Exchange bias field in mixed arrangement of NiO-Ni nanoparticles

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

Citation: AIP Conference Proceedings 1731, 050115 (2016); doi: 10.1063/1.4947769

View online: http://dx.doi.org/10.1063/1.4947769
View Table of Contents: http://aip.scitation.org/toc/apc/1731/1
Published by the American Institute of Physics
 Exchange bias field in mixed arrangement of NiO-Ni
nanoparticles
Sarveena1, Shalendra Kumar2, M. Singh1 and, S. K. Sharma3,1
1
Department of Physics, H. P. University, Shimla Pin 171005 India
2
Institute of Basic Sciences, Changwon National University, Gyeongnam 641-773, Republic of Korea
3
Instituto de Fisica Gleb Wataghin, UNICAMP, Campinas, 13.083-859, SP, Brazil

Abstract. Three samples of naturally mixed Ni (>120 nm) and NiO (~ 10 nm) were prepared with different particle
diameters/distributions and amount of metallic nickel. Exchange bias effect has been observed and strongly depends upon both
particle sizes/distributions and concentration of Ni, achieving the highest value (~ 2200 Oe at 5 K) for the pure NiO, while the
corresponding value for the sample with maximum Ni concentration is ~ 70 Oe. This is tentatively explained taking into account
the effect of induced dipolar field by bigger Ni particles on the stabilization of magnetically ordered surface regions of the
smaller NiO nanoparticles.
Keywords: Magnetic properties of nanostructures
PACS: 75.75.-c

INTRODUCTION
In magnetic recording devices, a large exchange bias
field, HEX is one of the important requirements for the
thermal stabilization of magnetic nanoparticles (NPs).
Furthermore, the enhancement and tunable HEX in
nanomaterials is currently an active area of research,
whereas the study of the internal magnetic structure
and interparticle interaction of magnetic NPs is of
great interest from both fundamental as well
technological points of view1-2.
In the present work we investigate the effect of the co-
existence of two different kinds of particles with
considerable dipole-dipole interactions. One kind of
particles is NiO NPs (mean size ~ 10-12 nm) with
core-shell morphology, labeled as NiO small particles.
The other type are Ni particles (size >100 nm), labeled
as big Ni particles. It is worth mentioning that the big
particles have the typical internal multi-domain
magnetic structure as in bulk-like magnetic materials.
It is observed that changing the relative amount of
each type of particle, i.e., the NiO/Ni number of
particle ratio, the HEX and the collective magnetic
response change drastically. Therefore, it is possible to
show that the big Ni nanoparticles in this type of
geometrical arrangement system can be conveniently
used as pinning magnetic centers for stabilization of
the frustrated magnetic structure within the core-shell
NiO nanoparticles.
EXPERIMENTAL DETAILS
Firstly, the Ni-metallic precursor was prepared from
the stoichiometric amount of Ni(NO3)2.6H2O (0.1
mmol, 0.029g), triphenylphosphine (0.3 mmol,
0.078g) and tetraethyl ammonium chloride hydrated
(0.03 mmol, 0.016g), which were mixed in 40 mL of
warm acetonitrile (ACN) and heated at 75 oC for 3-4
hours under continuous Ar flux with intermediate
stirring. Crystals of desired size can be achieved by
cooling the solution slowly to room temperature.
Thereafter, 30 mL of 1-octadecene and x mL (x = 1.5,
3.5 and 10 mL) of oleyamine (OLA) were slowly
added to this solid solution (keeping the molar ratio of
Ni/OLA=1:10, 1:25 and 1:70). The above mixture was
slowly heated up to a final temperature of 225 0C for 1
hour under Ar flux with heating rate of ~ 3 °C/min.
Finally, the solution was cooled down to room
temperature. The nanoparticles were washed adding
excess of ethanol and centrifugation. The samples
were thereafter designated as S10, S25 and S70,
respectively.
The particle diameters and its distribution were
measured by means of transmission electron
microscopy (TEM) (300 keV JEM 3010 microscope)
The structure was determined by X-ray diffraction
(XRD) (Philips, X-PERT) and the magnetic properties
were measured with a SQUID (Quantum Design,
MPMS XL) magnetometer as well as a commercial

DAE Solid State Physics Symposium 2015

AIP Conf. Proc. 1731, 050115-1–050115-3; doi: 10.1063/1.4947769
Published by AIP Publishing. 978-0-7354-1378-8/$30.00

050115-1
PPMS (Quantum Design) magnetometer installed with
VSM option with fields up to 140 kOe.
RESULTS AND DISCUSSION
Figure 1(a) and (b) highlights the morphology for NiO
(S10) NPs with the faceted-spherical shape and core-
shell internal structure, whereas the image in Fig. 1(c)
corresponds to S70.
Figure 1 TEM images for sample (a) S10 and (c) S70.
The inset (b) corresponds to the HR-TEM image for
one particle of sample S10 with core-shell internal
structure, (d-e) histogram of the bigger and smaller
particle size distribution for S25 and S70 samples
Briefly, the XRD (not shown here) pattern for S10 is
characteristic of cubic NiO phase, whereas S25 and
S70 consist of two set of diffraction peaks
corresponding to hexagonal (hcp) FM-Ni and cubic
AFM-NiO phases. For S10 the average particle size of
NiO NPs is ~ 8.0 ± 1.0 nm. Also, it is quite appealing
to examine that there is no major increase in its value
with the increase in Ni/OLA ratio (for samples S25
and S70). We have further estimated the amount of
hcp Ni and cubic NiO phase using the Reitveld fitting
profiles. For S25, the amount of NiO phase decreases
from S10 (pure NiO phase) to 75 (± 6.0), whereas for
S70, the calculated amount of NiO phase is ~ 68 (±
3.0). On the other hand, it is noted from Fig.1 (d-e)
that for S25 and S70 one can clearly see two different
size distributions and populations of particles (one
with diameter similar to NiO as obtained for S10 and
S25 and another, bigger one, with size ~190 ± 32 nm.)
Here, it is worth mentioning that the size of big
particles for S25 is ~ 145 ± 24 nm. Interestingly, the
population and the corresponding size distribution of
small particles for all the samples are almost same and
are ~ 10.0 ± 2.0 nm). This is also in good agreement
050115-2
with the XRD analysis, but quite different for the big
Ni particles (for S25 and S70) as shown in Fig. 1(d-e).
Figure 2 Illustrative sketch of the possible arrangement
of the particles in each sample along with respective
amounts of Ni and NiO phase.
In Figure 2, the red arrows in big Ni particles are an
illustrative picture of a simplified internal magnetic
structure with internal domain walls, where the
effective magnetization is zero for each Ni particle.
For sample S25, some of the small NiO particles are
closer to the big Ni ones, and their magnetic surface
contribution is stabilized, whereas for S70, all the
smaller NiO particles are closer to the big Ni ones and
hence their magnetic surface contribution is almost
vanished.
We have recorded M versus T curves for the three
samples measured under zero field cooling and field
cooling (ZFC and FC) conditions (H = 20 Oe). It was
observed a noticeable effect on magnetic contribution
arising from small NiO and big Ni particles (see
Figure 3). For S10, where the majority of magnetic
contribution corresponds to NiO core-shell
nanoparticles, MZFC consists of a maximum, TM ~ 53.4
K with TIRR ~ 200 K. Here TM is associated to the
mean blocking temperature, <T B> of the system and
TIRR is the irreversibility temperature, reflecting a large
energy barrier distribution. Contrary, the MZFC for S25
has a similar trend as for S10, but with different TM
and TIRR values, 63 K and 220 K, respectively. This
clear shift in TM could be assigned owing to the
susceptibility of thermally stabilized NiO phase, due to
the magnetic contribution of the big Ni particles.
Interestingly, for S70, where the majority of magnetic
contribution arise due to the presence of multi-domain
big Ni particles (DTEM ~ 186 ± 31 nm), the ZFC-FC
curves follow the expected susceptibility of the AFM
NiO phase, where the susceptibility increases
monotonically up to the Néel temperature (T~523 K).
In fact, the magnetic anisotropy associated with the
core-shell NiO nanoparticles is drastically reduced due
to the surface magnetic stabilization, as is confirmed in
the temperature dependent magnetization hysteresis
loops given in the later section.
Figure 3 ZFC and FC magnetization for the
investigated samples under an applied field of 100 Oe.
Magnetization hysteresis loops were measured (T <
TB), under ZFC and FC conditions (HFC= 20 kOe).
Some of striking features observed from the measured
ZFC curves (not shown) are: they consist of two
distinctive regimes with different magnetic
contributions; (i) a hysteresis contribution at low field
(it sharpens as the ratio of bigger to smaller particles
decreases), (ii) a linear component of magnetization at
high field, which might be associated to the magnetic
contribution of the shell of NiO nanoparticles.
Hysteresis loops measured at 5 K in FC modes are
depicted in Figure 4.
Figure 4 Low field regions of the hysteresis curves
taken in FC mode at 5 K.
Interestingly, the loops for all samples show a shift
along -ve field axis, which is associated to the
050115-3
exchange bias (HEX) effect. However, HEX decreases
considerably for S25, almost vanishing for S70. The
results observed for the small NiO core-shell
nanoparticles show that the particles do not behave as
an ideal Stoner-Wohlfarth (SW) system3. From
structural point of view, one may visualize the
following magnetic structure for the small NiO
nanoparticles: each particle constituted by a
structurally disordered shell and a crystalline core. On
the other hand, the value HEX at 5 K for S25 reduces to
~ 67 % of value in comparison to that observed for
S10 (HEX ~ 2.2 kOe). This is due to the fact that the
mean dipolar field induced by the big Ni particles is
strong enough for the partial stabilization of the
magnetic surface regions of the small NiO
nanoparticles. This effect is even more pronounced in
case of S70, where the HEX practically negligible in
comparison to that of S10. Here, one can say that the
dipolar field induced by the big Ni particles competes
with the coupling between the magnetic core and shell
components that occur within the small NiO
nanoparticles. As a result, HEX at low temperature is
drastically modified with the inclusion of the big Ni
particles.
ACKNOWLEDGMENTS
SKS are very grateful to FAPESP and CNPq for the
financial support.
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R. H. Kodama, A. Salah Makhlouf, and A. E. Berkowitz,
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B. Martínez, X. Obradors, Ll. Balcells, A. Rouanet, and C.
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M. Knobel, W. C. Nunes, L. M. Socolovsky, E De Biasi, J.
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