Bond-Orbital-Resolved Piezoelectricity in Sp(2)-Hybridized Monolayer Semiconductors

Sp(2)-hybridized monolayer semiconductors (e.g., planar group III-V and IV-IV binary compounds) with inversion symmetry breaking (ISB) display piezoelectricity governed by their σ- and π-bond electrons. Here, we studied their bond-orbital-resolved electronic piezoelectricity (i.e., the σ- and π-piezoelectricity). We formulated a tight-binding piezoelectric model to reveal the different variations of σ- and π-piezoelectricity with the ISB strength ([Formula: see text]). As [Formula: see text] varied from positive to negative, the former decreased continuously, but the latter increased piecewise and jumped at [Formula: see text] due to the criticality of the π-electrons’ ground-state geometry near this quantum phase-transition point. This led to a piezoelectricity predominated by the π-electrons for a small [Formula: see text]. By constructing an analytical model, we clarified the microscopic mechanisms underlying the anomalous π-piezoelectricity and its subtle relations with the valley Hall effect. The validation of our models was justified by applying them to the typical sp(2) monolayers including hexagonal silicon carbide, Boron-X (X = N, P, As, Ab), and a BN-doped graphene superlattice.