First-principles studies of spontaneous polarization in mixed poly(vinylidene fluoride)/2,3,3,3-tetrafluoropropene polymer crystals.

Spontaneous polarization P of mixed polymer crystals based on ß poly(vinylidene fluoride) (PVDF, -CH2-CF2-) and 2,3,3,3-tetrafluoropropene (TFP, -CH2-CF(CF3)-) was evaluated for ß-PVDF/iso-PTFP, ß-PVDF/P(VDF-alt-iso-TFP) and ß-PVDF/syndio-PTFP. A plane-wave-based density-functional theory (DFT) approach, combined with the Modern Theory of Polarization formalism utilizing maximally-localized Wannier functions for calculating P, indicates that all systems exhibit similarly high or even slightly larger polarization than that of perfectly crystalline ß-PVDF (0.18 C m-2). These properties stem from the substantial dipole moment of the TFP unit, which is estimated to be ∼2.3 D in an isolated chain, but is enhanced to ∼2.8 D in the crystal.

The stabilization of a single domain in free-standing ferroelectric nanocrystals.

High resolution electron microscopy, electron diffraction and electron holography were used to study individual free-standing ∼ 30 nm barium titanate nanocrystals. Large unidirectional variations in the tetragonal distortion were mapped across the smaller nanocrystals, peaking to anomalously large values of up to 4% at the centers of the nanocrystals. This indicated that the nanocrystals consist of highly strained single ferroelectric domains. Simulations using an effective Hamiltonian for modeling a nanocrystal under a small depolarizing field and negative pressure qualitatively confirm this picture. These simulations, along with the development of a phenomenological model, show that the tetragonal distortion variation is a combined effect of: (i) electrostrictive coupling between the spontaneous polarization and strain inside the nanocrystal, and (ii) a surface-induced effective stress existing inside the nanodot. As a result, a 'strain skin layer', having a smaller tetragonal distortion relative to the core of the nanocrystal, is created.

Novel complex phenomena in ferroelectric nanocomposites.

A first-principles-based effective Hamiltonian is used to investigate finite-temperature properties of ferroelectric nanocomposites made of periodic arrays of ferroelectric nanowires embedded in a matrix formed by another ferroelectric material. Novel transitions and features related to flux-closure configurations are found. Examples include (i) a vortex core transition, that is characterized by the change of the vortex cores from being axisymmetric to exhibiting a 'broken symmetry'; (ii) translational mode of the vortex cores; (iii) striking zigzag dipolar chains along the vortex core axis; and (iv) phase-locking of ferroelectric vortices accompanied by ferroelectric antivortices. These complex phenomena are all found to coexist with a spontaneous electrical polarization aligned along the normal of the plane containing the vortices.