We report on the structural and optical properties of porous silicon nanowires (PSiNWs) fabricated using silver (Ag) ions assisted electroless etching method. Silicon nanocrystallites with sizes <5 nm embedded in amorphous silica have been observed from PSiNW samples etched using the optimum hydrofluoric acid (HF) concentration. The strongest photoluminescence (PL) signal has been measured from samples etched with 4.8 M of HF, beyond which a significant decreasing in PL emission intensity has been observed. A qualitative model is proposed for the formation of PSiNWs in the presence of Ag catalyst. This model affirms our observations in PL enhancement for samples etched using HF < 4.8 M and the eventual PL reduction for samples etched beyond 4.8 M of HF concentration. The enhancement in PL signals has been associated to the formation of PSiNWs and the quantum confinement effect in the Si nanocrystallites. Compared to PSiNWs without Si-O-x,, the HF treated samples exhibited significant blue PL peak shift of 100 nm. This effect has been correlated to the formation of defect states in the surface oxide. PSiNWs fabricated using the electroless etching method can find useful applications in optical sensors and as anti-reflection layer in silicon-based solar cells. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4740051]
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