ABSTRACT
Metal-enhanced photoluminescence is able to provide a robust signal even from a single emitter and is promising in applications in biosensors and optoelectronic devices. However, its realization with semiconductor nanocrystals (e.g., quantum dots, QDs) is not always straightforward due to the hidden and not fully described interactions between plasmonic nanoparticles and an emitter. Here, we demonstrate nonclassical enhancement (i.e., not a conventional electromagnetic mechanism) of the QD photoluminescence at nonplasmonic conditions and correlate it with the charge exchange processes in the system, particularly with high efficiency of the hot-hole generation in gold nanoparticles and the possibility of their transfer to QDs. The hole injection returns a QD from a charged nonemitting state caused by hole trapping by surface and/or interfacial traps into an uncharged emitting state, which leads to an increased photoluminescence intensity. These results open new insights into metal-enhanced photoluminescence, showing the importance of the QD surface states in this process.
ABSTRACT
Plasmon-exciton coupling is of great importance to many optical devices and applications. One of the coupling manifestations is plasmon-enhanced fluorescence. Although this effect is demonstrated in numerous experimental and theoretical works, there are different particle shapes for which this effect is not fully investigated. In this work electrostatic complexes of gold nanorods and CdSe/CdZnS quantum dots were studied. Double-resonant gold nanorods have an advantage of the simultaneous enhancement of the absorption and emission when the plasmon bands match the excitation and fluorescence wavelengths of an emitter. A relationship between the concentration of quantum dots in the complexes and the enhancement factor was established. It was demonstrated that the enhancement factor is inversely proportional to the concentration of quantum dots. The maximal fluorescence enhancement by 10.8 times was observed in the complex with the smallest relative concentration of 2.5 quantum dots per rod and approximately 5 nm distance between them. Moreover, the influence of quantum dot location on the gold nanorod surface plays an important role. Theoretical study and experimental data indicate that only the position near the nanorod ends provides the enhancement. At the same time, the localization of quantum dots on the sides of the nanorods leads to the fluorescence quenching.