Chemical Physics Letters 408 (2005) 174–178

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Three-dimensional interconnected nanowire networks of ZnO

School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245,United States

Received 24 March 2005; in final form 1 April 2005

Abstract

In this Letter, three-dimensional (3D) interconnected networks of ZnO nanowires and nanorods are synthesized by a high
temperature solid–vapor deposition process. The nanorods and nanowires have diameters of 20–100 nm and they grow along the
c-axis. Due to the diverse orientation of the nanowires grown from a polycrystalline substrate, the networks are formed by a
sintering process of the crossed nanowires during growth. The thickness of the multilayer nano-network could be as thick as

30 lm. The sharp nanowire tips, the high degree of networking, and high surface area of these unique nanonetworks make them
a potential candidate for field emission, ultra-sensitive gas sensing, catalysts and filtering.

2005 Elsevier B.V. All rights reserved.

Wurtzite structured ZnO is of great importance due to process [21]. The experimental set-up consists of a hori-
its versatile applications in optoelectronic, photovoltaics zontal high temperature tube furnace
50 cm long, an
and sensors [1,2]. Quasi-one-dimensional nanostructures alumina tube (
75 cm in length), a rotary pump system
of ZnO, such as nanowires, nanobelts and nanotubes and a gas controlling system. Commercial (Alfa Aesa)
have been a revalent research topics in nanotechnology ZnO powder about 2 g was ground and then loaded in
for their unique properties and potential applications an alumina boat and positioned at the center of the alu-
[3–11]. The non-central symmetric crystallographic mina tube as the source material. The evaporation was
structure and spontaneous surface polarization charac- conducted at 1400 C for 30–120 min under a constant
teristics make ZnO one of the most exciting oxide nano- pressure of
300 mbar throughout the heating, high-
structures for investigating nanoscale physical and temperature synthesis and cooling processes. The Ar
chemical phenomena [12]. Unique structural configura- carrier gas flow rate was controlled at 50–100 sccm
tions such as nanojunction-arrays [13–15], piezoelectric (standard cubic centimeters per minute) after the tem-
nanobelts [16], nanosprings [17], nanorings [18,19], perature had reached 800 C. The 3D networks of
nanobows [20] etc., have been reported. In this Letter, ZnO nanowires were grown on either a polycrystalline
we report a new nanostructure of ZnO: three-dimen- Al2O3 substrate or on a (1 1 0) Si wafer in a temperature
sional (3D) interconnected nanowire network. The struc- zone of 700–800 C.
ture and growth process of the nanonetworks will be Scanning electron microscopy (FE-SEM) (field emis-
presented. The high temperature ÔweldingÕ and sintering sion LEO 1530 FEG at 5 & 10 kV) and transmission
effect on the formation of networks will be elaborated. electron microscopy (TEM) (field emission TEM
The structure reported here could find potential applica- Hitachi HF-2000 at 200 kV), and energy-dispersive X-
tions in field emission, gas sensing, catalysis and filtering. ray spectroscopy (EDS) attached to the SEM and
The interconnected networks of ZnO nanowires were TEM, respectively were used to investigate the morphol-
grown via a high temperature solid–vapor deposition ogy, crystal structure and composition of the as-grown
nanostructures.
*
Corresponding author. Fax: +1 404 894 8008. Fig. 1a is a typical low magnification SEM picture
E-mail address: [email protected] (Z.L. Wang). of the as-grown networks of ZnO nanowires and

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2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2005.04.024
 P.X. Gao et al. / Chemical Physics Letters 408 (2005) 174–178 175

Fig. 1. (a) A typical low magnification SEM image of the as-grown networks of ZnO nanowires and nanorods consisting two types of morphologies,
as indicated by area b (b,c) and c (d,e). (b,c) Enlarged SEM images of uniform networks of ZnO nanowires and nanorods. (d,e) Enlarged SEM
images of clumps of nanowires showing the interconnected nanowires and nanorods.

nanorods. Two typical morphologies were found: one nanowires joining with each other, forming intercon-
shown in the top of the figure is the area with distinct nected networks.
clumps of nanowires; the other in the middle area is a Fig. 2 shows three typical SEM images of the uniform
uniform layer of nanowires networks. The respectively networks of ZnO nanowires respectively, from top view
enlarged SEM pictures of the two areas are described (Fig. 2a), 45 tilted view (Fig. 2b), and cross section view
in Fig. 1b & c, and Fig. 1d & e. From Fig. 1b, the net- (Fig. 2c). The top view image indicates the intercon-
work feature is clearly displayed for which the mesh ele- nected and periodically spaced features of the network.
ment is composed of nanowires with diameters around The tilted view picture in Fig. 2b gives a description that
100 nm. The further magnified picture in Fig. 1c, de- these interconnected nanowires and nanorods have a
scribes the structure of the networks with certain 3D void tendency to align along a specific direction. The cross-
spaces confined by adjacent nanowires and nanorods. sectional image in Fig. 2c clearly proves that these net-
Fig. 1d and e depicted four clumps of radially grown work nanowires and nanorods are quasi-aligned normal

Fig. 2. Three typical SEM images of the uniform networks of ZnO nanowires: (a) viewed from top; (b) viewed at 45 tilt; and (c) cross section view.
176 P.X. Gao et al. / Chemical Physics Letters 408 (2005) 174–178

Fig. 3. A series of cross-sectional SEM and TEM images of the 3D network structures of ZnO. (a) A cross-sectional SEM image showing the
beginning layer of the network. (b) A comparatively dense network cross-sectional SEM image. (c) A TEM image of a broken network, three dotted
circles depicted atleast three-layer interconnected network of ZnO nanowires.

Fig. 4. (a,b) Interconnection types of ZnO nanowires in the nano-network. (c,d) Bright-field and dark-field TEM images of two nanowires
interconnected with each other, indicating that the two nanowires are single crystals but they have no orientation relationship. The circle area is used
for recording the selected area electron diffraction pattern (inset).
 P.X. Gao et al. / Chemical Physics Letters 408 (2005) 174–178 177

to the polycrystalline Al2O3 substrate with a uniform b, a joint node is formed if the two nanowires come to
height of around 15–20 lm. In addition, Fig. 2c a cross or if one terminates at the joint point. The
indicates several periodic layers of interconnected fea- images appear to suggest that the joint is a ÔweldingÕ
tures along the height direction. rather than a simple physical contact. This result has
To further investigate the extent of network structure, been confirmed by TEM analysis. Fig. 4c shows a bright
higher magnified cross-sectional SEM and TEM images field TEM image at the joint point of two nanowires.
are comparatively studied. Fig. 3a is an SEM image Electron diffraction pattern recorded from the nano-
showing the cross section at the beginning of a network. wires shows that the right-hand side nanowire is single
As indicated by circles, the first interconnection between crystal and oriented along ½0 1 1 0 with a growth direc-
the nanowires and nanorods occurs at around 5–10 lm tion of [0 0 0 1], while the nanowire on the left-hand side
along the length; a common sharp tips as thin as is at an arbitrary orientation whose diffraction spots are
10 nm is formed after the first merging at around indicated by two arrowheads in the pattern. Dark-field
5 lm. The cross section view of a comparatively dense TEM image (Fig. 4d) using one of the diffraction spot
network is described in Fig. 3b. Along the two nano- from the ½0 1 1 0 oriented nanowire indicates that it
wires for about 15 lm, four orders of joining nodes were has no orientation relationship with the nanowire on
clearly identified, as indicated by dotted circles 1, 2, 3 the left-hand side, but two of them join together with
and 4. The circle 4 represents the beginning of the fourth a clear grain boundary.
layer of interconnecting network of ZnO nanowires. To track the formation process of the nanowire net-
Then the question is how could these nanowires meet work, several samples were grown for different lengths
and interconnect with each other to form a network? of times. Fig. 5a is the initial stage of the nanowire
Under SEM, it is found that two nanowires can join if growth, which suggests that large crystals are formed
their tips are close enough. As shown in Figs. 4a and first, from which the nanowires are nucleated but with

Fig. 5. Formation process of the 3D network. (a) The initial stage of interconnected nanorods growth. (b) The first layer of networking between
short nanowires and nanorods. (c) The beginning of the second layer of networking. (d) Highly magnified SEM image giving a clear description
about the 3D ZnO networks with mesh space around 2 · 2 · 2 (lm).
178 P.X. Gao et al. / Chemical Physics Letters 408 (2005) 174–178

a diversity of orientations. As the growth continues, the Research and Engineering (DDR & 1E), and the
lengths of the nanowires increase, and they start to con- Defense Advanced Research Projects Agency (Award
tact with each other (Fig. 5b). Under the growth temper- No. N66001-04-1-8903).
ature of 700–800 C, sintering of nanowires is possible
[18,19], forming the ÔweldedÕ joints among the nanowires
(Fig. 5c). This is likely to be the first level of networking.
The crossed nanowires continue to grow until they meet References
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Thanks the support from NSF, the NASA Vehicle 6703.
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