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.
Femtosecond time-resolved second harmonic generation studies of the barrierless isomerization of an organic dye, malachite green (MG), have been carded out at several aqueous interfaces. A comparison of the dynamics at the air/aqueous, alkane/aqueous and silica/aqueous interfaces, indicates increased friction and increased water structure at the aqueous interfaces relative to bulk water, in support of molecular simulations, with the silica/aqueous interface being the most structured. The dynamics are slower at all of these interfaces than in bulk water, by a factor of three to five in the case of the air/aqueous and alkane/aqueous interfaces, and almost an order of magnitude in the case of the silica/aqueous interface. These investigations also indicate that the generally accepted isomerization model of twisting of the three aromatic rings about the central carbon atom requires modification in that the synchronous twisting of all three aromatic rings is not necessary for rapid internal conversion from the excited to ground electronic state. In contrast to MG, the dynamics of the activated photoisomerization of the cyanine dye, 3,3'-diethyloxadicarbocyanine iodide (DODCI), is faster at the air/aqueous interface than in bulk aqueous solution. The different dynamics of MG and DODCI suggest that the interface friction must be described in terms of the orientation and solvent structure in the vicinity of the chromophores involved in the isomerization process.
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.
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