JOURNAL OF SCIENCE OF HNUE DOI: 10.18173/2354-1059.

2016-0042
Mathematical and Physical Sci., 2016, Vol. 61, No. 7, pp. 138-143
This paper is available online at http://stdb.hnue.edu.vn

INFLUENCES OF GROWTH TEMPERATURE AND SOLUTION CONCENTRATION

ON HYDROTHERMAL PREPARATION OF ZnO NANOROD

Nguyen Dinh Lam, Nguyen Thanh Lap, Pham Van Vinh, Vuong Van Cuong,
Phuong Thi Thuy Hang, and Nguyen Van Hung
Faculty of Physics, Hanoi National University of Education

Abstract. ZnO nanorod structures were grown on glass substrates using a hydrothermal
method. Influences of growth temperature and hydrothermal solution concentration on
ZnO nanorod structures were investigated. The results indicate that diameter and length
of the ZnO nanorod increase with an increasing of growth temperature and hydrothermal
solution concentration. However, density of the ZnO nanorod can reach a maximum value
when growth temperature and hydrothermal solution concentration is 80 ◦ C and 20 mM,
respectively. The optical transmittance of the ZnO nanorod structure is strongly reduced if
growth temperature and hydrothermal solution concentration is increased. This reduction
can be explained based on the length of the ZnO nanorod.
Keywords: ZnO nanorod, hydrothermal method, photovoltaic.

1. Introduction
Zinc oxide (ZnO) is a semiconductor with a wide bandgap of 3.37 eV and large exciton
binding energy of 60 meV [1-3]. For optoelectronic device applications such as thin film solar
cells, transistors and sensors, ZnO is usually fabricated under film or one dimension (1D)
nanostructures [4-6]. Recent reports indicate that the performance of photovoltaic and light
emitting diode devices using ZnO nanostructures is much higher than that of those using ZnO
film [7, 8]. The improvement in the performances of these devices was explained as being due to a
larger effective surface area and higher electrical conductibility. ZnO nanostructures can be grown
on substrates via methods such as chemical vapor deposition (CVD), physical vapor deposition
(PVD), gold-catalyzed vapor transport, and hydrothermal [9-11]. Among them, the hydrothermal
method has the advantages of ease of control of chemical components, good uniformity of
nanostructure, low temperature synthesis, and economical production.
In this work, ZnO nanorod structures on glass substrates are fabricated using the
hydrothermal method. Influences of growth temperature and hydrothermal solution concentration
on diameter, length and density of ZnO nanorod were investigated in detail. Furthermore, the
optical transmittance property of fabricated ZnO nanorod structures was evaluated to determine
optimal conditions for photovoltaic fabrication.

Received July 22, 2016. Accepted September 14, 2016.

Contact Nguyen Dinh Lam, e-mail address: lam.nd@hnue.edu.vn

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Influences of growth temperature and solution concentration on hydrothermal preparation of ZnO nanorod

2. Content
2.1. Experimental details
Glass substrate was cleaned using a NaOH solution, methanol and deionized water in
sequence. The ZnO seed layers were coated on the glass substrates via sol-gel method using a
0.3 M solution of zinc acetate dehydrate (Zn(CH3 COO)2 .2H2 O). After the coating process, the
ZnO seed layers were dried at 150 ◦ C for 20 minutes in an oven to evaporate the solvent and
remove organic residuals and then annealed at 500 ◦ C for 1 h in air. In the process of hydrothermal
growth of ZnO NRs, a glass substrate with a ZnO seed layer and 100 mL solution was transferred
together into a Teflon-lined stainless steel autoclave and then annealed for 120 min. The solution
concentration varied from 10 mM to 30 mM. The growth temperature was changed from 70 to
90 ◦ C. The growth time and volume of solution were kept constant. After the growth process, the
autoclaves were allowed to cool naturally. The obtained samples were cleaned ultrasonically in
ethanol and distilled water for 30 min, followed by a drying treatment at 100 ◦ C.
The X-ray diffraction pattern of the ZnO nanorod was measured using a X-Ray
Diffractometer (XRD) D5000 with CuKα radiation (λ = 1.5406 Å) at room temperature. The
diameter, length and density of the rod were investigated using a Scanning Electron Microscope
(SEM). The optical spectra of the ZnO nanorod structures were studied using an UV-VIS-NIR
spectrophotometer in the wavelength range of 300 - 800 nm at room temperature.

2.2. Results and Discussion

2.2.1. ZnO seed layer
The SEM image of the ZnO seed layer was shown in Fig.1(a). The image indicates that ZnO
seed layer is made up of uniform ten nanometer thick particles.

Figure 1. (a) Top-view SEM image and (b) XRD pattern of ZnO seed layer

Figure 1(b) shows the X-ray diffraction pattern of the ZnO seed layer. The XRD patterns
indicate that the structure of the films is polycrystalline. The presence of the (100), (002), (101),
(102), (110), 103 and (112) peaks in the XRD patterns indicate a hexagonal wurtzite structure
of the ZnO. Diffraction peaks related to other impurity phases cannot be seen in the XRD
patterns. Using the Debye Scherer formula, a crystalline particle size of ≈18 nm can be calculated.
Furthermore, based on Bragg’s equation, the crystal lattice constants of ZnO were also determined

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 N. D. Lam, N. T. Lap, P. V. Vinh, V. V. Cuong, P. T. T. Hang and N. V. Hung

(a = b ≈ 3.2 Å and c ≈ 5.2 Å).

The optical transmittance spectrum of the ZnO seed layer is presented in Figure 2. The
spectrum shows that the average transmittance of this seed layer is over 95% in the visible range.
Based on the transmittance spectrum and J.Tauc equation [12], the bandgap of the ZnO seed layer
is determined to be about 3.23 eV (inset Figure 2).

Figure 2. Optical transmittance spectrum of ZnO seed layer. (Inset) Plots

of (αhν)2 vs. photon energy of the ZnO seed layer.

2.2.2. ZnO nanorod structures

* Growth temperature dependence
A ZnO nanorod structure was grown on glass substrate coated with a ZnO seed layer. In
this work, the hydrothermal solution concentration and growth time were kept constants at 20 mM
and 120 min, respectively. Growth temperature was varied from 70 to 90 ◦ C.

Figure 3. SEM images of ZnO nanorod structures at different growth temperature

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Influences of growth temperature and solution concentration on hydrothermal preparation of ZnO nanorod

Top- and side-view SEM images

of ZnO nanorod structures at different
growth temperatures are shown in
Figure 3. The images show that ZnO
nanorods are of uniform size and have
a tendency to orient perpendicular
to the surface of the glass substrate.
Moreover, the diameter, length and
density of ZnO nanorod are dependent on
growth temperature. These dependent
ZnO nanorod were extracted and
are depicted in Figure 4. This result
indicates that the diameter and lenght
Figure 4. Density and length of ZnO nanorod at
of ZnO nanorod increase with an
different growth temperatures
increase in growth temperature. The
longest rod length of 275 nm was obtained when the growth temperature was 90 ◦ C. This
can be attributed to high reaction and growth rates at high temperature. However, the
density of the ZnO nanorod reaches a maximum value at the growth temperatue of 80 ◦ C.
The influence of the optical
transmittance of the ZnO nanorod
structures on growth temperature is shown
in Figure 5. The optical transmittance of the
ZnO nanorod structue is strongly reduced
when the growth temperature increases.
This coulkd be due to the increased length
of the ZnO nanorod. However, the optical
transmittance of the ZnO nanorod structure
grown at 80 ◦ C is still higher 80% [not
understandable] in the visible region.
The study results indicate that the
density of the ZnO nanorod is greatest
when it is grown at 80 ◦ C. This means that
Figure 5. Optical transmittance spectra of ZnO
the surface area of this sample is the largest.
nanorod structures
In addition, the optical transmittance of this at different growth temperatures
sample is higher than 80% in the 400 - 800
nm range. Therefore, 80 ◦ C is a ZnO nanorod growth temperature that can create good structures
for photovoltaic application.
* Hydrothermal solution concentration dependence
In this part of the experiment, growth temperature and growth time were kept constant at
◦
80 C and 120 min, respectively. The hydrothermal solution concentration was varied from 10 to
30 mM.
Top- and side-view SEM images of the ZnO nanorod structures grown at different solution
concentrations are shown in Figure 6. The ZnO nanorods are of uniform size and are oriented
perpendicular to the surface of the glass substrates. The diameter, length and density of the ZnO

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 N. D. Lam, N. T. Lap, P. V. Vinh, V. V. Cuong, P. T. T. Hang and N. V. Hung

nanorod are strongly dependent on solution concentration. The diameter and length of the ZnO
nanorod increase as the solution concentration increases and reach the highest value when the
solution concentration is 30 mM in this investigation. However, the density of the ZnO nanorod
is highest when the solution concentration is 20 mM. These results were extracted from the SEM
images shown in Figure 6 and depicted in Figure 7.

Figure 6. SEM images of ZnO nanorod structures grown

at different solution concentrations

Figure 7. Density and length Figure 8. Optical transmittance spectra

of ZnO nanorod grown of ZnO nanorod structures grown
at different solution concentrations at different solution concentrations

Figure 8 shows the optical transmittance spectra of the ZnO nanorod structures grown at
different solution concentrations. When the solution concentration increases from 10 mM to 30
mM, the optical transmittance in visible region of ZnO nanorod structue is strongly reduced from

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Influences of growth temperature and solution concentration on hydrothermal preparation of ZnO nanorod

95% to 65%. This reduction in optical transmittance is attributed to the thickness of the ZnO
nanorod structure. However, the ZnO nanorod structure grown at a solution concentration of 20
mM shows potential for application in optoelectronic devices fabrication.

3. Conclusion
ZnO nanorod structures were successfully grown on glass substrates using the hydrothermal
method. The ZnO nanorod are of uniform size and have a tendency to orient perpendicular to
the surface of the glass substrate. The diameter and length of the ZnO nanorod increase with an
increase in the growth temperature and solution concentration. The density of the ZnO nanorod
reach a maximum value when the growth temperatue and solution concentration are 80 ◦ C and 20
mM, respectively. The optical transmittance of this sample is higher than 80% in the 400 - 800 nm
range. Therefore, a growth temperature of 80 ◦ C and solution concentration of 20 mM is suitable
for ZnO nanorod structure fabrication that can create good structures for photovoltaic application.
Acknowledgments: This research was funded by the Vietnam National Foundation for
Science and Technology Development (NAFOSTED) under Grant number 103.99-2014.60.

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