Fluorescence intermittency

Abstract: SEMICONDUCTOR nanocrystals offer the opportunity to study the evolution of bulk materials properties as the size of a system increases from the molecular scale1,2. In addition, their strongly size-dependent optical properties render them attractive candidates as tunable light absorbers and emitters in optoelectronic devices such as light-emitting diodes3,4 and quantum-dot lasers5,6, and as optical probes of biological systems7. Here we show that light emission from single fluorescing nanocrystals of cadmium selenide under continuous excitation turns on and off intermittently with a characteristic timescale of about 0.5 seconds. This intermittency is not apparent from ensemble measurements on many nanocrystals. The dependence on excitation intensity and the change in on/off times when a passivating, high-bandgap shell of zinc sulphide encapsulates the nanocrystal8,9 suggests that the abrupt turning off of luminescence is caused by photo-ionization of the nanocrystal. Thus spectroscopic measurements on single nanocrystals can reveal hitherto unknown aspects of their photophysics.

Abstract: SEMICONDUCTOR nanocrystals offer the opportunity to study the evolution of bulk materials properties as the size of a system increases from the molecular scale 1,2 . In addition, their strongly size-dependent optical properties render them attractive candidates as tunable light absorbers and emitters in optoelectronic devices such as light-emitting diodes 3,4 and quantum-dot lasers 5, 6 and as optical probes of biological systems'. Here we show that light emission from single fluorescing nanocrystals of cadmium selenide under continuous excitation turns on and off intermittently with a characteristic timescale of about 0.5 seconds. This intermittency is not apparent from ensemble measurements on many nanocrystals. The dependence on excitation intensity and the change in on/off times when a passivating, high-bandgap shell of zinc sulphide encapsulates the nanocrystal 8,9 suggests that the abrupt turning off of luminescence is caused by photoionization of the nanocrystal. Thus spectroscopic measurements on single nanocrystals can reveal hitherto unknown aspects of their photophysics.

Abstract: Semiconductor nanocrystal quantum dots (NQDs) comprise an important class of inorganic fluorophores for applications from optoelectronics to biology. Unfortunately, to date, NQD optical properties (e.g., their efficient and particle-size-tunable photoluminescence) have been susceptible to instabilities at the bulk and single-particle levels. Specifically, ensemble quantum yields (QYs) in emission are dependent upon NQD surface chemistry and chemical environment, while at the single-particle level, NQDs are characterized by significant fluorescence intermittency (blinking) that hinders applications as single-photon light sources for quantum informatics and biolabels for real-time monitoring of single biomolecules. Furthermore, while NQDs are significantly more photostable than their organic dye counterparts, traditional NQDs photobleach over periods of seconds to many minutes. Here, we demonstrate for the first time that by encapsulating the NQD core in a sufficiently thick inorganic shell, we are able to divorce NQD function from NQD surface chemistry and chemical environment. We show that our "giant" NQDs (g-NQDs) are functionally distinct from standard core-only, core/shell and even core/multishell NQDs. g-NQDs are substantially less sensitive to changes in surface chemistry. They do not photobleach under continuous laser excitation over periods of several hours repeated over several days, and they exhibit markedly different blinking behavior; >20% of the g-NQDs do not blink, while >40% have on-time fractions of >80%. All of these observations are in stark contrast with control samples comprising core-only and standard, thinner core/multishell NQDs.

Abstract: At a single-molecule level, fluorophore emission intensity fluctuates between bright and dark states. These fluctuations, known as blinking, limit the use of fluorophores in single-molecule experiments. The dark-state duration shows a universal heavy-tailed power-law distribution characterized by the occurrence of long non-emissive periods. Here we have synthesized novel CdSe-CdS core-shell quantum dots with thick crystalline shells, 68% of which do not blink when observed individually at 33 Hz for 5 min. We have established a direct correlation between shell thickness and blinking occurrences. Importantly, the statistics of dark periods that appear at high acquisition rates (1 kHz) are not heavy tailed, in striking contrast with previous observations. Blinking statistics are thus not as universal as thought so far. We anticipate that our results will help to better understand the physico-chemistry of single-fluorophore emission and rationalize the design of other fluorophores that do not blink.