Mobile charged defects, accumulated in the domain-wall region to screen polarization charges, have been proposed as the origin of the electrical conductivity at domain walls in ferroelectric materials. Despite theoretical and experimental efforts, this scenario has not been directly confirmed, leaving a gap in the understanding of the intriguing electrical properties of domain walls. Here, we provide atomic-scale chemical and structural analyses showing the accumulation of charged defects at domain walls in BiFeO. The defects were identified as Fe cations and bismuth vacancies, revealing p-type hopping conduction at domain walls caused by the presence of electron holes associated with Fe. In agreement with the p-type behaviour, we further show that the local domain-wall conductivity can be tailored by controlling the atmosphere during high-temperature annealing. This work has possible implications for engineering local conductivity in ferroelectrics and for devices based on domain walls.

Electrocaloric properties in relaxor ferroelectricElectro-caloric effect in PLZT (8/65/35) ceramic AIP Conf.

The interfaces in complex oxides present unique properties exploitable in nanoscale devices. Recent studies on ferroelectric BiFeO3, BaTiO3, and Pb(Zr,Ti)O3 have revealed an unusually high electric conductivity of the domain walls (DWs), adding another degree of freedom for controlling the local properties of these materials. While most of the investigations are focused on thin films for nanoscale applications, many practical devices, including piezoelectric sensors, actuators, and transducers, rely on the macroscopic properties of bulk polycrystalline materials where the average effect of local properties should be small. It is shown that in polycrystalline BiFeO3 the local domain‐wall conductivity interferes with the dynamics of the DWs within the grains, resulting in an unexpectedly large effect on the macroscopic piezoelectric response. The results thus bridge the local conductivity and the macroscopic piezoelectricity via domain‐wall dynamics, revealing that the domain‐wall conductivity must be considered when interpreting and controlling macroscopic electromechanical properties.

The electrocaloric effect (ECE), i.e., the conversion of electric energy into heat, is of great importance for application in new generation cooling or heating devices that would be friendlier to the environment. Here, utilizing direct measurements of the ECE change of the temperature ΔT via a high resolution calorimeter, we study the ECE as a function of the magnitude of the electric-field step E in the vicinity of the critical point in several bulk relaxor ferroelectric ceramic systems. Relatively large ΔT of ∼2 to 3 K were obtained at modest fields of 90 kV/cm, even in the case of ceramic materials. The effective responsivity ΔT/E as a function of the electric field shows a characteristic peak near the critical point, which demonstrates the importance of proximity to the critical point for the enhancement of the electrocaloric effect. Experimental results are in good agreement with the theoretical calculations based on the spherical random-bond random-field model.

Electromechanical properties such as d33 and strain are significantly enhanced at morphotropic phase boundaries (MPBs) between two or more different crystal structures. Many actuators, sensors and MEMS devices are therefore systems with MPBs, usually between polar phases in lead (Pb)-based ferroelectric ceramics. In the search for Pb-free alternatives, systems with MPBs between polar and non-polar phases have recently been theorized as having great promise. While such an MPB was identified in rare-earth (RE) modified bismuth ferrite (BFO) thin films, synthesis challenges have prevented its realization in ceramics. Overcoming these, we demonstrate a comparable electromechanical response to Pb-based materials at the polar-to-non-polar MPB in Sm modified BFO. This arises from ‘dual’ strain mechanisms: ferroelectric/ferroelastic switching and a previously unreported electric-field induced transition of an anti-polar intermediate phase. We show that intermediate phases play an important role in the macroscopic strain response, and may have potential to enhance electromechanical properties at polar-to-non-polar MPBs.

The energy band alignment at interfaces between different materials is a key factor, which determines the function of electronic devices. While the energy band alignment of conventional semiconductors is quite well understood, systematic experimental studies on oxides are still missing. This work presents an extensive study on the intrinsic energy band alignment of a wide range of functional oxides using photoelectron spectroscopy with in‐situ sample preparation. The studied materials have particular technological importance in diverse fields as solar cells, piezotronics, multiferroics, photo‐electrochemistry and oxide electronics. Particular efforts have been made to verify the validity of transitivity, in order to confirm the intrinsic nature of the obtained band alignment and to understand the underlying principles. Valence band offsets up to 1.6 eV are observed. The large variation of valence band maximum energy can be explained by the different orbital contributions to the density of states in the valence band. The framework provided by this work enables the general understanding and prediction of energy band alignment at oxide interfaces, and furthermore the tailoring of energy level matching for charge transfer in functional oxides. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

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Electro-mechanical interactions between charged point defects and domain walls play a key role in the functional properties of bulk and thin-film ferroelectrics. While for perovskites the macroscopic implications of the ordering degree of defects on domain-wall pinning have been reported, atomistic details of these mechanisms remain unclear. Here, based on atomic and nanoscale analyses, we propose a pinning mechanism associated with conductive domain walls in BiFeO3, whose origin lies in the dynamic coupling of the p-type defects gathered in the domain-wall regions with domain-wall displacements under applied electric field. Moreover, we confirm that the degree of defect ordering at the walls, which affect the domain-wall conductivity, can be tuned by the cooling rate used during the annealing, allowing us to determine how this ordering affects the atomic structure of the walls. The results are useful in the design of the domain-wall architecture and dynamics for emerging nanoelectronic and bulk applications.