ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]

Chemical ordering of FePt nanoparticle self-assemblies by

rapid thermal annealing
H. Zeng*, Shouheng Sun, R.L. Sandstrom, C.B. Murray
Thomas J. Watson Research Center, IBM Research Division, Route 134, P.O. Box 218, Yorktown Heights, NY 10598, USA

Received 27 September 2002; received in revised form 27 February 2003

Abstract

Self-assembled 4 nm FePt nanoparticle arrays were treated with rapid thermal annealing (RTA) process. The phase
transformation from the chemically disordered face-centered-cubic structure of the as-synthesized FePt nanoparticles to
the chemically ordered face-centered-tetragonal structure was realized by RTA, with both the annealing temperature
and time being greatly reduced, as compared to conventional annealing. The onset of chemical ordering occurred at the
annealing condition of around 400
C for only 5 s. Temperature-dependent coercivity measurements revealed strong
thermal effects of the nanoparticle assemblies. Curie temperatures (Tc ) of the annealed assemblies were derived from the
temperature-dependent hysteresis measurements. Tc of the annealed assemblies increases with increasing annealing
temperature, but is about 200–300 K lower than that of bulk FePt (750 K). The drastic reduction of Tc may be
attributed to size effect and partial chemical ordering of FePt nanoparticles.
r 2003 Elsevier B.V. All rights reserved.

Keywords: FePt; Nanoparticles; Rapid thermal annealing

1. Introduction However, making a hard magnetic nanoparticle

The requirements for ultra-high density mag-
netic recording have driven the development of
new magnetic thin film media with smaller grains,
higher coercivity, and minimal exchange coupling
between neighboring grains [1]. FePt- and CoPt-
based hard magnetic nanoparticle arrays have
been viewed as a promising candidate for future
recording media applications [2]. Recent solution
phase-based synthesis offers a convenient ap-
proach to monodisperse FePt nanoparticles with
the size being controlled down to only B4 nm [3].
*Corresponding author. Tel.: +1-914-945-1609; fax: +1-
914-945-4342.
E-mail address: haozeng@us.ibm.com (H. Zeng).
0304-8853/03/$ - see front matter r 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0304-8853(03)00482-7
assembly with controlled thickness, mechanical
robustness and the desired magnetic properties has
been a great challenge. Particular problems asso-
ciated with the formation of a hard magnetic FePt
nanoparticle assembly are the high temperature
and long annealing time required for the chemical
ordering of FePt, which may lead to nanoparticle
aggregation and inter-particle exchange coupling.
Severe aggregation will even destroy the self-
organized assembly, and lead to domain wall
formation [4].
Recent effort has been devoted to lowering the
ordering temperature in FePt thin films and
nanoparticle arrays by doping of elements such
as Cu and Ag [5,6]. Although the doping results in
significant reduction of the ordering temperature,
 ARTICLE IN PRESS
2 H. Zeng et al. / Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]
possible incorporation of impurities in FePt
lattices may lead to additional disorder, reducing
the achievable anisotropy and thermal stability.
Here we report the chemical ordering of FePt with
rapid thermal annealing (RTA). A reduction of the
ordering temperature in pure FePt comparable to
doped assemblies is observed, with the ordering
taking place within seconds. Curie temperatures
(Tc ) for assemblies annealed at different tempera-
tures are obtained from temperature-dependent
hysteresis loop measurements. A dramatic de-
crease in Tc is observed, as compared to bulk
alloy, which may result from size and surface
effects and chemical disorder. This may greatly
affect room-temperature magnetization, aniso-
tropy and thermal stability.
2. Synthesis and assembly of FePt nanoparticles
Monodisperse FePt nanoparticles were synthe-
sized by high temperature (297
C) decomposition
of Fe(CO)5 and reduction of Pt(acac)2 in the
presence of oleic acid and oleyl amine [3]. The Fe
and Pt composition is tuned by varying the molar
ratio of Fe(CO)5 and Pt(acac)2. The syntheses
show that 0.5 mmol of Fe(CO)5 and 0.5 mmol of
Pt(acac)2 yield Fe38Pt62, while 1.1 mmol of
Fe(CO)5 and 0.5 mmol of Pt(acac)2 lead to
Fe56Pt44 nanoparticle materials [7]. Alternatively,
the FePt nanoparticles were made by solution
phase reduction of FeCl2 and Pt(acac)2 [8]. The
advantage of this reduction approach is that the
final FePt composition can be readily controlled
by the actual molar ratio of FeCl2 and Pt(acac)2.
For example, a 0.6/0.4 ratio of FeCl2/Pt(acac)2
gives Fe60Pt40 nanoparticles, while a 0.5/0.5 ratio
yields Fe50Pt50 nanoparticles.
Under suitable conditions, the monodisperse
nanoparticles suspended in solution tend to self-
organize into ordered arrays after solvent evapora-
tion. This self-organization is influenced by
the nature of the interactions exhibited among
the particles, and between the particles and the
substrate. The synthetic strategy to nanoparticle
superlattices relies on a large number of weak and
non-directional interactions, such as ionic bonds,
hydrogen bonds and van der Waals interactions to
Fig. 1. SEM image of a highly ordered 4 nm FePt nanoparticle
self-assembly.
organize the particles’ self-assembly. The unifor-
mity in the size of the FePt nanoparticles is very
critical in forming 2-D and 3-D superlattices.
Fig. 1 illustrates the SEM image of a highly
ordered 4 nm FePt assembly on Si substrate, which
shows cubic assembly structure.
3. RTA and phase transformation
In this study, an AG Associates HeatPulse 410
Rapid Thermal Processing unit was used to anneal
the FePt nanoparticle assemblies on glass sub-
strates, with the annealing temperatures (Ta )
ranging from 300
C to 600
C, and the annealing
time (referring to time elapsed at the set tempera-
ture) from 1 to 30 s. The heating rate is 200
C/s
and the cooling profile can be roughly described by
Newton’s Law of Cooling, with the initial cooling
rate greater than 50
C/s for the first second. At the
annealing temperature of 600
C, the cooling time
from 600
C to 400
C is B7 s; at 500
C, the
cooling time from 500
C to 400
C is B5 s. RTA
was performed under clean nitrogen atmosphere,
with a flow rate of 40 cm3/s. All samples were pre-
dried in vacuum to evaporate the solvent.
As-synthesized FePt nanoparticles possess
disordered face-centered-cubic (FCC) structure,
as can be seen from the X-ray diffraction
(XRD) pattern shown in Fig. 2(a), and have
very low magnetocrystalline anisotropy, showing
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H. Zeng et al. / Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]] 3

(111) 26
24 a (300 K )
(001) (110) 580 C
(200) 22 b (300 K)
(e) (002) c (10 K)
Intensity (arb. unit)

(201) (112) 20
18
(d)

Hc (kOe)
550 C 16
(c) 14
500 C 12
(b) 10
460 C 8
6
(a) as-syn 4
2
20 30 40 50 60 70 0
350 400 450 500 550 600
2θ Ta (C)
Fig. 2. XRD (l ¼ 1:79 A, ( Co Ka radiation) pattern of 4 nm
Fig. 3. Hc as a function of the annealing temperature Ta for (a)
FePt nanoparticle self-assembly: (a) as-synthesized and an-
RTA for 5 s, measured at 300 K; (b) box oven annealing for
nealed by RTA for 5 s at annealing temperatures of (b) 460
C,
30 min, measured at 300 K; and (c) RTA for 5 s, measured at
(c) 500
C, (d) 550
C and (e) 580
C.
10 K.

superparamagnetic behavior at room temperature. for Ta o500
C, Hc increases with Ta slowly at a

Upon annealing, FePt undergoes a phase trans-
formation from disordered FCC to chemically
ordered face-centered-tetragonal (FCT), which
yields high magnetocrystalline anisotropy. Typi-
cally, annealing temperatures above 500
C are
required for the ordering of FePt nanoparticles.
Figs. 2(b)–(e) show the XRD patterns of samples
after RTA at from 460
C to 550
C for 5 s. It can
be seen that the superlattice (0 0 1), (1 1 0) and
(2 0 1) peaks of the FCT phase emerges at
Ta X460
C, indicating the formation of partially
ordered FCT structure. As the annealing tempera-
ture further increases, the intensity of these peaks
becomes stronger, and the original (2 0 0) FCC
peak become split into (2 0 0) and (0 0 2) tetragonal
peaks, suggesting the improvement in the degree of
ordering.
Magnetic measurements show that annealed
FePt nanoparticle assemblies are ferromagnetic.
Figs. 3(a) and (b) compare Hc as a function of Ta
for RTA samples and samples annealed in a box
oven for 30 min. With the annealing time fixed to
be 5 s, the room-temperature coercivity (Hc )
increases with increasing annealing temperatures,
from 300 Oe at Ta ¼ 360
C to 17,000 Oe at
Ta ¼ 580
C, as seen in Fig. 3(a), which is
consistent with the improvement of chemical
ordering. Hc ðTa Þ curve shows two distinct regions:
rate of about 30 Oe/
C; for 500oTa o550
C,
however, this rate jumps to 250 Oe/
C. Further
increases in Ta only increases Hc slightly, suggest-
ing that a high degree of ordering is already
achieved at Ta ¼ 550
C. We also noticed that
RTA samples show significantly higher Hc than
box furnace annealed specimens at roughly the
same annealing temperatures. Detailed studies on
such differences are still underway.
When FePt is annealed at high temperatures,
ordering and nanoparticle aggregation can occur
at the same time. Room-temperature coercivity
alone may not be a suitable indication of the
degree of ordering. This is because for FePt
nanoparticles as small as 4 nm, thermal fluctua-
tions to the energy barrier Ku V ; where Ku is the
anisotropy constant and V the particle volume,
would lead to a decrease in room-temperature
coercivity. The smaller the individual volume of
magnetization reversal, the stronger this thermal
effect. For well-isolated FePt assemblies, it is
reasonable to assume that the volume of magne-
tization reversal is equal to the particle volume, as
the reversal is likely cooperative within the whole
particle. When aggregation occurs, the effective
volume of magnetization reversal is increased. This
may lead to an increased energy barrier Ku V ; and
thus enhanced thermal stability, yielding relatively
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4 H. Zeng et al. / Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]
high room-temperature coercivity. To study the
effects of ordering and aggregation, the tempera-
ture dependence of coercivity was measured.
Fig. 3(c) shows Hc measured at 10 K for RTA
samples annealed at different temperatures. At
such a low measuring temperature, the contribu-
tion from thermal effects is negligible, and the
coercivity can serve as an indication of the degree
of ordering. It can be seen that at Ta ¼ 400
C, Hc
at 10 K reaches 6 kOe, suggesting the onset of
chemical ordering, although the XRD results
indicate that the superlattice (0 0 1) peak only
becomes visible at Ta ¼ 460
C. TEM observations
confirm that the nanoparticles are well isolated. As
Ta increases, Hc increases, suggesting improved
ordering. For Ta ¼ 580
C, Hc at 10 K is
24,000 Oe. This corresponds to Ku B2:5  107 erg/
cm3, which is consistent with values of highly
ordered FePt reported by others [9].
Fig. 4 shows the measured temperature-depen-
dent coercivity, normalized by Hc at 10 K, for
RTA samples with Ta ¼ 360
C, 460
C, 520
C and
580
C. For particle ensembles with a single energy
barrier, Hc ðTÞ behavior can be described by
Sharrock’s formula [10], provided that the reversal
mechanism is coherent rotation. Nevertheless, in
reality, the Hc ðTÞ behavior is rather complicated.
It can be seen that Hc of all samples decreases
dramatically with increasing measuring tempera-
tures, due to thermal fluctuations. However, Hc ðTÞ
1.0
0.8
Hc /Hc(10 K)
0.6
0.4
580 C
0.2 520 C
460 C
360 C
0.0
0 50 100 150 200 250 300
T (K)
Fig. 4. Normalized coercivity Hc =Hc (10 K) as a function of
measuring temperature for Ta =(a) 360
C, (b) 460
C, (c) 520
C
and (d) 580
C. The dashed lines are guides to the eye.
behaviors of samples annealed at low and high
temperatures show different trends: for low Ta
samples (p460
C), the rate of Hc reduction is
initially quite large, while decreases gradually as
the measuring temperature approaches 300 K;
for high Ta samples, this trend tends to be
reversed. According to Sharrock’s formula, the
temperature dependence of Hc may originate from
two factors: (1) the temperature dependence of
intrinsic properties such as Ms and Ku and (2) the
thermal fluctuation term kB T=ðKu V Þ: One of the
possible reasons for the difference in Hc ðTÞ
behaviors we observed may be that the tempera-
ture dependence of intrinsic properties is compet-
ing with the thermal fluctuation term. This
temperature dependence of Ms and Ku may
originate from various factors, including the size,
surface effects and disorder of nanoparticles.
Different Hc ðTÞ trends seem to suggest that for
the sample annealed at low Ta ; the thermal
fluctuation term kB T=ðKu V Þ is dominating; while
for the sample annealed at high Ta ; the dominating
effect is the temperature dependence of intrinsic
properties. The reason lies in that for high Ta
samples, strong inter-particle exchange coupling
and/or possible aggregation makes the thermal
fluctuation term less important.
For isolated, randomly oriented particles with
uniaxial anisotropy, the remanence ratio S ¼
Mr =Ms is 0.5 [11]. S greater than 0.5 suggests that
there may exist inter-particle exchange coupling.
Therefore, S can be used to study inter-particle
exchange interactions. Again, due to the thermal
effects, room-temperature S cannot be used for
such purposes. Instead, S at 10 K is measured for
these samples and is plotted as a function of Ta in
Fig. 5. It can be seen that S decreases gradually
and monotonically with decreasing Ta : However,
for samples annealed at Ta p400
C, S is still
greater than 0.5, even though our TEM analysis
suggests that the particles are well isolated. This
may be attributed to the fact that our low Ta
samples contain a mixture of both a uniaxial and
cubic anisotropy, which is consistent with partial
ordering observed from XRD results. It is known
that for isolated, randomly oriented particles with
cubic anisotropy, S is 0.83 for K1 > 0 and 0.87 for
K1 o0 [12].

H. Zeng et al. / Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]
0.74
0.72
0.70
S = Mr /Ms
0.68
0.66
0.64
0.62
0.60
350 400 450 500
Ta
Fig. 5. Remanence ratio S ¼ Mr =Ms measured at 10 K as a
function of Ta :
The intrinsic magnetic properties of Ms ; Ku and
the curie temperature Tc for the bulk FePt are
affected by size and surface effects, as well as
chemical disorder of the FePt nanoparticles. Ms as
a function of temperature was obtained from
temperature-dependent hysteresis loop measure-
ments for several FePt nanoparticle samples with
different Ta : Fig. 6 shows Ms ðTÞ=Ms ð0Þ vs. T=Tc
curves for Ta ¼ 360
C, 460
C and 520
C; the
theoretical curve calculated from Weiss’s theory
using the Brillouin function with quantum number
J ¼ 1=2 is also plotted. Tc for these samples can be
determined by fitting the experimental data with
the theoretical curve. As can be seen, Tc decreases
from 580 to 410 K as Ta decreases from 520
C to
360
C. Compared to Tc of 750 K for bulk FePt,
the reduction of Tc in FePt nanoparticle assem-
blies for Ta ¼ 520
C is 170 K and for Ta ¼ 360
C,
340 K. Okamoto et al. [13] reported a weak
dependence of Tc on ordering parameters in
epitaxial FePt thin films, from 750 K for the
ordering parameter of 0.79–700 K for the ordering
parameter of 0.5. Partial ordering in nanoparticle
assemblies due to insufficient heat treatment
therefore may account for part of the Tc reduction.
Another significant factor that contribute to the
reduction of Tc is the particle size and surface
effect. For 4 nm FePt nanoparticles, nearly 30% of
the atoms are at the surface if the thickness of the
surface layer is assumed to be 2 A. ( The surface
atoms have reduced exchange coupling, which
may contribute to the size dependent Tc change.
The size and surface effects on Ms of nanoparticles
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5
1.0 J=1/2
0.8
0.6
Ms/M0
0.4 Ta = 360 C, Tc = 410 K
0.2 Ta = 460 C, Tc = 450 K
Ta = 520 C, Tc = 580 K
0.0
0.0 0.2 0.4 0.6 0.8 1.0
550 600
T/Tc
Fig. 6. Ms ðTÞ=Ms ð0Þ vs. T=Tc for Ta =60
C, 460
C and
520
C.
lie in two-folds: in addition to the lose of moment
for the surface atoms, which leads to lower Ms for
smaller particles, the reduction of Tc also decreases
room-temperature Ms : For example, for bulk FePt
with Tc at about 750 K, room-temperature Ms is
only 1.5% less than Ms at 0 K; however, for the
sample annealed at Ta ¼ 360
C with Tc B410 K,
the reduction in Ms amounts to B20%. Finally, as
the magnetocrystalline anisotropy Ku decreases with
increasing temperature, and vanishes at around Tc ;
a reduction in Tc of about 200–300 K for nanopar-
ticle assemblies means that Ku decreases with
increasing temperature faster than that of bulk.
4. Conclusions
Chemical ordering for 4 nm FePt nanoparticle
self-assembly can be improved by rapid thermal
annealing, with significantly lowered annealing
temperature and shortened time. Partially ordered
assemblies show a remanence ratio greater than
0.5, which is attributed to a mixture of a cubic and
uniaxial anisotropy. Significant reduction in the
curie temperature is due largely to the particle size
and surface effects, as well as partial ordering. To
use these FePt nanoparticle assemblies for future
magnetic recording applications, further optimiz-
ing of annealing conditions leading to fully
ordered, well-isolated nanoparticles is required. It
may be advantageous to utilize particles larger
than 4 nm to alleviate problems associated with
nanoparticle size and surface effects.
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Acknowledgements
This work was supported in part by US DoD/
DARPA under grant DAAD 19-01-1-0546.
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