Inhomogeneous Oxygen Vacancy Distribution in Semiconductor Gas Sensors: Formation, Migration and Determination on Gas Sensing Characteristics

The density of oxygen vacancies in semiconductor gas sensors was often assumed to be identical throughout the grain in the numerical discussion of the gas-sensing mechanism of the devices. In contrast, the actual devices had grains with inhomogeneous distribution of oxygen vacancy under non-ideal conditions. This conflict between reality and discussion drove us to study the formation and migration of the oxygen defects in semiconductor grains. A model of the gradient-distributed oxygen vacancy was proposed based on the effects of cooling rate and re-annealing on semiconductive thin films. The model established the diffusion equations of oxygen vacancy according to the defect kinetics of diffusion and exclusion. We described that the steady-state and transient-state oxygen vacancy distributions, which were used to calculate the gas-sensing characteristics of the sensor resistance and response to reducing gases under two different conditions. The gradient-distributed oxygen vacancy model had the applications in simulating the sensor performances, such as the power law, the grain size effect and the effect of depletion layer width.

[1]  Zhaoxia Zhai,et al.  Characterization and Gas Sensing Properties of Copper-doped Tin Oxide Thin Films Deposited by Ultrasonic Spray Pyrolysis , 2016 .

[2]  Manish Sharma,et al.  Structural, optical and sensing properties of pure and Cu-doped SnO2 nanowires. , 2014, Journal of nanoscience and nanotechnology.

[3]  Ghenadii Korotcenkov,et al.  Grain Size Effects in Sensor Response of Nanostructured SnO2- and In2O3-Based Conductometric Thin Film Gas Sensor , 2009 .

[4]  Lin Quan,et al.  Simulation of Grain Size Effects on Gas Sensing Characteristics of Semiconductor Sensors in Nitrogen Oxides Detection , 2014 .

[5]  Dongxiang Zhou,et al.  Preparation of Tin Oxide Thin Films on Silicon Substrates via Sol–Gel Routes and the Prospects for the H 2 S Gas Sensor , 2011 .

[6]  Dongxiang Zhou,et al.  Influences of cooling rate on gas sensitive tin oxide thin films and a model of gradient distributed oxygen vacancies in SnO2 crystallites , 2010 .

[7]  Jiang Tang,et al.  Enhancement of hydrogen sulfide gas sensing of PbS colloidal quantum dots by remote doping through ligand exchange , 2015 .

[8]  Lin Quan,et al.  Evaluation of Depletion Layer Width in Antimony-Doped Tin Oxide Thin Films for Gas Sensors , 2015 .

[9]  Udo Weimar,et al.  Influences of Al, Pd and Pt additives on the conduction mechanism as well as the surface and bulk properties of SnO2 based polycrystalline thick film gas sensors , 2012 .

[10]  Jiang Tang,et al.  Resistive gas sensors based on colloidal quantum dot (CQD) solids for hydrogen sulfide detection , 2015 .

[11]  Dongxiang Zhou,et al.  Tin oxide thin films prepared by aerosol-assisted chemical vapor deposition and the characteristics on gas detection , 2010 .

[12]  Huan Shi.  Metal-oxide gas sensor , 2007 .

[13]  C. Zou,et al.  Synthesis and oxygen vacancy related NO2 gas sensing properties of ZnO:Co nanorods arrays gown by a hydrothermal method , 2015 .

[14]  Shuai Gao,et al.  SnO2 nanocrystals with abundant oxygen vacancies: Preparation and room temperature NO2 sensing , 2016 .

[15]  Norio Miura,et al.  Dilute hydrogen sulfide sensing properties of CuO–SnO2 thin film prepared by low-pressure evaporation method , 1998 .

[16]  Liang Gao,et al.  Chemiresistive gas sensors employing solution-processed metal oxide quantum dot films , 2014 .

[17]  Bing Yang,et al.  Both oxygen vacancies defects and porosity facilitated NO2 gas sensing response in 2D ZnO nanowalls at room temperature , 2016 .

[18]  Joachim Maier,et al.  Investigations of the bulk defect chemistry of polycrystalline tin(IV) oxide , 1988 .

[19]  Udo Weimar,et al.  Conduction mechanisms in SnO2 based polycrystalline thick film gas sensors exposed to CO and H2 in different oxygen backgrounds , 2011 .

[20]  Joshua M. Pearce,et al.  A novel synthesis of tin oxide thin films by the sol-gel process for optoelectronic applications , 2015 .

[21]  Baohui Zhang,et al.  Sensitive H2S gas sensors employing colloidal zinc oxide quantum dots , 2017 .

[22]  Dongxiang Zhou,et al.  Physically Flexible, Rapid‐Response Gas Sensor Based on Colloidal Quantum Dot Solids , 2014, Advanced materials.

[23]  Shougang Chen,et al.  DFT study of CO sensing mechanism on hexagonal WO3 (001) surface: The role of oxygen vacancy , 2014 .

[24]  Hung M. Le,et al.  Migrations of oxygen vacancy in tungsten oxide (WO3): A density functional theory study , 2014 .

[25]  Yuxiang Qin,et al.  DFT study on interaction of NO2 with the vacancy-defected WO3 nanowires for gas-sensing , 2016 .

[26]  Vinay Gupta,et al.  Study of collective efforts of catalytic activity and photoactivation to enhance room temperature response of SnO2 thin film sensor for methane , 2013 .

[27]  Yang Wang,et al.  Enhanced H2S gas sensing properties based on SnO2 quantum wire/reduced graphene oxide nanocomposites: Equilibrium and kinetics modeling , 2017 .

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

[29]  Nicolae Barsan,et al.  Sensing of CH4, CO and ethanol with in situ nanoparticle aerosol-fabricated multilayer sensors , 2007 .

[30]  Ming Hu,et al.  NO2-sensing properties of porous WO3 gas sensor based on anodized sputtered tungsten thin film , 2012 .

[31]  Wei Jin,et al.  Preparation and gas sensing property of Ag-supported vanadium oxide nanotubes , 2014 .

[32]  Yan Wang,et al.  Low-temperature CO gas sensors based on Au/SnO2 thick film , 2007 .

[33]  Miao Zhang,et al.  Defect distribution and evolution in He+ implanted Si studied by variable-energy positron beam , 1998 .

[34]  Dongxiang Zhou,et al.  Time-dependent oxygen vacancy distribution and gas sensing characteristics of tin oxide gas sensitive thin films , 2010 .

[35]  Zhaoxia Zhai,et al.  Numeral description of grain size effects of tin oxide gas-sensitive elements and evaluation of depletion layer width , 2015, Electronic Materials Letters.

[36]  S. Morrison,et al.  Semiconductor gas sensors , 1985 .

[37]  S. Morrison,et al.  Mechanism of semiconductor gas sensor operation , 1987 .

[38]  Peng Sun,et al.  Microwave assisted synthesis of hierarchical Pd/SnO2 nanostructures for CO gas sensor , 2016 .

[39]  Zhong Wei,et al.  Highly sensitive and rapid chemiresistive sensor towards trace nitro-explosive vapors based on oxygen vacancy-rich and defective crystallized In-doped ZnO , 2017 .

[40]  A R Plummer,et al.  Introduction to Solid State Physics , 1967 .

[41]  Yoshitaka Okada,et al.  Improvement of crystal quality of GaInNAs films grown by atomic hydrogen-assisted RF-MBE , 2005 .

[42]  Dongxiang Zhou,et al.  Tin oxide films for nitrogen dioxide gas detection at low temperatures , 2013 .

[43]  Thomas Maier,et al.  Comparison of the gas sensing performance of SnO2 thin film and SnO2 nanowire sensors , 2012 .

[44]  R. S. Niranjan,et al.  A novel hydrogen sulfide room temperature sensor based on copper nanocluster functionalized tin oxide thin films , 2002 .

[45]  Kengo Shimanoe,et al.  Theory of power laws for semiconductor gas sensors , 2008 .

[46]  Tae-Sung Oh,et al.  CO sensitivity of La2O3-doped SnO2 thick film gas sensor , 2013 .

[47]  K. Yong,et al.  Generation of oxygen vacancies in ZnO nanorods/films and their effects on gas sensing properties , 2015 .

[48]  Kengo Shimanoe,et al.  Roles of Shape and Size of Component Crystals in Semiconductor Gas Sensors , 2008 .

[49]  Noboru Yamazoe,et al.  Interactions of tin oxide surface with O2, H2O AND H2 , 1979 .

[50]  Miriam Susana Castro,et al.  Influence of frozen distributions of oxygen vacancies on tin oxide conductance , 1999 .

[51]  Kengo Shimanoe,et al.  Receptor function of small semiconductor crystals with clean and electron-traps dispersed surfaces , 2009 .

[52]  Lin Quan,et al.  Evaluation of depletion layer width and gas-sensing properties of antimony-doped tin oxide thin film sensors , 2015 .

[53]  Kengo Shimanoe,et al.  Diffusion equation-based study of thin film semiconductor gas sensor-response transient , 2002 .

[54]  Ghenadii Korotcenkov,et al.  Peculiarities of SnO2 thin film deposition by spray pyrolysis for gas sensor application , 2001 .

[55]  Y. Mortazavi,et al.  Low temperature CO and CH4 dual selective gas sensor using SnO2 quantum dots prepared by sonochemical method , 2010 .

[56]  Chao Zhang,et al.  Role of oxygen vacancy in tuning of optical, electrical and NO2 sensing properties of ZnO1-x coatings at room temperature , 2017 .

[57]  Kengo Shimanoe,et al.  Theory of gas-diffusion controlled sensitivity for thin film semiconductor gas sensor , 2001 .

[58]  C. Liu,et al.  Synthesis of quantum size ZnO crystals and their gas sensing properties for NO2 , 2011 .

[59]  Kengo Shimanoe,et al.  Theoretical approach to the gas response of oxide semiconductor film devices under control of gas diffusion and reaction effects , 2011 .

[60]  Khalifa Aguir,et al.  Ab initio study of oxygen point defects on tungsten trioxide surface , 2012 .

[61]  Robert H. Rediker,et al.  Electrical Properties of High‐Quality Stannic Oxide Crystals , 1971 .

[62]  Nidhi Verma,et al.  Synthesis and characterization of CuO–SnO2 nanocomposite and its application as liquefied petroleum gas sensor , 2014 .

[63]  Nicolae Barsan,et al.  Influence of annealing temperature on the CO sensing mechanism for tin dioxide based sensors–Operando studies , 2007 .

[64]  Changsheng Xie,et al.  Al-doping induced formation of oxygen-vacancy for enhancing gas-sensing properties of SnO2 NTs by electrospinning , 2014 .

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

[66]  Zhilong Song,et al.  Sensitive Room-Temperature H2S Gas Sensors Employing SnO2 Quantum Wire/Reduced Graphene Oxide Nanocomposites , 2016 .

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

[68]  Udo Weimar,et al.  Transport and gas sensing properties of In2O3 nanocrystalline thick films: A Hall effect based approach , 2009 .

[69]  Vincenzo Guidi,et al.  AC measurements and modeling of WO3 thick film gas sensors , 2005 .

[70]  Yadong Li,et al.  High sensitivity of CuO modified SnO2 nanoribbons to H2S at room temperature , 2005 .

[71]  E. W. Williams,et al.  Response behaviour of tin oxide thin film gas sensors grown by MOCVD , 2000 .

[72]  Chao-Nan Xu,et al.  Grain size effects on gas sensitivity of porous SnO2-based elements , 1991 .

[73]  Yang Wang,et al.  Solution-Processed Gas Sensors Employing SnO2 Quantum Dot/MWCNT Nanocomposites. , 2016, ACS applied materials & interfaces.

[74]  Hyoung J. Cho,et al.  Room temperature hydrogen response kinetics of nano–micro-integrated doped tin oxide sensor , 2007 .

[75]  Manish Sharma,et al.  Structural, Optical and Sensing Properties of Pure and Cu-Doped SnO 2 Nanowires , 2014 .

[76]  Xiaojing Zhao,et al.  Templated bicontinuous Tin oxide thin film fabrication and the NO2 gas sensing , 2016 .

[77]  Pietro Siciliano,et al.  Air quality monitoring by means of sol–gel integrated tin oxide thin films , 1999 .

[78]  N. K. Gaur,et al.  Copper doped SnO2 nanowires as highly sensitive H2S gas sensor , 2009 .

[79]  Zhaoxia Zhai,et al.  Simulation of the grain size effect in gas-sensitive SnO2 thin films using the oxygen vacancy gradient distribution model , 2015, Electronic Materials Letters.

[80]  Derek R. Miller,et al.  Nanoscale metal oxide-based heterojunctions for gas sensing: A review , 2014 .

[81]  Zhou Dongxiang,et al.  Highly sensitive SnO2 thin film with low operating temperature prepared by sol–gel technique , 2008 .

[82]  S. G. Ansari,et al.  Grain size effects on H2 gas sensitivity of thick film resistor using SnO2 nanoparticles , 1997 .

[83]  Kengo Shimanoe,et al.  Roles of Shape and Size of Component Crystals in Semiconductor Gas Sensors I. Response to Oxygen , 2008 .

[84]  Kengo Shimanoe,et al.  Contribution of electron tunneling transport in semiconductor gas sensor , 2007 .

[85]  Kengo Shimanoe,et al.  Extension of receptor function theory to include two types of adsorbed oxygen for oxide semiconductor gas sensors , 2012 .

[86]  Dongxiang Zhou,et al.  Gas sensing characteristics of SnO2 thin films and analyses of sensor response by the gas diffusion theory , 2009 .

[87]  Kengo Shimanoe,et al.  Basic approach to the transducer function of oxide semiconductor gas sensors , 2011 .

[88]  Kengo Shimanoe,et al.  New perspectives of gas sensor technology , 2009 .

[89]  Giorgio Sberveglieri,et al.  Stable and highly sensitive gas sensors based on semiconducting oxide nanobelts , 2002 .

[90]  Man Siu Tse,et al.  Semiconductor gas sensor based on Pd-doped SnO2 nanorod thin films , 2008 .

[91]  Zhaoxia Zhai,et al.  Gas-sensing properties and sensitivity promoting mechanism of Cu-added SnO2 thin films deposited by ultrasonic spray pyrolysis ☆ , 2017 .

[92]  Jingting Luo,et al.  Sensitive NO2 gas sensors employing spray-coated colloidal quantum dots , 2016 .

[93]  Zhaoxia Zhai,et al.  Effect of depletion layer width on electrical properties of semiconductive thin film gas sensor: a numerical study based on the gradient-distributed oxygen vacancy model , 2016 .

[94]  Nay Ming Huang,et al.  Aerosol assisted chemical vapour deposited (AACVD) of TiO2 thin film as compact layer for dye-sensitised solar cell , 2014 .

[95]  Marco Stefancich,et al.  Model for Schottky barrier and surface states in nanostructured n-type semiconductors , 2002 .

[96]  Kengo Shimanoe,et al.  Two types of moisture effects on the receptor function of neat tin oxide gas sensor to oxygen , 2013 .

[97]  Hubert B. Keller,et al.  New applications of tin oxide gas sensors: II. Intelligent sensor system for reliable monitoring of ammonia leakages , 1999 .

[98]  Dongxiang Zhou,et al.  The sensor response of tin oxide thin films to different gas concentration and the modification of the gas diffusion theory , 2009 .

[99]  Jyh-Jier Ho,et al.  Novel nitrogen monoxides (NO) gas sensors integrated with tungsten trioxide (WO3)/pin structure for room temperature operation , 2003 .

[100]  Pietro Siciliano,et al.  Core-shell Pd nanoparticles embedded in SnOx films. Synthesis, analytical characterisation and perspective application in chemiresistor-type sensing devices , 2006, Microelectron. J..

[101]  Jacek Rynkowski,et al.  Sensors Based on SNO2 As a Detector for CO Oxidation in Air , 2001 .

[102]  H. Grubin.  The physics of semiconductor devices , 1979, IEEE Journal of Quantum Electronics.

[103]  T. Seiyama,et al.  A New Detector for Gaseous Components Using Semiconductive Thin Films. , 1962 .

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

[105]  Lin Quan,et al.  Numerical Discussion of the Grain Size Effects on Tungsten Oxide and Indium Oxide Based Gas Sensors in NO X Detection , 2014 .

[106]  Baohui Zhang,et al.  Colloidal synthesis of tungsten oxide quantum dots for sensitive and selective H2S gas detection , 2017 .

[107]  J. Watson,et al.  Selectivity of semiconductor gas sensors , 1978, Proceedings of the IEEE.

[108]  L. A. Patil,et al.  Surface modified BaTiO3 thick film resistors as H2S gas sensors , 2006 .

[109]  Yongsheng Liu,et al.  The interaction between oxygen vacancies and doping atoms in ZnO , 2015 .