Professional Documents
Culture Documents
Redistribution subject to AVS license or copyright; see http://scitation.aip.org/termsconditions. Download to IP: 115.145.166.240 On: Mon, 16 Dec 2013 07:18:59
I. INTRODUCTION
Investigation of nanostructured materials is a focus in recent years because of properties and physics associated with
such systems.13 The vaporliquidsolid VLS crystal
growth mechanism has been widely used for the syntheses of
quasione-dimensional nanostructured materials, such as InP,
InAs, GaAs, GaN, and silicon nanowires,4 18 and the diameters of the fiber-like structures can be controlled within the
nanometer range. The most important factor of this mechanism is the catalyst added in the reaction, which plays an
important role in the nucleation and growth of high-quality
semiconductor nanowires between the vapor feed and solid
growth under chemical vapor deposition CVD conditions.
For example, Au as a common and important catalyst has
been used for syntheses IIVI and IIIV semiconductor fibers in the VLS process.1719 In or Ga/In flux has also been
found to serve as an intermediate for the syntheses of IIIV
semiconductor fibers or whiskers via solutionliquidsolid
crystal growth.20 Transition metals, such as Fe, Ni, and Co,
also play catalytic roles in the growth of some
nanowires.10,11,2123 Although He and his co-workers24 reported the synthesis of GaN nanowires by direct reaction of
Ga vapor with flowing NH3 without a catalyst at lower temperature 850900 C, it is an interesting problem how to
choose a catalyst to induce the growth of GaN nanowires.
To probe the importance of the catalyst during the GaN
nanowire growth through the CVD method, herein we attempted to fabricate GaN nanowires through direct reaction
of metalgalliumvapor with flowing ammonia using In, Fe,
and Ni nanoparticles, respectively. Au nanoparticles also
were used in this system to grow GaN nanowires. Scanning
electron microscopy SEM results showed that the reaction
of Ga and NH3 in the presence of catalysts In, Fe, and Ni
nanoparticles, respectively, produced a high yield of nanometer wire-like products. These results indicate that the catalysts In and transition metal Fe and Ni play an important
role in the synthesis of GaN nanowires. However, no nanoa
2415
1071-1023200321624155$19.00
2415
Redistribution subject to AVS license or copyright; see http://scitation.aip.org/termsconditions. Download to IP: 115.145.166.240 On: Mon, 16 Dec 2013 07:18:59
2416
2416
FIG. 2. XRD patterns taken on the GaN nanowires using different catalysts:
a In, b Fe, and c Ni.
FIG. 1. Typical SEM images of bulk GaN nanowires with different catalysts:
a In, b Fe, and c Ni.
spectively. These nanowires cross each other and are randomly distributed on the substrates. The diameters of the
nanowires range from 20 to 100 nm and with length up to
hundreds of micrometers.
XRD patterns in Figs. 2a2c revealed the overall crystal structure of the GaN nanowires. XRD patterns can be
indexed to a hexagonal wurtzite structure with lattice constants of a0.318 nm and c0.518 nm, which agree well
with the reported values of GaN bulk crystals.25 Miller indices are indicated on each diffracted peak. The reflection
peaks of 100, 002, 101, 102, 110, 103, 112, and
201 correspond to the hexagonal wurtzite GaN phase.
These XRD patterns Figs. 2a2c indicate that the
samples are hexagonal wurtzite GaN phase.
Further structural information about the GaN nanowires
was provided by TEM images. The wool-like products
stripped from the alumina plate were pulverized in ethyl alcohol, and then dispersed onto a carbon film on a copper
grid. The highly magnified TEM image in Fig. 3a shows
that the average diameter of an individual GaN nanowire is
approximately 40 nm with a uniform diameter. Along the
Redistribution subject to AVS license or copyright; see http://scitation.aip.org/termsconditions. Download to IP: 115.145.166.240 On: Mon, 16 Dec 2013 07:18:59
2417
2417
FIG. 3. a TEM image of two GaN nanowire. The image shows the nanowire with a uniform diameter. b The selecting area electron diffraction
pattern of an individual GaN nanowire. c HRTEM image of an individual
0 zone axis. The 002
GaN nanowire. The image was recorded along 01
direction is indicated by an arrow. The fringe spacing of about 0.259 nm
between arrow heads corresponds to the distance between two 002 planes.
The scale bar corresponds to 2.5 nm.
FIG. 4. a Typical SEM image of a GaN nanowire terminated with a nanoparticle at the tip, b EDS spectrum of the nanoparticle A, and c EDS
spectrum of the wire stem B.
substrate, Ga vapor, and N atoms. In the same way, Fe clusters and Ni clusters can be formed by aggregation of Fe or Ni
atoms on the surface of the substrates. Very small miscible
droplets of FeGa melting point about 1020 C and NiGa
melting point about 1200 C may be generated rapidly and
liquefy at high temperature in our case. The In Fe, Ni
GaN alloy droplet affixed to the whisker tip forms an inter-
Redistribution subject to AVS license or copyright; see http://scitation.aip.org/termsconditions. Download to IP: 115.145.166.240 On: Mon, 16 Dec 2013 07:18:59
2418
2418
show any GaN nanowires but many small plates and hillocks. The main reason may be the poor solubility between
gold and nitrogen,28 and nitrogen may not be transported
effectively to the liquid/solid growth interfaces of nanowires.
In our experiment, ultrafine AuGa eutectic liquid droplets
formed at about 450 C by alloying and then melting reaction between the Au clusters and Ga vapor Au clusters was
formed by aggregation of Au atoms on the substrate at high
temperature. The Ga vapor dissolved into the AuGa liquid
droplet. Because of the poor solubility between Au and N
atoms, N atoms may not be transported effectively to the
liquid/solid growth interfaces of nanowires. Based on the
above analysis, no GaN nanowires were prepared when Au
was used. Au does not have any catalytic activity in this
system.
Size-dependent melting-point depression is an important
phenomenon for particles of nanometer size. This is due to
the increased influence of the surface atoms as the ratio of
surface/bulk atom increases. As the particles size decrease,
the value of the melting point decreases from the bulk value.
Size-dependent melting point depression has been confirmed
experimentally over a broad range of particle sizes by using
a variety of methods.2934 In our experiment, we also note
that the experimental temperatures of prepared GaN nanowires using Fe 1000 C and Ni 1050 C nanoparticles
serving as catalyst are below the solidus temperatures in the
case of NiGa 1200 C and FeGa 1020 C. The reason
mostly is that the melting point of nanostructures is smaller
than that of a bulk material value, and is lower for smaller
nanostructures. The aggregation of Fe Ni atoms on the sur-
Redistribution subject to AVS license or copyright; see http://scitation.aip.org/termsconditions. Download to IP: 115.145.166.240 On: Mon, 16 Dec 2013 07:18:59
2419
2419
Redistribution subject to AVS license or copyright; see http://scitation.aip.org/termsconditions. Download to IP: 115.145.166.240 On: Mon, 16 Dec 2013 07:18:59