The interest in ferroelectric van der Waals crystals arises from the potential to realize ultrathin ferroic systems owing to the reduced surface energy of these materials and the layered structure that allows for exfoliation. Here, we quantitatively unravel giant negative electrostriction of van der Waals layered copper indium thiophosphate (CIPS), which exhibits an electrostrictive coefficient Q33 as high as -3.2 m 4 /C 2 and a resulting bulk piezoelectric coefficient d33 up to -85 pm/V. As a result, the electromechanical response of CIPS is comparable in magnitude to established perovskite ferroelectrics despite possessing a much smaller spontaneous polarization of only a few µC/cm 2 . In the paraelectric state, readily accessible owing to low transition temperatures, CIPS exhibits large dielectric tunability, similar to widely-used barium strontium titanate, and as a result both giant and continuously tunable electromechanical 3 response. The persistence of electrostrictive and tunable responses in the paraelectric state indicates that even few layer films or nanoparticles will sustain significant electromechanical functionality, offsetting the inevitable suppression of ferroelectric properties in the nanoscale limit. These findings can likely be extended to other ferroelectric transition metal thiophosphates and (quasi-) two-dimensional materials and might facilitate the quest towards novel ultrathin functional devices incorporating electromechanical response.

In the framework of the Landau-Ginzburg-Devonshire (LGD) approach we studied finite size effects of the phase diagram and domain structure evolution in spherical nanoparticles of uniaxial ferroelectric. The particle surface is covered by a layer of screening charge characterized by finite screening length. The phase diagram, calculated in coordinates "particle radius -screening length" has a wide region of versatile poly-domain structures separating single-domain ferroelectric and nonpolar paraelectric phases. Unexpectedly, we revealed a region of stable irregular labyrinthine domains in the nanoparticles of uniaxial ferroelectric CuInP2S6 with the first order paraelectric-ferroelectric phase transition. We established that the origin of labyrinthine domains is the mutual balance of LGD, polarization gradient and electrostatic energies. The branching of the domain walls appears and increases rapidly when the polarization gradient energy decreases below the critical value.Allowing for the generality of LGD approach, we expect that the gradient-induced morphological transition can be the source of labyrinthine domains appearance in many spatially-confined ferroics with long-range order parameter, including relaxors, ferromagnetics, antiferrodistortive materials and materials with incommensurate ferroic phases.

Using Landau-Ginzburg-Devonshire approach, we predict the intrinsic instability of the ferroelectricferroelastic domain walls in the multiferroic BiFeO3 emerging from the interplay between the gradient terms of the antiferrodistortive and ferroelectric order parameters at the walls. These instabilities are the interface analogue of the structural instabilities in the vicinity of phase coexistence in the bulk; and so they do not steam from incomplete polarization screening in thin films or its spatial confinement, electrostrictive or flexoelectric coupling. The effect of BiFeO3 material parameters on the 71 o , 109 o , and 180 o walls is explored, and it is shown that the meandering instability appears at 109 o , and 180 o walls for small gradient energies, and the walls become straight and broaden for higher gradients. In contrast to the 180 o and 109 o domain walls, uncharged 71 o walls are always straight, and their width increases with increasing the tilt gradient coefficient. The wall instability and associated intrinsic meandering provide a new insight into the behavior of morphotropic and relaxor materials, wall pinning, and mechanisms of interactions between order parameter fields and local microstructure.