Abstract
At the nanoscale, the surface becomes pivotal for the properties of semiconductors due to an increased surface-to-bulk ratio. Surface functionalization is a means to include semiconductor nanocrystals into devices. In this comprehensive experimental study we determine in detail the effect of a single thiol functional group on the electronic and optical properties of the hydrogen-passivated nanodiamond adamantane. We find that the optical properties of the diamondoid are strongly affected due to a drastic change in the occupied states. Compared to adamantane, the optical gap in adamantane-1-thiol is lowered by approximately 0.6 eV and UV luminescence is quenched. The lowest unoccupied states remain delocalized at the cluster surface leaving the diamondoid's negative electron affinity intact.
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