Photothermionic Effect-Assisted Ultrafast Charge Transfer in NbS₂/MoS₂ Heterostructure

Two-dimensional (2D) van der Waals heterostructures (vdW HSs) composed of transition metal dichalcogenides (TMDCs) have emerged as frontrunners in the optoelectronics field, owing to their exceptional optical and electrical properties. Recent research on the intrinsic interlayer charge transfer mechanism has been primarily focused on the Type II HSs, while metal–semiconductor (MS) vertical HSs, promising for advancing photodetector technology, have received comparatively less attention. Here, we reveal the first experimental observation of photothermionic effect-assisted ultrafast interlayer charge transfer in the NbS 2 /MoS 2 heterostructure using femtosecond transient absorption technology and first-principles calculations, effectively ignoring the Schottky barrier height. We demonstrate that within 500 fs, charge transfer occurs from NbS 2 to MoS 2 in the heterostructure, resulting in supplementary carrier generation in the visible spectrum when excited with infrared light below the MoS 2 bandgap, at wavelengths of 1030 and 1500 nm. Such promising characteristics of 2D NbS 2 -semiconductor heterostructures offer a potential platform for synergistically combining low contact resistance with broadband photocarrier generation, marking a significant advancement in optoelectronics and light harvesting.