Suzuki Taku T, Ohgaki Takeshi, Adachi Yutaka, Sakaguchi Isao, Nakamura Minoru, Ohashi Hideyuki, Aimi Akihisa, Fujimoto Kenjiro
National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
Department of Pure and Applied Chemistry, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan.
ACS Omega. 2020 Aug 11;5(33):21104-21112. doi: 10.1021/acsomega.0c02750. eCollection 2020 Aug 25.
Metal oxide semiconductor gas sensors have been widely studied for the selective detection of various gases with trace concentrations. The identification of the reaction scheme governing the gas sensing response is crucial for further development; however, the mechanism of ethanol (EtOH) gas sensing by ZnO is still controversial despite being one of the most intensively studied target gas and sensing material combinations. In this work, for the first time, the detailed mechanism of EtOH sensing by ZnO is studied by using a bulk single-crystalline substrate, which has a well-defined stoichiometry and atomic arrangement, as the sensing material. The sensing response is substantial on the ZnO substrate even with a millimeter-size thickness, and it becomes larger with resistance of the substrate. The large sensing response is described in terms of the adsorption/desorption of the oxygen species on the substrate surface, namely, oxygen ionosorption. The valence state of the ionosorbed oxygen involved in EtOH sensing is identified to be O regardless of the temperature. The increase in the sensing response with the temperature is attributed to the enhanced oxidation rate of the EtOH molecule on the surface as analyzed by pulsed-jet temperature-programmed desorption mass spectrometry, which has been newly developed for analyzing surface reactions in simulated working conditions.
金属氧化物半导体气体传感器已被广泛研究用于选择性检测各种痕量浓度的气体。确定控制气敏响应的反应机制对于进一步发展至关重要;然而,尽管乙醇(EtOH)气体与氧化锌(ZnO)的组合是研究最深入的目标气体和传感材料组合之一,但ZnO对EtOH的气敏机制仍存在争议。在这项工作中,首次使用具有明确化学计量和原子排列的块状单晶衬底作为传感材料,研究了ZnO对EtOH的气敏详细机制。即使衬底厚度为毫米级,在ZnO衬底上的气敏响应也很显著,并且随着衬底电阻的增加而增大。这种大的气敏响应是根据衬底表面氧物种的吸附/解吸来描述的,即氧离子吸附。参与EtOH气敏的离子吸附氧的价态被确定为O,与温度无关。通过脉冲喷射程序升温脱附质谱法分析,气敏响应随温度的增加归因于表面EtOH分子氧化速率的提高,该方法是为分析模拟工作条件下的表面反应而新开发的。