Recent advances in semiconductor nanostructure syntheses provide unprecedented control over electronic quantum confinement and have led to extensive investigations of their size- and shape-dependent optical/electrical properties. Notably, spectroscopic measurements show that optical bandgaps of one-dimensional CdSe nanowires are substantially (approximately 100 meV) lower than their zero-dimensional counterparts for equivalent diameters spanning 5–10 nm. But what, exactly, dictates the dimensional crossover of a semiconductor's electronic structure? Here we probe the one-dimensional to zero-dimensional transition of CdSe using single nanowire/nanorod absorption spectroscopy. We find that carrier electrostatic interactions play a fundamental role in establishing dimensional crossover. Moreover, the critical length at which this transition occurs is governed by the aspect ratio-dependent interplay between carrier confinement and dielectric contrast/confinement energies.

We provide, for the first time, direct experimental evidence for heterogeneous blinking in reduced graphene oxide (rGO) during photolysis. The spatially resolved intermittency originates from regions within individual rGO sheets and shows 1/f-like power spectral density. We describe the evolution of rGO blinking using the multiple recombination center (MRC) model that captures common features of nanoscale blinking. Our results illustrate the universal nature of blinking and suggest a common microscopic origin for the effect.

Fluorescence intermittency or blinking is observed in nearly all nanoscale fluorophores. It is characterized by universal power-law distributions in on- and off-times as well as 1/f behaviour in corresponding emission power spectral densities. Blinking, previously seen in confined zero- and one-dimensional systems has recently been documented in two-dimensional reduced graphene oxide. Here we show that unexpected blinking during graphene oxide-to-reduced graphene oxide photoreduction is attributed, in large part, to the redistribution of carbon sp2 domains. This reclustering generates fluctuations in the number/size of emissive graphenic nanoclusters wherein multiscale modelling captures essential experimental aspects of reduced graphene oxide's absorption/emission trajectories, while simultaneously connecting them to the underlying photochemistry responsible for graphene oxide's reduction. These simulations thus establish causality between currently unexplained, long timescale emission intermittency in a quantum mechanical fluorophore and identifiable chemical reactions that ultimately lead to switching between on and off states.