Taming non-radiative recombination in Si nanocrystals interlinked in a porous network.

A range of the distinctive physical properties, comprising high surface-to-volume ratio, possibility to achieve mechanical and chemical stability after a tailored treatment, controlled quantum confinement and the room-temperature photoluminescence, combined with mass production capabilities offer porous silicon unmatched capabilities required for the development of electro-optical devices. Yet, the mechanism of the charge carrier dynamics remains poorly controlled and understood. In particular, non-radiative recombination, often the main process of the excited carrier's decay, has not been adequately comprehended to this day. Here we show, that the recombination mechanism critically depends on the composition of surface passivation. That is, hydrogen passivated material exhibits Shockley-Read-Hall type of decay, while for oxidised surfaces, it proceeds by two orders of magnitude faster and exclusively through the Auger process. Moreover, it is possible to control the source of recombination in the same sample by applying a cyclic sequence of hydrogenation-oxidation-hydrogenation processes, and, consequently switching on-demand between Shockley-Read-Hall and Auger recombinations. Remarkably, irregardless of the recombination mechanism, the rate constant scales inversely with the average volume of individual silicon nanocrystals contained in the material. Thus, the type of the non-radiative recombination is established by the composition of the passivation, while its rate depends on the degree of the charge carriers' quantum confinement.

The effects of drying technique and surface pre-treatment on the cytotoxicity and dissolution rate of luminescent porous silicon quantum dots in model fluids and living cells.

Tailoring of the biodegradation of photoluminescent silicon quantum dots (Si QDs) is important for their future applications in diagnostics and therapy. Here, the effect of drying and surface pretreatment on the dissolution rate of Si QDs in model liquids and living cells was studied in vitro using a combination of photoluminescence and Raman micro-spectroscopy. Porous silicon particles were obtained by mechanical milling of electrochemically etched mesoporous silicon films, and consist of interlinked silicon nanocrystals (QDs) and pores. The samples were subjected to super-critical drying with CO2 solvent (SCD) or air drying (AD) and then annealed at 600 °C for 16 hours in 1% oxygen to obtain nano-sized Si QDs. The obtained samples were characterized by a core-shell structure with a crystalline silicon core and a SiO2 layer on the surface. The sizes of the crystalline silicon cores, calculated from Raman scattering spectra, were about 4.5 nm for the initial AD-SiQDs, and about 2 nm for the initial SCD-SiQDs. Both the AD-Si QDs and the SCD-Si QDs exhibited visible photoluminescence (PL) properties due to quantum confinement effects. The dissolution of the nanocrystals was evaluated through their PL quenching, as well as by the presence of a low-frequency shift, broadening, and a decrease in the intensity of the Raman signal. The stability of the AD-Si QDs and the complete dissolution of the SCD-Si QDs during 24 hours of incubation with cells have been demonstrated. This might explain the apparent lower cytotoxicity observed for SCD-Si QDs.

Green synthesis of mesoporous and biodegradable iron silicide nanoparticles for photothermal cancer therapy.

Photothermal nanomaterials have shown great potential for photothermal therapy. In this study, we developed a simple green method of magnesiothermic co-reduction for the synthesis of mesoporous, magnetic and biodegradable iron silicide nanoparticles (FeSi NPs) as applied to photothermal therapy (PTT). Starting from biogenic tabasheer extracted from bamboo and Fe2O3, the resultant FeSi NPs with a much lower band gap exhibited excellent optical absorption with a photothermal conversion efficiency of 76.2%, indicating a good photothermal performance. The weight extinction coefficient was measured to be 13.3 L g-1 cm-1 at 1064 nm (second near-infrared window, NIR-II), which surpassed the performance of other competitive Si-based and Fe-based photothermal agents. Results of the cell viability assay showed that cells could be killed by NIR-II laser irradiation with the synthesized FeSi NPs. In vivo results on mice showed clearly an efficient suppression of tumour growth by photothermal treatment with FeSi NPs. FeSi NPs were found to be biodegradable in simulated body fluids. The results from our work indicate that FeSi NPs are a new class of promising photothermal agents (PTAs) for application in cancer therapy.