Anisotropic Etching of Crystalline Silicon in Alkaline Solutions II . Influence of Dopants

The etching behavior of highly boron doped silicon in aqueous solutions based of ethylenediamine, KOH, NaOH, and LiOH was studied. For all etchants, a strong reduction of the etch rate for boron concentrations exceeding approximately 2 �9 10 ~9 cm -3 was observed. This value is in good agreement with published data for the onset of degeneracy of p-type silicon. The reduction of the etch rate was found to be inversely proportional to the fourth power of the boron concentration. For a given high boron concentration, the etch stop effect was found to be most effective for ethylenediamine-based solutions and low concentration KOH and least effective for highly concentrated KOH. On the basis of these results, a model is proposed attributing the etch stop phenomenon to electrical effects of holes rather than chemical effects of boron. Due to the high dopant concentration the width of the space charge layer on the silicon surface shrinks drastically. Therefore, electrons injected into the conduction band by an oxidation reaction cannot be confined to the surface and rapidly recombine with holes from the valence band. The lack of these electrons impedes the reduction of water and thereby the formation of new hydroxide ions at the silicon surface. Since the transfer of four electrons is required for the dissolution of one silicon atom the observed fourth power law for the decrease of the etch rate can be explained. The reduction of the etch rate on silicon doped with germanium or phosphorus is much smaller and follows a different mechanism.