On the origin of photoluminescence in silicon nanocrystals: Pressure-dependent structural and optical studies

A lack of consensus persists regarding the origin of photoluminescence in silicon nanocrystals. Here we report pressure-dependences of X-ray diffraction and photoluminescence from alkane-terminated colloidal particles. We determine the diamond-phase bulk modulus, observe multiple phase transitions, and importantly find a systematic photoluminescence red shift that matches the X _conduction-to-Λ _valence transition of bulk crystalline silicon. These results, reinforced by calculations, suggest that the efficient photoluminescence, frequently attributed to defects, arises instead from core-states that remain highly indirect despite quantum confinement.