Persistence of magic cluster stability in ultra-thin semiconductor nanorods

The progression from quasi zero-dimensional (Q0D) nanoclusters to quasi one-dimensional (Q1D) nanorods, and, with increasing length, to nanowires, represents the most conceptually fundamental transition from the nanoscale to bulk-like length scales. This dimensionality crossover is particularly interesting, both scientifically and technologically, for inorganic semiconducting (ISC) materials, where striking concomitant changes in optoelectronic properties occur.(1,2) Such effects are most pronounced for ultra-thin(3) ISC nanorods/nanowires, where the confining and defective nature of the atomic structure become key. Although experiments on ISC materials in this size regime have revealed especially stable (or magic) non-bulk-like Q0D nanoclusters,(4,5) all ISC Q1D nanostructures have been reported as having structures corresponding to bulk crystalline phases. For two important ISC materials (CdS and CdSe) we track the Q0D-to-Q1D transition employing state-of-the-art electronic structure calculations demonstrating an unexpected persistence of magic cluster stability over the bulk-like structure in ultra-thin nanorods up to >10 nm in length. The transition between the magic-cluster-based and wurtzite nanorods is found to be accompanied by a large change in aspect ratio thus potentially providing a route to nano-mechanical transducer applications.