Evolution of ultraflat band in the van der Waals kagome semiconductor Pd3P2(S1−xSex)8

Abstract

We investigate the evolutions of structural parameters, optical properties, and electronic structures of a van der Waals kagome semiconductor Pd$_{3}$P$_{2}$S$_{8}$ with Se doping. When the doping level of Se increases, the bandgaps of Pd$_{3}$P$_{2}$(S$_{1-x}$Se$_{x}$)$_{8}$ single crystals decrease gradually, accompanying with the expanded unit cells. The first-principles calculations show that there is a flat band (FB) near the Fermi level in bulk Pd$_{3}$P$_{2}$S$_{8}$. This FB mainly originates from the $d_{z^2}$-like orbitals of Pd atoms in the Pd kagome lattice, which have a finite interlayer electron hopping perpendicular to the PdS$_4$ square plane. The interlayer hopping can be reinforced with Se doping, inducing a stronger interlayer coupling via the chalcogen atoms at apical sites, which reduces the bandgap and enhances the cleavage energy. In contrast, the varnishing interlayer hopping in the two-dimensional limit results in the formation of ultra-FB in the monolayers of these compounds. The easy exfoliation and the existence of unique ultra-FB near $E_{\rm F}$ make Pd$_{3}$P$_{2}$(S$_{1-x}$Se$_{x}$)$_{8}$ a model system to explore the exotic physics of FB in 2D kagome lattice.