Efficient Hole Transfer from CdSe Quantum Dots Enabled by Oxygen-Deficient Polyoxovanadate-Alkoxide Clusters.

A limitation of the implementation of cadmium chalcogenide quantum dots (QDs) in charge transfer systems is the efficient removal of photogenerated holes. Rapid hole transfer has typically required the ex situ functionalization of hole acceptors with groups that can coordinate to the surface of the QD. In addition to being synthetically limiting, this strategy also necessitates a competitive binding equilibrium between the hole acceptor and native, solubilizing ligands on the nanocrystal. Here we show that the incorporation of oxygen vacancies into polyoxovanadate-alkoxide clusters improves hole transfer kinetics by promoting surface interactions between the metal oxide assembly and the QD. Investigating the reactivity of oxygen-deficient clusters with phosphonate-capped QDs reveals reversible complexation of the POV-alkoxide with a phosphonate ligand at the nanocrystal surface. These findings reveal a new method of facilitating QD-hole acceptor association that bypasses the restrictions of exchange interactions.

Quantum Dots for Improved Single-Molecule Localization Microscopy.

Colloidal semiconductor quantum dots (QDs) have long established their versatility and utility for the visualization of biological interactions. On the single-particle level, QDs have demonstrated superior photophysical properties compared to organic dye molecules or fluorescent proteins, but it remains an open question as to which of these fundamental characteristics are most significant with respect to the performance of QDs for imaging beyond the diffraction limit. Here, we demonstrate significant enhancement in achievable localization precision in QD-labeled neurons compared to neurons labeled with an organic fluorophore. Additionally, we identify key photophysical parameters of QDs responsible for this enhancement and compare these parameters to reported values for commonly used fluorophores for super-resolution imaging.

Size dependence of photocatalytic hydrogen generation for CdTe quantum dots.

CdTe quantum dots (QDs) are attractive photosensitizers for photocatalytic proton reduction due to their broad absorbance profile that can extend from the ultraviolet to near-infrared regions, providing access to a larger portion of the solar spectrum than possible with analogous CdSe and CdS QD photosensitizers. Here, the photocatalytic hydrogen (H2) generation from various sizes of dihydrolipoic acid (DHLA)-capped CdTe QDs, ranging from 2.5 to 7.5 nm in diameter, and a molecular Ni-DHLA catalyst in aqueous solutions was evaluated, and an unusual size-dependent photocatalytic activity with CdTe QDs was observed. Under optimized conditions, using 3.4 nm CdTe-DHLA and a 1:20 ratio of QD/Ni-DHLA catalyst, as many as 38 000 turnover numbers (mol H2 per mol QD) were achieved. However, below this critical size, the H2 production efficiency decreased; this behavior is attributed to the rapid oxidation of the QD surface, resulting in detrimental surface trap states. These results are consistent with ultrafast transient absorption spectroscopic measurements, which suggest the presence of extremely fast charge-trapping processes in the oxidized CdTe-DHLA QDs. While fast electron transfer from CdTe-DHLA QDs is observed in the presence of the Ni-DHLA catalyst, the charge trapping processes occur on a competitive time scale, thus lowering the efficiency of the CdTe/Ni-DHLA H2 production system. Understanding rapid charge trapping in CdTe QDs may help suggest potential improvements for the overall CdTe photocatalytic system.

Non-blinking single-photon emitters in silica.

Samples for single-emitter spectroscopy are usually prepared by spin-coating a dilute solution of emitters on a microscope cover slip of silicate based glass (such as quartz). Here, we show that both borosilicate glass and quartz contain intrinsic defect colour centres that fluoresce when excited at 532 nm. In a microscope image the defect emission is indistinguishable from spin-coated emitters. The emission spectrum is characterised by multiple peaks with the main peak between 2.05 and 2.20 eV, most likely due to coupling to a silica vibration with an energy that varies between 160 and 180 meV. The defects are single-photon emitters, do not blink, and have photoluminescence lifetimes of a few nanoseconds. Photoluminescence from such defects may previously have been misinterpreted as originating from single nanocrystal quantum dots.

Spectroscopic investigation of electrochemically charged individual (6,5) single-walled carbon nanotubes.

Individual single-walled carbon nanotubes (SWNTs) of (6,5) chirality were investigated by means of optical spectroscopy while their charge state was controlled electrochemically. The photoluminescence of the SWNTs was found to be quenched at positive and negative potentials, where the onset and offset varied for each individual SWNT. We propose that differences in the local environment of the individual SWNT lead to a shift of the Fermi energy, resulting in a distribution of the oxidation and reduction potentials. The exciton emission energy was found to correlate with the oxidation and reduction potential. Further proof of a correlation was found by deliberately doping individual SWNTs and monitoring their photoluminescence spectral shift.