10.1117/2.1201312.

005270

Zinc oxide nanostructures

for optoelectronic and
energy devices
Yeong Hwan Ko, Soo Hyun Lee, and Jae Su Yu

Nanostructures in wide-bandgap metal oxides could enhance light-

trapping for solar energy technology and LEDs.

Zinc oxide (ZnO), indium tin oxide (ITO), and titanium diox-
ide (TiO2 ) have wide bandgaps (the ‘energy gap’ in a solid
that defines its electrical conductivity) and are highly ef-
fective materials for electronic/optoelectronic and chemical
device applications.1–3 The oxides are characterized by low-
dimensional (0D, 1D, and 2D) nanostructures and architectures,
including nanorod arrays (NRAs), submicrorod arrays (SMRAs),
and cone-shaped subwavelength nanostructure arrays (SNAs).
These features exhibit superior optical and morphological prop-
erties not observed in bulk materials, due to quantum size ef-
fects. Such nanostructures have potential for high-performance
novel electronic and optoelectronic devices.
ZnO nanostructures have a rich variety of morphologies
with significant optical, electrical, mechanical, and piezoelectric
features,4 and it is possible to fabricate hierarchical examples us-
ing a 3D template. For example, urchin aggregation-shaped ZnO
architectures can be prepared by growing the ZnO NRAs on
silica microspheres (see Figure 1).5 Considering finite-difference
time-domain calculations, we expected these nanostructures
(ZnO NRAs on microspheres) to provide efficient diffuse light
scattering, dependent on the size of the spheres and the angle
at which the NRAs bent. We grew nanorods on monolayer ar-
rays of silica microspheres (970nm in size) and achieved a trans-
mittance haze ratio (the ratio of total transmittance to diffuse
transmittance) of >70% at wavelengths of 400–900nm, while
maintaining high total transmittance. This diffuse light scat-
tering enhancement may contribute to efficient light trapping,
offering the potential to improve the performance of thin-film
silicon solar cells.
To grow the ZnO NRAs on silica microspheres, we layered
aluminum-doped ZnO (AZO) as a seed layer over the surface
Figure 1. Schematic illustration of diffuse light scattering in urchin
aggregation-shaped zinc oxide nanorod arrays (ZnO NRAs), which is
dependent on the size of the spheres and the angle at which the NRAs
bend. AZO/ITO: Aluminum-doped ZnO deposited on indium tin ox-
ide. AZO/silica: Aluminum-doped ZnO deposited on silica. c : Contact
angle. UV PL: UV photoluminescence. a.u.: Arbitrary units.
of microspheres by radio-frequency magnetron sputtering.
Using a hydrothermal technique, we aligned the ZnO nanorods
vertically on the surface of the seed layer in line with the
c-axis direction of growth in wurtzite crystal structures. The
urchin aggregation-shaped ZnO architectures then formed on
the transparent substrate. For these nanostructures on silica
microspheres, we also observed enhanced UV photolumines-
cence (PL) intensity and their hydrophobic surface properties.5
We noted high UV PL emission intensity, owing to the increased
intensity of the ZnO NRAs on silica spheres. In comparison with
the ZnO NRAs without the spheres, the UV PL emission inten-
sity was 4.26 times greater. Additionally, the modified surface of
the urchin aggregation-shaped ZnO architectures changed the
contact angle (c ) from 36.65 to 90.51◦:
Continued on next page
 10.1117/2.1201312.005270 Page 2/3

Piezoelectric charge generation occurs when the ZnO NRAs

are deformed by an external influence. The surface morphology
of ZnO SMRAs (which are relatively large and are more closely
packed together than in ZnO NRAs) creates a rough surface on a
gold film electrode, which readily bends each ZnO nanorod (see
Figure 2).6 From the theoretical calculation for the strain distri-
bution of piezoelectric nanogenerator (NG) structures, it seems
highly possible that such rough gold film can transfer the me- Figure 3. Schematic diagram and beam pattern of the fabricated
chanical force to the side and edge parts of ZnO NRAs because aluminum-doped subwavelength nanostructure arrays (AZO SNAs)
they are bent with a large radius. We observed that output cur- on gallium nitride (GaN)-based green LEDs. CW: Continuous wave.
rent density was enhanced 1.54 times in the piezoelectric NG
with a very rough gold top electrode.
The GRIP considerably reduces the reflection loss between the
When we deposited gold on the discrete surface of ZnO
air and the substrate because of the change in refractive index.
SMRAs using thermal evaporation, the nanoparticles grew
Moreover, wide-bandgap metal oxide SWGs can offer highly
larger at the top surface of the arrays because of the coarsening,
transparent substrates or windows for optoelectronic device ap-
forming a highly rough gold top electrode. Under compression,
plications. In our work, we fabricated AZO SNAs by laser in-
we induced positive and negative potentials at the stretched
terference lithography and dry etching processes and applied
and compressed sides of ZnO NRAs, respectively, and electric
these as a top layer on gallium nitride (GaN)-based LEDs to
charges flowed from the ZnO to the top electrode. The rough
enhance their light extraction (see Figure 3).7 From rigorous
surface of the electrode increased the output current because
coupled-wave analysis, we reduced the internal reflection loss
it could efficiently bend the ZnO NRAs with a large radius.
to 5% at the wavelength of 525nm for indium gallium arsenide
Compared with a gold film deposited on bare polyethylene
(InGaN)/GaN multiple quantum well green LEDs when the pe-
terephthalate, the piezoelectric NG with the rough surface top
riod of the AZO SNAs was less than 320nm. Compared with
electrode improved output current density by 1.54 times under
the conventional LED (with only an ITO top layer), the light ex-
the same external force of 0.9kgf. This fabrication process is sim-
traction efficiency with AZO SNAs was enhanced by 19% at
ple and cost-effective enough to improve the performance of
100mA of injection current and 300K of temperature. Also, the
piezoelectric NGs because the ZnO NRAs and SMRAs can be
far-field radiation angle and intensity distribution were wider
prepared in the same way, without additional processes.
and increased for the overall angular position.
A further method to increase light absorption in solar cells is
In summary, the unique optical and morphological proper-
to use moth eye-inspired gallium arsenide or silicon subwave-
ties of wide-bandgap metal oxide nanostructures used in multi-
length grating structures (SWGs), which suppress surface re-
functional materials are advantageous for optoelectronic and
flection losses. The geometry of SWGs provides a continuously
energy device applications. For example, urchin aggregation-
graded effective refractive index profile (GRIP) when the period
shaped ZnO architectures induce diffuse light scattering while
of the SWGs is smaller than the wavelength of incident light.
keeping a high total transmittance, which is promising for im-
proving the light-trapping properties of thin-film silicon solar
cells. The novel surface morphology of ZnO SMRAs is favorable
for forming a highly rough top electrode, which bends the ZnO
nanorods of piezoelectric NGs and leads to an increase in output
current density. Furthermore, AZO SNAs can be employed as a
top layer for LEDs to increase light-extraction efficiency.
In future work, we will develop a fabrication method for in-
tegrating the ZnO nanostructures onto textile or polymer sub-
strates for use in wearable, flexible, or stretchable optoelectronic
Figure 2. Schematic diagram of piezoelectric nanogenerators with ZnO and energy devices. We will also extend the studies on the wide-
NRAs and submicrorod arrays (SMRAs) for efficient bending action of bandgap semiconductor nanostructures by incorporating TiO2 ,
ZnO NRAs owing to the highly rough gold (Au) top electrode (e) (left). tin dioxide, and cerium(IV) oxide.
Generated output current density (right). PET: Polyethylene tereph-
thalate. Continued on next page
 10.1117/2.1201312.005270 Page 3/3

Financial support for this work came from the Basic Science Research
Program through the National Research Foundation of Korea funded
by the Ministry of Science, ICT, and Future Planning (2013-010037)
and a grant from the Ministry of Knowledge Economy of the Republic
of Korea, under project 10039151.

Author Information

Yeong Hwan Ko, Soo Hyun Lee, and Jae Su Yu

Kyung Hee University
Yongin, South Korea

Jae Su Yu is director of the Institute for Laser Engineering. His

main research interests are optoelectronic and nano semiconduc-
tor devices.
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c 2013 SPIE