APPLIED PHYSICS LETTERS VOLUME 85, NUMBER 25 20 DECEMBER 2004

Atomic composition effect on the ordering of solution-phase synthesized

FePt nanoparticle films
Andrew C. C. Yu,a) M. Mizuno, Y. Sasaki, and H. Kondo
Sony Corporation, Sendai Technology Center, 3-4-1 Sakuragi, Miyagi 985-0842, Japan
(Received 6 July 2004; accepted 19 October 2004)
FePt nanoparticle monolayer films were fabricated with the nanoparticles stabilized on
organic-coupling-layer coated Si substrates. The as-prepared films were nonmagnetic. In order to
transform the nanoparticle phase from chemically disordered face-centered-cubic to chemically
ordered L10, the films were annealed at 800° C under nitrogen atmosphere for 30 min. The annealed
films showed different degrees of sintering depending on the organic coupling layer materials used.
At room temperature, sintered films exhibited high coercivity up to 2.4⫻ 104 Oe, while
monodispersive films with insignificant sintering showed a low coercivity of 1.1⫻ 102 Oe. Such
results can be explained by a large atomic composition distribution among the nanoparticles
together with the size effect on ordering. Improvement of the nanoparticle atomic composition
homogeneity is essential for applying the nanoparticle films for future ultrahigh-density data storage
applications. © 2004 American Institute of Physics. [DOI: 10.1063/1.1835998]

High anisotropy L10 type nanoparticles, such as FePt
and CoPt, have attracted much attention due to their potential
for the development of not only ultrahigh-density magnetic
recording media, but also various novel memory devices,
nanotechnological designs, and bio-medical applications.1–5
It is important to fabricate the nanoparticle heterostructures
on the substrates of interest that are either rigid or flexible in
nature in order to apply the heterostructures for various com-
mercial product development. We have reported a technique
for stabilizing monodispersive chemically synthesized nano-
particle films on Si wafer substrates by means of introducing
organosilane coupling layers deposited between the sub-
strates and the nanoparticle dispersions.6 As the as-
synthesized nanoparticles were nonmagnetic with chemically
disordered fcc phase, annealing should therefore be carried
out in order to transform the nanoparticles to chemically or-
dered L10 phase such that the nanoparticles will become
magnetic.1–3,7 Recently, we have observed that with the ap-
plication of different coupling layer materials, the annealed
monodispersive nanoparticle films exhibited different de-
grees of nanoparticle sintering resulting in showing signifi-
cantly different coercivity values for the films. The aim of
this letter is to report a chemical analysis investigation of the
nanoparticles in order to understand the atomic composition
effect on the coercivity variation of the films that show dif-
ferent degree of sintering.
FexPt100−x nanoparticles were chemically synthesized us-
ing a similar method reported by Sun et al.8 In order to
transform the FexPt100−x nanoparticles from nonmagnetic
chemically disordered fcc phase to magnetic chemically or-
dered L10 phase, the nanoparticle films were annealed at
800° C for 30 min under N2 atmosphere (note: the annealing
chamber was first evacuated to around 10−6 Torr before flux-
ing in N2 aimed at avoiding serious oxidation issue on the
nanoparticles during annealing). We observed that with the
application of different coupling layer materials, the an-
nealed nanoparticle films exhibited different degrees of sin-
a)
Author to whom correspondence should be addressed; electronic mail:
andrew.yu@jp.sony.com
tering resulting in different sintered particle sizes and size
distribution.9 Here we compared two representative series of
annealed samples (note: same FexPt100−x nanoparticle disper-
sion but different coupling layers were used for the fabrica-
tion of the two samples), one with serious sintering issue
(sample 1) while the other one showed insignificant sintering
(sample 2). Coercivity, Hc, of the nanoparticle films was
measured using a superconducting quantum interferometer
device. High resolution electron microscopy and high reso-
lution scanning electron microscopy were employed to char-
acterize the nanoparticle structure as well as the nanoparticle
film heterostructure. Chemical analyses of the nanoparticles
were done by field emission electron nano-beam energy dis-
persive spectrometry (EDS) and x-ray microanalysis (XMA).
Table I summarizes the Hc values, average nanoparticle
size, nanoparticle size distribution, and XMA data of the two
samples. The order of the Hc value of sample 1 was 102
times higher than that of sample 2 although the XMA data
indicated that both samples possessed the same atomic com-
position. Superparamagnetic effect could be one of the
causes for the low Hc value of sample 2 at room temperature,
however at 5 K, the Hc value of sample 2 was only 770 Oe,
which was still much smaller than the 3.0⫻ 104 Oe Hc value
of sample 1 at 5 K. It is therefore expected that some other
factors could lead to the difference in the Hc values. System-
atic chemical analysis of the nanoparticles using electron
nano-beam EDS equipped with a 300 kV field-emission
transmission electron microscope was carried out. The elec-
TABLE I. Summary of Hc, particle size, particle size distribution, and XMA
data for samples 1 and 2.
Sample 1 2
Hc共Oe兲 at room temperature 2.4⫻ 104 1.1⫻ 102
Hc共Oe兲 at 5 K 3.0⫻ 104 7.7⫻ 102
Average particle size before annealing 共nm兲 3.0 3.0
Average particle size after annealing 共nm兲 28 3.2
Particle size distribution after annealing 共␴ / nm兲 11 0.86
XMA Fe51Pt49 Fe51Pt49

0003-6951/2004/85(25)/6242/3/$22.00 6242 © 2004 American Institute of Physics

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Appl. Phys. Lett., Vol. 85, No. 25, 20 December 2004
TABLE II. Summary of EDS data for different number of FexPt100−x nano-
particles being detected for each measurement.
No. of nanoparticles
detected per EDS
measurement (order) Fe (average at.%) Pt (average at.%)
104 49.68 50.32
103 49.71 50.29
102 46.55 53.45
1 – 10 47.52 52.48
tron beam size was varied in order to measure the average
output signals generated by different numbers of nanopar-
ticles, while the smallest nano-beam size of around 5 nm in
diameter was used to detect the EDS signal emitted from
individual nanoparticles. Table II summarizes the average
FexPt100−x atomic compositions with different numbers of
nanoparticles detected per EDS measurement (note: each av-
erage data was a mean value of over 30–50 raw data points
obtained at different locations of the nanoparticle disper-
sion). According to the average atomic composition data, the
atomic composition distribution of the nanoparticles was
small while it was reasonably consistent with the XMA re-
sult.
We then carried out a series of EDS measurements on
individual nanoparticles. More than 100 individual nanopar-
ticles were measured from each dispersion sample and a total
of five identical samples were examined.10 Based on the ex-
perimental data obtained, we found that the atomic compo-
sition of each individual nanoparticle was different. Only
around 29.0% of the FexPt100−x nanoparticles were within the
composition of 40⬍ x ⬍ 60, while approximately 40.5% and
30.5% of the nanoparticles were Pt-rich (i.e., x ⬍ 40) and
Fe-rich (i.e., x ⬎ 60), respectively. According to the
FexPt100−x phase diagram, only when 40⬍ x ⬍ 60 could the
FexPt100−x phase transform to the L10 phase after annealing
resulting in high coercivity for the system.11 We selected
(from over 500 raw data points) six individual nanoparticles
with different atomic compositions as an example to demon-
strate the large atomic composition variation in the nanopar-
ticle dispersion, Table III. Particles 1 and 2 were Fe-rich, on
the contrary, particles 5 and 6 were Pt-rich. Only particles 3
and 4 fulfilled the phase transformation requirement, but the
other four nanoparticles might not be able to transform com-
pletely to the L10 phase even after high temperature anneal-
ing. Since there existed a large atomic composition distribu-
tion among the nanoparticle dispersion, the nanoparticles in
the annealed films with insignificant sintering could then
have different degrees of L10 phase transformation. There-
TABLE III. Atomic composition of six selected FexPt100−x nanoparticles S. Sun, E. E. Fullerton, D. Weller, and C. B. Murray, IEEE Trans. Magn.
demonstrating the atomic composition variation issue among individual
nanoparticles. EDS measurement was carried out on each individual nano-
particle.
Nanoparticle Fe (at.%) Pt (at.%)
1 66.89 33.11
2 65.82 34.18
3 54.07 45.93
4 46.52 53.48
5 33.24 66.76
6 21.92 78.08
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Yu et al. 6243
fore, in sample 2 only a small coercivity was observed while
a broad range of anisotropy field was expected among the
nanoparticle dispersion.12 On the other hand, in sample 1
nanoparticles sintered forming different sizes of nanoparticle
clusters, thus the atomic compositions of the clusters became
the average atomic composition values of the sintered nano-
particles, which could fulfill the 40⬍ x ⬍ 60 condition.
Therefore, the sintered films exhibited high coercivity as L10
phase transformation of the sintered nanoparticle clusters
was possible.
In addition to the atomic composition effect, size effect
is also another important factor affecting the ordering of
nanoparticles.13–16 It was reported that the fcc phase of 4 nm
chemically synthesized FePt nanoparticles was stable up to
560° C as long as coalescence did not occur.13 However,
based on our experimental results, we observed a coercivity
of 1.1⫻ 102 Oe for the 800° C-annealed nonsintered films
(Table I), while the as-prepared films were nonmagnetic at
room temperature. The existence of the small coercivity
could imply the occurrence of a very small degree of order-
ing in the nonsintered film, possibly resulting from the rela-
tively high annealing temperature (no coercivity was ob-
served when the films were annealed at 600° C or less).
Nevertheless, it is believed that the size effect could signifi-
cantly (but possibly not completely) hinder the ordering of
the nonsintered nanoparticles even for those which had
nearly equiatomic composition. Therefore, together with the
effect of atomic composition variation, the nonsintered an-
nealed films could not reveal large coercivity as the sintered
films did.
In conclusion, besides size effect, atomic composition
distribution of the nanoparticle dispersion also has significant
influence on the fcc to L10 phase transformation. In order to
apply L10 FexPt100−x nanoparticles for ultrahigh-density data
storage, it is important to control the nanoparticle atomic
composition in the range of 40⬍ x ⬍ 60 such that thermody-
namical phase transformation of the nanoparticles can easily
occur. Meanwhile, a small atomic composition distribution is
favorable for the consequent achievement of small bit size
made up of only one or just a few nanoparticles. Taking size
effect into concern, we suggest that FePt (as well as CoPt)
particle size around 6 – 8 nm would be suitable for various
magnetic product development.
The authors would like to thank M. Takahashi for the
provision of magnetic measurement facilities. A.C.C.Y. and
K.H. acknowledge partial support of the Nanotechnology
Support Project by the Ministry of Education, Culture,
Sports, Science and Technology, Japan.
1
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