Origin of Negative Longitudinal Piezoelectric Effect

Piezoelectrics with negative longitudinal piezoelectric coefficients will contract in the direction of an applied electric field. Such piezoelectrics are thought to be rare, but there is no fundamental physics preventing the realization of negative longitudinal piezoelectric effect in a single-phase material. Using first-principles calculations, we demonstrate that several hexagonal $ABC$ ferroelectrics possess significant negative longitudinal piezoelectric effects. The data mining of a first-principles-based database of piezoelectrics reveals that this effect is a general phenomenon. The origin of this unusual piezoelectric response relies on the strong ionic bonds associated with small effective charges and rigid potential energy surfaces. Moreover, ferroelectrics with negative longitudinal piezoelectric coefficients show anomalous pressure-enhanced ferroelectricity. Our results offer design principles to aid the search for new piezoelectrics for novel electromechanical device applications.

Figure 1

Polarization along the $c$ axis ($P_z$) of $ABC$ ferroelectrics as a function of hydrostatic pressure. Materials exhibiting pressure-enhanced ferroelectricity are underscored. The electrical polarization of KMgSb increases with the pressure until 3 GPa. The inset shows the structure of hexagonal $ABC$ ferroelectrics.

Figure 2

(a) Ferroelectric polarization and band gap of LiBeSb as a function of hydrostatic pressure. (b) Electronic band structure and (c) phonon spectrum of LiBeSb in the polar space group $P{6}_{3}mc$ at 85 GPa. The inset shows the Fermi surface near the $\mathrm{\Gamma }$ point.