JOURNAL DE PHYSIQUE Colloque C6, suppl&ment au no 12, Tome 37, Dkcembre 1976, page C6-621

SPIN REORIENTATION IN RARE EARTH ORTHOFERRITES

G. W. DURBIN, C. E. JOHNSON, L. A. PRELORENDJO and M. F. THOMAS
Oliver Lodge Laboratory, University of Liverpool, Liverpool, L69 3BX, England

Rhumb. - L'effet Mossbauer etait employ6 pour dkcouvrir la reorientation de spin des ions
Fe3+ dans des Bchantillons de cristal simple des orthoferrites de terres fares YFe03, GdFeO3 et
EuFeO3. La rkorientation de spin etait produite par moyen des champs magnktiques jusqu78
concurrence de 6 T le long de l'axe a du cristal (l'axe de I'antiferromagnetisme des ions Fe3+).Les
champs employks afin de produire la rkorientation complhte dans YFeO, B 293 K et 4,2 K ktaient
6,5 f 0,2 T et 7,7 & 0,2 T respectivement. Dans GdFeO, A 293 K, 77 K, 4,2 K et 2 K les champs
+
necessaires Btaient 7,6 -1: 0,2 T, 8,l & 0,2 T, 1,2 0,2 T et 0,7 f 0,l T et dans EuFe03 8 4,2 K,
6,7 & 0,2 T. On interprkte les rbsultats en fonction de l'effet de l'action rtkiproque entre la terre
rare et le fer sur la reorientation de spin.
Abstract. - The Mossbauer effect was used to detect spin reorientation of Fe3+ ions in single
crystal samples of the rare earth orthoferrites YFe03, GdFeO3 and EuEeO3. Spin reorientation
was induced by applying magnetic fields of up to 6 T along the crystal a axis (the axis of anti-
ferromagnetism of the Fe3f ions). The applied fields necessary to cause complete reorientation
in YFeO3 at 293 K and 4.2 K were 6.5 f 0.2 T and 7.7 5 0.2 T respectively. In GdFeO3 at 293 K,
77K,4.2Kand2Kthefieldsrequiredwere7.6 &0.2T,8.1 f 0.2T,1.2 & 0.2Tand0.7 & 0.1 T
and in EuFe03 at 4.2 K, 6.7 + 0.2 T. The results are interpreted in terms of the effect of rare
earth-iron interaction on spin reorientation.

1. Introduction. - The orthorhombic unit cell
of the rare earth orthoferrites (RFeO,) is illustrated in
figure 1 which also shows the arrangement into perovs-
kite pseudo cells. Magnetic interaction between Fe3+
FIG. I. - The structureRFe03(oxygen atoms omitted)showing
the orthorhombic cell and the pseudocubic subcells of the R
and Fe ions. The direction of the applied field and y rays are
related to the axial directions as indicated.
axis. However, in the orthoferrites TbFeO,, ErFeO,
and TmFeO, the axes of antiferromagnetism and
weak ferromagnetism begin to rotate as the tempera-
ture is decreased below a critical temperature TI and
rotation continues with falling temperature until at
temperature T, the antiferromagnetic axis is along the c
axis with weak ferromagnetism along the a axis [I].
The change in anisotropy energy causing this rota-
tion has been ascribed to the interaction of the Fe3+
system with the system of rare earth R3+ ions 12, 3,4].
The detail of this behaviour depends on the individual
R3+ ion. The application of a magnetic field along the
antiferromagnetic axis of the Fe3+ system acts to
destabilise it owing to the higher magnetic energy
of this configuration compared to that when the spins
are perpendicular to the applied field. The anisotropy
of the Fe3+ system can thus be measured against the
field necessary for complete reorientation. Since the
anisotropy energy depends on the R3+-Fe3+interac-
tion this method can balance the interaction against
the change in reorienting field.
The anisotropy of the Fe3+ system with no rare
earth-iron interactions present is investigated in
YFeO, with the diamagnetic Y ion on the rare earth
+

site [5]. With these results as a <( background >>

temperature of -
ions results in antiferromagnetic ordering below a Niel
650 K but slight canting of the ions
gives rise to weak ferromagnetism in a direction
- spin reorientation without R3+-Fe3+ interaction -
the results of measurements on GdFeO, and EuFeO,
are discussed in terms of the rare earth-iron interaction.
perpendicular to the antiferromagnetic axis. At room
temperature in all rare earth orthoferrites except 2. Experimental procedure. - Orthoferrite samples
SmFeO, the antiferromagnetic axis lies along the were prepared from single crystals grown with lead
crystal a axis with the weak ferromagnetism along the c oxide based flux and ultra pure materials. Slices were

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19766129

C6-622 G. W. DURBIN, C. E. JOHNSON, L. A. PRELORENDJO A N D M. F. THOMAS

cut with the c axis normal to the plane of the sample,
these were thinned to an equivalent thickness of 10-
20 mg cm-2 of natural iron and set in epoxy. The
spin direction in the plane of the sample was assigned
from morphological- examination and verified by
Mossbauer absorption using a source of polarised
14.4 keV gamma rays [6].
A conventional Mossbauer spectrometer was used
with a 100 mCi s7Co in rhodium source and an
argon/methane filled proportional counter to detect the
radiation. After amplification and selection of the
signal of the 14.4 keV radiation, the counts were gated
into a 256 channel subsection of a 4 096 channel
analyser used in the multiscaler mode to provide a
velocity spectrum.
Fields of up to 6 T were applied to the samples
using a superconducting magnet. Measurements were
made with the various magnetic fields applied at
sample temperatures of 2 K, 4.2 K, 77 K and 293 K.
The crystal slices were mounted inside the magnet
with the field direction coaxial with the antiferroma-
gnetic vector (a axis) and with the weak ferromagnetic
moment (along the c axis) perpendicular to the field
direction. The source-detector system was arranged
such that the gamma ray direction was perpendicular
to the field direction, i. e. the propogation of gamma
rays was along the c axis. With this arrangement,
deviation of the antiferromagnetic vector from the a
axis was observable from the change in the radiation
pattern displayed by the intensity of the Am = 0 lines
in the spectra. The relative intensities of a thin absor-
ber, six-line Mossbauer spectrum are 3 :
1 where a is the angle between the spin'direction a i d
the direction of propagation of the gamma rays and
the intensity of the Am = 0 lines are given by the mid-
dle expression.
An alternative method of detecting this orientation
is by measurement of the different effective fields ~ $ 1 , )
and Hi&), at the nuclei of the two antiferromagnetic
sublattices. This is caused by the applied field adding
to the hyperfine field of one sublattice and subtracting
from that of the other. An average value for the
angle 0 between the spin direction and field direction
is given, for fields less than the critical field required
for reorientation, by
where ~ $ and
2 H:f"f'are the measured effective fields
and Ha is the applied field.
3. Results. - A series of spectra taken at fields
up to 6 T on a 20 mg cm-2 sample of YFeO, at
4.2 K is shown in figure 2. The spectra exhibit a
progressive reduction in the intensity of the Am = 0
lines and a splitting of the 6 line pattern into two

Velocity t m m s-'1 V e l o c ~ t y (mm s-'1

FIG. 2. - Mossbauer spectra of 57Fe in YFeOj at 4.2 K with increasing magnetic field. The full line is a least-squares fit
of two series of 3 pairs of Lorentzian lines to the experimental data. The approximate orientation of the spins to the applied
magnetic field and the y ray direction are indicated.
 SPIN REORIENTATION IN RARE EARTH ORTHOFERRITES C6-623

series of 6 lines each associated with one sublattice.

The spectra were analysed to provide values of the
angle of orientation 0, the effective fields at nuclei
of each sublattice, quadrupole splitting and isomer
shift.
In the series of spectra illustrated the method of
sublattice splitting was used to evaluate 8 as the
splittings are sufficiently large to be fitted with accu-
racy and because the thickness of this sample makes
the intensity ratio of outer to inner lines deviate
appreciably from 3 : 1. With thinner (- 10 mg ~ m - ~ )
samples of GdFeO, and EuFeO, this intensity ratio
approached 3 : 1 and for GdFeO, at 2 K and 4.2 K the
method of intensity ratios was used to obtain 0 as the Applied field ( T )
small fields involved caused little splitting of the Fig. 5. - Field dependence of the orientation of Fe3+ spins in
sublattices. When both methods were appropriate as EuFe03 with respect to the field direction at 4.2 K.
in EuFeO, at 4.2 K values of 8 obtained by the two
+
methods agreed to within 3O. The rotation of the
antiferromagnetic axis (as sin 0) is plotted against applied field for the YFeO, sample at 293 K and
4.2 K in figure 3. Similar graphs for GdGeO, at
293 K and 4.2 K are shown in figure 4 and for EuFeO,
at 4.2 K in figure 5. Values of the critical applied field
HZ
necessary to cause complete reorientation (sin
8 = 1) at temperature T were taken from these and
similar plots and are collected in table I.

Critical fields H,, required to cause

complete reorientation of ~ e , +
from the crystal
a axis to the c axis
Sample Temperature (K) Hc* (T)
- - -
YFeO, 293 6.5 1- 0.2
YFeO, 4.2 7.7 1- 0.2
GdFeO, 293 +
7.6 0.2
GdFe03 77 8.1 1- 0.2
0 I/'
1 , I I I 1 GdFeO, 4.2 +
1.2 0.2
0 2 4
APPLIED FIELD. IT).
6 8
GdFeO, 2 +
0.7 0.1
EuFeO, 4.2 6.7 _+ 0.2
FIG.3. - Field dependence of the orientation of Fe3f spins in
YFe03 with respect to the field direction at 4.2 K and 293 K . ~
The values of isomer shift and hyperfine field and
quadrupole splitting at zero applied field are in good
general agreement with those in the literature [7].

4. Discussion. - In a pure (non canted) antifer-

romagnet an applied field along the axis of antiferro-
magnetism causes a sharp spin reorientation through
90° at a critical field H: given by HZ = (2 HE HA)'I2
where HEis the exchange field of the antiferromagnetic
system and HA is the anisotropy field. When a field is
applied along the antiferromagnetic axis of a canted
antiferromagnet the reorientation occurs continuously
18, 51 reaching completion at a field H: given by

FIG. 4. -Field dependence of the orientation of Fe3f spins in where HD is the Dzyaloshinsky field that causes the
GdFe03 with respect to the field direction at 4.2 K and 293 K. canting.
C6-624 G. W. DURBIN, C. E. JOHNSON, L. A. PRELORENDJO AND M. F. THOMAS

In YFeO, the diamagnetic Y3+ ion occupies the field of the Gd3+ ions. The value of H: (the field that
rare earth site and no interaction with the Fe3+ system would be required for complete reorientation in

has an anisotropy which increases by

temperature decreases from 293 K to 4.2 K.
-
occurs. The resuIts show that the bare Fe3+ system
12 % as the
GdFeO, in the absence of Gd3+-Fe3+interactions)
was obtained by scaling the YFeO, results to the value
of in GdFeO, where the value of < p >,, is
In GdFeO, the Gd3+ ions ('s,~,) possess magnetic small. The effect of the iron-rare earth interactions
moments and interact with the Fe3+ system. The are then represented in experimental terms by
Gd3+ ions order themselves at a temperature of 1.5 K
191 thus in the temFerature range used in these experi-
ments the Gd3+ ions behave paramagnetically. The In figure 6 the graph of AH against the mean moment
applied field aligns these ions to give a net moment < p >Gd indicates that the interaction between the
< p >Gd along the crystal a axis that can be estimated paramagnetic Gd3' system and the antiferromagnetic
from the Brillouin function B7!,(H/T) [lo]. Fe3+ system is proportional to < p >,, and can be
The total effective field required to cause complete represented by
reorientation of the Fe3+ spin system at temperature T,
H:, contains contributions from the applied critical
field at this temperature, HZand from the exchange
where the molecular field constant of the Gd3+ ions,
11 = 2.3 T per Bohr magneton.
Preliminary measurements on EuFeO, show that at
4.2 K the observed value of ~2~ is less than that
expected for the bare Fe3+ system as measured in
YFeO,. This difference between YFeO, and EuFeO,
at 4.2 K may be ascribed to a weak rare earth-iron
interaction in EuFeO,. The ground state of the Eu3'
ion (7F,) is diamagnetic but a J = 1 state at an
excitation of 255 cm-' is mixed into the ground
state by the exchange field of the Fe3+ system and the
applied field. This results in a small net moment for
the system of Eu3+ and a weak rare earth-iron interac-
tion. At higher temperatures the excited state of Eu3+
FIG. 6. - Graph of AH, representing the effect of GdjC-Fe3+
will become more populated changing the mean
interactions on the reorienting field, versus the mean Gd3+ < P >E", the rare earth-ion interaction and cons+
moment < N >ad. quently the reorienting field.

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