International Journal of Nanotechnology

and Application (IJNA)

ISSN(P): 2277-4777; ISSN(E): 2278-9391
Vol. 4, Issue 6, Dec 2014, 1-6
TJPRC Pvt. Ltd.

FABRICATION OF TRANSPARENT CONDUCTING OXIDE NANOMATERIAL AT LOW

TEMPERATURE AND STUDY OF ITS PROPERTIES
SREEDHAR D1, SRINIVASULU REDDY K2, VINOD REDDY Y3 & VASUDEVA RAO V4
1,2,3

Department of Mechanical Engineering, Sreenidhi Institute of Science and Technology, Ghatkesar,

Hyderabad, Telangana, India
4

Department of Mechanical and Industrial Engineering, Science Campus, Florida, South Africa

ABSTRACT
In the past years zero-dimensional and one-dimensional nanostructures of binary semiconducting oxides, such as
ZnO, TiO2, GaO, Cd2O3, SiO2 and SnO2, have attracted immense interest but for better development new materials like
ternary oxide semiconductors such as cadmium stannate (Cd2SnO4), galium doped ZnO (GZO), aluminium doped ZnO
(AZO) and zinc tin oxide (ZTO). This paper focuses on synthesis and properties studies of ternary semiconducting oxide,
Zinc-Tin-Oxide (ZnSnO3) which was synthesized with molar ratio of 1:1. Zinc tin oxide (ZTO) nanomaterial has been
successfully synthesised using Solvo-Thermal method in which zinc and tin powders were separately mixed with ethanol
solution under slow stirring. In this process a mild base, Na2CO3 is used as a mineralizer and ethanol as a solvent at
temperature about 100C. These ZTO nanomaterials are further characterized to study the properties such as morphology
and particle size by using SEM, crystal structure by using XRD, energy band gap by using UV-visible spectroscopy,
elemental analysis and chemical composition by using EDS, and also the weight loss percentage at different temperature
ranges by using TGA. These studies are useful to know the electronic and thermal properties of the material with respect to
the 1:1 composition ratio at 100C. Due to the nanoscale dimensions these ZTO nanomaterials can be used in developing
solar cells because of its less cost, less weight and other applications.

KEYWORDS: Zinc Tin Oxide (ZTO), SEM, XRD, EDS, UV-visible Spectroscopy and TGA
INTRODUCTION
From the past few years there is much development in nanotechnology for the designing of semiconductors so as
to match the properties of new emerging materials. In the past years zero-dimensional and one-dimensional nanostructures
of binary semiconducting oxides, such as ZnO, TiO2, GaO, Cd2O3, SiO2 and SnO2, have attracted immense interest but
for better development new materials like ternary oxide semiconductors such as cadmium stannate (Cd2SnO4), galium
doped ZnO (GZO), aluminium doped ZnO (AZO) and zinc tin oxide (ZTO)[1-6] are being prepared now a days. So among
all the above ternary semiconducting oxides ZTO, an inexpensive non-toxic material, has high electrical conductivity [2],
electron mobility [3] and attractive optical [4-5] photoluminescence properties [6], thermal properties and other attravtive
properties [7-8]. These properties has attracted in synthesizing and characterizing the ZTO nanomaterials. There are many
different synthesis techniques to synthesize ZTO such as physical vapor deposition (PVD), chemical vapor deposition
(CVD), flame-pyrolysis, laser-ablation, arc discharge, sol-gel method, hydrothermal method and solvo-thermal method. So
in order to reduce the impurities and crystal defects and to improve uniformity, ZTO nanomaterials were prepared by
chemical synthesis method.
www.tjprc.org

editor@tjprc.org

Sreedhar D, Srinivasulu Reddy K, Vinod Reddy Y & Vasudeva Rao V

This chemical method can have good control over the composition ratio also. In this method preparation of ZTO
was performed with zinc and tin powders as sources by using mild base Na2CO3, as a mineralizer and aqueous ethanol as
a solvent at temperature above 100C for 12hours. The particle properties such as size and morphology can be changed by
using this method by adjusting of parameters such as molar ratio [2, 3], reaction temperature [6], concentration and
reaction time.

MATERIAL FABRICATION PROCESS

In this synthesis method zinc and tin powders were used as sources of starting materials. In this experimental
process ZnSO4.7H2O and SnCl4.5H2O were dissolved in aqueous ethanol solution separately. Then, the prepared
SnCl4.5H2O solution was slowly added into of ZnSO4.7H2O solution under slow stirring. A molar ratio of Zn:Sn was
maintained as 1:1 throughout this work [2]. Thereafter, sodium carbonate solution was added drop wise into the reaction
mixture under vigorous stirring; Na2CO3 was used as a mineralizer because of its low basicity. With this mixture small
amount of CTAB dissolved in deionised water was slowly added under mild stirring to form the transparent white colored
solution. Thereafter, this solution mixture was transferred into a teflonlined stainless steel autoclave and subjected to
solvo-thermal conditions in the temperature range of 100C. After the reaction, autoclave was cooled into room
temperature. Then, the formed products were centrifuged in order to obtain the ZTO nanomaterials. These materials were
washed successively with deionized water and absolute ethanol in order to remove the by-products. Finally, the products
were dried at 80C in the oven for 12h. Then after the dried material is taken out and is made into fine powder by using
mortar and pestle. Then the fine powder is taken in to sample holders and is sent for the further characterization. These
ZTO nanomaterials were characterized by using SEM, EDS, XRD, TGA and UV-visible spectroscopy.
Sn(OH)62 + 2Zn(OH)42 ZnSnO3 + ZnO + 4H2O + 6OH

EXPERIMENTAL RESULTS
To analyze the effects of molar ratio on the formation and morphology of ZnSnO3, solvo-thermal reactions were
carried out around 100C with Zn:Sn ratio of 1:1.
The morphology and particle size of the prepared ZTO nanomaterials were analyzed with scanning electron
microscope (SEM) [2]. Figure 1 shows the SEM image of ZTO nanomaterials prepared around 100C. The least size of the
ZnSnO3 nanomaterials synthesized at 100 C was found to be 84.7 nm. This observation clearly indicates that the formation
of ZTO nanostructure was effective.

Figure 1: SEM Images of the ZTO Nanomaterials Prepared at 100C

Impact Factor (JCC): 1.8003

Index Copernicus Value (ICV): 3.0

Fabrication of Transparent Conducting Oxide Nanomaterial at Low Temperature and Study of its Properties

The crystal structure of the ZTO nanomaterials prepared at different temperature was characterized using X-Ray
diffraction (XRD). Figure 2 shows the XRD pattern of the ZTO nanomaterials prepared at 100C. Due to the low reaction
temperature, there is the presence of ZnO along with ZnSnO3 nanomaterials. The particle diameter size of around 70 nm
has been observed by using Debye Scherrer formula (D= K / cos ). From the data file 11-0274 of JCPDS, many
diffracted peaks are observed to be of perovskite face-centered zinc tin oxide material [10].

Figure 2 - XRD of ZnSnO3 prepared at 100C

Elemental analysis or chemical composition of the ZTO nanomaterials prepared at 100C was analyzed using
energy dispersive X-ray spectroscopy in scanning electron microscopy unit. As shown in Figure 3, it is found that the
peaks of Sn, Zn and oxygen are also observed. These data clearly confirm that the ZTO nanomaterials consist of Sn, Zn
and oxygen without any chemical contamination. Table 1 shows the chemical compositions of the ZTO nanomaterials
determined by the energy dispersive spectroscopy analysis (EDS). From this table it is clear that the chemical composition
of the ZTO nanomaterials is well within the expected ratio.

Figure 3: EDS Spectra of the ZTO Nanomaterials

Table 1: Chemical Composition of the ZTO Nanomaterial
Element
O-K
Zn-K
Sn-L

Wt. %
20.87
28.94
29.78

UV-visible spectroscopy [7] is related to the absorption spectroscopy of the materials in the ultraviolet-visible
spectral region. The optical bandgap of a semiconducting nanomaterial could be obtained from the absorption band edge in
the UV-vis spectrum. The absorbance measurements were carried out over the range of 190 - 800 nm. Figure 4a shows the
www.tjprc.org

editor@tjprc.org

Sreedhar D, Srinivasulu Reddy K, Vinod Reddy Y & Vasudeva Rao V

UV-visible absorption spectrum of the ZTO nanomaterials prepared at 100C. Figure 4b shows the (h)2 v/s h graph of
ZTO nanoparticles. The dashed line is the indication of extrapolation. Therefore the band gap value observed is 4.3eV
which is high due to the reaction temperature is at 100 C. Better results can be observed at high reaction temperatures
[10].

Figure 4: (a) UV-Visible Spectra and (b) (h)2 v/s h of ZnSnO3 Prepared at 100C
TGA is a technique used for the measuring of changes in mass as function of temperature. TGA results of the ZTO
nanomaterials prepared at 100C with molar ratios of 1:1 as shown in the figure 5. From these TGA analyses it is clearly
observed that the weight loss of the material is zero in room temperature (0 to 36C) and is less at the temperature range of
589C to 860C.

Figure 5: TGA of ZnSnO3 Prepared at 100C

Table 2: Weight Loss of the ZTO Nanomaterial by TGA
Temp Range C
0-36
36-250
250-589
589-860
860-1200

Wt. loss %
0
8.04
10.04
3.62
6.56

CONCLUSIONS
These results suggest that the solvo-thermal method using Na2CO3 as a mineralizer and aqueous ethanol as a
Impact Factor (JCC): 1.8003

Index Copernicus Value (ICV): 3.0

Fabrication of Transparent Conducting Oxide Nanomaterial at Low Temperature and Study of its Properties

solvent would be an efficient method to prepare the ZTO nanomaterials with high band gap. These materials can be
potentially used in the various fields. From the SEM, EDS, XRD, TGA and UV-visible spectroscopy results it can be seen
that the zn:sn composition ratio of 1:1 has better characteristics. The EDS studies revealed that the ZTO nanomaterials
consist of Sn, Zn and oxygen without any other chemical contamination. TGA results shows that the weight loss is zero
under room temperature and is less around 589 to 860C XRD results suggest that the particle diameter size of ZTO
nanoparticles is approximately around 70 nm. From UV-visible spectroscopy results it is proved that the bandgap of
synthesized ZTO nanomaterial is good when compared with other oxides. So by increasing the temperature and duration
time, the results may be vary and can obtain better results than the above result. Due to the nanoscale dimensions these
ZTO nanomaterials can be used in developing solar cells because of its less cost, less weight and other applications. ZTO is
a very important material in advanced technologies, such as photoelectron chemical cells, gas sensor [9], synergistic flame
retardants, photocatalytic materials and zinc-tin-oxide thin-film transistors [8]. In recent years, ZTO nanomaterials have
been prepared by high temperature, thermal evaporation, solgel method, etc. but compared with the recent years;
solvo-thermal method has got more interest because of its stability, simplicity, cost-efficiency, etc.

ACKNOWLEDGEMENTS
The authors would like to thank the management of Sreenidhi Institute of Science and Technology, Hyderabad for
the support and encouragement given for this research work. The authors would like to thank Sri. K.T. Mahhe (Secretary),
Dr. P. Narasimha Reddy (Director) and Dr. T. Ch. Siva Reddy (Head of Mechanical Engineering) of Sreenidhi Institute of
Science & Technology for their support and encouragement
Nomenclature
h

Planks constant.

Frequency

Absorption coefficient.

Particle diameter size.

Shape factor = 0.9.

X-Ray wavelength = 0.1541 nm.

Full width at half max (Intensity).

Bragg or diffraction angle.

REFERENCES
1.

Julia M. Phillips, R. J. Cava, G. A. Thomas, S. A. Carter, J. Kwo, T. Siegrist, J. J. Krajewski, J. H. Marshall,

W. F. Peck Jr., and D. H. Rapkine Zincindiumoxide: A high conductivity transparent conducting oxide Appl.
Phys. Lett. 67 (15), 9 October 1995.

2.

Yong-Hoon Kim, Jeong-In Han, and Sung Kyu Park Effect of Zinc/Tin Composition Ratio on the Operational
Stability of Solution-Processed ZincTinOxide Thin-Film Transistors IEEE Electron Device Letters, Vol. 33,
No. 1, January 2012.

www.tjprc.org

editor@tjprc.org

Sreedhar D, Srinivasulu Reddy K, Vinod Reddy Y & Vasudeva Rao V

3.

H. Q. Chiang, J. F. Wager, R. L. Hoffman, J. Jeong, and D. A. Keszler High mobility transparent thin-film
transistors with amorphous zinc tin oxide channel layer Appl. Phys. Lett. 86, 013503 (2005).

4.

W. B. Jackson, R. L. Hoffman, and G. S. Herman High-performance flexible zinc tin oxide field-effect
transistors Appl. Phys. Lett. 87, 193503 _2005.

5.

P. Grrn, P. Hlzer, T. Riedl, W. Kowalsky, J. Wang, T. Weimann, P. Hinze, and S. Kipp Stability of transparent
zinc tin oxide transistors under bias stress Appl. Phys. Lett. 90, 063502 _2007.

6.

Lisheng Wang, Xiaozhong Zhang1, Xing Liao and Weiguo Yang A simple method to synthesize
single-crystalline Zn2SnO4 (ZTO) nanowires and their photoluminescence properties Nanotechnology 16 (2005)
29282931.

7.

Christina Pang1, Bin Yan, Lei Liao2, Bo Liu, Zhe Zheng, TomWu, Handong Sun and Ting Yu3
Synthesis, characterization and opto-electrical properties of ternary Zn2SnO4 nanowires Nanotechnology 21
(2010) 465706 (4pp).

8.

Pradipta K. Nayak, Joana V. Pinto, Gonalo Gonalves, Rodrigo Martins, and Elvira Fortunato Environmental,
Optical, and Electrical Stability Study of Solution-Processed ZincTinOxide Thin-Film Transistors Journal of
Display Technology, Vol. 7, No. 12, December 2011.

9.

G.S. Herman1, J.S. Rajachidambaram1, M.S. Rajachidambaram1, S.Y. Han1, C.H. Chang1, S. Murali2,
J. F. Conley, Jr. Transparent Oxide Semiconductors: Recent Material Developments and New Applications
2011 IEEE.

10. Sunandan Baruah and Joydeep Dutta, doi:10.1088/1468-996/12/1/013004, Sci. Technol. Adv. Mater. 12 (2011)
013004 (18pp), "Zinc stannate nanostructures: hydrothermal synthesis.

Impact Factor (JCC): 1.8003

Index Copernicus Value (ICV): 3.0