J. Phys. Chem.

C 2008, 112, 1882118824

18821

Catalyst-Free Growth of Well Vertically Aligned GaN Needlelike Nanowire Array with
Low-Field Electron Emission Properties
Chaotong Lin, Guanghui Yu,* Xinzhong Wang, Mingxia Cao, Haifeng Lu, Hang Gong,
Ming Qi, and Aizhen Li
State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of microsystem and
information technology, Chinese Academy of Sciences, Shanghai 200050, Peoples Republic of China
ReceiVed: September 10, 2008; ReVised Manuscript ReceiVed: October 7, 2008

An array of high-density, vertically aligned GaN nanowires is fabricated through thermal evaporation of
GaN powder with the assistance of HCl gas. All GaN nanowires with needlelike tips are well-aligned with
the axis direction perpendicular to the substrate without the use of catalysts. A possible growth mechanism
of the vertical GaN nanowires array is proposed. Furthermore, field emission measurement shows that the
obtained GaN nanowires array has a lower turn-on field of 2.1 V/m, and the current density is about 1
mA/cm2 at a bias field of 4.5 V/m, which means such GaN nanowires are good candidates for large area
and uniform flat display applications.
Introduction
GaN, an important direct band gap semiconductor material,
has been widely used in UV or blue emitters and hightemperature/high-power electronic devices. GaN is also a
promising material for field emitters because of its low electron
affinity as well as its excellent physical and chemical stabilities.
Since one-dimensional semiconductor nanowires possess unique
properties, such as a high surface-to-volume ratio and quantum
confinement effect, in recent years, single-crystalline GaN
nanowires have already shown their ability in the realization of
nanoscale devices: blue light emitting diodes,1 short-wavelength
ultraviolet nanolasers,2 gas sensors,3 field effect transistors,4
Schottky diodes,5 and field emitters.6,7 To date, several methods,
such as carbon-nanotube-confined reactions,8 laser ablation,9,10
and catalytic chemical vapor deposition,11,12 have been reported
to grow GaN nanowires, but the obtained nanowires are always
disordered. Nevertheless, for commercial device application in
the future, fabrication of well-ordered nanostructures with high
density is very important because they can be effectually
incorporated into devices.13,14 Thus, preparation of a GaN
nanowire array with high alignment has been attracting considerable interest, and various approaches have been developed.
Vertically aligned and faceted GaN nanorods have been
produced by Parijat et al.15 using a catalyst-free templated
approach that employs a silicon dioxide mask fabricated using
a porous anodic alumina template. Quasi-aligned GaN nanowire
arrays have been fabricated by B. Liu et al.16 via a thermal
evaporation of the starting reactants Ga2O3/GaN. G. Wang et
al.17 report the growth of well-aligned and vertically oriented
GaN nanowires on (1-102) r-plane sapphire by metal organic
chemical vapor deposition (MOCVD). Q. Li et al.18 reported a
route to ultrahigh-density and highly aligned single-crystalline
GaN nanowires on sapphire by employing ultrathin Ni catalyst
films with submonolayer thicknesses. However, a catalyst or
pattern has been used in the above-mentioned papers. The
existence of the catalysts or the patterns induces the associated
concerns of contamination caused by the catalyst metal or
* Corresponding author.

decomposed products from the foreign patterns, which may be

prohibitive for many device applications.
In this letter, we have demonstrated a novel method to
fabricate high-density, well-aligned GaN needlelike nanowire
arrays over large areas without any catalyst or pattern. Uniformly
single-crystal GaN nanowires have been prepared through a
thermal evaporation of GaN powder with the assistance of HCl
gas. The formed nanowires with needlelike tips show no lateral
growth but are vertically aligned. It is expected that the sharp,
needlelike tips enable such GaN nanowires to exhibit better
electron emission properties due to their high aspect ratio and
small tip radii of curvature, which could provide a sufficiently
high geometric enhancement factor. Therefore, low-field electron
emission from the GaN nanowires in this work is measured.
Experiments
The GaN nanowires were prepared in a homemade chemical
vapor deposition system, which could be used for 3-in. wafer
growth. There were two vertically placed quartz boats for
loading the source and the substrate inside the chamber. The
vertical distance between the source and the substrate is about
1 cm. A 3-m-thick GaN film was deposited on a sapphire
substrate by MOCVD. The full width at half-maximum values
of high-resolution X-ray diffraction rocking curves for this GaN
film were 231 arc sec (002 reflection) and 328 arc sec (102
reflection), respectively. Then such substrate was transferred
into the growth chamber. For the growth of GaN nanowires,
GaN powder was utilized as the source and 1000 sccm N2 was
used as the carrier gas in the whole experimental process. When
the temperature reached 780 C, 50 sccm pure HCl gas was
introduced. After one hour of growth, the furnace was cooled
to room temperature, and a light white layer was found on the
surface of the substrate. As a result, the straight and well aligned
GaN nanowires with high density were uniformly grown in GaN
template, as observed in Figure 1.
Field-emission scanning electronic microscopy (SEM) and
energy dispersive X-ray spectroscopy (EDX) were employed
to characterize the morphological features and composition of
the resulting GaN materials. The crystal structures and growth

10.1021/jp808034m CCC: $40.75 2008 American Chemical Society

Published on Web 11/06/2008

18822 J. Phys. Chem. C, Vol. 112, No. 48, 2008

Lin et al.

Figure 2. EDX analysis (a) and XRD pattern (b) recorded from GaN
nanowires.

Figure 1. (a) Top view, (b) 45 side view and (c) cross-sectional view
field-emission SEM images of the obtained GaN nanowire array on
the thin GaN film template.

orientation of the GaN nanowires were investigated by X-ray

diffraction (XRD). The further structural characterizations of
GaN nanowires were performed using high-resolution transmission electron microscopy (TEM) and fast Fourier transform
(FFT) pattern analysis. Field emission measurements for the
GaN nanowires were conducted in a vacuum chamber at a
pressure of about 8 10-8 Torr at room temperature.
Results and Discussion
Figure 1 exhibits the (a) top view, (b) 45 side view, and (c)
cross-sectional view SEM images of the GaN nanowire array
on a thin GaN film template. Figure 1a shows the GaN
nanowires are in high density and uniform. As can be seen from
Figure 1b and c, the GaN nanowires with needlelike tips show
good alignment with the axis direction perpendicular to the
substrate. Moreover, the GaN nanowires possess quite straight
morphology and have a clean surface without any particles. The
diameters of the nanowires are about 80-100 nm, and their
lengths are mainly approximately 1.5 m.
Figure 2a shows the EDX spectrum of the specimen. It can
be seen that the product consists of only Ga and N elements
and that the atomic composition ratio of Ga/N is about 1:1,
which means pure GaN material was obtained. Figure 2b shows
the XRD pattern of as-synthesized GaN nanowire arrays. Two
diffraction peaks from the (0002) and (0004) planes of the

Figure 3. (a) Low magnification TEM image of the needlelike GaN

nanowire, and (b) high-resolution TEM image of a single-crystalline
wurtzite structure GaN nanowire and its corresponding FFT pattern
(inset).

wurtzite-type hexagonal GaN are observed, which indicates that

the formed GaN nanowires are preferentially oriented in the
c-axis direction.
Figure 3 displays the TEM images of the GaN nanowires
scratched from the substrate. The low-magnification TEM image
for a single GaN nanowire is shown in Figure 3a. It can be

GaN Needlelike Nanowire Array

Figure 4. Side view (45) field-emission SEM images of the GaN

nanowires grown at different growth times (under otherwise identical
growth conditions) of (a) 3, (b) 20, and (c) 60 min.

observed that the GaN nanowires with sharp needlelike tips have
a smooth surface. The high-resolution TEM image near the tip
of the nanowire confirms the single-crystal structure and the
c-axis growth direction of the GaN nanowires, as shown in
Figure 3b. The [0001] direction is parallel to the long axis of
the nanowires, indicating that the [0001] direction is the growth
direction of the GaN nanowires. The inset in Figure 3 b displays
the corresponding FFT pattern of the high-resolution TEM
image that indicates the GaN nanowires are preferentially
oriented in the c-axis direction, as well, and are indexed to the
reflections of the wurtzite structure, which is consistent with
the XRD result. The diffuse circular rings in the FFT pattern
are due to the presence of the underlying carbon membrane used
to load the sample during the TEM measurement.
To observe the evolution of the GaN nanowires growth,
further experiments at different growth times but under other
identical growth conditions were analyzed by SEM images.
Figure 4a shows that GaN materials were first nucleated as
nanodroplets with abrupt tips on the GaN template at the growth
time of 3 min. Then the nanodroplets turn into nanocones when
at a growth time of 20 min, as shown in Figure 4b. The vertical
direction of the GaN nanocones, which is the preferred growth
direction, develops faster than the lateral direction on the

J. Phys. Chem. C, Vol. 112, No. 48, 2008 18823

nanocone sides at the low growth temperature.19,20 Meanwhile,
only GaN powder and no additional ammonia gas introduced
into the experimental process makes for the growth conditions
under a relatively low V/III ratio, which has been reported to
result in the vertical growth of GaN.15,21,22 Therefore, the aligned
vertical GaN nanowires are found to be formed after 60 min of
growth, as shown in Figure 4C with the same specimen as that
in Figure 1. It should be mentioned that the elimination of HCl
gas or the GaN template in the experiments leads to the
deposition of only a few GaN materials. Without the assistance
of the HCl gas, the amorphous GaN powder source thermally
evaporated at 780 might produce deficient precursors for the
GaN nanowires growth. Furthermore, it is known that there is
a large mismatch of lattice parameters existing between the GaN
and sapphire substrate, and the surface of the bare sapphire
substrate without any treatment is not conducive to GaN material
nucleation. The GaN template grown by MOCVD at the early
stage could serve as nucleation sites for subsequent homoepitaxial growth of GaN nanowires with good vertical alignment.
Therefore, the HCl gas and GaN template are key roles for the
growth of GaN nanowires in these experiments. On the basis
of the above results, we propose a possible growth mechanism.
During the process of thermal evaporation of the GaN powders
under the atmosphere of the HCl gas, GaCl and NH3 are
produced in a direct reaction between the amorphous GaN
powders and the HCl gas. The GaCl reacts with NH3 to grow
GaN nanowires on the GaN template at the low growth
temperature.
The field emission characteristics from the synthesized GaN
needlelike nanowire array were studied. The field emission
measurement for the GaN nanowires was performed in a vacuum
chamber with a pressure of 8 10-8 Torr. The measurements
were made by adjusting the voltage from 1 to 1300 V at a fixed
distance of 270 m between the phosphor screen (anode) and
the sample (cathode). The dependence of field emission current
density on the applied electric field is shown in Figure 5a. The
turn-on field, which is defined as the field required to detect an
emission current density of 1 A/cm2, is evaluated to be about
2.1 V/m. The emission current density of the GaN nanowires
array reaches 1 mA/cm2 at a bias electric field of 4.5 V/m.
The turn-on field and threshold field are much lower than the
previously reported values of GaN nanowires without needlelike
tips.6,7,12 It is believed that the excellent electron emission
property is mainly attributed to the geometrical configuration
of the sharp needlelike tip, which can provide sufficiently high
geometrical enhancement factors. The corresponding FowlerNordheim (F-N) plots are shown in Figure 5b. The variation
of ln(I/E2), with 1/E being a nearly straight line, indicates that
the field emission process from the GaN nanowires is a barrier
tunneling, quantum mechanical process (F-N tunneling).23,24
According to the F-N electron emission theory, emission
current can be expressed as

J ) A(E)2 () exp(-B32 E)
where A ) 4.43 10-22 (AV-2 eV), B ) 6.83 109 (VeV-3/2
V m-1), is a field enhancement factor dependent on emitter
geometry, and is the work function (GaN ) 4.1 eV). From
the slope of the F-N plots, was estimated to be 2835.
Compared with some other GaN nanostrures,25-27 the vertically
aligned GaN needlelike nanowires show a relatively larger
value.
Conclusions
We have fabricated a high-density, vertically aligned GaN
nanowire array through thermal evaporation of GaN powder

18824 J. Phys. Chem. C, Vol. 112, No. 48, 2008

Lin et al.
Acknowledgment. The authors thank Tao Feng and Lifeng
Lin from East China Normal University for assistance in field
emission measurement. This work was supported by the Natural
Science Foundation Project (05ZR14139) and International
Cooperation Project (055207043) of the Shanghai Government
and National Science Foundation Project (60676060).
References and Notes

Figure 5. (a) Electron field emission current density versus applied

electric field curve for the GaN needlelike nanowires and (b) the
corresponding Fowler-Nordheim plot.

with the assistance of HCl gas. It is noted that this method is

free of foreign catalysts and pattern. Field-emission SEM images
show that the GaN nanowires with needlelike tips are wellaligned with the axis direction perpendicular to the substrate.
The XRD pattern and high-resolution TEM image indicate that
the obtained GaN nanowires have high single-crystal quality
with preferential growth along the [0001] direction. The possible
growth mechanism of the vertical GaN nanowires array is
discussed. Field emission measurement shows that the turn-on
field of GaN nanowires is 2.1 V/m and the current density is
about 1 mA/cm2 at a bias field of 4.5 V/m, which indicates
such GaN nanowires are good candidates for large area and
uniform flat display applications. It is also believed that the good
alignment allows the GaN nanowire arrays to be extensively
applied in future nanodevice design and integration.

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