Quantum confinement, carrier dynamics and interfacial processes in nanostructured direct/indirect-gap semiconductor-glass composites

The behavior of semiconductor clusters precipitated in an insulated matrix was investigated. Semiconductor compositions of CdTe, Si and Ge were studies and the insulating matrix was amorphous SiO2. As a function of size, quantum confinement effects were observed in all three composite systems. However significant differences were observed between the direct-gap column 2-6 semiconductors and the indirect-gap column 4 semiconductors. As observed by others, the direct-gap 2-6 semiconductors showed a distinct saturation in the energy-gap blue shift with decreasing size. Theoretical studies using a 20-band k dot p calculation of the electronic and valence bands for a 3-dimensionally confined CdTe semiconductor showed that mixing of the conduction band states leads to a flattening of the central valley. This increases the electron mass drastically and saturates the size dependent blue shift in the bandgap. In contrast, the blue shift in the Si and Ge nanocrystals showed no sign of saturation and increased drastically with decreasing size. In fact, Si and Ge crystals were formed with blue shift values that moved the bandgap to the near UV region. We examined the absorption curves to determine whether the bandgap was direct or indirect in the quantum dots. The results are that the absorption shows an indirect gap for all but the smallest Si crystals and an indirect gap for all Ge crystals. Raman studies showed negligible size dependence due to a lack of phonon confinement in the matrix embedded clusters. Exciton saturation and recovery times were found to be very short (of the order of 400fs) and are the fastest reported for any quantum dot system. Work to examine the type of confinement obtained in a matrix that consists of a transparent conductor is under way. Studies of the photoinduced absorption change in GeSe glasses showed a significant effect of photodarkening, regardless of composition. The photodarkening effect appears to be composed of permanent and transient effects, presumed to be associated with photo-induced structural changes in the glass. The transient effects appear to have recovery times in at least two different time scales--one in minutes and one in less than a microsecond. Time-resolved studies are under way to determine the structural origin of each photodarkening effect