Tuning the cation distribution and magnetic properties of single phase nanocrystalline

Dy3Fe5O12 garnet
M. Guillot, C. N. Chinnasamy, J. M. Greneche, and V. G. Harris

Citation: Journal of Applied Physics 111, 07A517 (2012); doi: 10.1063/1.3679020

View online: http://dx.doi.org/10.1063/1.3679020
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 JOURNAL OF APPLIED PHYSICS 111, 07A517 (2012)

Tuning the cation distribution and magnetic properties of single phase

nanocrystalline Dy3Fe5O12 garnet
M. Guillot,1,a) C. N. Chinnasamy,2 J. M. Greneche,3 and V. G. Harris2
1
Laboratoire National des Champs Magnetiques Intenses, CNRS BP 166, 38042 Grenoble, France
2
Department of Electrical and Computer Engineering, Northeastern University, Boston, Massachusetts 02115,
USA
3
Laboratoire de Physique de LEtat Condense, UMR CNRS 6087, Universite du Maine 72085 Le Mans Cedex
9 France
(Presented 31 October 2011; received 22 September 2011; accepted 30 November 2011; published
online 21 February 2012)
Synthesizing single phase nanocrystalline rare earth iron garnet is difficult owing due to its complex
crystal structure. In this report, single phase Dy3Fe5O12 nanoparticles with different grain sizes (50, 32,
and 22 nm) were prepared using the ball milling technique in a controlled atmosphere. The average
grain size decreases with milling time, and reaches 22 nm after 30 h of milling. The magnetization for
the as-prepared micron sized Dy3Fe5O12 is in quasi-perfect agreement with the single crystal values,
and all the Fe and Dy ions are in trivalent state. When the grain size is reduced below 50 nm (10 h), the
magnetization strongly depends upon the applied field, and no saturation is observed even at an applied
field of 280 kOe. The compensation temperature (Tcomp) for the nanocrystalline Dy3Fe5O12 samples are
a few degrees higher than that of the bulk. There is no evidence for the presence of Fe2 charge state in
the as-prepared garnets. However, Mossbauer spectroscopy studies show that about 1415 at. % Fe2
content was found in the 30 h (22 nm) milled sample at 77 K. Oxygen vacancies created during milling
induces the presence of Fe2 ions in the nanocrystalline Dy3Fe5O12 particles. V C 2012 American

Institute of Physics. [doi:10.1063/1.3679020]

I. INTRODUCTION coercivity, and enhanced Neel temperature has been

Rare earth iron garnets (REIG) with the chemical formula
R3Fe5O12 (where R is a rare earth cation) are promising materi-
als for use in high performance microwave and electrochemical
devices owing to their high resistivity, high Curie temperature,
and high chemical stability; they also possess unique magnetic,
optical, thermophysical, and mechanical properties.13 The
rare-earth iron garnets are ferrimagnetic compounds,4,5 in
which the two inequivalent 16 a and 24d iron(III) sites are anti-
ferromagnetically coupled and, for the heavier rare-earth ions,
the resultant net iron moment is antiferromagnetically coupled
with the 24 c rare earth magnetic moment. The magnetization
is usually oriented along the [111] direction of the cubic unit
cell, but spin reorientations occur6 at low temperatures for
Dy3Fe5O12. The opposed net iron and rare-earth magnetic
moments compensate each other at the compensation tempera-
ture, a temperature which can be varied through an appropriate
substitution of the trivalent rare-earth ion, in order to satisfy
specific technological applications. Due to the complex crystal
structure of REIG, synthesizing the single phase nanocrystal-
line REIG is more difficult compared with the synthesis of spi-
nel ferrites. In spinel ferrites, the grain size reduction induces
(i) the competition between the ferro- and antiferromagnetic
exchange interactions arising from Fe clustering, (ii) breaking
of superexchange bonds, (iii) spin canting, and (iv) Fe2
charge state due to oxygen vacancies while ball milling. As a
result, the change in cation distribution, magnetization,
a)
Author to whom correspondence should be addressed. Electronic mail:
maurice.guillot@grenoble.cnrs.fr.
observed.710 However, there are few reports available in the
literature about the structural and magnetic properties of single
phase nanocrytalline REIG garnets.11,12 Recently, we have
proved that the synthesis of single phase nanocrystalline
Gd3Fe5O12 by ball milling leads to a partial reduction of Fe3
to Fe2 due to milling, and hence the cation distribution was
changed compared with the bulk Gd3Fe5O12.13 Also, the grain
size dependent magnetic and magnetocaloric properties were
studied in nanocrystalline Gd3Fe5O12.13,14
II. RESULTS AND DISCUSSION
Dy3Fe5O12 particles were synthesized in polycrystalline
form by the solid-state reaction method from a mixture of
a-Fe2O3 (Sigma Aldrich, 99.99%) and Dy2O3 (Sigma Aldrich,
99.9%) in nominal compositions of 5:3. Milling of the
as-prepared particles was carried out for different durations in
a controlled atmosphere using a planetary ball mill (Fritsch
Pulverisette, P6). The crystal structure was characterized by
x-ray powder diffraction using Cu-Ka radiation (k 1.5404 A,
Rigaku Dimax 2000). dc magnetization studies were carried
out using a custom fabricated magnetometer under a high con-
tinuous magnetic field of up to 280 kOe using the extraction
technique in the range of 4300 K at the Grenoble High
Magnetic Field Laboratory, CNRS, Grenoble, France. The
57
Fe Mossbauer spectrometry studies were carried out at
300 K and 77 K using a constant acceleration Mossbauer spec-
trometer with a source of 57Co (25 mCi) diffused into a Rh
matrix. Natural iron foil was used as a standard for velocity
calibration. The x-ray diffraction patterns in Fig. 1(a) indicate

0021-8979/2012/111(7)/07A517/3/$30.00 111, 07A517-1 C 2012 American Institute of Physics

V

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 07A517-2 Guillot et al.
that the as-prepared and milled samples have the cubic struc-
ture and the lattice parameters in agreement with the literature
values.1 The surface morphology of the as-prepared samples
show the micron sized particles as shown in Fig. 1(b). The
milled Dy3Fe5O12 garnet particles retain their single phase
structure (JCPDS-23-0237). No RFeO3 (Rrare earth) ortho-
ferrite phase was detected by x-ray diffraction in any of the
milled samples. It should be noted that the peaks of the milled
samples for the (420) line exhibit a smaller shift toward a
lower angle with respect to those of the bulk as shown in Fig.
1(a). The (420) peak broadening increases with milling time
due to the redistribution of grain size and increase in the
atomic level strain. The lattice parameter for the milled sam-
ples increases with milling time due to the lattice expansion
(from 0.5299 nm for the bulk to 0.5309 nm for the 30 h milled
sample) as a result of the cation distribution and mechanically
induced stress. The average grain size was determined by
using the Scherrer formula from the full width at half maxi-
mum of the (420) diffraction peak for different milling times.
The average grain size for the as-prepared, 10, 20, and 30 h
milled samples were 100, 50, 32, and 22 nm, respectively.
The first quadrant hysteresis loops measured at 100 and
4 K are shown in Figs. 2(a) and 2(b) respectively. The meas-
ured magnetization value for the as-prepared Dy3Fe5O12 is
in quasi-perfect agreement with the single DyIG crystal
values; that confirms that all the Fe and Dy ions are in triva-
lent state. When the grain size is reduced below 50 nm
(10 h), the magnetization becomes strongly applied-field
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J. Appl. Phys. 111, 07A517 (2012)
FIG. 1. (Color online) (a) X-ray diffrac-
tion pattern of the bulk and ball-milled
Dy3Fe5O12 and (b) SEM-surface morphol-
ogy of the as-prepared (bulk) Dy3Fe5O12.
dependent, and no saturation is observed even at 280 kOe.
The coercivity of the nanocrystalline samples was signifi-
cantly increased at low temperatures compared with the bulk
sample. For example, the coercivity of the 30 h (22 nm)
milled sample was found to be about 2.25 kOe at 4.2 K (not
shown in Fig. 2(a)) compared with the coercivity of 100 Oe
for the as-prepared Dy3Fe5O12. Magnetocrystalline anisot-
ropy, surface anisotropy and shape anisotropy may all con-
tribute to such a high coercivity in the 50 nm DyIG
nanocrystalline particles. The magnetization (M) versus tem-
perature (T) was measured for all the samples from 4.2 K to
room temperature as shown in Figs. 2 (a) and 2(b). It is noted
immediately that the grain size decreases from 100 to 22 nm
lower magnetization values are observed whatever the field is.
To take into account the curvature of each isothermal MT(H)
two values of the spontaneous magnetization were deter-
mined: (i) MSpont (1) was deduced from the extrapolation to
zero applied field by fitting of the M(H) variations to a quad-
ratic H function (the quality of the fit is better than 0.5%) and
that in the 2060 kOe range; (ii) MSpont (2) results from the
extrapolation to zero applied field of the M variations in the
120280 kOe high field range (using a quadratic function of H
again). On the other hand in the 150280 kOe field range the
magnetization curves of the different milled samples are well
described (within 61%) by the law of approach to saturation
M MSat(1  b/H2) when T is smaller than about 150 K;
above this temperature M(H) curves become more and more
linearly H dependent and the determination of the saturation
FIG. 2. (Color online) First quadrant
magnetization curves for the various
hours milled Dy3Fe5O12 nanoparticles at
(a) 4.2 K and (b) 100 K.
 07A517-3 Guillot et al.
FIG. 3. (Color online) Saturation magnetization and spontaneous magnet-
ization (see text) vs the grain size for the bulk and milled Dy3Fe5O12 sam-
ples at 4.2 K (full symbols) and 100 K (empty symbols), respectively.
magnetization is no more accurate. When the grain size is
reduced below 100 nm MSpont (1) and MSpont (2) decrease. At
100 K we note that MSpont (1) and MSpont (2) are a linear func-
tion of the grain size (Fig. 3). On the contrary MSat appears
sensitive to the grain size only when the grains are smaller
than 50 nm (Fig. 3); this conclusion is valid at 4.2 K and at
100 K. One can also observe that there is a weak but noticea-
ble change in the compensation temperature (Tcomp). Tcomp
for the nanocrystalline Dy3Fe5O12 samples are few degrees
higher. The same effect was observed in nanostructured GdIG
samples.13 The 57Fe Mossbauer spectra were recorded at
300 K and 77 K for the as-prepared and 30 h (22 nm) milled
samples and a representative Mossbauer spectrum is shown in
Fig. 4. Due to space constraints, the detailed analysis of the
results will be presented elsewhere. The spectra were least-
square fitted, and the refined values of the hyperfine parame-
ters were then determined. For the as-prepared Dy3Fe5O12,
the spectra were described by means of three sextets corre-
sponding to three different Fe3 environments ([12a1 and 4a1]
and (24 d) sites, respectively). There is no evidence for the
presence of the Fe2 charge state in the as-prepared garnets.
On increasing the milling time, one observes the progressive
occurrence of a central quadrupolar feature at both 300 and
77 K, in addition to three magnetic sextets (at 77 K) with
decreasing intensity but increasing linewidth compared to that
of the as-prepared sample. These later components are unam-
biguously attributed to crystalline DyIG phase with structur-
ally disordered Fe3 environment induced during milling. The
quadrupolar feature has to be decomposed at both tempera-
tures into two broad line quadrupolar doublets. They are char-
acterized by two different isomer shift values which allow the
presence of ferric and ferrous species to be identified; it is im-
portant to emphasize that the intensity of the ferric doublet is
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J. Appl. Phys. 111, 07A517 (2012)
FIG. 4. (Color online) Mossbauer spectrum of the 30 h (22 nm) milled
Dy3Fe5O12 sample measured at 77 K.
systematically higher at 300 K. The Fe2 content was found
equal to about 1415 at. % in the 30 h(22 nm) milled sample,
to about 10 at. % in the 20 h(32 nm) milled sample and to
about 6 at. % in the 10 h(50 nm) milled sample, respectively.
In the three milled samples the Fe2 content values are not
modified by the temperature (300 and 77 K). The grain size
reduction due to milling induces the oxygen vacancies, and
hence some of the Fe3 ions converted to Fe2 ions as previ-
ously reported in milled ZnFe2O4 and Gd3Fe5O12 sam-
ples.10,13 The modified formulae of our DyIG particles is
given by Dy33Fe 5x3Fex2O212z taking into account the
presence of oxygen vacancies related to the Fe2 content (x).
15 at. % Fe2 content corresponds to z 0.375, i.e., only less
than 3% of oxygen vacancies.
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