ABSTRACT
We discuss fundamental differences in electronic structure as reflected in one- and two-photon absorption spectra of semiconductor quantum dots and organic molecules by performing systematic experimental and theoretical studies of the size-dependent spectra of colloidal quantum dots. Quantum-chemical and effective-mass calculations are used to model the one- and two-photon absorption spectra and compare them with the experimental results. Currently, quantum-chemical calculations are limited to only small-sized quantum dots (nanoclusters) but allow one to study various environmental effects on the optical spectra such as solvation and various surface functionalizations. The effective-mass calculations, on the other hand, are applicable to the larger-sized quantum dots and can, in general, explain the observed trends but are insensitive to solvent and ligand effects. Careful comparison of the experimental and theoretical results allows for quantifying the range of applicability of theoretical methods used in this work. Our study shows that the small clusters can be in principle described in a manner similar to that used for organic molecules. In addition, there are several important factors (quality of passivation, nature of the ligands, and intraband/interband transitions) affecting optical properties of the nanoclusters. The larger-size quantum dots, on the other hand, behave similarly to bulk semiconductors, and can be well described in terms of the effective-mass models.
ABSTRACT
Specially-treated glass substrates coated with a thin film of water soluble mercaptopropionic acid (MPA) capped CdTe nanocrystals (NCs) were prepared and found to undergo photoluminescence changes by as much as 40% when micro-droplets of organic molecules were placed in the nanometer-range proximity of the NCs. This imaging technique involving close proximity between a nano-crystal and an organic molecule is found to provide a 2 × -3 × enhanced contrast ratio over the conventional method of fluorescence imaging. Photoluminescence of NCs is recoverable upon removal of the organic molecules, therefore validating these NCs as potential all-optical organic molecular nanosensors. Upon optimization and with proper instrumentation, these nano-crystals could eventually serve as point-detectors for purposes of super-resolution optical microscopy. No solvents are required for the proposed sensing mechanism since all solutions were dried under argon flow. Fluorophores and fluorescent proteins were investigated, including fluorescein, Rhodamine 6G, and green fluorescent protein (GFP). Furthermore, NC photoluminescence changes were systematically quantified as a function of the solution pH and of the organic molecule concentration. Long duration (> 40 minutes) continuous excitation studies were conducted in order to evaluate the reliability of the proposed sensing scheme.
ABSTRACT
We demonstrate that core/graded-shell CdSe/CdSe1-xSx/CdS giant semiconductor nanocrystals (g-NCs) have robust photoluminescence (PL) temperature response. At a size of 10.2 nm in diameter, these g-NCs undergo a PL drop of only 30% at 355 K relative to their PL intensity at 85 K. In comparison, the core/step-shell CdSe/CdS g-NCs at the same diameter exhibit 80% PL drop at 355 K. Spectral shifting and broadening were found to be, respectively, 5-10 times and 2-4 times smaller than those observed in standard CdSe core and CdSe/CdS core/shell NCs. These core/graded-shell g-NCs are largely blinking suppressed and have insignificant photoluminescence decay even after excitation at very high irradiance (44 kW cm(-2)) for over an hour. These types of g-NC have potential applications as the active medium for thermally robust laser devices (in the visible range) or as temperature-insensitive bioprobes for biomedical imaging.
ABSTRACT
CdTe semiconductor nanocrystals (NCs) with 3-mercaptopropionic acid as the ligand exhibit a reversible response towards inter-switching oxygen and argon environments. The photoluminescence response is investigated at multiple oxygen concentrations, NC coverage and excitation intensities, in which all conditions exhibit full recovery upon exposure to flowing argon. The CdTe NC's large surface-to-volume ratio results in high sensitivity towards oxygen molecules with significant photoluminescence quenching at a concentration of 40 ppm. This suggests a novel approach to the creation of simple, inexpensive and ultrasensitive oxygen nanosensors.
