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Journal of Magnetism and Magnetic Materials: K. Bouziane, A. Yousif, H.M. Widatallah, J. Amighian
Journal of Magnetism and Magnetic Materials: K. Bouziane, A. Yousif, H.M. Widatallah, J. Amighian
Journal of Magnetism and Magnetic Materials: K. Bouziane, A. Yousif, H.M. Widatallah, J. Amighian
Site occupancy and magnetic study of Al3+ and Cr3+ co-substituted Y3Fe5O12
K. Bouziane a,, A. Yousif a, H.M. Widatallah a, J. Amighian b
a
Department of Physics, College of Science, Sultan Qaboos University, P.O. Box 36, PC 123, Muscat, Sultanate of Oman
b
Department of Physics, University of Isfahan, Isfahan, Iran
a r t i c l e in f o a b s t r a c t
Article history: Single-phased polycrystalline Y3Fe52xAlxCrxO12 garnet samples (x 0, 0.2, 0.4 and 0.6) have been
Received 25 August 2007 prepared by the conventional ceramic technique. Rietveld renement of X-ray diffraction patterns of the
Received in revised form samples shows them to crystallize in the Ia3d space group and the corresponding lattice constant to
4 March 2008
decrease with increasing Al3+ and Cr3+ contents (x). Mossbauer results indicate that Cr3+ substitutes for
Available online 10 May 2008
Fe3+ at the octahedral sites whilst Al3+ essentially replaces Fe3+ at the tetrahedral sites. This result
Keywords: indicates that co-doping of Y3Fe5O12 does not affect the preferential site occupancy for separate
Garnet individual substitution of either Cr3+ or Al3+. The magnetization measurements reveal that the Curie
Co-substitution temperature (Tc) monotonically decreases with increasing x while the magnetic moment per unit
Site occupancy
formula decreases up to x 0.4 and then slightly increases for x 0.6. This reects a progressive
Magnetism
weakening of the ferrimagnetic exchange interaction between the Fe3+ ions at octahedral and
tetrahedral sites due to co-substitution. The magnetic moment was calculated using the cations
distribution inferred from the Mossbauer data and the collinear ferrimagnetic model, and was found to
agree reasonably with the experimentally measured value. The phenomenological amplitude crossover,
characterized by the temperature T*, has also been observed in the doped YIG and briey discussed.
& 2008 Elsevier B.V. All rights reserved.
1. Introduction types of doping of Fe3+ sites have been performed. Among others,
substitution of magnetic Fe3+ by nonmagnetic Al3+ has shown
Since its discovery in 1956, yttrium iron garnet (YIG) and interesting features [6]. It was shown that Al3+ goes to the
substituted-YIG have attracted a lot of attention because of their tetrahedral 24d sites in Al-doped YIG [7,8] whereas Cr3+
application in microwaves domain [1] and magneto-optical preferentially occupies the unexpected octahedral site, which is
devices [2]. YIG has the chemical composition {Y3}[Fe3+ 3+
2 ]a(Fe3 )d attributed to the electronic conguration of Cr3+ [7,9]. On co-
O12, where Y ions occupy the dodecahedral site with 12 substituting nonmagnetic Al3+ and magnetic Cr3+ for Fe3+ ions
O2 ligands, a represents the octahedral site with six O2 ligands, [10], it was reported that Cr3+ and 60% of Al3+ ions go to the
and d the tetrahedral site with four O2 ligands. Its crystal tetrahedral sites whereas the remaining 40% of Al go to octahedral
structure is described in the cubic space group Ia3d by Bonnet sites. However, a recent study [11] showed both Cr3+ and Al3+
et al. [3] and in the trigonal space group R3 by Rodic et al. [4], to substitute for Fe3+ in the octahedral sites only. Therefore, the site
account for the lowering of symmetry due to spontaneous occupancy of both Cr3+ and Al3+ in YIG is controversial. It is to be
magnetostriction. YIG is ferrimagnetic with two magnetic a and mentioned that the cation distribution in the latter two studies
d sublattices of Fe3+ that are coupled antiparallelly. It is well was based on measurements at room temperature of either
established that composition modication alters the magnetic magnetization [10] or Mossbauer spectroscopy [11].
properties of garnets by magnetic dilution associated with the The canting effect induced by substitution of magnetic ions by
replacement of Fe3+ ions by diamagnetic ions of approximately non-magnetic or less magnetic ones leads to a decrease on one
the same size and by magnetoelastically active ion substitutions site of the effective exchange [12]. In fact, this phenomenon is
usually in small concentration [5]. Also, monitoring the selective very sensitive to local disorder and inhomogeneities in the
site doping can shed light on the magnetism of each sublattice substitutions. It can lead to various local canted structures with
from fundamental point of view as well as enable control of different hyperne elds, but the thermal disorder can only make
physical properties for applications purposes. Various levels and the difference when the balance of the exchange interactions is
close to the canting condition. However, the magnetic ordering of
ferrites like YIG changes signicantly from its arrangement at
Corresponding author. Tel.: +968 24415489; fax: +968 24414228. room temperature, as shown for x 0.4 and x 0.6 in this study.
E-mail address: bouzi@squ.edu.om (K. Bouziane). In particular, the thermal disorder would reduce the net
0304-8853/$ - see front matter & 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2008.04.163
ARTICLE IN PRESS
K. Bouziane et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 23302334 2331
magnetization, making the Neels collinear ferrimagnetic model to a cubic structure (space group Ia3d), reecting that the
not valid. For example, the cations distribution reported by compounds are single-phased. The lattice constant decreases
Lahlooh et al. [11] for Y3Fe52xAlxCrxO12 garnets would lead to with increasing concentration x of the doped ions as shown in
magnetic moment inconsistent with that obtained from magne- Fig. 2. Such a decrease in the lattice parameters is generally
tization measurements reported in this study. In this work, three attributed to the smaller ionic radii of Al3+ and Cr3+ relative to that
techniques, namely, X-ray diffraction, low temperature magneti- of high-spin Fe3+ ions at both tetrahedral and octahedral sites. It is
zation and Mossbauer spectroscopy, were employed to clarify the interesting to note that the lattice constant does not decrease
site preference of Cr3+ and Al3+ ions in Y3Fe52xAlxCrxO12 garnets. linearly, in line with the Vegrads law, as expected when both Al3+
It is shown that the preferential sites occupancy for Al and Cr in and Cr3+ substitute Fe3+ ions at either site. While Cr3+ ions are
co-doped YIG remains nearly identical to that corresponding to known to have a strong octahedral site preference [7,9], the
separate doping of either Cr3+ or Al3+ in YIG. decrease, though limited, in the lattice parameters with increasing
x value suggests that Al3+ ions do partly replace tetrahedral Fe3+
ones. The smaller tetrahedral ionic radius of Al3+ (0.53 A) relative
2. Experimental to that of tetrahedral Fe3+ (0.69 A) supports this view [13]. It
should be noted that the Rietveld analysis of the spectrum of
Samples with nominal composition Y3Fe52xAlxCrxO12 (x 0, sample x 0.4 has also revealed the presence of a very minor
0.2, 0.4 and 0.6) have been prepared by the conventional ceramic phase (67%) that was not identied but possibly magnetic
technique. The starting materials Y2O3, Fe2O3, Al2O3 and Cr2O3 (such as traces of YCrO3 or a-Fe2O3 impurity phases [9]), which
were weighted in appropriate proportions and wet-mixed for 1 h can be at the origin of the relatively larger broadening of the
in acetone to obtain homogeneous mixtures. The mixtures were Mossbauer spectrum as shown below.
dried and then calcined at 1200 1C for 10 h followed by mechanical The magnetization curves recorded at room temperature of the
milling for 1 h to get homogeneous sub-micronic powders. The four samples are shown in Fig. 3. It can be noticed that the
powders were pressed in blocks under 2 tons/cm2 using polyvinyl
alcohol (PVA) as binder and then sintered in oxygen atmosphere
at 1400 1C for 10 h. The sintered blocks were crushed into powder 12.38
and then annealed at 700 1C for 2 h.
The crystalline nature of the resulting compounds was
analyzed using a Philips PW 1700 X-ray diffractometer with a 12.36
Lattice constant, a (A)
30 x=0
0.2
x = 0.6
Intensity (arb. units)
20 0.4
0.6
x = 0.4 10
M (emu/g)
0
x = 0.2
640
642
-10
400
422
642
420
444
800
521
532
840
864
440
331
321
431
x=0
-20
30 40 50 60 70 80 -30
2 (deg) -15 -10 -5 0 5 10 15
H (kOe)
Fig. 1. Powder X-ray diffraction patterns of Y3Fe52xAlxCrxO12 garnet samples. The
symbol (*) indicates the presence of a non-identied impurity phase for x 0.4. Fig. 3. Room temperature hysteresis loops of Y3Fe52xAlxCrxO12 garnet samples.
ARTICLE IN PRESS
2332 K. Bouziane et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 23302334
Temperature (K)
0 100 200 300 400 500 600 reecting a decrease of the exchange coupling. The magnetic
40 moment mmes decreases almost linearly with x up to x 0.4 and
then slightly increases for x 0.6. This trend was not observed in
M(H) values at room temperature (Fig. 3) and suggests a certain
30
relative partial occupancy of both doped ions at either octahedral
or tetrahedral sites for xX0.4. Since Y3+ is known to be non-
20 magnetic in YIG systems, added to the fact that there is no doping
Magnetization at 13.5 kOe (emu/g)
K. Bouziane et al. / Journal of Magnetism and Magnetic Materials 320 (2008) 23302334 2333
Y3Fe5-2xAlxCrxO12 54 46.5
B hf -Octa
B hf -Tetra
x=0
4%
53
300
x = 0.2 45.5
T (K)
250
Absorption
3%
200
400 500 600
Tc (K)
52 45.0
x = 0.4
220 240 260 280 300
T (K)
2% Fig. 7. The hyperne elds at a and d sites for various x contents. Inset is the
amplitude crossover temperature T* versus Curie temperature.
x = 0.4
References
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