Enhancement and red shift of photoluminescence (PL) of fresh porous Si under prolonged laser irradiation or ageing: Role of surface vibration modes

We study the effect of a red shift and a considerable enhancement of photoluminescence (PL) intensity from a freshly etched porous Si (PS) thin film after prolonged laser irradiation or after aging in atmosphere. Both effects coincide with the appearance of Si–OH and Si–O–Si vibration modes in the Fourier transform infrared (FTIR) absorption spectra. The red shift is attributed to a pinning of the band gap of the light-emitting Si nanocrystals (NCs) due to the formation of Si–OH and Si–O–Si bonds. Using theoretical calculations, we estimated the electron and hole energy shifts caused by the interaction of the electronic states of the Si NCs with the surface vibrations, and correlated the observed PL enhancement with resonant coupling between the quantized valence sub-levels in the Si NCs and surface vibration modes.