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International Journal of Nanotechnology
and Application (IJNA)
ISSN(P): 2277-4777; ISSN(E): 2278-9391
Vol. 4, Issue 3, Jun 2014, 29-32
TJPRC Pvt. Ltd.

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF CD DOPED LCMO CMR
MANGANITES
P. SUBHASHINI, B. MUNIRATHINAM & M. KRISHNAIAH
Department of Physics, Sri Venkateswara University, Tirupathi, Andhra Pradesh, India

ABSTRACT
La
1-x
Ca
x
MnO
3
(LCMO) has attracted wide attention due to its significant colossal magneto resistance effect. It is
well known that the partial substitution of cations of different size at the A-site (site of La
3+
or Ca
2+
ions) induces
deformation in the unit cell structure and gives the occurrence of widely different electronic properties. Although Cd and
Ca ions have the same valence and similar cation sizes, their incorporation into vacancy doped La manganites induces
different properties. The replacement of Ca by Cd in La
0.5
Ca
0.5
MnO
3
(LCMO) manganites were successfully synthesized
by using the nitrate route method. The composition and structural properties were studied at various concentrations by
X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS).
The structural analysis showed that the Cd
2+
doped LCMO crystallized in an orthorhombic perovskite structure with Pnma
space group. The crystal size of the sample was calculated using Scherrer formula. The morphology of the samples was
studied and the corresponding grains are observed to be spherical in shape. The compositional studies showed that the
atomic percentages of elements are nearly stiocometric.
KEYWORDS: Manganites, Magnetoresistance, Structural Properties
INTRODUCTION
The discovery of colossal magnetoresistance(CMR) has attracted scientific and technological interest due to their
exotic physical properties. Since the middle of 1990s the CMR effects the rare earth doped manganite perovskites has a
strong interest because of their potential applications in spintronics [1,2]. The manganites have a crystal structure derived
from the cubic perovskite ABO
3
(RE
1-x
AE
x
MnO3), where Mn occupies the B site and rare-earth Lanthanides occupies the
A site. The perovskite manganese oxides have small e
g
electron band width. Charge-ordering, which is the real space
ordering of Mn
3+
- Mn
4+
is one of the interesting phenomena. In the mixed-valence manganese oxides, the strong
correlations among spin, orbital and lattice degree of freedom play crucial roles [3, 4] mainly for the
intermediate-hole-doped La
0.5
Ca
0.5
MnO3 compounds, generally characterized by relatively small A-site ionic
radius < r
A
>. Several reports have been published describing Ca
2+
(ionic radius 1.18A) as a divalent doping
element [57]. The close value of the Cd
2+
ionic radius (1.15A) seems to indicate that direct substitution of Ca ions by
Cd ones can be performed without dramatic changes in the structural and magnetic properties. In this work, the results
concerning the structural properties of the La
0.5
Ca
0.5
MnO
3
perovskite when Ca
2+
is replaced progressively by Cd
2+
.
EXPERIMENTAL METHOD
The LCMO compounds were prepared individually by using the nitrate route method. The required quantities of
99.9% pure nitrates such as La (NO
3
)
3
.6H
2
O, Ca (NO
3
)
2
. 4H
2
O, and acetate such as Mn (CH
3
COO)
2
. 4H
2
O were used to
prepare individually the solutions of specific molarity using distilled water. The mixed solutions were thoroughly stirred
30 P. Subhashini, B. Munirathinam & M. Krishnaiah

Impact Factor (JCC): 1.8003 Index Copernicus Value (ICV): 3.0
using magnetic stirrers and dried at 80 C and the resulting pulp was calcined first at 700C for 7 hours and then furnace
cooled to ambient temperature (30 C). The resulted soft black powder was then ground thoroughly in a mortar and again
calcined at 900 C for 14 hours before furnace cooling to ambient temperature. Around one gram of each powder prepared
through both the routes was then pressed into pellet and sintered in air at 900C for 14hours.
The XRD patterns of all the samples were recorded using a PAN alytical Xpert Pro diffractometer with Cu-K
radiation in angular steps of 0.02. The surface morphology was characterized by Scanning electron microscope (SEM) of
model EVO ma 15 manufactured by Carl Zeiss. The compositional analysis was studied using Energy Dispersive
Spectroscopy (EDS) attached with SEM of model Oxford instruments Inca Penta FET x3.
RESULTS AND DISCUSSIONS

Figure 1: X-ray Diffraction Patterns of La
0.5
Ca
0.5
MnO
3
and La
0.5
Cd
0.5
MnO
3

Figure 1 Shows the XRD patterns of La
0.5
Ca
0.5
MnO
3
and La
0.5
Cd
0.5
MnO
3
sample. Analysis of these patterns
reveals single phase orthorhombic structure with Pnma space group for all the samples. The crystallite size of the
synthesized samples is calculated using Debye -Scherer equation [8].
L = K x / x cos (1)
Where
= Full width at half maximum
K = constant (0.9)
= Wave length of X-ray
= Braggs angle
The highest intensity diffraction peak of both samples has been found at 2=32.6 [9] with (121) orientation along
with other reflexions (220), (202), (123) and (004). The average crystallite size of all samples is estimated to be around 34
nm.. In order to study the variation of lattice parameters of samples with composition parameter (x), the same has been
estimated using a standard software package.
The estimated values of lattice parameters and cell volume are given in Table 1. Due to the small ionic radius of
Cd
2+
ion than the Ca
2+
ion, cell parameters are decreased which should be expected as Cd enters into the composition of the
samples. Then the cell volume has been decreased to 115.3 (A) for the La
0.5
Cd
0.5
MnO
3
.
Synthesis and Structural Characterization of Cd Doped LCMO CMR Manganites 31

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Table 1: Unit Cell Parameters of Compounds
Lattice
Parameters
Sample
La
0.5
Ca
0.5
MO3 La
0.5
Cd
0.5
MO3
a (A) 5.4286 4.7109
b (A) 7.7870 6.0391
c (A) 5.4255 4.0535
V(A
3
) 229.353 115.321

The micro structural and composition analysis was studied by using SEM with EDS. The morphology of
obtaining samples shown in figure 2. It shows that the grains are uniform and near- spherical shape.

Figure 2: SEM Images of (a) La
0.5
Ca
0.5
MnO
3
(b) La
0.5
Cd
0.5
MnO
3


Figure 3: EDS Spectrum of (a) La
0.5
Ca
0.5
MnO
3
(b) La
0.5
Cd
0.5
MnO
3

The composition of each sample has been estimated using EDAX analysis shown in table 2. Figure 3 shows the
EDS spectra of both compounds. Elemental analysis revealed that the samples contain target elements and no other
impurity was detected in both compositions. The oxygen content can be increased to be observed in the La
0.5
Cd
0.5
MnO
3

compound.
Table 2: Elemental Composition of Compounds
Elements La
0.5
Ca
0.5
MnO
3
La
0.5
Cd
0.5
MnO
3

La(%) 17.9 12.6
Ca(%) 14.2 ---
Cd(%) --- 10.4
Mn(%) 29.2 23.04
O(%) 38.6 53.9

CONCLUSIONS
In this work it is concluded that the effect of Cd doped La
0.5
Ca
0.5
MnO
3
composition consists of a orthorhombic
structure with (Pnma) space group. The lattice parameter was found to be decreased in La
0.5
Ca
0.5
MnO
3
. The SEM images
show that the particles are nearly spherical shape. EDS analysis reveals that the synthesized samples are stoichiometric in
composition and no other impurities are present in both compositions.
32 P. Subhashini, B. Munirathinam & M. Krishnaiah

Impact Factor (JCC): 1.8003 Index Copernicus Value (ICV): 3.0
ACKNOWLEDGEMENTS
The authors would like to thank University Grants commission, New Delhi for the award of Shri Rajiv Gandhi
National Fellowship to pursue my doctoral degree research program at Sri Venkateswara University, Tirupati.
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