Journal of Magnetism and Magnetic Materials 391 (2015) 156160

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

Multiferroicity in polar phase LiNbO3 at room temperature

M. Manikandan a, K. Saravana Kumar b, N. Aparnadevi a, N. Praveen Shanker a,
C. Venkateswaran a,n
a
b

Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai 600 025, India
Department of Physics, SRM University, Ramapuram Campus, Chennai 600 089, India

art ic l e i nf o

a b s t r a c t

Article history:
Received 19 November 2014
Received in revised form
4 April 2015
Accepted 26 April 2015
Available online 28 April 2015

LiNbO3, prepared by ball milling assisted ceramic method, exhibits weak ferromagnetism and ferroelectricity at room temperature. X-ray diffraction pattern reveals the rhombohedral phase of LiNbO3 with
hexagonal unit cell symmetry. The weak ferromagnetic behavior, obtained using VSM, has been explained using DzyaloshinskiiMoriya interaction caused by the ferroelectric distortion in its magnetic
order. The PE loop measurement shows lossy natured ferroelectric loop. Electrical and dielectric
properties analyzed using impedance spectroscopy show two thermally activated conduction processes,
derived from the Arrhenius plot. A gradual increase in the dielectric constant below 493 K and a rapid
increase above 493 K reveals the contribution of polarization components and Lithium ion hopping.
& 2015 Elsevier B.V. All rights reserved.

Keywords:
Weak ferromagnetism
Ferroelectricity
Multiferroics

1. Introduction
LiNbO3 with the space group R3c is a well known ferroelectric
material and it exhibits excellent piezoelectric and pyroelectric
properties based on its asymmetric structure [1]. Due to this
LiNbO3 has attracted extensive scientic and technological interest
and has been widely used in many applications such as electrooptical, piezoelectrical and nonlinear optical devices [2]. Observation of magnetism along with ferroelectricity (Multiferroic
behavior) in non-centrosymmetric polar phase of LiNbO3 is anticipated to nd applications in future generation novel devices. In
the polar phase the Nb atom is displaced from the center of the
oxygen octahedra sharing its faces along the trigonal polar axis.
The next oxygen octahedra is empty and the one adjacent to it
contains a Li atom displaced from the oxygen face, which results in
the spontaneous polarization [3]. The displaced transition metal
causes magnetic interactions through neighboring neutral oxygen
vacancies. There are a few theoretical and experimental reports on
the multiferroic response of LiNbO3 [46] in which the authors
have explained the experimentally observed ferromagnetism
using oxygen vacancies [5,6]. The authors have theoretically suggested, using DFT calculation that in addition to the anion vacancies neutral cation vacancy also can cause ferromagnetism in
LiNbO3 [4]. However, investigation of electrical resistivity and dielectric behavior helps in the deep understanding of ferroelectricity in LiNbO3. There are some reports on impedance studies of
n

Corresponding author. Fax: 91 4422353309.

E-mail address: cvunom@hotmail.com (C. Venkateswaran).

http://dx.doi.org/10.1016/j.jmmm.2015.04.099
0304-8853/& 2015 Elsevier B.V. All rights reserved.

LiNbO3 prepared by different methods like chemical evaporation,

melt quenching and solgel methods [2,7,8]. To the best of our
knowledge there is no report on temperature and frequency dependent dielectric properties of LiNbO3 prepared by ball milling
assisted ceramic method. Ball milling followed by heat treatment
is a simple and efcient method where initial milling with optimum milling speed and time mechanically activates the precursors and thus reduces the phase formation temperature when
compared to the solid state reaction method [9].
Therefore, LiNbO3 has been synthesized using ball milling assisted sintering process. The observed weak ferromagnetism and
ferroelectricity in LiNbO3 are explained using Dzyaloshinskii
Moriya (DM) interactions and distortion of the centrosymmetry
structure, respectively. Moreover, the dielectric properties are investigated over the temperature range of 400650 K and frequency range of 100 Hz1 MHz. The possible conduction mechanism and dipole orientations with respect to temperature and
frequency are also discussed.

2. Experimental
Lithium carbonate (Li2CO3) and niobium oxide (Nb2O5) powders were taken in stoichiometric ratio, milled for 5 h at 250 rpm
using zirconia vials and balls with a ball to powder ratio of 8:2. The
milled powders were pressed into dense pellets of 12 mm diameter and sintered at 923 K in air for 6 h, subsequently furnacecooled to room temperature. The sintered pellets were nally
ground in a mortar to obtain LiNbO3 powder.

M. Manikandan et al. / Journal of Magnetism and Magnetic Materials 391 (2015) 156160

X-ray diffraction (XRD) was carried out using Cu-K radiation

for phase identication. High-resolution scanning electron microscopy (HR-SEM) was done in a FEI Quanta FEG 200 h microscope to study the surface morphological features. The ferroelectric loop was traced using Radiant Technologies Precision 4 kV
HVI instrument. Isothermal magnetization curves up to a maximum eld of 715 kOe were obtained in a Lakeshore VSM 7410
instrument. Dielectric measurements were done using an impedance spectrometer (Solartron impedance analyzer SI 1260) in
the frequency range of 100 Hz1 MHz and in the temperature
range of 400630 K.

3. Results and discussion

3.1. Structural and surface morphological studies
The diffraction pattern of LiNbO3 indicating the single-phase
nature with rhombohedral (trigonal) structure is shown in Fig. 1.
Generally, trigonal systems can have two different symmetry viz,
rhombohedral or hexagonal with an acentric space group R3c [10].
The renement is good with hexagonal polar symmetry and R3c
space group (No 161). The rened cell parameters a 5.144(4) ,
c 13.83(3) and, the corresponding cell volume V317 3 closely match with the JCPDS le no. 20-0631.
Surface morphological and microstructural features are shown
in Fig. 2(a) and (b). Fig. 2(a) shows the homogeneous distribution
of spherical shaped particles along with agglomerated islands at
few places. The particle size is in the range 102240 nm as shown
in Fig. 2(b).
3.2. PE loop measurement
The room temperature polarizationelectric eld (PE) loop
reveals the lossy natured ferroelectric behavior and is shown in
Fig. 3. The observed lossy nature is due to the oxygen vacancies
created during synthesis. The oxygen vacancies may suppress the
dipole formation due to the deciency in the charge densities, i.e.
unequal amount of positive and negative charges. This leads to low
resistivity and high leakage current in the presence of applied
electric eld leading to the lossy nature. The stoichiometry of
oxygen was calculated using iodometric titration [1113]. The titration was performed on 10 mg of prepared LiNbO3, thrice. An

157

excess of potassium iodide (KI) was dissolved in boiled distilled

water. The solution containing KI and LiNbO3 was made acidic by
the addition of 3 N hydrochloric acid. The solution was titrated
with standardized sodium thiosulfate (0.05 N). Standardization of
sodium thiosulfate was done using potassium dichromate and
starch was used as indicator. The estimated oxygen stoichiometry
is 2.85 70.01. The ferroelectricity in LiNbO3 is due to the structural
distortion of paraelectric centrosymmetric phase into the acentric
polar phase as a function of temperature. In the paraelectric phase
above the Curie temperature, the Li atoms lie in an oxygen layer
that is c/4 distance away from the Nb atom, and the Nb atoms are
centered between oxygen layers. These positions make the paraelectric phase (non-polar) [14]. The structure of paraelectric phase
is shown in Fig. 4(a). As the temperature decreases below the
Curie temperature, the elastic forces of the crystal become dominant, driving the lithium and niobium ions into new positions. The
charge separation resulting from this shift of ions along c direction
relative to the oxygen octahedral, shown in Fig. 4(b), causes the
spontaneous polarization. The value of remanent polarization
Pr 0.09 mC/cm2 and saturation polarization Ps 0.21 mC/cm2 obtained from the loop are close to the value reported by DazMoreno et al. [5].
3.3. Magnetic study
Fig. 5 shows the magnetization curve of LiNbO3 at room temperature. A weak ferromagnetic nature is observed with a saturation magnetization (Ms) of 0.02 emu/g and coercivity (Hc) of
415 Oe. The obtained Ms is close to the value (0.017 emu/g) reported for nanocrystalline LiNbO3 but the value of Hc is small
when compared to the value (750 Oe) reported for the nanocrystalline LiNbO3 [5]. This can be attributed to the growth of larger
particles i.e., as the particle size increases the coercivity decreases.
During the synthesis process some of the neutral oxygen is expected to escape from the sample in the form of O2 gas, resulting
in the loss of acceptor charges which leads to the extended state of
Nb-s electron in LiNbO3. The asymmetric nature of electron spins
(i.e., spin up and spin down) in Nb-s orbitals contribute to the
magnetic property since there is no magnetically active ion. In the
paraelectric phase the midpoint between two neighboring Nb ions
act as an inversion center. In this case the spin of Nb-s electrons
are arranged antiparallel to each other resulting in an antiferromagnetic coupling between NbNb. This is energetically more
favorable through the created oxygen vacancies [4]. This antiferromagnetic interaction is destroyed by the ferroelectric distortion, i.e displacement of Nb breaks the inversion center between
the Nb ions and hence creates a small canting between the magnetic moments (i.e., a small deviation from overall spin conguration illustrated in Fig. 6) of neighboring Nb ions. The exchange
interaction called as DM interaction [15] between the canted spins
gives rise to a small net magnetization in the prepared polar
(ferroelectric) phase LiNbO3 and hence a weak ferromagnetism is
observed. This kind of phenomena was also observed in R3c FeTiO3
[16] which is structurally isomorphic to LiNbO3 polar phase.
3.4. Impedance spectroscopy

Fig. 1. X-ray diffraction pattern of LiNbO3.

The dc resistivity plot is shown in Fig. 7. The resistivity values

were extracted from the Z Vs Z plot. A gradual decrease in resistivity with temperature is observed. The conductivity is
3.5  10  7 1 cm1 at 373 K and it increases to 3  104 1 cm1
at 663 K. The order of obtained conductivity is higher than that of
single crystal LiNbO3 [17]. It was found that the ionic conductivity
of LiNbO3 increases while going from single crystalline nature to
microcrystalline, nanocrystalline and amorphous [8].
The conduction mechanism is furthermore explained by the

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Fig. 2. HR-SEM of LiNbO3 (a) showing the homogeneous distribution of particles. (b) showing microsized particles.

Fig. 3. PE loop of LiNbO3 showing the lossy ferroelectric nature.

Arrhenius plot in the temperature range of 373623 K (Fig. 8). The

two activation energies, Ea1  0.15 eV at temperature below 493 K
and Ea2 1.04 eV above the temperature 493 K, indicate two
thermally activated conduction processes. The Ea1 value is attributed to the activation of electronic conduction, and Ea2 corresponds to the activation of Li ion conduction. The oxygen vacancies
are thermally activated with temperature, and facilitate the long
range motion of lithium ion. The activation energy Ea2  1.04 eV
obtained in the temperature range of 493623 K is less than 1.2 eV
found for single crystal [8] in the similar temperature region.
Masoud et al. [8] also reported a decrease in the activation energy
from the single crystal to microcrystalline, nanocrystalline and
amorphous phases.
The frequency and temperature dependent dielectric constant
() of LiNbO3 are shown in Fig. 9. The value of increases with
temperature, but decreases with frequency at all measured temperatures. The contributions from electronic and ionic polarization
are small at low temperatures. But starts increasing with rise in
temperature [2], resulting in the dielectric constant values to increase gradually, which becomes rapid above 493 K. The rapid
increase is due to the hopping of lithium ions between thermally
activated oxygen vacancies. However, at low frequencies electronic, ionic, dipolar and interfacial components contribute to the
total polarizability, and hence is high. The interfacial and dipolar
polarizations lag behind the ac electric eld [18] with increase in
frequency, resulting in low values of dielectric constant at high

Fig. 4. Hexagonal unit cell of LiNbO3 (a) paraelectric phase and (b) ferroelectric
phase (the displacement of ions are shown inside the cell for clarity). The dotted
circles are original positions of ions and the solid spheres are displaced positions of
ions.

Fig. 5. Isothermal magnetization curve showing weak-ferromagnetism.

frequencies.

4. Conclusions
The polar phase LiNbO3 with hexagonal symmetry was prepared by ball milling assisted ceramic method. Homogeneous

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159

Fig. 6. Schematic representing alignment of spins in (a) paraelectric state and (b) ferroelectric state.

Fig. 7. Resistivity plots of LiNbO3 obtained from impedance measurement.

Fig. 9. Frequency dependent dielectric constant plots of LiNbO3 in the temperature

range 403613 K.

Ea2  1.03 eV. The relatively high activation energy (Ea2) indicates
the contribution of lithium ion conduction among the oxygen
vacancies at temperatures above 493 K. The activation of oxygen
vacancies is evidenced also from the dielectric studies in the form
of a rapid increase in the dielectric constant above 493 K. It has
been observed from the magnetic and ferroelectric studies that the
created oxygen vacancies induce the magnetic property and
slightly affect the ferroelectricity in LiNbO3.

Acknowledgment
MM thanks UGC-UPE Phase II, UOM, DRDO, India, P. Manimuthu, Authors acknowledge Dr. N.V. Giridharan and Muneeswaran, NIT, Trichy for PE loop measurements, SAIF, IIT Madras in VSM and Viswanathan for HR-SEM studies.

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Fig. 8. Arrhenius plot of LiNbO3 showing two thermally activated conduction
processes.

distribution of large particles is observed from electron micrographs. PE loop measurement exhibits lossy natured ferroelectric
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neutral oxygen vacancies. The dc conductivity study reveals two
conduction processes one with the activation energy of
Ea1  0.15 eV and the other with the activation energy of

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