Journal of the Korean Physical Society, Vol. 41, No. 2, August 2002, pp.

232∼235

Mössbauer Spectroscopy on the Magnetic Hyperfine Interaction of

Nonstoichiometric Europium Iron Garnet

J. G. Kim,∗ S. H. Song, and K. H. Han

Department of Physics, Hanyang University, Seoul 133-791

J. S. Lee
Department of Metallurgy and Material Science, Hanyang University, Ansan 425-791

(Received 15 February 2002)

The microscopic physical properties of the nonstoichiometric garnet Eu1−x Fe1+x O3 (x=0.2) have
been studied by using X-ray diffraction at room temperature and Mössbauer spectroscopy within
the temperature range from liquid nitrogen temperature to 560 K. The X-ray diffraction patterns of
the sample show coexistence of dominant garnet and a small portion of an unknown crystal phase.
However, the Mössbauer spectrum for the sample near the Néel temperature, which was 549±5 K,
shows that, within experimental errors, there were no other crystal phases. The average area ratio of
a- to d-sites for the sample was 0.76, which implies the possibility of some vacancies exsisting at the
a- and/or the d-sites. The temperature dependence of the magnetic hyperfine fields was analyzed by
using the spin-wave theory and the molecular-field model. From the analysis, the average strength
of the interaction and the molecular-field coefficients were determined to be 37.484 K and (−60.0,
95.5, −29.8)(mole/cm3 ), respectively. From the relations among molecular-field coefficients, the ion
distribution at the a- and the d-sites was {Eu3 }[Fe1.95 ](Fe2.82 )O12 .

PACS numbers: 75.50.Gg

Keywords: Ferrimagnetics, Mössbauer, Molecular field theory, Nonstoichiometric garnet, Spinwave theory

I. INTRODUCTION ments affecting the physical properties of a system. Also,

Iron garnets have attracted much attention because
of their interesting magnetic properties [1–8]. The gen-
eral chemical structural formula for europium iron gar-
net (EuIG) is Eu3 Fe5 O12 or Eu1−x Fe1+x O3 (x=0.25).
The X-ray diffraction data show that EuIG belongs
h
to the space group O10 − Ia3d with an overall cu-
bic symmetry. The unit cell contains 8 formula units
{Eu3}[Fe2](Fe3)O12, where { }, [ ], and ( ) represent
a dodecahedral c-site, an octahedral a-site, and a tetra-
hedral d-site, respectively. Because the site preference
of the cations in the lattice is essentially determined by
their ionic radius, Eu3+ , Fe3+ and Fe3+ ions occupy the
c-, a-, and d-sites, respectively [1,2]. The superexchange
antiferromagnetic interaction between the trivalent iron
ions at the a- and the d-sites causes the garnet to be fer-
rimagnetic [3,4]. Accordingly, the cation distribution at
the a- and the d-sites of garnet is expected to be the most
important factor affecting the character of the magnetic
properties of the sample.
It is well known that the Mössbauer method is useful
for obtaining information about the microscopic environ-
∗ E-mail: kjgsldx@hanyang.ac.kr
-232-
the method is utilized to determine the magnetization in
terms of the magnetic field produced at the nuclei itself
without an externally applied field. The purpose of this
study is to carry out X-ray and Mössbauer spectroscopic
measurements on nonstoichiometric europium iron gar-
net Eu1−x Fe1+x O3 (x=0.2) to observe the changes in the
Mössbauer parameters by using some appropriate mod-
els and to examine the site preference of cations in the
sample.
II. EXPERIMENT
The sample was synthesized by using the usual ce-
ramic method [5,6] with Fe2 O3 and Eu2 O3 starting ma-
terials with purities better than 99.999 %. The X-ray
diffraction(XRD) pattern of the sample at room temper-
ature was obtained by using a Rigaku diffractometer with
CuK α radiation. The Mössbauer spectra were recorded
using an Austin constant acceleration Mössbauer spec-
trometer with a 10 mCi 57 Co source in a Rh matrix and
were measured at various absorber temperatures from
liquid nitrogen temperature to 560 K. To produce a uni-
form thickness of 57 Fe of approximately 0.12 mg/cm2
Mössbauer Spectroscopy on the Magnetic Hyperfine Interaction· · · – J. G. Kim et al.
Fig. 1. X-ray diffraction patterns of the sample.
over the area of the Mössbauer absorber, we mixed the
sample with boron-nitride powder and clamped it be-
tween two thin boron-nitride plates.
III. RESULTS AND DISCUSSION
As shown in Fig. 1, the X-ray diffraction patterns
of the sample show a coexistence of the dominant gar-
net and a small amount of an unknown crystal phase.
The lattice constant of the garnet phase was 12.484 Å.
This value of the lattice constant of the garnet phase
can be compared with the value of 12.498Å [2]. Some of
Mössbauer spectra for the sample below the Néel tem-
perature are shown in Fig. 2. The spectra of the sample
below Néel temperature were fitted to a mixed electric
quadrupole plus magnetic hyperfine pattern. The widths
that were assummed to be the same in respective sub-
spectra, and the overall absorption areas of the spectra
were independently varied as free parameters. However,
within the subspectra, the following constraints for the
areas of spectrum were imposed:
Ai,a = bd Ai,d ,
Ai = A7−i , (1)
where bd is the best-fit parameter, a and d are the spec-
tra for the a- and the d-sites and i goes from 1 to 3. The
absorption area of the subspectra for each site is pro-
portional to the concentration of Fe ions using the value
of the recoilless fractional ratio (fa /fd =0.94) [7] of a-
to d-subspectra for YIG at room temperature. Accord-
ingly, an ideal area ratio of a- to d-sites must be 0.627.
The average area ratio of the sample in the experimental
temperature range was 0.76, which implies the possibility
of some vacancies exisiting at the a- and/or the d-sites.
Figure 3(a) shows the Mössbauer spectrum for the sam-
ple near the Néel temperature TN and indicates that no
extra crystal phase appears in the X-ray diffraction pat-
terns. The isomer shifts at room temperature are found
to be 0.421 mm/s (a-site) and 0.197 mm/s (d-site) rela-
tive to Fe for the sample, which indicate Fe3+ . The Néel
-233-
Fig. 2. Mössbauer spectra of the sample at various tem-
peratures.
temperature for the sample was 549±5 K. The values of
the quadrupole interaction e2 qQ/2 for the sample were
0.387 and 0.891 mm/s for the a- and the d-sites, respec-
tively. They can be compared with the values of 0.408
(a-site) and 0.872 mm/s (d-site) for EuIG [8]. Figure
3(b) shows the spectrum of the sample at room tempera-
ture. The a-site line of the spectrum was fitted with two
sextets, ai and ai0 , under the assumption that there are
two possible angles between the principal axis of the elec-
tric field gradient and the magnetic field in the sample.
The area ratio of the two a-site lines which is expected
to be 3 [9,10], was 3.459.
Kubo [11] and Oguchi [12] calculated the temperature
dependence of the antiferromagnetic sublattice magne-
tization by using the spin-wave theory with negligible
anisotropy. Their result can be expressed as
"  2  4  6#
kT kT kT
H(T ) = H(0) 1 − A1 −A2 −A3 ,
J J J
(2)
where H(0) is the magnetic hyperfine field at 0 K. A1 ,
A2 , and A3 are constants, and their respective values are,
according to Oguchi’s model [12], 1.528×103 , 2.572×105 ,
and 2.007×108 for an orthoferrite, respectively. The
T 2 term in Eq. (2) represents the excitation of long-
wavelength spin waves deduced from Kubo’s “simple
spin-wave theory” [11], and the last two terms are given
-234- Journal of the Korean Physical Society, Vol. 41, No. 2, August 2002
Fig. 3. Mössbauer spectrum near (a) the Néel temperature
and at (b) room temperature, where the a-site line of the
spectrum was fitted with two sextet, ai and ai0 , under the
assumption that there are two possible angles between the
principal axis of the electric field gradient and the magnetic
field in the sample.
by Oguchi’s correction terms due to spin-wave interac-
tions. J represents the strength of the interaction be-
tween neighboring magnetic ions in the sample and pro-
vides a measure of the range of the magnetic interaction
[13,14].
The experimental data of the fields at the a- and the d-
sites for the sample were analyzed with the sum of terms
to order T 2 and to order T 4 in Eq. (2) by using a least-
square fitting program and best-fit constants A1 and A2
satisfying |Jd−a |/k = 36.44 K for DyIG [15]. From the
analysis, the average strength of interaction, |Jd−a |/k,
for the sample was 37.484 K, which is larger than the
value for other iron garnets [6, 15]. The result for the
temperature dependence of the fields is shown in Fig. 4.
As shown, a good fit was obtained to the experimental
values over a the wide range of temperatures T < 450 K
(∼ T 4 ), for the sample [16,17].
Fig. 4. Temperature dependence of the magnetic hyperfine
fields from the sum of the terms to order T 4 . A good fit
was obtained to the experimental values over a wide range of
temperatures.
Fig. 5. Reduced temperature dependence of the reduced
magnetic hyperfine fields obtained by using the molecular-
field theory (curves 1 and 2) and the equation (TC -T )β
(curves 3 and 4) for (a)the sample and for (b)DyIG[20].
In the Néel theory of ferrimagnetism, the temperature
dependence of the magnetic moment per mole of each
sublattice [18] may be expressed in terms of Brillouin
functions as
Ma (T ) = Ma (0)Bsa (xa ),
Md (T ) = Md (0)Bsd (xd ), (3)
in which the subscript a and d refer to the a and the
d sublattices these sublattices containing Fe3+ as a the
magnetic ion, where
xa = (Sa gµB /kT )(Nad Md (T ) + Naa Ma (T )),
xd = (Sd gµB /kT )(Ndd Md (T ) + Nda Ma (T )). (4)
In these equations Nad , Nda = Nad , and Ndd are the
molecular-field coefficients, Sa and Sd are the spin quan-
tum numbers (5/2 for Fe3+ ), g, the spectroscopic split-
ting factor, is equal to 2, µB is the Bohr magneton, and
k is the Boltzmann constant. The magnetic moments
per mole at 0 K can be expressed as
Ma (0) = 2gSa µB , N
Md (0) = 3gSd µB N, (5)
in which N is the Avogardro’s number while the factors
2 for (a) and 3 for (d) are the multiplicities of the Fe3+
ions per formula unit at the respective sites. From Eqs.
(3) and (4), the molecular fields are defined (in Gauss)
by
Hd = Ndd Md (T ) + Nda Ma (T ),
Ha = Nad Md (T ) + Naa Ma (T ). (6)
For a set of (p = Ndd /Nad , q = Naa /Nad ) values, Eqs.
(3) and (6) can be simultaneously solved to obtain Ma
and Md as functions of T /TN for the sample. Figure 5(a)
(curves 1 and 2) shows the result of the analysis for the
sample. The best-fit (p, q) was (−0.312, −0.628), and the
molecular-field coefficients (Naa , Nad , Ndd )(mole/cm−3 )
for the sample were (−60.0, 95.5, −29.8), which can be
compared with the set (−65.0, 97.0, −30.4) of Dionne
[19]. The result obtained by Crecelius et al. for DyIG
Mössbauer Spectroscopy on the Magnetic Hyperfine Interaction· · · – J. G. Kim et al.
[20], using the molecular-field coefficients of Dionne [19]
is shown in Fig. 5(b) (curve 1 and 2). Good agreement
between the experimental data and the theoretical val-
ues was obtained, as shown by curves 1 and 2 in Figs.
5(a) and (b). Dionne [19] obtained the following relations
among molecular-field coefficients by fitting the Néel the-
ory of ferrimagnetism to magnetic moment - temperature
data for several {Y3 }[Rx Fe2−x ](Qy Fe3−y )O12 composi-
tions, where R and Q represent diamagnetic a- and d-site
substitution, i.e., Sc3+ , In3+ , Ga3+ , and Al3+ :
Ndd = −30.4(1 − 0.43x),
Naa = −65.0(1 − 0.42y),
Ndd = 97.0(1 − 0.125x − 0.127y). (7)
Using the first and second equation of Eq. (7), we de-
termined the chemical structural formula for the sample
to be {Eu3 }[Fe2−x ](Fe3−y )O12 , where x and y were 0.05
and 0.18 (x/y = 0.70), respectively. The value of the ra-
tio x/y can be compared with the value of 0.81 calculated
by using the area ratio of the Mössbauer spectrum.
Heller [21] and Benedeck [22] have made very accurate
NMR measurements of the spontaneous magnetization of
an insulating ferromagnet near its Curie point TC ; they
found that the magnetization followed a (TC -T )β law and
that the experimental value of β was near to 1/3. Curves
3 and 4 in Figs. 5(a) and (b) show the result of afit to
the data. The value can be compared with 0.312 [23].
IV. CONCLUSION
In spite of the small portion of extra phases in the
X-ray diffraction patterns, the Mössbauer spectra of the
sample show that the sample has a single crystal phase.
If the site preferences of the cations in the lattice are
considered, the temperature dependence of the magnetic
hyperfine fields determined by using the spin-wave the-
ory and the molecular field model and the results of the
analysis of the area ratio of two a-site lines are in good
agreement with the fact that the sample has some va-
cancies at the a- and/or the d-sites. From the analysis,
the average strength of the interaction |Jd−a |/k and the
molecular-field coefficients (Naa , Nad , Ndd ) for the sam-
ple were 37.484 K and (−60.0, 95.5, −29.8) (mole/cm3 ),
respectively. From the relations among the molecular-
field coefficients, the ionic distribution at the a- and the
d-sites was {Eu3 }[Fe1.95 ](Fe2.82 )O12 .
-235-
ACKNOWLEDGMENTS
This study is supported by the National Research Lab-
oratory Project (M10104000049-01-02010).
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