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A broad family of the nowadays studied low-dimensional systems, including 2D materials, demonstrate many fascinating properties, which however depend on the atomic composition as well as on the system dimensionality. Therefore, the studies of the electronic correlation effects in the new 2D materials is of paramount importance for the understanding of their transport, optical and catalytic properties. Here, by means of electron spectroscopy methods in combination with density functional theory calculations we investigate the electronic structure of a new layered van der Waals    $$\hbox {FePX}_3$$  FePX 3 (X: S, Se) materials. Using systematic resonant photoelectron spectroscopy studies we observed strong resonant behavior for the peaks associated with the    $$3d^{n-1}$$  3 d n - 1 final state at low binding energies for these materials. Such observations clearly assign    $$\hbox {FePX}_3$$  FePX 3 to the class of Mott–Hubbard type insulators for which the top of the valence band is formed by the hybrid Fe-S/Se electronic states. These observations are important for the deep understanding of this new class of materials and draw perspectives for their further applications in different application areas, like (opto)spintronics and catalysis.

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Mott–Hubbard insulating state for the layered van der Waals $$\hbox {FePX}_3$$ (X: S, Se) as revealed by NEXAFS and resonant photoelectron spectroscopy