SnO2 Nanostructures: Effect of Processing Parameters on Their Structural and Functional Properties
© The Author(s). 2017
Received: 22 December 2016
Accepted: 24 April 2017
Published: 4 May 2017
Zero- and 1D (one-dimensional) tin (IV) oxide nanostructures have been synthesized by thermal evaporation method, and a comparison of their morphology, crystal structure, sorption properties, specific surface area, as well as electrical characteristics has been performed. Synthesized SnO2 nanomaterials were studied by X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM), N2 sorption/desorption technique, IR spectroscopy and, in addition, their current-voltage characteristics have also been measured. The single crystalline structures were obtained both in case of 0D (zero-dimensional) SnO2 powders and in case of 0D nanofibers, as confirmed by electron diffraction of TEM. It was found that SnO2 synthesis parameters significantly affect materials’ properties by contributing to the difference in morphology, texture formation, changes in IR spectra of 1D structure as compared to 0D powders, increases in the specific surface area of nanofibers, and the alteration of current-voltage characteristics 0D and 1D SnO2 nanostructures. It was established that gas sensors utilizing of 1D nanofibers significantly outperform those based on 0D powders by providing higher specific surface area and ohmic I–V characteristics.
Tin (IV) oxide (SnO2) is a typical n-type semiconductor with a wide direct band gap of 3.6 eV . SnO2 exhibits a number of interesting functional properties such as optical transparency in the visible spectrum , chemical stability at high temperatures , good surface adsorption properties of oxygen and availability of numerous oxygen species and active acid sites on its surface , high specific theoretical capacity , and excellent electrical characteristics [3, 6]. As a result, SnO2 is broadly used as a part of catalysts for oxidation of organic compounds [4, 7], as an anode material in lithium-ion batteries , as transparent electrodes in solar cells , as a host material and a buffer layer in many optoelectronic devices , or as a sensitive layer in gas sensors to detect harmful for human health and hazardous gases such as CO, NO x , H2S, H2, and CH4. [10–13]. Today, the development of superior gas sensors is extremely important because they not only allow safely controlling the environment at home and industrial settings  but also provide an easy diagnostic tool for detection of early stages of otherwise hard or impossible to detect diseases at air exhalation among other applications .
It was established  that nanostructured SnO2 provides far better gas sensing properties as compared to SnO2 micron size materials. Thermal evaporation , hydrothermal synthesis , sol-gel method [18, 19], template synthesis , and laser ablation  are the most explored methods for synthesis of SnO2 nanostructures. Thermal evaporation method is the most promising technique as it allows to produce single crystalline 0D (zero-dimensional) or 1D (one-dimensional) SnO2 nanoparticles with high specific surface area and excellent gas sensing properties [16, 22].
There are many papers recently published that study either 0D or 1D nanostructured SnO2 [15, 16, 23, 24]. However, the direct comparison of performance of these structurally very different materials is lacking. Therefore, the goal of this paper is to fill the gap by providing a comparison of structural and functional behavior of 0D and 1D SnO2 nanostructures.
The SnO2 sample with the fast heating rate was marked as TO1, and the SnO2 sample with slow heating rate was named TO2.
In X-ray diffractometer Ultima IV (Rigaku, Japan) with CuКα radiation at 40 kV, 30 mA was used to collect diffraction patterns of the SnO2 samples. The powdered samples were scanned from 20 to 80 2θ at 1°/min with a scanning step of 0.0001°. XRD patterns were analyzed by the PDXL software package using database ICDD/PDF-2 and COD. The crystalline size and lattice parameters of the materials were calculated automatically by the software.
Both Transmission Electron Microscopy PEM 100–01 (Selmi, Ukraine) and Scanning Electron Microscopy REM 106I (Selmi, Ukraine) were used for characterization of particle’s size and morphology of the obtained SnO2 samples.
Specific surface area of the samples was studied by adsorption/desorption of nitrogen (Quantachrome® Autosorb, Quantachrome Instruments, USA) using Langmuir isotherm and Brunauer-Emmett-Teller (BET)-based software.
IR 4000–400 cm−1 wavenumber spectra of SnO2 were collected using FTIR spectrometer (Thermo Nicolet Nexus FTIR, Thermo Fisher Scientific, USA). For spectra collection, SnO2 samples were mixed with pre-dried KBr (for spectroscopy, “Aldrich,” USA) at 1:30 SnO2/KBr ratio.
Results and Discussion
The Specific Surface Area
Structural characteristics of sample SnO2
The total pore volume (cm3/g)
The average conditional pore radius (nm)
Absorption spectra of synthesized SnO2 samples
Reference data (cm−1)
O2 − (chemical adsorption)
CO2 (physical adsorption)
O2 (physical adsorption)
CO2 (chemical adsorption)
2840, 2925 
As seen on Fig. 7, the current-voltage curves of these samples are different. For 0D SnO2 sample, I–V curves are non-ohmic at all temperatures while 1D tin (IV) oxide sample is characterized by linear (ohmic) current-voltage dependences. The various nature of curves for 0D and 1D nanostructures related to the different surface to volume ratios. Change in this ratio leads to a change in the I–V behavior of the material. It is known that both surface and bulk conductivities of the SnO2 contribute to the overall conductivity.
In addition, it is known that the ohmic behavior of current-voltage characteristics is very important for the sensing properties of the material, as the sensing properties of SnO2 are significantly improved if the material is showing ohmic type semiconducting behavior . Therefore, 1D nanostructures are more desirable for use in gas sensors.
The single crystalline particles of SnO2 of different morphology (zero-dimensional (0D) and one-dimensional (1D) nanostructures) were obtained by thermal evaporation method. Such significant difference in the morphology of the SnO2 nanostructures were achieved due to their different synthesis conditions, as it was found that slower heating rate during the thermal evaporation brings changes to the SnO2 morphology allowing to receive 1D nanofibers. The comparison of different properties of 0D and 1D SnO2 nanostructures is presented. It was determined that the morphology has significant impact on the structural and functional properties of SnO2 as it is reflected in changes in crystal structure where texture formation was recorded, variation of IR spectra, as well as different I–V characteristics of gas sensors based on 0D and 1D SnO2 structures. It was also established that considerable changes in behavior of SnO2 depends also on surface to volume ratios of nanostructures.
Based on the experimental data, 1D nanostructures are more desirable for use in gas sensors. Further comparative research of 0D and 1D nanostructures will be carried out regarding sensory properties.
The authors thank Astrelin Igor for his support in conducting this research.
TD carried out the coordination of the experimental research, analysis and interpretation of data, and drafted the manuscript. SN carried out the experimental studies, analysis and interpretation of data, and drafted the manuscript. VZ carried out the experimental studies. YY had given final approval of the version of the manuscript to be published. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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