Order–disorder, ferroelasticity and mobility of domain walls in multiferroic Cu–Cl boracite

Abstract

Abstract Domain walls in Cu–Cl boracite develop as a consequence of an improper ferroelastic, improper ferroelectric transition, and have attracted close interest because some are conductive and all can be mechanically written and repositioned by application of an electric field. The phase transition and its associated dynamical properties have been analysed here from the perspective of strain and elasticity. Determination of spontaneous strains from published lattice parameter data has allowed the equilibrium long-range order parameter for F 4 ̄ 3c → Pca21 to be modelled simply as being close to the order–disorder limit. High acoustic loss in the cubic phase, revealed by resonant ultrasound spectroscopy, is consistent with the presence of dynamical microdomains of the orthorhombic structure with relaxation times in the vicinity of ∼10−5–10−6 s. Low acoustic loss in the stability field of the orthorhombic structure signifies, on the other hand, that ferroelastic twin walls which develop as a consequence of the order–disorder process are immobile on this time scale. A Debye loss peak accompanied by ∼1% elastic stiffening at ∼40 K is indicative of some freezing of defects which couple with strain or of some more intrinsic freezing process. The activation energy of ⩾∼0.01–0.02 eV implies a mechanism which could involve strain relaxation clouds around local ferroelectric dipoles or freezing of polarons that determine the conductivity of twin walls.