Growth of semiconductor gallium nitride nanowires with different catalysts

Jun Zhang and Lide Zhang

Citation: Journal of Vacuum Science & Technology B 21, 2415 (2003); doi: 10.1116/1.1625968
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Growth of semiconductor gallium nitride nanowires with different catalysts

Jun Zhanga) and Lide Zhang
Department of Physics, Yantai University, Yantai 264005, Peoples Republic of China

Received 19 September 2002; accepted 22 September 2003; published 24 November 2003

Semiconductor gallium nitride nanowires had been prepared by different catalysts using chemical
vapor deposition. In, Fe, Ni, and Au nanoparticles were used in the growth of semiconductor GaN
nanowires. Preliminary results indicate that the In, Fe, and Ni are efficient catalysts in the
large-scale synthesis of GaN nanowires and the size of the nanowires depends on the size of catalyst
particle. The nanowires have a diameter of 20100 nm and a length of up to several hundreds of
micrometers. The growth of GaN nanowires obeys the vaporliquidsolid mechanism. However, no
GaN nanowires were observed on the substrate when Au was used. It may be because of the poor
solubility between Au and nitrogen. Au does not have any catalytic activity in this system. 2003
American Vacuum Society. DOI: 10.1116/1.1625968

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

Author to whom correspondence should be addressed; electronic mail:

jzhang@ytu.edu.cn

2415

J. Vac. Sci. Technol. B 216, NovDec 2003

wires were observed on the substrate according to SEM

analyses when Au nanoparticles were used in this system.
Therefore, the adoption of catalyst in the synthesis may provide a possible way to control the growth process of the
wires.
II. EXPERIMENT
Four alumina plates as substrates were rinsed with deionized water before use. A layer of metal In, Fe, Ni, and Au
about several tens of nanometers in thickness was evaporated onto one side of every alumina plate under high
vacuum (2105 Torr), respectively. About 2 g of high
pure metal Ga purity 99.999% was first put at the center of
one of four alumina crucibles. One of the four substrates was
placed at the downstream end of the alumina crucible and the
crucible was transferred into a quartz tube placed in a furnace. The quartz tube was degassed under vacuum and
purged with ammonia. Ammonia was introduced into the
quartz tube through a mass-flow controller at rates of 400
sccm. The temperature of the furnace was quickly increased
to 950 C Fe: 1000 C; Ni: 1050 C, Au: 1000 C, respectively from room temperature. The temperature was kept for
2 h under a constant flow of ammonia. After the quartz tube
was cooled down to room temperature, the ammonia flow
was turned off. A layer of light-yellow wool-like products
was found on the surface of the alumina plate when In Fe
and Ni was used as a catalyst. However, no wool-like product on the substrate was found when Au was used as catalyst.
The morphology and structure of the as-prepared products
were measured by SEM JEOL JSM-5610LV, transmission
electron microscopy TEM JEM-200CX, high-resolution
TEM HRTEM JEOL-2010, and x-ray diffraction XRD
Philips PW 1710 with Cu K radiation.
III. RESULTS AND DISCUSSION
Before the SEM observation, Au metal was evaporated on
the surface of the specimens to form a conducting film to
avoid electrostatic charging. Typical SEM images of the
three substrate surfaces in Figs. 1a1c indicated that the
reaction of Ga and NH3 with In, Fe, and Ni as catalysts
produced a high yield of nanometer wirelike structures, re-

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2003 American Vacuum Society

2415

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J. Zhang and L. Zhang: Growth of semiconductor gallium nitride nanowires

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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

nanowire, the selected area electron diffraction patterns

shown in Fig. 3b are essentially identical, revealing that
the nanowire is a single-crystal hexagonal wurtzite GaN. The
HRTEM image shown in Fig. 3c of an individual GaN
0 zone axis. The clear
nanowire was recorded along the 01
lattice fringes in this image indicated a single crystal structure of the nanowire. In this image, the 002 direction is a
growth direction in the GaN nanowire.
There are several possible models for the growth of conventional crystal whiskers or nanowires, the helical dislocation, VLS, solutionliquidsolid, and an oxide-assisted
mechanism. It is well known that the presence of a liquid
drop is essential for the effective operation of the VLS
mechanism. The solidified spherical droplets at the tip of the
nanowires are commonly considered to be evidence for the
operation of the VLS mechanism, which is in agreement with
our experimental conditions and observed results. A typical
small-scale SEM image in Fig. 4a of a single nanowire
confirmed further details of VLS growth mechanism in GaN
nanowires. This image showed a long nanowire terminating
in a nanoparticle at the tip. The energy dispersive x-ray spectroscopy EDS JEOL EX-54145 JMH analyses indicated
that the nanoparticle on the tip Fig. 4b consisted mainly
of Ni, Ga, and N, but the nanowire Fig. 4c was only
composed of Ga and N. The molecular ratio of Ga/N of the
nanowire calculated from the EDS quantitative analysis data
was close to that of a bulk GaN crystal. SEM and EDS
analyses altogether indicated that the In Fe, Ni only functioned as catalyst in GaN nanowires growth. The growth of
GaN nanowires obeys the VLS mechanism.11,26 The gas reaction of Ga vapor with ammonia can be expressed as
follows:

J. Vac. Sci. Technol. B, Vol. 21, No. 6, NovDec 2003

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J. Zhang and L. Zhang: Growth of semiconductor gallium nitride nanowires

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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.

2Ga g 2NH3 g 2GaN s 3H2 g .

Three well-defined stages shown in Fig. 5 of VLS growth

mechanism of GaN nanowires may be clearly identified: 1
the formation of metal alloy, 2 crystal nucleation, and 3
axial growth.
1 The formation of metal alloy Fig. 5I. During the
heating process of the reaction, NH3 decomposes stepwise to
NH2 , NH, and N, and that liquid Ga will vaporize. Ultrafine
InGa eutectic liquid droplets formed at about 20 C by
alloying and then melting reaction between the In clusters
formed by aggregation of In atoms on the surface of the

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-

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J. Zhang and L. Zhang: Growth of semiconductor gallium nitride nanowires

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FIG. 5. Schematic diagram illustrating

the catalytic synthesis of nanowires.
Reactant material, which is preferentially absorbed on the catalyst, is
added to the growing nanowire at the
catalystnanowire interface.

face with the growth surface. Another interface also exists

between the droplet and the vapor phase.
2 Crystal nucleation Fig. 5II. As the GaN composition of the In Fe, NiGaN alloy increases, it enters a
biphasic region In Fe, NiGaN alloy and GaN crystal.
This is where nanowire nucleation starts. The volume of the
In Fe, NiGaN alloy droplets increases sequentially, and
Ga atoms and ammonia molecules in the vapor phase decompose preferentially at the vaporliquid interface, depositing
the constituent element or elements of the crystal phase
into solution in the liquidflux droplets. In Fe, NiGaN
supersaturates then supports the growth of GaN nanowires at
the liquidsolid interface. The system selectively places the
face giving the lowest liquidsolid interfacial energy at the
liquidsolid interface. So the catalyst In Fe and Ni defines
the diameter of the structure and localizes the reactant at the
end of the growing nanowire much like a catalyst in biopolymerization. The liquid catalyst alloy cluster serves as a
preferential site for absorption of reactant, when supersaturated, the nucleation site for crystallization.
3 Axial growth Fig. 5III. Once the GaN nanocrystal
nucleates at the liquid/solid interface, further condensation/
dissolution of Ga and N vapor into the system will increase
the amount of GaN crystal precipitation from the In Fe,
NiGaN alloy. GaN rapid growth on this crystal facet at
the lowest liquidsolid interfacial energy produces the wire
morphology. Consequently, secondary nucleation events are
efficiently suppressed, and no solid/liquid interface will be
created. The existing interface will then be pushed forward
or backward to form a nanowire. While the In Fe, Ni
GaN supersaturation continues, preferential onedimensional GaN growth occurs in the presence of reactant
as long as the catalyst remains liquid. After the system cools,
the growth of nanowires is stopped and the alloy droplets
solidify on the nanowire tips.
As an important catalyst, Au has been used extensively
for the growth of IIVI and IIIV nanowires.1719,26,27 For
example, Duan and Lieber17,18 successfully prepared GaAs
nanowires using Au nanoparticles as catalyst. Yang and his
co-workers26,27 synthesized Ge and Si nanowires using Au
nanoparticles as catalysts. Here, we attempted to use Au
nanoparticles in the growth of GaN nanowires. However,
after the reaction of metalgalliumvapor and ammonia, no
nanowires were observed on the substrate according to SEM
image analyses. The magnified SEM image in Fig. 6 does not

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-

FIG. 6. SEM image of surface of the substrate when Au was used.

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2419

J. Zhang and L. Zhang: Growth of semiconductor gallium nitride nanowires

face of the substrate formed Fe Ni nanoclusters. Melting

temperature of Fe Ni nanoclusters is smaller than that of Fe
Ni bulk material. The solidus temperatures in the case of
NiGa and FeGa also decrease from that of the bulk values. These Ga particles could generate sufficient vapor to
condense onto the neighboring Fe or Ni nanoclusters. Very
small miscible droplets of FeGa NiGa were generated
rapidly and liquefy, and formed Fe NiGaN alloy with
reaction of N atoms. With an increasing amount of Ga and N
atoms, the volume of the Fe NiGaN alloy droplets increases. Fe NiGaN supersaturates, then supports the
growth of GaN nanowires at the liquidsolid interface.
Therefore, the experimental results show that the experimental temperatures are below the solidus temperatures in the
case of Ni and Fe. Based on the above experimental result
and analysis, it is concluded that the growth temperatures for
fabrication of one-dimensional nanowires through the VLS
mechanism are not high enough to support the existence of
the proposed liquid phase of bulk. However, size-dependent
melting-point depression in the growth one-dimensional nanomaterials using the VLS mechanism is a rather complicated process, and many issues remain open. Further detailed
work is needed to clarify the solidus temperatures for the
growth of one-dimensional nanostructures through the VLS
mechanism.
IV. CONCLUSION
In summary, the hexagonal wurtzite GaN nanowires with
diameters between 20 and 100 nm and lengths up to several
hundred micrometers were fabricated when metal In, transition metal Fe and Ni acted as a catalyst. However, no
nanowires were observed on the substrate when Au was
used. This indicates that use of a catalyst is an important
factor in the fabrication of quasione-dimensional nanostructured materials. The adoption of a proper catalyst in the synthesis via VLS crystal growth mechanism may both result in
a higher yield, and provide a possible way to control the
growth process of the wires which are critical for their potential application in nanoscale optoelectronic devices.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China Grant No. 60277023. The authors
gratefully acknowledge Dr. X. F. Wang at Rice University
USA and Dr. T. Gao at Institute of Physics China for
fruitful discussion and valuable suggestion.

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