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The phase diagram in nm-sized Au-Sb alloy system has been studied by transmission electron microscopy. With decreasing system size, the increase of solid solubilities in solid solution or intermetallic compounds are significantly enhanced. The formation of the highly disordered ultra-fine grain nanostructures may be related to the low heterogeneous nucleation probability.
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Phase diagrams in nanometer-sized alloy systems (1).pdf
The phase diagram in nm-sized Au-Sb alloy system has been studied by transmission electron microscopy. With decreasing system size, the increase of solid solubilities in solid solution or intermetallic compounds are significantly enhanced. The formation of the highly disordered ultra-fine grain nanostructures may be related to the low heterogeneous nucleation probability.
The phase diagram in nm-sized Au-Sb alloy system has been studied by transmission electron microscopy. With decreasing system size, the increase of solid solubilities in solid solution or intermetallic compounds are significantly enhanced. The formation of the highly disordered ultra-fine grain nanostructures may be related to the low heterogeneous nucleation probability.
H. Yasuda a, *, H. Mori b a Department of Mechanical Engineering, Faculty of Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan b Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, Yamadaoka, Suita, Osaka 565-0871, Japan Abstract The phase diagram in nm-sized AuSb alloy system has been studied by transmission electron microscopy. With decreasing system size, the increase of solid solubilities in solid solution or intermetallic compounds are signicantly enhanced. With a further decrease in the system size, the pure substance continuously changes into solid solution, a highly disordered ultra-ne grain nanostructure and then to intermetallic compound as the solute concentration increases. The formation of the highly disordered ultra-ne grain nanostructures may be related to the low heterogeneous nucleation probability. r 2002 Elsevier Science B.V. All rights reserved. Keywords: A1. Interfaces; A1. Nanostructures; A1. Phase diagrams; B1. Alloys; B1. Nanomaterials 1. Introduction It is well-known that phase transition tempera- tures of small particles in the size range from a few to several nanometers (nm) are signicantly depressed compared to those of the corresponding bulk materials. For example, phase transition temperatures such as the melting point and the orderdisorder critical temperature are markedly reduced with decreasing size of particles [15]. However, studies on the temperature-composition diagram in nm-sized alloy systems are few [68]. In the present work, the nanostructure and chemical composition of nm-sized AuSb alloy particles have been studied by transmission electron microscopy (TEM) in an attempt to investigate the difference in the phase diagram between a bulk and the corresponding nm-sized alloy system. The reasons for choosing the AuSb system as samples are two-fold; rst, it is well established that the solid solubility of antimony in gold for the bulk material is quite low; second, this system forms only one AuSb 2 , as shown in Fig. 1, and therefore the phase diagram for the bulk material is quite simple [9]. 2. Experimental procedure Preparation of size-controlled AuSb alloy particles was carried out using a double-source evaporator installed on the specimen holder of a 200 kV eld emission high-resolution electron microscope. The evaporator consists of two spiral-shaped tungsten laments. An amorphous carbon lm mounted on a molybdenum grid or a cleaved graphite substrate was used as a support- ing lm. They were baked out at about 1073 K for 60 s prior to the experiments. Using the evapora- tor, antimony (or gold) was rst evaporated from one source to produce nm-sized antimony (or *Corresponding author. Tel./fax: +81-78-803-6129. E-mail address: yasuda@mech.kobe-u.ac.jp (H. Yasuda). 0022-0248/02/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 2 - 0 2 4 8 ( 0 1 ) 0 1 8 8 1 - 4 gold) particles on the supporting lm. Gold (or antimony) was then evaporated from the other source onto the same lm. The supporting lm was kept at ambient temperature during the deposi- tion. The particles were then annealed in the microscope at about 510 K for 1.8 ks and slowly cooled from the annealing temperature to room temperature in 0.9 ks. This annealing treatment was done in an attempt to allow high atomic mobility in the particles, which would bring about phase equilibrium. The chemical composition of individual parti- cles on the lm was analyzed by energy-dispersive X-ray spectroscopy (EDS). The analyses were carried out using an electron probe of approxi- mately 1 nm in diameter. The characteristic X-ray of gold and antimony were collected with an ultra- thin window X-ray detector at a high take-off angle of 681. The background was simulated by curve tting, and then subtracted. The chemical composition of clusters was calculated from an intensity ratio of Sb L a1 to Au L a1 peak, using sensitivity factors. 3. Results and discussion Examples of AuSb alloy particles with dia- meters of approximately 8 nm are shown as a function of the composition in Fig. 2. An example of AuB15 at%Sb alloy particles is shown in Fig. 2(a). The particle is a single crystal- line particle. The mean diameter of the particle is approximately 7 nm. In Fig. 2(a), there appear lattice fringes with spacings of 0.24 and 0.20 nm. The former and latter spacings are nearly equal to the (1 1 1) and (2 0 0) lattice spacings of gold. These fringes make an angle of 551 to each other, showing that the incident beam direction is along the [1 1 0] of FCC gold. EDS spectrum was measured at the region encircled in Fig. 2(a). Antimony concentration was 15 at%Sb, as shown in the gure. These facts indicate that the particle is a gold-rich AuSb solid solution and that the solid solubility of antimony in approximately 7 nm-sized gold clusters amounts to at least 15 at%Sb, which is much higher than that in bulk gold. Examples of AuSb 2 compound particles with different chemical compositions are shown in Figs. 2(c) and (d). The mean diameter of the compound particles is approximately 8 nm. All the compound particles are single crystalline. The 0.24 nm-spaced fringes in the images are the (2 2 0) lattice fringes of AuSb 2 . These fringes make an angle of 601 to each other, showing that the incident beam direction is along the [1 1 1] of AuSb 2 with the C2 structure. EDS spectra indicate that antimony concentrations of particles shown in Figs. 2(c) and (d) are 52 at%Sb (which is B14 at% lower than the stoichiometric composition of AuSb 2 ) and 72 at%Sb (which is B6 at% higher than the stoichiometric composition of AuSb 2 ), respectively. Through the experiment, it is con- rmed that remarkable enhancement of solubility has been induced also in AuSb 2 compound particles, as compared with that in the correspond- ing bulk AuSb 2 . Examples of alloy particles which fall in the two- phase region in the phase diagram for the bulk alloy are shown in Figs. 2(b). The mean diameter of the alloy particle is approximately 9 nm. The particle consists of two grains; grains I and II. In grain I, the 0.24 nm-spaced fringes are equivalent to the (1 1 1) lattice fringes of gold. In grain II, the 0.27 nm-spaced fringes are the (2 1 1) lattice fringes of AuSb 2 . EDS spectra indicate that antimony concentrations of grains I and II in the particle Fig. 1. Phase diagram in the AuSb system. H. Yasuda, H. Mori / Journal of Crystal Growth 237239 (2002) 234238 235 shown in Figs. 2(b) are 15 at%Sb and 63 at%, respectively. This fact suggests that grain Is and II are gold-enriched solid solution and AuSb 2 , respectively. In this experiment, it becomes evident that the solid solubility of antimony increases signicantly in nm-sized gold particles compared with that for the corresponding bulk materials. The remarkable enhancement of solubility has also been observed in intermetallic compound AuSb 2 . The deviation from the stoichiometric composition of AuSb 2 amounts to several atomic percents. In addition, in the case of the alloy particles which fall in the two- phase region in the phase diagram for the bulk alloy, the result of the two-phase formation is consistent with that expected from the phase diagram for the corresponding bulk alloy. Examples of AuSb alloy particles with dia- meters below 5 nm are shown as a function of the composition in Fig. 3. Examples of AuSb 2 com- pound particles with different chemical composi- tions are shown in Figs. 3(b) and (c). The mean diameter of the compound particles is approxi- mately 5 nm. All the compound particles are again single crystalline. These lattice fringes show that the incident beam direction is along the [1 1 1] of AuSb 2 with the C2 structure, and these images correspond to those shown in Figs. 2(c) and (d). EDS spectra indicate that antimony concentra- tions of particles shown in Figs. 3(b) and (c) are 65 at%Sb (which is B2 at% lower than the stoichiometric composition of AuSb 2 ) and 77 at%Sb (which is B10 at% higher than the stoichiometric composition of AuSb 2 ), respec- tively. From the experiment, it is again evident that remarkable enhancement of solubility has been induced in AuSb 2 compound particles. An example of AuB36 at%Sb alloy particles which fall in the two-phase region in the phase diagram for the bulk alloy is shown in Figs. 3(a). Fig. 2. Examples of AuSb alloy particles with diameters of approximately 8 nm as a function of the composition. H. Yasuda, H. Mori / Journal of Crystal Growth 237239 (2002) 234238 236 The mean diameter of the alloy particle is approximately 4 nm. The particle consists of ultra-ne grains. The grain size in the interior of the particle is in the range of 12 nm in diameter. This result indicates that an ultra-ne grain phase similar to amorphous-like materials is formed in 4 nm-sized AuSb alloy particles which fall in the two-phase region in the bulk alloy phase diagram. Through the experiment, it was revealed that when the diameter of the AuSb alloy particles decreases to o5 nm, it becomes difcult to form the obviously two different phases in the interior of individual particles and consequently a highly disordered ultra-ne grain nanostructure (i.e., amorphous-like nanostructure) appears, even if the composition of alloy particles falls in the two- phase region in the corresponding bulk phase diagram. In this highly disordered nanostructure, it is considered that short-range structures which consist of unit cells of solid solutions or com- pounds distribute homogeneously because remark- ably stable phases are not present in the two-phase region. It is now well-known that in nm-sized particles, the lattice itself becomes elastically soft to a great extent [10,11]. It is then expected the lattice distortion induced by dissolution of solute atoms could be relaxed rather easily than in bulk materials. Consequently, it seems reasonable to consider such atomic arrangements that are under the control of only chemical interactions among constituent atoms which appear preferentially in the nm-sized particles. If the concentration of solute atoms is small in the solvent matrix, a solid solution with an enhanced solubility will be formed. Similarly at compositions slightly deviated from the stoichiometric composition of a very stable intermediate phase, an enhanced solubility will be achieved. If the composition falls in the middle of a two-phase region in the bulk phase diagram, there will be a possibility that the ultra- ne grain structure which exhibits less dened long-range periodicity of atom arrangement is formed. A possible highly disordered ultra-ne grain nanostructure of such a phase may be a mixture of unit cells in the neighboring stable phases (i.e., in the present examples, a mixture of unit cells of a solid solution and the AuSb 2 compound); namely, in these cases, it is expected that such highly disordered nanostructures with the structure, where the chemical environment around each individual atom is much valued as compared to the geometrical regularity (or geome- trical constraint) of atom arrangement, will appear. The phase diagram in nm-sized AuSb alloy system will be discussed from the observed phase stability in nm-sized AuSb alloy particles. The change in the phase diagram in nm-sized alloy system is shown as a function of system size in Fig. 4. Fig. 4(a) shows a bulk phase diagram in the Fig. 3. Examples of AuSb alloy particles with diameters below 5 nm as a function of the composition. H. Yasuda, H. Mori / Journal of Crystal Growth 237239 (2002) 234238 237 eutectic system. Fig. 4(b) shows the phase dia- gram, when the system size decreased to approxi- mately 10 nm. It is revealed that with decreasing the system size, the increase of solid solubilities in solid solution or intermetallic compounds are signicantly enhanced. Fig. 4(c) shows the phase diagram in case the system size decreased to o5 nm. When the solute concentration increases, the pure substance continuously changes into solid solution, a highly disordered ultra-ne grain nanostructure and then to intermetallic com- pound. The reason for the absence of the two- phase region may be that the main kinetic constraint imposed by small system size will have difculty in nucleating equilibrium phases due to the absence or low number density of heteroge- neous nucleation sites in the two-phase region in which remarkably stable phases are not present. It is suggested that such a low nucleation probability may lead to form the highly disordered ultra-ne grain nanostructures. 5. Conclusion The phase diagram in nm-sized AuSb alloy system has been studied by TEM. With decreasing system size, the increase of solid solubilities in solid solution or intermetallic compounds is signicantly enhanced. With a further decrease in the system size, the pure substance continuously changes into solid solution, a highly disordered ultra-ne grain nanostructure and then to inter- metallic compound, when the solute concentration increases. The formation of the highly disordered ultra-ne grain nanostructures may be related to the low heterogeneous nucleation probability. Acknowledgements This work was, in part, supported by Research for the Future Program, JSPS #96P00305, and by the Ministry of Education, Sports, Culture, Science and Technology under Grant-in-Aid for Scientic Research. References [1] M. Takagi, J. Phys. Soc. Jpn. 9 (1951) 359. [2] J.R. Sambles, Proc. R. Soc. Lond. A. 324 (1971) 339. [3] G.L. Allen, R.A. Bayles, W.W. Gile, W.A. Jesser, Thin Solid Films 144 (1986) 297. [4] T. Castro, R. Reinfenberger, E. Choi, R.P. Andres, Phys. Rev. B 42 (1990) 8548. [5] H. Yasuda, H. Mori, Z. Phys. D 37 (1996) 181. [6] L.S. Palatnik, B.T. Boiko, Phys. Metals Metallog. 11 (1961) 119. [7] G.L. Allen, W.A. Jesser, J. Crystal Growth 70 (1984) 546. [8] H. Yasuda, H. Mori, Z. Phys. D 31 (1994) 131. [9] H. Okamoto, T.B. Massalski, in: T.B. Massalski, J.L. Murray, L.H. Bennett, H. Baker, L. Kacprzak, B.P. Burton, T. Weintraub, J. Bhansali, C.E. Sirofchuck, J.S. Sims (Eds.), Binary Alloy Phase Diagrams, ASM, Metals Park, OH, 1986. [10] J. Harada, K. Ohshima, Surf. Sci. 106 (1981) 51. [11] T. Matsubara, Y. Iwase, A. Momokita, Prog. Theor. Phys. 58 (1977) 1102. Fig. 4. Phase diagram in nm-sized alloy system as a function of system size: (a) in the bulk system, (b) in the system size of approximately 10 nm, and (c) in the system size of o5 nm. H. Yasuda, H. Mori / Journal of Crystal Growth 237239 (2002) 234238 238