VOLUME 2, NUMBER 10, OCTOBER 2002

© Copyright 2002 by the American Chemical Society

Reduction of the fcc to L10 Ordering

Temperature for Self-Assembled FePt
Nanoparticles Containing Ag
Shishou Kang,† J. W. Harrell,†,‡ and David E. Nikles*,†,§

Department of Physics and Astronomy, Department of Chemistry and Center for

Materials for Information Technology, The UniVersity of Alabama,
Tuscaloosa, Alabama 35487-0209

Received May 15, 2002; Revised Manuscript Received August 9, 2002

ABSTRACT
[Fe49Pt51]88Ag12 nanoparticles were prepared by the simultaneous polyol reduction of platiunum acetylacetonate and silver acetate and the
thermal decomposition of iron pentacarbonyl, giving 3.5 nm diameter FePt particles with Ag atoms substituted in the lattice. The addition of
Ag promoted the fcc to tetragonal phase transition, thereby reducing the temperature required for this transition by some 100 to 150 °C
compared with pure FePt nanoparticles. After heat treatment at 400 °C for 30 min, the coercivity of the films containing [Fe49Pt51]88Ag12
nanoparticles was more than 3400 Oe, while the films containing FePt nanoparticles were superparamagnetic. This decrease in phase
transformation temperature allowed us to decrease the particle coalescence and loss in particle positional order seen when FePt nanoparticles
were transformed at temperatures above 550 °C.

One of the Chemistry Highlights of 20001 was the report by
S. Sun and workers at IBM of the synthesis, self-assembly,
and magnetic recording performance of FePt nanoparticles.2
This report has generated considerable interest in the use of
self-assembled FePt nanoparticles for recording media in
future high-density data storage magnetic hard disk drives.
Before this application can be realized some basic materials
science problems must be solved. One of the most challeng-
ing problems is the phase transformation from the fcc phase
to the tetragonal (L10) phase. As prepared, the particles have
an fcc structure and are superparamagnetic. The particles are
* Corresponding author. E-mail: dnikles@mint.ua.edu
† Center for Materials for Information Technology.
‡ Department of Physics and Astronomy.
§ Department of Chemistry.
10.1021/nl025614b CCC: $22.00 © 2002 American Chemical Society
Published on Web 09/06/2002
coated with organic surfactants (oleic acid and oleylamine)
and can be dispersed in hydrocarbon solvents. When the
dispersions are cast onto solid substrates and the solvent
evaporates, the particles self-assemble into close-packed
arrays. After heat treatment at temperatures above 500 °C,
the particles transform to the tetragonal phase, having high
magnetocrystalline anisotropy3 and giving films with high
coercivity. The coercivity depends on the heating tempera-
ture, and for complete phase transformation, the particles
must be heated to nearly 580 °C.4 However, when heated to
temperatures above 550 °C, there is considerable particle
coalescence and loss of particle positional order.5 Particle
coalescence leads to increased switching volumes, which
defeats the point of making small particles. The loss of
positional order comes from the decomposition of the
Figure 1. TEM images of self-assembled [Fe49Pt51]88Ag12 nanoparticles: as prepared, 1a, and after heat treatment at 400 °C for 30 min,
1b. These are negative images with the particles appearing as white spots.
surfactant layers allowing particle motion. It would be highly
desirable if the temperature required for the fcc to tetragonal
phase transformation were lower, at least below temperatures
where the particles coalesce, preferably below the temper-
ature where the organic surfactants decompose.
There have been many recent reports of the effect of
additives on the thermal ordering of sputtered films of either
CoPt or FePt alloys. Kitakami et al. have found that the
addition of Sn, Pb, Sb, Bi, or Ag into sputtered CoPt films
promotes the disordered fcc to ordered tetragonal transforma-
tion, resulting in significant reductions in the temperature
required for ordering.6,7 Quite recently, Maeda et al., from
Toshiba, observed a reduction of the ordering temperature
for FePt sputtered films by adding Cu.8 For films containing
[FePt]85Cu15, the coercivity was 5000 Oe after annealing at
300 °C, while the Hc for films containing FePt was only a
few hundred Oe after annealing at 300 °C. These reports
suggest a means of lowering the fcc to tetragonal phase
transformation for FePt nanoparticles by adding either copper
or silver. We set about preparing FePt nanoparticles contain-
ing either Ag or Cu. It is not obvious that the effect of Ag
or Cu will be the same in chemically synthesized nano-
particles as in sputtered films. In addition, unlike sputtered
thin films using a Ag or Cu target, a suitable chemical
procedure had to be found for introducing Ag or Cu into
FePt. Here we report the synthesis of [Fe49Pt51]88Ag12
nanoparticles and the beneficial effect of the added silver
on the phase transformation temperature.
Our initial attempts to add Ag to FePt used a modification
of the procedure we used to prepare FexCoyPt100-x-y nano-
particles.9 This involved the simultaneous polyol reduction
of platinum acetylacetonate and silver acetylacetonate and
the thermal decomposition of iron carbonyl in octyl ether.
Unfortunately, silver acetylacetonate was not adequately
soluble in octyl ether. Using silver acetate as the silver source
and phenyl ether as the reaction solvent, we were able to
prepare [Fe49Pt51]88Ag12 nanoparticles as follows. A 50 mL
three-necked round-bottom flask was equipped with magnetic
stirring, a reflux condenser, a thermometer, a rubber septum,
and an argon atmosphere. Teflon sleeves were used for all
ground glass joints. To the flask was added 0.50 mmol
platinum acetylacetonate, 0.25 mmol silver acetate, and 20
mL phenyl ether. The mixture was heated to 80 °C,
1034
whereupon it turned brown. Then 0.50 mmol oleic acid, 0.50
mmol oleylamine, and 1.4 mL (1.1 mmol) iron pentacarbonyl
were added by syringe. The septum was replaced with a glass
stopper and the reaction mixture heated to the reflux
temperature of phenyl ether (∼260 °C). After refluxing for
30 min, the reaction mixture was allowed to cool to room
temperature, giving a dark dispersion. Ethanol (25 mL) was
added to precipitate the particles, and the particles were
isolated by centrifuging. The particles were redispersed in
hexane, precipitated with ethanol, and isolated by centrifug-
ing. The particles were dried at room temperature under
vacuum to give 100 to 200 mg. The dispersion and
precipitation purified the particles; however, we did not
characterize the content of the washings. For comparison,
we also prepared Fe53Pt47 nanoparticles using the procedure
of S. Sun and co-workers.2
The particles were dispersed in a 50/50 mixture of hexane
and octane that included small amounts of oleic acid and
oleylamine. The dispersion was dropped onto a carbon-coated
copper TEM grid (200 mesh from SPI) and the solvent
evaporated to give a self-assembled film. The particle
composition, [Fe49Pt51]88Ag12, was determined by energy-
dispersive X-ray analysis on a Philips model XL 30 scanning
electron microscope. The particles assembled into a hex-
agonal closed-packed array as shown in Figure 1a, similar
to that seen for FePt and FexCoyPt100-x-y nanoparticles.9,10
They had an average diameter of 3.5 nm and a chemically
disordered fcc structure (Figure 2, curve a). The (111) lattice
spacing was expanded to 229 pm for the [Fe49Pt51]88Ag12
nanoparticle relative to 225 pm for Fe53Pt47, indicating that
silver was substituting into the FePt lattice. Heat treatments
were done in a Lindberg tube furnace with flowing argon
(containing 2% hydrogen) for 30 min at temperatures ranging
from 300 to 500 °C. The sequence of X-ray diffraction curves
in Figure 2 shows the progress of the fcc to L10 phase
transformation as a function of temperature. Careful exami-
nation of curve c in Figure 2 shows that very weak (001)
and (011) peaks for the tetragonal FePt phase appeared after
heat treatment at 350 °C. A shoulder appeared at the low
2θ side of the FePt (111) peak indicating that Ag was phase
separating from the particles. After heat treatment at 400
°C, curve d in Figure 2, the (001), (011), and (200) diffraction
peaks for the FePt L10 phase had clearly emerged, and the
Nano Lett., Vol. 2, No. 10, 2002
Figure 2. X-ray diffraction data for the films containing self-
assembled [Fe49Pt51]88Ag12 nanoparticles: as-prepared (curve a) and
after heat treatment at 300 °C (curve b), 350 °C (curve c), 400 °C
(curve d), 450 °C (curve e), or 500 °C (curve f).
Figure 3. Plot of d-spacing for the (111) diffraction peak as a
function of annealing temperature for films containing self-
assembled [Fe49Pt51]88Ag12 (closed circles) or Fe53Pt47 (open circles)
nanoparticles.
Ag (111) diffraction near 2θ ) 38° was more apparent. The
fcc to tetragonal phase transformation was beginning around
350 °C. The plots in Figure 3 compare values of the (111)
lattice spacing for [Fe49Pt51]88Ag12 and Fe53Pt47 as a function
of heat treatment temperature. For [Fe49Pt51]88Ag12 the (111)
lattice spacing approaches the bulk value for tetragonal FePt
(d111 ) 219.7 pm) at lower heat treatment temperatures than
for Fe53Pt47. It appears that the Ag atoms leave the FePt
lattice at temperatures less than 400 °C, leaving lattice
vacancies. These vacancies increase the mobility of the Fe
and Pt atoms, thus enhancing the kinetics for the phase
transformation. Although the X-ray diffraction data clearly
show that the Ag left the FePt particles, there was no
indication in the TEM for the formation of separate Ag
particles. Indeed, we do not know where the silver went,
perhaps it remained on the surface of the particles. We plan
to answer this question in future work.
In Figure 4 is a comparison of the in-plane magnetic
hysteresis curves (measured on a Princeton Measurements
Nano Lett., Vol. 2, No. 10, 2002
Figure 4. Magnetic hysteresis curves for films containing self-
assembled [Fe49Pt51]88Ag12 (solid curve) or Fe53Pt47 (dashed curve)
nanoparticles after heat treatment at 400 °C for 30 min.
Figure 5. Plots of coercivity as a function of heat treatment
temperature for films containing self-assembled [Fe49Pt51]88Ag12
(solid circles) or Fe53Pt47 (open circles) nanoparticles. Substitution
of Ag of in to FePt nanoparticles to give self-assembled [Fe49Pt51]88-
Ag12 nanoparticles (a) allowed transformation from the superpara-
magnetic fcc to the ferromagnetic L10 phase after heat treatment
at 400 °C for 30 min (b).
model 2900 alternating gradient magnetometer) for [Fe49-
Pt51]88Ag12 and Fe53Pt47 films heat treated at 400 °C. The
film containing the Fe53Pt47 was superparamagnetic, while
the film containing the [Fe49Pt51]88Ag12 was ferromagnetic
with an apparent coercivity of 3400 Oe. The actual value
probably exceeds 3400 Oe because the maximum field on
our AGM (19 000 Oe) was not sufficient to completely
saturate the loop. The curves in Figure 5 compare the
coecivity of the [Fe49Pt51]88Ag12 and Fe53Pt47 films as a
function of heat treatment temperature. Consistent with the
trends in Figure 3, Hc increases more rapidly with increasing
heat treatment temperature for the [Fe49Pt51]88Ag12 films. Hc
for the film heated to 350 °C was more than 1000 Oe,
indicating a significant amount of phase transformation at
this temperature. In fact, the film heat treated at 300 °C had
a small coercivity (200 Oe), indicating a small degree of
transformation.
1035
 If self-assembled films of tetragonal FePt nanoparticles
are to be used as granular thin film media, a means of
transforming the particles to the tetragonal phase, while
maintaining the small particle size and the high degree of
particle positional order, must be found. The results reported
here are a very important step toward that goal. Including
Ag in the FePt particles has allowed transformation of the
particles from the fcc to the high coercivity tetragonal phase
at a temperature some 100 to 150 °C lower than that for
FePt particles. An immediate benefit of the lowering
transformation temperature was a significant improvement
in the ability to maintain the particle positional order. In
Figure 1b is a TEM image of the film containing [Fe49Pt51]88-
Ag12 nanoparticles after heat treatment at 400 °C. There was
some degradation in particle positional ordering; however,
this was not as great as the loss in positional ordering for
FePt films heat treated at 600 °C.4,5 Furthermore, there was
less particle coalescence for the heat treated film containing
[Fe49Pt51]88Ag12 nanoparticles. δM curves obtained from
isothermal and dc magnetic remanence measurements show
negative values of δM for the films heat treated at or below
400 °C.11 Negative values of δM are consistent with
magnetostatic interactions, while positive values of δM
would indicate exchange interactions due to sintering.12
1036
Acknowledgment. This work was supported by the NSF
Materials Research Science and Engineering Center award
number DMR-9809423.
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NL025614B
Nano Lett., Vol. 2, No. 10, 2002