Understanding Nonradiative Recombination through Defect-Induced Conical Intersections.

Defects are known to introduce pathways for the nonradiative recombination of electronic excitations in semiconductors, but implicating a specific defect as a nonradiative center remains challenging for both experiment and theory. In this Perspective, we present recent progress toward this goal involving the identification and characterization of defect-induced conical intersections (DICIs), points of degeneracy between the ground and first excited electronic states of semiconductor materials that arise from the deformation of specific defects. Analysis of DICIs does not require the assumption of weak correlation between the electron and hole nor of stationary nuclei. It is demonstrated that in some cases an energetically accessible DICI is present even when no midgap state is predicted by single-particle theories (e.g., density functional theory). We review recent theoretical and computational developments that enable the location of DICIs in semiconductor nanomaterials and present insights into the photoluminescence of silicon nanocrystals gleaned from DICIs.