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Abstract Since the first isolation of graphene, the importance of van der Waals (vdW) interactions has become increasingly recognized in the burgeoning field of layered materials. In this work, infrared nanoimaging techniques and theoretical modeling are used to unravel the critical role played by interfacial vdW interactions in governing the stability of violet phosphorus (VP)—a recently rediscovered wide bandgap p‐type semiconductor—when exfoliated on different substrates. It is demonstrated that vdW interactions with the underlying substrate can have a profound influence on the stability of exfoliated VP flakes and investigate how these interactions are affected by flake thickness, substrate properties (e.g., substrate hydrophilicity, surface roughness), and the exfoliation process. These findings highlight the key role played by interfacial vdW interactions in governing the stability and physical properties of layered materials, and can be used to guide substrate selection in the preparation and study of this important class of materials. 

Abstract Violet phosphorus (VP) is garnering attention for its appealing physical properties and potential applications in optoelectronics. A comprehensive investigation of the photodegradation and thermal effects of exfoliated VP on SiO₂/Si substrates is presented. The degradation rate of VP is strongly influenced by the wavelength and exposure duration of light. Light illumination of VP above the bandgap leads to faster degradation, attributed to interactions with reactive oxygen species. Power‐dependent photoluminescence (PL) measurements at low temperature (T = 4 K) show neutral exciton (X⁰) and trion (T) intensities linearly increase with excitation power, while the energy difference between peak energies decreases. The T/X⁰spectral weight ratio increases from 0.28 at 300 K to 0.69 at 4 K, suggesting enhanced T formation due to reduced phonon scattering. Temperature‐dependent Raman is used to investigate the phonon properties of VP. Tracking peak positions of 9 Raman modes with temperature, the linear first‐order temperature coefficient is obtained and found to be linear for all modes. The results provide a deeper understanding of VP's degradation behavior and implications for optoelectronic applications. 

Abstract Engineering electronic bandgaps is crucial for applications in information technology, sensing, and renewable energy. Transition metal dichalcogenides (TMDCs) offer a versatile platform for bandgap modulation through alloying, doping, and heterostructure formation. Here, the synthesis of a 2D Mo_xW_1‐xS₂graded alloy is reported, featuring a Mo‐rich center that transitions to W‐rich edges, achieving a tunable bandgap of 1.85 to 1.95 eV when moving from the center to the edge of the flake. Aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy showed the presence of sulfur monovacancy, V_S, whose concentration varied across the graded Mo_xW_1‐xS₂layer as a function of Mo content with the highest value in the Mo‐rich center region. Optical spectroscopy measurements supported by ab initio calculations reveal a doublet electronic state of V_S, which is split due to the spin‐orbit interaction, with energy levels close to the conduction band or deep in the bandgap depending on whether the vacancy is surrounded by W atoms or Mo atoms. This unique electronic configuration of V_Sin the alloy gave rise to four spin‐allowed optical transitions between the V_Slevels and the valence bands. The study demonstrates the potential of defect and optical engineering in 2D monolayers for advanced device applications.