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

Patterning self-assembled FePt nanoparticles

Min Chena,b,*, David E. Niklesa, Huaqin Yina,1, Shoutao Wanga, J.W. Harrella,
Sara A. Majetichb
a
Center for Materials for Information Technology, The University of Alabama, Tuscaloosa, AL 35487-0209, USA
b
Department of Physics, Carnegie Mellon University, Pittsburgh, PA 1213-3890, USA

Received 30 September 2002

Abstract

We describe a potential way to extend the ordered domain of self-assembled FePt nanoparticles. The FePt particles,
with an average diameter of 3 nm, were prepared by simultaneous thermal decomposition of Fe(CO)5 and chemical
reduction of Pt(acac)2 and then were dispersed in a mixture of hexane and octane. When self-assembling on a plain
silicon wafer, FePt nanoparticles formed ordered hexagonal arrays in a range of tens to a few hundred nanometers. A
silicon wafer with patterned holes of a photoresist film, made using UV-lithographing technique, was used as a template
to direct the stacking direction of the FePt nanoparticles. The FePt dispersion was dropped on the patterned holes of
the photoresist film. After being heat-treated at 100 C for 30 min under vacuum condition, the photoresist was stripped
out by dipping the sample in acetone. The patterned disks, with an average diameter of 2.0 mm and a height of 250 nm,
of self-assembled FePt nanoparticles were examined using SEM and Auger mapping. Their magnetic properties were
measured using AGM. The Auger electrons of neither Fe LMM nor Pt MNN could be detected from the sample, which
indicated the adsorption of oleic acid and oleylamine on the surface of FePt nanoparticles. The coercivity of patterned
FePt significantly increased with the annealing temperature above 600 C.
r 2003 Elsevier B.V. All rights reserved.

PACS: 61.46.+w; 75.50.Tt; 75.50.Bb; 75.50.Ss; 81.07.Lk; 81.16.Dn

Keywords: FePt nanoparticles; UV-lithography; Coercivity; Patterned magnetic media

1. Introduction magnetocrystalline anisotropies. Since being de-

Sputter-deposited FePt thin films have been
widely studied for the ultrahigh density magnetic
hard media because of their large uniaxial
*Corresponding author. IBM T.J. Watson Research Center,
Nanoscale Material Devices (19-141), P.O. Box 218 1101,
Kitchawan Rd., Yorktown Heights, NY 10598, USA.
E-mail address: mchen30@us.ibm.com (M. Chen).
1
Current address: Seagate Technology, 7801 Computer
Avenue S, Minneapolis, MN 55435, USA.
monstrated by Sun et al. [1], the uniform nanoscale
FePt particles from chemical method have drawn
great interest during recent years. Such magnetic
nanoparticles can self-assemble into ordered per-
iodical arrays, which are promising candidates for
a new generation of magnetic high-storage media
[2]. However, the self-assembly of FePt nanopar-
ticles on a plain Si wafer only gave the ordered
domain in the range of tens to a few hundred
nanometers in diameters [3,4]. It is reported that a

0304-8853/03/$ - see front matter r 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0304-8853(03)00449-9
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2 M. Chen et al. / Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]
patterned template could affect the stacking
direction of the nanocrystals. When nanocrystals
were grown normal to a pattern of holes, a pave
FCC crystal was formed [5]. We initially report
here to restrict the self-assembly of FePt nano-
particles on patterned holes of a polymer film on a
silicon wafer to increase the ordered domains.
2. Experiment
Iron pentacarbonyl, platinum acetylacetonate,
1,2-hexadecanediol, octyl ether, oleic acid, and
oleyl amine were purchased from Aldrich. Etha-
nol, hexane and octane were purchased from
Fisher Scientific. A negative photoresist R1805
(containing propylene glycol monomethyl ether
acetate) and developer S351 (containing sodium
hydroxide) were purchased from Shipley, Co.,
Inc., MA. The carbon-coated copper grids were
purchased from Structure Probe Inc.
Sun’s synthetic procedure to prepare FePt
nanoparticles was used here [1]. 200 mg of
Pt(acac)2 was combined with 390 mg of 1,2-
hexadecanediol and 20 ml of dioctylether in a
three-neck flask and dissolved at 100 C under N2
protection. After the Pt(acac)2 completely dis-
solved, 0.10–0.13 ml of Fe(CO)5, 0.16 ml of oleic
acid and 0.17 ml of oleylamine were added to the
above mixture solution. The Fe(CO)5, oleic acid
and oleylamine were dispensed using 1 ml capacity
syringes. Under nitrogen gas protection, the
mixture solution was heated to 286 C (the boiling
temperature of dioctylether). After being refluxed
for 30 min, the reaction mixtures were allowed to
cool to room temperature. The particles precipi-
tated after adding 40 ml ethanol. The mixture was
centrifuged for 10 min and the supernatant liquid
was removed. A mother FePt dispersion was made
by dispersing B100 mg of dried particles in 10 ml
of mixture solvents of (1:1) hexane and octane,
containing 0.05 ml of oleic acid and 0.05 ml of
oleylamine. The diluted FePt dispersion (contain-
ing about 2.5 mg of nanoparticles in 1 ml of
mixture of hexane and octane) was dropped onto
a Si(1 0 0) wafer, containing its native oxide. The
solvent was allowed to slowly evaporate to give a
self-assembled film.
The Si substrate was first cleaned with acetone
and isopropane by sonication for 5 min, and then
was pre-baked at 115 C for 1 min. The negative
photoresist (R1805) was applied on the Si wafer
using photoresist spinner (mode R481). The spin
rate of 5000 rpm and time of 40 s corresponds to
the thickness of 500 nm for photoresist R1805.
Patterned holy arrays were transferred from an
antidote mask into the film using contact photo-
lithography with Quintel Contact/Proximity Mask
Aligner. The antidote presented here was about
2.0 mm in diameter with a separation of 1.5 mm.
After being exposed by UV light, the photoresist
was developed using developer S351. The Si wafer
with patterned image on the photoresist film was
washed using water, spin-dried and used as
template for the self-assembly of FePt nano-
particles.
The diluted FePt dispersion was slowly dropped
on patterned Si wafer. The solvents were allowed
to evaporate in 10–15 min. The Si wafer with
self-assembled FePt on patterned holes of photo-
resist was then heat-treated at 100 C for 30 min
under vacuum condition (vacuum pressure is
B3  110 7 Torr). Finally, the photoresist was
stripped off by dipping the Si wafer into the
acetone for 30 min and sonicating for 5 min. AFM
and SEM were used to examine the quality of
patterned self-assembly of FePt nanoparticles.
3. Results and discussion
A TEM image of the self-assembled FePt
nanoparticles is shown in Fig. 1, which shows
the ordered hexagonal arrays; however, the size
of the ordered domain is usually about tens to
a few hundred nanometers in diameter [3,4].
The primary purpose to self-assemble FePt nano-
particles on the patterned Si wafer is to increase
the ordered domain. In addition, magnetic pat-
terned media are the promising candidates for a
new generation of high storage of perpendicular
magnetic recording.
Two different kinds of patterned substrates have
been tried; (a) patterned holes of silicon wafer, and
(b) patterned holes of photoresist film on smooth
silicon wafer. If FePt nanoparticles directly
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M. Chen et al. / Journal of Magnetism and Magnetic Materials ] (]]]]) ]]]–]]]
Fig. 1. Hexagonal arrays of self-assembled FePt nanoparticles
on C-coated Cu grid.
self-assembled on the patterned-dot-Si wafer, it
was difficult to remove those particles on the holes.
However, if FePt nanoparticles first self-assembled
on the silicon supported patterned holes of
photoresist film which could be easily stripped
off from the silicon wafer by acetone, the dish-like
patterned FePt dots were finally left on the Si
wafer, as shown by SEM image in Fig. 2. The
section analysis of AFM shows that the patterned
FePt dots have an average diameter of 2 mm and a
height of 250 nm. Unfortunately, the surfaces of
the FePt dots are rough.
The Auger electron spectroscopy was used to
map the patterned FePt dots on silicon wafer using
Kratos Auger/XPS/SEM Spectrometer. However,
no signal was recorded for Auger electron of either
Fe LMM or Pt MNN even though Ar+ was used
to etch the sample surface. Three Auger electron
peaks for Fe LMM are in the range of 600–700 eV
[6]. The position of the main Auger electron peak
for Pt MNN is around 1970 eV [6]. As the escape
depths of Auger electrons for Fe LMM and
Pt MNN are both the order of a few atomic
3
Fig. 2. Patterned self-assembled FePt nanoparticles on a silicon
wafer.
layers [7], it indicates that the adsorbed oleic
acid and oleylamine on the particle surface might
block the Fe or Pt Auger electrons from being
detected.
Magnetic measurement was done using AGM.
After being annealed for 30 min, the coercivity of
the patterned self-assembled FePt particles in-
creased to 2980 Oe at 600 C, 4160 Oe at 650 C,
and 12400 Oe at 700 C.
4. Conclusion
The self-assembly of FePt nanoparticles was
patterned on a silicon wafer in order to increase
the ordered domain. A silicon wafer with pat-
terned holes of a photoresist film was used as a
template to direct the stacking direction of the
FePt nanoparticles. The patterned disks of self-
assembled FePt nanoparticles have an average
diameter of 2.0 mm and a height of 250 nm.
Unfortunately, the surface of the patterned dish-
like FePt dots was not smooth due to the limit of
UV-lithographing technique. The Auger mapping
indicated the adsorption of oleic acid and oleyla-
mine on the surface of FePt nanoparticles. The
coercivity of patterned FePt significantly increased
with the annealing temperature above 600 C. The
patterned media with ordered self-assembled FePt
arrays might be a good candidate for future high
storage of magnetic recording.
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Acknowledgements [2] D. Weller, A. Moser, L. Folks, M.E. Best, W. Lee, M.F.

This work was supported by the NSF Materials
Research Science and Engineering Center award
number DMR-9809423.
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