Appl. Phys.

A 80, 10491051 (2005)

Applied Physics A

DOI: 10.1007/s00339-004-3044-9

Materials Science & Processing

t.-w. kim1,,u
t. kawazoe1
s. yamazaki2
m. ohtsu1,2,

Low-temperature synthesis
and room temperature ultraviolet lasing
of nanocrystalline ZnO films
1 Japan

Science and Technology Corporation, 687-1, Tsuruma, Machida, Tokyo, 194-0004, Japan
Graduate School of Science and Engineering, Tokyo Institute of Technology, Yokohama,
Kanagawa, 226-8502, Japan

2 Interdisciplinary

Received: 4 March 2004/Accepted: 20 September 2004

Published online: 18 November 2004 Springer-Verlag 2004
ABSTRACT Nanocrystalline ZnO films were fabricated via
a simple method involving the oxidation of Zn films at a remarkably low temperature of 380 C. X-ray diffraction study confirmed that the Zn films were completely oxidized even at the
low temperature of 380 C and the ZnO films fabricated were
of polycrystalline wurtzite structure. Room temperature optical pumping using a frequency-quintupled Q-switched Nd:YAG
laser ( = 213 nm) exhibited that sharp peaks at around 3.12 eV
emerged above excitation powers of 7 MW/cm2 , demonstrating lasing in the ZnO films. These results represent that the
process is a simple, promising approach for fabricating ZnO of
sufficient optical performance for use as ultraviolet (UV) light
emitters and an alternative UV laser source; both are key components in short-wavelength photonic devices.
PACS 81.07.Bc; 61.46.+w;

68.55.-a; 78.55.Et; 42.55.Px

ZnO, which has a room temperature bandgap of 3.37 eV and

an exciton binding energy of 60 meV, is a promising wide
bandgap semiconductor for applications with photonic devices in ultraviolet (UV) region [13]. In particular, the high
exciton binding energy is feasible for fabricating the photonic devices emitting UV light or laser at room temperature
(RT) via an exciton recombination process. Few researchers
have report the room temperature observation of UV emission
and/or lasing in epitaxially grown ZnO films fabricated by
using several methods such as pulsed laser deposition [4, 5],
plasma-assisted molecular beam epitaxy [6], and metalorganic vapor phase epitaxy [7]. Recently, it was reported that
UV lasing were demonstrated in ZnO nanowires synthesized
at a relatively high temperature of about 1000 C using a vapor
phase transport process [8].
However, requirements of epitaxial growth of the film or
a high growth temperature might restrict an available substrate
material due to their lattice mismatches and higher endurance
against heat. Therefore, development of a low temperature
u Fax: +81-44-819-2053, E-mail: twkim90@ksp.or.jp
Present address: Kanagawa Academy of Science and Technology
(KAST), 3-2-1, Sakado, Takatsu-ku, Kawasaki, Kanagawa, 213-0012
Japan
Present address: School of Engineering, The University of Tokyo,
7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan

process for preparing high-quality ZnO films with reliable optical performances is strongly required to manufacture a variety of ZnO-based optical devices. In the previous report,
we have showed that ZnO nanocrystallites fabricated by the
same low temperature oxidation of metallic Zn precursors,
exhibited strong UV emission peak around 3.27 eV at room
temperature [9]. In addition, for fabricating a high-quality
ZnO nanodots, we have developed a technique with control
over the size and position, using near-field optical chemical
vapor deposition (NFO-CVD) [10]. Furthermore, the photoluminescence properties of a single ZnO nanodot fabricated
using the method were reported [11]. ZnO nanodots can be
a promising material for a nanophotonic switching device that
is indispensable for the realization of nanophotonic integrated
circuits (ICs) we proposed [12]. In this study, we report the
low temperature growth of nanocrystalline ZnO films and the
observation of UV lasing in the films.
We employed a simple method for fabricating nanocrystalline ZnO films via the oxidation of Zn films at a remarkably
low temperature of 380 C; Zn films with a nominal thickness
of 500 nm were deposited on CaF2 (111) substrate by thermal evaporation of pure metallic Zn powder (99.999%), and
then the sample was placed in a thermal furnace under a constant flow of high-purity oxygen gas. The crystal structure and
morphology of the samples were characterized using X-ray
diffraction (XRD) and scanning electron microscopy (SEM),
respectively. Optical pumping was carried out using a frequency quintupled Q-switched Nd:YAG laser ( = 213 nm,
20 Hz, 4 ns pulse width) at room temperature. The pump beam
was focused to a spot of 0.5 mm diameter on the film with the
45 oblique direction and the emission light were detected in
the normal direction to the film.
Figure 1 shows XRD patterns of as-deposited metallic Zn
films (a) and ZnO (b) obtained by the oxidation at 380 C for
6 h. For the as-deposited Zn thin films, a strong peak is observed at 2 = 36.39 , which corresponds to the (002) diffraction of hexagonal phase Zn (Fig. 1(a)). Annealing the sample
at 380 C transformed the Zn into ZnO, as shown in Fig. 1(b).
Diffraction peaks are observed at 2 = 31.88 , 34.56 , and
36.29 , which correspond to (100), (002), and (101) of ZnO
with wurtzite structure, respectively. Simple estimation of the
lattice constants with the position of each diffraction peak provides lattice constants of a = 0.324 and c = 0.519 nm, which
are in good agreement with those of bulk ZnO. In contrast,

1050

Applied Physics A Materials Science & Processing

FIGURE 1 XRD patterns of as-prepared Zn films and the ZnO fabricated at 380 C. For the as-prepared Zn films, a strong peak is observed at
2 = 36.39 , which corresponds to the (002) diffraction of hexagonal phase
Zn. After oxidation at 380 C, diffraction peaks are observed at 2 = 31.88 ,
34.56 , and 36.29 , which correspond to (100), (002), and (101) of ZnO with
wurtzite structure, respectively

no peak of Zn was observed for the sample. These indicate

that the Zn films are completely transformed into crystalline
ZnO at a temperature as low as 380 C. We have oxidized
the samples at various temperatures. According to the results, above 420 C single crystalline ZnO nanowires were
obtained instead of polycrystalline ZnO nanocrystallites. We
could not observe the laser action in the samples composed of
nanowires. We think that the result was caused by the thin film

thickness. The detailed experimental results on these were

given in our previous work [13]. In addition, we have also
tried to fully oxidize the sample below 380 C, but the samples oxidized below 380 C for 6 hrs were not fully oxidized.
This fact was confirmed by the XRD and X-ray photoelectron
spectroscopy measurements.
Figure 2 shows typical SEM images of as-prepared Zn
films with a different film thickness (a and b) and ZnO films
(c and d) formed after oxidation at 380 C for 6 h; a nominal
film thickness of 50 nm for a and c, and 500 nm for b and d.
Lots of separated hexagonal Zn plates, of which diameters
range from 100 to 900 nm with thicknesses from 20 to 50 nm,
are seen in Fig. 2a. We believe that the characteristic hexagonal shape is indicative of the formation of single-crystal
pure metal Zn. As the film thickness increases, layer structure
of Zn plates are seen in Fig. 2b. After oxidation, the hexagonal
Zn plates somewhat swelled due to the increase of the cell
volume caused by the incorporation of oxygen (see Fig. 2c,d).
We carried out optical pumping for the sample at room
temperature. Figure 3 shows the emission spectra observed
with the different pulse energies. And the inset illustrates the
measurement configuration. For the pulse energy of 0.022 mJ,
a broad emission peak is observed at around 385 nm, which
is attributed to a spontaneous emission of ZnO. As the excitation energy increases, the emission intensity rapidly increases
and sharp peaks emerge in the spectra, when the excitation
energy exceeded 0.043 mJ, showing the onset of laser action.
The full-width half maximum (FWHM) of the sharp peaks is
less than 0.6 nm, which is much smaller than that of the spontaneous emission peak. Figure 4 shows the integrated emission intensity as a function of incident pump pulse energy.
The threshold intensity for the lasing was determined to be

FIGURE 2 SEM images of asprepared Zn films with a different

film thickness ((a) and (b)) and
the ZnO films ((c) and (d)) formed
after oxidation at 380 C for 6 h;
a nominal film thickness of 50 nm
for (a) and (c), and 500 nm for (b)
and (d)

KIM et al.

Low-temperature synthesis and room temperature ultraviolet lasing of nanocrystalline ZnO films

1051

0.4 MW/cm2 . We believe that lasing in our sample resulted

from the same mechanism. However, it should be noted that
their samples were prepared with pulsed laser deposition at
a relatively high temperature (500 700 C) comparing with
that in our case (380 C). Meanwhile, S. Cho et al. reported the
observation of lasing in ZnO polycrystalline films fabricated
at 1000 C [15]. The threshold intensity of their sample was
9 MW/cm2 . Here, it may be worthy to notice that there is
a difference in the threshold intensities between the samples.
We think that the threshold intensity can be affected by several
parameters such as size of ZnO nanocrystals, film thickness,
and compactness of sample. In our case, the laser action can
be achieved using ZnO films fabricated at a remarkable low
temperature of 380 C.
In conclusion, we have fabricated nanocrystalline ZnO
films via a simple method involving the oxidation of Zn
films at a remarkably low temperature of 380 C. Room
temperature optical pumping using a frequency-quintupled
Q-switched Nd:YAG laser ( = 213 nm) exhibited that sharp
peaks at around 3.12 eV emerged above excitation powers of
7 MW/cm2 , demonstrating lasing in the ZnO films. These
results represent that the process is a simple, promising approach for fabricating ZnO of sufficient optical performance
for use as ultraviolet (UV) light emitters and an alternative UV
laser source; both are key components in short-wavelength
photonic devices.
FIGURE 3 Emission spectra from the nanocrystalline ZnO films when the
pump pulse energy is 0.022, 0.043, and 0.116 mJ (from bottom to top). The
inset illustrates the measurement configuration

ACKNOWLEDGEMENTS

We

gratefully

acknowledge

Dr. T. Yatsui for his useful discussions.

REFERENCES

FIGURE 4 Integrated emission intensity of the ZnO films as a function of

the incident pump pulse energy

7 MW/cm2 . Recently, there were a few reports on the lasing from polycrystalline ZnO film. For instance, H. Cao et al.
investigated the lasing in ZnO polycrystalline films composed
of fine ZnO nanoparticles with sizes of 50 150 nm [14]. According to their report, lasing action can be achieved in polycrystalline ZnO films by self-formed cavities due to strong
optical scattering in the films. And the threshold intensity was

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