Advanced Materials Research Vol.

789 (2013) pp 132-137

Online available since 2013/Sep/04 at www.scientific.net
© (2013) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.789.132

Optimizing the Nanostructural Characteristics of Chemical Bath

Deposition derived ZnO Nanorods by Post-Hydrothermal Treatments
Akhmad Herman Yuwono1,a, Amalia Sholehah1,2,b, Sri Harjanto1,
Donanta Dhaneswara1, Fajrika Maulidiah2
1
Department of Metallurgical and Materials Engineering, Universitas Indonesia, Indonesia
2
Department of Metallurgical Engineering, Universitas Sultan Ageng Tirtayasa, Indonesia
a
ahyuwono@metal.ui.ac.id, bamalia.sholehah@ft-untirta.ac.id

Keywords: ZnO nanorods, low temperature seeding solution, chemical bath deposition, post-
hydrothermal treatment

Abstract. Zinc oxide (ZnO) is an inorganic semiconductor material which has been widely studied
due to its various potential applications. Over the past decades, one-dimensional (1-D)
nanostructures such as nanowires and nanorods have stimulated significant scientific interests
because of their unique properties in comparison to bulk materials. For the application of dye
sensitized solar cell (DSSC), 1-D ZnO nanostructures are more desired than the spherical
nanoparticles since the former provides ballistic effect leading to faster electron transfer which in
turn can increase the device performance. Motivated by this consideration, in the current study ZnO
nanorods were deposited on ITO glass substrate via chemical bath deposition (CBD) process where
the seeding solution was prepared at 0oC. In order to increase their crystallinity and optical
properties, the as-deposited ZnO nanorods were subjected to post-hydrothermal treatment at 150oC
for 3, 6 and 9 hours. The scanning electron microscope (SEM) analysis revealed that the ZnO
nanorods were successfully grown as vertically-aligned hexagonal structure, while the X-ray
diffraction (XRD) study showed that the intensity of (002) crystal plane is the highest peak for all
nanorod samples. The optical study by UV-Vis spectroscopy showed that the absorption edge of the
as-deposited sample was slightly red-shifted to visible region after post-hydrothermal treatment.
The ZnO nanorods sample derived from post-hydrothermal treatment for 6 hours provided the
optimum nanostructural characteristics with an average diameter of 228 nm, crystallite size of 27.97
nm and the band gap energy, Eg, of 3.12 eV.

Introduction
Among other functional materials, zinc oxide (ZnO) has been well-known as both scientifically and
technologically important material. This semiconductor material possesses a wide band gap energy
(Eg) of 3.07 eV and large exciton binding energy of 60 meV at room temperature [1], which are
important for optoelectronics application. ZnO is also considered as one of strategic piezoelectric
materials due to lack of point symmetry in its wurtzite structure. Owing to these characteristics,
ZnO is very promising for applications in the areas of sensors [2], optoelectronic devices [3], and
piezoelectric devices [4]. In recent years, one dimensional (1-D) nanostructured materials in highly
ordered arrays, such as nanorods, nanowires and nanotubes, have attracted considerable attention
due to their remarkable physical properties and potential applications. In this context, moreover,
ZnO nanostructures are now considered as potential candidate to replace titanium dioxide (TiO2) in
dye sensitized solar cell (DSSC) [5]. With its characteristic as direct band gap semiconductor, ZnO
is expected to be more responsive in the photon absorption mechanism than TiO2, which is an
indirect band gap material. Moreover, reducing the size of ZnO down to nanometer scale has been
thought as one of strategies to enhance the performance of DSSC, considering a higher surface to
volume ratio in comparison to its bulk form, which in turn provides a more pronounced interaction
with the dye molecules. In terms of device performance enhancement, ZnO nanorods has been
thought to be more desired than the spherical nanoparticles since the former provides ballistic effect
leading to faster electron transfer.

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 Advanced Materials Research Vol. 789 133

ZnO nanorods can be synthesized through various procedures such as radio frequency
sputtering [6,7], chemical vapor deposition (CVD) [8], chemical bath deposition (CBD) [9,10], and
hydrothermal process [11]. CBD is well-known as a soft chemical route which is simple and cheap
while provides various advantages such as less energy consumption due to its low-temperature
process, high yield and easy control of the process condition [12]. Therefore, this method is suitable
for large scale production of ZnO nanorods [13]. By using CBD, Lang et al. [9] have successfully
grown ZnO nanorods on Si (100) substrate, where the growing solution was prepared at low
temperature of 5oC. However, the resulting nanorods still grew in a rather random orientation and
lack of crystallinity. In our previous work [14], we have combined CBD method with post-
hydrothermal treatments at 150oC for 3 and 12 hours to obtain vertically aligned ZnO nanorods.
Nevertheless, the nanorods obtained still needed further improvements. The present work is
therefore aimed at enhancing the nanostructural characteristics of ZnO nanorods derived from CBD.
For this purpose, post-hydrothermal treatments with pressurized water vapor were applied on the as-
deposited ZnO nanorods on ITO substrates, but with shorter period than that of in our previous
work. The effects of different duration of post-hydrothermal treatments on the morphology,
crystallite size, and band gap energy of the ZnO nanorods were further investigated.

Experimental Details

First, the seeding solution was prepared by dissolving 0.05 M zinc nitrate tetrahydrate
(Zn(NO3)2.4H2O) and hexamethylenetetramine, HMTA (C6H12N4) in cold water of 0oC. ITO glass
substrates were placed vertically in the seeding solution and heated in a muffle furnace at 90oC for 3
hours. The as-deposited ZnO nanorods were rinsed and dried at room temperature. In order to
improve the crystallinity and growth direction of the nanorods, they were subjected to the post-
hydrothermal treatments afterwards. This process was carried out by exposing the as-deposited ZnO
samples to pressurized water vapor inside a hydrothermal container (Parr Molline, Illinois) heated at
150oC. The duration of post-hydrothermal treatment was varied into 3, 6, and 9 hours, in
comparison to that of in our previous work, i.e. 3 and 12 hours. X-ray diffraction (XRD) patterns of
the samples were obtained at room temperature with Cu Kα radiation (λ = 1.5418 Å) for crystal
phase identification of ZnO (Shimadzu X-Ray Diffractometer 7000). The average crystallite size
was estimated using Scherrer’s formula [15,16]. The morphology of ZnO was observed using
scanning electron microscopy (JEOL JSM-6510LA), whereas UV-visible absorbance spectra of
samples were recorded on Shimadzu 2450. The respective band gap energy (Eg) of the samples was
determined by using Tauc equation [17] on the absorbance data.

Results and Discussion

Fig. 1 shows the SEM images of ZnO arrays on ITO substrate at various conditions. In general,
most of the ZnO nanorods were grown vertically with good coverage on the substrates and they
have hexagonal cross-sections. The as-deposited ZnO nanorods were grown in a rather bulky
vertically-aligned structure with an average diameter of ~325 nm (Fig. 1a). Among the nanorods,
there existed some voids unavoidably as a result of the irregular nanorods growth from the seeding
solution at 90oC. Moreover, the applied post-hydrothermal treatment has expectedly affected the
nanostructural arrangement of ZnO nanorods. It can be clearly seen in Fig. 1b that after 3 hours
treatment the nanorods became much smaller to ~165 nm, which consequently enabled a denser
coverage of nanorods on the ITO substrates. With increasing the duration of post-hydrothermal
treatment to 6 hours, the average diameter of nanorods increased back, reaching a value of ~228 nm
and the coverage of nanorods on substrate was still well-maintained (Fig. 1b). In addition, the
nanorods were more vertically aligned than that of with 3 hours treatment.
134 Advances in Materials, Processing and Manufacturing

Fig. 1 Top-view SEM images of ZnO nanorods: (a). as-deposited at 90oC for 3 hours; and after
post-hydrothermal treatment at 150oC for: (b) 3, (c) 6, and (d) 9 hours.

Further increase of post-hydrothermal treatment to 9 hours has enlarged the average diameter of
nanorods to be ~261 nm. However, this was adversely accompanied with the collapse of regular
arrangement on the nanorods. Instead, the nanorods grew as flower-like shape nanostructures,
reducing significantly their highly ordered coverage on ITO substrates. Observation with higher
SEM magnification (Fig. 1d, inset) also revealed that the individual tips of each nanorods were
rather combining. The evolution of nanorods diameter under as-deposited and post-hydrothermal
treatment conditions is summarized in Table 1.

Table 1: The nanostructural characteristics of as-deposited and post-hydrothermally treated ZnO

nanorods.
Post-hydrothermal treatments time (hours)
Nanostructural characteristics As-deposited
3 6 9
Average diameter (nm) 325 165 228 261
Average crystallite size (nm) 22.85 26.87 27.97 28.55

The x-ray diffractogram patterns of the as-deposited and post-hydrothermally treated ZnO
nanorods are shown in Fig. 2. Initially, the as-deposited sample provided three diffraction peaks at
2θ of 32.05, 34.71 and 36.53o which can be indexed with JCPDS no. 36-1451 as (100), (002), (101)
crystal planes of wurtzite structure ZnO [12, 18]. In addition, two additional peaks at 2θ of 47.72
and 63.26o belonging to (102) and (103) planes were also found, although their intensity is much
lower than those first three peaks. It should be noted that the diffraction at 2θ of 35o is the peak
belonging to the ITO substrate. By applying post-hydrothermal treatment for 3 hours, the above
diffraction peaks become slightly sharper, accompanied with the appearance of one additional peak
at 2θ of 56.75o which referred to (110) crystal planes. Further increase of post-hydrothermal
treatment duration to 6 and 9 hours has enhanced the crystallinity of the nanorods, as represented
with much sharper diffraction peak intensities. Among the three strongest peak in all nanorods
samples, i.e. (100), (002) and (101), it is obviously demonstrated that (002) peak shows the highest
intensity, indicating that the nanorods were grown vertically along the c-axis. This fact agrees well
with the morphology of nanorods array as shown previously by SEM study in Fig. 1. In terms of
 Advanced Materials Research Vol. 789 135

crystallite growth, the post-hydrothermal treatments 3 and 6 hours still allowed good vertical
alignment of ZnO nanorods on the surface of ITO, although the presence of other planes such as
(100) and (101) is appreciable. Further extending post-hydrothermal treatment to 9 hours has caused
the nanorods to grow in oblique direction, as indicated with the higher peaks obtained by (100) and
(101) crystal planes.

Fig. 2 X-ray diffractograms of ZnO nanorods: (a) as-deposited at 90oC for 3 hours; and after post-
hydrothermal treatment at 150oC for: (b) 3, (c) 6, and (d) 9 hours.

For further analysis, the average crystallite size of the wurtzite phase in nanorods samples was
estimated by using Scherrer’s formula on the broadening peak of diffraction data. In order to
perform an accurate calculation, the broadening due to the non-uniform strain and the instrumental
line width in the XRD apparatus was removed [15,16]. From Table 1, it can be seen that the
crystallite size of the as-deposited ZnO has been enhanced from 22.85 to 26.87 nm when subjected
to 3 hours treatment, and furthermore to 27.97 and 28.55 nm with 6 and 9 hours treatment.
Fig. 3 shows the effect of post-hydrothermal treatments on the optical properties of nanorods.
All the absorbance spectra of post-hydrothermally treated ZnO nanorods (Fig. 3b-d) show a red-
shift to higher wavelength of about 400 nm in comparison to that of the as-deposited nanorods at
about 350 nm (Fig.3a). It should be noted that the nanorods with 9 hours treatment demonstrates
slightly different shaped spectrum where a wavy pattern consisting of two peaks was observed. This
might be due to the occurrence of other phase aside from ZnO nanorods. Further investigation with
various instrumental techniques is needed in the future to determine the phase content in this
sample.

Fig. 3 Absorption spectra of ZnO nanorods: (a) as-deposited at 90oC for 3 hours; and after post-
hydrothermal treatment at 150oC for: (b) 3, (c) 6, and (d) 9 hours.
136 Advances in Materials, Processing and Manufacturing

The respective band gap energy, Eg of ZnO nanorods was measured by using Tauc’s equation based
on each absorption edges. For this purpose, a plot of (αhν)2 versus hν constructed for each spectrum
is given in Fig. 4, where the extrapolation of linear parts of the curves to the energy axis provides an
estimated band gap energy of 3.63 eV for the as-deposited sample, and 3.15, 3.12 and 3.07 eV for
the samples with post-hydrothermal treatments for 3, 6 and 9 hours, respectively (Table 2).

Fig. 4 Band gap energy (Eg) of ZnO nanorods: (a) as-deposited at 90oC for 3 hours; and after post-
hydrothermal treatment at 150oC for: (b) 3, (c) 6, and (d) 9 hours.

Table 2: Respective band gap energy of ZnO nanorods at as-deposited condition and after post-
hydrothermal treatments.
Post-hydrothermal treatments time (hours)
Optical properties As-deposited
3 6 9
Band gap energy, Eg (eV) 3.63 3.15 3.12 3.07

The results presented in Table 1 and 2 confirm that the crystallite size of semiconductor
nanostructures significantly affects their band gap energies, as has been observed with our previous
studies with CBD derived ZnO nanorods [14], pre-hydrothermally treated ZnO nanoparticles [19],
ZnO tetrapods [20], sol-gel derived TiO2 nanoparticles [21], and TiO2 nanotubes [22,23]. The
smaller band gap energy was obtained with a bigger size of nanocrystallites, provided the
nanostructures are still in nanometer regime. The decreased value of band gap energy obtained with
ZnO nanorods in this study shows their potential for dye sensitized solar cell and photocatalysist
applications. Lowering the band gap will ease the excitation of electrons from valence band to
higher energy conduction band. Indeed, another important factor such as the surface area and the
presence of doping elements also plays important role.

Conclusion

ZnO nanorods on ITO substrates were successfully synthesized on ITO via simple and cheap CBD
process at low temperature. Further application of post-hydrothermal treatments at 150oC for 3 and
6 hours has enhanced not only the crystallinity of the wurtzite phase in nanorods, but also improved
the vertical alignment, density and coverage of nanorods on the substrate surface. Extending the
post-hydrothermal treatment duration up to 9 hours, however, has caused the crystallite growth in
oblique direction and thus decreased the highly ordered nanostructures, although this treatment still
worked well in terms of the crystallite size improvement at nanometer scale. The current works
confirm that the crystallite size of semiconductor nanostructures significantly affects the band gap
energy. The lowest band gap energy of 3.07 eV and the biggest crystallite size of 28.55 nm were
obtained by the sample with 9 hours treatment. However, the optimum nanostructural
characteristics was provided by the sample with 6 hours treatment considering their average
 Advanced Materials Research Vol. 789 137

crystallite size improvement up to 27.97 and the decrease in band gap energy down to 3.12 eV,
which are accompanied with very uniform and dense coverage of highly-vertically grown ZnO
nanorods on ITO substrate. This condition is very useful for the application of ZnO nanorods in dye
sensitized solar cell and photocatalysist.

Acknowledgments

The authors are grateful for the main financial support from Competitive Research Grant of
Universitas Sultan Ageng Tirtayasa, with grant no. of 330/UN43.9/PL/VIII/2012. Partial support
upon the initial work of this project from Directorate of Research and Community Services-
Universitas Indonesia through UI Excellence Research Grant (RUUI) Year 2011 with contract no.
of. 1367/H2.R12/PPM.00.01Sumber Pendanaan/2011 is also acknowledged.

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Advances in Materials, Processing and Manufacturing
10.4028/www.scientific.net/AMR.789

Optimizing the Nanostructural Characteristics of Chemical Bath Deposition Derived ZnO Nanorods by
Post-Hydrothermal Treatments
10.4028/www.scientific.net/AMR.789.132

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