensities increased with increasing leadcontent. This can conrm the apparition of additional peaks in DRX
spectra related to the presence of Fe3O4 and Ca2Fe2O5 secondary
phases, as proved by DRX study. On the other hand, we note the
apparition of an additional mode located at about 830 cm1, which
is not observed in the spectra of pure La0.8Ca0.2FeO3. This mode is
characteristic for adsorbed oxygen species on the surface of
La0.8Ca0.2xPbxFeO3 (x > 0.0) nanoparticles [30].
In addition, modes located at about 150, 220 and 410 cm1 can
be associated to Fe3O4 phase (Fig. 3(b)) [31]. These results are in
good coincidence with the DRX study previously mentioned.
ssbauer spectroscopy
3.3. Mo
ssbauer study was performed on La0.8Ca0.2xPbxFeO3
A Mo
samples at room temperature and the obtained spectra with their
ssbauer spectra show well
tting are shown in Fig. 4. The Mo
resolved peaks with a shape which changes when the composition
of iron increases suggesting a modication in the local iron environment. It is clear, that the insertion of Pb2 ion does not signi ssbauer spectra but leads to a
cantly affect the global form of the Mo
narrowing of the sextuplet peaks. The spectra were calculated with
the superposition of three magnetic sub-spectra (S1, S2 and S3) and
one doublet (d). Parameters derived from the calculated spectra
and including the area in percent, hyperne eld (Hhyp), isomer
shift (IS), quadruple splitting (QS) and the average hyperne eld
(<Hhyp>) are reported in Table 1. For all the spectra, we notice the
presence of the sub-spectrum S1 and the doublet d independently
of the content of iron. As the isomer shift reects the s-electron
density at the iron nucleus, which is very sensitive to the iron
oxidation state and coordination number, the sub-spectrum S1
with IS in the range 0.35e0.37 mms1 to Fe3 ions is attributed in
the tetrahedral site. The presence of the doublet indicates the
presence of a paramagnetic nature of some of iron in the samples.
For x > 0.05 samples, and according to Table 1, the hyperne parameters revealed the presence of the Fe3O4 phase (sub-spectra S2
and S3). The apparition of the later phase is conrmed by the XRD
results. The determined isomer shift values are in good argument
with those reported in the literature for LaFeO3 [32], SrFeO2.5 [33]
and LaMn0.5Fe0.5O3 [34] compounds.

A. Benali et al. / Materials Chemistry and Physics 149-150 (2015) 467e472

469

Fig. 1. Observed (circle), calculated (continuous line) and difference patterns (at the bottom) of X-ray diffraction data for La0.8Ca0.2xPbxFeO3 (x 0.00 and 0.10) compounds. The
vertical tick indicates the allowed reections.

From Table 1, we can note an increase of Fe3 ions in the

tetrahedral site when increasing the lead-content. Also, the
percentage of the Fe3O4 phase increases and reaches a maximum
for the x 0.10 sample and decreases for x 0.15 and 0.20
samples.

3.4. Magnetic characterization

The temperature (T) dependence of the magnetization (M) for
La0.8Ca0.2xPbxFeO3 (x 0.00, 0.05, 0.10, 0.15 and 0.20) compounds
is displayed in Fig. 5 measured at two different applied magnetic
elds m0H 0.05 and 2 T. All samples underwent a

470

A. Benali et al. / Materials Chemistry and Physics 149-150 (2015) 467e472

200

400

600

800

1000
x = 0.00

x = 0.20

x = 0.05

x = 0.15

x = 0.10

x = 0.15

x = 0.10
x = 0.20

-12

-8

-4

12

Velocity (mm/s)
Fig. 4. Room temperature spectra of La0.8Ca0.2xPbxFeO3 (x 0.00e0.20) samples
tted with three sextets and one doublet.

x = 0.05

x = 0.00

200

400

600

800

1000

-1

Raman shift (cm )

Fig. 2. Raman scattering of La0.8Ca0.2xPbxFeO3 (x 0.00e0.20) compounds.

ferromagneticeparamagnetic transition phase at TC temperature,

dened as the temperature at which the dM/dT-T curves reached a
minimum (Fig. 6). For all samples, the TC value was approximately
constant and about 670 K.
As shown in Fig. 5, the magnetization (M) decreased rst for
samples with x  0.10 and then increased for compounds with
x > 0.10. As known, Fe ion presents 3d6 4s2 valence electrons. In
the case of low spin state of Fe2 ions, all 3d6 ions are compensated
([Y[Y[Y, S 0) and they do not contribute to the total magnetic
moment of oxide. In Fe3 doped samples, 3d5 electrons in the low
spin state can participate in a ferromagnetic ordering ([Y[Y[,
S 1/2). To explain the behavior of the magnetic curves for x 0.00

sample, the magnetization was due to the low ferromagnetic interactions between the Fe3 ions in the tetrahedral site. Based on
this, an enhancement of the magnetization was expected when
increasing the Pb-content given that the percentage of the Fe3 ions
in the tetrahedral site increases as previously mentioned in the
ssbauer part. However, the magnetization decreased for x 0.05
Mo
and 0.10 samples. This contradiction can be correlated to the
apparition of the 2 and 3 iron valence, related the octahedral site
ssbauer part. The
of Fe3O4 phase as mentioned previously in the Mo
apparition of the two valence state led to the introduction of antiferromagnetic interactions between these Fe3 and Fe2 octahedral site ions. In addition, H.D. Zhou et al. [35] proved that the Fe3/
Fe2 redox couple is removed from the Fe4/Fe3 redox couple by a
large intra-atomic interaction Ueff U De. So, it can be assumed
that there is a competition between the Fe3eFe3 tetrahedral
ferromagnetic interactions and the octahedral antiferromagnetic
ones. Going deeper, T. Maitra et al. [36] conrmed that the presence
of Fe2 makes the FM phase less stable compared to the tetrahedral
case. The antiferromagnetic phase, therefore, stabilizes and become
more predominant.

Table 1
ssbauer parameters of La0.8Ca0.2xPbxFeO3 (x 0.00e0.20) compounds at
Fitted Mo
300 K.
Samples

Sub-spectrum

Area (%)

Hhyp (kOe)

IS
(mm/s)

QS
(mm/s)

<Hhyp>
(kOe)

x 0.00

S1
S2
S3
d
S1
S2
S3
d
S1
S2
S3
d
S1
S2
S3
d
S1
S2
S3
d

22.2
20
54
3.8
33.7
20.5
42.1
3.7
34.8
13.5
50
1.7
62.7
5.7
26
5.5
85
2.3
6
5.4

492.8
468.8
418.0
//
503.0
484.1
437.2
//
512.3
463.0
492
//
516.5
463.0
492.0
//
523.8
463.0
492.0
//

0.36
0.35
0.32
0.38
0.36
0.31
0.30
0.43
0.37
0.67
0.29
0.36
0.35
0.67
0.29
0.36
0.35
0.67
0.29
0.36

//
//
//
2.32
//
//
//
2.42
//
//
//
2.82
//
//
//
2.82
//
//
//
2.82

428.7

x 0.05

x 0.10

x 0.15

x 0.20

Fig. 3. Raman scattering of the magnetite Fe3O4 phase [28].

452.8

486.7

478.1

485.4

A. Benali et al. / Materials Chemistry and Physics 149-150 (2015) 467e472

Magnetization (emu/g)

This competition leads to the reduction of the magnetization as

can be seen for samples with x 0.05 and 0.10. Note that, from the
ssbauer study, it is deduced that the percentage of the Fe3O4
Mo
phase reaches a maximum for this sample, which can explain the
lower value of the magnetization for x 0.10 sample. When
continuing to increase the Pb-content, the Fe3O4 phase percentage
decreases, leading as a result to the decrease of the antiferromagnetic interactions and simultaneously there is an increase of the
ferromagnetic interactions between the tetrahedral Fe3. All this
can explain the enhancement of the magnetization for x 0.15 and
0.20 samples. For these two samples, the ferromagnetic interactions become very strong and the antiferromagnetic ones
become very poor, which explains the spectacular magnetization
improvement of the magnetization for x 0.20 sample.
Fig. 7 shows the applied magnetic eld (m0H) dependence of the
magnetization (M) at two different temperatures of 5 and 300 K.
The M (m0H) curves reveal that for m0H > 0.5 T, the magnetization
increases linearly with the increase of the lead-content, which indicates the suppression of the antiferromagnetic component
observed at low applied magnetic eld. However, the absence of
the saturation of the magnetization until an applied magnetic eld
of 10 T is noticeable. This signies that the suppression of the antiferromagnetic interactions is only partial.

x = 0.00
x = 0.05
x = 0.10
x = 0.15
x = 0.20

0H = 0.05 T

0
200

300

400

500

600

700

T(K)

Magnetization (emu/g)

x = 0.00
x = 0.05
x = 0.10
x = 0.15
x = 0.20

0H = 2 T

471

4. Conclusion
2

200

300

400

500

600

T(K)

This work investigated the effect of the insertion of the Pb ion on

ssbauer and magnetic properties of
the structural Raman, Mo
La0.8Ca0.2xPbxFeO3 (x 0.00, 0.05, 0.10, 0.15 and 0.20) compounds

700

Fig. 5. Temperature dependence of magnetization of La0.8Ca0.2xPbxFeO3

(x 0.00e0.20) compounds in magnetic eld m0H 0.05 and 2 T.

0.00

0.6

x = 0.05

-0.01
0.3

dM/dT (emu/g.K)

Magnetization (emu/g)

0.9

TC = 669 K

0.0
200

300

400

500

600

700

800

T (K)

0.00

0.8

x = 0.15

-0.01

0.4

dM/dT (emu/g.K)

Magnetization (emu/g)

1.2

-0.02
TC = 670 K

0.0
200

300

400

500

600

700

800

T (K)
Fig. 6. Temperature dependence of magnetization and the Curie temperature of
La0.8Ca0.2xPbxFeO3 (x 0.05 and 0.15) compounds.

Fig. 7. Magnetic eld dependence (m0H) of magnetization (M) curves at two different
temperatures of 5 and 300 K of La0.8Ca0.2xPbxFeO3 (x 0.00e0.20) compounds.

472

A. Benali et al. / Materials Chemistry and Physics 149-150 (2015) 467e472

synthesized by the solegel method. The structural study revealed

that all samples crystallize in the Pnma orthorhombic phase with
the apparition of Ca2Fe2O5 and Fe3O4 secondary phases for samples
with x  0.05. The presence of these latest phases was conrmed by
the Raman spectroscopic study.
ssbauer study revealed the presence of Fe3 tetrahedral
The Mo
site and a doublet for x 0.00 sample. For x > 0.00 samples, the
ssbauer patterns t results have shown the presence other
Mo
sextuplets related to the Fe3O4 phase. From the t results, an increase of Fe3 ions in the tetrahedral site when increasing the Leadcontent was induced and the percentage of the Fe3O4 phase
increased and reached a maximum for the x 0.10 sample and
decreased for x 0.15 and 0.20 samples.
The variation of the magnetization (M) as a function of the
temperature (T), under an applied magnetic eld of 0.05 T, has
shown the presence of a ferromagneticeparamagnetic transition,
occurring at the Curie temperature (TC), for all samples, which does
not change signicantly with the lead-content. However, the substitution of calcium by lead introduces a change on the magnitude
of the magnetization curves. This behavior was related to the
competing mechanisms between the Fe3- Fe3 tetrahedral ferromagnetic interactions and the octahedral antiferromagnetic ones
between Fe3 and Fe2 ions.
Acknowledgment
This work, within the frame work of collaboration, is supported
by the Tunisian Ministry of Higher Education and Scientic
Research and the Portuguese Ministry of Higher Education and
Scientic Research (Portuguese Agency for Science and Technology
FCT) Project TP/46/2012.
References
[1] L. Lisi, G. Bagnasco, P. Ciambelli, S.D. Rossi, P. Russo, M. Turco, J. Solid State
Chem. 146 (1999) 176e183.
[2] J.F. Hu, C.J. Ji, H.W. Qin, J. Chen, Y.M. Hao, Y.X. Li, J. Magn. Magn. Mater. 241
(2002) 271e275.
[3] H.W. Qin, C.J. Ji, H.D. Niu, L.M. Zhu, J. Magn. Magn. Mater. 263 (2003) 249e252.

[4] C.M. Chiu, J.F. Hu, C.J. Ji, Y.H. Chang, Thin Solid Films 342 (1999) 15e19.
[5] Z.Y. Peng, X. Li, M.Y. Zhao, H. Cai, S.Q. Zhao, G.D. Hu, Thin Solid Films 286
(1996) 270e273.
[6] C.M. Chiu, Y.H. Chang, Mater. Sci. Eng. A 266 (1999) 93e98.
[7] C.M. Chiu, Y.H. Chang, Sens. Actuat. B 54 (1999) 236e242.
[8] N.N. Toan, S. Saukko, V. Lantto, Sens. Actuat. B 327 (2003) 279e282.
[9] L.B. Kong, Y.S. Shen, Sens. Actuat. B 54 (1996) 217e221.
[10] Y.D. Wang, J.B. Chen, X.H. Wu, Mater. Lett. 49 (2001) 361e364.
[11] M. Tomoda, S. Okano, Y. Itagaki, H. Aono, Y. Sadaoka, Sens. Actuat. B 97 (2004)
190e197.
[12] D. Mantzavinos, A. Hartley, I.S. Metcalfe, M. Sahibzada, Solid State Ionics 134
(2000) 103e109.
[13] M.J. Akhtar, Z.N. Akhtar, J.P. Dragun, C.R.A. Catlow, Solid State Ionics 104
(1997) 147e158.
[14] S.J. Skinner, J. Inorg. Mater. 3 (2001) 113e121.
[15] V.V. Kharton, A.V. Kovalevsky, A.A. Yaremchenko, F.M. Figueiredo,
E.M. Naumovich, A.L. Shaulo, F.M.B. Marques, J. Membr. Sci. 195 (2002)
277e287.
[16] V.V. Kharton, A.A. Yaremchenko, A.V. Kovalevsky, A. Viskup, E.M. Naumovich,
P.F. Kerko, J. Membr. Sci. 163 (1999) 307e317.
[17] L.L. Barcells, R. Enrich, A. Callega, J. Fontcuberta, X. Obradors, J. Appl. Phys. 81
(1997) 4298e4300.
[18] Y.Q. Liang, N.L. Di, Z.H. Cheng, Phys. Rev. B 72 (2005) 134416.
[19] J. Li, Hyperne Interact. 69 (1991) 573e576.
[20] Y.Q. Liang, N.L. Di, Z.H. Cheng, J. Magn. Magn. Mater. 306 (2006) 35e39.
[21] M.A. Ahmed, S.I. El-Dek, Mater. Sci. Eng. B 128 (2006) 30.
[22] A. Benali, S. Azizi, M. Bejar, E. Dhahri, M.F.P. Graa, Ceram. Int. 40 (2014)
14367e14373.
[23] M.P.F. Graa, C. Nico, M. Peres, M.A. Valente, T. Monteiro, J. Nanosci. Nanotechnol. 12 (2012) 1e7.
[24] M.P.F. Graa, P.R. Prezas, M.M. Costa, M.A. Valente, J. Sol Gel Sci. Technol. 64
(2012) 78e85.
[25] R.A. Young, The Rietveld Method, Oxford University Press, New York, 1993.
[26] C. Nico, R. Fernandes, M.P.F. Graa, M. Elisa, B.A. Sava, R.C.C. Monteiro, L. Rino,
T. Monteiro, J. Luminescence 145 (2014) 582e587.
[27] H.M. Rietveld, J. Appl. Crystallogr. 2 (1969) 65.
[28] M. Popa, J. Frantti, M. Kakihana, Solid State Ionics 154e155 (2002) 135e141.
[29] Y. Wang, J. Zhu, L. Zhang, X. Yang, L. Lude, X. Wang, Mater. Lett. 60 (2006)
1767e1770.
[30] Y.M. Choi, H. Abernathy, H.T. Chen, M.C. Lin, M. Liu, Chem. Phys. Chem. 7
(2006) 1957.
[31] C. Guo, Y. Hu, H. Qian, J. Ning, S. Xu, Mater. Charact. 62 (2011) 148e151.
[32] F.M.A. Da Costa, A.J.C. Dos Santos, Inorg. Chim. Acta 140 (1987) 105.
[33] L. Fournes, Y. Potin, J.C. Grenier, G. Demazeau, M. Pouchard, Solid State
Commun. 62 (1987) 239.
[34] K. De, R. Ray, R.N. Panda, S. Giri, H. Nakamura, T. Kohara, J. Magn. Magn. Mater.
288 (2005) 339.
[35] H.D. Zhou, J.B. Goodenough, J. Solid State Chem. 178 (2005) 3679e3685.
[36] T. Maitra, R. Valent, J. Phys. Condens. Matter 17 (2005) 7417e7431.