NANO

LETTERS

Synthesis, Self-Assembly, and Magnetic 2002

Vol. 2, No. 3
Properties of FexCoyPt100-x-y 211-214
Nanoparticles
Min Chen and David E. Nikles*

Department of Chemistry and Center for Materials for Information Technology,

The UniVersity of Alabama, Tuscaloosa, Alabama 35487-0209

Received October 22, 2001; Revised Manuscript Received December 21, 2001

ABSTRACT
FexCoyPt100-x-y alloy nanoparticles were prepared by the simultaneous reduction of cobalt acetylacetonate and platinum acetylacetonate and
the thermal decomposition of iron pentacarbonyl. The relative amounts of iron, cobalt, and platinum in the particles depended on the amount
of iron, cobalt and platinum charged to the reaction. As prepared, the particles were superparamagnetic and had a distorted fcc structure. The
average particle diameter was 3.5 nm and the size distribution was very narrow. The particles could be dispersed in hydrocarbon solvents and
formed films consisting of hexagonal close-packed particles on carbon-coated copper TEM grids. The films were sputter coated with amorphous
carbon and then annealed at temperatures ranging from 550 to 700 °C to transform the particles to the tetragonal (L10) phase. The coercivity
of the annealed films increased with increasing annealing temperature. For films with a similar degree of transformation to the tetragonal
phase, increasing the cobalt content decreased the coercivity of the films.

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 super-
paramagnetic limit. This has led to a search for new materials
and new microstructures for longitudinal recording. The L10
phase of FePt has a very high magnetocrystalline anisotropy
(Ku ∼ 6.6 to 10 × 107 erg/cm3).1 Sun et al. have prepared
spherical FePt nanoparticles by the simultaneous reduction
of platinum acetylacetonate and thermal decomposition of
iron pentacarbonyl.2 As prepared, the particles were spherical,
with a very narrow size distribution, superparamagnetic, and
had a disordered face-centered cubic structure. 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 transformed to the L10 (tetragonal)
phase. The annealed films were ferromagnetic with coer-
civities 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
magnetic recording medium. This demonstration has aroused
our interest in the synthesis and self-assembly of FePt
nanoparticles.
We have modified the synthetic procedure reported by Sun
et al. to prepare FexCoyPt100-x-y nanoparticles. In a three-
necked round-bottom flask under a nitrogen atmosphere, a
solution platinum acetylacetonate (0.5 mmol) and cobalt
* Corresponding author. E-mail: dnikles@mint.ua.edu
10.1021/nl015649w CCC: $22.00 © 2002 American Chemical Society
Published on Web 01/23/2002
acetylacetonate (0.1 mmol) in 10 mL octyl ether was heated
to 100 °C. To this was added a solution of 1,2-hexade-
canediol (1.5 mmol) in 10 mL dioctyl ether at 80 °C, which
gave a purple solution. To this solution was added via syringe
oleylamine (0.5 mmol), oleic acid (0.5 mmol), and iron
pentacarbonyl (1 mmol). The mixture was heated to reflux
and allowed to reflux for 30 min. This gave a black
dispersion. The dispersion was allowed to cool to room
temperature, and then 40 mL ethanol was added to precipitate
the particles. The mixture was centrifuged to isolate the
particles from the yellow-brown supernatant. The particles
were redispersed in hexane, precipitated with ethanol, and
isolated by centrifuging. The particles were dried at room
temperature in a vacuum oven to give 100 to 200 mg of
particles. The dispersion and precipitation removed impuri-
ties. The contents of the supernatant solution were not
characterized. The relative amounts of platinum acetylac-
etonate, cobalt acetylacetonate, and iron pentacarbonyl were
varied in order to produce nanoparticles with different
compositions, Table 1. The particle composition was deter-
mined by energy-dispersive X-ray analysis on a Philips
model XL 30 scanning electron microscope. The iron content
in the particles was always much lower than the amount
charged to the reaction, as iron pentacarbonyl. The fate of
the missing iron was not determined. By eliminating the
cobalt acetylacetonate, FePt particles were prepared in a
manner similar to that reported by Sun et al. As prepared,
the particles had a disordered face-centered cubic structure
with a unit cell parameter, a ) 390 pm. The average
 Figure 2. TEM image of a thick film consisting of Fe49Co7Pt44
particles. The inset shows the low angle electron diffraction.
Figure 1. TEM image of a thin film consisting of Fe49Co7Pt44
particles.

Table 1: Composition and Size of the FexCoyPt100-x-y

Nanoparticles as Prepared, before Annealing
Fe Co Pt diam
batch (mole %) (mole %) (mole %) (nm)
1 charged 67 0 33
found 48 0 52 3.5
2 charged 63 6 31
found 49 7 44 3.4
3 charged 57 14 29
found 40 17 43 3.5
4 charged 47 21 32
found 34 19 47 3.6
5 charged 37.5 25 37.5
found 23 27 50 3.6

Figure 3. TEM image of a self-assembled film of Fe48Pt52 particles

crystallite size, Table 1, was estimated by Scherrer analysis3
of the line width of the 〈111〉 diffraction peaks, The crystallite
size of 3.4 to 3.6 nm agreed with the particle size observed
in the TEM images described below.
The particles were dispersed in a 50/50 mixture of hexane
and octane (2.5 mg particles in 1 mL solvent), containing
0.1 mL of a 50/50 mixture of oleylamine and oleic acid.
The dispersion was dropped onto a carbon-coated copper
TEM grid (200 mesh from SPI) and the solvent slowly
evaporated. Using octane in the solvent mixture slowed the
solvent evaporation rate, relative to pure hexane. TEM
images for the films (Figures 1 and 2) showed that the
particle assembled into hexagonal arrays. In thin regions of
the films, Figure 1, the particles formed a honeycomb array
consistent with AB stacking of the particles. In thicker
regions of the film, Figure 2, the particles assembled into
an ABC close-packed structure. The inset in Figure 2 shows
the low-angle electron diffraction, indicating a high degree
of ordering. The average particle size was 3.5 nm, in
agreement with values of crystallite size determined from
X-ray diffraction data. The space between the particles was
occupied by the surfactants, oleic acid, and oleylamine.
212
sputter coated with amorphous carbon.
As prepared, the particles were superparamagnetic. The
films were sputter coated with a 10 nm amorphous carbon
layer to inhibit sintering during annealing, Figure 3. The films
were annealed in a vacuum annealer or in a tube furnace
with flowing 2% hydrogen in argon to transform the particles
to the L10 phase. Annealing distorted the quality of the
particle ordering, Figure 4, and finding annealing conditions
that maintain the particle ordering is the subject of ongoing
research. For CoPt and FePt the degree of tetragonal ordering
(S) can be calculated by eq 1, where c100 and a100 are the
unit cell parameters for the 100% tetragonal phase.
c
1-
a
S) (1)
c100
1-
a100
With increasing tetragonal ordering, the value of S should
increase to a limiting value of 1. However, for the
Nano Lett., Vol. 2, No. 3, 2002
 Table 2: Effect of Annealing Conditions on the Tetragonal
Ordering and Grain Growth of the FexCoyPt100-x-y Films
0.5 h 1.0 h 3.0h
temp (°C) 550 600 700 700 700
Fe48Pt52 a (pm) 3.85 3.87 3.86 3.86
c (pm) 3.79 3.76 3.73 3.72
c/a 0.984 0.971 0.966 0.965
d (nm) 4.7 7.9 16.4 21.2
Fe49Co7Pt44 a (pm) 3.85 3.85 3.85 3.72
c (pm) 3.80 3.75 3.72 3.85
c/a 0.988 0.976 0.966 0.966
d (nm) 4.5 6.4 16.2 21.6
Fe40Co17Pt43 a (pm) 3.82 3.83
c (pm) 3.71 3.69
c/a 0.971 0.964
d (nm) 6.1 15.7
Figure 4. TEM image of a film containing Fe48Fe52 particles after Fe34Co19Pt47 a (pm) 3.81 3.81 3.81
annealing at 600 °C for 30 min. c (pm) 3.76 3.70 3.69
c/a 0.987 0.970 0.967
d (nm) 4.9 16.4 20.2
Fe23Co27Pt50 a (pm) 3.83 3.85 3.84
c (pm) 1.00 3.84 3.73
c/a 3.6 0.998 0.971
d (nm) 6.0 18.9

of the particles to transform to the tetragonal phase. Values

Figure 5. Effect of annealing temperature on the degree of
transformation to the tetragonal phase, as quantified by the quotient
c/a, and on the coercivity of the annealed films. The values of c/a
are plotted as filled symbols and the values of coercivity are plotted
as open symbols. The compositions were Fe48Pt52 (circles), Fe49-
Co7Pt44 (squares), and Fe40Co17Pt43 (triangles).
FexCoyPt100-x-y particles, the values a and c for the L10 phase
are not well-established and will vary with composition. We
were not comfortable with using eq 1 to quantify the degree
of tetragonal ordering. Accordingly, the degree of transfor-
mation to the tetragonal phase was quantified by the quotient
c/a, where a and c are the unit cell parameters determined
by X-ray diffraction. For the face-centered cubic phases, a
) c, and c/a ) 1. When transformed to the tetragonal phase,
the value of c/a decreased to a limiting value. For the FePt
L10 phase, the unit cell parameters are a ) 385.23 pm and
c ) 371.33 pm and the quotient c/a is 0.96392. For the L10
phase of CoPt, a ) 380.3 pm, c ) 370.1 pm, and c/a )
0.9732. In this work for any given composition with
increasing annealing temperature or increasing annealing
time, the value of c/a decreased, Table 2 and Figure 5,
indicating a more complete transformation to the tetragonal
phase. For the films annealed at 600 °C for 30 min, small
increases in the amount of Co had little effect on the ability
Nano Lett., Vol. 2, No. 3, 2002
of c/a were in the range 0.971 to 0.976 for Fe48Pt52,
Fe49Co7Pt44, and Fe40Co17Pt43. Annealing at 700 °C for 30
min decreased the values of c/a to 0.964 to 0.966. However,
further increasing the Co content inhibited the transformation.
Fe34Co19Pt47 or Fe23Co27Pt50 were only completely trans-
formed after annealing at 700 °C for 3 h. Annealing also
increased the average crystallite size, as measured by Scherrer
analysis of the 〈111〉 peak in the X-ray diffraction. There
was a slight increase in average crystallite size upon anneal-
ing at 550 °C. The crystallite size increased greatly when
annealing at temperatures beyond 600 °C. These results are
in agreement with a recent paper by Dai, et al., which re-
ported that FePt nanocrystals coalesce to form larger grains
when annealed at temperatures above 600 °C.4 For films hav-
ing small amounts of Co and annealed at 600 °C, the average
crystallite size decreased with increasing Co content. How-
ever the films annealed at other temperatures showed little
effect of composition on crystallite size. The films containing
higher amounts of Co (Fe34Co19Pt47 and Fe23Co27Pt50) were
not as susceptible to coalescing. Annealing at 600 °C for 30
min resulted in smaller increases in average crystallite size.
Even after 1 h annealing at 700 °C, the average crystallite
size was still smaller than that for the films containing lower
amounts of Co.
Magnetic hysteresis curves were measured on a Princeton
Micromag 2900 alternating gradient magnetometer using a
18 kOe saturating field. After annealing, the films were
ferromagnetic with an in-plane coercivity that depended on
the annealing temperature and the composition, Table 3. We
were not able to determine values of Ms, because of the
unknown amount of surfactants in the films. The coercivity
for the film containing Fe48Pt52 and annealed at 700 °C was
so high that the AGM magnet (maximum field 18 kOe) could
not saturate the sample and only a minor loop was obtained.
213

Table 3: Effect of Annealing Conditions on the Coercivity of
the FexCoyPt100-x-y Films
0.5 h 1.0 h 3.0 h
temp (°C) 550 600 700 700 700
Fe48Pt52 3970 6500 >11 600a >12 300a
Fe49Co7Pt44 2430 4500 8700 9170
Fe40Co17Pt43 3800 6500
Fe34Co19Pt47 2180 6630 6990
Fe23Co27Pt50 242 4590 9090
a Minor loop.
In Figure 5 are plots of the quotient c/a and the coercivity
as a function of annealing temperature for films containing
Fe48Pt52, Fe49Co7Pt44, and Fe40Co17Pt43. Values of c/a de-
crease with increasing annealing temperature and appear to
be reaching some limiting value as the phase transition
becomes complete. However, the coercivity continues to
increase with increasing annealing temperature because of
particle grain growth due to coalescence. For the films
annealed at 700 °C having similar values of c/a and similar
average crystallite sizes, the coercivity decreased as the cobalt
content increased. This can be qualitatively explained by the
lower value of magnetocrystalline anisotropy for CoPt (Ku
) 4.9 × 107 erg/cm3) relative to FePt (6.6 to 10 × 107 erg/
cm3).1 However, when completely transformed by annealing
at 700 °C for 3 h the film with the highest Co content, Fe23-
Co27Pt50, had a high coercivity (Hc ) 9090 Oe). This could
not be explained by grain size, since the average crystallite
size was comparable (18.9 nm) to that for the samples
annealed at 700 °C for 1 h. The magnetic properties of the
films containing self-assembled FexCoyPt100-x-y particles
were consistent with the properties of thin alloy films
prepared by rf sputtering5 or by electron beam evaporation.6
Films prepared by rf sputtering at low temperatures (<400
°C), had a disordered fcc structure and a low coercivity. After
annealing at 650 to 700 °C in a vacuum, the films
transformed to the tetragonal phase and had high coercitives
that decreased with increasing cobalt content. For the case
of the particles described in our work, the relationship
between the coercivity of the films and the cobalt content
was complex, particularly for the films having high cobalt
content.
Films containing self-assembled FePt alloy nanoparticles
are promising candidates for granular thin film media in
future high density magnetic hard disk systems. A number
of problems must be solved before they can find application.
Perhaps the most challenging problem is how to maintain
the highly ordered structure without particle coalescence/
sintering after annealing to transform the particles to the
tetragonal phase. We have also found that films containing
partially transformed FePt particles have a broad distribution
of magnetic anisotropies.7 One explanation is that there was
extensive particle coalescing leading to a distribution of
particles sizes. This underscores the need to find annealing
conditions where the particles transform without coalescence.
Another explanation is that the broad distribution of magnetic
anisotropies arises from a broad distribution of degrees of
transformation from the fcc to the L10 phase. This suggests
214
that one must completely transform the particles to the
tetragonal phase to achieve a narrow distribution of magnetic
anisotropies. However, in the case of FePt, the magneto-
crystalline anisotropy is so high that the completely trans-
formed particles had coercivties in excess of 10 000 Oe,
much too high to be useful in magnetic recording. The
FexCoyPt100-x-y alloy particles described here provide an
opportunity to prepare self-assembled films that are com-
pletely transformed but have lower coercivity.
The results presented here underscore the utility of the
procedure developed by Sun et al. to prepare FePt nanopar-
ticles.2 The reaction involved the reduction of platinum
acetylacetonate to platinum metal while also thermally
decomposing iron pentacarbonyl to iron metal. One would
expect a mixture of iron particles and platinum particles.
However the reaction conditions favored the co-deposition
of iron and platinum into the particles. The mechanism of
this co-deposition is not understood; however, the presence
of the oleic acid/oleylamine cosurfactants was important.
Presumably the particles were formed in a surfactant as-
sembly. The preparation of FexCoyPt100-x-y particles required
the co-deposition of iron, cobalt, and platinum. Again one
would expect the product to be a mixture of iron particles,
cobalt particles, and platinum particles, or perhaps CoPt and
FePt. Somehow in this process nucleation occurs, followed
by a heterogeneous growth process to give FexCoyPt100-x-y
particles. The mechanism of this process deserves further
study to give insight into how to control the nanostructure
of the particles. Are the nuclei Pt clusters formed by
reduction of the Pt(acac)2, or are Fe clusters formed by
thermal decomposition of Fe(CO)5? Do oleic acid and
oleylamine form micelles or other types of surfactant
assemblies in octyl ether and do the particles form in those
assemblies? Is the composition of each particle the same or
is there a distribution of particle compositions? A distribution
of particle compositions would also explain the distribution
of magnetic anisotropies. Seeking answers to these questions
is the subject of our ongoing research.
Acknowledgment. This work was supported by the NSF
Materials Research Science and Engineering Center award
number DMR-9809423.
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(3) Cullity, B. D.; Stock, S. R. Elements of X-ray Diffraction, 3rd ed.;
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(4) Dai, Z. R.; Sun, S.; Wang, Z. L. Nano Lett. 2001, 1(8), 443-447.
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NL015649W
Nano Lett., Vol. 2, No. 3, 2002