Materials Chemistry and Physics 88 (2004) 421426

Sonochemical and microwave-assisted synthesis of linked

single-crystalline ZnO rods
Xian-Luo Hu, Ying-Jie Zhu , Shi-Wei Wang
State Key Laboratory of High Performance Ceramics and Superne Microstructure, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, 1295 Ding-Xi Road, Shanghai 200050, PR China

Received 25 May 2004; received in revised form 3 August 2004; accepted 18 August 2004

Abstract

Both sonochemical and microwave-assisted solution-phase routes to the fabrication of linked ZnO rods have been developed. The two
methods do not need templates, seeds or surfactants and are suitable for large-scale production. Linked ZnO rods with various morphologies
such as bipods, tripods, tetrapods have been prepared. ZnO rods grow along [0 0 0 1] direction and the formation of linked ZnO rods may be
controlled by the oriented attachment mechanism. The influence of the irradiation time, reactant concentration and reactant molar ratio on
the formation of linked ZnO rods were investigated. X-ray powder diffraction (XRD), transmission electron microscopy (TEM), selected-
area electron diffraction (SEAD) and energy dispersive spectroscopy (EDS) were used for the characterization of the as-prepared products.
Photoluminescence (PL) spectrum of linked ZnO rods was also investigated at room temperature.
2004 Elsevier B.V. All rights reserved.

Keywords: Ultrasound; Microwave; Zinc oxide; Rods

1. Introduction tetrapods and multipods, are highly desired for applications

as interconnects and interconnected functional components
Zinc oxide (ZnO), a wide bandgap (3.37 eV) semiconduc- in the future nanodevices [18].
tor with large exciton binding energy, has been used in a The sonochemical method has been proven to be a useful
wide range of applications such as solar cells, sensors, op- technique to obtain novel materials with interesting proper-
toelectronic devices, and surface acoustic waveguides [14]. ties. It is based on acoustic cavatition resulting from the con-
Recently, one-dimensional (1D) structures of ZnO have at- tinuous formation, growth and implosive collapse of bubbles
tracted much interest for applications in short-wavelength in a liquid [19]. Gedanken and coworkers [20,21] synthesized
light-emitting, transparent conductor, piezoelectric materials crystalline nanoporous ZnO spheres and ZnOpolyvinyl al-
and room temperature ultraviolet (UV) lasing [57]. A num- cohol composite by ultrasonic irradiation. Jiang and cowork-
ber of techniques such as high-temperature chemical vapor- ers [22] reported a sonochemical synthesis of spherical ZnO
phase transport and physical vapor deposition [812], anodic nanocrystals.
alumina membrane templates [13], microemulsion [14,15], Microwave heating as a heating method in synthetic
and hydrothermal process [16,17], have been employed to chemistry has been a very rapidly developing research
prepare 1D ZnO. However, simple and mild routes for the area [2329]. Compared with the conventional heating, mi-
preparation of high-quality ZnO still need to be explored. crowave heating is promising due to its unique effects, such as
Furthermore, higher order complexities composed of rods or rapid volumetric heating, higher reaction rates, higher reac-
wires, such as branched structures including bipods, tripods, tion selectivity, higher yields of products, and energy saving.
In our previous work [3032], we have successfully prepared
Corresponding author. Tel.: +86 21 52412616; fax: +86 21 52413122. 1D nanostructures of tellurium (Te) and gold (Au) by mi-
E-mail address: [email protected] (Y.-J. Zhu). crowave heating.

0254-0584/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2004.08.010
422 X.-L. Hu et al. / Materials Chemistry and Physics 88 (2004) 421426

To the best of our knowledge, there has been no report on selected-area electron diffraction (SAED) and energy disper-
the preparation of 1D ZnO structures through a sonochemical sive spectroscopy (EDS) were recorded on a JEOL JEM-2010
or a microwave-assisted route. Herein, we demonstrate that transmission electron microscope using an accelerating volt-
linked ZnO rods can be fabricated by ultrasonic irradiation age of 200 kV. Photoluminescence (PL) spectrum was exam-
under ambient conditions and by microwave heating at 90 C ined at room temperature by a Fluorolog-3 Jobin Yvon-SPEX
in a short time (2 min). Both methods are seedless, surfactant- spectrometer using a Xe lamp with an excitation wavelength
free and template-free, which avoids subsequent complicated of 325 nm.
workup procedures for the removal of seeds, surfactants or
templates. Furthermore, they are expected to be suitable for
large-scale production of linked ZnO rods in terms of speed- 3. Results and discussion
iness, low cost, simplicity and energy saving.
The crystallinity and phase of the products were examined
by XRD. The XRD patterns of the two typical as-prepared
2. Experimental details products (samples 1 and 2) are shown in Fig. 1. Both samples
have similar XRD patterns. All the reflections can be indexed
2.1. Sonochemical synthesis of linked ZnO rods to the pure hexagonal phase of ZnO [space group: P63 mc
(186)] with lattice constants a = 3.248 A and c = 5.206 A,
Zn(NO3 )2 6H2 O and (CH2 )6 N4 (hexamethylenete- which are in good agreement with the reported data (JCPDS,
tramine, HMT) were of analytical grade and used as 79-0206). No characteristic peaks were observed for impu-
received without further purification. In a typical procedure, rities such as Zn(OH)2 . The yields of ZnO powders after
Zn(NO3 )2 6H2 O (0.074 g) was dissolved in deionized water washing and drying are reproducibly higher than 90%.
to form a 50 mL solution ([Zn2+ ] = 0.005 mol L1 ). Then, The morphologies and microstructures of the as-prepared
HMT (0.035 g) was added to the above solution ([HMT] = products were investigated by TEM. As shown in Fig. 2AC,
0.005 mol L1 ). The solution was ultrasonically irradiated at samples 1 and 2 consist predominantly of ZnO bipods. It is
ambient condition for 30 min with a high-density ultrasonic interesting to note that each bipod consists of two rods that
probe (Xin-Zhi, JY92-2D, Ti-horn, 20 kHz) immersed are linked in line. This novel morphology of ZnO is quite
directly in the solution. During the ultrasonic irradiation, the different from the ZnO nanorod and nanowire arrays obtained
temperature of the reaction solution rose to around 80 C. by hydrothermally treating an aqueous solution of HMT and
After the reaction was complete, the white products were Zn(NO3 )2 [17]. ZnO bipods from sample 1 have an average
collected by centrifugation, washed with deionized water diameter of 160 nm and an average arm length of 1 m
three times and absolute ethanol one time, and dried in a (Fig. 2A and B). ZnO bipods from sample 2 have an average
vacuum at 60 C for 2 h. diameter of 280 nm and an average arm length of 0.7 m
(Fig. 2C).
2.2. Microwave synthesis of linked ZnO rods

In a typical procedure, Zn(NO3 )2 6H2 O (0.074 g) and

HMT (0.035 g) were dissolved in deionized water to form
a 50 mL solution in a round-bottom flask ([Zn2+ ] = [HMT]
= 0.005 mol L1 ). Then, the solution was microwave-heated
at 90 C for 2 min by a focused single-mode microwave syn-
thesis system (Discover, CEM, USA). The magnetic stirring
was used to assure the complete mixing of reactants during
the reaction process. The temperature was accurately con-
trolled by automatically adjusting microwave power. The mi-
crowave synthesis system was equipped with a water-cooled
condenser outside the microwave cavity. After the reaction
was complete, the white products were collected by centrifu-
gation, washed with deionized water three times and absolute
ethanol one time, and dried in a vacuum at 60 C for 2 h.

2.3. Characterization

X-ray diffraction (XRD) was preformed with a Rigaku

Fig. 1. (A) XRD pattern of sample 1 prepared by ultrasonically irradiating
D/max 2550 V X-ray diffractometer using graphite- an aqueous solution of 0.005 mol L1 Zn(NO3 )2 and 0.005 mol L1 HMT
monochromatized high-intensity Cu K radiation ( = under ambient condition for 30 min. (B) XRD pattern of sample 2 prepared
1.54178 A). Transmission electron microscopy (TEM), by microwave heating the same solution as sample 1 at 90 C for 2 min.
 X.-L. Hu et al. / Materials Chemistry and Physics 88 (2004) 421426 423

Fig. 2. (A) and (B) TEM images of sample 1. (C) TEM image of sample 2.

The microstructures of the ZnO bipods were investi-

gated by SAED and high-resolution transmission electron
microscopy (HRTEM). The SAED patterns taken from the
different positions either at the junction or along the two arms
of a single bipod are essentially the same, indicating that these
bipods are structurally single-crystalline as a whole. A typ- Fig. 4. EDS pattern of a single ZnO bipod from sample 2.
ical single bipod with a diameter of 160 nm and a length
of 1.3 m from sample 1 is shown in Fig. 3A and its cor-
responding SAED pattern is shown in Fig. 3B. The inset of consistent with the XRD results. Fig. 3E and F show the cor-
Fig. 3A shows the magnified TEM micrograph of the junction responding HRTEM micrographs of the arm and the junction
of the bipod. Fig. 3C shows the TEM micrograph of a typ- of the bipod as shown in Fig. 3A, respectively. The periodic
ical single bipod with a diameter of 220 nm and a length fringe spacing of 2.60 A along the bipod corresponds to the
of 1.25 m from sample 2 and its corresponding SAED d-spacing of (0 0 0 2) planes. This indicates that ZnO rods
pattern is shown in Fig. 3D. Both SAED patterns can be in- had a preferential growth direction along [0 0 0 1] (c-axis of
dexed as the [1 1 0 0] zone axis of hexagonal ZnO, which are the crystal lattice). A HRTEM micrograph at the junction of
the bipod (Fig. 3F) shows that two rods grew together to be-
come a structurally single-crystalline bipod as a whole. As
a result, perfect structural continuity across the interface has
been achieved.
EDS was performed to further confirm the composition of
the as-prepared products. Fig. 4 shows that a single bipod is
composed of Zn and O with a ratio of 1:1, giving a stoi-
chiometric formula of ZnO. The Cu peak in the spectrum is
attributed to the copper meshes of the TEM sample holder.
In a few cases, some unlinked individual ZnO rods
(Fig. 2B, labeled with a circle) and multipods (Fig. 5AD), for
example, tripods (T-shaped) and tetrapods (X-shaped) were
also observed in the products prepared by both sonochemical
and microwave methods.
Fig. 6 shows the room temperature PL spectrum of sample
2. A strong ultraviolet emission at 394 nm is attributed to
a well-known recombination of free excitons [33]. Besides,
two relatively weak blue bands at 448 and 466 nm were
observed, which may be in correlation with the defect struc-
tures.
The formation process of the linked ZnO rods may be ex-
plained as follows: (i) nucleation stage. OH ions formed as
a result of the reaction of H2 O with NH3 which was produced
by decomposition of HMT. Subsequently, ZnO nuclei formed
Fig. 3. (A) TEM image of a single ZnO bipod from sample 1 and magnified rapidly; (ii) crystal growth stage. The in situ generated ZnO
image of the junction of a single ZnO bipod (inset). (B) SAED pattern of the
nuclei grew preferentially along the [0 0 0 1] direction, result-
bipod shown in Fig. 3A. (C) TEM image of a single ZnO bipod from sample
2. (D) SAED pattern of the bipod shown in Fig. 3C. (E) and (F) HRTEM ing in the formation of single-crystalline ZnO rods; (iii) link-
images of the arm and the junction of the bipod shown in Fig. 3A, the fringe age stage. The newly formed rods were linked on {0 0 0 1}
spacing of 2.60 A corresponds to the (0 0 2) planes of hexagonal ZnO. planes to form single-crystalline bipods. The mechanism for
424 X.-L. Hu et al. / Materials Chemistry and Physics 88 (2004) 421426

NH3 + H2 O NH4 + + OH (2)

Zn2+ + 2OH ZnO + H2 O (3)

Suslick [19] reported that there are three regions of sono-

chemical activity: (i) the inside of the collapsing bubble (T
> 5000 K), (ii) the interface between the bubble and liquid
(T 1900 K), and (iii) the bulk solution which is at ambient
temperature. We propose that the formation of ZnO occurs at
the interfacial region and NH3 evolves when HMT decom-
poses by ultrasonic irradiation. Varying the ultrasonic irra-
diation time from 10 min (sample 3) to 60 min (sample 4),
the average length of these rods was increased from 0.5
to 1.5 m (Fig. 8A and B), while their average diame-
ter was nearly the same. When r (=[HMT]/[Zn2+ ]) was in-
creased from 1 (sample 1) to 10 (sample 5), while [Zn2+ ] was
fixed at 0.005 mol L1 , the average diameter of the ZnO rods
decreased from 160 to 110 nm and the average length
decreased from 1 to 0.50 m (Figs. 2B and 8C). How-
Fig. 5. (A)(C) TEM images of ZnO multipods from sample 1. (D) TEM ever, by varying [Zn2+ ] in the range of 0.0010.050 mol L1 ,
image of a single ZnO tripod from sample 2. while r was fixed at 1, little influence was observed on the
size of these rods.
Microwave irradiation played a critical role in the fast for-
mation of linked ZnO rods. In fact, different results obtained
by microwave heating and conventional heating had already
been observed [34,35]. Water has a high dipole moment that
makes it a good solvent for microwave-assisted reactions.
The movement and polarization of the molecules under the
rapidly changing electromagnetic field of the microwave re-
actor may result in transient, anisotropic micro-domains and
localized high temperatures for the reaction system, facili-
tating the anisotropic growth of ZnO rods and the formation
of linked ZnO rods. We have investigated the influence of

Fig. 6. Room temperature PL spectrum of sample 2.

the three stages can be illustrated schematically in Fig. 7.

The major chemical reactions for the formation of ZnO in
the aqueous solution can be summarized as Eqs. (1)(3):

(CH2 )6 N4 + 6H2 O 4NH3 + 6HCHO (1)

Fig. 8. TEM images of as-prepared samples prepared by ultrasonically irra-

diating an aqueous solution of 0.005 mol L1 Zn(NO3 )2 and 0.005 mol L1
HMT for (A) 10 min (sample 3) and (B) 60 min (sample 4). (C) TEM im-
age of sample 5 prepared by ultrasonically irradiating an aqueous solution
of 0.050 mol L1 Zn(NO3 )2 and 0.005 mol L1 HMT for 30 min. (D) TEM
image of ZnO star-shaped structures (multipods) from sample 6 prepared
Fig. 7. Schematic representation of the formation process of linked ZnO by microwave heating an aqueous solution of 0.005 mol L1 Zn(NO3 )2 and
rods. 0.005 mol L1 HMT for 30 min.
 X.-L. Hu et al. / Materials Chemistry and Physics 88 (2004) 421426 425

4. Conclusions

In summary, we have developed two novel routes to the

fabrication of linked ZnO rods (e.g., bipods, tripods, tetrapods
and multipods) by ultrasonic irradiation and microwave heat-
ing. The yields of ZnO powders were higher than 90%. Both
methods do not need any templates, seeds or surfactants, and
are suitable for large-scale production in terms of speediness,
Fig. 9. Illustration of the wurtzite ZnO crystal structure.
low cost, simplicity and energy-efficiency. These linked ZnO
structures may find new applications in electronic and opto-
electronic devices. Furthermore, these methods may be ex-
microwave irradiation time on the formation of ZnO. As tended to synthesize 1D structures of other metal oxides, and
shown in Fig. 2C, sample 2 consists mainly of linked related research is in progress.
rods (bipods) for a 2 min microwave heating. If the mi-
crowave heating time was increased to 30 min (sample
6), the yield did not increase any more and the dimen- Acknowledgements
sion of the individual rods was almost kept unchanged.
However, the morphology of sample 6 was star-shaped Financial support from Chinese Academy of Sciences un-
structures (Fig. 8D). When the microwave heating time der the Program for Recruiting Outstanding Overseas Chi-
was further increased to 60 or 120 min, little influence nese (Hundred Talents Program) is gratefully acknowledged.
was observed on the dimension and morphology of the We thank the fund for Innovation Research from Shanghai
products. Institute of Ceramics, Chinese Academy of Sciences and the
Reduction in surface energy is the primary driving force fund from Shanghai Natural Science Foundation.
for crystal growth and morphology evolution. The phe-
nomenon that ZnO rods were linked as single-crystalline
bipods cannot be explained by the most cited Ostwald ripen-
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