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Japanese Journal of Applied Physics

Vol. 44, No. 2, 2005, pp. 1147–1149


#2005 The Japan Society of Applied Physics

Fine Tuning of the Sizes of FePt Nanoparticles


Satoru M OMOSE, Hiroyoshi K ODAMA, Takuya U ZUMAKI and Atsushi T ANAKA
Advanced Magnetic Recording Laboratory, Fujitsu Laboratories Ltd., Kanagawa 243-0197, Japan
(Received July 7, 2004; accepted November 4, 2004; published February 8, 2005)

Fine tuning of the sizes of FePt nanoparticles has been realized by a simple modification of a solution phase synthesis, which
consists of the decomposition of Fe(CO)5 and the reduction of Pt(acac)2 . The key method used to control the particle size is
the use of surfactants, and only a change in their amount is required to vary the average sizes of the FePt nanoparticles from 2
to above 4 nm. The resultant nanoparticle volume is proportional to the surfactant amount; this makes the synthesis of FePt
nanoparticles of desired sizes possible. [DOI: 10.1143/JJAP.44.1147]
KEYWORDS: FePt nanoparticles, nanocrystalline metal particles, monodispersed particles, chemical synthesis, particle size
control

1. Introduction 2. Experimental
Recently, nanometer-sized particles of magnetic materials 2.1 Synthesis
such as FePt,1–4) Co,5–7) CoPt,8–10) and Fe3 O4 11–16) have been The synthesis was carried out using standard airless
fabricated by solution phase synthesis. These chemically techniques in an argon atmosphere. The reagents were
synthesized nanoparticles are characterized by uniform size obtained from commercial sources and used without further
distributions. At the same time, high-anisotropy-density purification. A typical synthetic procedure is as follows:
materials such as FePt17) allow a reduction in size to 4 nm or Pt(acac)2 (198 mg, 0.5 mmol), 1,2-hexadecanediol (389 mg,
less, because of their high magnetic stability.18,19) Chemi- 1.5 mmol), dioctylether (20 mL), oleic acid (0.16 mL,
cally synthesized FePt nanoparticles, with diameters report- 0.5 mmol), oleyl amine (0.17 mL, 0.5 mmol), and Fe(CO)5
ed to be 4 nm, are therefore very attractive candidates for (0.13 mL, 1 mmol) were mixed and heated to 230 C, and
ultrahigh density magnetic recording media, because high then the temperature was maintained for 30 min with
recording densities require a small material grain and a stirring. The reaction vessel was cooled to room temper-
narrow size distribution.18,19) Generally, the magnetic prop- ature, and the black product was precipitated by the addition
erties of materials highly depend on grain size, and since of ethanol (40 mL) and centrifugation. The black precipitate
magnetic recording media require rigorous control of their was then dispersed in hexane (20 mL) and centrifuged, and
magnetic properties, the tuning of the sizes of the magnetic the resultant supernatant was added to ethanol (20 mL) and
nanoparticles used in magnetic recording applications is also centrifuged to precipitate out FePt nanoparticles. In this
required. However, since many factors can affect the particle study, the only modifications in the reaction conditions were
size during synthesis, and those effects are complex, no changes in the amounts of surfactants, oleic acid and oleyl
general procedure previously existed for the tuning of the amine (the total amounts are 0.13, 0.25, 0.5, 1.0 and
sizes of alloy systems, even though a successful case with 2.0 mmol). The molar ratio of the acid to the amine was
CoPt3 has been reported.20,21) fixed at 1.
Here, we will report on the development of a method for
FePt nanoparticle synthesis that easily enables the fine 2.2 Characterization
tuning of the particle size. The key point of this method is The particle size was determined by transmission electron
the ability to control the particle growth using a surfactant. microscopy (TEM). TEM samples were prepared by
Whatever the particle growth mechanism, the separation of depositing a droplet of the diluted nanoparticle dispersion
nucleation and growth in time is required for the formation onto a carbon-coated copper grid. TEM observations were
of particles with a near-monodisperse size distribution.22) carried out at 200 keV using JEOL JEM-2010F. The crystal
For this kind of system, some procedures are necessary in structure of the nanoparticles was studied by X-ray powder
order to alter the particle size. These include controlling the diffraction (XRD) analysis on a Rigaku ATX-G diffractom-
reaction time or, following nucleation, changing the quantity eter under Cu K radiation. Fe and Pt elemental analyses of
of materials that contribute to particle growth. However, the the nanoparticles were performed on an ICP-atomic emis-
former is applicable only to adequately slow reactions, and sion spectrometer (Perkin Elmer 4300DV).
the latter is difficult to apply except in cases of adding
materials. Another technique is the control of the number of 3. Results and Discussion
nuclei at the first step of particle formation, because an Figure 1(c) shows a TEM image of FePt nanoparticles
increase in this number can be expected to result in small created under the aforementioned typical reaction conditions
particles. The tendency of materials to nucleate is most (total surfactant amount is 1.0 mmol). Figures 1(a), 1(b) and
likely related to the affinity between the nucleating material 1(d) similarly show nanoparticles created with total surfac-
and solvent, which can be controlled using a favorable tant amounts of 0.13, 0.25, and 2.0 mmol, respectively. It is
surfactant. We, therefore, examined a method for FePt clearly visible that the sizes of the particles increase with an
nanoparticle synthesis that is based on the reduction of increase in surfactant amount. Both oleic acid and oleyl
platinum(II) acetylacetonate (Pt(acac)2 ) and the decomposi- amine have a double bond in the hydrocarbon chain;
tion of iron carbonyl (Fe(CO)5 ),1,2) using various surfactant accordingly, they are good ligands for metal atoms.23,24) It
quantities. is also clear that an increase in surfactant amount results in
1147
1148 Jpn. J. Appl. Phys., Vol. 44, No. 2 (2005) S. MOMOSE et al.

FePt (111)
a b FePt (200)
2.1 (2.2) nm Fe47Pt53

Intensity (arb. units)


2.6 (2.7) nm Fe46Pt54

3.0 (3.0) nm Fe50Pt50

3.3 (3.2) nm Fe53Pt47

10 nm 10 nm 4.3 (4.1) nm Fe48Pt52

c d 35 40 45 50 55 60
2θ (deg)

Fig. 2. XRD patterns of as-synthesized FePt nanoparticles of various


average TEM sizes. In parentheses, XRD sizes calculated using the
Debye–Sherrer equation are also indicated.

30
Particle Volume (nm 3)

10 nm 10 nm
20
Fig. 1. TEM images of (a) 2.1 nm FePt nanoparticles synthesized using a
total of 0.13 mmol of surfactants: oleic acid and oleyl amine, (b) 2.6 nm
FePt nanoparticles synthesized using 0.25 mmol of the surfactants, (c)
10
3.3 nm FePt nanoparticles synthesized using 1.0 mmol of the surfactants,
and (d) 4.3 nm FePt nanoparticles synthesized using 2.0 mmol of the
surfactants.
0
0 1 2 3 4 5
Surfactant to Pt(acac)2 molar ratio
Table I. Experimental conditions and resultant nanoparticles.

Surfactant Precursor Ave. diameter (TEM) Fig. 3. Molar ratio of surfactant to Pt(acac)2 vs average volumes of
Yield Composition resultant FePt nanoparticles; the solid line represents a least-squares
amount mole ratio (nm)
(mg) Fe : Pt fitting, and error bars are standard deviations.
(mmol) Fe : Pt (Dispersion, %)
0.13 2.00 121 47 : 53 2.1 (17)
0.25 1.95 89 46 : 54 2.6 (20) parameters is observed from the graph.
0.5 2.01 89 50 : 50 3.0 (11) This linear relationship can be explained qualitatively
1.0 1.99 106 53 : 47 3.3 (10) according to a suggestive precedent by Watzky and Finke.22)
2.0 2.05 124 48 : 52 4.3 (12) They evidenced a growth mechanism for Ir nanoparticles
that consists of a slow, continuous nucleation step and a fast
surface growth step, and that this schematic formation
increases in the stability and affinity of metal atoms to the process was thermodynamically reasonable. Namely, the
solvent. This effect is expected to prevent the metal atoms surface growth should proceed irreversibly because of the
from nucleation, and thus, the number of nuclei decreases metal–metal bond stability, while the critical nucleus is the
and each resultant particle volume increases. The corre- state of balance between the energy gain by metal–metal
spondence of reaction conditions to resultant nanoparticles is bond formation and the cost due to surface tension enthalpy
indicated in Table I. Substantially, equiatomic compositions increase with entropy loss, thus the nucleation should be a
were obtained in all cases. XRD patterns indicated in Fig. 2 reversible and relatively slow process. Accordingly, metal
show the chemically disordered fcc crystal structure of these nanoparticles, perhaps, are generally formed by a similar
nanoparticles and the broadening of the peaks with decreas- process under homogeneous reaction conditions. Then
ing particle size. Figure 2 also indicates that the average monodispersed particles are formed when the growth rate
sizes of the nanoparticles from XRD, calculated using the is significantly larger than the nucleation rate, and the
Debye–Sherrer equation, are similar to those from TEM. growth step is adequately short, because whole particles
Figure 3 shows a plot of the molar ratio of the surfactant to grow simultaneously and nuclei are formed continuously
Pt(acac)2 versus particle volume: the average volumes of the during the reaction.22) This argument seems to be applicable
particles are calculated from the average sizes, assuming that to our FePt nanoparticles. Under this mechanism, the
they are spherical. A linear relationship between these resultant nanoparticle volume in principle turn proportion-
Jpn. J. Appl. Phys., Vol. 44, No. 2 (2005) S. MOMOSE et al. 1149

ally decreases as the number of nuclei at the end of the increases with the surfactant amount, thus allowing the
nucleation step increases. Since the critical nucleus volume simple fabrication of nanoparticles of preferred sizes. This
likely depends on the material substance and is constant relationship may imply that the surfactant amount deter-
irrespective of the reaction conditions, the nanoparticle mines the number of nuclei via nucleation rate control,
volume may turn proportionally decrease as the nucleation which results from the coordination of the surfactants to
rate increases. metal atoms.
On the other hand, Watzky and Finke also revealed an
effect of the initial concentration of a ligand on the Acknowledgement
nucleation rate. In their reaction system, Ir cation, which is This work was supported in part by the IT program
dissociated from the polyoxoanion complex, is reduced and (RR2002) of the Ministry of Education, Culture, Sports,
then the resultant Ir atom contributes to the particle Science and Technology.
formation. The rate-determining step is the dissociation of
the complex. Since the dissociation rate is determined from
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