基于MEMS技术的氧气微传感器机理研究与设计
摘要
氧气传感器是气体传感器的主要分支之一。氧气传感器已广泛地应用于冶金、食品保鲜、医疗、生物、环保等领域。长期以来，各种氧气传感器的研究异常活跃。传统的氧检测方法能精确地分析氧的浓度，但其成本高、装置复杂、耗时长、使用和维修麻烦，不能满足实时监控或原位、在线测量的要求。大多数的光学氧气传感器灵敏度较低、稳定性较差。有些氧气传感器需要工作在高温下(500℃～600℃以上)，要实现室温测量较为困难。气体传感器的敏感性能一般与工作温度密切相关，MEMS技术很容易将气敏元件和加热元件、温度探测元件制作在一起，保证了气体传感器的优良性能。MEMS(Micro Electro-Mechanical System)技术的发展对于半导体气体传感器的微型化、集成化、智能化、多功能化，以及提高其选择性、可靠性和稳定性都有重要的意义。目前基于MEMS技术的氧气微传感器在IEEE的各种刊物上已有一些相关的报道。本文的主要研究工作如下：
1．以配位化合物的晶格结构理论为基础，对于二氧化锆立方固溶体结构进行分析，得出在二氧化锆中掺杂氧化钇，即钇稳定立方相二氧化锆(YSZ)，其具有一定的氧离子空位，从而具有离子导电性，并讨论了氧化钇掺杂浓度对YSZ电导率的影响。
2．以溶胶-凝胶(Sol-gel)理论为基础，制备钇稳定立方相二氧化锆(YSZ)溶胶-凝胶膜，并对不同的药品配比进行测试与比较。
3．提出平板电容式氧气传感器的初始模型，并对其工作机理进行探讨。实验结果表明，该敏感膜具有较好的气体选择性和测量重复性。
4．从传感器微型化方面考虑，结合MEMS技术和半导体工艺。设计MOS电容式氧气微传感器，并从半导体能带的角度出发，阐明其工作原理。
5．以MOS电容式氧气微传感器的分析为基础，设计MOSFET氧气微传感器结构，在器件中集成了加热元件和测温元件。并设计了MOSFET氧气微传感器、加热元件及测温元件的具体工艺流程和模版。仿真实验结果表明MOSFET氧气微传感器不仅具有一般MOSFET的典型特性曲线，并且单位面积电容值(2.0×10~(-7)pF/μm~2)的微小变化能转换为较明显的电压信号(ΔV_(T max)=8mV)。MOSFET氧气微传感器结构为今后进行MOSFET氧气微传感器设计提供一定的参考价值。
Oxygen sensor is a primary branch of gas sensor. Oxygen sensor has widely applied to a lot of fields,such as metallurgy,keeping-fresh of food,medical treatment,biology,environmental protection and so on. For a long period of time,the study of oxygen sensor has been very active. The methods of traditional oxygen detection can accurately analyze the concentration of oxygen,but those factors such as high cost,complicated device,long time consumption and inconvenient operation and maintenance have restricted the application of real-time monitor and control and online measure. Most optical oxygen sensors can not solve the problems of low sensitivity and poor stability. Some oxygen sensors require working at high temperature (higher than 500C-600C) . It is difficult for them to work at room temperature. In a general way,the sensitive performance of gas sensor is closely relative to the working temperature. It is very easy for MEMS to integrate the gas sensitive element,the heater and temperature sensor together. T
he development of MEMS provides the possibility of micromation,integration,intelligentization,multi-function of semiconductor gas sensor. And it also has very important significance to improve selectivity,reliability and stability of semiconductor gas sensor. Nowadays,there are some reports on oxygen micro-sensor based on MEMS in the references of IEEE. The following is the primary research work in this thesis.
1. Based on the crystal lattice theory of coordinate chemical compound,the crystal lattice of zirconia was analyzed. Some results were obtained that adulterating zirconia with yttria,viz. Yttria-Stabilized Zirconia (YSZ),has some oxygen ion vacancies,sequentially has ionic conductivity. And the influence on YSZ ion conductivity of the different adulterated concentration of yttria was discussed.
2. Based on the theory of Sol-gel,YSZ sol-gel membrane was made. And YSZ sol-gel membranes with the different zirconia concentration were tested.
3. The initial model of flat capacitive oxygen sensor was proposed. Then the working mechanism of flat capacitive oxygen sensor was discussed. The experimental results show that the sensitive membrane is characterized by favorable selectivity and repetition.
4. In view of micromation of sensor and MEMS fabrication processing,MOS capacitive oxygen micro-sensor was devised. According to theory of semiconductor energy band,the working principle of MOS capacitive oxygen micro-sensor was elucidated.
5. Based on MOS capacitive oxygen micro-sensor,the structure of MOSFET oxygen micro-sensor was presented. The heater and temperature sensor are integrated into the device. Then the specific technological process and the masks of MOSFET oxygen micro-sensor,the heater and the temperature sensor were designed. Simulating curves indicate that MOSFET oxygen micro-sensor has the typical characteristic curves alike general MOSFETs. The minute
variety of unit area capacitance (2.0x10-7 pF/um2) can be transformed into relatively obvious
voltage signal (VTmax = 8/mV). The structure of MOSFET oxygen micro-sensor provides reference for the design of MOSFET oxygen micro-sensor for the future.
1．以配位化合物的晶格结构理论为基础，对于二氧化锆立方固溶体结构进行分析，得出在二氧化锆中掺杂氧化钇，即钇稳定立方相二氧化锆(YSZ)，其具有一定的氧离子空位，从而具有离子导电性，并讨论了氧化钇掺杂浓度对YSZ电导率的影响。
2．以溶胶-凝胶(Sol-gel)理论为基础，制备钇稳定立方相二氧化锆(YSZ)溶胶-凝胶膜，并对不同的药品配比进行测试与比较。
3．提出平板电容式氧气传感器的初始模型，并对其工作机理进行探讨。实验结果表明，该敏感膜具有较好的气体选择性和测量重复性。
4．从传感器微型化方面考虑，结合MEMS技术和半导体工艺。设计MOS电容式氧气微传感器，并从半导体能带的角度出发，阐明其工作原理。
5．以MOS电容式氧气微传感器的分析为基础，设计MOSFET氧气微传感器结构，在器件中集成了加热元件和测温元件。并设计了MOSFET氧气微传感器、加热元件及测温元件的具体工艺流程和模版。仿真实验结果表明MOSFET氧气微传感器不仅具有一般MOSFET的典型特性曲线，并且单位面积电容值(2.0×10~(-7)pF/μm~2)的微小变化能转换为较明显的电压信号(ΔV_(T max)=8mV)。MOSFET氧气微传感器结构为今后进行MOSFET氧气微传感器设计提供一定的参考价值。
Oxygen sensor is a primary branch of gas sensor. Oxygen sensor has widely applied to a lot of fields,such as metallurgy,keeping-fresh of food,medical treatment,biology,environmental protection and so on. For a long period of time,the study of oxygen sensor has been very active. The methods of traditional oxygen detection can accurately analyze the concentration of oxygen,but those factors such as high cost,complicated device,long time consumption and inconvenient operation and maintenance have restricted the application of real-time monitor and control and online measure. Most optical oxygen sensors can not solve the problems of low sensitivity and poor stability. Some oxygen sensors require working at high temperature (higher than 500C-600C) . It is difficult for them to work at room temperature. In a general way,the sensitive performance of gas sensor is closely relative to the working temperature. It is very easy for MEMS to integrate the gas sensitive element,the heater and temperature sensor together. T
he development of MEMS provides the possibility of micromation,integration,intelligentization,multi-function of semiconductor gas sensor. And it also has very important significance to improve selectivity,reliability and stability of semiconductor gas sensor. Nowadays,there are some reports on oxygen micro-sensor based on MEMS in the references of IEEE. The following is the primary research work in this thesis.
1. Based on the crystal lattice theory of coordinate chemical compound,the crystal lattice of zirconia was analyzed. Some results were obtained that adulterating zirconia with yttria,viz. Yttria-Stabilized Zirconia (YSZ),has some oxygen ion vacancies,sequentially has ionic conductivity. And the influence on YSZ ion conductivity of the different adulterated concentration of yttria was discussed.
2. Based on the theory of Sol-gel,YSZ sol-gel membrane was made. And YSZ sol-gel membranes with the different zirconia concentration were tested.
3. The initial model of flat capacitive oxygen sensor was proposed. Then the working mechanism of flat capacitive oxygen sensor was discussed. The experimental results show that the sensitive membrane is characterized by favorable selectivity and repetition.
4. In view of micromation of sensor and MEMS fabrication processing,MOS capacitive oxygen micro-sensor was devised. According to theory of semiconductor energy band,the working principle of MOS capacitive oxygen micro-sensor was elucidated.
5. Based on MOS capacitive oxygen micro-sensor,the structure of MOSFET oxygen micro-sensor was presented. The heater and temperature sensor are integrated into the device. Then the specific technological process and the masks of MOSFET oxygen micro-sensor,the heater and the temperature sensor were designed. Simulating curves indicate that MOSFET oxygen micro-sensor has the typical characteristic curves alike general MOSFETs. The minute
variety of unit area capacitance (2.0x10-7 pF/um2) can be transformed into relatively obvious
voltage signal (VTmax = 8/mV). The structure of MOSFET oxygen micro-sensor provides reference for the design of MOSFET oxygen micro-sensor for the future.
引文
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