Key Engineering Materials Vols.

510-511 (2012) pp 527-531

Online available since 2012/May/14 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/KEM.510-511.527

Synthesis and AC Electrical Characterization of

Co Doped Bismuth Manganite Nanoparticles
Khush Bakhat Akrama, M.S. Darb, Faheem-ul-Hassanc
and M. Anis-ur-Rehmand
Applied Thermal Physics Laboratory, Department of Physics,
COMSATS Institute of Information Technology, Islamabad, Pakistan
a
[email protected], [email protected],
c
[email protected], [email protected]

Keywords: Multiferroics, manganites, dielectric response, co-precipitation method.

Abstract: Multiferroic bismuth manganites (BiMnO3) possess both ferromagnetic and ferroelectric
properties. Their electrical properties can be controlled by doping for useful applications. In this
work single-phase cobalt doped bismuth manganite nanoparticles having general formula BiMn1-
xCoxO3 (x=0, 0.2, 0.4, 0.6) were synthesized by co-precipitation method. Structural properties like
lattice parameters and crystallite size of samples were determined by the data obtained by X-rays
diffraction. The dielectric constant (ε) and dielectric loss tangent (tanδ) of samples were
investigated as a function of frequency from 20Hz-3MHz using ac measurement data. For all the
compositions dielectric constant was decreased with increasing frequency, however it increased
with the increase in cobalt content. However cobalt addition causes a decrease in loss tangent as
compared to pure BiMnO3 composition. The origin of this behavior is discussed in terms of
Maxwell-Wagner and Koops model. Substitution of Mn with Co, in BiMnO3-based compounds is
supposed to cause better properties in terms of tangent loss.

Introduction
The term multiferroic has been coined to describe materials in which two or all three ferroic
properties, namely, ferroelectricity, ferromagnetism, and ferroelasticity coexist in the same phase
[1]. This indicates that these materials have spontaneous polarization, magnetization, and strain.
These order parameters can be regulated by the application of electric fields and/or magnetic fields,
and/or by using mechanical stress. These compounds have gained renewed and ever-increasing
research interest in the last three decades [2]. Multifunctional systems are an important current
focus in material research due to fundamental and technological opportunities arising from coupling
of distinct order parameters. Ferromagnetics and ferroelectrics permit magnetic control of electrical
polarization and associated multiple state memory applications. However the availability of these
materials is low because of incompatibility between magnetism and ferroelectricity [3]. BiMnO3
with a highly distorted perovskite structure has been extensively studied as a multiferroic material.
Among ABO3-type multiferroic oxides, BiMnO3 is a unique compound that displays true
ferromagnetic behaviour [4]. Ferromagnetism (at temperature less than 100K) and ferroelectricity
(at room temperature coexist) in BiMnO3 [5]. The multiferroic behavior of BiMnO3 is typically
attributed to the existence of two different sublattices: the stereochemical activity of Bi (6s2) lone
pairs is believed to be the origin of the structural distortions (having the C2 symmetry) and the
inversion symmetry breaking, which gives rise to the ferroelectricity, while the Mn sublattice is
responsible for the magnetism [6]. This point of view dominated over several years and was
documented in many review articles [7]. In 2007 Belik et al. have re-examined the crystal structure
of BiMnO3 and argued that below 770 K it is best described by the space group C2c, which has the
inversion symmetry [8]. This finding was later confirmed by Montanari et al. [9]. RMO (R is rare
earth Bi, M is transition metal Mn) family has attracted much attention due to its colossal
magnetodielectric and multiferroicity [10].

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528 Advanced Materials XII

In the present paper we report the effect of cobalt substitution on the structural parameters and
dielectric response of BiMnxCo1-x O3 (x=0, 0.2, 0.4, 0.6) samples with the variation of applied ac
frequency.

Experimental
Polycrystalline ceramic samples were prepared by co-precipitation reaction of stoichiometric
quantities of Mn(NO3)2, Co(NO3)3 and Bi(NO3)3 salts. 0.4 molar aqueous solutions of
stoichiometric quantities of Mn(NO3)2.4H20 and Co(NO3)3.6H2O were prepared. Required quantity
of Bi(NO3)3.5H2O was dissolved in nitric acid (30ml). The precipitating agent aqueous NaOH was
used up to the pH~12, followed by the continuous stirring of solution for 1-2hrs at temperature
around 70-80 oC. The washed products were dried, grounded and pelletized using hydraulic press.
The pellets of BiMn1-xCoxO3 (x=0, 0.2, 0.4, 0.6) samples were sintered at 550 oC, 573 oC, 595 oC
and 618 oC respectively, for 4 hr each, with a heating rate of 7 oC/min. The phase constitution and
the crystal structure of the sintered samples were identified by X-ray diffraction (PANalytical,
XPertPro) at room temperature using Cu-Kα (λ=1.5406Å) radiations. The dielectric characterization
was conducted on the silver pasted pelletized samples at room temperature and as a function of
frequency (20 Hz to 3 MHz) range.

Results and discussions

Phase composition and structure: The room temperature X-ray diffraction patterns recorded for
the sintered samples show almost single phase samples, consisting of the well-crystallized
perovskite phase (Fig. 1). From the structural point of view, the XRD data pointed out that all the
samples investigated here exhibit monoclinic C2c symmetry (α=γ=90°, β=110.667°), similar to the
structure of BiMnO3 compound. The increase of the cobalt content has not induced a modification
of the space group.

450
(310)
400

350
(321)
300
Intensity (a.u)

250
(422) (510)(521)
(600)
x=0.6
200

150 x=0.4

100 x=0.2
50
x=0.0
0

20 30 40 50 60 70 80

Position 2ϑ

Fig. 1. Room temperature XRD patterns of the BiMn1−xCoxO3 ceramics

The increase of the cobalt concentration induces an obvious decrease of both b and c lattice
parameters (Fig. 2) and, therefore, a gradual contraction of the unit cell volume is pointed out.
 Key Engineering Materials Vols. 510-511 529

6.640

Lattice constant 'b' (Angstrom)

9.970
Lattice constant 'a' (Angstrom)

9.965 6.635

9.960
6.630
9.955

9.950 6.625

9.945
6.620
9.940

0.0 0.1 0.2 0.3 0.4 0.5 0.6

0.0 0.1 0.2 0.3 0.4 0.5 0.6
Composition (x) Composition (x)

(i) (ii)

9.920
Lattice constant 'c' (Angstrom)

9.915

9.910

9.905

9.900

0.0 0.1 0.2 0.3 0.4 0.5 0.6

Composition (x)

(iii)
Fig. 2. Influence of the cobalt content in BiMn1−xCoxO3 ceramics on lattice parameters
(i) a (ii) b and (iii) c

Dielectric Properties: The frequency dependence of the dielectric permittivity (ε) and loss factor
(tanδ) for BiMn1−xCoxO3 (x=0, 0.2, 0.4, 0.6) at room temperature in the frequency range 20Hz-
3MHz is presented in Fig. 3. It is evident that dielectric constant and loss tangent decrease with
increasing frequency. Very high values of permittivity in the range of 667 to 25,000 are observed
in the starting low frequency range, except for x=0.0 for which the highest value of permittivity is
4.39 at lowest frequency 20Hz, followed by a monotonous decrease with frequency at room
temperature, for all the compositions (Fig. 3(a)). Losses above unity is characteristic for these
ceramics, particularly at low frequency, for which tanδ is about a few tenths (Fig. 3(b)). The losses
also are strongly diminishing with increasing frequency and they reduce below unity for f =106 Hz.
The high values of permittivity at low frequency are not intrinsic properties of the ceramic
compounds, but they are rather related to conductive properties [12]. The highest values of
permittivity are found for x = 0.6 among all the Co doped BiMnO3 compositions; Fig. 3(a). The
highest values of losses are found for undoped BiMnO3 compositions; Fig. 3(b).
530 Advanced Materials XII

26000 1000
24000 x=0.0
22000
x=0.0
x=0.2 800 x=0.2
20000
x=0.4 x=0.4
18000
x=0.6 x=0.6
16000 600
14000

tanδ
12000
400
10000
ε

8000
6000 200
4000
2000
0
0
-2000
2 4 6 8 10 12 14 16 2 4 6 8 10 12 14 16

lnf (Hz) lnf (Hz)

(a) (b)

Fig. 3. Dielectric properties of the BiMn1−xCoxO3 ceramics at room temperature in the frequency
range 20Hz–3MHz: (a) permittivity (ε) vs. frequency and (b) tangent loss (tanδ) vs. frequency

The frequency dependence of the permittivity indicates the presence of a complex dielectric
relaxation and/or conduction contributions, as result of various local amounts of oxygen vacancies.
Fig. 3(a) shows that the decrease of ε is sharp at lower frequencies and shows almost frequency-
independent behavior at higher frequencies. The grain boundary in polycrystalline ceramics and
various defect structures (such as twin boundaries, dislocations) in single crystals and interphases in
composites play an important role in this mechanism. All of these effects create a complex
dielectric behavior with multiple relaxation and conduction components, which might be different
according to the degree of substitutions and microstructural characteristics of each of the present
Co-doped BiMnO3 ceramics. The observed variation in ε is in accordance with the Maxwell–
Wagner model [13, 14]. The inhomogeneous structure of manganites consists of conducting grains
and poorly conducting grain boundaries [15]. The voltage applied to the samples drops mainly at
the grain boundaries, and space charge polarization occurs at the grain boundaries. According to
Koops model, the effect of grain boundaries is dominant for lower frequencies. Also, the decrease
in dielectric constant with an increase in frequency can be attributed to the electron exchange
occurring between Mn+3 and Mn+4 ions. This exchange phenomenon cannot follow the change of
external applied field after a certain frequency [16].

Conclusions
We have studied the effect of Co substitution in the BiMnO3 ceramics on the dielectric behavior.
Single phase BiMn1−xCoxO3 (x=0, 0.2, 0.4, 0.6) ceramics were prepared by co-precipitation
reaction. In the studied conditions, the cobalt solute is completely incorporated in the BiMnO3
perovskite lattice. The samples exhibit a monoclinic C2c structure. The lattice parameters and the
unit cell volume decreased with the increase of cobalt content.
All the compositions present a decreasing permittivity with frequency and very high losses, which
seems to be characteristic of a relaxation, conduction behavior and grain boundary phenomena as a
result of various local amounts of oxygen vacancies.

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Advanced Materials XII
10.4028/www.scientific.net/KEM.510-511

Synthesis and AC Electrical Characterization of Co Doped Bismuth Manganite

Nanoparticles
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