660
2, FEBRUARY 2005
Chemically Synthesized L10-Type FePt Nanoparticles
and Nanoparticle Arrays via Template-Assisted
Self-Assembly
Yuichi Sasaki, M. Mizuno, A. C. C. Yu, T. Miyauchi, D. Hasegawa, T. Ogawa, M. Takahashi, B. Jeyadevan, K. Tohji,
K. Sato, and S. Hisano
Abstract—Chemically ordered L10 -type FePt nanoparticle ag-
glomerates were synthesized directly by the co-reduction of Fe(III)
and Pt(II) acetylacetonates in tetraethylene glycol at 300 C in the
absence of surfactants. These nanoparticles could be dispersed in
n-hexane by coating with oleic acid and oleylamine. However, the
dispersed particles exhibited only chemically disordered fcc phase
and superparamagnetic behavior. The FePt nanoparticle film
composed of dispersed particles and stabilized using amino-silane
began to structurally transform to ordered L10 phase at 600 C,
which is lower compared to that prepared by the hot soap method.
Rotational hysteresis loss measurement suggested that the or-
dering was incomplete at 600 C and the nanoparticle film had
the distribution of magnetocrystalline anisotropy field values. The
FePt nanoparticle array was fabricated using the template-assisted
self-assembly technique. To produce periodic dots on a substrate,
positive-biased pulse voltage was applied to the substrate coated
with octadecyltrichlorosilane monolayer by using a conducting
cantilever used in a scanning probe microscope. This process
induced electrochemical modification of CH3 groups into polar
ones. The resulting template had well-aligned sub-100-nm dot
arrays with sub-100-nm periodicity. The FePt nanoparticles were
fixed on the patterned areas selectively.
Index Terms—Dispersion, electrochemical modification, FePt
nanoparticle, L10 structure, magnetic anisotropy field, polycrys-
talline, polyol process, scanning probe lithography, template-as-
sisted self-assembly.
I. INTRODUCTION
T HE -type alloys such as FePt and CoPt have great
potential as the promising candidates for ultrahigh den-
sity recording media because of their high magnetocrystalline
anisotropy (FePt: , CoPt:
) [1]. Chemically synthesized FePt and CoPt
nanoparticles have attracted much attention due to narrow size
distribution as well as the dimensions with a few nanometer
scale compared to those fabricated by the existing sputtering
technique [2]–[9]. As-grown FePt and CoPt nanoparticles are
mostly face-centered cubic (fcc) and show superparamagnetic
Manuscript received August 20, 2004.
Y. Sasaki, M. Mizuno, A. C. C. Yu, and T. Miyauchi are with Sony Cor-
poration Sendai Technology Center, Tagajo, Miyagi 985-0842, Japan (e-mail:
Yuichi.Sasaki@jp.sony.com).
D. Hasegawa, T. Ogawa, and M. Takahashi are with Graduate School of En-
gineering, Tohoku University, Sendai, Miyagi 980-8579, Japan.
B. Jeyadevan and K. Tohji are with Graduate School of Environmental
Studies, Tohoku University, Sendai, Miyagi 980-8579, Japan.
K. Sato and S. Hisano are with Dowa Mining Corporation, Honjo, Saitama
367-0002, Japan.
Digital Object Identifier 10.1109/TMAG.2004.838040
0018-9464/$20.00 © 2005 IEEE
IEEE TRANSACTIONS ON MAGNETICS, VOL. 41, NO.
behavior. To obtain ordered structure, high temperature an-
nealing is required. A self-assembled array of such particles
shows well-aligned close-packed nanostructures on a substrate,
however, each particle strongly coalesces during annealing [10],
which results in undesirable increase in size and its distribu-
tion. Though doping with a third element (Ag) was effective in
reducing the transformation temperature to 350 C, it was im-
possible to prevent particles from coalescing completely [11].
We recently reported that -type FePt nanoparticles could
be obtained directly in solution phase at 300 C by using the
“modified polyol process”, which opened up the possibility for
the fabrication of the ultrahigh density nanoparticle thin film
media without heating process [12]. As the nanoparticle syn-
thesis was carried out without using any stabilizers such as sur-
factants in solution, these particles agglomerated strongly so
that the coating of the nanoparticles on a substrate was diffi-
cult. In the first part of this paper, the dispersion of the directly
synthesized -type FePt nanoparticles in an organic solvent
is investigated. The unique morphological and crystallographic
characteristics are examined and compared with those synthe-
sized by the hot-soap method [13]. The investigation of their
magnetic properties focusing on the magnetic anisotropy is also
discussed.
The ultimate goal in the development of ultrahigh density
recording media is to store one bit per one magnetic unit. To
achieve this, the establishment of periodic arrays is necessary.
Various lithographic techniques have been used to fabricate
the magnetic arrays [14], [15], however, periodic assembly of
nanoparticles system with an extended area has not been accom-
plished. We demonstrated the application of amino-functional
silane as a coupling layer for FePt nanoparticles dispersion,
resulting in the formation of a monolayered film on a rigid
substrate [16]. This fabrication method offered the possibility
of a long-range array of the nanoparticles, however, no periodic
array was formed. We have recently proposed the template as-
sisted self-assembly technology, which incorporated scanning
probe lithography as a promising tool for the establishment of
such arrays [17]. In the second part of this paper, successful
production of well-aligned FePt nanoparticles array is demon-
strated.
II. EXPERIMENT
FePt nanoparticles with structure were synthesized by
co-reduction of Fe(III) and Pt(II) acetylacetonates in tetraethy-
SASAKI et al.: FePt NANOPARTICLES AND NANOPARTICLE ARRAYS VIA TEMPLATE-ASSISTED SELF-ASSEMBLY 661

Fig. 1. Powder XRD pattern of FePt nanoparticles agglomerates synthesized

by modified polyol process at 300 C.

lene glycol (TEG) at 300 C [9]. Contrary to the hot-soap

method, the above method did not involve the stabilization of
particles by surfactants. Thus the nanoparticles formed agglom-
erates and precipitated out. Dispersion of the nanoparticles in
a nonpolar organic solvent was then carried out as follows:
Oleic acid and oleylamine were injected into the solution after
cooling down to room temperature, and a designated amount
of n-hexane was added. The mixture was transferred into an
airtight container, and agitated vigorously using a shaker. After
several hours, the suspension separated into TEG and n-hexane
phases. The n-hexane phase turned from colorless to dark
brown, which is an indication of the presence of nanoparticles.
Meanwhile, part of the nanoparticles remained at the interface
between the two solvents. Thus this process was repeated to
bring more particles into the n-hexane phase.
The FePt nanoparticles monolayered films were formed on a
thermally oxidized Si wafer using a coupling layer of amino-
silane [16]. Then, the monolayered film was annealed under a
vacuum of Torr at 600 C for 30 min to evaluate the crys-
tallographic features and magnetic properties.
The crystallographic textures and average grain sizes of
the FePt nanoparticle monolayered films were investigated
by in-plane X-ray diffraction (XRD) measurements with the
X-ray incidence angle set at 0.25 from the plane. The in-plane
XRD measurements were done using a RIGAKU ATX-G with
Cu radiation. On the other
hand, the as-prepared and agglomerated FePt nanoperticles Fig. 2. HR-TEM images of the (a) dispersed portion of FePt nanoparticles
were examined using powder XRD. The particle morphology synthesized by modified polyol process and (b) those prepared by the hot soap
method.
evaluation was carried out using high-resolution transmis-
sion electron microscopy (HR-TEM). Chemical compositions
were determined by X-ray microanalysis (XMA). Magnetic of (001) and (110) superlattice reflections suggested the exis-
properties were measured using a superconducting quantum tence of structure in the as-prepared FePt nanoparticles.
interference device and high-sensitivity torque magnetometer. The ratio calculated using the (111) and (200) peaks was
0.972 and was slightly larger compared to that of the ideal bulk
III. MAGNETIC PROPERTIES AND CRYSTALLOGRAPHIC value which is only 0.964 [18]. This suggested the presence of
STRUCTURES OF DIRECTLY SYNTHESIZED -TYPE partially ordered phase. As previously reported [12], the
FePt NANOPARTICLES sample consisted of agglomerates of nanoparticles with diame-
ters ranging between 5 and 10 nm.
A. Morphology and Crystallographic Structures The HR-TEM image of the FePt nanoparticles dispersed in
Fig. 1 shows the powder XRD pattern of the as-prepared n-hexane is shown in Fig. 2(a). Mismatched lattice planes ob-
FePt nanoparticles before dispersion. Their average chemical served in almost all the particles confirmed the polycrystalline
composition analyzed using XMA was . The presence nature of the particles. This morphology was characteristic
662
Fig. 3. In-plane XRD patterns for the as-coated and 600 C annealed FePt
nanoparticle monolayered films. (a) and (b) denote the dispersed portion of the
nanoparticles synthesized by modified polyol process and those prepared by
hot-soap method, respectively.
of the FePt nanoparticles synthesized by the modified polyol
process (polycrystalline), and was different from that obtained
by the hot-soap method (single crystalline) [13] as indicated in
Fig. 2(b). The mean diameter of the particles was 7.6 nm with a
standard deviation of 1.4 nm (18%). From XMA, the chemical
composition of the dispersed FePt nanoparticles was found to
be . The reason for this phenomenon is not clear yet,
however, dissolution by oleic acid could be considered as a
possible reason.
Fig. 3(a) shows the in-plane XRD patterns for the as-coated
and 600 C-annealed FePt monolayered films. The nanopar-
ticles used here correspond to the dispersed portion of the
particles synthesized by the modified polyol process. The
profiles for the monolayered films of the FePt nanoparticles
prepared by the hot-soap method are shown in Fig. 3(b) for
comparison. Before annealing, only the chemically disordered
fcc (111) and (200) peaks were observed for the film of the
nanoparticles synthesized by the modified polyol process.
This meant that the as-coated nanoparticles did not possess
the structure. The reason for this structural difference
between the as-synthesized particles and the dispersed particles
is unclear. A chemically ordered (110) peak appeared for
the 600 C-annealed film of the nanoparticles produced by the
modified polyol process and had a ratio of 0.986 compared
with 0.964 for the bulk [18]. Therefore, the sample has to be
annealed at higher temperatures than 600 C for more complete
ordering. Conversely, no superlattice peak was confirmed
in the XRD pattern for the film prepared using the particles
synthesized by the hot-soap method even after annealing at
600 C. From these results, we concluded that the structural
transformation of the FePt nanoparticles synthesized by the
modified polyol process occurred at lower temperatures than
those by the hot-soap method. Besides the differences in the
IEEE TRANSACTIONS ON MAGNETICS, VOL. 41, NO. 2, FEBRUARY 2005
Fig. 4. In-plane hysteresis loops for the 600 C annealed film of the dispersed
FePt nanoparticles synthesized by modified polyol process measured at RT and
5 K.
reaction kinetics of the two preparation techniques, this phe-
nomenon could be due to the following additional reasons, that
is, the difference in morphological features of the nanoparticles
prepared by both procedures and size dependence of ordering.
As noted above, FePt nanoparticles synthesized by the mod-
ified polyol process were polycrystalline, while those by the
hot-soap method were single crystalline. With a polycrystalline
structure, ordering progresses due to interdiffusion of atoms
within grains and at grain boundaries. The latter is expected
to possess lower activation energy barrier, contributing to the
reduction of the phase transformation temperature. Another
possible reason is the dependence of phase transformation on
the particle size. Recently, Takahashi et al. reported that smaller
FePt particles were harder to chemically transform by applying
the diffuse-interface theory [19]. The average grain diameter
of the as-synthesized nanoparticles prepared by the hot-soap
method, which was calculated by the Scherrer’s equation using
the full width at half maximum of the (111) peak, was 3.4 nm,
which was slightly smaller than that by the modified polyol
process of 4.1 nm. The former kept constant after annealing at
600 C, while the latter increased up to 5.6 nm. Consequently,
the ordering in nanoparticles prepared by the hot-soap method
seems to be more difficult to progress. The grain diameter of
the 600 C-annealed nanoparticles was smaller than the average
particle diameter measured by TEM observation, suggesting
that the interparticle coalescence did not occur.
B. Magnetic Properties
The as-synthesized FePt nanoparticle agglomerates showed
ferromagnetic behavior with a coercivity of 2.2 kOe at
room temperature (RT). On the other hand, the as-coated film
of the dispersed nanoparticles showed superparamagnetic be-
havior at RT, which was consistent with the crystallographic fcc
structure with low magnetic anisotropy. Fig. 4 shows in-plane
hysteresis loops of the 600 C-annealed film measured at RT and
5 K. It exhibited small value of 290 Oe at RT, and 4.6 kOe
at 5 K, which arises from the complicated contribution of in-
complete ordering, slightly Pt-rich composition and small grain
size of around 5 nm. The rotational hysteresis loss for
the 600 C-annealed film of FePt nanoparticles synthesized by
the modified polyol process is plotted as a function of the ap-
plied field up to 25 kOe in Fig. 5. As a reference, curve
SASAKI et al.: FePt NANOPARTICLES AND NANOPARTICLE ARRAYS VIA TEMPLATE-ASSISTED SELF-ASSEMBLY
Fig. 5. Rotational hysteresis loss curves for FePt nanoparticles prepared by
the modified polyol process measured at RT. Open and closed circles denote the
as-synthesized agglomerates and the dispersed nanoparticle monolayered film
afler annealing at 600 C, respectively.
for the as-synthesized FePt nanoparticle agglomerates by the
modified polyol process is shown. The curve for the 600 C-an-
nealed film of FePt nanoparticles synthesized by the modified
polyol process had two maximum fields of about 7 and
15 kOe, leading to two different uniaxial magnetic anisotropy
fields of at least 14 and 30, respectively, according to
classical single domain theory. However, these estimated
values were larger than double of the at 5 K with minimal
thermal effects. Namely, of the 600 C-annealed film
indicated smaller value compared to the theoretical one of non-
interacting, magnetically isolated Stoner–Wohlfarth-type grains
of 0.479 (for random orientation) [20]. We consider this reason
to be mainly due to the distribution of of nanoparticles. The
magnetization reversal which is characteristic of the polycrys-
talline particles could not be discussed here because of the exis-
tence of this distribution of . Interaction between and within
the particles seems not to be dominant in this case because the
interparticle coalescence was not likely to occur after annealing
and the particles were separated enough. Nevertheless detailed
investigation based on some magnetic measurements should be
made for further understanding. On the other hand, a single peak
was observed for the film composed of as-synthesized nanopar-
ticles by the modified polyol process. It had extremely small
value of 200 Oe compared to the estimated of nearly 30 kOe,
which is thought to be due to the distribution in the switching
field caused by that in the degree of ordering and the exchange
coupling between the nanoparticles. The estimated one is con-
sidered to be the maximum value in the film.
IV. FePt NANOPARTICLE ARRAYS VIA TEMPLATE-ASSISTED
SELF-ASSEMBLY
A. Fabrication Method of Nanoparticle Array
The periodic array of FePt nanoparticles was fabricated using
the template-assisted self-assembly technique, which involved
scanning probe lithography. The procedure was composed of
the following three steps. First, the monolayered octadecyl-
trichlorosilane (OTS) was formed on a P-type silicon wafer by
dipping it in the solution, which allowed the termination of the
methyl group on the substrate. Second, the CH terminated
663
Fig. 6. Schematic diagram for electrochemical patterning of the periodic small
0
dot arays on a CH , terminated substrate.
0
Fig. 7. LFM images of (a) CH , terminated (before patterned) and
(b) electrochemically patterned surfaces on a Si substrate.
surface was electrochemically modified using a conducting
cantilever used in scanning probe microscopes. Fig. 6 shows
the schematic diagram for patterning periodic small dot arrays
on the substrate. The conducting cantilever was scanned on the
substrate with the contact mode, applying a positive pulse bias
of 9.5 V with frequency of 20 Hz and 10 ms per pulse. The
scanning rate was 2 m/s. Finally, the modified substrate was
immersed in n-hexane based FePt nanoparticle dispersion, then
taken out, and rinsed by n-hexane.
The patterned surface was observed using a scanning probe
microscope with two different modes, namely, atomic force mi-
croscope (AFM) and lateral force microscope (LFM). The ob-
servation of the resulting nanoparticle array was carried out
using a field emission scanning electron microscope (FE-SEM).
B. Analysis of Patterned Surface and Nanoparticle Array
Fig. 7 indicates LFM images of (a) CH terminated (before
patterned) and (b) electrochemically patterned surfaces on a Si
substrate. The difference in frictional force is reflected in the
contrast as shown in the figure. There was almost no contrast
in the image before patterning. Conversely, periodic dark spots,
which corresponded to the periodicity of the modification condi-
tion, appeared in the image after patterning. Therefore, we rec-
ognize these spots as the modified areas. The average diameter
of the spots was about 70 nm and they were well aligned with a
separation of about 80 nm between centers. Each dark area had
relatively higher friction, which meant that CH terminated
groups were changed into some polar ones by the electrochem-
ical reaction. Fig. 8 shows the AFM images of (a) CH ter-
minated (before patterned) and (b) electrochemically patterned
surfaces. Topographic change after patterning was not observed
from the AFM results. Thus, the electrochemical patterning was
carried out without any change in roughness of the substrate.
The FE-SEM image of the FePt nanoparicle arrays coated on
the patterned substrate is shown in Fig. 9. It could be found that
FePt nanoparticles were fixed on the patterned areas selectively.
664
0
Fig. 8. AFM images of (a) CH terminated (before patterned) and (b)
electrochemically patterned surfaces on a Si substrate.
Fig. 9. FE-SEM image of the FePt nanoparticle array coated on the patterned
substrate. White dots correspond to the FePt nanoparticles.
The modified polar sites are thought to work as templates for an-
choring the nanoparticles effectively. The number of nanoparti-
cles per dot was around 33 with a standard deviation of 4.8 and
the dot density corresponded to 0.1 Tparticles/in . Ideally, this
should be decreased to one particle per dot when the application
to recording media is taken into consideration. The possibility of
the same is being investigated now. Thus, the template-assisted
self-assembly technique to fabricate the periodic nanoparticle
array was successfully demonstrated and can be the promising
tool for developing future ultrahigh-density recording media.
V. CONCLUSION
Chemically ordered -type FePt nanoparticles were syn-
thesized directly without surfactants in the solution phase
through the co-reduction of Fe(III) and Pt(II) acetylacetonates
at 300 C. These nanoparticles could be dispersed in a nonpolar
solvent such as n-hexane by coating the particles with surfac-
tants with long alkyl chains. However, the dispersed particles
were of only chemically disordered fcc phase and exhibited
superparamagnetic behavior. This may be due to the deficiency
of the Fe content caused by the dispersion treatment. An alter-
native dispersion technique is being developed. The dispersed
FePt nanoparticle film stabilized using amino-silane began
to structurally transform to the ordered phase at 600 C.
This phenomenon could be explained by the characteristic
polycrystalline nature and the relatively large crystal size of the
particles synthesized by the modified polyol process. Rotational
hysteresis loss measurement suggested that the nanoparticle
film annealed at 600 C was not completely ordered.
IEEE TRANSACTIONS ON MAGNETICS, VOL. 41, NO. 2, FEBRUARY 2005
The periodic array of FePt nanoparticles was fabricated using
the template-assisted self-assembly technique. For making peri-
odic dots on a substrate, a positive-biased pulse voltage was ap-
plied to the CH terminated surface by a conducting cantilever
of a scanning probe microscope, which induced electrochem-
ical modification into polar groups. The resulting template had
well-aligned sub-100-nm dot arrays with sub-100-nm period-
icity. We also succeeded in selectively fixing the FePt nanopar-
ticles on the patterned areas.
REFERENCES
[1] D. Weller and A. Moser, “Thermal effect limits in ultrahigh-density mag-
netic recording,” IEEE Trans. Magn., vol. 35, no. 6, pp. 4423–4439, Nov.
1999.
[2] S. Sun, C. B. Murray, D. Weller, L. Folks, and A. Moser, “Monodisperse
FePt nanoparticles and ferromagnetic FePt nanocrystal superlattices,”
Science, vol. 287, pp. 1989–1992, 2000.
[3] S. Sun, E. E. Fullerton, D. Weller, and C. B. Murray, “Compositionally
controlled FePt nanoparticle materials,” IEEE Trans. Magn., vol. 37, no.
4, pp. 1239–1243, Jul. 2001.
[4] A. C. C. Yu, M. Mizuno, Y. Sasaki, H. Kondo, and K. Hiraga, “Structural
characteristics and magnetic properties of chemically synthesized CoPt
nanoparticles,” Appl. Phys. Lett., vol. 81, pp. 3768–3770, 2002.
[5] S. Sun, S. Anders, T. Thomson, J. E. E. Baglin, M. F. Toney, H. F.
Hamann, C. B. Murray, and B. D. Terris, “Controlled synthesis and
assembly of FePt nanoparticles,” J. Phys. Chem. B, vol. 107, pp.
5419–5425, 2003.
[6] M. Chen and D. E. Nikles, “Synthesis, self-assembly, and magnetic
properties of Fe Co Pt nanoparticles,” Nano Lett., vol. 2, pp.
211–214, 2002.
[7] C. Chen, O. Kitakami, S. Okamoto, and Y. Shimoda, “Large coercivity
and granular structure of CoPt=SiO films,” IEEE Trans. Magn., vol.
35, no. 5, pp. 3466–3468, Sep. 1999.
[8] M. Yu, Y. Liu, A. Moser, D. Weller, and D. J. Sellmyer, “Nanocomposite
CoPt:C films for extremely high-density recording,” Appl. Phys. Lett.,
vol. 20, pp. 3992–3994, 1999.
[9] M. Watanabe, M. Masumoto, D. H. Ping, and K. Hono, “Microstrucutre
and magnetic properties of FePt-Al-O granular thin films,” Appl. Phys.
Lett., vol. 76, pp. 3971–3973, 2000.
[10] Z. R. Dal, S. Sun, and Z. L. Wang, “Phase transformation, coalescence,
and twinning of monodisperse FePt nanocrystals,” Nano Lett., vol. 1, pp.
443–446, 2001.
[11] S. Wang, S. S. Kang, D. E. Nikles, J. W. Harrell, and X. W. Wu, “Mag-
netic properties of self-organized L1 FePtAg nanoparticle arrays,” J.
Magn. Magn. Mater., vol. 266, pp. 49–56, 2003.
[12] B. Jeyadevan, K. Urakawa, A. Hobo, N. Chinnasamy, K. Shinoda, K.
Tohji, D. J. Djayaprawira, M. Tsunoda, and M. Takahashi, “Direct syn-
thesis of fct-nanoparticles by chemical route,” Jpn. J. Appl. Phys., vol.
42, pp. L350–L352, 2003.
[13] Y. Sasaki, M. Mizuno, A. C. C. Yu, M. Inoue, K. Yazawa, I. Ohta, M.
Takahashi, B. Jeyadevan, and K. Tohji, “Crystallographic structures and
magnetic properties of L1 -type FePt nanoparticle monolayered films
stabilized on functionalized surfaces,” J. Magn. Magn. Mater., vol. 282,
pp. 122–126, 2004.
[14] C. A. Ross, “Patterned magnetic recording media,” Annu. Rev. Mater.
Res., vol. 31, pp. 203–235, 2001.
[15] S. Anders, S. Sun, C. B. Murray, C. T. Rettner, M. E. Best, T. Thomson,
M. Albrecht, J.-U. Thiele, E. E. Fullerton, and B. D. Terris, “Lithography
and self-assembly for nanometer scale magnetism,” Microelectron. Eng.,
vol. 61–62, pp. 569–575, 2002.
[16] A. C. C. Yu, M. Mizuno, Y. Sasaki, M. Inoue, H. Kondo, I. Ohta, D.
Djayaprawira, and M. Takahashi, “Fabrication of monodispersive FePt
nanoparticle films stabilized on rigid substrates,” Appl. Phys. Lett., vol.
82, pp. 4532–4534, 2003.
[17] M. Mizuno, Y. Sasaki, and M. Inoue, “Fabrication of FePt nanoparticle
arrays via template-assisted self-assembly,” in Extended Abst. 51th Spr.
Meeting Jpn. Soc. Appl. Phys., 2004, p. 194.
[18] JCPDS-International Centre for Diffraction Data, 1999.
[19] Y. K. Takahashi, T. Koyama, M. Ohnuma, T. Ohkubo, and K. Hono,
“Size dependence of ordering in FePt nanoparticles,” J. Appl. Phys., vol.
95, no. 5, pp. 2690–2696, 2004.
[20] E. C. Stoner and E. P. Wohlfarth, “A mechanism of magnetic hys-
teresis in heterogeneous alloys,” Trans. R. Soc. London, vol. A240, pp.
599–642, 1948.