Enhanced radiative transition in SinGem nanoclusters

Using an ab initio molecular-dynamics scheme ~the ‘‘fireball’’ scheme!, we determined the equilibrium structure of intermediate-size SinGem (n1m571) nanoclusters with and without hydrogen passivation on the surface. Due to the strong surface distortion, defect states are found to permeate the energy gap of SinGem clusters. However, the defect states are removed by adding H atoms on the surface of SinGem clusters, and the gap opens up to a few eV, indicating a blueshift for photoluminescence. It is also found that the radiative transition between the highest occupied molecular orbital ~HOMO! and the lowest unoccupied molecular orbital ~LUMO! states is enhanced by one to two orders of magnitude for SinGem nanoclusters with respect to the corresponding pure Si clusters. This significant increase of the emission probability is attributed to the strong overlap of HOMO and LUMO wave functions centered mostly on the Ge atoms.