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INSTITUTE OF PHYSICS PUBLISHING NANOTECHNOLOGY

Nanotechnology 16 (2005) 1603–1607 doi:10.1088/0957-4484/16/9/033

Optimized synthesis and annealing


conditions of L10 FePt nanoparticles
I Zafiropoulou1 , V Tzitzios1 , D Petridis1 , E Devlin1 , J Fidler2 ,
S Hoefinger2 and D Niarchos1
1
Institute of Materials Science, NCSR ‘Demokritos’ Agia Paraskevi, 15310 Athens, Greece
2
Vienna University of Technology, Wiedner Hauptstrasse 8-10/138, A-1040 Vienna, Austria

E-mail: sabine.hoefinger@ifp.tuwien.ac.at and dniarchos@ims.demokritos.gr

Received 5 January 2005, in final form 2 March 2005


Published 1 July 2005
Online at stacks.iop.org/Nano/16/1603
Abstract
The fabrication of ∼3 nm FePt nanoparticles and detailed studies of the
effect of the annealing conditions (temperature and time) on the formation
of the face-centred tetragonal phase and on the magnetic properties are
described. Additionally, the effect of the precursor molar ratio on the final
product and the composition of the as-prepared samples were studied. The
main criteria for the determination of the best alloy are the properties desired
for applications in the field of magnetic recording media.

1. Introduction source in a high boiling point organic solvent, e.g. dioctyl


ether [4]. The reaction is conducted in the presence of oleic
Iron–platinum alloy nanoparticles exhibit remarkable mag- acid and oleylamine. These surface-active compounds coat
netic properties according to their size, form, and crystal struc- the surface of each particle with organic matter that prevents
ture. In particular, the high magnetocrystalline anisotropy undesired effects such as agglomeration and oxidation. This
(6.6 × 107 ergs cm−3 ) [1] of the face-centred tetragonal modification simultaneously provides the necessary solubility
(fct) phase permits a reduction in the size of nanoparticles in organic non-polar solvents for spontaneous self-assembly
below 10 nm while retaining the stability of their magnetiza- into three-dimensional superlattices.
tion against thermal fluctuations and demagnetizing effects [2]. Understanding the process of the fct phase formation is
These features make the fct phase of FePt very desirable in the the key point for the production of FePt nanoparticles with
field of ultra-high-density information storage [3]. However, the largest possible percentage of the fct phase under mild
there are particular values of the coercivity and magnetiza- annealing conditions. Accordingly, the object of the present
tion, as well as of the size and size distribution of the alloy work is to study the synthesis conditions, i.e. molar ratio and
nanoparticles, that are necessary for the successful application annealing conditions (temperature and time), on the size and
in recording media. The coercivity should range between 4 magnetic properties of the nanoparticles. The synthetic route
and 8 kOe, so as to be high enough for stable storage, but also followed was that of Sun et al [4], which leads to very small
low enough for overwriting to be possible. The magnetization nanoparticles (as low as 2 nm) with a narrow size distribution.
should be of significant magnitude so as to produce an intense In previous work of our research group the commercially
signal for reading. The size of the nanoparticles should be available and inexpensive polyethyleneglycol (PEG) has been
as small as possible (preferably 10 nm maximum) in order to successfully used as the reducing agent for the preparation of
obtain the best storage density (bits in−2 ). Finally, the size re- CoPt nanoparticles, instead of the 1,2-hexanodiol [5].
duction should be accompanied by a narrow size distribution Mössbauer spectroscopy was found to be a very useful
and weak interparticle interactions in order to keep the signal tool for this study. This technique enables the identification and
to noise ratio within acceptable levels. quantification of the magnetic and other iron-containing phases
A successful way to address the above requirements is to and their evolution in the course of the process. In the present
employ chemical routes for the fabrication of monodispersed case the fcc and fct phases have spectra with distinct Mössbauer
FePt nanoparticles. A general method applied successfully parameters. The isomer shift (IS) values for both phases are
for the synthesis of these nanoparticles involves the reduction very similar because of the very similar electronic state of the
of Pt(acac)2 by a diol, e.g. 1,2-hexadecanediol, with the iron. The different environments of the iron atoms in each
concurrent thermal decomposition of an organometallic iron phase, however, induce different quadrupole splittings (QSs)

0957-4484/05/091603+05$30.00 © 2005 IOP Publishing Ltd Printed in the UK 1603


I Zafiropoulou et al

FePt 111 40
a b
30
III

FePt 200
III

FePt 002
20

FePt 311
FePt 202
FePt 110
FePt 001

FePt 220
FePt 201

Magnetization, emu/g
FePt 222
FePt 113
FePt 112
II

FePt 221

FePt 301
Intensity, a.u.

10
I
0

II -10
Pt 111

-20
I
Pt 200

Pt 220

Pt 311

Pt 222
-30

20 30 40 50 60 70 80 90 -40
2 theta, deg -20 -10 0 10 20
Field, kOe

100,1
c d
100,0
100,0

99,5 Theoretical
Experimental 99,9
oxide = 22%
Absorption %

Theoretical

Absorption %
99,0 oxide = 29% 99,8 Experimental
oxide = 45% fct = 100%
fcc = 4% 99,7
98,5
99,6
98,0
99,5
I III
97,5 99,4
-10 -5 0 5 10 -10 -5 0 5 10
Velocity, mm/s Velocity, mm/s

Figure 1. XRD patterns (a), hysteresis loops (b) and Mössbauer spectra ((c), (d)) for the equiatomic FePt. I: as-prepared, II: annealed at
700 ◦ C for 1 h and III: annealed at 700 ◦ C for 3 h.

and magnetic hyperfine fields (HFs) in the two phases. The The structure of the as-prepared and annealed nanopar-
cubic phase has a high hyperfine field of 340–350 kG and a zero ticles was determined using x-ray powder diffraction (XRD)
quadrupole splitting, while the tetragonal phase has a lower measurements with a D 500 Siemens diffractometer. The sam-
field, 310–315 kG, and a quadrupole splitting in the range 0.09– ples were measured in the range 2θ = 20◦ –90◦ , with Cu Kα
0.15 mm s−1 . Thus the application of Mössbauer spectroscopy radiation (λ = 1.5418 cm−1 ). The XRD data were also used
enabled the identification and estimation of the iron phases for the estimation of nanoparticle mean size via the Scherrer
formed during the fcc to fct transformation. Iron oxide phases formula [6]. Magnetic properties were measured at room tem-
were also identified from their characteristic values. perature using a VSM PAR Model 155. Mössbauer spectrom-
etry was carried out using a constant acceleration spectrometer
2. Experimental section with a 57 Co(Rh) source calibrated at room temperature using
an iron metal foil. The low-temperature measurements were
The experimental procedure for the synthesis of iron–platinum carried out using an Oxford Variox cryostat. For the TEM pic-
nanoparticles was as follows. About 20 ml of diphenylether tures an HRTEM JEOL JEM 2000 FX microscope was used.
were heated to 100 ◦ C under N2 atmosphere in a round The samples were dispersed in chloroform and the solution
flask. Pt(acac)2 was then added, followed by PEG 600, was dropped on a carbon-coated Cu grid.
oleic acid and oleylamine. Finally the Fe(CO)5 was added,
after which the system was fitted with a condenser. The 3. Results and discussion
temperature was raised to 250 ◦ C and the system was refluxed
for at least 45 min. Nanoparticle formation was indicated 3.1. Effect of molar ratio on FePt properties
by the solution becoming a dense black suspension. At
the end of the reaction, the suspension was left to cool at Initially a series of alloys were synthesized with a molar ratio
room temperature and ethanol (about 50 ml) was added to Fe/Pt ranging between 4.5/1 and 1/3. The x-ray diffraction
precipitate the nanoparticles. The product was separated by patterns indicated that all the as-prepared samples crystallized
centrifugation, washed repeatedly with ethanol and exposed in the fcc phase, but after annealing only the equiatomic
to dry in air on a flat glass surface. The amount of the Fe sample showed the desired transformation to the fct phase
precursor was varied in order to synthesize alloys with different (figure 1(a)). Hysteresis loops led to the same conclusion, since
compositions. The FePt nanoparticles were annealed under a only the equiatomic alloy showed a significant improvement
reducing atmosphere (95% Ar + 5% H2 ) for various times and in the magnetic properties (coercivity and magnetization) after
at different temperatures. annealing (figure 1(b)).

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Optimized synthesis and annealing conditions of L10 FePt nanoparticles

Figure 2. HRTEM images and electron diffraction pattern from the as-prepared equiatomic FePt.

The mean nanoparticle sizes, extracted from the XRD 200


patterns (using the Scherrer equation), range between 3 and
o
4 nm for the as-prepared samples and after annealing rise 35.3
to 18 nm (1 h) and 29 nm (3 h). Grain growth is through 150

agglomeration and sintering [7, 8]. A small decrease in the


coercivity values is seen in all samples after 3 h annealing
Intensity, a.u.
o
100 29.9
compared to 1 h. This is likely due to the continuing growth
of the nanoparticles above a critical value where non-coherent
modes of magnetization reversal are allowed [9, 10]. 50
For the equiatomic composition, figure 1(b) shows the
hysteresis curves, which show an initial increase in coercivity
0
on annealing from 0.1 kOe for the as-prepared sample to 7 kOe
for the sample annealed for 1 h, and then a slight decrease to
20 30
6.5 kOe on annealing for 3 h. Figures 1(c) and (d) show the 2 theta, deg
Mössbauer spectra from the as-prepared and the 3 h annealed
equiatomic FePt alloy. The majority of the as-prepared sample Figure 3. XRD pattern of the as-prepared FePt at the region of
(figure 1(c)) consists of iron oxide (96%), and only 4% of the 2θ 20◦ –38◦ , measured with high scanning rate.
sample forms the FePt alloy. Nevertheless, after 3 h annealing,
this sample gave a Mössbauer spectrum (figure 1(d)), showing (fcc) of the FePt alloy. According to our Mössbauer results,
complete reduction and phase 100% transformation to the fct the fcc phase represents only 4% of the sample, while the rest
phase. The as-prepared equiatomic FePt alloy was also studied of the sample consists of iron oxides and probably metallic
with an HRTEM (figure 2). The nanoparticles are spherical in platinum. The same conclusion is reached from the XRD
shape with a size between 3 and 5 nm, in good agreement patterns. Here the (111) peak of the fcc alloy would be expected
with that evaluated from the XRD patterns using the Scherrer to appear at 2θ = 40.986◦ . A strong reflection appearing at
formula. 2θ ∼ 39.96◦ is wrongly taken to indicate the formation of the
A key issue refers to the formation of iron oxides during the fcc phase. This peak should be attributed to the metallic Pt (in
synthesis of the fcc FePt phase from the thermal decomposition accordance to the data base [11] where the (111) peak of Pt is
of Fe(CO)5 . The XRD results of the as-prepared sample, as at 2θ = 39.763◦ ). The peak is very intense and obscures that
shown in figure 1(a), do not indicate the formation of the fcc of the iron oxides due to the high atomic number of Pt [12].
phase. In fact, when the XRD pattern was confined to the Our conclusion is that there is no need to use Fe(CO)5 as an
region of 2θ values up to 38◦ the characteristic reflections at iron precursor, since it does not prevent the formation of iron
2θ 29.9◦ and 36.3◦ of the ferrite phase [9] (Fe3 O4 , γ -Fe2 O3 ) oxides and in addition possesses numerous disadvantages such
are quite clear (figure 3). The Mössbauer spectrum, on the as its chemical instability and toxicity.
other hand (figure 1(c)), provides not only qualitative but also
quantitative evidence for the formation of the iron oxide phase;
3.2. Effect of annealing conditions on FePt properties
the analysis of the spectrum from the as-prepared sample
showed 96% iron oxide in this sample. The oxide present in the Based on the above results, the equiatomic sample was chosen
sample is cubic, with parameters suggesting either γ -Fe2 O3 or for the study of the annealing conditions required to yield the
Fe3 O4 . Because of the small size of the nanoparticles and their fct phase. In the first stage the effect of annealing temperature
non-stoichiometry, these two oxides cannot be distinguished, (Tan ) was examined. The samples were annealed for 2 h at
but haematite can be excluded due to the absence of any 400, 450, 500, 600 and 700 ◦ C. The XRD measurements show
significant quadruple splitting. The presence of iron oxide in the gradual formation of the fct phase (figure 4(a)). This is
the as-prepared samples disagrees with many literature reports accompanied, as expected, with a corresponding increase in
which claim that the synthesis leads directly to the cubic phase the coercivity values, with a maximum value of 7 kOe at 600 ◦ C

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I Zafiropoulou et al

2500
a 60 b
O
2000 700 C 40

Magnetization, emu/g
O
600 C 20
1500
Intensity, a.u.

as-prepared
O
500 C 0 O
400 C
1000 O
O
450 C
450 C -20 O
500 C
O
600 C
O O
500 400 C 700 C
-40

as-prepared
-60
0
20 30 40 50 60 70 80 90 -20 -10 0 10 20
2 theta, deg Field, kOe

Figure 4. XRD patterns (a) and hysteresis loops (b) for samples annealed at various Tan for 2 h.

80
1000 a b
60
120 min
800 40
Magnetization, emu/g 10’
60 min 30’
20 60’
Intensity, a.u.

600 120’
0 as-prepared
30 min
400
-20
10 min
200 -40
as-prepared
-60
0
-80
20 30 40 50 60 70 80 90 -20 -10 0 10 20
2 theta, deg Field, kOe

Figure 5. XRD patterns (a) and hysteresis loops (b) for samples annealed at 450 ◦ C for various times.

(figure 4(b)). We note that the sample annealed at 700 ◦ C has the Tan and tan . In this spectrum (figure 6(a)) iron oxides are
a lower coercivity than that annealed at 600 ◦ C, because the also present, presumably since 10 min is too short a time for
700 ◦ C annealing is accompanied by a significant increase in their reduction. For the 120 min annealed samples the fct
the nanoparticle size from 20 to 28 nm. It is also important to percentage increases to 48%. Consequently, the evolution of
point out that the coercivity values achieved after annealing the fct phase is a process which slows down with increasing
at 400 ◦ C (1.4 kOe, size 6 nm), and especially at 450 ◦ C the Tan or tan . For this reason, there is no need to apply strong
(4.5 kOe, size 9.5 nm), are satisfactory for many applications annealing conditions. Annealing at 450 ◦ C for 30 min leads to
and, accordingly, there is no need for annealing at the more the formation of 42% fct phase accompanied by a 3.5 kOe
elevated temperatures mentioned in the literature. For these coercivity, while the nanoparticle size remains at 8.5 nm.
reasons the temperature of 450 ◦ C was selected to examine the These values are satisfactory enough for future technological
effect of the annealing time (tan ) on the coercivity. applications of this system.
In this second stage the equiatomic alloy was annealed
at 450 ◦ C for 10, 30 60 and 120 min. In the XRD patterns, 4. Conclusions
figure 5(a), there is no clear evidence for the formation of
the fct phase. There is, however, a gradual development of In conclusion, the fabrication of hard magnetic L10 FePt
the characteristic doublet at 2θ values, indicating the partial nanoparticles (with a size of 3–5 nm) is reported, along with a
formation of the fct phase. Because of the low Tan the size study of the effect of molar ratio of the metallic precursors
of nanoparticles remains low, reaching a maximum value of on the composition and magnetic properties of the alloy.
9.5 nm for the 120 min annealing time. The coercivity values Although Fe(CO)5 was used as the source of metallic iron, the
increase with increasing the annealing time, as shown by the as-prepared nanoparticles consist mainly of iron oxides and
hysteresis loops (figure 5(b)). This increase happens abruptly metallic platinum. This leads to the conclusion that for the
at first but slows down as tan increases. For example, after synthesis of FePt iron precursors other than Fe(CO)5 , which
30 min annealing the coercivity is 3.5 kOe, and after 60 min it is toxic, explosive and chemically unstable, can be used. The
increases only to 3.7 kOe. study of the annealing conditions (temperature and time) on
This conclusion was further supported by the Mössbauer the magnetic properties of the equiatomic alloy showed that
spectra obtained from samples annealed for 10 and 120 min a temperature of 450 ◦ C is sufficient for a adequate coercivity
(figures 6(a) and (b)). The sample annealed for 10 min contains value to develop (3.5 kOe), while the size is maintained below
42% of the fct phase, a surprisingly large amount considering 10 nm. As far as the annealing time is concerned, 30 min was

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Optimized synthesis and annealing conditions of L10 FePt nanoparticles

100,1 100,05
100,00
100,0
99,95
99,9
99,90
Absorption %

99,8

Absorption %
Theoretical 99,85
Theoretical
Experimental
99,80 Experimental
99,7 fcc = 50%
fcc = 52%
fct = 42% 99,75 fct = 48%
99,6 Oxide = 5%
Oxide = 3% 99,70
99,5 99,65
99,60
99,4 a b
99,55
-10 -5 0 5 10 -10 -5 0 5 10
Velocity, mm/s Velocity, mm/s

Figure 6. Mössbauer spectra for two samples annealed at 450 ◦ C for 10 min (a) and 120 min (b).

adequate for the desired properties, since the formation of the [4] Sun S, Murray C B, Weller D, Folks L and Moser A 2000
fct phase seems to be a process that starts rapidly but slows Science 287 1989–92
down with both temperature and the annealing time. [5] Tzitzios V, Niarchos D, Gjoka M, Fidler J and Petridis D 2005
Nanotechnology 16 287–91
[6] Klug H P and Alexander L E 1974 X-Ray Diffraction
Acknowledgment Procedures for Polycrystalline and Amorphous Materials
2nd edn (New York: Wiley) pp 687–90
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[8] Dai Z R, Sun S and Wang Z L 2001 Nano Lett. 1 443–7
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