Evidence for energy relaxation via a radiative cascade in surface-passivated PbS quantum dots

Multiple emission peaks have been observed from surface passivated PbS nanocrystals displaying strong quantum confinement. The emission spectra are shown to be strongly dependent on the excited-state parity. We also find that intraband energy relaxation from initial states excited far above the band-edge is nearly three orders of magnitude slower than that found in other nanocrystal quantum dots, providing evidence of inefficient energy relaxation via phonon emission. The initial-state parity dependence of the photoluminescent emission properties suggests that energy relaxation from the higher excited states occurs via a radiative cascade, analogous to energy relaxation in atomic systems. Such radiative cascade emission is possible from ideal zero-dimensional semiconductors, where electronic transitions can be decoupled from phonon modes.

Direct observation of mixed-parity excited states in surface-passivated PbS nanocrystals

Photoluminescent emission is observed from surface-passivated PbS nanocrystals following the two-photon excitation of high-energy excitonic states. The emission appears directly at the excitation energy with no detectable Stokes-shift for a wide range of excitation energies. The observation of direct emission from states excited by two-photon absorption indicates that the parity of the excited states of surface-passivated PbS nanocrystals is partially mixed.

A new approach to the synthesis of nanocrystal conjugated polymer composites

A novel one pot process has been developed for the preparation of PbS nanocrystals in the conjugated polymer poly 2-methoxy,5-(2 ethyl-hexyloxy-p-phenylenevinylene) (MEH-PPV). Current techniques for making such composite materials rely upon synthesizing the nanocrystals and conducting polymer separately, and subsequently mixing them. This multi-step technique has two serious drawbacks: templating surfactant must be removed before mixing, and co-solvent incompatibility causes aggregation. In our method, we eliminate the need for an initial surfactant by using the conducting polymer to terminate and template nanocrystal growth. Additionally, the final product is soluble in a single solvent. We present materials analysis which shows PbS nanocrystals can be grown directly in a conducting polymer, the resulting composite is highly ordered and nanocrystal size can be controlled.

Time-resolved photoluminescence spectroscopy of ligand-capped PbS nanocrystals

PbS nanocrystals are synthesized using colloidal techniques and have their surfaces capped with oleic acid. The absorption band edge of the PbS nanocrystals is tuned between 900 and 580 nm. The PbS nanocrystals exhibit tuneable photoluminescence with large non-resonant Stokes shifts of up to 500 mcV. The magnitude of the Stokes shift is found to be dependent upon the size of PbS nanocrystals. Time-resolved photoluminescence spectroscopy of the PbS nanocrystals reveals that the photouminescence has an extraordinarily long lifetime of 1 mus. This long fluorescence lifetime is attributed to the effect of dielectric screening similar to that observed in other IV-VI semiconductor nanocrystals.

Highly efficient luminescence from a hybrid state found in strongly quantum confined PbS nanocrystals

We report that high quality PbS nanocrystals, synthesized in the strong quantum confinement regime, have quantum yields as high as 70% at room temperature. We use a combination of modelling and photoluminescence up-conversion to show that we obtain a nearly monodisperse size distribution. Nevertheless, the emission displays a large nonresonant Stokes shift. The magnitude of the Stokes shift is found to be directly proportional to the degree of quantum confinement, from which we establish that the emission results from the recombination of one quantum confined charge carrier with one localized or surface-trapped charge carrier. Furthermore, the surface state energy is found to lie outside the bulk bandgap so that surface-related emission only commences for strongly quantum confined nanocrystals, thus highlighting a regime where improved surface passivation becomes necessary.