Crystalline silicon anodic dissolution

The formation of etch pits and tunnels on n-Si during anodization in HF solutions was reported in the early 1970 s. It was found that the solid surface layer is the remaining substrate silicon left after anodic dissolution. The large current observed on n-Si at an anodic potential was postulated to be due to barrier breakdown.5,6 By early 80 s7"11 it was established that the brown films formed by anodization on silicon substrate of all types are a porous material with the same single crystalline structure as the substrate. 

The mechanism of electrochemical etching to produce porous silicon has been studied by a number of researchers [11-13]. Although it is certain that several different reactions are occurring simultaneously, anodic etching of crystalline silicon ultimately leads to oxidation and dissolution of the surface to silicon hexafluoride (Scheme 16.1). Under these conditions, Si-Si bonds are electrochemically activated and react with fluoride ions to form soluble, molecular perfluoro species solvation of these silicon fluorides by the etching medium yields a physically irregular, high area porous silicon matrix. Visual indicators for the anodization are the appearance... 

In the positive branch of the i/V graph, anodic dissolution process will remove material from silicon crystals. The conditions for optimal etching of silicon have been extensively explored for micromachining or surface polishing in the fabrication of electronic devices. Most generally, the etch rate of silicon in HF solutions is isotropic among the various crystalline orientations. The etch rate of silicon at room temperature at the open-circuit potential (OCP) is very low, on the order of 10 nm s , which is equivalent to 100 nA cm in aqueous HF solutions. 

A New Model. The results of the studies on anodic oxide films (see section 5.9 and chapter 3 on passive film and anodic oxides) show that anodic oxide properties (oxidation state, degree of hydration, 0/Si ratio, degree of crystallinity, electronic and ionic conductivities, and etch rate) are a function of the formation field (the applied potential). Also, they vary from the surface to the oxide/silicon interface, which means that they change with time as the layer of oxide near the oxide/silicon interface moves to the surface during the formation and dissolution process. The oxide near the silicon/oxide interface is more disordered in composition and structure than that in the bulk of the oxide film. Also, the degree of disorder depends on the formation field which is a function of thickness and potential. The range of disorder in the oxide stmcture is thus responsible for the variation in the etch rate of the oxide formed at different times during a period of the oscillation. The etch rate of silicon oxides is very sensitive to the stmcture and composition (see Chapter 4). 

---