Zhang Jie, Zhang Lin, Wang Wei, Han Lianhuan, Jia Jing-Chun, Tian Zhao-Wu, Tian Zhong-Qun, Zhan Dongping
State Key Laboratory of Physical Chemistry of Solid Surfaces (PCOSS) , Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM) , Department of Chemistry , College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 , China . Email:
Chem Sci. 2017 Mar 1;8(3):2407-2412. doi: 10.1039/c6sc04091h. Epub 2016 Dec 16.
Although metal assisted chemical etching (MacEtch) has emerged as a versatile micro-nanofabrication method for semiconductors, the chemical mechanism remains ambiguous in terms of both thermodynamics and kinetics. Here we demonstrate an innovative phenomenon, , the contact electrification between platinum (Pt) and an n-type gallium arsenide (100) wafer (n-GaAs) can induce interfacial redox reactions. Because of their different work functions, when the Pt electrode comes into contact with n-GaAs, electrons will move from n-GaAs to Pt and form a contact electric field at the Pt/n-GaAs junction until their electron Fermi levels () become equal. In the presence of an electrolyte, the potential of the Pt/electrolyte interface will shift due to the contact electricity and induce the spontaneous reduction of MnO anions on the Pt surface. Because the equilibrium of contact electrification is disturbed, electrons will transfer from n-GaAs to Pt through the tunneling effect. Thus, the accumulated positive holes at the n-GaAs/electrolyte interface make n-GaAs dissolve anodically along the Pt/n-GaAs/electrolyte 3-phase interface. Based on this principle, we developed a direct electrochemical nanoimprint lithography method applicable to crystalline semiconductors.
尽管金属辅助化学蚀刻(MacEtch)已成为一种用于半导体的通用微纳制造方法,但其化学机理在热力学和动力学方面仍不明确。在此,我们展示了一种创新现象,即铂(Pt)与n型砷化镓(100)晶片(n-GaAs)之间的接触起电可引发界面氧化还原反应。由于它们的功函数不同,当Pt电极与n-GaAs接触时,电子将从n-GaAs移动到Pt,并在Pt/n-GaAs结处形成接触电场,直至它们的电子费米能级()相等。在电解质存在的情况下,Pt/电解质界面处的电位会因接触起电而发生偏移,并促使Pt表面的MnO阴离子自发还原。由于接触起电的平衡受到干扰,电子将通过隧道效应从n-GaAs转移到Pt。因此,n-GaAs/电解质界面处积累的正空穴使n-GaAs沿Pt/n-GaAs/电解质三相界面发生阳极溶解。基于这一原理,我们开发了一种适用于晶体半导体的直接电化学纳米压印光刻方法。