Phase competition and negative piezoelectricity in interlayer-sliding ferroelectric ZrI2

The so-called interlayer-sliding ferroelectricity was recently proposed as an unconventional route to pursuit electric polarity in van der Waals multi-layers, which was already experimentally confirmed in WTe$_2$ bilayer even though it is metallic. Very recently, another van der Waals system, i.e., the ZrI$_2$ bilayer, was predicted to exhibit the interlayer-sliding ferroelectricity with both in-plane and out-of-plane polarizations [Phys. Rev. B \textbf{103}, 165420 (2021)]. Here the ZrI$_2$ bulk is studied, which owns two competitive phases ($\alpha$ \textit{vs} $\beta$), both of which are derived from the common parent $s$-phase. The $\beta$-ZrI$_2$ owns a considerable out-of-plane polarization ($0.39$ $\mu$C/cm$^2$), while its in-plane component is fully compensated. Their proximate energies provide the opportunity to tune the ground state phase by moderate hydrostatic pressure and uniaxial strain. Furthermore, the negative longitudinal piezoelectricity in $\beta$-ZrI$_2$ is dominantly contributed by the enhanced dipole of ZrI$_2$ layers as a unique characteristic of interlayer-sliding ferroelectricity, which is different from many other layered ferroelectrics with negative longitudinal piezoelectricity like CuInP$_2$S$_6$.