The exchange bias in NiFe2O4-CoO nanocomposite prepared by polyol process

Sarveena, M. Singh, and S. K. Sharma

Citation: AIP Conference Proceedings 1832, 050141 (2017); doi: 10.1063/1.4980374

View online: http://dx.doi.org/10.1063/1.4980374
View Table of Contents: http://aip.scitation.org/toc/apc/1832/1
Published by the American Institute of Physics
 The Exchange Bias in NiFe2O4-CoO Nanocomposite
Prepared by Polyol Process
Sarveena1, M. Singh1 and S. K. Sharma1, 2
1
Department of Physics, H. P. University, Shimla, 171005, HP India
2
Departamento de Física, Universidade Federal do Maranhão, 65085-580 São Luis, Brazil
Email: [email protected]

Abstract. Exchange coupled NiFe2O4-CoO nanocomposite (NFOC) was synthesized by polyol process using NiFe2O4
seed. The nanocomposite was characterized by x-ray diffraction (XRD), transmission electron microscopy (TEM) and
SQUID magnetometer. A Field cooled hysteresis curve of NFOC at 4 K is clear signature of strong internal interaction
and co-existence of different magnetic phases into the individual particles. The strong interfacial exchange coupling
between the AFM and FiM part results in high value of coercivity with completely shifted loop along negative field axis.
Keywords: polyol process, multiple nanodomains, irreversibility temperature, exchange bias.
PACS: 81.07.Bc,78.67. Sc, 75.50.Ee, 75.50.Gg, 75.30.Gw, 75.60.Jk, 75.70.Cn

INTRODUCTION spintronics devices, and gas and humidity sensors due

to its rich electronic and magnetic properties with
Recent technological breakthroughs and the desire chemical and thermal stability [4]. On other side, CoO
for new functions generate an enormous demand of is known to be an insulating antiferromagnet (TN ~ 298
novel materials for innovative applications. Scientists K) with rocksalt cubic structure [5]. Although there are
and engineers realized that mixtures of materials can some reports on the synthesis of CoO in bulk form, but
show superior properties compared with their pure this material is difficult to obtain in pure form often
counterparts to realize its multi-functionality. One of being contaminated with Co metal or Co3O4 spinel
the most successful examples is the group of phase. Additionally, there might be ample probability
composites which are formed by the incorporation of a to obtain CoO phase without any contamination from
basic structural material into a second substance [1, 2]. Co or Co3O4 by using seeds of NiFe2O4. Indeed, when
In brief, there is a great demand of nanomaterials with a soft FiM is in get contact with an AFM one, the
diverse and tunable magnetic properties in order to coupling at the interface give rise to unidirectional
utilize them for technological applications. It is well anisotropy known as exchange bias (EB). EB effect is
known that a range of novel properties such as changes a keystone of the device and operation of spin valve
in the magnetization reversal modes, devices. It is also a straightforward way to beat the
superparamagnetism, high saturation field, extra superparamagnetic limit imposed by nanometric size
anisotropy contributions or shifted loops after field particles in magnetic recording media. In the present
cooling, arise in both ferrimagnetic material (FiM) work, we report the synthesis, and an investigation of
and Antiferrimagnetic material (AFM) materials, as the magnetic properties of NiFe2O4-CoO
the size is reduced [3]. These phenomena arise from nanocomposite starting from NiFe2O4 seeds.
finite size and surface effects that dominate the
magnetic behaviour of individual nanoparticles. EXPERIMENTAL DETAILS
Hence it is appealing to investigate how does size
reduction affect FiM–AFM coupled systems. NiFe2O4-CoO was prepared by polyol process. To
NiFe2O4 is one of the most versatile and prepare NiFe2O4-CoO nanocomposites, firstly we have
technologically important soft ferrimagnetic material prepared NiFe2O4 nanoparticles by thermal
widely used in electromagnetic devices and magnetic decomposition of metallic precursor [M (acac) n, n =2
components such as resonators, phase shifters, or 3, acac = acetylacetonate or carbonyls] using high

DAE Solid State Physics Symposium 2016

AIP Conf. Proc. 1832, 050141-1–050141-3; doi: 10.1063/1.4980374
Published by AIP Publishing. 978-0-7354-1500-3/$30.00

050141-1
boiling point organic solvent 1-octadecene etc.) nanoparticles in NFOC is estimated to be
containing surfactant (oleic acid and oleyamine)and approximately 7.0 ± 1.5 nm.
reducing agent (1,2-hexadecanediols) or polyol
process (using diethylene glycol). NiFe2O4 is used as
starting seeds to grow the nanocomposites. We have
tested several syntheses in order to fully optimize the
nanoparticle structure, but we are presenting here the
results for a sample prepared using x = 100 mg
concentration of NiFe2O4. Here ‘x’ is the concentration
of NiFe2O4 seeds. In a typical synthesis, an appropriate
amount of NiFe2O4 (100 mg) seeds and diethylene
glycol (DEG, b. p. = 246oC) were mixed in a three
neck flask along with Co(ac) 2 4H2O (0.02 M), while
keeping the hydrolysis ratio h = 24. The solution was
then heated up to reflux at a temperature fixed by the
water/polyol ratio, not exceeding 215oC (6oC/min) in
Figure 1. X-ray diffraction pattern for the NiFe2O4-CoO
the present case and maintained at this temperature for
nanocomposites.
24 hours. The solution turned into black in color at this
stage. Finally, the solution was cooled down to room
temperature. The nanoparticles were washed adding Figure 2 highlights the TEM of NFOC
access of ethanol and centrifugation at 25000 rpm for nanocomposite samples taken in both low as well as
15 minutes. This procedure was repeated thrice by high resolution modes. Spherical nanoparticles of
dispersing the nanoparticles in excess of ethanol and NFCO sample were revealed in low magnification
centrifugation. Finally, the sample was dried overnight TEM images as shown in the Figure 2(a). These
in an oven at 50oC. particles have average particle size of ~ 135 ± 10 nm.
The nanocomposites was characterized using Interestingly their high resolution image in Figure 2(b)
means of transmission electron microscopy (TEM, reveals unusual aggregation of particles which are
3010 JEOL 3010 operating at 200 keV), x-ray made up of several small particles. It is observed that
these small particles join together during
diffraction (XRD, PANanalytical X’pert with Co KD
heterogeneous nucleation to form large aggregates of
radiations) and a SQUID magnetometer (Quantum
size ~ 135 ± 10 nm with ideal orientated planes. It is
Design MPMS XL). The samples for the TEM were
quite remarkable that the aggregated nanoparticle
prepared by placing a drop of a dilute ethanol
possesses an almost mono crystalline diffraction
dispersion of nanocomposites on a carbon coated
pattern with spots like appearance as shown in Figure
copper grid and allowing it to dry.
2(c) of selected area electron diffraction (SAED)
pattern. However, a slight lengthened diffraction spots
Results and Discussion suggests the presence of multiple nanodomains with
small misorientation deviating from perfect
Figure 1 shows the XRD pattern for NFOC arrangement among nanocrstallites.
nanocomposites. The x-ray peaks correspond to only
pure cubic rock salt phase of CoO. This is probably
due to very small concentrations of NFO seeds in the
nanocomposite sample. The particle size was
estimated using the Scherrer formula [6] by taking the
full width at half maximum (FWHM) of the most
intense peak obtained from the pattern according to
formula given below:

kO
D B2 = B2M -B2S (1)
BCosT
Where D is the particle size in Å, k is the shape factor FIGURE 2. (a) Low resolution TEM, (b) HRTEM and (c)
SAED micrographs of NiFe2O4-CoO nanocomposites.
(usually taken as 0.9), O is the X-ray wavelength
(1.78Å), BM and BS are the measured peak broadening Figure 3 shows the magnetization versus
and instrumental broadening in radian respectively and temperature curves for NFOC nanocomposite samples
T is Bragg's angle in degrees. The size of the CoO

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measured ZFC and FC conditions. The ZFC and FC existence of different magnetic phases into the
measurements were carried out as follow: the sample individual particles. Therefore, this particular structure
was first cooled down from 350 K to 5 K in a zero will generate exchange bias (HEB) field below the Neel
magnetic field, then a static magnetic field (H = 50 temperature, TN of CoO phase [8]. Upon field cooling
Oe) was applied and MZFC was measured during of sample from 300 K to 4 K below the TN of CoO (~
warming up from 5 K to 350 K; finally the sample was 298 K), the magnetic hystersis loop exhibit a set of
cooled down to 5 K under the same field and MFC was interesting and unique features arising from the strong
measured during the cooling cycle. The MZFC maxima interfacial exchange coupling between the AFM and
occurs at ~ 248 K. Alternatively, going to lower FiM part. It is surprising to note that the NFOC sample
temperatures the MFC show a temperature-independent is showing very high value of coercivity with
behavior below TB, indicating the presence of long- completely shifted loops along negative field axis. The
range magnetic interparticle interactions among the value of HEB for sample NFOC is ~ 2.09 kOe.
nanoparticles. The MFC and MZFC curves split below a In conclusion, we have synthesized NiFe2O4-CoO
temperature called the irreversibility temperature nanocomposite with spherical nanoparticles of size
(TIRR), which is associated with the blocking of the approximately 7.0 ± 1.5 nm. The strong interfacial
biggest particles [7]. exchange coupling between the AFM and FiM part
results in loop shifted along the negative field axis
with HEB ~ 2.09 kOe.

ACKNOWLEDGMENTS
Sarveena is thankful to UGC-DAE CSR, Indore
Centre for financial support under CRS Scheme. SKS
is grateful to FAPEMA for providing financial support

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FIGURE 4. Field cooled hysteresis curve of NiFe2O4-CoO
nanocomposite at 4 K.

The M-H curve in figure 4 shows non-linearity

below the Nèel temperature and no saturation was
observed in a high field of 70 kOe. These are the clear
signature of strong internal interaction and co-

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