Cross‐Substitution Promoted Ultrawide Bandgap up to 4.5 eV in a 2D Semiconductor: Gallium Thiophosphate

Exploring 2D ultrawide bandgap semiconductors (UWBSs) will be conductive to the development of next-generation nanodevices, such as deep-ultraviolet photodetectors, single-photon emitters, and high-power flexible electronic devices. However, a gap still remains between the theoretical prediction of novel 2D UWBSs and the experimental realization of the corresponding materials. The cross-substitution process is an effective way to construct novel semiconductors with the favorable parent characteristics (e.g., structure) and the better physicochemical properties (e.g., bandgap). Herein, a simple case is offered for rational design and syntheses of 2D UWBS GaPS₄ by employing state-of-the-art GeS₂ as a similar structural model. Benefiting from the cosubstitution of Ge with lighter Ga and P, the GaPS₄ crystals exhibit sharply enlarged optical bandgaps (few-layer: 3.94 eV and monolayer: 4.50 eV) and superior detection performances with high responsivity (4.89 A W^-1 ), high detectivity (1.98 × 10¹² Jones), and high quantum efficiency (2.39 × 10³ %) in the solar-blind ultraviolet region. Moreover, the GaPS₄ -based photodetector exhibits polarization-sensitive photoresponse with a linear dichroic ratio of 1.85 at 254 nm, benefitting from its in-plane structural anisotropy. These results provide a pathway for the discovery and fabrication of 2D UWBS anisotropic materials, which become promising candidates for future solar-blind ultraviolet and polarization-sensitive sensors.