SnO_2基纳米材料的合成及其气敏性能研究
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摘要
SnO_2作为一种宽禁带半导体气敏材料,由于本身的物理、化学性质稳定,不需要添加贵金属就对还原性气体有较好的敏感性、稳定性和一定的选择性等优点。以往的研究多侧重于材料的制备方法与气敏性能以及组成成分与气敏性能的关系,而本论文将对材料的制备方法、形貌结构、掺杂对气敏性能的影响作一系统的研究。
采用沉淀法、水热合成法以及包覆法制备多孔纳米SnO_2、珊瑚状纳米SnO_2以及空心球状纳米SnO_2三种不同结构的材料,采用XRD、SEM以及BET对材料的组成成分、晶粒尺寸、结构形貌以及等温吸附曲线进行了表征,并以这三种不同形貌结构的SnO_2纳米材料为原料,通过传统的旁热式气敏传感器制备技术制作成气敏元件,测试其电阻随温度的变化特性以及对几种挥发性气体的敏感特性。结果如下:
(1)合成的三种SnO_2纳米材料均结晶良好,为四方晶系。多孔SnO_2呈现出均一的孔状结构,平均粒径为8.6nm,珊瑚状SnO_2在外观上和海洋生物珊瑚形貌非常相似,样品由密集的触须构成,平均粒径为13.5nm,中空球状SnO_2微球的直径大小约为1~4μm,微球表面较光滑,但部分微球表面有坑洞,从坑洞可以看出,微球内部为空心结构,且球壁较薄,纳米晶粒的平均粒径为22.7nm。
(2)所制备的几种材料都具有较高的灵敏度和较低的工作温度,在工作温度在190℃时,几种材料对100ppm的乙醇气体的灵敏度都在20以上,且随着气体浓度的升高,灵敏度与浓度表现出一定的线性关系。符合工业应用标准。
(3)材料的比面积、孔径大小以及孔隙容积对材料的气敏性能影响很大。相同条件下,珊瑚状SnO_2的灵敏度比多孔SnO_2和中空球状SnO_2的灵敏度都高,其比表面积为40.19m~2/g,平均孔径为297.0nm,孔隙容积为0.2984cc/g。而掺杂Ni离子的多孔SnO_2材料在相同条件下灵敏度比这三种材料都高,说明离子掺杂相对于结构控制对材料的灵敏度有着更直接的影响。
SnO_2 is a wide bandgap semiconductor gas-sensing material, because its physical and chemical stability, there are many advantages to reducing gas without doping precious metal, such as sensitivity, stability and certain selectivity. The past research mostly focused on the preparation methods or the compositions relation with the gas-sensing properties. This thesis will make systematic study for the relation of preparation methods, morphology and doped with the gas sensing properties.
Porous, coral-like and hollow spherical nano-SnO_2 materials were produced by precipitation, hydrothermal synthesis and coating method. The morphology, microstructure and isothermal adsorption-desorption curves were characterized by SEM, XRD and BET. The indirect heating gas sensors were prepared using the three materials. Characteristics of resistance varied with temperature and gas sensitivity of several reducing gases were studied. Results are as follows:
(1) The three SnO_2 nano-materials are well crystallized tetragonal system. The porous SnO_2 showing a uniform porous structure, average pore diameter is 8.6nm, the coral-like SnO_2 architecture exhibits a coral-like morphology with many tentacle-like structures, average pore diameter is 13.5nm, the diameter of SnO_2 hollow spherical microspheres are about 1~4μm, the surface of microspheres is very smooth, but there are holes on its surface, from holes can see that the microspheres are hollow structure with thin walls. The average pore diameter of nanometer grain is 22.7 nm.
(2) The prepared materials have higher sensitivities and lower operating temperature. When the operating temperature at 190℃, the sensitivity of the three materials for 100ppm ethanol gas are over 20, as gas concentration increased, the sensitivity and the concentration show a certain linear relationship. Meet the standards for industrial applications.
(3) The specific surface area, pore size and pore volume of materials have great influence on gas sensing properties. Under the same conditions, coral-like porous SnO_2 material is more sensitive than porous SnO_2 and hollow spherical SnO_2 materials, and its specific surface area is 40.19m~2/g, average pore size is 297.0nm, the pore volume is 0.2984cc/g. But the Ni ion doped SnO_2 porous material under the same conditions is more sensitive than the all three materials. Doping control relative to the structure of the material has a more direct effect on the sensitivity.
采用沉淀法、水热合成法以及包覆法制备多孔纳米SnO_2、珊瑚状纳米SnO_2以及空心球状纳米SnO_2三种不同结构的材料,采用XRD、SEM以及BET对材料的组成成分、晶粒尺寸、结构形貌以及等温吸附曲线进行了表征,并以这三种不同形貌结构的SnO_2纳米材料为原料,通过传统的旁热式气敏传感器制备技术制作成气敏元件,测试其电阻随温度的变化特性以及对几种挥发性气体的敏感特性。结果如下:
(1)合成的三种SnO_2纳米材料均结晶良好,为四方晶系。多孔SnO_2呈现出均一的孔状结构,平均粒径为8.6nm,珊瑚状SnO_2在外观上和海洋生物珊瑚形貌非常相似,样品由密集的触须构成,平均粒径为13.5nm,中空球状SnO_2微球的直径大小约为1~4μm,微球表面较光滑,但部分微球表面有坑洞,从坑洞可以看出,微球内部为空心结构,且球壁较薄,纳米晶粒的平均粒径为22.7nm。
(2)所制备的几种材料都具有较高的灵敏度和较低的工作温度,在工作温度在190℃时,几种材料对100ppm的乙醇气体的灵敏度都在20以上,且随着气体浓度的升高,灵敏度与浓度表现出一定的线性关系。符合工业应用标准。
(3)材料的比面积、孔径大小以及孔隙容积对材料的气敏性能影响很大。相同条件下,珊瑚状SnO_2的灵敏度比多孔SnO_2和中空球状SnO_2的灵敏度都高,其比表面积为40.19m~2/g,平均孔径为297.0nm,孔隙容积为0.2984cc/g。而掺杂Ni离子的多孔SnO_2材料在相同条件下灵敏度比这三种材料都高,说明离子掺杂相对于结构控制对材料的灵敏度有着更直接的影响。
SnO_2 is a wide bandgap semiconductor gas-sensing material, because its physical and chemical stability, there are many advantages to reducing gas without doping precious metal, such as sensitivity, stability and certain selectivity. The past research mostly focused on the preparation methods or the compositions relation with the gas-sensing properties. This thesis will make systematic study for the relation of preparation methods, morphology and doped with the gas sensing properties.
Porous, coral-like and hollow spherical nano-SnO_2 materials were produced by precipitation, hydrothermal synthesis and coating method. The morphology, microstructure and isothermal adsorption-desorption curves were characterized by SEM, XRD and BET. The indirect heating gas sensors were prepared using the three materials. Characteristics of resistance varied with temperature and gas sensitivity of several reducing gases were studied. Results are as follows:
(1) The three SnO_2 nano-materials are well crystallized tetragonal system. The porous SnO_2 showing a uniform porous structure, average pore diameter is 8.6nm, the coral-like SnO_2 architecture exhibits a coral-like morphology with many tentacle-like structures, average pore diameter is 13.5nm, the diameter of SnO_2 hollow spherical microspheres are about 1~4μm, the surface of microspheres is very smooth, but there are holes on its surface, from holes can see that the microspheres are hollow structure with thin walls. The average pore diameter of nanometer grain is 22.7 nm.
(2) The prepared materials have higher sensitivities and lower operating temperature. When the operating temperature at 190℃, the sensitivity of the three materials for 100ppm ethanol gas are over 20, as gas concentration increased, the sensitivity and the concentration show a certain linear relationship. Meet the standards for industrial applications.
(3) The specific surface area, pore size and pore volume of materials have great influence on gas sensing properties. Under the same conditions, coral-like porous SnO_2 material is more sensitive than porous SnO_2 and hollow spherical SnO_2 materials, and its specific surface area is 40.19m~2/g, average pore size is 297.0nm, the pore volume is 0.2984cc/g. But the Ni ion doped SnO_2 porous material under the same conditions is more sensitive than the all three materials. Doping control relative to the structure of the material has a more direct effect on the sensitivity.
引文
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[2]常剑,蒋登高,詹自力,宋文会,半导体金属氧化物气敏材料敏感机理概述[J].传感器世界,2003(08):0014—05.
[3] Jun Tamaki et al. Sensing properties to dilute chloride gas of indium oxide based thin film sensors prepared by electron beam evaporation[J].Sensors and Actuators, B 4181 2002,(1-5).
[4] Niranjanrs, Hwang Y K, Kim D-K, et al. Nanostructured tin oxide: synthesis and gas-sensing properties[J].Materials chemistry and physics,2005,92:384-388.
[5]胡英,周晓华. CuO-ZnO敏感材料气敏机理的研究[J].电子元件与材料,2001,20(2):5-7.
[6]向蓝翔.低温氧化锆氧传感器的研究[J].传感器技术,1998,17(1):25-27.
[7] Maskell W C. Progress in the development of zirconia gas sensors [J]. Solid State Ionics, 2000, 134(1-2): 43-50.
[8] Penza M, Martucci C, Cassano G. NOx gas sensing characteristics of WO3 thin films activated by noble metals (Pd, Pt, Au) layers[J]. Sensors and Actuators B, 1998, 50(1): 52-59.
[9] Niranjan R S, Patil K R, Sainkar S R, et al. Morphological and sensing properties of spray-pyrolysed Th: SnO_2 thin films[J]. Materials Chemistry and Physics, 2004, 84(1): 37-45.
[10]王智民,张新,张艳熹等.旁热TiO_2/MoO3复合厚膜邻二甲苯气敏陶瓷元件的制备及特性表征[J].黑龙江大学自然科学学报, 2003, 20(2):89-92.
[11] Camelia Matei Ghimbeu,Martine Lumbreras,Maryam Siadat,Robert C.van Landschoot,Joop Schoonman.Electrostatic sprayed SnO_2 andCu-doped SnO_2 films for H2S detection[J].Sensors and Actuators B 133 (2008):694-698.
[12] Korotcenkov G, Brinzari V, Boris Y, et al. Influence of surface Pd doping on gas sensing characteristics of SnO_2 thin films deposited by spray pirolysis[J]. Thin Solid Films, 2003, 436(1): 119-126
[13] Neri1 G, Bonavita1 A, Galvagno S, et al. Preparation, characterization and CO sensing of Au/iron oxide thin films[J]. Journal of Materials Science: Materials in Electronics, 2002, 13(9):561-565
[14] Penza M, Martucci C, Cassano G. NOx gas sensing characteristics of WO3 thin films activated by noble metals (Pd, Pt, Au) layers[J]. Sensors and Actuators B, 1998, 50(1):52-59
[15] Niranjan R S, Patil K R, Sainkar S R, et al. Morphological and sensing properties of spray-pyrolysed Th: SnO_2 thin films[J]. Materials Chemistry and Physics, 2004, 84(1):37-45
[16] Comini E, Ferroni M, Guidi V, et al. Effects of Ta/Nb-doping on titania-based thin films for gas-sensing[J]. Sensors and Actuators B, 2005, 108(1-2):21-28
[17] Jinkawa T, Sakai G, Tamaki J, et al. Relationship between ethanol gas sensitivity and surface catalytic property of tin oxide sensors modified with acidic or basic oxides[J]. Journal of Molecular Catalysis A, 2000, 155(1-2):193-200
[18] Chowdhuri A, Gupta V, Sreenivas K. Fast response H2S gas sensing characteristics with ultra-thin CuO islands on sputtered SnO_2[J]. Sensors and Actuators B, 2003, 93(1-3):572-579
[19]王毓德,吴兴惠,田子华.一种实现气敏元件互补增强原理的新结构[J].云南大学学报(自然科学版), 1997, 19(1):25-28
[20]唐小红,张云,张萍等.纳米二氧化钛的光催化性能研究[J].功能材料, 2004, 35(2): 236-238.
[21] Camagni P, Faglia G, Galinetto P, et al. Photosensitivity activation ofSnO_2 thin film gas sensors at room temperature [J]. Sens Actuat B-Chem, 1996,31: 99–103.
[22] G. Sberverlieri. Recent decelopments in semiconducting thin-film gas sensors [J]. Sensors and Actuators B, 1995, 23:103-109.
[23] Caihong Wang,ChuXiangfeng,Wu Mingmei.Highly sensitive gas sensors based on hollow SnO_2 spheres prepared by carbon spere template method[J].Sensors and Actuators B 120(2007) 508-513.
[24]李茂琼,顾应龙,吴兴惠等.无需掺入贵金属的多元氧化物气敏材料[J].传感技术学报. 2002(3):248-250.
[25] Zhu B.L, Xie C.S, Wang W.Y, et al. Improvement in gas sensitivity of ZnO thick film to volatile organic compounds (VOCs) by adding TiO_2[J]. Materials Letters, 2004, 58:624-629.
[26] Srivastava A.K. Detection of volatile organic compounds (VOCs) using SnO_2 gas-sensor array and artificial neural network [J]. Sensors and Actuators B, 2003, 96:24-37.
[27] Ichiro M, Kouta H, Norimitsu M, et al. Preparation of intercalative organic/MoO3 anohybrids and their VOC gas sensing properties[J]. The 10th International Meeting on Chemical Sensors, 2002:276-277.
[28] Zhi-dong Lin, Gao-feng Chen et al, et al. The gas sensitivity of nano TiO_2-SnO_2 film doped wity Cd(II) ion[J].Materials Letters, 2009,63: 2277-2279.
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