TiO_2纳米晶材料对三甲胺（TMA）气敏特性的研究
摘要
介观物理的理论研究表明：决定物质性质的不仅是物质的组成和结构，还有粒度和与之相关的表面状态。纳米材料超细的晶粒、高浓度的界面以及晶界原子的临界状态决定了它们具有明显区别于无定形态、普通多晶和单晶的特异性能，也正是由于这种结构特点使得纳米材料具有一系列与尺寸大小有关的新效应，如表面效应、小尺寸效应以及宏观量子隧道效应等。由于纳米材料在催化、磁性、力学、光学等方面所显示的独特性能，使他作为新型的材料在许多领域得到了广泛应用。金属氧化物纳米材料是一种重要的材料，有许多用途，在材料科学中起着十分重要的作用。
本论文采用硬脂酸凝胶法合成了两种不同晶型的纳米晶TiO2材料。利用差热-热重（DTA-TG）、X射线衍射(XRD)、XPS等测试方法对合成过程及TiO2纳米晶的结构、组成和表面态进行了表征和分析。
差热-热重分析和X射线衍射结果表明，在焙烧温度高于550℃时，随温度和时间的增加，TiO2的晶型会由锐钛矿型逐渐转变为金红石型。同时通过XRD对主峰衍射强度的测定可以确定TiO2重量中各晶型的含量。
制成了对三甲胺气体（TMA）敏感的Ag/ TiO2敏感材料，并以之为原料研制出三甲胺气体敏感元件，并对其性能进行了测试。测试结果当掺杂入Ag为5％时，Ag/ TiO2型元件对三甲胺气体（TMA）有很好的敏感性能。
进一步测试，得到该元件在三甲胺气体浓度250ppm时最佳工作电流为135mA,元件在此最佳工作电流下灵敏度最高并且其灵敏度随三甲胺气体浓度的增大而增大，当三甲胺气体浓度超过2000ppm以后元件灵敏度变化很小。
According to the theory of meso-physics, the property of substance is not only depending on its composition and structure but also depending on its particle size and outline of particle surface. A nanocrystalline material is formed with nano-meter sized particles and can just be described with this theory. The particles in nanocrystalline material have the size of about 1nm to 100nm, and as a result several new effects, such as micro-sized effect, quantum-size effect and macro-quantum tunnelling effect, were discovered.Those effects in turn brings out different characteristics on mechanics, thermodynamics, electricity and chemistry.Those new characteristics have found wind applications in many fields.Therefore from the moment of its appearance , nanocrystalline material had been attracting more and more attentions of scientists on it.
The raw powders of two different crystalline TiO2 nanocrystals were synthesized by stearic acid-gel method. Differential thermal analysis-thermogravimetry (DTA-TG)、X-ray diffraction (XRD)、XPS were used to characterize the synthesis progress and the structure、composition and surface morphology of TiO2 nanocrystals..
The results of DTA-TG and XRD indicated that the crystal forms of TiO2 and would gradually change from anatase to rutile with the calcining temperature increasing and calcining time lengthening when the calcining temperature was over 550℃. At the same time the relative content of anatase and rutile can be determined by the intensity of main peak in TiO2 XRD patterns.
In these experiments the author also produced trimethylamine gas (TMA)
and an Ag/TiO2-sensitive material, with which as the raw material the author further constructed a TMA-sensitive element. The initial performance tests were carried out and the result showed that this Ag/TiO2 element has a good TMA sensitivity when it contains 5% of Ag.
Some further tests reveal that with trimethylamine gas concentration of 250 ppm the optimum working current is 135mA, under which this element gives the highest sensitivity and the sensitivity increases with the concentration until the concentration reaches 2000 ppm when the sensitivity becomes constant.
本论文采用硬脂酸凝胶法合成了两种不同晶型的纳米晶TiO2材料。利用差热-热重（DTA-TG）、X射线衍射(XRD)、XPS等测试方法对合成过程及TiO2纳米晶的结构、组成和表面态进行了表征和分析。
差热-热重分析和X射线衍射结果表明，在焙烧温度高于550℃时，随温度和时间的增加，TiO2的晶型会由锐钛矿型逐渐转变为金红石型。同时通过XRD对主峰衍射强度的测定可以确定TiO2重量中各晶型的含量。
制成了对三甲胺气体（TMA）敏感的Ag/ TiO2敏感材料，并以之为原料研制出三甲胺气体敏感元件，并对其性能进行了测试。测试结果当掺杂入Ag为5％时，Ag/ TiO2型元件对三甲胺气体（TMA）有很好的敏感性能。
进一步测试，得到该元件在三甲胺气体浓度250ppm时最佳工作电流为135mA,元件在此最佳工作电流下灵敏度最高并且其灵敏度随三甲胺气体浓度的增大而增大，当三甲胺气体浓度超过2000ppm以后元件灵敏度变化很小。
According to the theory of meso-physics, the property of substance is not only depending on its composition and structure but also depending on its particle size and outline of particle surface. A nanocrystalline material is formed with nano-meter sized particles and can just be described with this theory. The particles in nanocrystalline material have the size of about 1nm to 100nm, and as a result several new effects, such as micro-sized effect, quantum-size effect and macro-quantum tunnelling effect, were discovered.Those effects in turn brings out different characteristics on mechanics, thermodynamics, electricity and chemistry.Those new characteristics have found wind applications in many fields.Therefore from the moment of its appearance , nanocrystalline material had been attracting more and more attentions of scientists on it.
The raw powders of two different crystalline TiO2 nanocrystals were synthesized by stearic acid-gel method. Differential thermal analysis-thermogravimetry (DTA-TG)、X-ray diffraction (XRD)、XPS were used to characterize the synthesis progress and the structure、composition and surface morphology of TiO2 nanocrystals..
The results of DTA-TG and XRD indicated that the crystal forms of TiO2 and would gradually change from anatase to rutile with the calcining temperature increasing and calcining time lengthening when the calcining temperature was over 550℃. At the same time the relative content of anatase and rutile can be determined by the intensity of main peak in TiO2 XRD patterns.
In these experiments the author also produced trimethylamine gas (TMA)
and an Ag/TiO2-sensitive material, with which as the raw material the author further constructed a TMA-sensitive element. The initial performance tests were carried out and the result showed that this Ag/TiO2 element has a good TMA sensitivity when it contains 5% of Ag.
Some further tests reveal that with trimethylamine gas concentration of 250 ppm the optimum working current is 135mA, under which this element gives the highest sensitivity and the sensitivity increases with the concentration until the concentration reaches 2000 ppm when the sensitivity becomes constant.
引文
干福熹, 《信息材料》,2000.12, 242-253
华中一，第一届全国纳米科学与技术会议论文集，抚顺：中国真空学会，1992
A.Kawabata, R.Kubo, J.Phys.Soc.Jpn.,1966, 21:1765
张立德，牟季美, 《纳米材料学》 1994.10
张志锟，崔作林, 《纳米技术与纳米材料》2000.10
许振嘉 ,《近代半导体材料的表面科学基础》 2002.3
Ulrije Diebold. Suface Science Reports 48(2003) 53-229 143
潘海波等,功能材料与器件学,Vol.7,NO.1,2001.3,101-106
周伟 孙成文 杨芝洲 《无机材料学报》 Vol.13,No.3 (1998.6) 275-281
Ti2/V2O5双层薄膜的TMA气敏特性研究《传感器技术》2000 Vol.19 No.4 5-10
冷藏期间淡水鱼新鲜度变化的研究 《华南农业大学学报》18(3) 1997:100-104
掺铝氧化锌厚膜制备及其对三四胺和海产品鲜度的敏感性《海洋与湖沼》1997.9 Vol 28 No.5 549-552
Nb2O5对TiO2响应TMA气敏特性的改善 《传感技术学报》2000.3 No.1 50-52
张忠孝，耿曼利，李厚福,Ru/TiO2型三甲胺（TMA）传感元件的研制。传感器技术，1996，（2）：27
张忠孝，隋艳，顾沛然。Ru/TiO2三甲胺传感元件与化学分析法测定鱼鲜度。传感器技术，1999，第18卷（2）：28
T.Harbold, R.Bohn, et al., Mater. Sci. &Enger. A 153(1-2)(1992)679
P.Matterazzi, D.Basset, et al., Nanostructured Materials, 2(1993)217
仇海波、高濂等， 无机材料学报，9（3）（1994）365
苏勉曾，固体化学导论，北京大学出版社，（1986）
Xi.Li, Synthesis of Perovokite Type Composite Oxide of Nanocrystalline Materials, Changchun, Jilin University Press, 1992,33-38Ulrije Diebold. Suface Science Reports 48(2003) 53-229 143
Jin-Ming Wu..Satoshi Hayakawa. et al,Crystal Growth &Design Vol.2,NO.2 2002
范雄 X射线金属学，机械工业出版社， 1980
索辉，吴凤清等。柠檬酸盐法合成的纳米晶La0.7Sr0.3FeO3材料酒敏特性研究。功能材料，1998，29（3）
富菊霞。TiO2及其掺杂金属离子的纳米晶材料的制备和光催化性能的研究。吉林大学硕士学位论文，2001年5月
索辉。纳米晶气敏材料的合成、表征及纳米晶薄膜栅FET式新型气敏元件的研制。吉林大学博士学位论文，1998年12月
F.A. Grant Rev.Mod.Phys. 31(1959)646.
G.V. samsonov,The Oxide Handbook,IFI/Plenum Press, New York,1982
M. Mabrook,P. Hawkins, Sensors and Actuators B 75(2001) 197-202
O.I. Bomk et al.Sensors and Actuators B 62 2000 131–135
R.M.Wallton et al.,Applied Surface Science 125(1998) 187-198
林化新，范淑华, 提高半导体气敏元件性能稳定性和可靠性的新途径,化学传感器.1993,13(2),14-19
严六明等，多晶TiO2氧敏特性及其机制的研究，华南理工大学学报,Vol.23 NO.4 1997.08 462-466
刘国华,杜忻锐, 半导体气敏传感器的原理及应用, 煤炭技术, Vol.20,No.9,2001.9
R.K. Sharma, M.C. BhatnagarrSensors and Actuators B 56 1999 215–219
M.C. Carotta et al. ,Sensors and Actuators B 58 (1999) 310-317
I. Hayakawa et al.rSensors and Actuators B 62 2000 55-60
N. Bonini et al.rSensors and Actuators B,68 2000 274-280
A. Ruiz et al.rMaterials Science and Engineering C, 19 2002 105-109
Y．Li et al., Sensors and Actuators B 83(2002) 160-163
阮圣平，纳米晶氧化物的合成及其介电性能的研究，吉林大学博士学位论文，2001.10 16-17
Amrendra Vijay and Grey Mills,Horia, J.Chem.Phys.2003.4.8,Vol.118,NO.14, 6536-6551
R.K.Sharma et al. Sensors and Actuators B 46 (1998) 194-201
R.K.Sharma et al. Sensors and Actuators B 45 (1997) 209-215
H.E.Chao et al. Journal of the European Ceramic
Society,23(2003) 1457-1464
L.M.Arabatzis et al. Applied Catalysis B: Environmental,42(2003) 187-201
K.Luo,T.P.St.Clair,X.Lai, and D.W.Goodman, J.Phy.Chem.B, Vol.104,NO.14,2000 3050-3057
Journal of Catalysis 168 (1997) 117-120
贺永宁,武宇红,PdCl2对TiO2氧传感器响应特性的影响，郑州轻工业学院学报，Vol.15 NO.4,12(2000) 29-33
L. Gao et al. Sensors and Actuators B, 71 (2000) 179-183
张梅，魏志锋等，稀有金属,Vol.25 NO.1(2001)
M.Ferroni et al.,Sensors and Actuators B,77(2001) 163-166
Y. Yamada et al.,Sensors and Actuators B, 66 2000 164–166
E.Comini et al.,Sensors and Actuators B,77(2001) 16-21
Y. Sun et al.,Materials Science and Engineering B 86 (2001) 185–188
X. Liu et al.,Materials Science and Engineering A,289 (2000) 241-245
L. Gao et al.,Sensors and Actuators B 71 (2000) 179-183
G.Montesperell et al.,Sensors and Actuators B,24-25(1995) 705-709
Y. Wang et al.,Journal of Non-Crystalline Solids, 319 (2003) 109-116
Y. Zhang et al., Materials Letters 54 (2002) 375–381
M.Z. Atashbar et al.，Thin Solid Films 326 (1998) 238–244
华中一，第一届全国纳米科学与技术会议论文集，抚顺：中国真空学会，1992
A.Kawabata, R.Kubo, J.Phys.Soc.Jpn.,1966, 21:1765
张立德，牟季美, 《纳米材料学》 1994.10
张志锟，崔作林, 《纳米技术与纳米材料》2000.10
许振嘉 ,《近代半导体材料的表面科学基础》 2002.3
Ulrije Diebold. Suface Science Reports 48(2003) 53-229 143
潘海波等,功能材料与器件学,Vol.7,NO.1,2001.3,101-106
周伟 孙成文 杨芝洲 《无机材料学报》 Vol.13,No.3 (1998.6) 275-281
Ti2/V2O5双层薄膜的TMA气敏特性研究《传感器技术》2000 Vol.19 No.4 5-10
冷藏期间淡水鱼新鲜度变化的研究 《华南农业大学学报》18(3) 1997:100-104
掺铝氧化锌厚膜制备及其对三四胺和海产品鲜度的敏感性《海洋与湖沼》1997.9 Vol 28 No.5 549-552
Nb2O5对TiO2响应TMA气敏特性的改善 《传感技术学报》2000.3 No.1 50-52
张忠孝，耿曼利，李厚福,Ru/TiO2型三甲胺（TMA）传感元件的研制。传感器技术，1996，（2）：27
张忠孝，隋艳，顾沛然。Ru/TiO2三甲胺传感元件与化学分析法测定鱼鲜度。传感器技术，1999，第18卷（2）：28
T.Harbold, R.Bohn, et al., Mater. Sci. &Enger. A 153(1-2)(1992)679
P.Matterazzi, D.Basset, et al., Nanostructured Materials, 2(1993)217
仇海波、高濂等， 无机材料学报，9（3）（1994）365
苏勉曾，固体化学导论，北京大学出版社，（1986）
Xi.Li, Synthesis of Perovokite Type Composite Oxide of Nanocrystalline Materials, Changchun, Jilin University Press, 1992,33-38Ulrije Diebold. Suface Science Reports 48(2003) 53-229 143
Jin-Ming Wu..Satoshi Hayakawa. et al,Crystal Growth &Design Vol.2,NO.2 2002
范雄 X射线金属学，机械工业出版社， 1980
索辉，吴凤清等。柠檬酸盐法合成的纳米晶La0.7Sr0.3FeO3材料酒敏特性研究。功能材料，1998，29（3）
富菊霞。TiO2及其掺杂金属离子的纳米晶材料的制备和光催化性能的研究。吉林大学硕士学位论文，2001年5月
索辉。纳米晶气敏材料的合成、表征及纳米晶薄膜栅FET式新型气敏元件的研制。吉林大学博士学位论文，1998年12月
F.A. Grant Rev.Mod.Phys. 31(1959)646.
G.V. samsonov,The Oxide Handbook,IFI/Plenum Press, New York,1982
M. Mabrook,P. Hawkins, Sensors and Actuators B 75(2001) 197-202
O.I. Bomk et al.Sensors and Actuators B 62 2000 131–135
R.M.Wallton et al.,Applied Surface Science 125(1998) 187-198
林化新，范淑华, 提高半导体气敏元件性能稳定性和可靠性的新途径,化学传感器.1993,13(2),14-19
严六明等，多晶TiO2氧敏特性及其机制的研究，华南理工大学学报,Vol.23 NO.4 1997.08 462-466
刘国华,杜忻锐, 半导体气敏传感器的原理及应用, 煤炭技术, Vol.20,No.9,2001.9
R.K. Sharma, M.C. BhatnagarrSensors and Actuators B 56 1999 215–219
M.C. Carotta et al. ,Sensors and Actuators B 58 (1999) 310-317
I. Hayakawa et al.rSensors and Actuators B 62 2000 55-60
N. Bonini et al.rSensors and Actuators B,68 2000 274-280
A. Ruiz et al.rMaterials Science and Engineering C, 19 2002 105-109
Y．Li et al., Sensors and Actuators B 83(2002) 160-163
阮圣平，纳米晶氧化物的合成及其介电性能的研究，吉林大学博士学位论文，2001.10 16-17
Amrendra Vijay and Grey Mills,Horia, J.Chem.Phys.2003.4.8,Vol.118,NO.14, 6536-6551
R.K.Sharma et al. Sensors and Actuators B 46 (1998) 194-201
R.K.Sharma et al. Sensors and Actuators B 45 (1997) 209-215
H.E.Chao et al. Journal of the European Ceramic
Society,23(2003) 1457-1464
L.M.Arabatzis et al. Applied Catalysis B: Environmental,42(2003) 187-201
K.Luo,T.P.St.Clair,X.Lai, and D.W.Goodman, J.Phy.Chem.B, Vol.104,NO.14,2000 3050-3057
Journal of Catalysis 168 (1997) 117-120
贺永宁,武宇红,PdCl2对TiO2氧传感器响应特性的影响，郑州轻工业学院学报，Vol.15 NO.4,12(2000) 29-33
L. Gao et al. Sensors and Actuators B, 71 (2000) 179-183
张梅，魏志锋等，稀有金属,Vol.25 NO.1(2001)
M.Ferroni et al.,Sensors and Actuators B,77(2001) 163-166
Y. Yamada et al.,Sensors and Actuators B, 66 2000 164–166
E.Comini et al.,Sensors and Actuators B,77(2001) 16-21
Y. Sun et al.,Materials Science and Engineering B 86 (2001) 185–188
X. Liu et al.,Materials Science and Engineering A,289 (2000) 241-245
L. Gao et al.,Sensors and Actuators B 71 (2000) 179-183
G.Montesperell et al.,Sensors and Actuators B,24-25(1995) 705-709
Y. Wang et al.,Journal of Non-Crystalline Solids, 319 (2003) 109-116
Y. Zhang et al., Materials Letters 54 (2002) 375–381
M.Z. Atashbar et al.，Thin Solid Films 326 (1998) 238–244