We report a photoluminescence study of silicon nanoclusters produced by laser ablation. It was found that by varying the preparation parameters it was possible to change the mean cluster size in the range 1–5 nm. Within this size variation, the photoluminescence band shifts in a wide spectral region from near ultraviolet to near infrared. This size-dependent photoluminescence of Si nanoclusters is consistent with a quantum confinement effect. The observed influence of cluster oxidation on the luminescence properties also supports the quantum confinement interpretation. We proposed a discrete size model which supposes that the spectral position of the luminescence band is essentially determined by the volume of clusters with a complete outer atomic layer. In the framework of this model, we were able to deconvolute the observed luminescence bands into a set of fixed Gaussian bands. The model is supported by the observation of a size selective doping of Si nanoclusters whose effect was well explained by Auger recombination. Finally, our model allowed us to obtain a dependence of the optical gap on the cluster size which is in good agreement with existing calculations of Si nanocrystal electronic structure.

This work presents hybrid bulk heterojunction solar cells based on dye-sensitized zinc oxide (ZnO) nanorods blended with poly(3-hexylthiophene) (P3HT). Tetra(4-carboxyphenyl)porphyrin (TCPP) molecules were grafted onto the surface of ZnO nanorods to enlarge the absorption spectrum of the blend. We demonstrate that additional bands in the external quantum efficiency (EQE) spectra corresponding to Soret and Q-band absorption can already been observed at very low dye concentration at the ZnO surface. Therefore, direct grafting of TCPP onto ZnO nanorods leads to very efficient electron injection process into the ZnO nanorods after the light absorption of the dye. However, the overall photocurrent of the devices decreases gradually with TCPP concentration at the ZnO nanorod surface. The recombination dynamics of the photogenerated charges at the P3HT:ZnO interface are investigated by transient absorption spectroscopy on micro-to millisecond time scales. We observe that the lifetime of the P3HT polarons is reduced by an order of magnitude by grafting TCPP of already low concentration at the ZnO surface. Furthermore, high-resolution transmission electronic microscopy analysis of the blend morphology reveals that aggregation of ZnO nanorods within the P3HT is strongly increased by TCPP grafting. Therefore, we conclude that TCPP grafting is beneficial for additional photocurrent generation in the P3HT:ZnO blend but introduces strong modification of the blend morphology and charge carrier dynamics at the P3HT/ZnO interface, which finally reduces the overall photocurrent generation.