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Diamond & Related Materials 17 (2008) 1780 1784

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Fabrication of gallium nitride nanowires by nitrogen plasma

Wen-Chi Hou a , Liang-Yih Chen b , Franklin Chau-Nan Hong a,
a

Department of Chemical Engineering and Center for Micro/Nano Science and Technology,
National Cheng Kung University, 1 University Road, Tainan 70101, Taiwan
Department of Chemical Engineering, National Taiwan University of Science and Technology,
43 Keelung Road, Section 4 Taipei 106-07, Taiwan
Available online 13 February 2008

Abstract
The growth of high-quality straight GaN nanowires has been achieved by the reaction of Ga vapor with N2 plasma in a horizontal furnace with
dielectric barrier discharge (DBD). The diameters of GaN nanowires range from 70100nm, depending on the particle sizes of Au catalysts, and
their lengths are up to several micrometers. On the other hand, GaN nanowires of vermicular-shape were observed on the substrate when using N2
gas reactant without igniting the discharge. High-resolution transmission electron microscopy (TEM) analysis reveals the formation of high
crystalline quality single-crystal GaN nanowires with elongation along [100] direction. The results demonstrate that DBD-type N2 plasma
effectively induces high-quality growths of GaN nanowire single crystallites using the furnace.
2008 Elsevier B.V. All rights reserved.
Keywords: Gallium nitride (GaN); Plasma CVD; Nanostructures; Nanofibers

1. Introduction
III-nitride semiconductor materials have attracted worldwide
enthusiastic interest in the past decade due to their great potentials for many important applications [1,2]. Gallium nitride
(GaN), owing to its direct and wide band gap of 3.4eV at room
temperature and relatively large exciton binding energy of
28meV, is highly promising for many important applications
such as blue light emitting diodes [3], laser diodes [4], detectors,
high-speed field effect transistors, high-temperature electronic
devices [5,6], etc. GaN nanowires have been regarded as a
potential building block for nanoscale electronics and optoelectronic devices such as nanolasers [7,8], nanowire transistors [9],
etc. since they possess one-dimensional geometry with strong
quantum confinement of electrons, holes, and photons. GaN
nanowires have been synthesized by various techniques such as
carbon nanotube template filling [10], porous membrane template deposition [11], laser ablation [12], catalytic metal reaction
[13], hydride vapor phase epitaxy [14], metalorganic chemical
vapor deposition (MOCVD) [15], ammonification of Ga2O3
Corresponding author. Tel.: +886 6 275 7575x62662; fax: +886 6 238 5423.
E-mail address: hong@mail.ncku.edu.tw (F.C.-N. Hong).
0925-9635/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2008.02.003

[16], molecular beam epitaxy (MBE) [17], etc. In previous

studies on the growth of GaN nanowires in a furnace, NH3
was always used as a nitrogen source to react with Ga metal or
other Ga-containing precursors at a high temperature. Ga vapor
reacts with NH3 to form GaN nanowires due to the low energy
of NH bond (~ 3.5eV). For example, NH3 is known to decompose stepwise into NH2, NH, N and H at a low temperature
(~ 850C). An alternative method, plasma-assisted molecular
beam epitaxy (PAMBE), is often employed using a nitrogen
plasma source generated by a radio frequency (RF, 13.56MHz)
or by electron cyclotron resonance (ECR, 2.45GHz) [18]. Here,
we report a novel fabrication method for GaN nanowires by
introducing N2 plasma using dielectric barrier discharge in a
horizontal furnace. DBD was often used in generating atmospheric plasma [19,20]. Due to the low cost and stable generation, DBD is suitable for a high-pressure and hightemperature environment. High-quality GaN nanowires have
been easily and reproducibly produced using DBD in a furnace.
2. Experiment
GaN nanowires were grown in a horizontal furnace. The
experimental setup is schematically shown in Fig. 1. A c-plane

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1781

Fig. 1. A schematic diagram of the nanowire growth apparatus. The crucible containing Ga metal was placed at the center of furnace and the substrate was placed on the
top of the crucible with the growth surface facing Ga metal in the crucible. The distance between the substrate and the Ga metal was 2 cm.

sapphire plate coated with a 5nm thick Au layer was employed

as the substrate. Before coating the Au catalyst, the substrate
was cleaned in an ultrasonic bath of detergent, DI-water, ethanol, and isopropanol for 30min at 50C. An alumina crucible
containing Ga metal (99.999%, metal basis) was placed at the
center of a 3-in-diameter quartz tube in the furnace. The sapphire substrate was placed on the top of the crucible with the
growth surface facing the Ga metal. The distance between the
Ga source and the substrate was approximately 2cm. The
nanowires were grown under a nitrogen atmosphere with a
purity of 99.9999%. The nitrogen flow rate was controlled at
100sccm by using a mass flow controller under a pressure of
200Torr. The furnace temperature was increased at a rate of
30C/min from room temperature to the reaction temperature of
900C. The furnace was then maintained at 900C for 1h to
grow nanowires. The base pressure of the furnace is 1mTorr.
During the growth of GaN nanowires, N2 plasma was generated to produce active nitrogen radicals and ions using the DBD
method. A long NiCr cylindrical rod inserted into a 7-mm O.D.
quartz tube with one end sealed was employed as the highvoltage electrode. A piece of long NiCr wire firmly wound
around the outer surface of the quartz tube was employed as the
ground electrode. The sealed quartz tube functioned as the
dielectric layer to electrically isolate the high-voltage electrode
from the ground electrode. A uniform dielectric barrier discharge
was produced by applying a high voltage (4.3KV) power supply
of a medium frequency (9KHz) to the high-voltage electrode. N2
plasma was generated near the crucible which produced active N
atoms for the growth of GaN nanowires. After the reaction, the
substrate was cooled to room temperature with a light-yellow
film observed on the surface.
The surface morphology of the nanowires was analyzed
using scanning electron microscopy (SEM) (Philip XL40FEG). The crystal structure of the nanowires was characterized by X-ray diffraction (XRD) (Rigaku, Cu-K) and highresolution transmission electron microscopy (HRTEM) (JEOL,
JEM-2010, 200KV).

3. Result and discussion

The N2 plasma generated can react with Ga vapor to produce a
high yield of highly straight GaN nanowires, as shown in the

Fig. 2. SEM images of the GaN nanowires grown by employing (a) N2 plasma,
and (b) N2 gas only without igniting the plasma.

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Fig. 3. (a) A low-magnification TEM image of the GaN nanowires grown by employing N2 gas only without igniting the plasma. (b) An HRTEM image of the square
area, I, marked in (a). The vermicular-like nanowire possessed several dislocations, marked by an arrow, in the highly curved portion. (c) An HRTEM image and the
selected area diffraction pattern (in the inset) of the straight-portion, II, marked in (a).

scanning electron microscopy (SEM) image in Fig. 2(a) with Au

nanoparticles as the catalyst. The diameters of nanowires range
from 70 to 100nm, depending on the particle sizes of catalysts,
with lengths up to several micrometers. The growth of nanowires
using N2 gas without igniting the discharge was also attempted to
study the effects of plasma on the GaN nanowire structure. The
SEM image in Fig. 2(b) shows that vermicular-shaped nanowires
were observed on the substrate using N2 gas reactants without
turning-on the discharge. The highly curved portions of the
vermicular-shaped nanowires possessed many dislocation
defects, which are clearly shown in Fig. 3 by the HRTEM pictures. In Fig. 3(c), many defects are observed on the surface of the
vermicular-shaped nanowire. According to the HRTEM image
and the diffraction pattern in Fig. 3(c), the plane distance of (100)
is 2.8 which agree with the spacing of the wurtzite structure of
GaN. The results demonstrate that the active species such as N
radicals, N+ ions, etc. in the nitrogen plasma effectively assist the
growth of high-quality GaN nanowire crystallites. The DBD-type
plasma plays a crucial role and is suitable for the growth of GaN
nanowires in a horizontal furnace. The HRTEM image shown in
Fig. 4(a) reveals that the diameters of GaN nanowires are around
4080nm. The clear lattice fringes observed in the image confirm
that each nanowire is composed of single crystal. The HRTEM

image shows that the long axis of the nanowire is along [100]
direction, indicating [100] growth direction in N2 plasma. In the
literature, the growth of metal-catalyzed GaN nanowires was
usually along [100] direction, because [100] growth induces the
formation of (100) planes which are closest-packed planes and
thermodynamically favorable [12,13]. In Fig. 4(c), a lowmagnification TEM image of a typical single nanowire illustrates
the nanowire growth mechanism in this study. The end of the
nanowire was terminated with a Au particle, indicating that the
nanowires follow the vaporliquidsolid (VLS) growth mechanism. The X-ray diffraction (XRD) pattern shown in Fig. 5 further
reveals the high crystalline quality and phase purity of nanowires.
The sharp diffraction peaks in the pattern indicate that GaN
nanowires have hexagonal wurtzite structure with lattice
constants of a = 3.18 and c = 5.18 , which are consistent
with the reported values. The sharp GaN diffraction peaks and
their strong intensities relative to the background reveal that the
nanowires comprise high-quality wurtzite GaN crystallites.
4. Conclusion
High-quality and single crystal GaN nanowires have been
successfully grown by using Ga metal with DBD-type N2

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Fig. 4. (a) A low-magnification image and the selected area diffraction pattern (in the inset) of the GaN nanowire. (b) An HRTEM image captured along the [001] zone
axis indicating the [110] direction of the long axis; and (c) An HRTEM image of the GaN nanowire terminated with a Au nanoparticle at the end.

plasma in a horizontal furnace. The growths of single crystal

GaN nanowires along the [100] direction are observed to follow
the VLS growth mechanism, as characterized by XRD and
HRTEM. This is the first successful attempt to introduce stable
DBD-type plasma into a horizontal furnace system to grow GaN

nanowires using N2. This system combines the advantages of

plasma-assisted MBE and high temperature furnace for growing
GaN nanowires. It is demonstrated that the DBD-type N2
plasma can supply sufficient active nitrogen species, e.g., nitrogen atoms or ions, to react with Ga vapor forming GaN nanowires and the N2 plasma system is capable of replacing
ammonia for the effective growth of high-quality GaN nanowires. Consequently, we have demonstrated the possibility of
the furnace-based fabrication of nitride nanowires (GaN, AlN
and InN) using nitrogen plasma.
Acknowledgments
The authors are grateful for the assistance of I. H. Chen in the
HRAEM analysis. We thank Mr. Patrick Chen for valuable
discussions. We gratefully acknowledge the support for this
work from the National Science Council, under the NSC-962221-E-006-057.
References

Fig. 5. XRD pattern of the GaN nanowires. The corresponding (hkl) values of
the wurtzite structure are shown at the top of each peak.

[1] M.A. Reshchikov, H. Morko, J. Appl. Phys. 97 (2005) 061301.

[2] S. Nakamura, Science 281 (1998) 956.

1784

W.-C. Hou et al. / Diamond & Related Materials 17 (2008) 17801784

[3] F.S. Choa, J.Y. Fan, P.-L. Liu, J. Sipior, G. Rao, G.M. Carter, Y.J. Chen,
Appl. Phys. Lett. 69 (1996) 3668.
[4] S. Nakamura, M. Senoh, S. Nagahama, N. Iwasa, T. Yamada, T.
Matsushita, Y. Sugimoto, H. Kiyoku, Jpn. J. Appl. Phys. Part II 36
(1997) L1059.
[5] S.N. Mohammad, H. Morko, Prog. Quantum Electron. 20 (1996) 361.
[6] F.A. Ponce, D.P. Bour, Nature 386 (1997) 351.
[7] J.C. Johnson, H.J. Choi, K.P. Knutsen, R.D. Schaller, P. Yang, R.J.
Saykally, Nat. Mater. 1 (2002) 106.
[8] H.M. Kim, T.W. Kang, K.S. Chung, Adv. Mater. 15 (2003) 567.
[9] Y. Huang, X. Duan, Y. Cui, C.M. Lieber, Nano Lett. 2 (2002) 101.
[10] W. Han, S. Fan, Q. Li, Y. Hu, Science 277 (1997) 1287.
[11] G.S. Cheng, L.D. Zhang, Y. Zhu, G.T. Fei, L. Li, C.M. Mo, Y.Q. Mao,
Appl. Phys. Lett. 75 (1999) 2455.
[12] X. Duan, C.M. Lieber, J. Am. Chem. Soc. 122 (2000) 188.
[13] C.C. Chen, C.C. Yeh, Adv. Mater. 12 (2000) 738.
[14] H.M. Kim, D.S. Kim, Y.S. Park, D.Y. Kim, T.W. Kang, K.S. Chung, Adv.
Mater. 14 (2002) 991.

[15] T. Kuykendall, P. Pauzauskie, S. Lee, Y. Zhang, J. Goldberger, P. Yang,

Nano Lett. 3 (2003) 1063.
[16] C. Xue, Q. Wei, Z. Sun, Z. Dong, H. Sun, L. Shi, Nanotechnology 15
(2004) 724.
[17] J. Ristic, E. Calleja, M.A. Sanchez-Garcia, J.M. Ulloa, J. Sanchez-Paramo,
J.M. Calleja, U. Jahn, A. Trampert, K.H. Ploog, Phys. Rev. B 68 (2003)
125305;
N.A. Sanford, L.H. Robins, M.H. Gray, Y.S. Kang, J.E. Van-Nostrand, C.
Stutz, R. Cortez, A.V. Davydov, A. Shapiro, I. Levin, A. Roshko, Phys.
Stat. Sol. (c) 2 (2005) 2357.
[18] R. Calarco, R.J. Meijers, R.K. Debnath, T. Stoica, E. Sutter, H. Lth, Nano
Lett. 7 (2007) 2248.
[19] U. Reitz, J.G.H. Salage, Schwarz, Surf. Coat. Technol. 59 (1993) 144.
[20] T. Claire, T. Christelle, T. Pascal, D. Jean, L. Philippe, Spectrochim. Acta
Part B 61 (2006) 2.