Antiferroelectricity in lanthanum doped zirconia without metallic capping layers and post-deposition/-metallization anneals

We report the effects of lanthanum doping/alloying on antiferroelectric (AFE) properties of ZrO₂. Starting with pure ZrO₂, an increase in La doping leads to the narrowing of the AFE double hysteresis loops and an increase in the critical voltage/electric field for AFE → ferroelectric transition. At higher La contents, the polarization-voltage characteristics of doped/alloyed ZrO₂ resemble that of a non-linear dielectric without any discernible AFE-type hysteresis. X-ray diffraction based analysis indicates that the increased La content while preserving the non-polar, parent AFE, tetragonal P4₂/nmc phase leads to a decrease in tetragonality and the (nano-)crystallite size and an increase in the unit cell volume. Furthermore, antiferroelectric behavior is obtained in the as-deposited thin films without requiring any capping metallic layers and post-deposition/-metallization anneals due to which our specific atomic layer deposition system configuration crystallizes and stabilizes the AFE tetragonal phase during growth.