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Mesurement of Passive Film Growth and Breakdown, and Excitation of Local Phenomena on Electrode By Using Electrochemical AFM・STM

使用电化学AFM·STM测量钝化膜的生长、破坏以及电极局部现象的激发

基本信息

批准号：
07650984
负责人：
AZUMI Kazuhisa
金额：
$ 1.41万
依托单位：
HOKKAIDO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

In this research in-situ electrochemical AFM/STM technique was applied to passivated metal surface to obtain valuable information for analysis of electrode process such as passive film formation and growth, and breakdown. Micro-modification and excitation of local electrochemical process on electrodes were also aimed. (1) In-situ electrochemical AFM was applied to Ti film electrode sputtered onto quartz glass, Ti plate electrode, and Al electrode to observe growth and breakdown processes of the passive film under polarization condition. For Ti film proceeding of micro-crystallization due to very high electric field during film growth was found, resulting in surface roughening of the oxide surface, known as breakdown of the passive film. (2) Electrochemical tunneling spectroscopy technique was applied to the passive films formed on Fe and Ti to investigate their electronic properties. Tunneling barrier shape as a function of potential scanning in the electrochemical system, and effect of tip electrode on polarization condition through the space charge layr in the semiconductive electrode were evaluated. (3) Morphological change of corbon steel surface during active dissolution was observed by AFM.Results were compared with images obtained by SEM and conforcal laser microscopy. Corroding process was discussed concerning with the pearlite structure in the carbon steel. (4) AFM tip was used to achieve micro-modification of Al surface after anodic oxide film growth. After modification, however, tip was mechanically damaged resulting in degradation of AFM image observed. For such purpose development of more sophisticated technique for modification is required.

在这项研究中，原位电化学AFM/STM技术被应用到钝化金属表面，以获得有价值的信息，分析电极过程，如钝化膜的形成和生长，以及击穿。对电极进行微修饰，激发局部电化学过程。(1)利用原位电化学原子力显微镜（AFM）对溅射在石英玻璃上的钛膜电极、钛板电极和铝电极进行了电化学原位观察，研究了极化条件下钝化膜的生长和击穿过程。对于Ti膜的微晶化过程中，由于非常高的电场在膜生长过程中被发现，导致表面粗糙的氧化物表面，被称为击穿的钝化膜。(2)利用电化学隧道谱技术研究了Fe和Ti表面钝化膜的电子性质。研究了在电化学体系中，钨极势垒形状随电位扫描的变化规律，以及尖端电极通过钨极电极中的空间电荷层对极化状态的影响。(3)用原子力显微镜观察了碳钢表面在活性溶解过程中的形貌变化，并与扫描电镜和激光共聚焦显微镜的观察结果进行了比较。讨论了碳钢中珠光体组织对腐蚀过程的影响。(4)利用原子力显微镜针尖对阳极氧化膜生长后的铝表面进行微修饰。然而，修改后，针尖被机械损坏，导致观察到的AFM图像的退化。为此目的，需要开发更先进的改性技术。