phys. stat. sol. (b) 241, No. 12, 2775 2778 (2004) / DOI 10.1002/pssb.

200404989

Gallium nitride nanowires with a metal initiated

metal-organic chemical vapor deposition (MOCVD) approach
Sang-Kwon Lee*, 1, Heon-Jin Choi2, Peter Pauzauskie3, Peidong Yang3, Nam-Kyu Cho4,
Hyo-Derk Park4, Eun-Kyung Suh1, Kee-Young Lim1, and Hyung-Jae Lee1
1
2
3
4

Dept. of semiconductor science and technology, Chonbuk National University, Korea

Division of material science and technology, Korea Institute of Science Technology, Korea
Dept. of chemistry, University of California at Berkeley, CA 94720, USA
Nano-mechatronics research center, Korea Electronics Technology Institute, Korea

Received 26 June 2004, accepted 5 July 2004

Published online 2 September 2004
PACS 73.63.Bd, 81.07.Bc, 81.15.Gh
We have studied structural and electrical properties of one dimensionally grown single crystalline gallium
nitride (GaN) nanowires (NWs) for nanoscale devices using a metal-initiated metal-organic chemical vapor deposition (MOCVD). GaN nanowires were formed via the vapor-liquid-solid (VLS) mechanism with
gold, iron, or nickel as growth initiators and were found to have triangular cross-sections with widths of
15 200 nm and lengths of 5 20 m. TEM confirmed that the nanowires were single crystalline and
were well oriented along the [210] or [110] direction on substrate depending on the metal initiators. For
electrical transport properties of un-doped GaN nanowires, the back-gated field effect transistors (FET)
were also fabricated by standard e-beam lithography. In our electrical measurement, the carrier concentration and mobility were 2 4 1018 cm3 and 60 70 cm2/V s, respectively.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Introduction

In recent years, one-dimensional (1D) semiconductor nanowires have received a remarkable amount
attention as building blocks for future nanoscale devices [1]. 1D semiconductor nanowires provide a
good system to investigate the dependence of electrical and thermal transport or mechanical properties
on dimensionality and size reduction or quantum confinement [1 2]. They would play an important role
as both interconnect and functional units in fabricating electronic, optoelectronic, electrochemical, and
electro mechanical devices with nanoscale dimensions. Among the various semiconductor nanowires,
one of the wide-bandgap semiconductors, gallium nitride is promising candidate for short wavelength
opto-electronic devices, high power and high temperature operation devices due to its novel intrinsic
properties such as high melting point, high carrier mobility, and high electrical breakdown field [3].
Recently, there have been several reports on the synthesis and fabrication of GaN nanowires by laserassist catalytic growth, chemical vapor deposition (CVD), and hydride vapor phase epitaxy (HVPE)
method [4 6]. In this article, we report the synthesis and electrical characterization of GaN nanowires
using a metal-initiated MOCVD approach for growing of single crystalline GaN nanowires.

2 Growth and device fabrication

Trimethylgallium (TMG) and ammonia source materials were used as Ga and N precursor. Thermally
evaporated metals such as Ni, Fe, and Au (2 10 nm thick) have been used as initiators for vapor-liquid*

Corresponding author: e-mail: sk_lee@chonbuk.ac.kr, Phone: +82-63-270-3973, Fax: +82-63-270-3585

2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

2776

S.-K. Lee et al.: Gallium nitride nanowires with a metal initiated MOCVD approach

vapor
nanowire
metal
catalysts

Fig. 1 (online colour at: www.pss-b.com) Schematic illustration showing the growth of a nanowire via the vapor-liquid-solid mechanism.

alloy
liquid

solid (VLS) nanowires. As shown in Fig. 1, a typical VLS process starts with the dissolution of gaseous
reactants into nanosized liquid droplets of a catalyst metal, followed by nucleation and growth of singlecrystalline rods and then wires. The 1D growth is mainly induced essentially unchanged during the entire
process of wire growth. Yang and coworkers have well investigated and confirmed this VLS growth
mechanism by observation the in-situ growth of Ge nanorods and GaN nanowires within the TEM
chamber equipped with a temperature-controllable stage [7 8]. GaN nanowires (NWs) were grown on a
sapphire substrate and oriented predominantly along the [210] or [110] direction on c-plane and a-plane
sapphire substrates. The VLS growth of GaN NWs occurred at a substrate temperature of 800 1000 C.
Nitrogen, used as a carrier gas, was percolated through the TMG precursor and coupled with a second
nitrogen line. The detailed growth condition can be found in reference [2]. Field-emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD) were used to investigate the nanowire length,
shape overall substrate coverage, and the structure of GaN NWs on a substrate. For the electrical measurement, GaN nanowires were prepared on a highly doped Si substrate, which acts as a back-gate of field
effect transistor (FET) with a 0.4 m-thick thermally grown oxide layer on the top. Source and drain
electrodes (Ti/Au = 40/70 nm) were deposited via thermal evaporation on the patterned substrate after
standard electron-beam lithography (EBL) process. The electronic transport measuring drain current (Id),
source-drain voltage (Vds), and gate voltage (Vg) was performed using a back-gated FET configuration
with three-probe scheme.

Results and discussion

From FE-SEM observation the nanowires have diameters of 15 100 nm and lengths of 5 10 m. We
have observed that there are preferred nanowire orientations on substrate, indicating that the epitaxial

Fig. 2 (a) Lattice resolved high resolution TEM image of the nanowire. (b) TEM image of a GaN nanowire with a
Au metal alloy droplet on its tip. Insets are electron diffractions taken along [001] zone axis. The lower inset is the
same electron diffraction pattern, but purposely defocused to reveal the wire growth direction. (c) FESEM image of
the GaN nanowires grown on Au coated c-plane sapphire substrate. Inset shows a nanowire with the triangular crosssection.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

phys. stat. sol. (b) 241, No. 12 (2004) / www.pss-b.com

2777
Fig. 3 (online colour at: www.pss-b.com)
Current voltage measurement at different
gate voltage for the GaN nanowire.

-6

Drain Current ( x 10 A)

0
G ate v oltage
-20V
-10V
0V
+10V
+20V

-2

-4
-6

-4

-2

Source-Drain V oltage (V)

growth of nanowires on a sapphire substrate is possible. GaN nanowires were dispersed on transmission
electron microscopy (TEM) grids for structural and compositional analysis. Figure 2a shows a highresolution TEM image of the nanowire, indicating exactly the (100) lattice plane perpendicular to the
wire axis. A TEM image of an individual GaN nanowire, where a gold metal droplet can be clearly seen
on its tip, is shown in Fig. 2b. The images of FESEM shown in Fig. 2c indicate the overview coverage of
GaN nanowires grown on a c-plane sapphire substrate with a triangular cross-section. Extensive TEM
characterization reveals that the [210] direction is the predominant growth direction, but we have also
observed that for a small faction of the nanowires the wire axis can be normal to the (014) or (112) plane
and other high-index lattice planes. Iron and nickel were also used as metal initiators for GaN nanowire
growth. For nanowires grown on a Fe-coated sapphire substrate, the diameter and length are quite similar
to those grown on Au-coated sapphire substrate. However, we found the predominant nanowire growth
electrical transport properties were direction to be [110] instead of [210]. For GaN NWs grown on Nicoated sapphire substrate, we observed triangular cross-sections with the similar size to those grown on
Au- and Fe-coated sapphire substrate from the SEM image of GaN NWs. TEM images and electron
diffraction date showed that the NWs were also single crystalline with the wire axis oriented along the
crystallographic [210] direction, same as those Au initiated GaN NWs. The electrical properties of
MOCVD GaN nanowires were investigated using back-gated three-probe scheme. Figure 3 shows the
current voltage (Id Vsd) characteristics of MOCVD GaN NW at different gate voltage (from +20 V to
20 V with 10 V step). The current versus source-drain voltage and gate voltage were measured the
nanowire conductance increases for Vg greater than zero and decreases for Vg less than zero (see Fig. 3),
indicating that these nanowires have n-type of dopants. Inset in Fig. 3 shows FESEM image o f the GaN
nanowire connected with two electrodes for the electrical transport measurements using conventional ebeam lithography. From many bulk GaN studies [9], this n-type behavior of as-grown un-doped GaN
EC-(30-34) meV

EC-(20-25) meV

EC
ON

Si
3.4 eV

200 meV (Mg)

EV

Fig. 4 (online colour at: www.pss-b.com)

Schematic energy band diagram, shown the
energy level of oxygen and silicon from conduction band.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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S.-K. Lee et al.: Gallium nitride nanowires with a metal initiated MOCVD approach

nanowires is due to the contribution of nitrogen vacancies or oxygen impurities as shown in Fig. 4. The
capacitance (C 2 0L/ln (4h/a) where h is the dielectric thickness, r is the radius of nanowire can be
also calculated with a quasi-circular cross-section approximation. The carrier mobility () for our
nanowires is on the order of 60 70 cm2/V s. In addition, the carrier concentration (ne = Q/e 0.433a2L) is
estimated to be 2 4 1018 cm3. We also observed that some of MOCVD grown single crystalline GaN
NWs had no gate effect even though high voltage was applied into the back gate. We believe that it
might be due to the high concentration of impurities such as oxygen and metal impurities during the
growth.

4 Conclusion
We report here the production of single crystalline GaN nanowires using a MOCVD process for the first
time. One unique feature of these MOCVD nanowires is that they are well-facetted and most of them
have triangular cross sections. Electrical transport measurement indicates that our GaN nanowires have
high electron mobility. The advantage of this MOCVD process is that it can be easily scaled up to wafer
scale production and would enable doping with conventional precursors.
Acknowledgement This paper was supported (in part) by research funds of Chonbuk National University.

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2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim