Anomalous Motion of Charged Domain Walls and Associated Negative Capacitance in Copper-Chlorine Boracite.

During switching, the microstructure of a ferroelectric normally adapts to align internal dipoles with external electric fields. Favorably oriented dipolar regions (domains) grow at the expense of those in unfavorable orientations and this is manifested in a predictable field-induced motion of the walls that separate one domain from the next. Here, the discovery that specific charged 90°domain walls in copper-chlorine boracite move in the opposite direction to that expected, increasing the size of the domain in which polarization is anti-aligned with the applied field, is reported. Polarization-field (P-E) hysteresis loops, inferred from optical imaging, show negative gradients and non-transient negative capacitance, throughout the P-E cycle. Switching currents (generated by the relative motion between domain walls and sensing electrodes) confirm this, insofar as their signs are opposite to those expected conventionally. For any given bias, the integrated switching charge due to this anomalous wall motion is directly proportional to time, indicating that the magnitude of the negative capacitance component should be inversely related to frequency. This passes Jonscher's test for the misinterpretation of positive inductance and gives confidence that field-induced motion of these specific charged domain walls generates a measurable negative capacitance contribution to the overall dielectric response.

Elastic distortion determining conduction in BiFeO3 phase boundaries.

It is now well-established that boundaries separating tetragonal-like (T) and rhombohedral-like (R) phases in BiFeO3 thin films can show enhanced electrical conductivity. However, the origin of this conductivity remains elusive. Here, we study mixed-phase BiFeO3 thin films, where local populations of T and R can be readily altered using stress and electric fields. We observe that phase boundary electrical conductivity in regions which have undergone stress-writing is significantly greater than in the virgin microstructure. We use high-end electron microscopy techniques to identify key differences between the R-T boundaries present in stress-written and as-grown microstructures, to gain a better understanding of the mechanism responsible for electrical conduction. We find that point defects (and associated mixed valence states) are present in both electrically conducting and non-conducting regions; crucially, in both cases, the spatial distribution of defects is relatively homogeneous: there is no evidence of phase boundary defect aggregation. Atomic resolution imaging reveals that the only significant difference between non-conducting and conducting boundaries is the elastic distortion evident - detailed analysis of localised crystallography shows that the strain accommodation across the R-T boundaries is much more extensive in stress-written than in as-grown microstructures; this has a substantial effect on the straightening of local bonds within regions seen to electrically conduct. This work therefore offers distinct evidence that the elastic distortion is more important than point defect accumulation in determining the phase boundary conduction properties in mixed-phase BiFeO3.