JOURNAL OF APPLIED PHYSICS VOLUME 91, NUMBER 10 15 MAY 2002

Synthesis of spherical FePd and CoPt nanoparticles

Min Chena) and David E. Nikles
Department of Chemistry and Center for Materials for Information Technology, The University of Alabama,
Tuscaloosa, Alabama 35487-0209
Co48Pt52 nanoparticles were prepared by the simultaneous chemical reduction of platinum
acetylacetonate and the thermal decomposition of cobalt tricarbonyl nitrosyl. Similarly, Fe50Pd50
nanoparticles were prepared by the simultaneous reduction of palladium acetylacetonate and the
thermal decomposition of iron pentacarbonyl. The average diameter for the Co48Pt52 particles was
7 nm, while the average diameter for the Fe50Pd50 particles was 11 nm. Films of the particles were
cast onto silicon wafers from hydrocarbon solution. Only after annealing at 700 °C for three hours
did the Co48Pt52 films transform to the L10 phase. However there was no evidence for the tetragonal
phase for the films containing Fe50Pd50 particles after annealing at 700 °C for three hours. © 2002
American Institute of Physics. 关DOI: 10.1063/1.1456406兴

INTRODUCTION 关 Co共CO兲3 NO兴 was purchased from Strem Chemicals. Etha-

Magnetic recording technology has made tremendous
gains in data storage density, partially by scaling down the
grain size of thin film media. However, further scaling to
support future increases will bring the grain sizes near the
superparamagnetic limit. This had led to a search for new
materials and new microstructures for longitudinal recording.
The L1 0 phase of FePt has a very high magnetocrystalline
anisotropy (K u ⫽6.6– 10⫻107 erg/cm2 ). 1 Sun et al. have
prepared spherical FePt nanoparticles by the simultaneous
reduction of platinum acetylacetonate and thermal decompo-
sition of iron pentacarbonyl.2 As prepared the particles were
spherical, superparamagnetic and had a distorted face-
centered cubic structure. The particles had a very narrow size
distribution. They were dispersed in hexane, the dispersion
cast onto a silicon wafer to dry to highly ordered, self-
assembled films consisting of close-packed particles. Upon
annealing at temperatures above 550 °C, the particles trans-
formed to the L1 0 共tetragonal兲 phase. The annealed films
were ferromagnetic with coercivities that depended on the
annealing conditions. They were able to record on the films
and demonstrated that the thermal stability factor (KV/kT
⬎48) was suitable for a thin film medium. This demonstra-
tion has aroused our interest in the synthesis and self-
assembly of FePt nanoparticles. Earlier we modified the syn-
thetic procedure reported by Sun et al. to prepare
Fex Coy Pt100⫺x⫺y nanoparticles.3,4 Here we describe the syn-
thesis of CoPt and FePd nanoparticles. The L1 0 phases of
these alloys also have a high magnetocrystalline anisotropy
共CoPt K u ⫽4.9⫻107 erg/cm3 and FePd K u ⫽1.8
⫻10 erg/cm3 兲.1
7
EXPERIMENT
Iron pentacarbonyl 关 Fe共CO兲5 兴 , platinum acetylacetonate
关 Pt共acac兲2 兴 , palladium acetylacetonate 关 Pd共acac兲2 兴 , 1,2-
hexadecanediol, octyl ether, oleic acid, and oleyl amine were
purchased from Aldrich. Cobalt tricarbonyl nitrosyl,
a兲
Electronic mail: chen004@bama.ua.edu
nol, hexane and octane were purchased from Fisher Scien-
tific. The carbon-coated copper grids 共400-count model No.
2450兲 were purchased from Structure Probe Inc.
CoPt nanoparticles: Platinum acetylacetonate 共0.50
mmol兲 and 1,2-hexadecanediol 共1.5 mmol兲 were dissolved in
20 mL dioctyl ether in a three-necked round bottom flask
with magnetic stirring under nitrogen at 100 °C. After the
Pt共acac兲2 completely dissolved, Co共CO兲3 NO 共1.0 mmol兲,
oleic acid 共0.50 mmol兲, and oleylamine 共0.50 mmol兲 were
added to the reaction mixture. The mixture was heated to
286 °C 共the boiling point of dioctyl ether兲 and the mixture
allowed to reflux for 30 minutes. The reaction mixture was
allowed to cool to room temperature, giving a black disper-
sion. Ethanol 共20 mL兲 was added to precipitate the particles.
The particles were isolated by centrifuging, then washed
with ethanol.
FePd nanoparticles: Palladium acetylacetonate 共0.50
mmol兲 and 1,2-hexadecanediol 共1.5 mmol兲 was dissolved in
20 mL of dioctyl ether in a three-neck flask with magnetic
stirring at 100 °C under N2 protection. After the Pd共acac兲2 ,
completely dissolved, iron pentacarbonyl 共0.75 mmol兲, oleic
acid 共0.50 mmol兲, and oleylamine 共0.50 mmol兲 were added
to the reaction mixture. The mixture was heated to reflux and
allowed to reflux for 30 minutes. After refluxing for 30 min-
utes, the reaction mixture was allowed to cool to room tem-
perature and 20 mL ethanol was added to precipitate the
particles. The particles were isolated by centrifuging and
washed twice with ethanol to remove the byproducts.
Film deposition: A mother dispersion was prepared by
dispersing 200 mg particles in 20 mL of a 1:1 mixture of
hexane and octane, containing 0.05 mL of oleic acid and 0.05
mL of oleylamine. The mother dispersion was dropped onto
a Si 共100兲 wafer having its native oxide. The solvent was
allowed to evaporate to give films. The mother dispersion
was diluted four times with the mixture of 共1:1兲 hexane and
octane. The diluted dispersion was then dropped onto a
carbon-coated copper TEM grid for electron microscopy.
Films were annealed under vacuum (⬍1⫻10⫺7 Torr) for 30
minutes. Alternatively the films were annealed under flowing

0021-8979/2002/91(10)/8477/3/$19.00 8477 © 2002 American Institute of Physics

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8478 J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 M. Chen and D. E. Nikles

TABLE I. Effect of the amount of Co(CO) 3 NO and Pt(acac) 2 charged to TABLE II. Effect of annealing conditions on the order parameter and coer-
the reaction on the composition of the as-prepared particles. civity of films containing Co48Pt52 nanoparticles.

Co(CO) 3 NO 共mmol兲 Pt(acac) 2 共mmol兲 Composition Temperature 共°C兲 600 700 700
Time 共min兲 30 60 180
0.75 0.50 Co25Pt75 Condition vacuum tube furnace tube furnace
1.0 0.50 Co48Pt52 a 共pm兲 384 380 381
c 共pm兲 384 375 371
S 0 0.487 0.972
H c 共Oe兲 145 466 630
argon containing 2% hydrogen in a tube furnace.
The particle composition was determined by energy dis-
persive x-ray analysis on a Philips model XL 30 scanning
electron microscope. Images of the magnetic particles were The reaction gave a dispersion of CoPt particles that could
obtained on a Hitachi model H-8000 transmission electron be isolated by adding ethanol and centrifuging. The compo-
microscope. Thin film x-ray diffraction measurements 共␪-2␪ sition of the particles depended on the relative amount of
scans兲 were made on a Rigaku model D/MAX-2BX thin film Co共CO兲3 NO and Pt共acac兲2 added to the reaction mixture,
diffractometer. Magnetic hysteresis curves were measured on Table I. For the first case, when the amount was 0.75 mmol
a Princeton Micromag 2900 alternating gradient magnetome- Co共CO兲3 NO to 0.5 mmol Pt共acac兲2 , the composition of the
ter using a 18 kOe saturating field. particles was Co25Pt75 . For the second case, where he molar
ratio was 1.0–0.5, the composition was Co48Pt52 . We chose
RESULTS AND DISCUSSION to focus attention on the particles with the composition
Co48Pt52 .
Our initial attempts to prepare CoPt nanoparticles used As-prepared the Co48Pt52 particles were superparamag-
two approaches, 共1兲 simultaneous reduction of cobalt acety- netic and could be dispersed in hydrocarbon solvents. TEM
lacetonate and platinum acetylacetonate or 共2兲 reduction of images of films cast on carbon-coated copper TEM grids,
platinum acetylacetonate and thermal decomposition of dico- Fig. 1, showed an average particle size of 7 nm. This was
balt octacarbonyl, Co2 (CO) 8 . The first approach gave a mix- twice as large as the FePt particles we prepared using the
ture of ferromagnetic cobalt-rich, CoPt particles and super- procedure of Sun et al.5,6 The distribution of particle sizes
paramagnetic Pt-rich CoPt particles. The cobalt-rich particles was greater for the Co48Pt52 particles, indicating the need for
precipitated from the reaction mixture, while the Pt-rich par- further work to narrow the particle size distribution and
ticles remained in dispersion. The second approach gave achieve a highly ordered particle assembly.
large cobalt particles that precipitated from the reaction mix- The films on silicon wafers were annealed to transform
ture. Co2 (CO) 8 was not very soluble in dioctyl ether and it the particles to the tetragonal (L1 0 ) phase. Calculating the
decomposed heterogeneously to give Co particles. We found ordering parameter, S, using Eq. 共1兲, where c and a are the
success in preparing CoPt nanoparticles by the simultaneous unit cell parameters obtained by x-ray diffraction quantified
chemical reduction of platinum acetylacetonate and thermal the degree of tetragonal ordering.
decomposition of cobalt tricarbonyl nitrosyl. This procedure
was analogous to that used to prepare FePt nanoparticles by 共 1⫺c/a 兲
S⫽ . 共1兲
Sun et al., except Co共CO兲3 NO was substituted for Fe共CO兲5 . 1⫺0.973

FIG. 1. TEM micrograph of Co48Pt52 nanoparticles. FIG. 2. TEM micrograph of Fe50Pt50 nanoparticles.

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J. Appl. Phys., Vol. 91, No. 10, 15 May 2002 M. Chen and D. E. Nikles 8479

TABLE III. Effect of annealing conditions on the order parameter and co- tempt transform the particles to the tetragonal (L1 0 ) phase.
ercivity of films containing Fe50Pd50 nanoparticles.
Even after annealing for three hours at 700 °C, Table III,
Temperature 共°C兲 As-prepared 550 600 700 700 there was no evidence for the tetragonal phase. The coerciv-
Time 共min兲 0 30 30 60 180 ity increased to 685 Oe after annealing at 550 °C, but then
Condition vacuum vacuum vacuum Ar– H2 Ar– H2 decreased for film annealed at higher temperatures.
a 共ppm兲 386 383 383 381 379 The procedure described by Sun et al. for the synthesis
c 共pm兲 386 383 383 381 379
of FePt nanoparticles can be modified to prepare FeCoPt,3,4
S 0 0 0 0 0
H c 共Oe兲 12 685 548 421 297 CoPt or FePd nanoparticles. This opens up a rich new area of
magnetic particle chemistry by providing a general route to
the synthesis of spherical particles in the size range 3–10
nm. The particle size distribution CoPt and FePd particle
Only after annealing for 3 h at 700 °C, Table II, did the described here needs to be narrowed before we can realize
particles transform to the tetragonal phase with a high degree the particle self-assembly into close-packed films seen with
of tetragonal ordering. The annealed films had a relatively FePt or FeCoPt particles.
low coercivity. ACKNOWLEDGMENT
Iron palladium alloy nanoparticles were prepared by the
simultaneous reduction of palladium acetylacetonate and the This work was supported by the NSF Materials Research
thermal decomposition of iron pentacarbonyl. This procedure Science and Engineering Center Award No. DMR-9809423.
was entirely analogous to that used to prepare FePt nanopar- 1
D. Weller, A. Moser, L. Folks, M. E. Best, W. Lee, M. F. Toney, M.
ticles by Sun et al. In this case Pd共acac兲2 substituted for Schwickert, J.-U. Thiele, and M. F. Doerner, IEEE Trans. Magn. 36, 10
Pt共acac兲2 . The reaction gave a dispersion of FePd particles 共2000兲.
2
that could be isolated by adding ethanol and centrifuging. S. Sun, C. B. Murray, D. Weller, L. Folks, and A. Moser, Science 287,
1989 共2000兲.
The composition was Fe50Pd50 . As-prepared the Fe50Pd50 3
M. Chen and D. E. Nikles, Mater. Res. Soc. Symp. Proc. 674, U4.7
particles were ferromagnetic but still could be dispersed in 共2001兲.
hydrocarbon solvents. TEM images of films cast on carbon-
4
M. Chen and D. E. Nikles, NanoLetters 共to be published兲.
5
M. Chen and D. E. Nikles, Mater. Res. Soc. Symp. Proc. 674, U4.8
coated copper TEM grids, Fig. 2, showed an average particle
共2001兲.
size of 11 nm with a relatively broad distribution of particle 6
J. W. Harrell, S. Wang, D. E. Nikles, and M. Chen, Appl. Phys. Lett. 79,
sizes. The films on silicon wafers were annealed in an at- 4393 共2001兲.

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