Size-Dependent Photobleaching Mechanism and Kinetics Induced by Nanosecond Laser Pulses in Colloidal Semiconductor Quantum Dots

Abstract

An experimental-theoretical approach is proposed to investigate the size-dependent photobleaching of colloidal semiconductor quantum dots (QDs) excited by a nanosecond pulsed laser. In the experimental background, the ground-state absorption and photoluminescence (PL) spectra of chemically prepared QDs are monitored over an excitation time at distinct laser irradiances. The magnitude of photobleaching in the QD solution is quantified by the decay rate of the PL signal as a function of the excitation time and the laser power. A theoretical spectroscopy model is then used to estimate the particle size distribution (PSD) in colloidal solution from the absorption data generated at different laser powers. The resulting evolution of the PSD of the QD ensemble under irradiation is analyzed in terms of classical crystallization theories dealing with the formation, growth, and dissolution of colloidal particles in a supersaturated medium. The QD response to laser irradiation is also interpreted by a simple mechanical model that correlates the photoinduced hydrostatic strain at the solid/liquid interface and the predicted variation of the mean particle size. The reported experimental and theoretical methods are used to completely elucidate the basic physico-chemical processes responsible for the laser-induced photobleaching kinetics of glutathione-capped CdTe aqueous QDs with very small mean sizes. For this purpose, we synthesized a series of colloidal QD samples with mean particle diameters ranging from 1.95 to 2.68 nm. Our results indicate that a faster photobleaching rate occurs in QD samples with smaller sizes in which particle dissolution under laser irradiation is predominant. On the other hand, the photobleaching rate becomes slower in samples with larger dot sizes, possibly due to the formation of core/shell structures in solution via thermal degradation of thiol ligands either during the chemical synthesis or as a consequence of the subsequent interaction with the excitation laser.