光波导元件检测酸性及挥发性有机气体的研究
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摘要
空气是人类赖以生存的基本要素之一。随着国民经济的快速发展,各类污染源的产生量越来越大,其中酸性有毒气体和挥发性有机化合物对人类生存空间的污染更为突出。因此有效检测污染和防止灾害,研究安全、可靠、能够连续、快速,现场检测痕量气体的有效方法或新型传感器具有十分重要的意义。光波导传感器具有灵敏度高、响应快、易微型化、可连续在线监测、抗电磁干扰、电绝缘性好、成本低等诸多特点,在环境监测、工业过程控制、生化检测和国土安全等领域有着广泛应用前景。本论文以SnO2、Fe2O3- SnO2、碱性品红、SnCl2.2H2O-碱性品红分别作为敏感试剂并固定在锡掺杂玻璃光波导表面,研制出检测二甲苯、SO2、氯苯、甲醛、甲苯等酸性及挥发性有机物气体的高灵敏光波导化学传感器。
文章前沿部分,介绍了大气污染和室内空气污染的来源、种类及给人类带来的危害、传感器技术及其应用、化学传感器及其分类。对光波导化学传感器的发展进行评述,并着重介绍了光波导传感器的特点和分类。最后提出了本论文的研究目标和内容。本论文围绕光波导传感技术作了以下几个方面的研究工作：
1.(在第三章中)SnO2是目前使用较广泛的一种金属氧化物半导体气敏材料,它具有灵敏度较高、物理和化学稳定性好、成本低等优点。本章中筛选SnO2作为敏感试剂,并将其固定在锡掺杂玻璃光波导表面研制了SnO2薄膜光波导传感元件,同时研究了该传感元件对二甲苯蒸气的气敏性。研究结果表明,该敏感元件对体积分数2.5×10-7(0.25ppm)的二甲苯蒸气有良好的响应,其它气体对检测二甲苯的干扰较少。
2.(在第四章中)第三章的基础上对SnO2敏感膜进行了改性：由于Fe2O3掺杂量不同时Fe2O3-SnO2复合薄膜对气体的选择性和灵敏度也不同。本章中筛选了三种掺杂量分别为5%、0.8%、0.3%的FezO3-SnO2作为敏感试剂,并将固定在锡掺杂玻璃光波导表面研制了Fe203-Sn02复合薄膜／锡掺杂玻璃光波导传感元件,并且分别对SO2、甲醛、氯苯进行检测。实验结果表明该传感元件对SO2、甲醛、氯苯有一定的选择性,响应最低浓度分别为1×10-6、1×10-7、2×10-6(1ppm、0.1ppm、2ppm)(体积分数)
3.(在第五章)碱性品红是一中碱性染料,在氧化态时显红色,还原态时变为浅黄色,在强酸性介质中品红分子容易还原变为浅黄色。从这一点出发,碱性品红作为敏感试剂,研制了碱性品红薄膜／锡掺杂玻璃光波导传感元件。同时研究了该传感元件对S02等酸性气体的气敏性,并且敏感机理进行探讨。研究结果表明,该传感元件对S02气体有良好的响应,能够检测到体积分数5×10-7(0.5ppm)的S02气体。
4.(在第六章)研制出了SnCl2.2H2O-碱性品红薄膜／锡掺杂玻璃光波导气体传感元件,并对挥发性有机物气体进行检测。结果显示该元件对甲苯气体有较好的选择性响应,响应最低浓度5×10-5(50ppm)(体积分数)。
本论文所研制的传感元件灵敏度高、响应快、再现性高、容易制备等优点,且具有较好的使用价值。
Air is one of the main factors on which human existence depend on. The amount of pollutants are becoming more along with the development of national economy, acidic gases and vapor of volatile organic compounds (VOCs) are the main cause that accrue pollution in human living area.Therefore to effectively detect and prevent disasters, it is important to study new sensors which are safe, reliable, continuous, rapid, and in-stiu detection of remnant gases. The optical waveguide (OWG) sensor has many characters such as:high sensitivity, rapid response, easy micromation, easy realization for on-line continuous monitoring, anti-disturbance of electromagnetism, good insulation, low cost etc, therefore it has extensive application foreground in the area of environmental monitoring, industrial process control, biochemical detection and homeland security. In this dissertation, high sensitive OWG chemical sensors for detection of hazardous gases such as xylene,SO2,chlorobenzene, formaldehyde and toluene have been developed by immobilizing SnO2、Fe2O3-SnO2,fuchsin basic and SnCl2.2H2O-fuchsin basic onto the surface of tin-diffused glass optical waveguide.
The article began by describing the source of atmospheric pollution and indoor air pollution, species and the direct hazard to human health. The sensor technology and its applications, chemical sensors and its classification were introduced.The developments of OWG sensors were reviewed and the characters and classification of OWG sensors were mainly introduced. At last the purpose and the main content of the dissertation are put forward. In this dissertation some research work were done on planar OWG sensor system described below:
1.(In chapter three)SnO2 is one of the semi-conducting metal oxides sensitive element which widly used and it has a high sensitivity, physical and chemical stability and low cost. In this chapter the SnO2 selected as sensitive material, the highly sensitive element of this sensor was made by coating the SnO2 film over a tin-diffused glass OWG. We used the optical waveguide (OWG) sensor to detect xylene gas as a typical example VOCs gases. The sensor exhibits a linear response to xylene in the range of 2.5×10-7 (0.25 ppm) to 1×10-3 (1000ppm) volume fraction with response time less than 5 s and other gases for this sensor have less obstruction.
2.(In chapter four),becouse of the difference of the adulterate measurements lead to Fe2O3-SnO2 composite film have the different selectivity and sensitivity for the gases. In this chapter the Fe2O3-SnO2 selected as sensitive material and adulterate measurements 5%、0.8%、0.3%,respectively. The highly sensitive element of this sensor was made by coating the Fe2O3-SnO2 composite film over a tin diffused glass OWG. We used the Fe2O3-SnO2 composite film/tin diffused glass OWG sensor to detect SO2, formaldehyde and chlorobenzene, and the sensor has the good selectivity, and respond to the volume fraction are 1×10-6, 1×10-7,2×10-6 (1ppm, 0.1ppm, 2ppm),respectively.
3.Fuchsin basic is one of the alkalescence dye.When the oxidize attitude it shows red, and when the reductive attitude it shows pale yellow. When in the strong acid medium fuchsin molecule easy reduced and changed red into the pale yellow. We set off this point, fuchsin basic selected as sensitive material, and developed the fuchsin basic thin film/tin-diffused glass OWG. At the same time we start to study film/tin-diffused glass OWG for SO2 gas detection and investigate the sensitive principle.The research results shows that, the optical waveguide sonsor has the good sensitivity to SO2 gas, and it can be detect lower than 5×10-7(0.5ppm)volume fraction the SO2 gas.
4. In this chapter we developt the SnCl2.2H2O-fuchsin basic film/tin-diffused glass OWG, and detect to the volatile organic compounds(VOCs).The results shows that,the sensor has a linear response to toluene concentration,and sensitivity up to 5×10-5(50ppm) volume fraction.
This OWG system proved to be fast in response, reversible, and highly sensitive good recurrence, for VOCs and SO2 gases, and Current results indicates parts-per-billion detection could be achieved by controlling the adsorption properties of the sensing layer, and the sensor has the useful value.
文章前沿部分,介绍了大气污染和室内空气污染的来源、种类及给人类带来的危害、传感器技术及其应用、化学传感器及其分类。对光波导化学传感器的发展进行评述,并着重介绍了光波导传感器的特点和分类。最后提出了本论文的研究目标和内容。本论文围绕光波导传感技术作了以下几个方面的研究工作：
1.(在第三章中)SnO2是目前使用较广泛的一种金属氧化物半导体气敏材料,它具有灵敏度较高、物理和化学稳定性好、成本低等优点。本章中筛选SnO2作为敏感试剂,并将其固定在锡掺杂玻璃光波导表面研制了SnO2薄膜光波导传感元件,同时研究了该传感元件对二甲苯蒸气的气敏性。研究结果表明,该敏感元件对体积分数2.5×10-7(0.25ppm)的二甲苯蒸气有良好的响应,其它气体对检测二甲苯的干扰较少。
2.(在第四章中)第三章的基础上对SnO2敏感膜进行了改性：由于Fe2O3掺杂量不同时Fe2O3-SnO2复合薄膜对气体的选择性和灵敏度也不同。本章中筛选了三种掺杂量分别为5%、0.8%、0.3%的FezO3-SnO2作为敏感试剂,并将固定在锡掺杂玻璃光波导表面研制了Fe203-Sn02复合薄膜／锡掺杂玻璃光波导传感元件,并且分别对SO2、甲醛、氯苯进行检测。实验结果表明该传感元件对SO2、甲醛、氯苯有一定的选择性,响应最低浓度分别为1×10-6、1×10-7、2×10-6(1ppm、0.1ppm、2ppm)(体积分数)
3.(在第五章)碱性品红是一中碱性染料,在氧化态时显红色,还原态时变为浅黄色,在强酸性介质中品红分子容易还原变为浅黄色。从这一点出发,碱性品红作为敏感试剂,研制了碱性品红薄膜／锡掺杂玻璃光波导传感元件。同时研究了该传感元件对S02等酸性气体的气敏性,并且敏感机理进行探讨。研究结果表明,该传感元件对S02气体有良好的响应,能够检测到体积分数5×10-7(0.5ppm)的S02气体。
4.(在第六章)研制出了SnCl2.2H2O-碱性品红薄膜／锡掺杂玻璃光波导气体传感元件,并对挥发性有机物气体进行检测。结果显示该元件对甲苯气体有较好的选择性响应,响应最低浓度5×10-5(50ppm)(体积分数)。
本论文所研制的传感元件灵敏度高、响应快、再现性高、容易制备等优点,且具有较好的使用价值。
Air is one of the main factors on which human existence depend on. The amount of pollutants are becoming more along with the development of national economy, acidic gases and vapor of volatile organic compounds (VOCs) are the main cause that accrue pollution in human living area.Therefore to effectively detect and prevent disasters, it is important to study new sensors which are safe, reliable, continuous, rapid, and in-stiu detection of remnant gases. The optical waveguide (OWG) sensor has many characters such as:high sensitivity, rapid response, easy micromation, easy realization for on-line continuous monitoring, anti-disturbance of electromagnetism, good insulation, low cost etc, therefore it has extensive application foreground in the area of environmental monitoring, industrial process control, biochemical detection and homeland security. In this dissertation, high sensitive OWG chemical sensors for detection of hazardous gases such as xylene,SO2,chlorobenzene, formaldehyde and toluene have been developed by immobilizing SnO2、Fe2O3-SnO2,fuchsin basic and SnCl2.2H2O-fuchsin basic onto the surface of tin-diffused glass optical waveguide.
The article began by describing the source of atmospheric pollution and indoor air pollution, species and the direct hazard to human health. The sensor technology and its applications, chemical sensors and its classification were introduced.The developments of OWG sensors were reviewed and the characters and classification of OWG sensors were mainly introduced. At last the purpose and the main content of the dissertation are put forward. In this dissertation some research work were done on planar OWG sensor system described below:
1.(In chapter three)SnO2 is one of the semi-conducting metal oxides sensitive element which widly used and it has a high sensitivity, physical and chemical stability and low cost. In this chapter the SnO2 selected as sensitive material, the highly sensitive element of this sensor was made by coating the SnO2 film over a tin-diffused glass OWG. We used the optical waveguide (OWG) sensor to detect xylene gas as a typical example VOCs gases. The sensor exhibits a linear response to xylene in the range of 2.5×10-7 (0.25 ppm) to 1×10-3 (1000ppm) volume fraction with response time less than 5 s and other gases for this sensor have less obstruction.
2.(In chapter four),becouse of the difference of the adulterate measurements lead to Fe2O3-SnO2 composite film have the different selectivity and sensitivity for the gases. In this chapter the Fe2O3-SnO2 selected as sensitive material and adulterate measurements 5%、0.8%、0.3%,respectively. The highly sensitive element of this sensor was made by coating the Fe2O3-SnO2 composite film over a tin diffused glass OWG. We used the Fe2O3-SnO2 composite film/tin diffused glass OWG sensor to detect SO2, formaldehyde and chlorobenzene, and the sensor has the good selectivity, and respond to the volume fraction are 1×10-6, 1×10-7,2×10-6 (1ppm, 0.1ppm, 2ppm),respectively.
3.Fuchsin basic is one of the alkalescence dye.When the oxidize attitude it shows red, and when the reductive attitude it shows pale yellow. When in the strong acid medium fuchsin molecule easy reduced and changed red into the pale yellow. We set off this point, fuchsin basic selected as sensitive material, and developed the fuchsin basic thin film/tin-diffused glass OWG. At the same time we start to study film/tin-diffused glass OWG for SO2 gas detection and investigate the sensitive principle.The research results shows that, the optical waveguide sonsor has the good sensitivity to SO2 gas, and it can be detect lower than 5×10-7(0.5ppm)volume fraction the SO2 gas.
4. In this chapter we developt the SnCl2.2H2O-fuchsin basic film/tin-diffused glass OWG, and detect to the volatile organic compounds(VOCs).The results shows that,the sensor has a linear response to toluene concentration,and sensitivity up to 5×10-5(50ppm) volume fraction.
This OWG system proved to be fast in response, reversible, and highly sensitive good recurrence, for VOCs and SO2 gases, and Current results indicates parts-per-billion detection could be achieved by controlling the adsorption properties of the sensing layer, and the sensor has the useful value.
引文
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