Surfactant-Induced Modulation of Light Emission in Porous Silicon Produced by Metal-Assisted Electroless Etching

Photoluminescent porous silicon (PSi) was produced by Pt-assisted electroless chemical etching of p^--Si in a 1:1:2 (v/v/v) solution of HF, methanol, and H₂O₂. Upon irradiation with ultraviolet light PSi produced under these conditions luminesces with a peak emission near 590 nm that is sufficiently intense to be visible by eye. Because PSi light emission is an attractive modality for chemical sensing, the effect of charged surfactant adsorbates on the photoluminescence (PL) intensity was investigated. PSi was exposed to aqueous solutions of cationic, cetyltrimethylammonium bromide (CTAB), and anionic, sodium dodecyl sulfate (SDS), surfactants as a function of solution concentration and pH. Adsorption produces both chemical and physical changes at the PSi−solution interface, which were followed by a combination of PL and infrared absorption spectroscopy. Luminescence is quenched in the presence of CTAB and enhanced in the presence of SDS, both in a pH-dependent manner, the behavior being explained by a depletion layer model. PSi crystallites generated from p-Si exhibit a hole-depletion layer at the Si−solution interface, and the depletion layer expands in the presence of cationic surfactant and contracts in the presence of anionic surfactant. Because the surface depletion region is nonemissive (dead layer), surfactant adsorbate-induced modulation of the depletion layer width determines the luminescence intensity of PSi. At very basic pH, PL quenching was observed independent of surfactant identity or concentration, an observation likely tied to the dissolution of the PSi nanocrystallites in strong base.