Abstract
Using first-principles calculations we model the out-of-plane switching of local dipoles in CuInP2S6 (CIPS) that are largely induced by Cu off-centering. Previously, a coherent switching of polarization via a quadruple-well potential was proposed for these materials. In the supercells we considered, we find multiple structures with similar energies but with different local polar order. Our results suggest that the individual dipoles are weakly coupled in-plane, and under an electric field at very low temperatures these dipoles in CIPS should undergo incoherent disordered switching. The barrier for switching is determined by the single Cu-ion switching barrier. This in turn suggests a scale-free polarization with a switching barrier of ∼203.6–258.0 meV, a factor of five smaller than that of HfO2 (1380 meV), a prototypical scale-free ferroelectric. The mechanism of polarization switching in CIPS is mediated by the switching of each weakly interacting dipole rather than the macroscopic polarization itself as previously hypothesized. These findings reconcile prior observations of a quadruple well with sloping hysteresis loops, large ionic conductivity even at 250 K, well below the Curie temperature (315 K), and a significant wake-up effect where the macroscopic polarization is slow to order and sets in under an applied electric field. We also find that computed piezoelectric response and the polarization show a linear dependence on the local dipolar order. This is consistent with having scale-free polarization and other polarization-dependent properties and opens doors for engineering tunable metastability by design in CIPS (and related families of materials) for neuromorphic applications.
