Corrosion of Late- and Post-Transition Metals into Metal–Organic Chalcogenolates and Implications for Nanodevice Architectures

Abstract

Metal chalcogenide compounds have attracted interest as materials for next-generation semiconductors, catalysts, and device architectures. Hybrid compounds containing both a metal chalcogenide architecture and a supporting organic lattice combine the interesting structural and electronic properties of the material class with a configurable hybrid component that can lead to a wide range of tailorable materials. However, many of the methods available for preparing inorganic coordination polymers in this class require specialized solution-phase chemical preparations that are incompatible with solid-state fabrication techniques. Here, we prepare metal−organic chalcogenolates (MOChas) of copper, indium, lead, and tin from benzeneselenol or benzenethiol directly from the organochalcogen and corresponding metal in a tube furnace at a relatively modest temperature. Scanning electron microscopy and X-ray diffraction confirmed the conversion of the precursors to crystalline MOChas. X-ray photoelectron spectroscopy was used to investigate the chemical bonding for each of the materials and provides insight into the elemental composition of the synthesized compounds. This straightforward approach for preparing crystalline hybrid materials may be generalizable for the preparation of a wide variety of coordination compounds and complexes in form factors useful for subsequent development of device architectures.

Strongly Quantum-Confined Blue-Emitting Excitons in Chemically Configurable Multiquantum Wells

“…The 2D confinement in the multilayered structure results in a large exciton binding energy of about 0.4 eV, allowing clear observation of robust excitons at room temperature, making this family of MOCha materials a promising candidate for exploring and engineering many-body states. For optoelectronic device applications, mithrene features high photoluminescence efficiency, ultrafast exciton radiative dynamics, and structural tunability with the potential to exchange ligands, metal atoms and chalcogen atoms to tailor its properties. ,− As such, the emerging family of easily synthesized, strongly excitonic MOCha materials are promising for optoelectronic devices such as photodetectors, on-chip lasers, ultrafast modulators, and exploration of quantum phenomena such as high-temperature exciton-polariton condensation.…”

Anisotropic 2D excitons unveiled in organic–inorganic quantum wells

“…While few previous studies have investigated such self-assembled hybrid metalorgano-chalcogen coordination networks, 12,13,46,48 the optoelectronic properties of these quantum-confined systems and their potential tunability due to structural design are still largely unexplored. [14][15][16]47 Importantly, due to their structural complexity, ab initio calculations of the excited state properties in these materials, as well as a comprehensive understanding of the relation between the electronic and excitonic properties and the atomic configuration, are lacking. In this study, we use an optical pump detuning of transient absorption spectroscopy 17 to determine an exciton binding energy higher than 380 meV in layered bulk silver benzeneselenolate, which we denote as [AgSePh] N where Ph indicates interlayer phenyl groups.…”

Sterically Invariant Carborane-Based Ligands for the Morphological and Electronic Control of Metal–Organic Chalcogenolate Assemblies

“…The formed structures, more recently referred to as metal-organic chalcogenolate assemblies (MOCHAs, Figure 1a), have shown great promise in the preparation of low-dimensional metal-chalcogenide materials. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] More specifically, some MOCHAs have been synthesized using a biphasic approach from aqueous metal cations (e.g. copper(I) 20 , silver(I) 24 ) layered with chalcogenols (e.g.…”