ARTICLE IN PRESS

Journal of Crystal Growth 292 (2006) 227–229

www.elsevier.com/locate/jcrysgro

Growth of ZnO photonic crystals by self-assembly

J. Xie, H. Deng, Z.Q. Xu, Y. Li, J. Huang
School of Microelectronics and Solid State Electronics, University of Electronic Science and Technology of China, Chengdu 610054, PR China
Available online 18 May 2006

Abstract

In this paper, a novel method for the synthesis of monodispersed ZnO colloidal spheres is presented. The size of the colloidal spheres
varies inversely and monotonically with the amount of an intermediate product. These spheres were self-assembled into photonic crystals
and their microstructures were characterized by a scanning electron microscope. The photonic crystals exhibited a clear band gap in
specular reflectivity measurements. The position of the observed reflectance peak scales remarkably well with the diameter of the spheres,
indicating an intrinsic feature of the photonic crystals. The positions of the band gap shifted to a shorter wavelength with decrease in
ZnO particles size. Photoluminescence measurements showed efficient emission of the ZnO photonic crystals in the UV as well as a
defective emission band at longer wavelength.
r 2006 Elsevier B.V. All rights reserved.

PACS: 42.70.Qs; 81.16.Dn; 78.67.Bf

Keywords: A3. Self-assembly; B1. Colloidal spheres; B1. Photonic crystals; B1. Zinc oxide

1. Introduction Numerous techniques have been devised in an effort to

Photonic crystals (PCs) have recently attracted much
attention from both fundamental and practical points of
view, because novel physical concepts such as a photonic
band gap (PBG), have been theoretically predicted and
various applications of PCs have been proposed. PCs are
periodic dielectric structures designed to control the
propagation of electromagnetic (EM) waves by defining
allowed and forbidden energy bands in the photon
dispersion spectrum. One of the characteristic properties
of PCs is the presence of a PBG. At the PBG wavelength,
propagation of photons is inhibited inside the PC structure.
This creates a periodically varying scattering potential for
light, giving the material optical properties similar to the
electrical properties of a semiconductor [1–3]. This opens
intriguing perspectives in photonic applications like optical
fibers or high-bending-angle waveguides. However, it is a
great challenge to fabricate these PCs with a PBG at
optical and near-infrared frequencies, and to show a
significant effect on the spontaneous emission rate.
Corresponding author. Tel.: +86 28 83202551; fax: +86 28 83202569.
E-mail address: hdeng@uestc.edu.cn (H. Deng).
produce these periodic arrays [4]. Many techniques have
been used to fabricate PCs, such as lithography and a ‘top-
down’ approach. However, these approaches are relatively
expensive and time-consuming processes. In contrast,
chemical assembly of ordered dielectrics provides a simpler
and less costly approach to generating large-scale PCs.
These techniques make use of the spontaneous assembly of
submicron particles into specific well-ordered lattice
structures. ZnO is an important wide electronic band gap
semiconductor material, which has a higher refractive
index than other materials. In addition, ZnO has been
found to be an efficient emitter, exhibiting lasing behavior
in the near-UV. Therefore, ZnO is another promising
candidate for optically active self-assembled photonic
crystals. However, little research has been reported on
ZnO PCs [5].
In this paper, a novel method for synthesis of ZnO
colloidal spheres is presented. In addition, we have
proposed a tunable PC, in which the PBG can be tuned
as desired by controlling parameters such as size and
temperature of the ZnO colloidal sphere. The transmission
spectra of the PC shift systematically with the spheres size,
providing evidence of photonic crystal effects. Photolumi-

0022-0248/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2006.04.007
 ARTICLE IN PRESS
228 J. Xie et al. / Journal of Crystal Growth 292 (2006) 227–229

nescence (PL) measurements show efficient emission of the

ZnO photonic crystals in the UV as well as a defective
emission band at longer wavelength.

2. Experimental procedure

The method of synthesizing ZnO colloidal spheres

involves two steps. In a primary reaction, zinc acetate
dehydrate (ZnAc, 0.02 mol) was added into 150 ml of
diethylene glycol (DEG). This reaction solution was heated
to 180 1C. After reaching the working temperature, the
ZnO spheres precipitated. The intermediate product was
placed in a centrifuge. The polydispersed powder was
discarded and the supernatant (DEG, dissolved reaction
products, and unreacted ZnAc and water) was used in the
second step. A secondary reaction was then performed to
produce the monodispersed ZnO spheres, which began in
the same way as the primary reaction. ZnAc (0.02 mol) was
added to 150 ml DEG and the reaction solution was heated
under reflux. Prior to reaching the working temperature
(170 1C), a different volume of the primary reaction
supernatant was added to the solution. Following this
addition, there was a temperature drop, and precipitation
typically occured at a lower temperature than without such
an addition. After reaching 180 1C, the reaction was stirred
for 1 h, and then the ZnO colloidal suspension was
prepared. The size of the ZnO colloidal spheres was
controlled by varying the amount of supernatant added.
Photonic crystals were produced from the ZnO colloidal
spheres using a self-assembly sedimentation process. The
reaction solution was dropped onto a glass substrate at a
temperature ranging from 30 to 300 1C, and as the solvent
evaporated, the particles spontaneously assembled into
periodic arrays with different particle sizes.
The surface of the ZnO PCs was observed with a
scanning electron microscope (SEM, JSM-5900LV), the
optical properties were analyzed by a UV-VIS-NIR Fig. 1. SEM images of ZnO photonic crystals.
double-beam spectrophotometer (UV-2550, SHIMAD-
ZU), and the PL emission spectra by a fluorescence
spectrophotometer (RF-5301, SHIMADZU). (Fig. 2). The initial sphere sizes were measured directly
from SEM images of the ordered structures of ZnO
3. Results and discussion spheres.
The prominent feature is a specular reflectivity peak for
The SEM images in Fig. 1 reveal that the ordered each structure, which systematically shifts from 400 to
structures of ZnO were synthesized using this technique, 1000 nm over the range of photonic crystals. The wave-
and that the size of the colloidal spheres varied inversely length of the specular peak corresponds very well to the
and monotonically with the amount of primary super- size of ZnO colloidal spheres. The wavelengths of the
natant added. This result provides a method to easily reflectivity peaks cover the entire visible spectrum and
synthesize monodispersed ZnO colloidal spheres over a extend well into the near-infrared spectrum. In addition,
broad size range (100–600 nm), with good control over the there is a gradual but featureless increase in reflectivity at
diameter. It is possible to extend this method to produce longer wavelengths in several samples (Fig. 2). This is due
particles larger or smaller than those that have been to the rough surface of the PCs appearing smoother when
synthesized so far. probed at longer wavelengths. This increases the specular
Large-area reflectance measurements were made to reflectivity, with an accompanying decrease of the diffuse
detect the presence of a photonic stop band. The specular reflectance at longer wavelengths.
reflectance at near-normal incidence from our ordered The position of the observed reflectivity peak scales
structures is shown for different sizes of colloidal spheres remarkably well with the diameter of the spheres (Fig. 3),
 ARTICLE IN PRESS
J. Xie et al. / Journal of Crystal Growth 292 (2006) 227–229
Fig. 2. Reflectance spectra of ZnO films.
Fig. 3. Stop band position lc vs. the spheres’ diameter D.
indicating an intrinsic feature of the photonic crystals.
With the decrease in size of the colloidal spheres, the
reflectance spectra of these ordered structures blue shift.
This is an observation of the optical signature of a
photonic crystal together with the required scaling with
sphere size, which has been seen in some typical PCs like
polystyrene [6].
Fig. 4 shows the PL emission spectra of a typical film. PL
measurements show efficient emission of the ZnO photonic
crystals in the UV as well as a defective emission band at
longer wavelength. This proves that the self-assembly
technique produces high-quality films.
For samples with band gaps overlapping the emission
spectrum, we observed modification and suppression of
229
Fig. 4. PL image of ZnO film.
emission due to the modified densities of photonic states,
and a detailed investigation of the band structures and their
influence on the PL and lasing properties of ZnO is
currently being conducted.
4. Conclusion
In summary, we have developed a rapid, economical,
and simple technique to produce large-area ZnO optical
photonic crystals. It is important that this technique allows
close and predictable control of the size of the colloidal
spheres during the secondary reaction by varying the
amount of primary reaction supernatant added. The
specular reflectance experiments yielded an ordered crystal-
line structure. It is found that with the decrease in the size
of the colloidal spheres, the reflectance spectra of these
ordered structures blue shift.
Acknowledgment
The authors wish to thank the Chinese Nature Science
Fundamental Committee (Grant no. 60390073) and Na-
tional ‘‘973’’ (Project no. 51310Z09) for financial support.
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