The Band Gap in Silicon Nanocrystallites

The gap in semiconductor nanocrystallites has been extensively studied both theoretically and experimentally over the last two decades. We have compared a recent 'state-of-the-art' theoretical calculation with a recent 'state-of-the-art' experimental observation of the gap in Si nanocrystallite. We find that the two are in substantial disagreement, with the disagreement being more pronounced at smaller sizes. Theoretical calculations appear to overestimate the gap. To reconcile the two we present two scenarios. (i) Recognizing that the experimental observations are for a distribution of crystallite sizes, we proffer a phenomenological model to reconcile the theory with the experiment. We suggest that similar considerations must dictate comparisons between the theory and experiment vis-?-vis other properties such as radiative rate, decay constant, and absorption coefficient. (ii) Either surface passivation or surface orientation may also resolve the conflict between the theory and the experiment. We have carried out tight-binding calculations on silicon clusters to study the role of surface passivation and surface orientation.