The light-induced spectral diffusion and fluorescence intermittency (blinking) of semiconductor nanocrystal quantum dots are investigated theoretically using a diffusion-controlled electron-transfer (DCET) model, where a light-induced one-dimensional diffusion process in energy space is considered. Unlike the conventional electron-transfer reactions with simple exponential kinetics, the model naturally leads to a power-law statistics for the intermittency. We formulate a possible explanation for the spectral broadening and its proportionality to the light energy density, the −3∕2 power law for the blinking statistics of the fluorescence intermittency, the breakdown of the power-law behavior with a bending tail for the “light” periods, a lack of bending tail for the “dark” periods (but would eventually appear at later times), and the dependence of the bending tail on light intensity and temperature. This DCET model predicts a critical time tc (a function of the electronic coupling strength and other quantities), such that for times shorter than tc the exponent for the power law is −1∕2 instead of −3∕2. Quantitative analyses are made of the experimental data on spectral diffusion and on the asymmetric blinking statistics for the “on” and “off” events. Causes for deviation of the exponent from the ideal value of −3∕2 are also discussed. Several fundamental properties are determined from the present experimental data, the diffusion correlation time, the Stokes shift, and a combination of other molecular-based quantities. Specific experiments are suggested to test the model further, extract other molecular properties, and elucidate more details of the light-induced charge-transfer dynamics in quantum dots.

A mechanism involving diffusion-controlled electron transfer processes in Debye and non-Debye dielectric media is proposed to elucidate the power-law distribution for the lifetime of a blinking quantum dot. This model leads to two complementary regimes of power law with a sum of the exponents equal to 2, and to a specific value for the exponent in terms of a distribution of the diffusion correlation times. It also links the exponential bending tail with energetic and kinetic parameters.

Fluorescence blinking in nanocrystal quantum dots is known to exhibit power-law dynamics, and several different mechanisms have been proposed to explain this behavior. We have extended the measurement of quantum-dot blinking by characterizing fluctuations in the fluorescence of single dots over time scales from microseconds to seconds. The power spectral density of these fluctuations indicates a change in the power-law statistics that occurs at a time scale of several milliseconds, providing an important constraint on possible mechanisms for the blinking. In particular, the observations are consistent with the predictions of models wherein blinking is controlled by diffusion of the energies of electron or hole trap states.

Apart from broadband absorption of solar radiation, the performance of photovoltaic devices is governed by the density and mobility of photogenerated charge carriers. The latter parameters indicate how many free carriers move away from their origin, and how fast, before loss mechanisms such as carrier recombination occur. However, only lower bounds of these parameters are usually obtained. Here we independently determine both density and mobility of charge carriers in a perovskite film by the use of time-resolved terahertz spectroscopy. Our data reveal the modification of the free carrier response by strong backscattering expected from these heavily disordered perovskite films. The results for different phases and different temperatures show a change of kinetics from two-body recombination at room temperature to three-body recombination at low temperatures. Our results suggest that perovskite-based solar cells can perform well even at low temperatures as long as the three-body recombination has not become predominant.

Light-induced diffusion-controlled electron transfer is proposed as an underlying mechanism for the intermittency (power law and breakdown) of a single quantum dot and ensemble-averaged fluorescence decay. The intensity decay can be approximated to a stretched exponential expression. The physical links to the free energy gap, reorganization energy, electronic coupling, and diffusion correlation times are discussed. A procedure is described for extracting these molecular-based parameters from experiments and is demonstrated with examples using existing data.