Structure and energetics of ferroelectric domain walls in LiNbO3 from atomic-level simulations

Atomistic simulations with empirical potentials and density-functional theory calculations are used to characterize the structure, energetics, and ferroelectric properties of domain walls in LiNbO3. The two methods yield similar polarization patterns and atomic structures at the domain walls. The structure of the domain wall on the mixed anion-cation planes is very different from that of the domain wall on planes of alternating cations and anions. The breaking of the uniaxial symmetry of the ferroelectric phase by the domain walls leads to nonuniaxial contributions to the polarization in the domain-wall region. In particular, a polarization component parallel to the domain walls leads to a Bloch-type rotation while a polarization component normal to the domain walls leads to Neel-type rotation. The polarization profiles at the domain walls are fitted to Ginzburg-Landau-Devonshire theory. The comparison of energetics at equilibrium and at transition states yields estimates of the energy barrier heights for domain-wall motion.