JOURNAL OF APPLIED PHYSICS 99, 093520 2006

Enhancement of near-band-edge photoluminescence of ZnO thin films in

sandwich configuration at room temperature
Ruijin Honga
Research and Development Center for Optical Thin Film Coatings, Shanghai Institute of Optics and Fine
Mechanics, Chinese Academy of Sciences, Shanghai 201800, Peoples Republic of China and
Graduate School of Chinese Academy of Sciences, Beijing 100864, Peoples Republic of China

Jianda Shao, Hongbo He, and Zhengxiu Fan

Research and Development Center for Optical Thin Film Coatings, Shanghai Institute of Optics and Fine
Mechanics, Chinese Academy of Sciences, Shanghai 201800, Peoples Republic of China

Received 8 July 2005; accepted 29 March 2006; published online 15 May 2006
ZnO/ITO/ZnO sandwich structure films were fabricated. The effects of buffer layer on the
structure and optical properties of ZnO films were investigated by x-ray diffraction XRD,
photoluminescence, optical transmittance, and absorption measurements. XRD spectra indicate that
a buffer layer has the effects of lowering the grain orientation of ZnO films and increasing the
residual stresses in the films. The near-band-edge emissions of ZnO films deposited on both single
indium tin oxide ITO buffer and ITO/ZnO double buffers are significantly enhanced compared
with that deposited on a bare substrate due to the quantum confinement effect. 2006 American
Institute of Physics. DOI: 10.1063/1.2198934
I. INTRODUCTION

II. EXPERIMENTS

Recently, ZnO and related oxides are attracting much

attention as promising candidates for optoelectric applications in visible and ultraviolet UV regions, such as light
emitting devices, owing to large exciton binding energy
that permits excitonic recombination even at room
temperature.13 Several techniques have been employed to
synthesize high-quality ZnO films, such as laser ablation,
molecular beam epitaxy, spray pyrolysis, and radio frequency magnetron sputtering.46 The optoelectronic properties of ZnO films are sensitive to its crystal perfection. Photoluminescence PL spectroscopy is a powerful tool in
characterizing the optical quality of semiconductor materials.
The quality of ZnO films is determined not only by the
growth processes, but also by the postgrowth treatment, for
example, thermal annealing. However, high temperature is
not desirable for many processes. In most cases, multilayer
thin films have shown different physical properties than the
conventional single layer thin films. The quality of films deposited on a buffer layer was found to be superior to those
grown directly on a substrate. ZnO / Mg, ZnO multilayer
thin films have attracted much attention due to their potential
applications. A quantum-well structure is proven to be an
important approach to improve the structural and optical
properties of films.79
Tin-doped indium oxide ITO is an n-type wide-bandgap semiconductor. It is ubiquitous in all kinds of flat panel
displays and solar cells, and it is commercially available,10
though very few reports have focused on the PL related property of ITO. In this letter, we reported the study of the influences of an ITO buffer layer on the structure and PL of ZnO
thin films.

ZnO films were deposited by magnetron reactive sputtering using a Zn target 99.99%. Film growth was carried
out in the growth ambient with a mixture of argon 40% and
oxygen 60% and at a constant working pressure of 0.15 Pa.
ITO films were grown by thermal evaporation from sintered
ITO ceramics 99.99% containing 5 wt % SnO2. The structures of the samples were shown in Fig. 1. Both ZnO and
ITO films were deposited at a thickness of 100 120 nm. The
crystal structure of the films was characterized by x-ray diffraction XRD using a Rigaku D/Max-B system, with
Cu K radiation = 0.154 08 nm. PL spectra were acquired
in a JASCO fluorespectrometer from 300 to 750 nm, with
248 nm excitation light. The optical transmittance and absorption of the films were measured with an UV-VIS-NIR
double beam spectrophotometer Perkin Elmer, USA. All
the measurements were carried out at room temperature.
III. RESULTS AND DISCUSSION

XRD spectra as shown in Fig. 2 reveal the influence of a

buffer layer on the structure of the ZnO thin film. It was
apparent that the ZnO films deposited on fused silica consisted of a single ZnO phase with its c axis oriented normal
to the substrate surface; no diffraction from randomly oriented grains or impurity phases can be observed. The surface

FAX: 86-21-69918028; electronic mail: rjhong@mail.siom.ac.cn

FIG. 1. Schematic structures of samples with and without buffer layers.

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2006 American Institute of Physics

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J. Appl. Phys. 99, 093520 2006

Hong et al.

FIG. 2. XRD patterns of ZnO thin films with and without buffer layers.

energy density of the 002 orientation is the lowest in the

ZnO crystal. Grains with the lower surface energy will become larger as the film grows. Then, the growth orientation
develops into one crystallographic direction of the lowest
surface energy. This means that the 002 textured film must
form in an effective equilibrium state, where enough surface
mobility is given to impinging atoms under a certain deposition condition. Nonequilibrium conditions give rise to other
grain orientations, which are detected as other XRD peaks
such as 100 and 101.11 Very good textured ITO films can
be grown on glass with a thin ZnO buffer. Yi et al. proposed
that it is due to a small lattice mismatch 3% between the
neighboring oxygen-oxygen OO distance on the closestpacked 111 plane of ITO and 0001 plane of ZnO.12 However, with an ITO buffer, the XRD intensity of the ZnO film
decreases drastically compared to that without a buffer layer.
When ITO/ZnO double buffers were applied, the crystalline
quality of ZnO was improved. It can be seen from Fig. 2 that,
when a buffer layer was applied, besides the 002 peak,
other peaks such as 100 and 101 appeared in the XRD
pattern. This indicates that the introduction of a buffer induces the increase of the surface energy of films. According
to Table I, the introduction of ITO/ZnO double buffer layers
has the effects of narrowing the diffraction peak, indicating
that grain growth has occurred, and shifting the 002 peaks
to higher 2 angles, a result of the partial increase of residual
stresses within the films.
Figure 3 shows the transmittance spectra for the samples
with and without buffer layers. The transmittance spectra
have shown that all films exhibit high transmittance
80% in the 400 1200 nm range. The variety of transmittance in the visible region is simply due to an etalon
interference effect. Transmission, however, falls very sharply
in the UV region due to the onset of fundamental absorption.
The absorption edge shifted towards longer wavelength with

FIG. 3. Optical transmittance spectra of ZnO thin films with and without
buffer layers.

the increase of the buffer layer, which would be caused by

both the difference of their overall thicknesses and the diffusion of the indium to the ZnO layer.13 The optical band-gap
energy Eg was calculated from the 2 vs Eg plot by assuming that 2 h Eg, where is the absorption coefficient
and h is the photon energy for the samples. The sample
deposited on bare substrate, ITO buffer, and ITO/ZnO double
buffers have optical band-gap energies of 3.20, 3.19, and
3.17 eV, respectively.
Figure 4 shows the room temperature PL spectra of
samples with and without a buffer layer. The shape of all the
spectra, being similar to those reported by others,14 was featured by an emission near UV peaking and the deep level
emission in the visible region. We know that visible luminescence, which is related to deep level emissions, is mainly due
to defects such as Zn interstitials and oxygen vacancies. The
UV emission originates from free excitonic emission.15 All
the PL peaks show a Stokes shift, i.e., the peak energies are
lower than the absorption energy, as seen in Fig. 4. With a
buffer layer, the intensities of the UV emission peaks were
improved remarkably compared with that without a buffer
layer. In general, the emission intensity is determined by the
radiative and nonradiative transitions. The luminescence
efficiency of the light emission can be described by the following formula:16

TABLE I. The data evaluated from XRD -2 scans for the samples with
and without an ITO buffer layer.

Sample
ZnO
ZnO/ITO/ZnO

Interplanar spacing FWHM Average grain

Stress
film MPa
d nm

size nm
0.2604
0.2603

0.449
0.398

37.04
41.80

107.336
152.060
FIG. 4. PL spectra of ZnO thin films with and without buffer layers.

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J. Appl. Phys. 99, 093520 2006

Hong et al.

IR
,
IR + INR

where is the luminescence efficiency, and IR and INR are

radiative and nonradiative transition probabilities, respectively. In the case of ZnO, the nonradiative transition is induced by crystal imperfections, such as point defects, dislocations, and grain boundaries. For the as-grown ZnO films
prepared by a dc reactive sputtering method, the chemical
component is nonstoichiometric due to excess Zn atoms.17
Therefore, many lattice defects and surface defects are contained in the as-grown ZnO films. These defects produce
various nonradiative centers and reduce the emission intensity from the ZnO. Thus, the nonradiative transition probability INR is high for the as-grown film, and the light emission is
weak for such film. For the multilayer films consisting of
ZnO/ITO/fused silica or ZnO/ITO/ZnO/fused silica, a
quantum-well structure was fabricated. The intensities of UV
emission were enhanced significantly, and visible emissions
were quenched. We suggest that this kind of improvement
can be explained by the enhanced binding energy of excitons
due to the radiative recombination of electron-hole pairs in
terms of quantum-confined effect.
IV. CONCLUSIONS

In summary, we investigated the influence of an ITO

buffer layer on the structure and optical properties of ZnO
thin films. By applying a single ITO buffer layer, the ZnO

film showed a drastic decrease in crystallinity, while the

adoption of ITO/ZnO double buffers significantly improved
the crystallinity of ZnO thin films. Both single and double
buffers have the effects of enhancing UV emission and
quenching visible emission of ZnO thin films.
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