The influence of a single thiol group on the electronic and optical properties of the smallest diamondoid adamantane

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 ∼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.