Journal of Crystal Growth 237239 (2002) 234238

Phase diagrams in nanometer-sized alloy systems

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