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Metal-semiconductor interfaces are ubiquitous in modern electronics. These quantum-confined interfaces allow for the formation of atomically thin polarizable metals and feature rich optical and optoelectronic phenomena, including plasmon-induced hot-electron transfer from metal to semiconductors. Here, we report on the metal-semiconductor interface formed during the intercalation of zero-valent atomic layers of tin (Sn) between layers of MoS 2 , a van der Waals layered material. We demonstrate that Sn interaction leads to the emergence of gap states within the MoS 2 band gap and to corresponding plasmonic features between 1 and 2 eV (0.6-1.2 μm). The observed stimulation of the photoconductivity, as well as the extension of the spectral response from the visible regime toward the mid-infrared suggests that hot-carrier generation and internal photoemission take place.