1D Hybrid Semiconductor Silver 2,6-Difluorophenylselenolate.

Organic-inorganic hybrid materials present new opportunities for creating low-dimensional structures with unique light-matter interaction. In this work, we report a chemically robust yellow emissive one-dimensional (1D) semiconductor, silver 2,6-difluorophenylselenolate─AgSePhF2(2,6), a new member of the broader class of hybrid low-dimensional semiconductors, metal-organic chalcogenolates. While silver phenylselenolate (AgSePh) crystallizes as a two-dimensional (2D) van der Waals semiconductor, introduction of fluorine atoms at the (2,6) position of the phenyl ring induces a structural transition from 2D sheets to 1D chains. Density functional theory calculations reveal that AgSePhF2 (2,6) has strongly dispersive conduction and valence bands along the 1D crystal axis. Visible photoluminescence centered around λp ≈ 570 nm at room temperature exhibits both prompt (110 ps) and delayed (36 ns) components. The absorption spectrum exhibits excitonic resonances characteristic of low-dimensional hybrid semiconductors, with an exciton binding energy of approximately 170 meV as determined by temperature-dependent photoluminescence. The discovery of an emissive 1D silver organoselenolate highlights the structural and compositional richness of the chalcogenolate material family and provides new insights for molecular engineering of low-dimensional hybrid organic-inorganic semiconductors.

Size and Quality Enhancement of 2D Semiconducting Metal-Organic Chalcogenolates by Amine Addition.

The use of two-dimensional (2D) materials in next-generation technologies is often limited by small lateral size and/or crystal defects. Here, we introduce a simple chemical strategy to improve the size and overall quality of 2D metal-organic chalcogenolates (MOCs), a new class of hybrid organic-inorganic 2D semiconductors that can exhibit in-plane anisotropy and blue luminescence. By inducing the formation of silver-amine complexes during a solution growth method, we increase the average size of silver phenylselenolate (AgSePh) microcrystals from <5 µm to >1 mm, while simultaneously extending the photoluminescence lifetime and suppressing mid-gap emission. Mechanistic studies using 77Se NMR suggest dual roles for the amine in promoting the formation of a key reactive intermediate and slowing down the final conversion to AgSePh. Finally, we show that amine addition is generalizable to the synthesis of other 2D MOCs, as demonstrated by the growth of single crystals of silver 4-methylphenylselenolate (AgSePhMe), a novel member of the 2D MOC family.

Light Emission in 2D Silver Phenylchalcogenolates.

Silver phenylselenolate (AgSePh, also known as "mithrene") and silver phenyltellurolate (AgTePh, also known as "tethrene") are two-dimensional (2D) van der Waals semiconductors belonging to an emerging class of hybrid organic-inorganic materials called metal-organic chalcogenolates. Despite having the same crystal structure, AgSePh and AgTePh exhibit a strikingly different excitonic behavior. Whereas AgSePh exhibits narrow, fast luminescence with a minimal Stokes shift, AgTePh exhibits comparatively slow luminescence that is significantly broadened and red-shifted from its absorption minimum. Using time-resolved and temperature-dependent absorption and emission microspectroscopy, combined with subgap photoexcitation studies, we show that exciton dynamics in AgTePh films are dominated by an intrinsic self-trapping behavior, whereas dynamics in AgSePh films are dominated by the interaction of band-edge excitons with a finite number of extrinsic defect/trap states. Density functional theory calculations reveal that AgSePh has simple parabolic band edges with a direct gap at Γ, whereas AgTePh has a saddle point at Γ with a horizontal splitting along the Γ-N1 direction. The correlation between the unique band structure of AgTePh and exciton self-trapping behavior is unclear, prompting further exploration of excitonic phenomena in this emerging class of hybrid 2D semiconductors.

Morphological Control of 2D Hybrid Organic-Inorganic Semiconductor AgSePh.

Silver phenylselenolate (AgSePh) is a hybrid organic-inorganic two-dimensional (2D) semiconductor exhibiting narrow blue emission, in-plane anisotropy, and large exciton binding energy. Here, we show that the addition of carefully chosen solvent vapors during the chemical transformation of metallic silver to AgSePh allows for control over the size and orientation of AgSePh crystals. By testing 28 solvent vapors (with different polarities, boiling points, and functional groups), we controlled the resulting crystal size from <200 nm up to a few µm. Furthermore, choice of solvent vapor can substantially improve the orientational homogeneity of 2D crystals with respect to the substrate. In particular, solvents known to form complexes with silver ions, such as dimethyl sulfoxide (DMSO), led to the largest lateral crystal dimensions and parallel crystal orientation. We perform systematic optical and electrical characterizations on DMSO vapor-grown AgSePh films demonstrating improved crystalline quality, lower defect densities, higher photoconductivity, lower dark conductivity, suppression of ionic migration, and reduced midgap photoluminescence at low temperature. Overall, this work provides a strategy for realizing AgSePh films with improved optical properties and reveals the roles of solvent vapors on the chemical transformation of metallic silver.