Frustrated Lewis Pair Adduct of Atomic P(-1) as a Source of Phosphinidenes (PR), Diphosphorus (P2 ), and Indium Phosphide.

We report phosphinidenes (PR) stabilized by an intramolecular frustrated Lewis pair (FLP) chelate. These adducts include the parent phosphinidene, PH, which is accessed via thermolysis of coordinated HPCO. The reported FLP-PH species acts as a springboard to other phosphorus-containing compounds, such as FLP-adducts of diphosphorus (P2 ) and InP3 . Our new adducts participate in thermal- or light-induced phosphinidene elimination (of both PH and PR, R=organic group), transfer P2 units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution.

Molecular Sn(II) precursors for room temperature deposition of crystalline elemental tin.

We report mild routes for the deposition of crystalline films of elemental tin via the formation and subsequent decomposition of unstable tin(II) hydrides. Specifically, we take advantage of efficient OtBu/H metathesis involving Sn(II) alkoxide precursors and the hydride source pinacolborane (HBpin); related -N(SiMe3)2/H exchange also afforded elemental tin as a final (insoluble) product.

Facile synthesis of high-entropy alloy nanoparticles on germanane, Ge nanoparticles and wafers.

The unique solid-solution structure and multi-element compositions of high-entropy alloy nanoparticles (HEA NPs) have garnered substantial attention. Various methods have been developed to prepare a diverse array of HEA NPs using different substrates for support and stabilization. In this study, we present a facile surface-mediated reduction method to prepare HEA NPs (AuAgCuPdPt) decorated germanane (HEA NPs@GeNSs), and employ X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) to characterize their structure, composition, and morphology. Subsequently, we demonstrate that the HEA NPs can be liberated from the surfaces of GeNSs as freestanding systems via straightforward exposure to UV light. We also explore germanium nanoparticles (GeNPs) as an alternative substrate for HEA NP formation/production, given their similarity to germanane and their Ge-H surface. Finally, we extend our investigation to bulk Ge wafers and demonstrate successful deposition of HEA NPs.

Understanding silicon monoxide gas evolution from mixed silicon and silica powders.

Silicon on silica materials are ubiquitous in 21st century technology. From nanoparticles to integrated circuits, these systems are integral for modern semiconductor fabrication. While the Si-SiO2 interface is often (incorrectly) presumed to be stable, the direct reduction of silica by silicon is possible at high temperatures, resulting in the evolution of silicon monoxide (SiO) gas. Under appropriate conditions, this somewhat unexpected reaction can complicate solid state nanomaterial syntheses by etching away the desired products. This report describes an investigation into the SiO evolution reaction by interrogation of powdered Si-SiO2 mixtures before and after thermal treatment. The impacts of processing temperature, time, and sample composition are examined and discussed. Of particular importance, this investigation reveals the underappreciated role of silica crystallinity (cristobalite) in this solid-state reaction under comparatively low temperature conditions (ca. 1200 °C). With an improved understanding of SiO evolution, we hope to inspire new creative pathways for Si-SiO2 interface manipulation.