ARTICLES
nature materials | VOL 2 | DECEMBER 2003 | www.nature.com/naturematerials 821
E
xtended and oriented nanostructures are desirable for many
applications, including microelectronic devices, chemical and
biological sensing and diagnosis, energy conversion and storage
(photovoltaic cells, batteries and capacitors, and hydrogen storage
devices), light-emitting displays, catalysis, drug delivery, separation, and
optical storage. Previously, oriented carbon nanotubes
1,2
and oriented
ZnO nanorods
3–10
have been prepared by high-temperature vacuum
deposition techniques. Similar techniques were used for making
nanowires of Si (ref. 11) and silicon carbide/nitride
12
, and nanobelts of a
wide range of oxide materials
13
. Recently, hydrothermal solution
synthesis
14,15
and electrochemical deposition in porous membranes
16–19
were also investigated to produce oriented ZnO nanorods and tubes.
Although oriented nanowires and nanorods have attracted wide
attention, the direct fabrication of large arrays of complex
nanostructures with controlled crystalline morphology, orientation
and surface architectures remains a significant challenge.
We developed a low-temperature, environmentally benign,
solution-based method to prepare complex ZnO nanostructures. ZnO
is an important wide-bandgap semiconducting ceramic material with
many useful properties (for reviews see ref. 20) such as piezoelectricity,
conductivity, optical absorption and emission, high voltage–current
nonlinearity, sensitivity to gases and chemical agents, and catalytic
activity
21
. It has been extensively investigated for applications in
luminescence
4,13,22,23
and as window and electrode material for solar
cells
24
, phosphors
25
, piezoelectric transducers and actuators
26
, surface
acoustic coatings
27
, varistors
28
, microsensors
29
, photocatalysts
30
,
decontamination agents
27
and so on. The properties of the ZnO depend
closely on the microstructures of the materials, including crystal size,
orientation and morphology, aspect ratio and even crystalline density.
The surface area and morphology (how the crystals are stacked) also
have a crucial role in many applications (such as photo-emitters,
transducers, actuators, varistors, sensors and catalysts).
We used a seeded growth procedure that we developed
31–33
to
control the nucleation event, and citrate anions to control the crystal
morphologies. We chose citrate because it adsorbs strongly on metal
34
and mineral surfaces
35
and significantly alters the surface properties
36,37
and mineral growth behaviour
38
. The use of citrate anions will also allow
us to develp molecular modelling and spectroscopic techniques in future
to enhance our understanding of how these organic molecules bind to
the different ZnO surfaces and affect crystal growth. Organic molecules
are known to either promote or inhibit crystal growth.Although organic
Extended and oriented nanostructures are desirable
for many applications, but direct fabrication of complex
nanostructures with controlled crystalline morphology,
orientation and surface architectures remains a significant
challenge. Here we report a low-temperature, environmentally
benign, solution-based approach for the preparation of
complex and oriented ZnO nanostructures, and the
systematic modification of their crystal morphology.
Using controlled seeded growth and citrate anions that
selectively adsorb on ZnO basal planes as the structure-
directing agent, we prepared large arrays of oriented ZnO
nanorods with controlled aspect ratios, complex film
morphologies made of oriented nanocolumns and
nanoplates (remarkably similar to biomineral structures in
red abalone shells) and complex bilayers showing in situ
column-to-rod morphological transitions. The advantages
of some of these ZnO structures for photocatalytic
decompositions of volatile organic compounds were
demonstrated. The novel ZnO nanostructures are expected
to have great potential for sensing, catalysis, optical
emission, piezoelectric transduction, and actuations.
Complex and oriented ZnO nanostructures
ZHENGRONG R. TIAN
1
, JAMES A. VOIGT
1
, JUN LIU
1
*, BONNIE MCKENZIE
1
, MATTHEW J. MCDERMOTT
1
,
MARK A. RODRIGUEZ
1
, HIROMI KONISHI
2
AND HUIFANG XU
2
1
Materials and Process Sciences Center, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA
2
Department of Earth and Planetary Sciences, University of New Mexico, New Mexico 87131, USA
*e-mail: jliu@sandia.gov
Published online: 23 November 2003; doi:10.1038/nmat1014
©2003 Nature Publishing Group