IEEE TRANSACTIONS ON MAGNETICS, VOL. 37, NO.
4, JULY 2001
Compositionally Controlled FePt Nanoparticle
Materials
Shouheng Sun, Eric E. Fullerton, Dieter Weller, and C. B. Murray
Abstract—High temperature solution phase decomposition
of Fe(CO)5 and reduction of Pt(acac)2 in the presence of
stabilizers oleic acid and oleyl amine are employed to produce
4 nm diameter FePt nanoparticles. The Fe and Pt composition of
the nanoparticle materials can be tuned by adjusting the molar
ratio of Fe(CO)5 to Pt(acac)2 , and the compositions ranging
from Fe30 Pt70 to Fe80 Pt20 are obtained. The nanoparticle
materials are easily dispersed into alkane solvent, facilitating their
self-organization into nanoparticle superlattices. As synthesized
FePt nanoparticles possess disordered fcc structure and show su-
perparamagnetic behavior. Thermal annealing induces the change
of internal particle structure and thus the magnetic properties of
the particles. Composition dependent structure analysis shows
that an annealed FePt nanoparticle assembly with a composition
around Fe55 Pt45 will lead to the highly ordered fct phase. This
Fe55 Pt45 nanoparticle assembly yields high coercivity, and will
be a candidate for future ultra-high density magnetic recording
media applications.
Index Terms—FePt nanoparticle, high u FePt, magnetic
recording, nanoparticle synthesis, self-assembly, thermal
annealing.
I. INTRODUCTION
T HE REQUIREMENTS for ultra-high density magnetic
recording have driven the development of new magnetic
thin film media with smaller grains, higher coercivity, low mag-
netization and minimal magnetic exchange coupling between
neighboring grains. The FePt-based nanostructured materials
are excellent candidates for this approach because of their
good chemical stability and high magnetocrystalline anisotropy
erg cm observed in the ordered intermetallic phase [1],
[2]. This large crystalline anisotropy allows for thermally stable
grain diameters down to 2.8 nm. A well-organized magnetic
array of such particles will contribute to an effort to design
a magnetic medium capable of recording densities beyond
1 Tb/in [3].
The challenges to realize this Tb/in goal are to make
uniform high-coercivity FePt nanoparticles and nanoparticle
assemblies with controlled assembly thickness, surface rough-
ness, and mechanical robustness. Various vacuum deposition
techniques have been developed to fabricate high coercive
FePt nanocrystalline films [1], [2], [4]–[6]. Post deposition
Manuscript received October 13, 2000.
S. Sun and C. B. Murray are with the IBM T. J. Watson Research Center,
Yorktown Heights, NY 10598 USA (e-mail: ssun@us.ibm.com).
E. E. Fullerton is with the IBM Almaden Research Center, San Jose, CA
95120 USA (e-mail: eef@almaden. ibm.com).
D. Weller was with the IBM Almaden Research Center, San Jose, CA 95120
USA. He is now with Seagate Research, Pittsburgh, PA 15203 USA (e-mail:
dieter_weller@seagate.com).
Publisher Item Identifier S 0018-9464(01)06007-1.
0018–9464/01$10.00 © 2001 IEEE
1239
annealing has proven essential to transform the as-deposited
chemically disordered fcc structure into the chemically ordered
fct phase that has high magnetocrystalline anisotropy. Random
nucleation in the initial stages of the growth, however, typically
results in broad distributions of particle sizes, which may
be further aggravated by agglomeration during annealing.
Research efforts on preventing this uncontrolled agglomeration
have recently been focused on embedding the FePt particles
into a variety of insulator matrixes, such as [7] [8],
[9], [10] and [11]. We recently reported that solu-
tion phase chemistry could be used to prepare monodispersed
FePt nanoparticle materials [12]. The procedure involved
decomposition of and polyol reduction of
in solution with oleic acid and oleyl amine. Controlled evapora-
tion of the solvent from dispersed particles followed by thermal
treatment led to self-organized ferromagnetic nanocrystalline
assemblies that can support high-density magnetic recording.
In this paper, we report on the generalized synthesis and char-
acterization of 4 nm FePt nanoparticle materials. The Fe and
Pt compositions are easily tuned by controlling the molar ratio
of and . As-synthesized FePt nanoparticles
have the disordered fcc structure and are superparamagnetic
at room temperature. Thermal annealing induces the change
of internal particle structure and thus the magnetic properties
of the particles. Both structure and magnetic properties of the
FePt nanoparticle materials are very sensitive to the particle
composition. Composition dependent structural and magnetic
data reveal that is the optimum composition for FePt
nanoparticle materials with high quality fct phase formation and
high coercivity .
II. EXPERIMENTAL PROCEDURES
A. Synthesis of FePt Nanoparticles
The synthetic experiments were carried out using standard
airless procedures and commercially available reagents. The
compositionally controlled synthesis is as follows: platinum
acetylacetonate (197 mg, 0.5 mmol), 1,2-hexadecanediol
(390 mg, 1.5 mmol), and dioctylether (20 mL) were mixed
and heated to 100 C. Oleic acid (0.16 mL, 0.5 mmol), oleyl
amine (0.17 mL, 0.5 mmol) and (see Fig. 1 for the
amount added to control the composition of the final product)
were added and the mixture was heated to reflux (298 C)
for 30 minutes. The heat source was then removed and the
reaction mixture was allowed to cool to room temperature. The
inert gas protected system could then be opened to ambient
environment. The black product was precipitated by adding
ethanol mL and separated by centrifugation. The
1240
Fig. 1. Compositional relation between Fe(CO) and x in Fe Pt
based on 0.5 mmol of Pt(acac) .
yellow-brown supernatant was discarded. The black precipitate
was dispersed in hexane mL in the presence of oleic
acid mL and oleyl amine mL . Then,
ethanol mL was added to the dispersion. The resulting
dispersion was centrifuged to remove any remaining unsolved
precipitation. The product was precipitated out by adding more
ethanol mL to the dispersion and centrifuging. Further
purification of the product was performed by dispersing the
product into hexane, precipitating it out with ethanol, and
centrifuging. The materials were re-dispersed in hexane, and
stored under . aggregation and very small separate Pt particles are formed.
B. Synthesis of Nanoparticle Assemblies
To form a self-organized assembly, 0.05 mL of hexane dis-
persed FePt nanoparticles mg/ml were deposited on
a solid substrate cm . The solvent was allowed
to evaporate slowly (5–10 minutes) at room temperature. The
as-deposited thin film was then transferred into a glove box
( concentration ppm) and annealed in a Thermolyne
1300 furnace. The temperature was raised to 580 C from room
temperature over a period of 14 minutes and maintained at this
temperature for 30 minutes. The sample was taken out of the
furnace and cooled to room temperature in the box. The
cooled FePt nanoparticle assembly is smooth, reflective, and can
be handled and stored under ambient condition.
C. Characterization of FePt Nanoparticles and Nanoparticle
Assemblies
Fe and Pt elemental analyses of the as-synthesized FePt
nanoparticle materials were performed on an ICP-Atomic
Emission Spectrometer at Galbreith Lab, Tennessee. Compo-
sition and thickness of the FePt nanoparticle assembly were
determined by Rutherford backscattering spectrometry. Micro-
analyzes of both single FePt nanoparticle and FePt nanoparticle
IEEE TRANSACTIONS ON MAGNETICS, VOL. 37, NO. 4, JULY 2001
assembly were performed on a Hitachi HF-2000 TEM equipped
with the parallel-detection electron energy-loss spectroscopy
(PEELS) and energy dispersive x-ray spectroscopy (EDS) [13].
Particle size was determined using a Philips EM 430 TEM
(300 KV). A thin FePt nanoparticle assembly was made by
spreading a dilute particle dispersion onto a grid. Leo
1560 HRSEM was used to study the annealed FePt nanopar-
ticle assemblies on naturally oxidized silicon substrates. The
nanoparticle structure was determined by X-ray powder diffrac-
tion on a Siemens D-500 diffractometer under Co radiation
. The sample was m thick on a micro
slide substrate cm .
Magnetic studies were carried out using a MPMS2 Quantum
Design SQUID magnetometer with fields up to 5 T and temper-
atures from 5 K to 350 K. Measurements were done on thick
nanoparticle assemblies nm on a micro slide or MgO
(100). The substrate was loaded parallel to the magnetic field.
III. RESULTS AND DISCUSSION
A. Synthesis and Stabilization of the FePt Nanoparticles
Solution phase metal salt reduction and organometallic
precursor decomposition are well-known techniques for
the preparation of monodisperse magnetic metal particles
[14]–[17]. However, the technique cannot easily be applied
to synthesize binary metal nanoparticles. The reduction or
decomposition of two metal-containing precursors often
does not proceed in a way that facilitates the formation of
binary metal nuclei. In most cases, the product contains two
phase-separated elemental nanoparticles. For example, the
decomposition of and reduction of in
the same reaction condition as that in the FePt synthesis did
not yield CoPt nanoparticle materials. Instead, Co particle
Therefore, forming the binary nuclei in solution phase is key
for the synthesis of binary metal nanoparticles. It is well known
that chemical modification of metal precursor can either change
its reduction potential or thermal stability. To make binary
metal nanoparticles, care should be taken in choosing the
stabilizer, solvent, reducing agent, and reaction temperature.
Polymers have been widely used to control particle growth,
stabilize metal dispersions and limit oxidation of the particles.
However, in our reaction, they would not yield monodispersed
nanoparticles. This may be because a polymer usually contains
multiple uneven coordination sites within its chain; these
uneven coordination sites would lead to nonhomogeneous
nucleation. Oleic acid and oleyl amine are proven to be a
good ligand combination for FePt formation and stabilization.
Oleic acid has long been used to stabilize varieties of colloids
including Fe nanoparticles [14]. Alkyl amines, on the other
hand, are good stabilizing ligand for noble metal such as Pt.
The structural similarity between oleic acid and oleyl amine
provides a smooth ligand shell around each FePt nanoparticle,
facilitating superlattice formation. The FePt nanoparticles are
prepared by the combination of polyol reduction of
and thermal decomposition of in the presence of oleic
acid and oleyl amine and can be easily dispersed into alkane
solvent [12].
SUN et al.: COMPOSITIONALLY CONTROLLED FePt NANOPARTICLE MATERIALS
Fig. 2. TEM image of a 4 nm Fe Pt nanoparticle assembly.
B. FePt Compositional Control
The composition of FePt nanoparticle materials is tuned via
the molar ratio of and . Based on 0.5 mmol
each of the , oleic acid and oleyl amine, and 20 mL
of dioctylether, the molar amount of and the resulting
are shown in Fig. 1. It can be seen that not all
the contributes to the FePt formation. has a
low boiling point (103 C). At reaction temperature of 298 C,
is actually in the vapor phase. The formation of this
vapor phase results in the slow decomposition of
at a rate that matches with the reduction rate of . FePt particle assemblies show no obvious aggregation upon
The FePt nanoparticles are formed in a shorter period of time.
Therefore the consumption of cannot be completed
on this synthetic time scale. As a result, 0.5 mmol of
and 0.5 mmol of yield , while 1.1 mmol
of and 0.5 mmol of lead to
nanoparticle materials. The elemental analysis from both EELS
on a group of isolated FePt particles and EDX on the FePt
nanoparticle assembly shows that the composition of either
a single FePt nanoparticle or a group of FePt nanoparticles
matches well with that from ICP analysis of bulk FePt nanopar-
ticle materials. This indicates that the composition of the FePt
nanoparticle materials is relatively uniform. TEM analysis on
monolayer assemblies of the FePt nanoparticles shows that the
image contrast from particle to particle is about the same. As
the electron density of Fe differs from that of Pt, the uniform
contrast image of the FePt nanoparticles also suggests that
the Fe and Pt form uniform composition in each of the FePt
nanoparticles.
C. Formation of Nanoparticle Assemblies
When the FePt nanoparticle dispersions are spread on a
substrate, and the carrier solvent is allowed to slowly evapo-
rate, FePt nanoparticle superlattices are produced. For TEM
observation, a drop L of a dilute FePt dispersion
mg/mL was deposited on a -coated copper grid.
Fig. 2 is a TEM image of a cubic assembly of 4 nm
particles. Although the cubic assembly symmetry will be
ideal for future ultra-high density recording media, in re-
ality, we do not have, as yet, control of the symmetry of the
1241
Fig. 3. XRD patterns of (a) Fe Pt , (b) Fe Pt , (c) Fe Pt , and
(d) Fe Pt nanoparticle assemblies annealed at 580 C for 30 minutes.
self-organization process. Extensive studies on nanoparticle
assembly have shown that the symmetry depends on many
factors, such as particle size, shape and relative dimensions
of the particle core and the organic capping [18], [19]. These
annealing at temperatures up to 600 C under static atmos-
phere (1 atm). Rutherford backscattering measurements on
these annealed 4 nm FePt particle assemblies indicate 40–50%
(at.%) carbon content. This shows that annealing at high
temperature does not result in the loss of stabilizing ligands;
rather, they are converted to a carbonatious coating around each
particle, effectively protecting particles from agglomeration.
D. FePt Nanoparticle Structure
X-ray diffraction of the as-synthesized FePt particles reveals
a typical chemically disordered fcc structure. Annealing induces
the Fe and Pt atoms to rearrange into the long range chemically
ordered fct structure. The change of the internal particle struc-
ture upon annealing depends on annealing temperature, as well
as the Fe, Pt composition. XRD [12] and Kerr effect measure-
ments [20] on annealed particle assemblies show that
the onset of this phase change occurs at about 500 C. While an-
nealing at higher temperatures or for longer time can increase
the chemical ordering, too high a temperature, e.g., C,
or too long an annealing time, will result in either particle’s par-
tial aggregation or phase separation. XRD combined with TEM
and HRSEM studies show that the optimum temperature for the
phase transformation is 580 C. It is worth mentioning, however,
that the exact structure after thermal annealing depends strongly
on particle composition. Fig. 3 shows a series of XRD patterns
of differently composed FePt assemblies annealed at 580 C for
30 minutes. It shows that among all these 580 C annealed FePt
nanoparticle assemblies, only the assembly yields a
high quality fct phase.
1242 IEEE TRANSACTIONS ON MAGNETICS, VOL. 37, NO. 4, JULY 2001

Fig. 4. Hysteresis loops of the as-synthesized Fe Pt nanoparticle

assembly at (a) 5 K, (b) 15 K, (c) 35 K, and (d) 85 K.

E. Magnetic Properties of the FePt Nanoparticle Assembly

Fig. 5. Room temperature hysteresis loops of Fe Pt nanoparticle
The role of the annealing temperature on the chemical assemblies annealed at (a) 500 C, (b) 550 C, and (c) 580 C.
ordering and magnetic properties was probed by measuring
the temperature dependent magnetic properties. SQUID mag-
netometry measurements of the as-synthesized FePt particles
show that they are superparamagnetic at room temperature.
At low temperature, however, they all show ferromagnetic
properties, even though there exist large variations among
differently composed FePt nanoparticle materials. The temper-
ature dependent hysteresis behavior of are shown in
Fig. 4. The coercivity drops sharply as temperature is raised
from 5 K to 15 K, indicating these small nanoparticles are
thermally unstable. This is consistent with the low magne-
tocrystalline anisotropy of the fcc structure of the particles.
Shown in Fig. 5 are the room temperature hysteresis loops for
4 nm particles that were annealed at 500, 550 and
580 C. The values increase dramatically with annealing
temperature showing the transition from superparamagnetic
to ferromagnetic behavior. The sample annealed at 500 C
appears nearly superparamagnetic at room temperature. An
expanded view of the low-field part of the loop shows an
value of 330 Oe and the loop is hysteretic up to 6 kOe fields.
This likely results from a minority fraction of the particles
having sufficient anisotropy to be ferromagnetically ordered
at room temperature. Increasing the annealing temperature to Fig. 6. Composition dependent coercivity Hc of 580 C annealed FePt
nanoparticle assemblies.
550 C increases the ferromagnetic fraction of particles with
the value increasing to 3200 Oe. However, there is still
an inflection in the magnetization near , indicating nanoparticle material, the coercivities of these annealed FePt
some low particles. Annealing at C results particles depend strongly on FePt composition, as shown in
in a room temperature value just over 9000 Oe with a Fig. 6. The extrapolation of the Gaussian type fit yields the best
loop shape characteristic of an isotropic distribution of high composition of FePt to be , a conclusion that matches
anisotropy particles. Hysteresis data of 580 C annealed FePt that obtained from the as-synthesized FePt materials and from
nanoparticle assemblies show that, like the as-synthesized FePt FePt thin films [21].
SUN et al.: COMPOSITIONALLY CONTROLLED FePt NANOPARTICLE MATERIALS 1243

the magnetization should be stable for more than ten years and
makes this material suitable for magnetic storage application.

IV. CONCLUSION REMARKS

The present synthesis provides general procedures for the
preparation of 4 nm differently composed FePt nanoparticle ma-
terials and nanoparticle assemblies. Detailed structure and mag-
netic analyses of these nanoparticles show that the FePt compo-
sition control in FePt nanoparticle materials is the key to control
the FePt particle structure transformation and magnetic hard-
ness, and the optimized composition for the highest coercive
FePt nanoparticle materials is . The synthetic search
for 2D arrays of these ferromagnetic dots is underway.

H
Fig. 7. Temperature dependent c of (a) 500 C, (b) 550 C, and (c) 580 C
ACKNOWLEDGMENT
annealed Fe Pt nanoparticle assemblies. The solid symbols are the The authors thank A. Kellock of IBM Research for RBS ex-
measured values and the lines are the fits.
periments, Z. L. Wang of Georgia Institute of Technology for
elemental microanalysis of single FePt nanoparticles, and L.
Shown in Fig. 7 is the temperature dependence of for the Folks and A. Moser of IBM Research for fruitful discussions.
three annealing temperatures. Each sample shows a monotonic
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