Hybrid SnO2/TiO2 Nanocomposites for Selective Detection of Ultra-Low Hydrogen Sulfide Concentrations in Complex Backgrounds

In this paper, we present a chemiresistive metal oxide (MOX) sensor for detection of hydrogen sulfide. Compared to the previous reports, the overall sensor performance was improved in multiple characteristics, including: sensitivity, selectivity, stability, activation time, response time, recovery time, and activation temperature. The superior sensor performance was attributed to the utilization of hybrid SnO2/TiO2 oxides as interactive catalytic layers deposited using a magnetron radio frequency (RF) sputtering technique. The unique advantage of the RF sputtering for sensor fabrication is the ability to create ultra-thin films with precise control of geometry, morphology and chemical composition of the product of synthesis. Chemiresistive films down to several nanometers can be fabricated as sensing elements. The RF sputtering technique was found to be very robust for bilayer and multilayer oxide structure fabrication. The geometry, morphology, chemical composition and electronic structure of interactive layers were evaluated in relation to their gas sensing performance, using scanning electron microscopy (SEM), X-ray diffraction technique (XRD), atomic force microscopy (AFM), Energy Dispersive X-ray Spectroscopy (EDAX), UV visible spectroscopy, and Kelvin probe measurements. A sensor based on multilayer SnO2/TiO2 catalytic layer with 10% vol. content of TiO2 demonstrated the best gas sensing performance in all characteristics. Based on the pattern relating material’s characteristics to gas sensing performance, the optimization strategy for hydrogen sulfide sensor fabrication was suggested.

[1]  J. Wager.  Transparent electronics: Schottky barrier and heterojunction considerations , 2008 .

[2]  Dongxiang Zhou,et al.  Properties and mechanism study of SnO2 nanocrystals for H2S thick-film sensors , 2009 .

[3]  Jinhuai Liu,et al.  Stability of SnO2/Fe2O3 multilayer thin film gas sensor , 2000 .

[4]  J. Sambrano,et al.  Preparation of TiO2/SnO2 thin films by sol-gel method and periodic B3LYP simulations. , 2014, The journal of physical chemistry. A.

[5]  Helena Teterycz,et al.  Analysis of SnO2|WO3 Heterocontact Properties during the Detection of Hydrogen Sulphide , 2014, Sensors.

[6]  H. Woo,et al.  Selective oxidation of H2S to elemental sulfur over TiO2/SiO2 catalysts , 1998 .

[7]  Wojtek Wlodarski,et al.  Physisorption-Based Charge Transfer in Two-Dimensional SnS2 for Selective and Reversible NO2 Gas Sensing. , 2015, ACS nano.

[8]  Richard J. Ewen,et al.  Thick film organic vapour sensors based on binary mixtures of metal oxides , 2003 .

[9]  Bin Su,et al.  Superwettability Strategy: 1D Assembly of Binary Nanoparticles as Gas Sensors. , 2017, Small.

[10]  Chunling Zhu,et al.  Two-dimensional net-like SnO2/ZnO heteronanostructures for high-performance H2S gas sensor , 2016 .

[11]  N. Yamazoe,et al.  Role of hetero-junctions in oxide semiconductor gas sensors , 1996 .

[12]  Yingkai Liu,et al.  Room temperature ppb level H2S detection of a single Sb-doped SnO2 nanoribbon device , 2015 .

[13]  Marina N. Rumyantseva,et al.  CuO/SnO2 thin film heterostructures as chemical sensors to H2S , 1998 .

[14]  Hsin‐Tsung Chen,et al.  Density Functional Theory Study of the Adsorption and Reaction of H2S on TiO2 Rutile (110) and Anatase (101) Surfaces , 2009 .

[15]  L. A. Patil,et al.  Surface cupricated SnO2-ZnO thick films as a H2S gas sensor , 2004 .

[16]  Jianmin Ma,et al.  Gas Sensing of SnO2 Nanocrystals Revisited: Developing Ultra-Sensitive Sensors for Detecting the H2S Leakage of Biogas , 2014, Scientific Reports.

[17]  Kai Wang,et al.  H2S Detection by Vertically Aligned CuO Nanowire Array Sensors , 2008 .

[18]  R. Binions,et al.  Gas Sensing Studies of an n-n Hetero-Junction Array Based on SnO2 and ZnO Composites , 2016 .

[19]  G. Lu,et al.  A pulse-driven sensor based on ordered mesoporous Ag2O/SnO2 with improved H2S-sensing performance , 2016 .

[20]  Dongxiang Zhou,et al.  Nanocrystalline In2O3–SnO2 thick films for low-temperature hydrogen sulfide detection , 2011 .

[21]  L. A. Patil,et al.  Heterocontact type CuO-modified SnO2 sensor for the detection of a ppm level H2S gas at room temperature , 2006 .

[22]  Qing Wang,et al.  Gas Sensors Based on Semiconducting Metal Oxide One-Dimensional Nanostructures , 2009, Sensors.

[23]  W. Guo,et al.  High-response H2S sensor based on ZnO/SnO2 heterogeneous nanospheres , 2016 .

[24]  K. Sreenivas,et al.  Contribution of adsorbed oxygen and interfacial space charge for enhanced response of SnO2 sensors having CuO catalyst for H2S gas , 2010 .

[25]  Xin Zhang,et al.  H2S-Selective Catalytic Oxidation: Catalysts and Processes , 2015 .

[26]  Seok-Jin Yoon,et al.  Highly Sensitive H2S Sensor Based on the Metal-Catalyzed SnO2 Nanocolumns Fabricated by Glancing Angle Deposition , 2015, Sensors.

[27]  Xincun Tang,et al.  High surface area SnO2 nanoparticles: Synthesis and gas sensing properties , 2008 .

[28]  Guojia Fang,et al.  Room temperature H2S sensing properties and mechanism of CeO2-SnO2 sol-gel thin films , 2000 .

[29]  Vinay Gupta,et al.  A highly sensitive SnO2–CuO multilayered sensor structure for detection of H2S gas , 2012 .

[30]  A. Yu,et al.  Adsorption of the OH Group on SnO2(110) Oxygen Bridges: A Molecular Dynamics and Density Functional Theory Study , 2013 .

[31]  Soumen Das,et al.  SnO2: A comprehensive review on structures and gas sensors , 2014 .

[32]  Xuchuan Jiang,et al.  Experimental and theoretical studies on noble metal decorated tin oxide flower-like nanorods with high ethanol sensing performance , 2015 .

[33]  Jingli Luo,et al.  Highly cost-effective and sulfur/coking resistant VOx-grafted TiO2 nanoparticles as an efficient anode catalyst for direct conversion of dry sour methane in solid oxide fuel cells , 2015 .

[34]  N. Yamazoe,et al.  Proposal of contact potential promoted oxide semiconductor gas sensor , 2013 .

[36]  V. F. Gromov,et al.  Gas Semiconducting Sensors Based on Metal Oxide Nanocomposites , 2012 .

[37]  Katarzyna Zakrzewska,et al.  SnO2–TiO2 solid solutions for gas sensors , 1998 .

[38]  Byeong Kwon Ju,et al.  Enhanced H2S sensing characteristics of SnO2 nanowires functionalized with CuO , 2009 .

[39]  Imtiaz S. Mulla,et al.  Fe-doped SnO2 nanomaterial : A low temperature hydrogen sulfide gas sensor , 2008 .

[40]  Francis Levy,et al.  Electrical and optical properties of TiO2 anatase thin films , 1994 .