Defect driven flexo-chemical coupling in thin ferroelectric films

TL;DR

This study uses Landau-Ginzburg-Devonshire theory to explore how flexoelectro-chemical coupling influences size effects, phase transitions, and domain structures in thin ferroelectric films with elastic defects, revealing phenomena relevant for device miniaturization.

Contribution

It demonstrates the significant impact of flexo-chemical coupling on ferroelectric properties and phase behavior in defect-laden thin films, including ferroelectricity at ultra-thin scales.

Findings

Strong effect of Vegard stresses and flexoelectric effect on transition temperature and polarization.

Persistence of ferroelectricity below 4 nm thickness and 350 K temperature.

Control of transition temperature maxima via defect type and concentration.

Abstract

Using Landau-Ginzburg-Devonshire theory, we considered the impact of the flexoelectro-chemical coupling on the size effects inpolar properties and phase transitions of thin ferroelectric films with a layer of elastic defects. We investigated a typical case, when defects fill a thin layer below the top film surface with a constant concentration creating an additional gradient of elastic fields. The defective surface of the film is not covered with an electrode, but instead with an ultra-thin layer of ambient screening charges, characterized by a surface screening length. This geometry is typical for the scanning probe piezoelectric force microscopy. Obtained results revealed an unexpectedly strong effect of the joint action of Vegard stresses and flexoelectric effect (shortly flexo-chemical coupling) on the ferroelectric transition temperature, distribution of the spontaneous polarization and elastic fields, domain wall structure and period in thin PbTiO3 films containing a layer of elastic defects. A nontrivial result is the ferroelectricity persisting at film thicknesses below 4 nm, temperatures lower than 350 K and relatively high surface screening length (~0.1 nm). The origin of this phenomenon is the re-building of the domain structure in the film (namely the cross-over from c-domain stripes to a-type closure domains) when its thickness decreases below 4 nm, conditioned by the flexoelectric coupling and facilitated by negative Vegard effect. For positive Vegard effect, thicker films exhibit the appearance of pronounced maxima on the thickness dependence of the transition temperature, whose position and height can be controlled by the defect type and concentration. The revealed features may have important implications for miniaturization of ferroelectric-based devices.