Professional Documents
Culture Documents
www.elsevier.com/locate/stam
Received 31 August 2005; received in revised form 20 October 2005; accepted 14 November 2005
Available online 2 March 2006
Abstract
FePd nanoparticles were prepared by the modified polyol process, i.e. simultaneous reduction of palladium acetylacetonate and thermal
decomposition of iron pentacarbonyl in a solvent. The well-dispersed FePd particles, with the average particle size of w8.4 nm, were obtained
using diphenyl ether as a solvent. The structure of FePd nanoparticles transformed to L10 structure from face centered cubic (fcc) structure after
annealing at 600 8C for 1 h in vacuum. The coercivity of the ordered FePd nanoparticles increased to w2 kOe at 5 K from w0.6 kOe in the fcc as-
made FePd nanoparticle. On the other hand, FePd nanoparticles, synthesized based on the conventional modified polyol process using dioctyl
ether as a solvent, showed no structural transformation after annealing up to 700 8C. This is explained in terms of the interruption of thermal
diffusion of Fe and Pd atoms during the thermal treatment due to the mixture of interstitial carbon impurity in the synthesis process using dioctyl
ether as a solvent.
q 2006 Elsevier Ltd. All rights reserved.
Fig. 3. The hysteresis loops at 5 K of the Fe49.2Pd50.8 samples with the fcc (as-
made sample) and the L10 structures (600 8C-annealed sample). Fig. 4. X-ray diffraction patterns of the Pd and FePd nanoparticles. (a) Pd
nanoparticles synthesized using diphenyl ether. (b) Pd nanoparticles
synthesized using dioctyl ether. (c) Fe47.1Pd52.9 nanoparticles synthesized
2040 Oe, respectively. Thus, the increase in coercive force of using diphenyl ether. (d) Fe49.1Pd50.9 nanoparticles synthesized using dioctyl
the FePd nanoparticles, synthesized by the modified polyol ether.
process, is induced by the transformation to L10 from fcc
structure. As a result, the structural transformation in FePd In FePd nanoparticles the similar tendency is observed, i.e. the
nanoparticles, prepared by the synthesis using thermal impurity content is larger in FePd nanoparticles synthesized
decomposition of Fe(CO)5, was confirmed based both on the using dioctyl ether.
structural and magnetic analysis. The XPS data of the Pd nanoparticles, synthesized using
dioctyl ether and diphenyl ether, are shown in Table 2. In
3.2. Ordering process of FePd nanoparticles addition, the XPS data of Pd nanoparticles, prepared by gas
evaporation method, are also shown for comparison. The
We discuss the ordering process of the FePd nanoparticles, binding energies of the as-made Pd nanoparticles were 335.1–
synthesized by the modified polyol process, and especially the 335.2 eV (Pd 3d5/2) and 340.3–340.5 eV (Pd 3d3/2) indepen-
reason why the present nanoparticle sample of FePd showed dent of solvents. These binding energies are the same as those
the structural transformation by annealing in contrast to the of the bulk Pd and the Pd nanoparticles prepared by gas
previous study [3]. The comparison of the preparation evaporation. In addition, the binding energies are intrinsically
procedure by Chen and Nikles [3] with the present procedure constant even after annealing at 600 8C. These XPS data
suggests that the difference of solvents used with the reflux suggest that the impurity in Pd nanoparticles, synthesized by
relates with the L10 transformation. In order to clarify the polyol process, does not form the rigid binding state with the
contribution of solvent to the structural transformation, the Pd Pd matrix. This indicates that the impurity in Pd nanoparticles
nanoparticles were synthesized by the polyol process using the is not substitutional but interstitial.
two kinds of solvents, where the dissolubility of Pd(acac)2 is In order to specify the element of interstitial impurities,
significantly higher in diphenyl ether than in dioctyl ether. EPMA was used. As a result, carbon was exclusively detected
Fig. 4 shows the XRD patterns of the Pd and FePd other than Pd in the Pd nanoparticle sample. The result of
nanoparticles which are synthesized using two kinds of EPMA indicates that only specified C atom can be impurity
solvents. The obtained lattice constants are summarized in element mixed in the Pd nanoparticles, although C atoms are
Table 1, in which the data of Pt nanoparticle and bulk Pd are
also shown. The lattice constants of Pd nanoparticles,
Table 1
synthesized by polyol process, are larger than that of the bulk Lattice constant of FePd nanoparticles synthesized by polyol process by X-ray
Pd and moreover, than that of the Pt nanoparticles synthesized diffraction patterns
by polyol process, where the lattice constant of Pd is smaller
Nanoparticles Bulk (Å)
than that of Pt in bulk. This indicates that Pd nanoparticles
include some impurities in Pd lattice so as to increase the lattice Diphenyl ether Dioctyl ether
constants. In addition, the expansion of lattice in Pd Pd 3.937 Å 3.961 Å 3.890
nanoparticles using dioctyl ether is larger than that using Pt 3.929 Å 3.923
FePd 3.869 Å (Fe47.1Pd52.9) 3.895 Å (Fe49.1Pd50.9)
diphenyl ether. This indicates that the substitution of diphenyl
ether for dioctyl ether reduces the impurity in Pd nanoparticles. The date of pure bulk Pd and Pt are also shown.
148 K. Watanabe et al. / Science and Technology of Advanced Materials 7 (2006) 145–149
Table 2 Table 3
The Pd 3d5/2 and 3d3/2 binding energies determined by XPS measurements Lattice constants of Pd and Fe54.5Pd45.5 nanoparticles synthesized by polyol
process using dioctyl ether
Peak Anneal Dioctyl Diphenyl Gas Pure bulk
ether (eV) ether (eV) evaporation (eV) (eV) As-made (Å) 500 8C 700 8C
3d5/2 As-made 335.145 335.184 335.119 335.1 Pd 3.961 3.931 Å 3.908 Å
600 8C 335.125 335.116 Fe54.5Pd45.5 3.874 3.854 Å 3.839 Å
3d3/2 As-made 340.381 340.545 340.494 340.3
600 8C 340.369 340.328
we can evaluate the amount of C atoms in the as-made sample,
synthesized in dioctyl ether, to be 8.7% and that in the 700 8C-
mainly included in the organic stabilizer. Thus, we claim that annealed sample to be 2.2% according to the Vegard’s law. On
the Pd nanoparticles include C atoms into the Pd lattice and the other hand, the amount of interstitial C atoms in as-made Pd
the Pd1KxCx solid solution is formed. It was reported that the nanoparticles, synthesized using diphenyl ether, is 5.7%. Thus,
Pd1KxCx phase, having fcc structure, was formed by heating the 3% decrease in C concentration is induced by changing the
the Pd in an atmosphere of ethylene, acetylene or carbon solvent from dioctyl ether to diphenyl ether. In other words, the
monoxide [6]. The maximum amount of carbon atoms in Pd or FePd nanoparticles with less impurity can be obtained
Pd1KxCx phase is xZ0.15, and the solid solution is metastable using diphenyl ether as solvent in the synthesis process. We
and decomposes at temperatures above 600 8C at which the note that the lattice constant of Pt, synthesized in dioctyl ether,
expulsion of C atoms occurs [7]. scarcely changes from that in bulk Pt as shown in Table 1.
Fig. 5 shows the XRD patterns of Pd and Fe54.5Pd45.5 Therefore, we estimate that the admixture of interstitial C atom
nanoparticles synthesized by the modified polyol process using is negligible in chemical preparation process of Pt and FePt
dioctyl ether. The lattice constants, obtained by the XRD nanoparticles.
peaks, are shown in Table 3. The lattice constant of Pd The impurities in FePd nanoparticles form the interstitial
nanoparticles decreased as the temperature for annealing solid solution. Therefore, a large amount of interstitial C atoms
increases and down to 3.908 Å after the 700 8C annealing. significantly interrupt the thermal diffusion of Fe and Pd atoms
This suggests that Pd nanoparticles form the Pd1KxCx solid during the thermal treatment so as to prevent the transform-
solution, because the expulsion of C atoms from the Pd1KxCx is ation to L10 structure. This is the case of the FePd nanoparticles
significantly induced by annealing at temperatures above synthesized using dioctyl ether. The decrease in C concen-
tration in FePd nanoparticles, synthesized using diphenyl ether,
600 8C. In FePd nanoparticles, similarly, the lattice constant
leads to the high diffusion rate of atoms during the thermal
decreased by annealing. Therefore, we estimate that the FePd
treatment so as to induce the L10 transformation in FePd
nanoparticles also include C atoms and the expulsion of C
nanoparticles.
atoms occurs by annealing. Based on the relation between the
The mechanism for the introduction of C impurity into Pd or
lattice constant and the C concentration in bulk Pd1KxCx [8],
FePd nanoparticles may be complicatedly related to various
parameters such as the dissolubility of Pd(acac)2 in solvent and
the concentration of Pd(acac)2. In order to explain the relation
between the solvents used with the reflux and the amount of the
C impurity in the synthesis of Pd or FePd nanoparticles, the
further work, based on the characterization techniques to
monitor the synthesis process, is needed.
4. Conclusions
FePd nanoparticles is essential for the transformation to L10 [2] S. Sun, C.B. Murray, D. Weller, L. Folks, A. Moser, Monodisperse FePt
structure. nanoparticles and ferromagnetic FePt nanocrystal superlattices, Science
287 (2000) 1989–1992.
[3] M. Chen, D.E. Nikles, Synthesis of spherical FePd and CoPt nanoparticles,
Acknowledgements J. Appl. Phys. 91 (2002) 8477–8479.
[4] S. Kang, Z. Jia, D.E. Nikles, J.W. Harrell, Synthesis and phase transition of
We would like to thank Katsuyoshi Komatsu of Keio self-assembled FePd and FePdPt nanoparticles, J. Appl. Phys. 95 (2004)
6744–6746.
University for useful advice for sample preparation. This work
[5] H. Kura, T. Sato, Synthesis of L10-(FeyPt100Ky)100KxCux nanoparticles
was performed in FY 2002 The 21st Century COE Program. with high coercivity by annealing at 400 8C, J. Appl. Phys. 96 (2004) 5771–
This work was partially supported under a Grant-in-Aid for 5774.
Scientific Research from the Ministry of Education, Culture, [6] S.B. Ziemecki, G.A. Jones, D.G. Swartzfager, Coexistence of hydrogen
Sports, Science, and Technology of Japan. and carbon solutes in the palladium lattice, J. Less-Common Met. 131
(1987) 157–162.
[7] P. Canton, C. Meneghini, P. Riello, A. Balerna, A. Benedetti, Thermal
References evolution of carbon-supported Pd nanoparticles studied by time-resolved
X-ray diffraction, J. Phys. Chem. B 105 (2001) 8088–8091.
[1] D. Weller, A. Moser, L. Folks, M.E. Best, W. Lee, M.F. Toney, [8] J.A. McCaulley, Temperature dependence of the Pd K-edge extended
M. Schwickert, J.U. Thiele, M.F. Doerner, High Ku materials approach X-ray-absorption fine structure of PdCx (xw0.13), Phys. Rev. B 47 (1993)
to 100 Gbit/in2, IEEE Trans. Magn. 36 (2000) 10–15. 4873–4879.