Accurate Assessments of the Electronic Structures of Ultrathin PtSe₂: Bandgap Quantification and Critical Thickness for the Metal–Semiconductor Transition

Ultrathin PtSe₂, a member of the group-10 transition metal dichalcogenides, has emerged as a promising two-dimensional material due to its layer-dependent, tunable bandgap. Notably, a unique semiconductor-to-metal transition is predicted as the layer number of this material increases; however, pinpointing the exact critical thickness for this transition and reliably quantifying the energy gaps of the semiconducting layers remain formidable challenges. In this work, all-van der Waals assembled multiprobe schemes and planar tunnel junctions are employed to systematically investigate the thickness-sensitive charge transport properties and energy gaps of ultrathin PtSe₂ films. Temperature-dependent measurements reveal that PtSe₂ exhibits semiconducting behavior from monolayer to five layers, with a transition to a semimetallic state at six layers. Furthermore, using electron tunneling spectroscopy, we accurately quantify the energy gaps of monolayer, bilayer, and trilayer PtSe₂ and identifies that PtSe₂ in monolayer form behaves as an n-type semiconductor but intriguingly transitions to a p-type semiconductor in bilayer form. First-principles calculations highlight the importance of correctly evaluating interlayer distances to select the appropriate density functional theory functional, enabling reliable predictions of the critical thickness of ultrathin PtSe₂ for the semiconductor-to-metal transition and corresponding electronic structures.