Dynamic Stabilization of Metastable States in Triple-Well Ferroelectric Sn2 P2 S6.

Polarization dynamics in ferroelectric materials is governed by the effective potential energy landscape of the order parameter. The unique aspect of ferroelectrics compared to many other transitions is the possibility of more than two potential wells, leading to complicated energy landscapes with new fundamental and functional properties. Here, direct dynamic evidence is revealed of a triple-well potential in the metal thiophosphate Sn2 P2 S6 compound using multivariate scanning probe microscopy combined with theoretical simulations. The key finding is that the metastable zero polarization state can be accessed through a gradual switching process and is stabilized over a broad range of electric fields. Simulations confirm that the observed zero polarization state originates from a kinetic stabilization of the nonpolar state of the triple-well, as opposed to domain walls. Dynamically, the triple-well of Sn2 P2 S6 becomes equivalent to antiferroelectric hysteresis loops. Therefore, this material combines the robust and well-defined domain structure of a proper ferroelectric with dynamic hysteresis loops present in antiferroelectrics. Moreover, the triple-well enhances mem-capacitive effects in Sn2 P2 S6 , which are forbidden for ideal double-well ferroelectrics. These findings provide a path to tunable electronic elements for beyond binary high-density computing devices and neuromorphic circuits based on dynamic properties of the triple-well.

Uncovering the mystery of ferroelectricity in zero dimensional nanoparticles.

It is generally accepted that chemically synthesized nanoparticles lose their ferroelectricity (spontaneous polarization) as the particles become smaller. In contrast, ball-milled ferroelectric nanoparticles have an enhanced ferroelectric response at remarkably small sizes (≤10 nm). Although prior theory suggests that surface stress influences ferroelectricity, the source of such a stress and how it physically influences ferroelectricity in zero-dimensional nanoparticles has remained a mystery. In this paper, we demonstrate that the top-down approach of wet ball-milling not only results in fragmented materials on the nanoscale, but it also is responsible for a mechanochemical synthesis of metal carboxylates forming at the nanoparticles' surface. We prove that the presence of such a compound with a particular type of binding mode chemisorbed at the nanoparticles' surface is responsible for producing surface stress. This surface stress results in a stabilization and dramatic enhancement of the spontaneous polarization, which is 5 times greater than that of the bulk material and 650 times greater than what is measured in materials fabricated using standard chemical synthesis techniques. The results of this study have further led to the development of a new process that produces ferroelectric nanoparticles (≤10 nm) with uniform shape and size using a combination of wet chemistry and mechanochemical synthesis.

Molecular catalysis at polarized interfaces created by ferroelectric BaTiO3.

The local environment at polarized solid-liquid interfaces provides a unique medium for chemical reactions that could be exploited to control the selectivity of non-faradaic reactions. Polarized interfaces are commonly prepared by applying a voltage to an electrode in an electrolyte solution, but it is challenging to achieve high surface charge densities while suppressing faradaic reactions. Ferroelectric materials have permanent surface charge densities that arise from the dipole moments of ferroelectric domains and can be used to create polarized solid-liquid interfaces without applying a voltage. We studied the effects of ferroelectric oxides on the selectivity of a Rh porphyrin-catalyzed carbene rearrangement. The addition of ferroelectric BaTiO3 nanoparticles to the reaction solution changed the product ratio in the same direction and by a similar magnitude as performing the reaction at an electrode-electrolyte interface polarized by a voltage. The results demonstrate that colloidal suspensions of BaTiO3 nanoparticles act as a dispersible polarized interface that can influence the selectivity of non-faradaic reactions.