Enroute to phase purity in CaMn7O12

Cite as: AIP Conference Proceedings 1832, 090041 (2017); https://doi.org/10.1063/1.4980594

Published Online: 23 May 2017

Kamini Gautam, D. K. Shukla, R. J. Choudhary, et al.

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AIP Conference Proceedings 1832, 090041 (2017); https://doi.org/10.1063/1.4980594 1832, 090041

© 2017 Author(s).
 Enroute To Phase Purity In CaMn7O12

Kamini Gautam*, D. K. Shukla, R. J. Choudhary, D. M. Phase

UGC-DAE Consortium for Scientific Research, Khandwa Road, Indore, 452001, India
*Email:kamini.gautam@gmail.com

Abstract. We present structural, magnetic and X-ray absorption spectroscopy investigations on multiferroic CaMn7O12
material. Traces of impurities (viz CaMn2O4, Mn3O4, and Mn2O3) are reported to be inevitable in this compound [J.
Phys: Condense Matter 14, 5747 (2002)]. We have shown that the synthesis temperature plays a significant role in phase
control of this compound. Samples, synthesized using two different temperatures are studied. X-ray absorption spectra
measured across Mn L3, 2 edges of both the samples show the mixed valence states of Mn (Mn3+ and Mn4+), and
increasing Mn4+ content for sample sintered at elevated temperature, which supports the stabilization of pure CaMn7O12
phase, also confirmed from XRD. Both the samples show reported antiferromagnetic transitions, TN1 ~ 90 K and TN2 ~
45 K, however, with different magnetic anisotropies at lower temperatures.
Keywords: X-ray absorption spectroscopy, Magnetization
PACS: 78.70.Dm, 75.60.Ej

INTRODUCTION
Perovskite manganites exhibiting multiferroicity are
typical type-ii multiferroic materials, which show large
magnetoelectric coupling [1]. CaMn7O12 is one of
these, a quadruple perovskite belonging to the
AC3B4O12 family. It has cubic structure (s. g. Im-3) at
high temperatures, above 440K, with four perovskite
units in each unit cell. This cubic cell distorts into
rhombohedral lattice (s.g.R-3) below ~ 440K [2]. In
CaMn7O12, the polarization, along the c-axis of
rhombohedral axis ([111] qseudocubic axis), reaches
the value 2870 μc/m2 at low temperatures, which is the
largest measured polarization till date among type-ii
multiferroics [3]. Observation of such a large electrical
polarization in CaMn7O12 has accelerated the research
on this compound. However, obtaining single phase
CaMn7O12 remains a challenging task. It is to be noted
that no group so far has yet been able to produce single
phase powder samples of CaMn7O12, to the best of our
knowledge. There remains always the traces of known
impurities, namely CaMn2O4, Mn3O4 and Mn2O3. In
this work, we have performed the structural, magnetic
and X-ray absorption spectroscopy across Mn-L-edges
on CaMn7O12 samples sintered at two different
ஈ ஈ
temperatures (850 C and 920 C).
EXPERIMENTAL
The stoichiometric mixture of high purity CaCO3 and
MnO2 were calcined at 500ஈC and 700ஈC with
intermediate grinding, followed by final sintering at
two different temperatures, 820ஈC and 920ஈC, for 12
hours. Magnetization measurement as a function of
temperature and magnetic field were measured by
employing a commercial 7-tesla SQUID-Vibrating
sample magnetometer (SVSM; Quantum Design Inc.,
USA). X-ray absorption measurements on these well
characterized samples along with reference compound
Mn2O3 were carried out at room temperature at the
soft X-ray absorption spectroscopy (SXAS) beam line,
BL-01 at Indus-2, RRCAT, Indore, India. The
measurements have been carried out at room
temperature in the total electron yield (TEY) mode.
Energy resolution at Mn-L-edge energy was about
0.2eV.
RESULTS AND DISCUSSION
Rietveld refined XRD patterns of CaMn7O12 samples
sintered at two different temperatures, namely 920 C
ஈ
ஈ
and 820 C, are shown in Fig. 1(a) & (b). Patterns were
fitted by considering impurities as secondary phases.
We could identify all the reported impurities
CaMn2O4, Mn3O4 and Mn2O3 [2]. Fraction of impurity
CaMn2O4 is found to be largest, which considerably

DAE Solid State Physics Symposium 2016

AIP Conf. Proc. 1832, 090041-1–090041-3; doi: 10.1063/1.4980594
Published by AIP Publishing. 978-0-7354-1500-3/$30.00

090041-1
reduces on higher temperature. Reflections of main
Yobs
phase CaMn7O12 can be indexed in hexagonal structure (a) Ycal
with the space group settings of R-3, as reported Yo-Yc
920oC
before [4]. The refined lattice parameter for Bragg position
CaMn7O12, sintered at 820oC are found to be

a=b=10.463 Å and c=6.349 Å, while for 920oC
sintered sample has a=b=10.439 Å and c=6.334Å,
which is good matches with the reported lattice
parameters for CaMn7O12 [2].
.
The X-ray absorption spectra recorded across Mn L3,2
edges for both the samples along with reference
compound Mn2O3 are shown in Fig. 2. The Mn L-edge
XAS directly probes the transitions of electrons from
2p core level to the unoccupied 3d valence states. Fig.
2. shows two clear peaks labeled as L3 (2p3/2 to 3d) and
L2 (2p1/2 to 3d ), which are spin-orbit splitted peaks. In
case of transition metal ions XAS, L3 edges are more
susceptible to changes due to modified local
environment, such as crystal field effects, varying
oxidation states etc. In our spectra also, changes at L3
edges are apparent while L2 edge is almost identical
for both the samples. Our spectra resembles the
similarities with Mn2O3 (Mn 3+) spectra, due to largest
fraction of Mn in our samples also being 3+ only
(inclusive of impurity phases). However, for the
sample sintered at 920ஈC, its leading edge position
together with peak position exhibits slight shift
towards higher energy side, which is clear indication
of increasing overall Mn valence state in comparison
to the sample sintered at 820ஈC. It is to be noted that, in
CaMn7O12, out of seven Mn ions, six Mn ions are
known to possess +3 valence state while one Mn ion is
in +4 state.
Intensity(arb. unit)
(b)
820oC
10 20 30 40 50 60 70 80 90
2T(degree)
Fig. 1: Rietveld refined XRD patterns of CaMn7O12
samples sintered at two different temperatures, 820oC and
920o C.
Increasing overall Mn valence state is due to
appearance of Mn4+ ions at the expanse of Mn3+ ions.
This is possible with stabilization of CaMn7O12 pure
phase. This is commensurate to the results obtained
from XRD.
At the same time when inflection point of L3-edge
shifts towards higher energy for 920ஈC samples, a
small narrowing of L3-edge in 920ஈ C sample is also
observed. The intensity of Mn L3-edge is comprised of
un-occupancies in t2g and eg orbitals. Hence narrowing
down of the L3-edge is representative of the decreased
crystal field splitting (splitting of t2g and eg orbitals),
which may facilitate the high spin states of Mn ions in
920ஈ sample, which has considerably reduced impurity
phase.

Mn L3,2edge 820oC
Normalized absorption (arb. units)

920oC

Mn2O3
L3 L2

635 640 645 650 655

Photon energy (eV)

Fig. 2: XAS of Mn-L3,2 edges of CaMn7O12 samples sintered

at two different temperatures, along with reference of
Mn2O3.

090041-2
In Fig. 3, dc magnetization data (M), in ZFC and FC CONCLUSIONS
mode, as a function of temperature (T) is shown for
both the samples. Both the samples show reported X-ray absorption spectroscopy together with X-ray
characteristic antiferromagnetic (AFM) transitions at ~ diffraction and magnetization measurements employed
90K and at ~45K. Bifurcation of FC and ZFC data is on CaMn7O12 samples confirm the stability of pure
also seen for both the samples, which is larger in CaMn7O12 phase when sintered at higher temperature,
sample sintered at 920oC. 920oC. Rietveld refinement is used to refine the lattice
parameters and identify the impurities. Subtle
8 electronic changes observed across Mn-L3,2 edges
30 FC 6000 TN1
support to diffraction data. Magnetization
7 measurements confirm both the magnetic transitions,
25 4000 in both the samples, however only sample sintered at
6 920oC shows the close resemblance with earlier report
F(10-4emu/g.Oe)

20 2000
5 on single phase sample. Observed magnetic behavior
TN2
TN1 0 is supported by XRD and XAS results.
15
50 100 150 4
10 ZFC 920 C 0
ACKNOWLEDGMENTS
3
820 0C
5 2 Authors acknowledge Layantha Behra and M. Gupta
for XRD measurement, and Pankaj Pandey for help
0 1 during magnetization measurements.

Temperature (K) REFERENCES

Fig.3: Magnetization vs T behaviour of both the samples, 1. K.F. Wang, J. M. Liu, Adv. phys.58, 321, (2009).
performed at 500 Oe field. Inset : Inverse of M vs. T. 2. R. Przenioslo, I. Sosnowska, E. Suard, A Hewat and
A.N. Fitch, J. Phys: Condense Matter 14, 5747 (2002).
3. R. D. Johnson, L.C. Chapon, D.D Khalyavin, P. Manuel,
P.G. Radaelli and C. Martin, Phys. Rev. lett. 102
Bifurcation in FC and ZFC data may be attributed to 067201(2012).
the magnetic anisotropy present in the system, due to 4. Guoquan Zhang, Shuai Dong, Zhibo Yan, Yanyan Guo,
presence of mixed Mn valence states. Larger Qinfang Zhang, Seiji Yunoki, Elbio Dagotto
bifurcation and shifting of cusp towards higher PRB 84, 174413 (2011).
ஈ
temperature in ZFC and FC data of 920 C sintered
ஈ
sample in comparison to 820 C sintered sample
indicates large anisotropy present in 920oC sintered
sample. Considering magnetization data together with
XRD and XAS results (which supports the
stabilization CaMn7O12 phase in 920oC sample)
indicate that the observed increasing magnetic
anisotropy is intrinsic to the CaMn7O12. Also, from
XAS data, decreased crystal field splitting observed in
920oC sintered sample may be a possible reason for
increased magnetic moment due to stabilization of
more high spin states of Mn ions. Transitions in our
M-T data of both the samples match with earlier
reports [4]. Guoquan Zhang et al.,[4] claimed no
impurity in their sample and their M-T data shows
close resemblance with our 920oC sintered sample. For
clear visualization of magnetic transitions, inverse of
M vs T is shown in Fig. 3.

090041-3