Etching of Si in a variety of solutions is known to cause staining. These stain layers consist of porous material similar to that produced by anodic etching of Si in HF solutions. We have observed photoluminescence peaked in the red from stain-etched Si wafers of different dopant types, concentrations, and orientations produced in solutions of HF:HNO3:H2O. Luminescence is also observed in stain films produced in solutions of NaNO2 in HF, but not in stain films produced in solutions of CrO3 in HF. The luminescence spectra are similar to those reported recently for porous Si films produced by anodic etching in HF solutions. However, stain films are much easier to produce, requiring no special equipment.

Characterization of light-emitting porous Si films with x-ray photoelectron spectroscopy is reported. Only traces of O are detected on HF-etched samples, in contradiction to an earlier report that oxides are a significant component of porous Si. Si 2p and valence-band measurements demonstrate that the near-surface region of high porosity films which exhibit visible luminescence consists of amorphous Si.

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