Structural and Magnetic Properties of

LaPbMnO3 Nanowires
M. Ramesh Babua, Junyang Chenb, K. Prabhac, X.F. Hanb and R. Jayavela
a
Crystal Growth Centre, Anna University Chennai, Chennai-600025, India
b
State Key Laboratory of Magnetism MO2 group, Beijing National Laboratory for Condensed Matter
Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100080, China
c
Department of Physics, Loyola College, Chennai -600034 , India

Abstract. Nanoscale one-dimensional structures have attracted much interest because of their
novel magnetic, electronic and optical properties as a result of their low dimensionality and
quantum confinement effect. La1-xPbxMnO3 (LPMO) nanowires are prepared using a simple sol–
gel process and alumina oxide template. The as prepared LPMO nanowires are 200 nm in
diameter and tens of microns in length. Prepared nanowires were annealed at 700˚C for one hour
and exhibit polycrystalline perovskite structure was confirmed from powder X-ray diffraction.
The surface morphology of as grown and annealed sample was studied using scanning electron
microscope. Magnetization measurements were performed from low temperature to room
temperature. Field cooled and zero field cooled magnetic measurement with 500 Oe field reveals
the cluster glass behaviour of the nanowires below the Curie temperature. Room temperature
hysteresis measurements shows paramagnetic like behavior.
Keywords: Colossal magnetoresistance, Sol-Gel, Nanowires, Manganites, Cluser glass.
PACS:74.25.F, 75.47.Gk, 75.50.Lk, 75.50.Tt, 75.60.Ej.

1. INTRODUCTION
The perovskite manganites, La1-xAxMnO3 (A = Ca, Sr, Ba) are very attractive
materials due to their spectacularly large magnetoresistance which could not be
compared with any other forms of magnetoresistance. This discovery of CMR raised
expectations of a new generation of magnetic devices and sensors, such as magnetic
data storage and magnetic-read heads [1]. Compositional variations of resistivity,
magnetic and magnetotransport properties of Pb-doped manganites can be interpreted
in the framework of the double exchange model [2] considering the electron transfer
with spin memory between the Mn ions of different valence as the basic physical
mechanism responsible for conductivity. In these materials, the interaction between
the electrons and lattice vibrations (phonons) is unusually strong [3], leading to a wide
range of striking physical phenomena and, most crucially, can be "tuned" over a wide
range by variation of chemical composition, temperature and magnetic field. The
nanostructured materials
CREDIT could exhibit enhanced
LINE (BELOW) electronic and
TO BE INSERTED ONmagnetic properties as
compared with their conventional microscale counterparts
THE FIRST PAGE OF EACH PAPER [4]. Regarding the template
for the growth of nanoscale CMR manganites, the porous anodized alumina oxide
(AAO) template has proven to be very flexible. Recently, the fabrication of

CP1276, International Conference on Advanced Nanomaterials and Nanotechnology (ICANN-2009)

edited by P. K. Giri, D. K. Goswami, A. Perumal, and A. Chattopadhyay
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335
La0.67Ca0.33MnO3 ordered arrayed nanowires was done and it was found that the
reported ferromagnetic transition point TC is higher than that for single crystals [5].
The growth of La0.67Sr0.33MnO3 oriented nanowires within the pores of AAO
templates was also reported [6]. In the present work, we investigated systematically
the structure and magnetic properties of LPMO nanowires prepared by using AAO
template.
2. Experiment
The LaPbMnO3 precursor was prepared by dissolving a stoichiometric ratio of
lanthanum nitrate [La(NO3)3·6H2O], manganese acetate [Mn(CH3COO)2·4H2O] and
lead acetate [Pb(CH3COO)2] in water and acetic acid, respectively. About 3 ml of
acetyl acetone (C5H8O2) was added to the solution to stabilize the LPMO solution. The
concentration of the final solution was adjusted to 0.3 M and the pH value of 4–5. The
AAO templates were pasted on glass plate and dipped in to the precursor solution for
12 h. Then surfaces of the template cleaned to remove the particle on the surface of the
template after the growth. Heating the templates containing the precursor in air at
700˚C for 1 h using a thermal annealing furnace was sufficient to obtain the desired
perovskite phase of LPMO. This annealing temperature is lower than the sintering
temperature for LPMO powders using the solid state reaction route (above 1100˚C).
The sintered template was partially dissolved using NaOH solution for structural and
morphology measurements. The morphology and structure of the LPMO nanowires
were investigated using x-ray diffraction (XRD) and scanning electron microscopy
(SEM). Magnetic properties of the LPMO nanowires were characterized by a
superconductive quantum interference device (SQUID) from room temperature to
10K. The composition of the nanowires was determined by EDX measurement.

3. Results and Discussions

Fig. 1 shows the XRD spectrum for the synthesized nanowires with partially
dissolved AAO template and inset of the figure shows (220) peak corresponding to
LPMO. The powder XRD pattern consists of two sets of peaks. According to the
standard JCPDS cards, one set corresponds to the La0.7Pb0.3MnO3 hexagonal cell with
lattice parameters of a=11.1232(0.09) Å, and c= 13.1903(0.22) Å, and the other to -
Al2O3. Therefore, the single-phase perovskite LPMO can be obtained by sol–gel
process with AAO template at low temperature of 700˚C, while, it is generally
obtained at elevated temperatures. The mixture of the constituents of LPMO at
molecular (atomic) level in the sol–gel process is the most important factor for the
reduced firing temperature.

FIGURE 1 Powder XRD pattern of La0.7Pb0.3MnO3 nanowires with partially dissolved AAO template.
Inset of the figure shows peak corresponding to (220) plane.

336
 Fig. 2 shows the morphology of partially dissolved AAO template wih
nanoparticle. Before annealing some part of the template was filled with nano particle
and nanowires. The diameter of the nanowires are around 180 nm after annealing at
700˚C. The growth of nanowires using AAO template channels by space confinement
across the diameter and compound in the form of solution enter in the NCA’s
channels. The obtained nanowires diameter is lower than the diameter of AAO
channels [7]. The composition of the fabricated nanowires is determined from EDX
measurement and consistent with our initial composition.

FIGURE 2 Surface morphology of partially dissolved AAO template with some nanoparticles

FIGURE 3 Cross section view of as grown La0.7Pb0.3MnO3 nanowires after dissolving AAO template.

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 The temperature dependent hysteresis measured at 10K and 300K are shown in the
Fig. 4. Room temperature hysteresis showed diamagnetic like behavior due to the
AAO template and LPMO paramagnetic nature dominated by diamagnetic properties
of the template. The low temperature hysteresis showed saturated hysteresis at higher
field. Low value of coercive field and remanent field observed from the hysteresis
measurements. The temperature dependence of DC magnetization (M) for
La0.7Pb0.3MnO3 nanowires is shown in Fig. 5. The data were obtained in the heating
process at zero-field-cooled (ZFC) mode and field cooled (FC) under an applied
magnetic field of (H=500 Oe) in the temperature range of 10−300 K. It shows that all
studied samples undergo a sharp paramagnetic-ferromagnetic (PM-FM) transition
around Curie temperature TC = 191K (defined as the one corresponding to the peak of
dM/dT in the M vs T curve). Inset of Fig.3 Shows the Curie-Weiss plot and clearly
indicate the paramagnetic properties after the Curie temperature.

FIGURE 4 Temperature dependent hysteresis of LPMO nanowiers combined with partially dissolved
AAO template.

FIGURE 5 Temperature dependent magnetization in zero field cooled and field condition with 500 Oe
field.Inset shows temperature dependent inverse susceptibility.

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 The observed Curie temperature is lower than bulk materials may due to the
insulating layers are formed in the outer layer of the nanowires. It is reported that
Increase of the Curie temperature was observed in LCMO nanowires due to hardening
of the Jahn–Teller (JT) phonon mode !ph as the size is reduced [5]. In our case the
size of the nanowires around 180 nm and the hardening of JT polarons are ruled out.
Above the Curie temperature magnetization was not reached zero and shows some
magnetization near to room temperature. The paramagnetic property is clearly seen in
the Curie-Weiss fit and is shown in the inset of Fig.5. The paramagnetic Curie
temperature is 193K and clearly indicated that ferromagnetic clustering effect not
presented in the nanowires. The bifurcation between ZFC and FC indicate spin glass
properties of the synthesized nanowires and may be due to the short range order in the
surface of the nanowires.

CONCLUSIONS

Nanowires of LPMO were prepared by a template-aided sol-gel process. The

diameters of the synthesized nanowires are around 180nm and length in tenth of
microns. The Curie temperature of the nanowires was significantly reduced that of the
bulk materials. Surface defect increases the spin glass property and decreases the
Curie temperature.

ACKNOWLEDGMENTS
One of the authors (MR) acknowledges CAS and TWAS for the award of CAS-
TWAS 08 fellow ship to carryout part of his research work in the Institute of Physics,
China. Also acknowledges CSIR for the award of CSIR-SRF fellowship.

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