The integration of metal atoms and clusters in well-defined dielectric cavities is a powerful strategy to impart new properties to them that depend on the size and geometry of the confined space as well as on metal-host electrostatic interactions. Here, we unravel the dependence of the electronic properties of metal clusters on space confinement by studying the ionization potential of silver clusters embedded in four different zeolite environments over a range of silver concentrations. Extensive characterization reveals a strong influence of silver loading and host environment on the cluster ionization potential, which is also correlated to the cluster's optical and structural properties. Through fine-tuning of the zeolite host environment, we demonstrate photoluminescence quantum yields approaching unity. This work extends our understanding of structure-property relationships of small metal clusters and applies this understanding to develop highly photoluminescent materials with potential applications in optoelectronics and bioimaging.
Silica nanoparticles are versatile platforms with many intrinsic features, such as low toxicity. Proper design and derivatization yields particularly stable colloids, even in physiological conditions, and provides them with multiple functions. A suitable choice of dyes and synthetic strategy may, in particular, yield a very bright nanosystem. Silica nanoparticles thus offer unique potential in the nanotechnology arena, and further improvement and optimization could substantially increase their application in fields of high social and economic impact, such as medical diagnostics and therapy, environmental and food analysis, and security. This paper describes silica-based, multicomponent nanosystems with intrinsic directional energy- and electron-transfer processes, on which highly valued functions like light harvesting and signal amplification are based.
Irradiation of 2D sheets of transition metal dichalcogenides with ion beams has emerged as an effective approach to engineer chemically active defects in 2D materials. In this context, argon-ion bombardment has been utilized to introduce sulfur vacancies in monolayer molybdenum disulfide (MoS ). However, a detailed understanding of the effects of generated defects on the functional properties of 2D MoS is still lacking. In this work, the correlation between critical electronic device parameters and the density of sulfur vacancies is systematically investigated through the fabrication and characterization of back-gated monolayer MoS field-effect transistors (FETs) exposed to a variable fluence of low-energy argon ions. The electrical properties of pristine and ion-irradiated FETs can be largely improved/recovered by exposing the devices to vapors of short linear thiolated molecules. Such a solvent-free chemical treatment-carried out strictly under inert atmosphere-rules out secondary healing effects induced by oxygen or oxygen-containing molecules. The results provide a guideline to design monolayer MoS optoelectronic devices with a controlled density of sulfur vacancies, which can be further exploited to introduce ad hoc molecular functionalities by means of thiol chemistry approaches.
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