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Abstract
Self-assembled 4 nm FePt nanoparticle arrays were treated with rapid thermal annealing (RTA) process. The phase
transformation from the chemically disordered face-centered-cubic structure of the as-synthesized FePt nanoparticles to
the chemically ordered face-centered-tetragonal structure was realized by RTA, with both the annealing temperature
and time being greatly reduced, as compared to conventional annealing. The onset of chemical ordering occurred at the
annealing condition of around 400 C for only 5 s. Temperature-dependent coercivity measurements revealed strong
thermal effects of the nanoparticle assemblies. Curie temperatures (Tc ) of the annealed assemblies were derived from the
temperature-dependent hysteresis measurements. Tc of the annealed assemblies increases with increasing annealing
temperature, but is about 200–300 K lower than that of bulk FePt (750 K). The drastic reduction of Tc may be
attributed to size effect and partial chemical ordering of FePt nanoparticles.
r 2003 Elsevier B.V. All rights reserved.
(111) 26
24 a (300 K )
(001) (110) 580 C
(200) 22 b (300 K)
(e) (002) c (10 K)
Intensity (arb. unit)
(201) (112) 20
18
(d)
Hc (kOe)
550 C 16
(c) 14
500 C 12
(b) 10
460 C 8
6
(a) as-syn 4
2
20 30 40 50 60 70 0
350 400 450 500 550 600
2θ Ta (C)
Fig. 2. XRD (l ¼ 1:79 A, ( Co Ka radiation) pattern of 4 nm
Fig. 3. Hc as a function of the annealing temperature Ta for (a)
FePt nanoparticle self-assembly: (a) as-synthesized and an-
RTA for 5 s, measured at 300 K; (b) box oven annealing for
nealed by RTA for 5 s at annealing temperatures of (b) 460 C,
30 min, measured at 300 K; and (c) RTA for 5 s, measured at
(c) 500 C, (d) 550 C and (e) 580 C.
10 K.
high room-temperature coercivity. To study the behaviors of samples annealed at low and high
effects of ordering and aggregation, the tempera- temperatures show different trends: for low Ta
ture dependence of coercivity was measured. samples (p460 C), the rate of Hc reduction is
Fig. 3(c) shows Hc measured at 10 K for RTA initially quite large, while decreases gradually as
samples annealed at different temperatures. At the measuring temperature approaches 300 K;
such a low measuring temperature, the contribu- for high Ta samples, this trend tends to be
tion from thermal effects is negligible, and the reversed. According to Sharrock’s formula, the
coercivity can serve as an indication of the degree temperature dependence of Hc may originate from
of ordering. It can be seen that at Ta ¼ 400 C, Hc two factors: (1) the temperature dependence of
at 10 K reaches 6 kOe, suggesting the onset of intrinsic properties such as Ms and Ku and (2) the
chemical ordering, although the XRD results thermal fluctuation term kB T=ðKu V Þ: One of the
indicate that the superlattice (0 0 1) peak only possible reasons for the difference in Hc ðTÞ
becomes visible at Ta ¼ 460 C. TEM observations behaviors we observed may be that the tempera-
confirm that the nanoparticles are well isolated. As ture dependence of intrinsic properties is compet-
Ta increases, Hc increases, suggesting improved ing with the thermal fluctuation term. This
ordering. For Ta ¼ 580 C, Hc at 10 K is temperature dependence of Ms and Ku may
24,000 Oe. This corresponds to Ku B2:5 107 erg/ originate from various factors, including the size,
cm3, which is consistent with values of highly surface effects and disorder of nanoparticles.
ordered FePt reported by others [9]. Different Hc ðTÞ trends seem to suggest that for
Fig. 4 shows the measured temperature-depen- the sample annealed at low Ta ; the thermal
dent coercivity, normalized by Hc at 10 K, for fluctuation term kB T=ðKu V Þ is dominating; while
RTA samples with Ta ¼ 360 C, 460 C, 520 C and for the sample annealed at high Ta ; the dominating
580 C. For particle ensembles with a single energy effect is the temperature dependence of intrinsic
barrier, Hc ðTÞ behavior can be described by properties. The reason lies in that for high Ta
Sharrock’s formula [10], provided that the reversal samples, strong inter-particle exchange coupling
mechanism is coherent rotation. Nevertheless, in and/or possible aggregation makes the thermal
reality, the Hc ðTÞ behavior is rather complicated. fluctuation term less important.
It can be seen that Hc of all samples decreases For isolated, randomly oriented particles with
dramatically with increasing measuring tempera- uniaxial anisotropy, the remanence ratio S ¼
tures, due to thermal fluctuations. However, Hc ðTÞ Mr =Ms is 0.5 [11]. S greater than 0.5 suggests that
there may exist inter-particle exchange coupling.
Therefore, S can be used to study inter-particle
exchange interactions. Again, due to the thermal
1.0
effects, room-temperature S cannot be used for
such purposes. Instead, S at 10 K is measured for
0.8
these samples and is plotted as a function of Ta in
Hc /Hc(10 K)
Ms/M0
0.68
0.4 Ta = 360 C, Tc = 410 K
0.66
0.2 Ta = 460 C, Tc = 450 K
0.64
Ta = 520 C, Tc = 580 K
0.62
0.0
Fig. 5. Remanence ratio S ¼ Mr =Ms measured at 10 K as a Fig. 6. Ms ðTÞ=Ms ð0Þ vs. T=Tc for Ta =60 C, 460 C and
function of Ta : 520 C.
The intrinsic magnetic properties of Ms ; Ku and lie in two-folds: in addition to the lose of moment
the curie temperature Tc for the bulk FePt are for the surface atoms, which leads to lower Ms for
affected by size and surface effects, as well as smaller particles, the reduction of Tc also decreases
chemical disorder of the FePt nanoparticles. Ms as room-temperature Ms : For example, for bulk FePt
a function of temperature was obtained from with Tc at about 750 K, room-temperature Ms is
temperature-dependent hysteresis loop measure- only 1.5% less than Ms at 0 K; however, for the
ments for several FePt nanoparticle samples with sample annealed at Ta ¼ 360 C with Tc B410 K,
different Ta : Fig. 6 shows Ms ðTÞ=Ms ð0Þ vs. T=Tc the reduction in Ms amounts to B20%. Finally, as
curves for Ta ¼ 360 C, 460 C and 520 C; the the magnetocrystalline anisotropy Ku decreases with
theoretical curve calculated from Weiss’s theory increasing temperature, and vanishes at around Tc ;
using the Brillouin function with quantum number a reduction in Tc of about 200–300 K for nanopar-
J ¼ 1=2 is also plotted. Tc for these samples can be ticle assemblies means that Ku decreases with
determined by fitting the experimental data with increasing temperature faster than that of bulk.
the theoretical curve. As can be seen, Tc decreases
from 580 to 410 K as Ta decreases from 520 C to
360 C. Compared to Tc of 750 K for bulk FePt, 4. Conclusions
the reduction of Tc in FePt nanoparticle assem-
blies for Ta ¼ 520 C is 170 K and for Ta ¼ 360 C, Chemical ordering for 4 nm FePt nanoparticle
340 K. Okamoto et al. [13] reported a weak self-assembly can be improved by rapid thermal
dependence of Tc on ordering parameters in annealing, with significantly lowered annealing
epitaxial FePt thin films, from 750 K for the temperature and shortened time. Partially ordered
ordering parameter of 0.79–700 K for the ordering assemblies show a remanence ratio greater than
parameter of 0.5. Partial ordering in nanoparticle 0.5, which is attributed to a mixture of a cubic and
assemblies due to insufficient heat treatment uniaxial anisotropy. Significant reduction in the
therefore may account for part of the Tc reduction. curie temperature is due largely to the particle size
Another significant factor that contribute to the and surface effects, as well as partial ordering. To
reduction of Tc is the particle size and surface use these FePt nanoparticle assemblies for future
effect. For 4 nm FePt nanoparticles, nearly 30% of magnetic recording applications, further optimiz-
the atoms are at the surface if the thickness of the ing of annealing conditions leading to fully
surface layer is assumed to be 2 A. ( The surface ordered, well-isolated nanoparticles is required. It
atoms have reduced exchange coupling, which may be advantageous to utilize particles larger
may contribute to the size dependent Tc change. than 4 nm to alleviate problems associated with
The size and surface effects on Ms of nanoparticles nanoparticle size and surface effects.
ARTICLE IN PRESS
Acknowledgements [6] J.W. Harrel, D.E. Nikles, S.S. Kang, S. Wang, Fourth
International Conference on Fine Particle Magnetism,
Pittsburg, 2002 (Abstract BA4I).
This work was supported in part by US DoD/
[7] S. Sun, E.E. Fullerton, D. Weller, C.B. Murray, IEEE
DARPA under grant DAAD 19-01-1-0546. Trans. Magn. 37 (2001) 1239.
[8] S. Sun, et al., J. Phys. Chem. B 107 (2003) 5419.
[9] A. Cebollada, R.F.C. Farrow, M.F. Toney, Structure
and magnetic properties of chemically ordered magnetic
References binary alloys in thin film form, in: H.S. Nalwa (Ed.),
Magnetic Nanostructures, American Scientific Publishers,
[1] D. Weller, A. Moser, IEEE Trans. Magn. 35 (1999) 4423. Los Angeles, 2002.
[2] D. Weller, et al., IEEE Trans. Magn. 36 (2000) 10. [10] M.P. Sharrock, J. Appl. Phys. 76 (1994) 6413.
[3] S. Sun, C.B. Murray, D. Weller, L. Folks, A. Moser, [11] B.D. Cullity, Introduction to Magnetic Materials,
Science 287 (2000) 1989. Addison-Wesley, Reading, MA, 1972.
[4] H. Zeng, S. Sun, T.S. Vedantam, P. Liu, Z. Dai, Z.L. [12] J. Garcia-Otero, M. Porto, J. Rivas, A. Bunde, J. Appl.
Wang, Appl. Phys. Lett. 80 (2002) 2583. Phys. 85 (1999) 2287.
[5] T. Maeda, T. Kai, A. Kikitsu, T. Nagase, J. Akiyama, [13] S. Okamoto, N. Kikuchi, O. Kitakami, T. Miyazaki,
Appl. Phys. Lett. 80 (2002) 2147. Y. Shimada, Phys. Rev. B 66 (2002) 024413.