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Journal of Magnetism and Magnetic Materials 378 (2015) 50–53

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Journal of Magnetism and Magnetic Materials


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

Magnetic and vibrational properties of Gd2(Mo0.9W0.1O4)3 and


Gd1.8Er0.2(MoO4)3
L. Bufaiçal a,n, G. Barros b, L. Holanda b, I. Guedes c
a
Instituto de Física, Universidade Federal de Goiás, 74001-970 Goiânia, GO, Brazil
b
Universidade Federal Rural do Semi-Árido, 59900-000 Pau dos Ferros, RN, Brazil
c
Departamento de Física, Universidade Federal do Ceará, 60455-760 Fortaleza, CE, Brazil

ar t ic l e i nf o a b s t r a c t

Article history: In this work, we report on the analysis of both vibrational and magnetic properties of heavy rare-earth
Received 22 October 2014 molybdates Gd2(Mo0.9W0.1O4)3 and Gd1.8Er0.2(MoO4)3. The crystal structures, as determined by X-ray
Received in revised form powder diffraction and the Rietveld refinement analysis, established that at room temperature both of
31 October 2014
these materials belong to orthorhombic Pba2 space group. Magnetization measurements showed that no
Available online 10 November 2014
saturation is present up to 8 T at T¼ 10 K, and the magnetic susceptibility curves show paramagnetic
Keywords: behavior down to T ¼10 K. The effective magnetic moments and possible short-range magnetic inter-
Molybdates actions between Gd3 þ ions are treated and discussed. Raman spectra of both of these molybdates are
Structure similar to that of the pure compound Gd2(MoO4)3, indicating that changes in the Raman spectra due to
Magnetic properties
the introduction of either Er or W doping are negligible at the subject dopant concentrations.
Vibrational properties
& Elsevier B.V. All rights reserved.

1. Introduction changes in the magnetic and vibrational properties of Gd2(MoO4)3


when W replaces Mo and Er replaces Gd.
The rare-earth (RE) molybdate compounds of the type
RE2(MoO4)3 have been a subject of significant interest since the
1960s due to the connection between their ferroelectric and fer- 2. Experimental details
roelastic properties [1]. Generally these materials crystallize in a
tetragonal structure above 1000 °C, but on cooling, they undergo The single-phase compounds were grown by the Czochralski
phase transitions and exhibit orthorhombic Pba2 β′− structure [2]. method where Gd2O3, Er2O3, MoO3 and WO3 powders were
As a rule, the ferroelectricity and ferroelasticity in these com- weighed in stoichiometric amounts, mixed and homogenized in an
pounds are strongly connected to their low symmetry [3]. agate mortar and subjected to a first step by heating at 700 °C for
Recently, studies of magnetism for β-RE2(MoO4)3 where 10 h in an air atmosphere. The resulting powders were then
RE¼Gd Tb and Sm showed that their saturation magnetic mo- pressed into pellets and sintered at 700 °C for 10 h in air. To obtain
ments depend on the direction of magnetic field [4–6], and in the single-phase compounds, the polycrystalline seeds were then
particular for RE ¼Tb it was observed as a giant magnetic aniso- heated in Ir crucibles using a 2 kHz frequency in a Eurotherm 2604
tropy in the paramagnetic Tb2(MoO4)3 [7]. Furthermore, magneto- equipment. The x-ray powder diffraction (XRD) experiments were
electric switching effects were observed. These results indicate the performed at room temperature using a Philips Panalytical X'Pert
Pro MPD diffractometer, operating with Co-Kα radiation
existence of a magnetic mechanism that is closely related to both
(λ ¼1.7890 Å) in the Bragg–Brentano geometry. The Rietveld re-
ferroelectricity and ferroelasticity.
finements were performed with the GSAS package and its gra-
In the present research, the Czochralski method was used to
phical interface program [8,9]. Magnetometric measurements
synthesize β′− Gd2(Mo0.9W0.1O4)3 and β′− Gd1.8Er0.2(MoO4)3 com-
were carried out in the zero field cooled (ZFC) mode using a
pounds. The main goal of the present work was to investigate
Quantum Design Physical Property Measurement System (PPMS)
and a vibrating sample magnetometer (VSM). The backscattered
n
Corresponding author. unpolarized Raman spectra at 300 K were recorded on a Jobin-
E-mail address: lbufaical@ufg.br (L. Bufaiçal). Yvon Model T64000 triple spectrometer with a spectral resolution

http://dx.doi.org/10.1016/j.jmmm.2014.10.175
0304-8853/& Elsevier B.V. All rights reserved.
L. Bufaiçal et al. / Journal of Magnetism and Magnetic Materials 378 (2015) 50–53 51

Fig. 1. Observed (dots) and calculated by Rietveld method (solid lines) XRD pat-
terns at room temperature.

of 2 cm  1. The instrument was equipped with a liquid-N2-cooled


charge-coupled device system. For excitation, green 514.5 nm ra-
diation from a Coherent Model Innova 70 Ar þ -ion laser operating
at 30 mW was employed.

3. Results and discussion Fig. 2. Magnetic susceptibility and its inverse as a function of temperature for
Gd1.8Er0.2(MoO4)3 (a) and Gd2(Mo0.9W0.1O4)3 (b).

The prototype β′− Gd2(MoO4)3 crystallizes in the orthorhombic


space group Pba2 (point symmetry group mm2) with four mole- adherence to the Curie–Weiss law
cules per unit cell (Z¼4). Fig. 1 shows the observed XRD and
C
the corresponding Rietveld-calculated patterns for the β′− Gd2 χ= ,
T − ΘCW (1)
(Mo0.9W0.1O4)3 and β′− Gd1.8Er0.2(MoO4)3 compounds. Both com-
pounds crystallize with the orthorhombic space group Pba2, in- where C is the Curie constant and ΘCW is the Curie–Weiss
dicating that at these levels of doping no structural change is temperature.
observed. The quality of the refinement, estimated from χ2, Rwp The fitted values of the effective magnetic moments (μeff) and
and Rp goodness-of-fit parameters, agrees with the values found θCW are displayed in Table 2. The values of θCW at T ∼ 0 K confirm
for other rare-earth molybdates [3,10,11]. the paramagnetic character of the samples, indicating that mag-
The lattice parameters obtained from the Rietveld refinement netic ordering should occur at very low temperatures (for
are listed in Table 1. The unit cell volume of β′− Gd2(Mo0.9W0.1O4)3 is Gd2(MoO4)3 TN ≃ 0.3 K [2]).
For Gd2(Mo0.9W0.1O4)3, μeff = 5.6 μ B/RE is smaller than its ex-
slightly larger than that of β′− Gd2(MoO4)3, which is consistent
with the fact that the W6 þ ionic radius (0.42 Å) is slightly larger pected value in the ground state 8S7/2 (μeff ≃ 7 μ B/Gd3 +) [14]. This is
than Mo6 þ (0.41 Å) in tetrahedral coordination [13]. On the other likely to be associated with the magnetic anisotropy since the
hand, the unit cell volume of β′− Gd1.8Er0.2(MoO4)3 is ∼1% smaller applied magnetic field was not oriented along any particular
than that of β′− Gd2(MoO4)3 owing to the fact that Er3 þ ionic radius
(1.00 Å) is smaller than that of Gd3 þ (1.05 Å) in an 8-coordinate Table 2
site. Curie–Weiss temperatures θCW and effective magnetic moments μeff.
Fig. 2 shows the temperature-dependent behavior of the
Compound θCW (K) μeff (μB/RE)
magnetic susceptibility (χ) and its reciprocal (χ −1) for both com-
pounds. They present paramagnetic-type curves with no magnetic Gd1.8Er0.2(MoO4)3  3.3 6.1
ordering from 400 K down to 10 K. Both compounds exhibit good Gd2(Mo0.9W0.1O4)3 2.7 5.6

Table 1
Main parameters obtained from the Rietveld refinement.

Compound a (Å) b (Å) c (Å) V (Å3) Rp (%) Rwp (%) χ2

Gd1.8Er0.2(MoO4)3 10.3606(3) 10.3855(3) 10.6657(2) 1147.6(1) 14.7 21.6 4.8


Gd2(Mo0.9W0.1O4)3 10.3916(2) 10.4226(2) 10.7001(2) 1158.9(1) 13.2 19.2 3.0
Gd2(MoO4)3a 10.3858(1) 10.4186(1) 10.7004(1) 1157.8(1) 9.3 14.2 5.8

a
Extracted from [12].
52 L. Bufaiçal et al. / Journal of Magnetism and Magnetic Materials 378 (2015) 50–53

that thermal energy acts to avoid the magnetic saturation, this


result indicates the presence of magnetic anisotropy since the
samples were not crystallographically oriented to the applied
magnetic field. This is a usual behavior of heavy rare-earth mo-
lybdates [2,7]. Another possibility is the occurrence of short-range
antiferromagnetic (AFM) interactions between rare-earth ions at
low temperatures.
In Fig. 4(a)–(c) we show the un-polarized Raman spectrum of
Gd2(MoO4)3, Gd1.8Er0.2(MoO4)3 and Gd2(Mo0.9W0.1O4)3, respec-
tively. These are very similar since the lattice distortions owing to
the Er and W doping are nearly negligible. Because of the tightly
bound MoO4 tetrahedra in RE2(MoO4)3, a simplified structure can
be considered as being composed of two sub-lattices of Re ions
and MoO4 “molecules”, with both Re and MoO4 occupying the C1
point-symmetry site. As an isolated entity, the MoO4 tetrahedron
has four distinct internal vibrational modes ν1, ν2, ν3 and ν4 which
correspond to symmetric stretch, symmetric bending, anti-sym-
metric stretch, and anti-symmetric bending, respectively.
Group Theory analysis predicts 201 optical-active modes,
Fig. 3. Magnetization as a function of applied magnetic field at 10 K.
where 93 are associated with translation-like (T) and rotation-like
(R) external modes that involve both the RE and MoO4 ions, and
crystallographic axis. The low positive θCW value obtained for this
108 are internal modes of the MoO4 tetrahedra. According to Lu-
compound may be associated to a small ferromagnetic contribu-
cazeau and Machon [16] the Raman spectrum of RE2(MoO4)3 can
tion due to a canting effect or even due to ferrimagnetic interac-
be divided into three regions: (i) a low-wavenumber region
tions between rare-earth ions, as previously proposed for
(10–250 cm-1) which contains the T and R modes of MoO4 tetra-
RE2(MoO4)3 compounds [15].
hedra as well as the T modes of RE ions, (ii) a middle-wavenumber
The increase of μeff for Gd1.8Er0.2(MoO4)3 was expected since
region (250–400 cm-1) where the bending modes ν2 and ν4 ap-
Er3 þ has a larger effective magnetic moment in the ground state
pear, and (iii) the high-wavenumber region (740–1000 cm  1)
4
I15/2/(μ Er 3 + ≃ 9 μ B) than Gd3 þ [14]. The differences observed are which displays the stretching modes ν1 and ν3.
either related to deviations from the paramagnetic behavior due to The modes appearing in the regions (i) and (ii) are broad and
short-range interactions [15], and/or due to thermal excitation of overlapping which makes their assignment very difficult. This also
some ions to different J states at high temperatures [14]. happens in the region of the ν3 modes. In fact, the only modes that
Fig. 3 shows the field dependence of magnetization at 10 K. No can be unambiguously assigned are those appearing at 944 and
magnetic saturation (Ms) is observed up to 8 T. Surprisingly, the 960 cm  1 and assigned as ν1 vibrations. Recall that there are three
magnetization for Gd2(Mo0.9W0.1O4)3 is larger than that of MoO4 tetrahedra in the unit cell of the orthorhombic Pba2 struc-
Gd1.8Er0.2(MoO4)3. The magnetic ordering on RE2(MoO4)3 com- ture. Therefore, three ν1 vibrations are supposed to be observed
pounds is expected to occur below 1 K [2], and despite the fact and not two as shown in Fig. 4(a)–(c). However, for two out of

Fig. 4. Un-polarized Raman spectrum of (a) Gd2(MoO4)3, (b) Gd1.8Er0.2(MoO4)3 and (c) Gd2(Mo0.9W0.1O4)3.
L. Bufaiçal et al. / Journal of Magnetism and Magnetic Materials 378 (2015) 50–53 53

three tetrahedra, the MoO4 distances are very close [10], and their The authors are indebted to L.A. Boatner of the Oak Ridge National
wavenumbers are degenerate and correspond to the vibration at Laboratory for providing the samples and a careful reading of the
∼944 cm−1. paper.

4. Conclusions References

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Acknowledgments

This work was supported by the Brazilian Funding Agencies


CNPq (Grants nos. 470.613/2012-2 and 304173/2011-8), and Capes.