Investigation of spin reorientation in YMn1-xFexO3 (x = 0.55, 0.6, 0.7, 0.8, 0.9, and 1.

0)
by Mössbauer spectroscopy
Jung Tae Lim, Young Jai Choi, and Chul Sung Kim

Citation: Journal of Applied Physics 117, 17D918 (2015); doi: 10.1063/1.4918564

View online: https://doi.org/10.1063/1.4918564
View Table of Contents: http://aip.scitation.org/toc/jap/117/17
Published by the American Institute of Physics

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 JOURNAL OF APPLIED PHYSICS 117, 17D918 (2015)

Investigation of spin reorientation in YMn12xFexO3 (x 5 0.55, 0.6, 0.7, 0.8, 0.9,

and 1.0) by Mo€ ssbauer spectroscopy
Jung Tae Lim,1 Young Jai Choi,2 and Chul Sung Kim1,a)
1
Department of Physics, Kookmin University, Seoul 136-702, South Korea
2
Department of Physics, Yonsei University, Seoul 120-749, South Korea
(Presented 7 November 2014; received 22 September 2014; accepted 23 November 2014; published
online 22 April 2015)
YMn1xFexO3 (x ¼ 0.55, 0.6, 0.7, 0.8, 0.9, and 1.0) polycrystalline samples were prepared by the
solid-state-reaction method. The crystal structure and magnetic properties of samples were
investigated with x-ray diffractometer (XRD), vibrating sample magnetometer, and M€ossbauer
spectroscopy. The XRD patterns at 295 K, analyzed by Rietveld refinement method, showed that
all samples were single-phased orthorhombic of Pnma with both Bragg (RB) and structure (RF) fac-
tors less than 5%. M€ossbauer spectra of all samples were obtained at various temperatures ranging
from 4.2 to 500 K, and the spectra below TC were fitted by least-square method as a function of the
Fe and Mn distribution. Isomer shift (d) values of all samples indicated that the charge states were
Fe3þ. In addition, temperature-dependent hyperfine field (Hhf), averaged electric quadrupole shift
hEQi, and averaged isomer shift hdi have shown abrupt changes around TSR due to the change in
C 2015 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4918564]
the charge state of Mn ions. V

I. INTRODUCTION YMn1xFexO3. Then, the mixture was ground for 1 h, and

Recently, the multiferroic materials, where the electric or
magnetic properties can be controlled by external magnetic or
electric field, have been extensively studied for new device
applications such as high-efficient memory and sensor devi-
ces. Unfortunately, the practical application of these materials
is limited by low temperature and weak coupling.1–4
However, among the multiferroic materials, RFeO3 (R ¼ rare-
earths or yttrium) with ferroelectric-antiferromagnetic cou-
pling have been extensively investigated with Dzyaloshinskii-
Moriya exchange interaction.5,6 Especially, Mn-doped YFeO3
shows the magnetoelectric (ME) effect as a magnetic transi-
tion due to spin reorientation, originated from the coupling
between weak ferromagnetic and antiferromagnetic order. In
general, YMn1xFexO3 has orthorhombically distorted perov-
skite structure with six Fe ions around the octahedral Fe site.
In addition, with increasing Mn concentration, the spin reor-
ientation temperature (TSR) increases, while Curie temperature
(TC) decreases.7
In this paper, we have studied the crystalline and mag-
netic properties of YMn1xFexO3 (x ¼ 0.55, 0.6, 0.7, 0.8,
0.9, and 1.0) to investigate the effect of Fe-ion substitution
by using x-ray diffractometer (XRD), vibrating sample mag-
netometer (VSM), and M€ossbauer spectrometer.
II. EXPERIMENT
The samples of polycrystalline YMn1xFexO3 (x ¼ 0.55,
0.6, 0.7, 0.8, 0.9, and 1.0) were synthesized by the solid-state
reaction method. The high-purity Y2O3, Fe2O3, and MnO2
powder were used as staring materials and these reagents
were mixed in appropriate stoichiometric ratio for
a)
Author to whom correspondence should be addressed. Electronic mail:
cskim@kookmin.ac.kr. Tel.: þ82-2-910-4752. FAX: þ82-2-910-5170.
calcined at 1100  C for 5 h in air. The calcined powder was
sintered at 1200  C for 12 h in air, and sintered again at
1300  C for 30 h to obtain good homogeneity. The crystalline
structure and phase purity of samples were characterized by
XRD using Cu-Ka (k ¼ 1.5406 Å) radiation. The measure-
ments of magnetic properties were carried out with VSM
and M€ossbauer spectrometer at various temperatures ranging
from 4.2 to 500 K. M€ossbauer spectra were obtained in trans-
mission mode using a 57Co source in a rhodium matrix.
III. RESULTS AND DISCUSSION
The measured XRD patterns of YMn1xFexO3
(x ¼ 0.55, 0.6, 0.7, 0.8, 0.9, and 1.0) at 295 K were analyzed
using Rietveld refinement method, as shown in Fig. 1. The
crystal structure of YMn1xFexO3 (x ¼ 0.55, 0.6, 0.7, 0.8,
0.9, and 1.0) was determined to be single-phased orthorhom-
bic with space group Pnma. With increasing Fe ion concen-
tration, the lattice constant a0 decreases from 5.679 for
x ¼ 0.55 to 5.595 Å for x ¼ 1.0, whereas b0, c0, and unit cell
volume (Vu) increase from b0 ¼ 7.509, c0 ¼ 5.268 Å, and
Vu ¼ 224.632 Å3 for x ¼ 0.55 to b0 ¼ 7.608, c0 ¼ 5.283 Å,
and Vu ¼ 224.878 Å3 for x ¼ 1.0.
Fig. 2 shows the field-dependent magnetization curves
of YMn1xFexO3 (x ¼ 0.55, 0.6, 0.7, 0.8, 0.9, and 1.0) under
10 kOe at 295 K, indicating the various spin structures
depending on the Fe substitution. The samples show the spin
reorientation from antiferromagnetic to weak ferromagnetic
ordering, and TSR decreases with increasing Fe ion concen-
tration. Also, for x ¼ 1.0, one can notice the disappearance of
spin reorientation. Therefore, below x ¼ 0.6, the samples
show linear antiferromagnetic behavior, while above x ¼ 0.6,
the samples show weak ferromagnetic behavior due to Fe-O-
Fe and Fe-O-Mn.7,8

0021-8979/2015/117(17)/17D918/3/$30.00 117, 17D918-1 C 2015 AIP Publishing LLC

V
17D918-2 Lim, Choi, and Kim J. Appl. Phys. 117, 17D918 (2015)

FIG. 1. XRD patterns of YMn1xFexO3 (x ¼ 0.55, 0.6, 0.7, 0.8, 0.9, and 1.0)
refined by using the Rietveld refinement method.

To investigate the hyperfine interaction in YMn1x

FexO3 (x ¼ 0.55, 0.6, 0.7, 0.8, 0.9, and 1.0), we have
obtained M€ ossbauer spectra at 295 K. Fig. 3 shows the result-
ing M€ ossbauer spectra, and M€ossbauer parameters are listed
in Table I. The M€ossbauer spectra of all samples are fitted
with one sextet due to the octahedral Fe site, corresponding
to YFeO3 crystallography site. However, we observed the
broadening line-width (FWHM) with decreasing Fe ions
concentration, indicating the presence of a number of differ-
FIG. 3. M€ ossbauer spectra of YMn1xFexO3 (x ¼ 0.55, 0.7, 0.8, 0.9, and
ent sites due to the random distribution of Mn ions around 1.0) at 295 K.
octahedral Fe site. Therefore, the experimental spectra were
least-squares fitted, considering the random distribution of concentration. The hyperfine fields at different octahedral B
Fe and Mn ions on the octahedral sites. The probability of sites are assumed to obey the relation of Hn ¼ H0(1  nDH),
octahedral site having n nearest-neighboring Mn atoms was where H0 is the hyperfine field at Fe ion without neighbor-
calculated using the binomial formula9 ing Mn site and DH is the fractional decrease in the
TABLE I. M€
ossbauer hyperfine parameters of YMn1xFexO3 at 295 K.
6! 6n
Pðn; xÞ ¼ ð x Þn ð 1  x Þ ;
n!ð6  nÞ! Site

where n is the number of Mn ions among the nearest- x Hhf (kOe) EQ (mm/s) d (mm/s) P(n,x) Area (%) Environment
neighboring octahedral Fe site and x is the Mn ion 0.55 A1 355.53 0.12 0.22 13.59 16.25 5Fe, 1Mn
A2 303.46 0.07 0.21 27.80 26.79 4Fe, 2Mn
A3 253.30 0.13 0.25 30.32 33.01 3Fe, 3Mn
A4 245.91 0.03 0.26 18.61 18.23 2Fe, 4Mn
A5 225.18 0.14 0.26 6.09 5.73 1Fe, 5Mn
0.6 A1 400.33 0.09 0.26 18.66 21.42 5Fe, 1Mn
A2 369.34 0.13 0.26 31.10 34.43 4Fe, 2Mn
A3 346.26 0.12 0.22 27.65 28.99 3Fe, 3Mn
A4 295.85 0.17 0.19 13.82 15.16 2Fe, 4Mn
0.7 A0 461.38 0.00 0.26 11.76 14.68 6Fe
A1 435.43 0.01 0.25 30.25 30.92 5Fe, 1Mn
A2 405.06 0.01 0.27 32.41 35.23 4Fe, 2Mn
A3 359.06 0.01 0.23 18.52 19.18 3Fe, 3Mn
0.8 A0 477.74 0.00 0.25 26.21 26.35 6Fe
A1 461.63 0.04 0.25 39.32 40.17 5Fe, 1Mn
A2 436.44 0.06 0.26 24.58 24.01 4Fe, 2Mn
A3 397.63 0.11 0.24 8.19 9.48 3Fe, 3Mn
0.9 A0 491.61 0.01 0.25 53.14 56.00 6Fe
A1 475.97 0.03 0.25 35.43 32.18 5Fe, 1Mn
A2 457.58 0.04 0.27 9.84 11.81 4Fe, 2Mn
FIG. 2. The field-dependent magnetization curve of YMn1xFexO3 1.0 A0 500.28 0.00 0.25 100 100 6Fe
(x ¼ 0.55, 0.6, 0.7, 0.8, 0.9, and 1.0) up to 10 kOe at 295 K.
17D918-3 Lim, Choi, and Kim
FIG. 4. M€ossbauer spectra of YMn0.4Fe0.6O3 at various temperatures.
hyperfine field due to the substitution of Mn ions.9,10 With
decreasing Fe ions, the average value of hyperfine field
hHhfi decreases due to the weaker super-exchange interac-
tion Fe3þ-O2-Mn3þ when compared to Fe3þ-O2-Fe3þ.
Also the obtained value of isomer shift (d) indicates that the
charge state of Fe ions is Fe3þ.
The temperature-dependent M€ossbauer spectra of
YMn0.4Fe0.6O3 sample are shown in Fig. 4. Based on the
model of random distribution of Fe and Mn ions at the octahe-
dral sites, M€ossbauer spectra of YMn0.4Fe0.6O3 were fitted
with four-sextets. Fig. 5 shows the temperature dependence of
the averaged electric quadrupole shift hEQi, the averaged iso-
mer shift hdi, and the magnetic hyperfine field (Hhf), as well
as the magnetization curves at 100 Oe of YMn0.4Fe0.6O3.
From dM/dT of ZFC curves, TSR and TC were determined to
be 311 and 395 K, respectively. With increasing temperature,
the values of Hhf at four different sites decrease due to the
reduction of super-exchange interaction. In addition,
temperature-dependent Hhf, hEQi, and hdi show abrupt
changes around TSR. Below TSR, we expect that positive value
of hEQi indicates the antiferromagnetic spin structure at Fe
and Mn sites. Above TSR, hEQi is negative, suggesting the
coexistence of antiferromagnetic and canted antiferromagnetic
spin structure above TSR.10 Also, the increasing value of hdi
around TSR is due to the change in charge states of Mn ions.10
J. Appl. Phys. 117, 17D918 (2015)
FIG. 5. Temperature dependence of (a) the averaged electric quadrupole
shift hEQi, (b) the averaged isomer shift hdi, (c) magnetic hyperfine field
(Hhf), and (d) magnetization curves at 100 Oe of YMn0.4Fe0.6O3.
IV. CONCLUSIONS
In summary, we have studied the crystalline and mag-
netic properties of YMn1xFexO3 (x ¼ 0.55, 0.6, 0.7, 0.8, 0.9,
and 1.0) polycrystalline samples by XRD, VSM, and
M€ossbauer spectrometer. From the XRD measurements, ana-
lyzed by Rietveld refinement, the crystal structure of all sam-
ples was found to be orthorhombic with space group of
Pnma. The lattice parameter a0 decreases, whereas b0 and c0
increase with increasing Fe ion concentration. M€ossbauer
spectra of all samples were obtained at various temperatures
ranging from 4.2 to 500 K, and below TC, they were least-
squares fitted as a function of the Fe and Mn atom distribu-
tion. With decreasing Fe ions, the average value of hyperfine
field hHhfi decreases due to the weaker super-exchange inter-
action Fe3þ-O2-Mn3þ, compared to Fe3þ-O2-Fe3þ. In
addition, the temperature-dependent hyperfine field (Hhf),
averaged electric quadrupole shift hEQi, and averaged isomer
shift hdi have shown abrupt changes around TSR due to the
change in charge states of Mn ions.
ACKNOWLEDGMENTS
This work was supported by Mid-Career Researcher
Program through the National Research Foundation of Korea
(NRF) grant funded by the Ministry of Education, Science
and Technology (MEST) (NRF-2014R1A2A1A05002488).
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