Bandgap Shrinkage and Charge Transfer in 2D Layered SnS2 Doped with V for Photocatalytic Efficiency Improvement

Abstract

Effects of electronic and atomic structures of V-doped 2D layered SnS₂ are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS₂ layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS₂ is ≈4⁺ but also the charge transfer (CT) from V to ligands, supported by V L_α,β resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS₂ . Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS₂ compare to pristine SnS₂ and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS₂ .

Keywords: V-doped 2D layered SnS 2; X-ray absorption; band-gap shrinkage; charge transfer; density functional theory; resonant inelastic X-ray scattering.