Why do Si quantum dots with stronger fast emission have lower external photoluminescence quantum yield?

Silicon quantum dots (QDs) are a promising non-toxic alternative to the already well-developed platform of light-emitting semiconductor QDs based on III-V and II-VI materials. Oxidized SiQDs or those surface-terminated with long alkyl chains typically feature long-lived orange-red photoluminescence originating in quantum-confined core states. However, sometimes an additional short-lived PL band, whose mechanism is still highly debated, is reported. Here, we perform a detailed study of the room-temperature PL of SiQDs using samples covering three main fabrication techniques. We find evidence for the presence of only one set of radiative processes in addition to the typical long-lived PL. Moreover, we experimentally determine the ratio between the short- and long-lived PL component, obtaining a wide range of values (0.003 - 0.1) depending on the type of sample. In accordance with an already published report, we observe a tendency of SiQDs with stronger short-lived PL to have lower external quantum yield. We explain this trend using a model of the optical performance of an ensemble of QDs with widely varying optical characteristics through a mechanism we call selective lifetime-based quenching.

One-step synthesis of photoluminescent nanofluids by direct loading of reactively sputtered cubic ZrN nanoparticles into organic liquids.

ZrN nanofluids may exhibit unique optoelectronic properties because of the matching of the solar spectrum with interband transitions and localized surface plasmon resonance (LSPR). Nevertheless, these nanofluids have scarcely been investigated, mainly because of the complexity of the current synthetic routes that involve aggressive chemicals and high temperatures. This work aims to validate reactive dc magnetron sputtering of zirconium in Ar/N2 as an environmentally benign, annealing-free method to produce 22 nm-sized, highly crystalline, stoichiometric, electrically conductive, and plasmonic ZrN nanoparticles (NPs) of cubic shape and to load them into vacuum-compatible liquids of different chemical compositions (polyethylene glycol (PEG), paraffin, and pentaphenyl trimethyl trisiloxane (PTT)) in one step. The nanofluids demonstrate LSPR in the red/near-IR range that gives them a bluish color in transmittance. The nanofluids also demonstrate complex photoluminescence behavior such that ZrN NPs enhance the photoluminescence (PL) intensity of paraffin and PEG, whereas the PL of PTT remains almost invariable. Based on DFT calculations, different energetic barriers to charge transfer between ZrN and the organic molecules are suggested as the main factors that influence the observed optoelectronic response. Overall, our study provides a novel approach to the synthesis of transition metal nitride nanofluids in an environmentally friendly manner, deepens the understanding of the interactions between ZrN and organic molecules, and unveils new optoelectronic phenomena in such systems.

The red and blue luminescence in silicon nanocrystals with an oxidized, nitrogen-containing shell.

Traditionally, two classes of silicon nanocrystals (SiNCs) are recognized with respect to their light-emission properties. These are usually referred to as the "red" and the "blue" emitting SiNCs, based on the spectral region in which the larger part of their luminescence is concentrated. The origin of the "blue" luminescence is still disputed and is very probably different in different systems. One of the important contributions to the discussion about the origin of the "blue" luminescence was the finding that the exposure of SiNCs to even trace amounts of nitrogen in the presence of oxygen induces the "blue" emission, even in originally "red"-emitting SiNCs. Here, we obtained a different result. We show that the treatment of "red" emitting, already oxidized SiNCs in a water-based environment containing air-related radicals including nitrogen-containing species as well as oxygen, diminishes, rather than induces the "blue" luminescence.