Appl Phys A (2009) 94: 241–245
DOI 10.1007/s00339-008-4755-0
Efficient synthesis of ZnO nanoparticles, nanowalls, and
nanowires by thermal decomposition of zinc acetate at a low
temperature
Ruey-Chi Wang · Chun-Cheng Tsai
Received: 19 May 2008 / Accepted: 2 June 2008 / Published online: 3 July 2008
© Springer-Verlag 2008
Abstract ZnO nanoparticles, nanowires, and nanowalls
were synthesized rapidly on Si via thermal decomposition
of zinc acetate by a modified chemical vapor deposition
at a low substrate temperature of 200–250°C for the first
time. The diameters of the synthesized nanoparticles and
nanowires are around 100 and 30 nm, respectively, and the
thickness of nanowalls is around 20 nm. High-resolution
transmission electron microscopy shows that the nanowires
as well as nanowalls are single-crystalline, and the nanopar-
ticles are highly-textured poly-crystalline structures. Room-
temperature photoluminescence spectra of the nanostruc-
tures show strong ultraviolet emissions centered at 368–
383 nm and weak violet emissions at around 425 nm, in-
dicating good crystal quality. The study provides a simple
and efficient route to synthesize ZnO diverse nanostructures
at low temperature.
PACS 81.07.-b · 81.16.-c · 81.07.Bc · 81.05.Dz · 81.15.Gh
1 Introduction
ZnO, a wide-bandgap semiconductor (Eg = 3.37 eV at
300 K) with a large exciton binding energy (60 meV), is
a multifunctional material for a variety of practical applica-
tions due to its excellent physical and chemical properties.
Notably, ZnO low dimensional nanomaterials have attracted
great interest because of their unique and fascinating opti-
cal, electrical, mechanical, and piezoelectric properties, to-
gether with their wide use in fundamental scientific research
R.-C. Wang () · C.-C. Tsai
Department of Chemical and Materials Engineering,
National University of Kaohsiung, Kaohsiung, Taiwan 81148
e-mail: rcwang@nuk.edu.tw
and potential technical applications, such as nano-ultraviolet
lasers [1], piezoelectric devices [2], field emission [3], gas
sensors [4], dye-sensitized solar cells [5], and photocata-
lysts [6].
Up to now, many methods, such as thermal chemical va-
por deposition (CVD) [7–9], thermal evaporation [10–12],
metal–organic CVD [13, 14], solution route [15, 16], and
sputtering [17] have been shown to synthesize ZnO nanos-
tructures. Of these, thermal CVD and thermal evaporation
using Zn [7–9] and ZnO [10–12] as sources are usually
viewed as cheap, low-toxic, and efficient methods to fab-
ricate various ZnO nanostructures with high crystal qual-
ity. However, the nanostructures reported were synthesized
at high temperatures of 500–1000°C. Such high substrate
temperature is unfavorable in the practical applications of
opto-electronics nanodevices, in which transparent conduct-
ing oxides (TCOs), such as Indium Tin Oxides (ITO) or
Al doped ZnO (AZO), are usually used as transparent elec-
trodes, since the conductivity of TCO usually decays rapidly
at high annealing temperatures of more than 500°C [18, 19].
In addition, high temperature is also disadvantageous in
the fabrication of nanophotonic integrated circuits, because
thermal drift [20] makes it difficult to manipulate the size
and position of nanomaterials. Therefore, a low-temperature
process is desirable for nanostructures. However, while solu-
tion routes [15, 16] are usually performed at a lower temper-
ature, it usually takes at least several hours. The simple and
rapid synthesis of ZnO nanostructures is still very difficult.
Recently, zinc acetate has been used as source to synthesize
ZnO nanostructures by CVD at low temperature. However,
only nanoparticles [21, 22] and nanoflowers [23] were re-
ported. Apparently, it remains a challenge to synthesize ZnO
nanowires and nanowalls efficiently at low temperature.
In this study, ZnO nanoparticles, nanowalls, and nano-
wires were quickly synthesized in 10 min without catalysts
242
by thermal decomposition of zinc acetate at a low substrate
temperature of 200–250°C. The experimental results are re-
peatable. The photoluminescence spectra of the synthesized
nanomaterials show strong ultraviolet (UV) emissions and
weak violet missions, indicative of good crystal qualities.
This work thus provides a simple and efficient route to syn-
thesize ZnO diverse nanostructures at a low temperature.
2 Experimental
The diverse ZnO nanostructures were synthesized by a mod-
ified CVD on Si (100). Figure 1 shows the experimental
setup of the CVD system. Zinc acetate dihydrate (purity:
99.5%, PA) was used as the source and placed in an alu-
minum boat located in the upstream region inside a 2 in di-
ameter horizontal quartz tube reactor. Silicon substrates A,
B, C, and D were put in the A, B, C, and D regions of the
tube, as shown in Fig. 1. The system was then heated at a rate
of 20°C/min from room temperature to 400°C. Argon was
introduced as the carrier gas at the beginning, with a flow
rate of 54 sccm and working pressure kept at 10 Torr. As the
temperature reached 260°C, oxygen was introduced with a
flow rate of 1.2 sccm. When the system reached 400°C, the
local temperature of the source and substrates A, B, C, and
D was measured by a movable thermal couple to be around
330, 200, 400, 250, and 230°C, respectively.
Fig. 1 Experimental setups of the CVD system for production of di-
verse ZnO nanostructures in different regions
Fig. 2 SEM images of
as-synthesized ZnO diverse
nanostructures a nanoparticles
synthesized on substrate A,
b nanostructural films
synthesized on substrate B,
c low-magnification image of
nanowalls synthesized on
substrate C,
d high-magnification image of
as-synthesized nanowalls,
e nanowires/nanoparticles
synthesized on substrate D
R.-C. Wang, C.-C. Tsai
After heating at 400°C for 10 min, the substrate was
slowly cooled down to room temperature in the furnace. The
as-prepared nanostructures were then examined by field-
emission scanning electron microscopy (FE-SEM) with
JEOL 6700 F, X-ray diffraction with D/MAX-2500, field-
emission transmission electron microscopy (FE-TEM) with
Philips Tecnai G2 F20 FEG-TEM and photoluminescence
(PL) with HITACHI F7000 for morphologies, crystallogra-
phy, microstructures, and PL characterization, respectively.
3 Results and discussion
The as-synthesized products were first examined by SEM.
Figure 2a shows quasi-spherical ZnO nanoparticles synthe-
sized on silicon substrate A with a local temperature of
200°C in the downstream region of the quartz tube. The di-
ameter of the nanoparticles is around 100 nm. Figure 2b ex-
hibits a flat ZnO nanostructural films on silicon substrate B
with a local temperature of 400°C in the downstream region
of the quartz tube. The film is composed of flat nanoparticles
with diameters in the range of 80 to 120 nm. The nanoparti-
cles were spread uniformly on the Si to form a compact film
rather than a porous film, as shown in Fig. 2a. Compared
to the particles in Fig. 2a, the flat particles have a polyhe-
dral rather than quasi-spherical shape, indicative of sintered
features. Figure 2c demonstrates a low-magnification SEM
image of ZnO nanowalls synthesized on silicon substrate C
with a local temperature of 250°C in the upstream region
of the quartz tube. The nanowalls were mostly formed on
ZnO particles, and Fig. 2d shows a high-magnification SEM
image of these. The thickness of the nanowalls was around
20 nm. Figure 2e is the SEM image of ZnO nanostructures
synthesized on silicon substrate D with a local temperature
of 230°C in the upstream region of the quartz tube. It shows
several nanowires grown on nanoparticles, and the diame-
Efficient synthesis of ZnO nanoparticles, nanowalls, and nanowires by thermal decomposition 243
Fig. 3 TEM characterization of
as-synthesized ZnO
nanoparticles
a low-magnification bright-field
image, b medium-magnification
bright-field image,
c high-magnification bright-field
image with the inset for the
electron diffraction pattern of a
single particle, d high-resolution
image of a nanoparticles

ter and length of the former are around 20 nm and 200 nm,
respectively.
The TEM examinations of the diverse nanostructure
are shown in Figs. 3 and 4. Figures 3a–b show low and
medium-magnification TEM bright-field images of the as-
synthesized nanoparticles shown in Fig. 2a. The particles
with diameters in the range of 80–110 nm disperse uni-
formly on the carbon membrane of a TEM copper grid.
Figure 3c is a high-magnification image of nanoparticles,
which show quasi-six-folded symmetry. The electron dif-
fraction pattern of a single nanoparticle is shown in the inset
of Fig. 3c, exhibiting poly-crystalline and highly textured
characteristics. Figure 3d is a high-resolution image of a
nanoparticle, which exhibits highly textured features, con-
sistent with the characterization from the diffraction pattern.
Figure 4a is a low-magnification bright-field image of ag-
gregations of nanowalls. The nanowalls exhibit hexagonal
features. The high-resolution image of a single nanowall in
Fig. 4b with corresponding electron diffraction in the inset
demonstrates that the nanowalls are single-crystalline struc-
tures, and the surface of the nanowall is the (0001) plane of
the wurtzite structure. Figure 4c shows a low-magnification
TEM image of the ZnO nanowires. The corresponding elec-
tron diffraction pattern in the inset of Fig. 4c and high-
resolution image in Fig. 4d indicate that the nanowires are
single-crystalline wurtzite structures growing along the c-
axis. The inset of Fig. 4d shows that the d-spacings of (0001)
and (1010) are 0.52 and 0.28 nm, respectively.
In the experiments, zinc acetate dihydrate powders were
used as the source materials. As temperature increases
rapidly to 400°C, zinc acetate is decomposed intensively
to form Zn vapor through the following chemical reac-
tions [24]:
Zn(CH3 COO)2 · 2H2 O(s)
heat
−→ Zn(CH3 COO)2 (s) + 2H2 O(v) ↑, (1)
heat
Zn(CH3 COO)2 (s) −→ Zn(v) + 2CH3 COO(s ∗ ), (2)
where s, v, and s ∗ represent solid, vapor, and activated
states, respectively. Subsequently, Zn vapor condenses and
develops the ZnO clusters afterward in an O2 /Ar at-
mosphere.
heat
Zn(l) + O2 (g) −→ ZnO(s), (3)
where l and g represent liquid and gas, respectively. The
ZnO clusters are easy to aggregate to nanoparticles under
a high concentration of ZnO vapor. As the nanoparticles
transport to substrate A with a local temperature of 200°C
in the downstream region of the tube, they deposit on the
substrate directly and form a porous film constructed of
quasi-spherical nanoparticles, as shown in Fig. 2a. Owing
244
Fig. 4 TEM characterization of
a low-magnification bright-field
image of aggregations of ZnO
nanowalls, b high-resolution
image of a single nanowall with
the inset for the corresponding
diffraction pattern,
c low-magnification bright-field
image of ZnO nanowires,
d high-resolution image of a
nanowire with the inset showing
the d-spacings of (0002) and
(1010)
to the high speed of aggregation, the crystal quality of the
nanoparticles is not good enough. Therefore, the nanopar-
ticles are characterized as textured structures rather than
single-crystalline by HRTEM. Obviously, the nanoparticles
were formed in the atmosphere, irrelevant to the substrate ef-
fect. Other materials such as copper foils, glass, or CuO have
also been used as substrates to confirm this. On the other
hand, the nanoparticles transporting to substrate B with a
high local temperature of 400°C have polyhedral shapes.
They tend to spread and form a flat and compact layer on
the Si substrate rather than a porous film, which is ascribed
to the higher diffusion rate of ZnO at a higher local temper-
ature. The driving force for the diffusion of ZnO to form a
compact film may be to reduce the surface energy.
Regarding the growth mechanisms of nanowalls and
nanowires, they should be formed by a two-step process,
since both the nanowalls and nanowires are grown on the
nanoparticles, according to the SEM observation. Since
the deposition parameters were kept constant during the
process, the growth of nanowalls and nanowires on early-
formed nanoparticles is ascribed to the lower deposition rate
due to lower vapor concentration at lower temperature dur-
ing the cooling process. Since substrates C and D are in the
upstream regions near the sources and with lower local tem-
peratures of 250 and 230°C, respectively, the residual vapor
could diffuse to the rough surface of nanoparticles on sub-
strates C and D and proceed to second-stage growth. The
R.-C. Wang, C.-C. Tsai
rough sites of the nanoparticles where stress relaxes most
would be the ideal sites for the nucleation of the subsequent
ZnO nanowires [25]. Furthermore, the nanowires tend to as-
semble themselves along the trajectory of high stress relax-
ation into nanowalls and eventually form a two-dimensional
network. Conversely, sample A is far from the source, and
thus it is difficult for residual vapor to transport to the region.
Although sample B is near the source, the diffusion on the
surface of the nanoparticles is enhanced due to higher local
temperature. Consequently, the surface of the nanoparticles
on sample B is smoother, and no nanowires or nanowalls are
grown on them.
Figure 5 is the room-temperature PL spectra of the
as-synthesized ZnO nanostructures. The UV emissions of
different nanostructures were normalized. The spectra of
nanowires, nanowalls, and nanoparticles exhibit relatively
strong UV emissions centered at 368, 368, and 383 nm,
respectively. The UV emissions are attributed to near
band edge excitonic emissions. Since the sizes of the as-
synthesized nanostructures were larger than Bohr radius of
ZnO, the blue shift is not attributed to the quantum confined
effect [26]. One possible reason for the blue shift is the
surface effect which results from the higher concentration
of native defects on the surface of the nanostructures [27].
Spectral shifts due to different defect concentrations are ex-
pected to occur in nanostructures with different sizes due to
different surface–to–volume ratios. In addition, the spectra
Efficient synthesis of ZnO nanoparticles, nanowalls, and nanowires by thermal decomposition
Fig. 5 Room-temperature PL spectra of the as-synthesized ZnO
nanowires, nanowalls, and nanoparticles
of nanowires, nanowalls, and nanoparticles show relatively
weak violet emissions at around 425 nm, which are ascribed
to zinc interstitials [28]. Theoretical calculations [29] on
the energy levels of intrinsic point defects demonstrate that
zinc interstitials produce a shallow donor level at 0.5 eV
below the bottom of the conduction band. Therefore, the re-
combination of an electron at zinc interstitials and a hole in
the valence band should excite a violet emission at around
421 nm. The Zn interstitials in the ZnO nanostructures may
be caused by the rapid condensation and slower oxidation of
Zn in an oxygen deficient atmosphere. Furthermore, all the
spectra exhibit negligible green emissions at around 500 nm,
which is usually attributed to defect related emissions, espe-
cially from oxygen vacancies [30, 31].
4 Summary
In this study, ZnO nanoparticles, nanowires, and nanowalls
were fabricated rapidly on Si substrates via thermolysis
of zinc acetate in 10 min at a low substrate tempera-
ture of 200–250°C. HRTEM shows that the nanowires as
well as nanowalls are single-crystalline, and the nanoparti-
cles are poly-crystalline highly-textured structures. Room-
temperature PL spectra show strong UV emissions at 368–
383 nm and weak violet emissions at around 425 nm, indi-
cating good crystal quality The study provides a simple and
efficient route to synthesize ZnO diverse nanostructures at
low temperature.
Acknowledgements The work was supported by research grants
NSC96-2221-E-390-016 and 97-2815-C-390-007-E from the National
Science Council of Taiwan. The authors thank the Center for Mi-
245
cro/Nano Technology Research at National Cheng Kung University,
and the Center for Nanoscience and Nanotechnology at National Sun
Yat-Sen University, Taiwan, for the provision of HRTEM and FESEM.
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