JOURNAL OF APPLIED PHYSICS VOLUME 95, NUMBER 11 1 JUNE 2004

Size and structure control of magnetic nanoparticles by using a modified

polyol process
T. Hinotsu, B. Jeyadevan,a) C. N. Chinnasamy, K. Shinoda, and K. Tohji
Graduate School of Environmental Studies, Tohoku University, Sendai 980-8579, Japan
共Presented on 9 January 2004兲
Synthesis strategies for the size and structure controlled Ni, Co, and FePt nanoparticles by
manipulating the reaction kinetics of the polyol process are reported. In the case of Ni, particle size
varied from a few micron to a few tens of nanometer, and the structure from fcc to a mixture of fcc
and hcp was realized. The Co particle structure has been changed from a mixture of fcc and hcp at
micron size range, to the fcc dominant mixture of fcc and hcp in the submicron size range, then to
␧- and hcp-Co and finally to hcp-Co in the nanosize range. In the case of FePt, particles had fcc and
fct phases with 5–10 nm in diameter. The magnetic properties of these particles are also reported.
© 2004 American Institute of Physics. 关DOI: 10.1063/1.1688534兴

I. INTRODUCTION During this stage, metal precursor undergoes dissolution and

Structural, electronic, and catalytic properties of many
materials are strongly size dependent in the nanometer re-
gime. Significant progress has been achieved in the prepara-
tion of metal nanocrystals by employing hot organometallic
synthetic routes where the nanocrystals can nucleate and
grow at about 423–573 K in high boiling solvents.1–3
Though considerable work has been done in formulating the
strategies to control the size and size distribution, little has
been done to control the structure of the nanoparticles of
metals and alloys. In magnetic materials, the control of size
and structure of nanoparticles is very important for their use
in nanotechnology applications. The modified polyol process
is an effective technique to synthesize nanoparticles with re-
quired size and structure when the reaction kinetics is prop-
erly controlled. Though the conventional process produces
particles in the micrometer size range with reactions extend-
ing over a few hours, we have succeeded in modifying the
same to obtain nanometer size particles with various crystal
structures by controlling the reaction kinetics. Here, we re-
port the synthesis of magnetic nanoparticles such as Ni, Co,
and FePt with controlled particle size and structure through a
modified polyol process.
II. EXPERIMENT
A. Synthesis
The experiments were carried out using cobalt and
nickel acetate tetrahydrate, iron and platinum acetyl aceto-
nate metal precursors. The standard synthesis procedure is as
follows: First, specified amounts of metal precursors were
dissolved in 100 ml of polyol like ethylene glycol or trim-
ethylene glycol or tetraethylene glycol as the case may be.
Then, the solution was transferred to a vessel with reflux
attachment and placed in an oil-bath/mantle heater and
heated at a constant rate under gentle mechanical stirring.
a兲
Author to whom correspondence should be addressed; electronic mail:
jeya@mail.kankyo.tohoku.ac.jp
reduced to metal ions, and then the formation of nucleus and
particle growth takes place.
B. Characterization
The structure and morphology of the as-prepared par-
ticles were analyzed using an x-ray powder diffraction
共XRD兲 共Rigaku-Cu K ␣ radiation兲 technique and a high-
resolution transmission electron microscopy 共TEM兲 共Hitachi
HF 2000兲. The composition of the as-synthesized nanopar-
ticles was determined by using energy dispersive x-ray spec-
troscopy. The specific magnetization (M s ) and coercivity
(H c ) of the unoriented assemblies were measured at room
temperature 共RT兲 in a maximum applied field of 15 kOe
using a vibrating sample magnetometer 共VSM兲 共Tamakawa
model TM-VSM1230-HHHS兲. The phase transition tempera-
ture T t was determined by using differential scanning calo-
rimetry 共DSC兲 共Rigaku-DSC 8270兲 in N2 atmosphere.
III. RESULTS AND DISCUSSION
A. Strategies for size and structure control
The production of monodispersed particles requires the
separation of nucleation and growth steps4 depends on the
reaction system and the parameters controlling the reaction.
In the polyol process, the reaction can be either accelerated
or retarded by controlling the various rate determining steps
viz.: 共i兲 formation and dissolution of the intermediate phases,
共ii兲 reduction of metal ions, 共iii兲 nucleation and growth
through the addition of hydroxyl ions, 共iv兲 selection of the
type of polyol, and 共v兲 the introduction of seed-induced het-
erogeneous nucleation.
For example, the reducing power of the trimethylene
glycol 共TMEG兲 is the highest reducing power compared to
that of the ethylene glycol 共EG兲 and tetraethylene glycol as
determined from a study of the reduction of Pt nanoparticles
in different polyols.5
To synthesize Ni particles, the experiments were carried
out in a polyol medium using nickel acetate tetrahydrate as

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7478 J. Appl. Phys., Vol. 95, No. 11, Part 2, 1 June 2004
FIG. 1. The SEM micrographs of Ni particles synthesized at OH⫺ /Ni ratios
of: 共a兲 0, 共b兲 10, 共c兲 50, and 共d兲 150.
the starting material. The presence of hydroxyl ions in EG
influenced the reaction kinetics. The introduction of an OH⫺
ion, which coexisted with the Ni–ethylene glycol solution,
changed the morphology of the nickel particles from micron
size irregular plate-like structure to somewhat spherical par-
ticles of about a few hundred nanometer in diameter as
shown in Fig. 1共a兲. The XRD analysis showed formation of
the fcc phase. The increase of hydroxyl ion concentration
accelerated the rate determining steps and progressively re-
duced the particle size to a few tens of nanometer as shown
in the scanning electron microscope observation of Figs.
1共b兲–1共d兲. The reduction in the size of primary particles that
form the agglomerates in Fig. 1共d兲 indicates the enhancement
of reaction kinetics with hydroxyl ion concentration. The
XRD analysis also showed that the average grain size de-
creased from 50 to 16 nm when the OH⫺ /Ni ratio was in-
creased from 0 to 50, respectively.5 The room temperature
magnetization values were between 55 and 38 emu/g. The
decrease in the magnetization value could be attributed to the
formation of nonmagnetic hcp Ni with its fractional volume
increasing with OH⫺ ion concentration even though XRD
could not reveal the presence of the small amount of the hcp
phase as the most intense line of the hcp Ni coincides with
that of the fcc Ni. When the Ni particles were synthesized in
TMEG, the reaction kinetics was enhanced further and the
unstable hcp Ni phase appeared as seen from XRD in Fig. 2.
Since the hcp Ni was nonmagnetic,6,7 the magnetization of
the Ni particles decreased from 55 to 21 emu/g when the
structure changed from pure fcc to a mixture of fcc and hcp
Ni. Hence, by increasing the reaction kinetics, the particle
size of Ni was reduced from about a few micron to a few
tens of nm along with a shape change from irregular plate-
like morphology to spherical shape. Also a structural change
from fcc to a mixture of fcc and hcp was brought in.
The micron size Co particles synthesized in EG had a
mixture of fcc and hcp phases by using cobalt acetate tet-
rahydrate as a starting precursor 关Fig. 3共a兲兴. However, by
introducing the hydroxyl ions, we could accelerate the for-
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Hinotsu et al.
FIG. 2. The XRD pattern of the: 共a兲 fcc and 共b兲 fcc⫹hcp Ni.
mation and dissolution of the intermediate phase to control
the agglomeration and reduce the particle diameter to about
300 nm with an enhanced volume fraction of the fcc phase as
shown by XRD in Fig. 3共b兲. To accelerate the reaction fur-
ther, the synthesis was carried out using a strongly reducing
TMEG and the particle size was reduced to less than 100 nm
and a mixture of fcc and hcp phases were observed. The RT
magnetization and coercivity for the biphase of (hcp⫹fcc)
Co particles were 135 emu/g and 161 Oe, respectively. For
the fcc dominant Co nanoparticles 关Fig. 3共b兲兴 the magnetiza-
tion and coercivity were 145 emu/g and 70 Oe, respectively.
Along with the reduction of particle diameter, the crystal
structure of Co particles changed from the stable fcc phase,
which is the case for fine particles, to metastable ␧- and
hcp-Co phases as seen from XRD in Fig. 4共a兲. There are only
two crystal phases expected for the elemental Co at ambient
pressures. However, in our modified polyol process it is pos-
sible to synthesize ␧-Co nanoparticles related to the beta
phase of manganese.8,9 The TEM micrograph of Fig. 4共b兲
shows the particle sizes of hcp Co phase and the average
particle diameter is about 20 nm. The room temperature
magnetization and coercivity of the hcp Co particles were 67
emu/g and 535 Oe, respectively, as shown in Fig. 4共c兲. The
coercivity for the present 20 nm particles is lower than that
of the micron sized hcp Co (M s ⫽161.8 emu/g and H c
⫽1600 Oe) particles.10 The small size of the particles and
surface oxidation might have contributed to the reduction of
magnetization and coercivity of the hcp Co nanoparticles. In
FIG. 3. The XRD pattern of: 共a兲 a mixture of fcc and hcp Co and 共b兲 fcc
dominant Co.
J. Appl. Phys., Vol. 95, No. 11, Part 2, 1 June 2004
FIG. 4. The 共a兲 XRD patterns of ␧- and hcp-Co phases, 共b兲 the TEM micrograph of hcp Co, and 共c兲 RT hysteresis loop of the hcp Co nanoparticles.
addition to the structural change, the shortening of reaction
time was also observed when the particle size changed from
micron to nanometer level.
The disordered fcc FePt is believed to be an unstable
phase, formed as a consequence of faster reaction kinetics.
Thus, unlike in the case of Co or Ni, reaction kinetics has to
be slowed down to synthesize fct FePt particles. We synthe-
sized the FePt particles with diameter between 3 and 4 nm by
reducing Pt acetylacetonate in the presence of Fe acetylac-
etonate in ethylene glycol at 473 K. The polyol/Pt mole ratio
was found to influence the properties of the end product.11
Under an optimum condition, the as-prepared FePt nanopar-
ticles were ferromagnetic in nature and had a phase transfor-
mation temperature of 594 K for the fcc to fct transforma-
tion. This was probably due to the slow reaction kinetics. In
order to reduce the phase transformation temperature further,
the FePt nanoparticles were synthesized in a polyol medium
having a slow reducing capability such as TEG. By this we
could further reduce the phase transformation temperature to
553 K. The diameter of the particles was between 5 and 10
nm. The XRD pattern of the particles produced in TEG at
553 K showed the superlattice reflections of the L1 0 phase of
fct structure against the fcc structure observed in EG as
shown in Fig. 5. The FePt particles synthesized in TEG were
ferromagnetic and had a RT magnetization and coercivity of
55 emu/g and 2.1 kOe, respectively. In the literature, the
FIG. 5. The XRD pattern of: 共a兲 fcc and 共b兲 fcc⫹fct FePt nanoparticles.
Downloaded 12 Mar 2005 to 129.107.240.2. Redistribution subject to AIP license or copyright, see http://jap.aip.org/jap/copyright.jsp
Hinotsu et al. 7479
as-prepared FePt nanoparticles were in the disordered fcc
structure and did not show any coercivity due to
superparamagnetism.12 In the present study, we could
achieve partial L1 0 ordering with a coercivity of 2.1 kOe in
the as-prepared state itself. The relatively low magnetization
共50 emu/g兲 at RT for our particles is due to the superpara-
magnetism of the fcc particles coexisting with the ferromag-
netic fct particles. The measured magnetic properties con-
firmed that the as-prepared particles had the ordered L1 0
structure. The degree of ordering has been determined by
using Mössbauer spectroscopy and the results have been dis-
cussed in detail elsewhere.
IV. CONCLUSION
We conclude that the size and structure of the nanopar-
ticles have been controlled by manipulating the rate deter-
mining steps. Both in the case of Ni and Co the metastable
phases were obtained by accelerating the reaction kinetics.
On the other hand, FePt nanoparticles with particle diameter
below 10 nm and with fcc and a mixture of fcc and fct
phases were obtained by decelerating the reaction. Also, it
was demonstrated that a control over the reaction kinetics
could lower the phase transformation temperature.
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