- Nano Express
- Open Access
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.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
- Munnix S, Schmeits M (1982) Surface electronic structure of tin (IV) oxide. Solid State Commun 43:867View ArticleGoogle Scholar
- Sanon G, Rup R, Mansingh A (1991) Band-gap narrowing and band structure in degenerate tin oxide (SnO2) films. Phys Rev B Condens Matter 44(11):5672–5680View ArticleGoogle Scholar
- Tan L, Wang L, Wang Y (2011) Hydrothermal synthesis of SnO2 nanostructures with different morphologies and their optical properties. J Nanomater 2011:1–10View ArticleGoogle Scholar
- Xu X, Zhang R, Zeng X, Han X, Li Y, Liu Y, Wang X (2013) Effects of La, Ce, and Y oxides on SnO2 catalysts for CO and CH4 oxidation. ChemCatChem 5:2025–2036View ArticleGoogle Scholar
- Lee S-Y, Park K-Y, Kim W-S, Yoon S, Hong S-H, Kang K, Kim M (2016) Unveiling origin of additional capacity of SnO2 anode in lithium-ion batteries by realistic ex situ TEM analysis. Nano Energy 19:234–245View ArticleGoogle Scholar
- Janotti A, Varley JB, Lyons JL, Van de Walle CG (2011) Controlling the conductivity in oxide semiconductors. In: Functional metal oxide nanostructures (springer series in materials science), vol 149., pp 23–35View ArticleGoogle Scholar
- Liberkova K, Touroude R (2002) Performance of Pt/SnO2 catalyst in the gas phase hydrogenation of crotonaldehyde. J Mol Catal A Chem 180:221–230View ArticleGoogle Scholar
- Ray S, Dutta J, Barua AK (1991) Bilayer SnO2:In/SnO2 thin films as transparent electrodes of amorphous silicon solar cells. This Solid Films 199(2):201–207View ArticleGoogle Scholar
- Tran V-H, Ambade RB, Ambade SB, Lee S-H, Lee I-H (2017) Low-temperature solution-processed SnO2 nanoparticles as a cathode buffer layer for inverted organic solar cells. ACS Appl Mater Interfaces 9(2):1645–1653View ArticleGoogle Scholar
- Nagirnyak SV, Lutz VA, Dontsova TA, Astrelin IM (2016) Synthesis and characterization of Tin (IV) oxide obtained by chemical vapor deposition method. Nanoscale Res Lett 11(1):343View ArticleGoogle Scholar
- Salehi A (2003) A highly sensitive self heated SnO2 carbon monooxide sensor. Sensors Actuators B 96:88–93View ArticleGoogle Scholar
- Starke TKH, Coles GSV, Ferkel H (2002) High sensitivity NO2 sensors for environmental monitoring produced using laser ablated nanocrystalline metal oxides. Sensors Actuators B 85:239–245View ArticleGoogle Scholar
- Ghimbeu CM, Lumbreras M, Schoonman J, Siadat M (2009) Electrosprayed metal oxide semiconductor films for sensitive and selective detection of hydrogen sulfide. Sensors 9:9122–9132View ArticleGoogle Scholar
- Pradhan UU, Bhat P (2015) Breathe analysis for medical diagnostics—a review. Int J Innov Res Dev 4(12):240–246Google Scholar
- Miller TA, Bakrania SD, Perez C, Wooldridge MS (2006) Nanostructured tin dioxide materials for gas sensor applications. Funct Mater 30:1–24Google Scholar
- Konga MH, Kwonb YJ, Kwakb DS, Khaib TV et al (2012) The synthesis of crystalline SnO2 whiskers via a metalorganic chemical vapor deposition process. J Ceram Proc Res 13(6):667–671Google Scholar
- Chiu HC, Yeh CS (2007) Hydrothermal synthesis of SnO2 nanoparticles and their gas-sensing of alcohol. J Phys Chem 111:7256–7259View ArticleGoogle Scholar
- Dontsova TA, Ivanenko IM, Astrelin IM, Nagirnyak SV (2014) Stabilization of nanoscale tin (IV) oxide on the surface of carbon nanotubes. J Electr Eng 2(1):34–39Google Scholar
- Ivanenko IN, Dontsova TA, Astrelin IM, Trots VV (2016) Low-temperature synthesis, structure-sorption characteristics and photocatalytic activity of TiO2 nanostructures. J Water Chem Technol 38(1):14–20View ArticleGoogle Scholar
- Farrukh MA, Heng BT, Adnan R (2010) Surfactant-controlled aqueous synthesis of SnO2 nanoparticles via the hydrothermal and conventional heating methods. Turk J Chem 34:537–550Google Scholar
- Yang H, Song X, Zhang X, Ao W, Qui G (2003) Synthesis and characyerization of SnO2 nanoparticles for carbon absorbing applications. Mater Lett 57:3124–3127View ArticleGoogle Scholar
- Nagirnyak S, Lutz V, Dontsova T, Astrelin I (2016) The effect of the synthesis conditions on morphology of tin (IV) oxide obtained by vapor transport method. Springer Proc Phys 183:331–341View ArticleGoogle Scholar
- Mondal SP (2010) Temperature dependent growth and optical properties of SnO2 nanowires and nanobelts. Bull Mater Sci 33(4):357–364View ArticleGoogle Scholar
- Chinh N.D., Toan N.V., Quang V.V., Duy N.V., Hoa N.D., Hieu N.V. Comparative NO2 gas-sensing performance of the self-heated individual, multiple and networked SnO2 nanowire sensors fabricated by a simple process. Sensors Actuators B Chem. 2014:7–12.Google Scholar
- Fedoseeva TI, Sobolev EV, Takher EA (1972) Obtaining mechanically strong acid-resistant and wear resistant sitall grade BL from fused basal. Steklo Keram 1:29–31Google Scholar
- McCarthy GJ, Welton JM (1989) X-Ray diffraction data for SnO2. An illustration of the new powder data evaluation methods. Powder Diffract 4(3):156–159View ArticleGoogle Scholar
- Zhai T, Fang X, Liao M, Xu X, Zeng H, Yoshio B, Golberg D. (2009) A Comprehensive Review of One-Dimensional Metal-Oxide Nanostructure Photodetectors. Sensors 9(8):6504-6529Google Scholar
- Amarlic-Popescu D, Bozon-Verduraz F (2001) Infrared studies on SnO2 and Pd/SnO2. Catal Today 70:139–154View ArticleGoogle Scholar
- Avila HA, Rodrigues-Paez JE (2009) Solvent effects in the synthesis process of tin oxide. J Non Cryst Solids 355:885–890View ArticleGoogle Scholar
- Mihaiu S, Atkinson I, Mocioiu O, Toader A, Tenea E, Zaharescu M (2011) Phase formation mechanism in the ZnO-SnO2 binary system. Rev Roum Chim 56:465–472Google Scholar
- Babar AR, Shinde SS, Moholkar AV, Rajpure KY (2010) Electrical and dielectric properties of co-precipitated nanocrystalline tin oxide. J Alloys Compd 505:743–749View ArticleGoogle Scholar
- Gnanam S, Rajendran V (2010) Anionic, cationic and nonionic surfactants-assisted hydrothermal synthesis of tin oxide nanoparticles and their photoluminescence property. Dig J Nanomater Biostruct 5(2):623–628Google Scholar
- Liu CM, Zu XT, Wei QM (2006) Fabrication and characterization of wire-like SnO2. J Phys D Appl Phys 39:2494–2497View ArticleGoogle Scholar
- Agekyan VT (1977) SnO2 solid thin films. Phys Status Solidi 43(1):11–42View ArticleGoogle Scholar
- Wang Y, Ramos I (2007) Preparation and electrochemical properties of SnO2 nanowires. J Appl Phys 102:1–7View ArticleGoogle Scholar