Electroless deposition of metal particles on silicon (Si) followed by the metal-assisted etching (metal-assisted chemical etching) is a simple way to fabricate Si nanostructures. A composite porous structure consisting of straight macropores and a mesoporous layer can be created by platinum (Pt)-particle-assisted etching. In this work, we studied the composite structure formation on a highly-doped p-Si (ca. 5×1018 cm−3) in comparison with a moderately-doped p-Si (ca. 1×1015 cm−3). The composite structure drastically changed: the ratio of mesoporous layer thickness to macropore depth increased to 1.1 from 0.16 by using the highly-doped Si instead of the moderately-doped Si. The open-circuit potential of Si in the etching solution shifted to the positive direction by the Pt deposition. The potential shift of highly-doped Si was smaller than that of moderately-doped Si, which can be explained by the polarization characteristics. We calculated the band bending in Si by using a device simulator that reproduced the conditions of Pt-particle-assisted etching. The results indicated that, in the case of highly-doped Si, the consumption rate of positive holes at the Si surface away from the Pt particles increases due to the tunneling effect, which is consistent with the thick mesoporous layer formation.

Platinum (Pt) is one of the interesting catalysts in metal-assisted etching (metal-assisted chemical etching) of silicon (Si). The Pt-assisted etching induces not only the dissolution of Si under the Pt catalysts but also the formation of mesoporous layer on the Si surface away from them. In this work, we etched n-Si and p-Si by using patterned Pt films with a diameter of 5 μm and an interval of 50 μm. For both cases, the Si surface under the Pt catalysts was selectively etched and macropores with a diameter of 5 μm were formed. The macropores formed on n-Si were deeper than those formed on p-Si. The mesoporous layer was observed only around the macropores on n-Si, while it was observed over the entire surface of p-Si. We also measured the open circuit potential of Si in the etching solution. The positive shift of potential of n-Si by the Pt deposition was smaller than that of p-Si except for the initial stage of etching, which can be explained by the polarization characteristics. We discussed the etching behavior of n-Si and p-Si on the basis of the results of structure observation and electrochemical measurements.