Steady-state pore growth

The steady-state potential (or current density) is related to a steady growth of the porous oxide into the solution, maintaining a constant number of pores and a constant pore radius. This scheme is supported by electron microscopic observations reported by Xu et a/.102... 

The capacitance determined from the initial slopes of the charging curve is about 10/a F/cm2. Taking the dielectric permittivity as 9.0, one could calculate that initially (at the OCP) an oxide layer of the barrier type existed, which was about 0.6 nm thick. A Tafelian dependence of the extrapolated initial potential on current density, with slopes of the order of 700-1000 mV/decade, indicates transport control in the oxide film. The subsequent rise of potential resembles that of barrier-layer formation. Indeed, the inverse field, calculated as the ratio between the change of oxide film thickness (calculated from Faraday s law) and the change of potential, was found to be about 1.3 nm/V, which is in the usual range. The maximum and the subsequent decay to a steady state resemble the behavior associated with pore nucleation and growth. Hence, one could conclude that the same inhomogeneity which leads to pore formation results in the localized attack in halide solutions. 

In contrast to the micro- and mesoporous regimes, for which only a few empirical laws for the growth rate and porosity are available, the detailed pore geometry for macropore arrays in n-type silicon can be pre-calculated by a set of equations. This is possible because every pore tip is in a steady-state condition characterized by = JPS [Le9]. This condition enables us to draw conclusions about the porosi-... 

The steady-state condition (/ap=Jps) at the pore tip determines not only the pore diameter but also the pore growth rate. The rate rp of macropore growth can be calculated if the local current density at the pore tip is divided by the dissolution valence nv (number of charge carriers per dissolved silicon atom), the elementary charge e (1.602 xlO-19 C) and the atomic density of silicon Nsi (5xl022 cm-3) ... 

It follows from Equation (7.13) that the lateral growth of an individual pore through the vacancy mechanism ceases when the pore radius reaches a specific steady-state value in a time t. Figure 7.9 depicts the... 

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