Académique Documents
Professionnel Documents
Culture Documents
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)).
1604
Optimized synthesis and annealing conditions of L10 FePt nanoparticles
Figure 2. HRTEM images and electron diffraction pattern from the as-prepared equiatomic FePt.
1605
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
1606
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
Work supported by E C Growth Program HIDEMAR. [7] Hadjipanayis G C 1999 J. Magn. Magn. Mater. 200 373–91
[8] Dai Z R, Sun S and Wang Z L 2001 Nano Lett. 1 443–7
References [9] Skomski R and Coey J M D 1999 Studies in Condensed Matter
Physics: Permanent Magnetism (Bristol: Institute of
[1] Ovanov O A, Solina L V and Demshina V A 1973 Phys. Met. Physics Publishing)
Metallogr. 35 81 [10] Okamoto S, Kitakami O, Kikuchi N, Miyasaki T and
[2] Yu M, Liu Y, Moser A, Weller D and Sellmyer D J 1999 Appl. Shimada Y 2003 Phys. Rev. B 67 94422–7
Phys. Lett. 75 3992–4 [11] JCPDS-ICDD 1997 International Center for Diffraction Data
[3] Coffey K R, Parker M A and Howard J K 1995 IEEE Trans. [12] Teng X, Black D, Watkins N J, Gao X and Yang H 2003 Nano
Magn. 31 2737–9 Lett. 3 261–4
1607