Porous silicon structural evolution from in-situ luminescence and Raman measurements

The authors performed in-situ photoluminescence and Raman measurements on an anodized silicon surface in the HF/ethanol solution used for anodization. The porous silicon thereby produced, while resident in HF/ethanol, does not immediately exhibit intense photoluminescence. Intense photoluminescence develops spontaneously in HF/ethanol after 18--24 hours or with replacement of the HF/ethanol with water. These results support a quantum confinement mechanism in which exciton migration to traps and nonradiative recombination dominates the de-excitation pathways until silicon nanocrystallites are physically separated and energetically decoupled by hydrofluoric acid etching or surface oxidation. The porous silicon surface, as produced by anodization, shows large differences in photoluminescence intensity and peak wavelength over millimeter distances. Parallel Raman measurements implicate nanometer-size silicon particles in the photoluminescence mechanism