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

Magnetic Nanoparticles: FePt, CoPt, Etc. Dieter Weller, Chairman

FePt and Fe nanocomposite by annealing self-assembled FePt nanoparticles

M. H. Lu,a) T. Song, and T. J. Zhou
Data Storage Institute, 5 Engineering Drive 1, NUS, Singapore 117608, Singapore
J. P. Wang
MINT and Electrical and Computer Engineering Department, University of Minnesota,
Minneapolis, Minnesota 55455
S. N. Piramanayagam and W. W. Ma
Data Storage Institute, 5 Engineering Drive 1, NUS, Singapore 117608, Singapore
H. Gongb)
Department of Materials Science, National University of Singapore, Kent Ridge, Singapore 119260,
Singapore
共Presented on 6 January 2004兲
We present a simple fabrication of FePt and Fe nanocomposite by annealing self-assembled FePt
nanoparticles. 5 nm FePt nanoparticles were prepared by simultaneous reduction of platinum
acetylacetonate and thermal decomposition of iron pentacarbonyl in the presence of oleic acid
and oleylamine as stabilizers. The as-synthesized FePt nanoparticles can self-organize well on
a clean SiO/Si substrate and, then, were annealed in a vacuum using a rapid thermal process
at different temperatures for 0.5 h. It is found that the annealing temperature plays a key role
in determining the final products. The samples annealed at 550 °C and 700 °C consist of a
FePt-face-centered-tetragonal 共fct兲 phase with a coercivity of around 1000 and 8800 Oe,
respectively, whereas, the samples annealed at 580 °C are composed of two phases: one is the
FePt-fct phase and the other is a Fe-body-centered-cubic phase. The hysteresis loop of the sample
annealed at 580 °C is also two-phase like with a kink at low field and its coercivity is around 8000
Oe. That indicates that Fe can be segregated from FePt by proper annealing, forming FePt and Fe
nanocomposites. © 2004 American Institute of Physics. 关DOI: 10.1063/1.1652412兴

I. INTRODUCTION cursors to previously synthesized 3 nm particles. Three-

The synthesis and assembly of small hard magnetic
nanoparticles have attracted more and more attention be-
cause of their potential applications in ultrahigh-density
magnetic recording,1 ferrofluids,2 advanced nanocomposite
permanent magnets,3,4 and even biological microsystems.
The chemically ordered FePt face-centered-tetragonal 共fct兲
phase is an excellent candidate for those applications due to
their good chemical stability and high magnetocrystalline an-
isotropy, K u (108 erg/cm3 ). 5,6 Sun et al.7 synthesized mono-
disperse FePt nanoparticles by the simultaneous reduction of
platinum acetylacetonate (Pt (acac) 2 ) and thermal decompo-
sition of iron pentacarbonyl in the presence of oleic acid and
oleylamine as stabilizers. The composition was adjusted by
changing the molar ratio of the two precursors. The particle
size could be varied from 3 to 10 nm by adding more pre-
a兲
Also at: Department of Materials Science, National University of Sin-
gapore, Kent Ridge, Singapore 119260.
b兲
Author to whom correspondence should be addressed; electronic mail:
masgongh@nus.edu.sg
dimensional 共3D兲 superlattices could be generated when the
solvent was evaporated slowly. The interparticle spacing
could be tuned by controlling the chain length of the surfac-
tants. Recently, Zeng et al.3 and Sun et al.7 fabricated FePt
and Fe3 Pt exchange-coupled nanocomposites using nanopar-
ticle self-assembly. They mixed hexane dispersions of FePt
and Fe3 O4 nanoparticles with selected concentration, vol-
ume, and sizes under ultrasonic agitation. The FePt and
Fe3 O4 nanoparticles form binary assemblies, which were
converted into FePt–Fe3 Pt nanocomposites by annealing un-
der a flow of Ar⫹5% H2 at 650 °C for 1 h. By optimizing
the exchange coupling, they produced exchange-coupled iso-
tropic FePt–Fe3 Pt nanocomposites with an energy product of
20.1 MG Oe.3
Although the work of Zeng et al.3 is an exciting devel-
opment for making strong magnets for practical applications,
there are still many challenges to be faced and the fabricating
processes are also a little complicated. Here, we report an
approach to fabricate FePt and Fe nanocomposites by simply
annealing self-assembled FePt nanoparticles at certain tem-
perature using a rapid thermal process.

0021-8979/2004/95(11)/6735/3/$22.00 6735 © 2004 American Institute of Physics

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6736 J. Appl. Phys., Vol. 95, No. 11, Part 2, 1 June 2004
FIG. 1. TEM micrographs of 5 nm FePt nanoparticles: 共A兲 One layer as-
sembly, 共B兲 3D hexagonal assembly, 共C兲 3D cubic assembly, and 共D兲
selected-area electron diffraction.
II. EXPERIMENT
The synthesis of Fe48Pt52 in principle followed the
method reported by Sun et al.1 Pt (acac) 2 共197 mg, 0.5
mmol兲, 1,2-hexadecanediol 共390 mg, 1.5 mmol兲, and octyl
ether 共20 ml兲 were added to a three-necked flask equipped
with an Ar in/outlet, septa rubber, and thermometer in glove
box. The flask was transferred out and connected to an Ar
atmosphere system. The mixture was heated to 100 °C. Oleic
acid 共0.16 ml, 0.5 mmol兲, oleyl amine 共0.24 ml, 0.5 mmol兲,
and Fe (CO) 5 共0.098 ml, 0.75 mmol兲 were added, and the
solution was continuously heated to reflux at 297 °C for 15
min. The heating source was removed and the black mixture
was cooled to room temperature. 40 ml ethanol was added to
the mixture and the mixture was centrifugated. The yellow-
brown supernatant was discarded. The black precipitate was
then dispersed in hexane 共25 ml兲 in the presence of oleic acid
共0.05 ml兲 and oleyl amine 共0.05 ml兲 and precipitated out by
adding ethanol 共20 ml兲, followed by the centrifugation of the
mixture. The black precipitate was dispersed in hexane 共20
ml兲 and centrifugated again to remove unsolved precipitate
共almost no precipitate兲. 15 ml ethanol was further added to
precipitate out the product. The black precipitate was finally
redispersed in hexane and stored in glove box.
The composition of as-synthesized FePt nanoparticles
was analyzed using inductively coupled plasma-optic emis-
sion spectrometry. Transmission electron microscopy
关共TEM兲 Hitachi H-8100兴 was used to observe the self-
assembled-particle pattern and determine the particle size.
X-ray diffraction 共XRD兲 was applied to check the structure
of as-synthesized and annealed FePt particles. Magnetic
properties were measured using a vibrating sample magneto-
meter 共produced by DMS兲 and an alternating gradient mag-
netometer.
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Lu et al.
FIG. 2. XRD patterns of FePt particle assemblies: 共A兲 As-synthesized, 共B兲
annealed at 550 °C, 共C兲 annealed at 580 °C, and 共D兲 annealed at 700 °C.
III. RESULTS AND DISCUSSION
Nanoparticle assembly was performed on a naturally
oxidized silicon substrate. One or more drops of hexane-
dispersed FePt nanoparticles were deposited on a SiO2 /Si
substrate. The solvent was allowed to evaporate slowly at
room temperature, and FePt nanoparticles were self-
assembled into 3D superlattices or a two-dimensional regular
array at different evaporate rates with different concentra-
tions.
5 nm FePt particles were synthesized 关Figs. 1共A兲–1共C兲兴.
The FePt nanoparticles can self-organize into a regular one
layer array 关hexagonal pattern with larger intergrain distance,
Fig. 1共A兲兴, close-packed 3D hexagonal superlattice 关Fig.
1共B兲兴, or cubic multilayer 关Fig. 1共C兲兴. The intergrain distance
is 4 nm for a one-dimensional self-assembled array 关Fig.
1共A兲兴, whereas, it is about 2 nm for a 3D hexagonal and
cubic superlattice 关Figs. 1共B兲 and 1共C兲兴, which is maintained
by oleic acid/oleylamine stabilizers. Figure 1共D兲 shows the
selected-area electron diffraction pattern of the as-
synthesized FePt nanoparticles, which reveals that the par-
ticles are structurally face-centered cubic 共fcc兲.
The as-synthesized FePt nanoparticles were annealed at
550 °C, 580 °C, and 700 °C for 30 min in a vacuum better
than 5⫻10⫺6 Torr using a rapid thermal process. Figures
2共A兲–2共D兲 show the XRD patterns of as-synthesized, an-
nealed at 550 °C, 580 °C, and 700 °C particle assemblies,
respectively. The as-synthesized particle assembly exhibits
very broad peaks, which can be indexed by using the struc-
ture of fcc FePt, further confirming that the as-synthesized
particles are structurally fcc. When annealed at 550 °C, the
peaks become narrow and shift to a high-angle side, indicat-
ing the growth of grain and ordering of Fe and Pt atoms. As
the peak positions are between those of fcc FePt and fct
FePt, the particles are partially chemically ordered. By in-
creasing the annealing temperature to 580 °C, a few peaks
appear and the existing peaks are narrowed further and shift
to a higher-angle side. Most of peaks can be indexed by
using the structure of fct FePt except one positioned at 2 ␪
⫽44.8 °C, which can be attributed to body-centered-cubic
共bcc兲 iron, indicating that those films are composed of two
J. Appl. Phys., Vol. 95, No. 11, Part 2, 1 June 2004
FIG. 3. Hysteresis loops of FePt nanoparticles annealed at different tem-
peratures: 共A兲 550 °C, 共B兲 580 °C, and 共C兲 700 °C.
phases: One is fct FePt and the other is bcc Fe 共Fe-rich FePt
alloy兲 关Fig. 2共C兲兴. Further increasing the annealing tempera-
ture to 700 °C, no peaks of bcc Fe are found and all peaks
can be fully indexed by using the structure of fct FePt, indi-
cating that the films become single fct-FePt phase.
The in-plane and out-of-plane hysteresis loops of an-
nealed films are shown in Figs. 3共A兲–3共C兲. For films an-
nealed at 550 °C, the in-plane and out-of-plane coercivity are
954.6 Oe and 1021 Oe, respectively 关Fig. 3共A兲兴, further con-
firming that the particles are partially chemically ordered due
to a relatively low annealing temperature. For the films an-
nealed at 580 °C, the in-plane and out-of-plane hysteresis
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Lu et al. 6737
loops are two phaselike with a kink at low field 关Fig. 3共B兲兴,
revealing that the films consist of one magnetically hard
phase and one magnetically soft phase. The in-plane coeciv-
ity is more than 8000 Oe and out-of-plane coecivity is
around 7500 Oe 关Fig. 3共B兲兴. Combined with the XRD re-
sults, it is believed that the magnetically hard phase is fct-
FePt and the magnetically soft phase is bcc-Fe 共Fe-rich FePt
alloy兲, indicating that Fe can be segregated from FePt by
proper annealing and FePt and Fe nanocomposite are
formed. Increasing the annealing temperature to 700 °C, the
hysteresis loops become single phaselike with in-plane and
out-of-plane coercivity of 8676 Oe and 8813 Oe, respec-
tively 关Fig. 3共C兲兴, which agrees well with the XRD results.
The observed results could be explained as follows.
When the films were annealed in a vacuum using rapid ther-
mal processes, the phase transition for fcc to fct takes place.
There possibly exists one intermediate phase, which is an
Fe-rich bcc Fe phase, at a special annealing temperature.
Once cooled down very fast at this temperature, this inter-
mediate phase could be maintained. When increasing the an-
nealing temperature, the intermediate phase may not appear,
therefore, only one phase is observed.
In summary, a simple method in the fabrication of fct-
FePt and Fe 共Pt兲 nanocomposite was presented. It is found
that the annealing temperature plays a key role in determin-
ing the final products using a rapid thermal process. When
annealed at 550 °C, the particles consist of a single phase
partially chemically ordered fct FePt. When annealed at
580 °C, two phases appear, which are magnetically hard fct-
FePt and magnetically soft Fe-rich bcc iron. By increasing
the temperature to 700 °C, the particles are composed of a
chemically ordered fct-FePt single phase.
1
D. Weller, A. Moser, L. Folks, M. E. Best, W. Lee, M. F. Toney, M.
Schwickert, J.-U. Thiele, and M. F. Doerner, IEEE Trans. Magn. 36, 10
共2000兲.
2
B. M. Berkovsky, V. F. Medvedev, and M. S. Krakov, Magnetic Fluids:
Engineering Applications 共Oxford University Press, Oxford, 1993兲.
3
H. Zeng, J. Li, J. P. Liu, Z. L. Wang, and S. H. Sun, Nature 共London兲 420,
395 共2002兲.
4
M. Watanabe, T. Masumoto, D. H. Ping, and K. Hono, Appl. Phys. Lett.
76, 3971 共2000兲.
5
A. Cebolleda, D. Weller, J. Sticht, G. R. Harp, R. F. C. Farrow, R. F.
Marks, R. Savoy, and J. C. Scott, Phys. Rev. B 50, 3419 共1994兲.
6
R. F. C. Farrow, D. Weller, R. F. Marks, M. F. Toney, A. Cebollada, and G.
R. Harp, J. Appl. Phys. 79, 5967 共1996兲.
7
S. H. Sun, C. B. Murray, D. Weller, L. Folks, and A. Moser, Science 287,
1989 共2000兲.