Evolution of exciton states near the percolation threshold in two-phase systems with II–VI semiconductor quantum dots

From studies of two-phase systems (borosilicate matrices containing ZnSe or CdS quantum dots), it was found that the systems exhibit a specific feature associated with the percolation phase transition of charge carriers (excitons). The transition manifests itself as radical changes in the optical spectra of both ZnSe and CdS quantum dot systems and by fluctuations of the emission band intensities near the percolation threshold. These effects are due to microscopic fluctuations of the density of quantum dots. The average spacing between quantum dots is calculated taking into account their finite dimensions and the volume fraction occupied by the quantum dots at the percolation threshold. It is shown that clustering of quantum dots occurs via tunneling of charge carriers between the dots. A physical mechanism responsible for the percolation threshold for charge carriers is suggested. In the mechanism, the permittivity mismatch of the materials of the matrix and quantum dots plays an important role in delocalization of charge carriers (excitons): due to the mismatch, “a dielectric trap” is formed at the external surface of the interface between the matrix and a quantum dot and, thus, surface exciton states are formed there. The critical concentrations of quantum dots are determined, such that the spatial overlapping of such surface states provides the percolation transition in both systems.