The nature of exciton-plasmon interactions in Au-tipped CdS nanorods has been investigated using femtosecond transient absorption spectroscopy. The study demonstrates that the key optoelectronic properties of composite heterostructures comprising electrically coupled metal and semiconductor domains are substantially different from those observed in systems with weak interdomain coupling. In particular, strongly coupled nanocomposites promote mixing of electronic states at semiconductor-metal domain interfaces, which causes a significant suppression of both plasmon and exciton excitations of carriers.

We report on organometallic synthesis of luminescent (ZnSe/CdS)/CdS semiconductor heterostructured nanorods (hetero-NRs) that produce an efficient spatial separation of carriers along the main axis of the structure (type II carrier localization). Nanorods were fabricated using a seeded-type approach by nucleating the growth of 20-100 nm CdS extensions at [000 +/- 1] facets of wurtzite ZnSe/CdS core/shell nanocrystals. The difference in growth rates of CdS in each of the two directions ensures that the position of ZnSe/CdS seeds in the final structure is offset from the center of hetero-NRs, resulting in a spatially asymmetric distribution of carrier wave functions along the heterostructure. Present work demonstrates a number of unique properties of (ZnSe/CdS)/CdS hetero-NRs, including enhanced magnitude of quantum confined Stark effect and subnanosecond switching of absorption energies that can find practical applications in electroabsorption switches and ultrasensitive charge detectors.

We employ femtosecond transient absorption spectroscopy to get an insight into ultrafast processes occurring at the interface of type II ZnSe/CdS heterostructured nanocrystals fabricated via colloidal routes and comprising a barbell-like arrangement of ZnSe tips and CdS nanorods. Our study shows that resonant excitation of ZnSe tips results in an unprecedently fast transfer of excited electrons into CdS domains of nanobarbells (<0.35 ps), whereas selective pumping of CdS components leads to a relatively slow injection of photoinduced holes into ZnSe tips (tau(h)= 95 ps). A qualitative thermodynamic description of observed electron processes within the classical limit of Marcus theory was used to identify a specific charge transfer regime associated with the ultrafast electron injection into CdS. Potential photocatalytic applications of the observed fast separation of carriers along the main axis of ZnSe/CdS barbells are discussed.

High-quality ZnSe/CdS core/shell nanocrystals, exhibiting a type II carrier localization regime, were fabricated via a traditional pyrolysis of organometallic precursors. The two-step synthesis involved fabrication of 4.5-6 nm ZnSe seeds followed by a subsequent deposition of the CdS shell. An efficient spatial separation of electrons and holes between the core and the shell was observed for heterostructures containing more than three monolayers of CdS, which was primarily evidenced by the spatially indirect emission tunable from 480 to 610 nm for a fixed core diameter. Because of a large (type II) offset of band edges at the core/shell interface, fabricated nanocrystals exhibited a relatively low spectral overlap between emission and absorption profiles, with associated Stokes shifts of up to 110 nm. The quantum yield of as-prepared samples was 12-18% and was further improved to 20% after purification of nanocrystals through multiple hexane/methanol extractions. Novel properties of synthesized ZnSe/CdS nanocrystals as well as their applicability to practical realizations in areas of biomedical imaging, solar sells, and quantum dot-based lasers are discussed.

We report on a colloidal synthesis of barbell-shaped nanocrystals comprising a type II heterojunction of ZnSe and CdS domains and showing compelling evidence of photoinduced charge separation at the interface of ZnSe and CdS materials. The nanobarbells were fabricated in a two-step procedure by growing ZnSe caps onto polar facets of CdS nanorods. Under present synthetic conditions, minimal growth of ZnSe shell in the lateral direction and focusing of the barbell length distribution were observed. Formation of epitaxial interfaces between nearly lattice-matched ZnSe and CdS crystal phases was primarily evidenced by the observation of "spatially indirect" fluorescence and long radiative lifetimes corresponding to the decay of charge transfer states.