JOURNAL OF APPLIED PHYSICS VOLUME 93, NUMBER 10 15 MAY 2003

Magnetic Nanostructures and Arrays K. V. Rao, Chairman

Phase transformation and magnetic moment in FePt nanoparticles

Y. Ding,a) S. Yamamuro, D. Farrell, and S. A. Majetichb)
Department of Physics, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213-3890
共Presented on 13 November 2002兲
The phase transformation from fcc to L1 0 in FePt nanoparticles was investigated in both thick film
samples and self-assembled arrays as a function of the annealing temperature, using transmission
electron microscopy, x-ray diffraction, differential scanning calorimetry, and magnetometry. A
significant fraction of the surfactant decomposes into gaseous products below 500 °C, removing the
steric barrier between particle cores. This causes the particles to coalesce at the same annealing
temperatures where the transformation to the high anisotropy phase occurs. © 2003 American
Institute of Physics. 关DOI: 10.1063/1.1544495兴

I. INTRODUCTION sufficient signal. A previous DSC study found a large, sharp

endothermic peak at 378 °C for the decomposition of oleic
Self-assembled FePt nanoparticle arrays have been the
acid on magnetite nanoparticles,3 so the FePt samples were
subject of much interest due to their potential use as ultra-
first annealed at 400 °C in H2 for 30 min. Hydrogen was
high density magnetic storage media.1 The advantage of the
passed through the sample tube prior to transfer to the preset
self-assembly approach is the high degree of uniformity in
furnace, during annealing, and after removal while it cooled.
the grain size and position. However, as-made low anisot-
The sample mass was measured before and after annealing.
ropy fcc phase must be transformed into the chemically or-
A Perkin Elmer DSC7 differential scanning calorimeter
dered, high magnetocrystalline anisotropy L1 0 phase2 by an-
was used with an empty copper holder as a reference. The
nealing, and at the same time the particles sinter together,
sample pretreated at 400 °C in H2 was equilibrated at 300 °C
destroying the key advantage over existing media. Here we
in flowing argon, and then the temperature was raised to
compare the crystalline structure and morphology with the
700 °C at a rate of 40 °C/min while the heat flow was mea-
magnetic properties following different annealing conditions
sured.
to identify conditions favoring phase transformation without
X-ray diffraction 共XRD兲 measurements were done in a
grain growth.
Rigaku x-ray diffractometer using Cu K ␣ radiation (␭
⫽0.154 nm), to determine the FePt phase after annealing
II. EXPERIMENT
samples from the same batch at different temperatures. Thick
FePt nanoparticles were synthesized by standard high films 共⬃10 mg, or ⬃104 layers兲 were used to obtain a rea-
temperature chemical methods.1 The surfactant coating was a sonable signal-to-noise ratio.
1:1 mixture of oleic acid and oleylamine. The particles were The magnetic properties of FePt of thick films were
washed with ethanol, centrifuged, and redispersed in hexane measured at room temperature by a Quantum Design super-
several times, with additional surfactant to retain a good sur- conducting quantum interference device 共SQUID兲 magneto-
face coating. meter.
To form nanoparticle arrays, a droplet of the hexane so-
III. RESULTS AND DISCUSSION
lution was evaporated on a transmission electron microscope
共TEM兲 grid. The arrays were examined with a Philips During pretreatment at 400 °C, there was a mass loss of
EM420 TEM operating at 120 keV to determine the particle ⬃25%. Further heating did not change the mass significantly.
diameter, the interparticle spacing, and the degree of order-
ing.
To prepare samples for differential scanning calorimetry
共DSC兲, the washed and redispersed particle solution was
added to a small copper cup, and the hexane was evaporated.
Larger amounts 共⬃10 mg, or ⬃104 layers兲 of particles were
used than in the arrays 共several layers兲, in order to obtain

a兲
Author to whom correspondence should be addressed; electronic mail: FIG. 1. Heat flow vs temperature for a thick film of FePt nanoparticles
yding@andrew.cmu.edu annealed in argon with a heating rate of 40 °C/min. The sample was prean-
b兲
Electronic mail: sm70@andrew.cmu.edu nealed in H2 at 400 °C for 30 min.

0021-8979/2003/93(10)/7411/3/$20.00 7411 © 2003 American Institute of Physics

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7412 J. Appl. Phys., Vol. 93, No. 10, Parts 2 & 3, 15 May 2003
FIG. 2. X-ray diffraction intensities as a function of angle, for various
annealing temperatures. The peaks at 69° and 34° are from the Si sample
holder, and the broad peak at 24° in the 700 °C pattern is from the glass
substrate.
DSC shows two endothermic peaks, one from 450 to 550 °C
and the other from 550 to 650 °C 共Fig. 1兲. The peak starting
at 450 °C may be due to reaction of the remaining surfactant
with the particles. Surprisingly, there is no exothermic peak
associated with the FePt phase transformation from the
chemically disordered fcc to the L1 0 phase, as has been re-
ported in FePt thin films.4 The phase transformation tempera-
ture for bulk FePt alloy and FePt thin films are 1300 and
⬃400 °C respectively,4 but could be different for nanopar-
ticles, due to their increased surface area and surfactant coat-
ing.
Figure 2 shows the XRD intensity as a function of scat-
tering angle for the unannealed FePt sample and samples
annealed at 550, 650, and 700 °C. The as-made FePt sample
shows broad peaks consistent with an fcc structure. In the
sample annealed at 550 °C, there are initial signs of the
共002兲, 共201兲, and 共112兲 L1 0 peaks. This suggests that the
endothermic DSC peak may mask the phase transformation.
The L1 0 peaks become sharper as the annealing temperature
increases, indicating significant grain growth. From the 共111兲
diffraction peak ( ␪ ⫽41°), the average particle sizes found
by the Scherrer method are 3.3, 11, 27, and 30 nm for the
unannealed, 550, 650, and 700 °C samples, respectively, cor-
recting for an instrumental broadening of 3.1 mrad. While
Scherrer analysis neglects the contributions of structural dis-
order, the suggested particle growth was qualitatively con-
firmed by TEM images of the arrays, as shown in Fig. 3.
FIG. 3. TEM bright field images of FePt arrays: 共a兲 unannealed, 共b兲 an-
nealed at 550 °C for 30 min, and 共c兲 annealed at 650 °C for 30 min. The
unannealed image shows a typical particle size of 3 nm and a typical inter-
particle spacing of 4 nm.
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Ding et al.
FIG. 4. SQUID hysteresis loops of the FePt thick film samples, as a function
of the annealing temperature. The unannealed sample has no coercivity and
a very small moment at saturation. The coercivity increases monotonically
for samples annealed at 400, 550, and 650 °C.
Figure 3共a兲 shows the morphology of thin, unannealed
FePt arrays. The size of the FePt nanoparticles is measured
to be 2.7⫾0.6 nm by National Institutes of Health 共NIH兲
image.5 Figures 3共b兲 and 3共c兲 show typical regions of similar
arrays annealed at 550 and 650 °C, respectively. While it is
possible to find regions where the array ordering has been
preserved, most of the particles had sintered 共similar to the
results reported before兲.6 The DSC measurements were made
with a rapid heating rate, and the TEM results are consistent
with assignment of the low temperature peak to surfactant
decomposition and the high temperature peak to sintering.
Without the surfactant barrier, the particles coalesce due to
atomic diffusion and van der Waal’s attractions between par-
ticle cores. We observed that thicker arrays had more sinter-
ing at a fixed temperature.
Since the magnetic behavior of the fcc and L1 0 FePt
phases is quite different, SQUID magnetometry was used to
monitor the phase transformation. Figure 4 shows room tem-
perature SQUID magnetization curves of the FePt thick film
共⬃10 mg or ⬃104 layers兲 samples. The unannealed FePt
nanoparticles were superparamagnetic at 293 K. From a fit to
a Langevin function, the unannealed FePt moment is esti-
mated to be on the order of 10⫺18 emu/particle, equivalent to
a specific magnetization of 5 emu/g. This estimate assumes
that all of the mass following pretreatment is FePt, and FePt
nanoparticles have bcc packing.7 After annealing, FePt be-
comes ferromagnetic, with a magnetization of 54 and 69
emu/g at 50 kOe for samples annealed at 550 and 650 °C,
respectively. While XRD results suggest that the phase trans-
formation starts near 550 °C, the sample annealed at 400 °C
already shows H c ⬎500 Oe. If even a small fraction of the
particles transform, their ferromagnetic contribution will
dominate the magnetization. Both H c and the specific mag-
netization increase at higher annealing temperatures. At the
same time the average particle size increases, as seen in
TEM and XRD. Since the coercivity increases rapidly with
grain or particle size, up to a maximum monodomain size,8,9
共⬃several hundred nm for FePt兲,10 the increase in H c could
be due to sintering in combination with the transformation of
some of the particles. Preliminary measurements have been
made on single TEM grids. These grids have thinner arrays
and a reduced degree of sintering. We observe smaller coer-
J. Appl. Phys., Vol. 93, No. 10, Parts 2 & 3, 15 May 2003
civities than in the thick film samples for the same annealing
temperature.
IV. CONCLUSIONS
The structural and morphological properties of FePt
nanoparticles were correlated with changes in the magnetic
behavior during annealing. TEM studies showed that particle
coalescence begins at random locations within nanoparticle
arrays by 550 °C, and that once started, grain growth in these
regions is rapid. This occurred following the decomposition
of the surfactant barriers surrounding the particles, which
differential scanning calorimetry showed was completed be-
low 500 °C. A second endothermic DSC peak was noted at
620 °C, most likely due to particle sintering and not to the
fcc to L1 0 phase transformation, which is expected to be
exothermic. The phase transformation is most likely masked
by the other heat flow features, and the peak at 620 °C may
be due to a chemical reaction of the residual carbon with
FePt or Fe. XRD demonstrated the presence of the L1 0 phase
and the beginning of grain growth by 550 °C, and magnetic
measurements indicated room temperature coercivity after
annealing at temperatures as low as 400 °C.
While monolayer films of FePt nanoparticle arrays,
oxygen-free annealing atmospheres, and rapid heating reduce
the likelihood of particle coalescence during annealing,
modifications are needed in order to obtain the benefits of
high coercivity and high quality spatial ordering. This could
be done by alloying the FePt to reduce the transformation
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Ding et al. 7413
temperature, or by increasing the interparticle separation or
modifying the thermal stability of the interparticle barrier.
ACKNOWLEDGMENTS
The authors would like to thank Data Storage System
Center 共DSSC兲 at Carnegie Mellon University. They are
grateful to Professor Katayun Barmak and Dr. Jihwan Kim
for help with DSC measurements. S.A.M. acknowledges
support from the National Science Foundation Grant No.
CTS-0227645, and the American Chemical Society Petro-
leum Research Fund Grant No. 37578-AC5.
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