Applied Physics A

DOI: 10.1007/s00339-003-2286-2

Materials Science & Processing

a.b. hartanto1
x. ning2
y. nakata1
t. okada1,u

Growth mechanism of ZnO nanorods

from nanoparticles formed
in a laser ablation plume
1 Graduate

School of Information Science and Electrical Engineering, Kyushu University,

6-10-1 Hakozaki, Fukuoka 812-8581, Japan
2 Fudan University, Shanghai, P.R. China

Received: 11 June 2003/Accepted: 1 July 2003

Published online: 23 September 2003 Springer-Verlag 2003

We have succeeded in synthesizing ZnO nanorods by pulsed-laser ablation at comparatively high gas pressures without using a catalyst. The nanorods had an
average size of 300 nm and a length of about 6 m. Stimulated emission was observed
from the nanorods at 388 nm by optical pumping. As a catalyst was not used in our
method, nanorod growth was not controlled by the vapor-liquid-solid (VLS) mechanism. We found that nanoparticles formed by condensation of ablated particles in the
laser ablation plume play an important role in nanorod growth.
ABSTRACT

PACS 61.46.+w;

81.07.Bc; 78.66.Hf; 78.67.Bf; 81.16.Mk

Introduction

In the past few years, nanosized wide-gap semiconductor materials, such as nanorods, nanowires, and
nanobelts, have been of growing interest
due to their importance in both scientific
research and potential technological applications, including nano-optical devices. Zinc oxide (ZnO), a wide-gap
compound IIVI semiconductor that
has a direct band gap of about 3.37 eV
at room temperature, is a well-known
material suitable for generating ultraviolet (UV) light. Furthermore, a large
exciton binding energy of about 60 meV
in ZnO, which is significantly larger
than the thermal energy at room temperature (26 meV), ensures efficient exciton emission at room temperature
under low excitation energy [1]. Thus,
considerable effort has been devoted
to the synthesis and study of nanoscale ZnO materials. For example, ZnO
nano-materials have been synthesized
by various approaches, such as chemical vapor deposition [2], physical vapor
deposition [3], molecular beam epi-

taxy [4], and a simple method that just

involves heating a Zn powder containing
catalyst nanoparticles [5]. All these approaches apply the vaporliquidsolid
(VLS) mechanism for nanowire growth,
in which a metal or oxide catalyst is
necessary to dissolve feeding source
atoms in the molten state to initiate
the growth of nano-materials. UV stimulated emission at room temperature
from optically pumped nanowires has
also been reported [6]. ZnO nanobelts
have been successfully synthesized by
simply evaporating ZnO powders without the presence of catalyst [7]. But
a very high temperature, as high as the
melting point of bulk ZnO, is needed in
such method.
Pulsed-laser ablation is also a very
simple method and is widely used for
the synthesis of various thin films.
But this method has only been employed in a few instances to synthesize nano-scale ZnO materials such as
nanowires or nanorods. In this letter,
we report the growth of large quantities of ZnO nanorods by pulsed-laser
ablation without using a catalyst. We

u Fax: +81-92/642-3965, E-mail: okada@ees.kyushu-u.ac.jp

found that nanoparticles formed by the

condensation of ablated species in the
high-pressure gas phase play an important role in the growth of the ZnO
nanorods.
2

Experimental

In our experiment, sintered

ZnO of 99.99% purity was used as the
source material for the synthesis of the
nanorods. This material was ablated
with a KrF excimer laser, which operated at a wavelength of 248 nm, repetition rate of 20 Hz, and fluence of about
3 J/cm2 , in a chamber filled with oxygen background gas. Ablated species
were then deposited on a sapphire substrate that was mounted on a heater.
The targetsubstrate distance was fixed
to be 20 mm and the chamber pressure
was set to be relatively high, at more
than 1 Torr. The morphology and crystallinity of the as-deposited products
were observed by scanning electron microcopy (SEM) and X-ray diffractometry (XRD), respectively.
3

Results and discussion

After 30 min of deposition,

a white-colored product was found to
cover the substrate surface. SEM analysis of the as-deposited products showed
that ZnO nanorods grew at substrate
temperatures of more than 600 C. Figure 1a shows an SEM image of the top
of a ZnO nanorod array grown on the
sapphire substrate at 700 C and a background gas pressure of 5 Torr. Figure 1b
shows an SEM image of a single ZnO
nanorod taken from the ZnO rod array.
Nanorods with an average size of about
300 nm and a uniform length of about

Rapid communication

Appl. Phys. A 78, 299301 (2004)

300

Applied Physics A Materials Science & Processing

6 m were grown perpendicular to the

substrate surface. The nanorods had
hexagon edges and were isolated from
each other. We can also see from Fig. 1b
that there was a layer with a thickness of several tens of nanometers between the substrate and the nanorods.
Since a catalyst was not used, it is suggested that this layer plays an important role in nanorod growth. A typical
XRD pattern of the ZnO nanorod array is shown in Fig. 1c. Only diffraction
lines from the (002) and (004) planes
can be observed, indicating that the
nanorod arrays were almost entirely caxis oriented.
In order to explore possible stimulated emission from the nanorods,
photoluminescence (PL) from isolated
nanorods was observed by optical pumping using the third harmonic (THG) of
a Nd:YAG laser operating at 355 nm.
Figure 2 shows the evolution of the
emission spectra as the pump energy
was increased. Stimulated emission
was observed in the UV region around
388 nm, with a full width at half maximum (FWHM) of approximately 7 nm,
when the pump energy exceeded about
50 mJ/cm2 .
In order to understand the growth
mechanism of the nanorods synthesized
by our method, it is important to know
the initial stage of nanorod growth. Figure 3ad shows SEM images of the
film surface after 10, 60, 120, and 300 s
of deposition, respectively. After 10 s,
ZnO thin-film islands with thicknesses
of several tens of nanometers, which almost cover the substrate surface, can be
observed in Fig. 3a. XRD analysis revealed that these thin film islands were
c-axis oriented. These results, which
are consistent with Fig. 1b, indicate
that these films correspond to the thin
layer between the nanorods and the substrate. The surface morphology of the
film after 60 s of deposition (Fig. 3b)
shows a lot of very small ball-like crystals stacked on the film islands. Further
deposition made these ball-like crystals grow horizontally, forming the base
of the nanorods. At a time of 120 s
after the start of deposition, the base
of the nanorods was completely formed
and the horizontal growth had stopped
(Fig. 3c). From this stage, the crystal
growth was then dominated by vertical
growth and the nanorods grew longer
and longer. We can see from Fig. 3d

FIGURE 1 SEM images and XRD spectrum of ZnO nanorods. a SEM image of ZnO nanorod arrays
deposited at 700 C. b SEM image of a single ZnO nanorod. c XRD spectra from ZnO nanorod arrays

FIGURE 2 Photoluminescence spectra from ZnO nanorods

FIGURE 3

SEM images of films for different deposition times: a 10, b 60, c 120, and d 300 s

HARTANTO et al.

Growth mechanism of ZnO nanorods from nanoparticles formed in a laser ablation plume

301

FIGURE 4 SEM images of ZnO rods. a Top view of the film deposited at 600 C for 10 min (Step 1). b Cross-sectional view of the film deposited at 300 C
for 1 min after Step 1 (Step 2). c Cross-sectional view of the film annealed at 700 C for 20 min after Step 2

that with only 5 min of deposition, ZnO

nanorods could be produced by our
methods.
In a previous report we demonstrated
the visualizations of particles behavior
in the gas phase by the UV-Rayleigh
scattering (UV-RS) method [8]. It revealed that in a high oxygen gas pressure of more than 1 Torr, nanoparticles
were formed in the gas phase by the condensation of ablated species, and then
reached the substrate surface. We also
confirmed that nanorods could grow
at such high gas pressures and that
no nanorods but only thin films were
formed when deposition was conducted
at low gas pressure. As a consequence,
we suggested that nanoparticles formed
in the gas phase play a very important
role in nanorod growth.
An additional set of experiments was
conducted to support this suggestion.
Firstly, in Step 1, we synthesized ZnO
nanorods for 10 min of deposition time
at a substrate temperature of 600 C.
The top view of the film after Step 1
can be seen in Fig. 4a, which shows that

ZnO nanorod arrays were formed. In

Step 2, the substrate temperature was set
to 300 C and 1 min of deposition was
performed after Step 1. Figure 4b shows
the cross-sectional SEM image of the
film after Step 2. Nanoparticles stacked
on top of the nanorods can be observed
in Fig. 4b. Finally, in Step 3 we annealed
this film at 700 C for 20 min. The crosssectional SEM image of the film after
Step 3 can be seen in Fig. 4c, which
shows that there were no particles on
the top of nanorods after this step. The
nanoparticles had melted at 700 C, supporting nanorod growth. These results
give direct evidence that nanoparticles
formed in the gas phase which reach the
substrate surface play an important role
in nanorod growth.
In conclusion, we have demonstrated a new growth method for ZnO
nanorods by pulsed-laser ablation. We
have proved that nanoparticles formed in
the laser ablation plume are transported
onto the substrate, where they fuse with
the nanorods. Stimulated emission from
the ZnO nanorods was observed in the

UV region around 388 nm by optical

pumping.
ACKNOWLEDGEMENTS The authors gratefully acknowledge Mr. M. Kawakami
for his contribution to this research. The authors
would also like to thank Prof. Y.F. Lu at the
University of Nebraska, Lincoln, for his valuable
comments. Part of the experimental work was carried out at the Center of Advanced Instrumental
Analysis, Kyushu University.

REFERENCES
1 D.M. Bagnall, Y.F. Chen, Z. Zhu, T. Yao,
S. Koyama, M.Y. Shen, T. Goto: Appl. Phys.
Lett. 70, 2230 (1997)
2 J.J. Wu, S.C. Liu: Adv. Mater. 14, 215 (2002)
3 Y.C. Kong, D.P. Yu, B. Zhang, W. Fang,
S.Q. Feng: Appl. Phys. Lett. 78, 407 (2001)
4 Y.W. Heo, V. Varadarajan, M. Kaufman,
K. Kim, D.P. Norton, F. Ren, P.H. Fleming:
Appl. Phys. Lett. 81, 3046 (2002)
5 Y.W. Wang, L.D. Zhang, G.Z. Wang, X.S. Peng,
Z.Q. Chu, C.H. Liang: J. Cryst. Growth. 234,
171 (2002)
6 P. Yang, H. Yan, S. Mao, R. Russo, J. Johnson, R. Saykally, N. Morris, J. Pham, R. He,
H.J. Choi: Adv. Funct. Mater. 12, 323 (2002)
7 Z.W. Pan, Z.R. Dai, Z.L. Wang: Science 291,
1947 (2001)
8 M. Kawakami, B.H. Agung, Y. Nakata,
T. Okada: Jpn. J. Appl. Phys. 42, 33 (2003)