Primary Photodynamics of Water-Solubilized Two-Dimensional CdSe Nanoribbons
journal contributionposted on 2011-10-13, 00:00 authored by Arthur Thibert, F. Andrew Frame, Erik Busby, Delmar S. Larsen
The primary photodynamics of water-solubilized 2D CdSe nanoribbons (NRs) was characterized with femtosecond transient absorption spectroscopy and modeled using global analysis. The measured signals were decomposed into the constituent dynamics of three transient populations: hot tightly bound excitons, relaxed tightly bound excitons, and separated trapped carriers (holes and electrons). The influences of three external factors affecting the observed dynamics were explored: (1) excitation wavelength, (2) excitation fluence, and (3) presence of the hole scavenger HS–. Both higher-energy excitation photons and higher-intensity excitation induce slower relaxation of charge carriers to the band edge due to the need to dissipate excess excitation energy. Nonlinear decay kinetics of the relaxed exciton population is observed and demonstrated to arise from bimolecular trapping of excitons with low-density trap sites located at CdSe NR surface sites instead of the commonly resolved multiparticle Auger recombination mechanism. This is supported by the observed linear excitation-fluence dependence of the trapped-carrier population that is numerically simulated and found to deviate from the excitation fluence dependence expected of Auger recombination kinetics. Introducing hole scavenging HS– has a negligible effect on the exciton kinetics, including migration and dissociation, and instead passivates surface trap states to induce the rapid elimination of holes after exciton dissociation. This increases the lifetime of the reactive electron population and increases measured photocatalytic H2 generation activity. A broad (200 nm) and persistent (20 ps) stimulated emission observed in the tightly bound excitons suggests their potential use as broadband microlasers.
exciton kineticsAuger recombination kineticsreactive electron populationcharge carriersabsorption spectroscopyHSexciton dissociationtrap sitesNonlinear decay kineticsCdSe NR surface sitesexcitation energyphotocatalytic H 2 generation activityPrimary Photodynamicsexcitation fluence dependenceconstituent dynamicsbroadband microlasersmultiparticle Auger recombination mechanismband edgeexciton populationpassivates surface trap states