Size‐Dependent Chemical and Magnetic Ordering in L10‐FePt Nanoparticles

FePt nanoparticles have great application potential in advanced magnetic materials such as ultrahigh-density recording media and high-performance permanent magnets. The key for applications is the very high uniaxial magnetocrystalline anisotropy of the L10-FePt phase, which is based on crystalline ordering of the face-centered tetragonal (fct) structure, described by the chemical-ordering parameter S. Higher chemical ordering results in higher magnetocrystalline anisotropy. Unfortunately, as-synthesized FePt nanoparticles take a disordered face-centered cubic (fcc) structure that has low magnetocrystalline anisotropy. Heat-treatment is necessary to convert the fcc structure to the ordered fct structure. Several previous theoretical and experimental investigations have been reported on the size-dependent chemical ordering of FePt nanoparticles. It has been observed that the degree of ordering decreases with decreasing particle size of the sputtered FePt nanoparticles. Theoretical simulation predicted that the ordering would not take place when the particle size is below a critical value. However, there have not been systematic experimental studies on quantitative size dependence of chemical ordering of FePt nanoparticles due to the lack of monodisperse L10-FePt nanoparticles with controllable sizes. There are also few studies reported to date on the quantitative particle size dependence of magnetic properties, including the Curie temperature, coercivity, and magnetization of the L10-FePt phase, although it has been well accepted that there is a size effect on the ferromagnetism of any low-dimensional magnets. Additionally, the magnetic properties of FePt ferromagnets, as observed in thin-film samples, are affected by the degree of chemical ordering, which is in turn size dependent. It is therefore highly desirable to understand the size and chemical-ordering effects, and their influence on the magnetic properties of the nanoparticles. A major hurdle in obtaining the particle size dependence of structural and magnetic properties of the L10 phase is particle sintering during heat-treatments that convert the fcc phase to the fct phase. This long-pending problem has been solved recently by adopting the salt-matrix annealing technique. With this technique, particle aggregation during the phase transformation has been avoided so that the true size-dependent properties of the fct phase can be measured. In this paper, we report results on quantitative particle size dependence of the chemical-ordering parameter S and selected magnetic properties, including the Curie temperature, Tc, magnetization, Ms, and coercivity, Hc, with the particle size varying from 2 to 15 nm. Figure 1 shows the transmission electron microscopy (TEM) images of the FePt nanoparticles with different sizes before and after annealing in a salt matrix at 973 K for 4 h. The images, from left to right, show nanoparticles with nominal diameters of 2, 4, 6, 8, and 15 nm, respectively. The upper and lower rows are images of as-synthesized and salt-matrixannealed nanoparticles, respectively. As shown in Figure 1, the particle size is retained well upon annealing. Both the assynthesized and annealed nanoparticles are monodisperse with a standard deviation of 5–10 % in diameter. TEM observations also revealed that when the particle size is smaller than or equal to 8 nm, the fct nanoparticles are monocrystalline, whereas the 15 nm fct particles are polycrystalline. It is interesting to see that the L10 nanoparticles, tiny ferromagnets at room temperature, are dispersed very well without agglomeration despite the dipolar interaction between the particles, if a solvent with high viscosity is chosen and if the solution is diluted. Extensive TEM and X-ray diffraction (XRD) analyses have proved that the technique of salt-matrix annealing can be applied to heat-treatments of the FePt nanoparticles without leading to particle agglomeration and sintering, if a suitable salt-to-particle ratio and proper annealing conditions are chosen. Figure 2 shows the XRD patterns of the 4 nm, as-synthesized, fcc-structured nanoparticles and the particles annealed in a salt matrix at 873 K for 2 h, 973 K for 2 h, and 973 K for 4 h (from bottom to top), respectively. As shown in the figure, the positions of the (111) peaks shift in the higher-anC O M M U N IC A TI O N