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Abstract Interest in high‐entropy inorganic compounds originates from their ability to stabilize cations and anions in local environments that rarely occur at standard temperature and pressure. This leads to new crystalline phases in many‐cation formulations with structures and properties that depart from conventional trends. The highest‐entropy homogeneous and random solid solution is a parent structure from which a continuum of lower‐entropy offspring can originate by adopting chemical and/or structural order. This report demonstrates how synthesis conditions, thermal history, and elastic and chemical boundary conditions conspire to regulate this process in Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O, during which coherent CuO nanotweeds and spinel nanocuboids evolve. We do so by combining structured synthesis routes, atomic‐resolution microscopy and spectroscopy, density functional theory, and a phase field modeling framework that accurately predicts the emergent structure and local chemistry. This establishes a framework to appreciate, understand, and predict the macrostate spectrum available to a high‐entropy system that is critical to rationalizing property engineering opportunities. 

Abstract Oxygen vacancy is the most common type of point defects in functional oxides, and it is known to have profound influence on their properties. This is particularly true for ferroelectric oxides since their interaction with ferroelectric polarization often dictates the ferroelectric responses. Here, we study the influence of the concentration of oxygen vacancies on the stability of ferroelectric domain walls (DWs) in BiFeO₃, a material with a relatively narrow bandgap among all perovskite oxides, which enables strong interactions among electronic charge carriers, oxygen vacancies, and ferroelectric domains. It is found that the electronic charge carriers in the absence of oxygen vacancies have essentially no influence on the spatial polarization distribution of the DWs due to their low concentrations. Upon increasing the concentration of oxygen vacancies, charge‐neutral DWs with an originally symmetric polarization distribution symmetric around the center of the wall can develop a strong asymmetry of the polarization field, which is mediated by the electrostatic interaction between polarization and electrons from the ionization of oxygen vacancies. Strongly charged head‐to‐head DWs that are unstable without oxygen vacancies can be energetically stabilized in the off‐stoichiometric BiFeO_3−δwithδ∼ 0.02 where ionization of oxygen vacancies provides sufficient free electrons to compensate the bound charge at the wall. Our results delineate the electrostatic coupling of the ionic defects and the associated free electronic charge carriers with the bound charge in the vicinity of neutral and charged DWs in perovskite ferroelectrics. 

Abstract Mott metal–insulator transitions possess electronic, magnetic, and structural degrees of freedom promising next‐generation energy‐efficient electronics. A previously unknown, hierarchically ordered, and anisotropic supercrystal state is reported and its intrinsic formation characterized in‐situ during a Mott transition in a Ca₂RuO₄thin film. Machine learning‐assisted X‐ray nanodiffraction together with cryogenic electron microscopy reveal multi‐scale periodic domain formation at and below the film transition temperature (T_Film ≈ 200–250 K) and a separate anisotropic spatial structure at and aboveT_Film. Local resistivity measurements imply an intrinsic coupling of the supercrystal orientation to the material's anisotropic conductivity. These findings add a new degree of complexity to the physical understanding of Mott transitions, opening opportunities for designing materials with tunable electronic properties. 

Abstract Piezoresponse force microscopy (PFM) is used for investigation of the electromechanical behavior of the head‐to‐head (H‐H) and tail‐to‐tail (T‐T) domain walls on the non‐polar surfaces of three uniaxial ferroelectric materials with different crystal structures: LiNbO₃, Pb₅Ge₃O₁₁, and ErMnO₃. It is shown that, contrary to the common expectation that the domain walls should not exhibit any PFM response on the non‐polar surface, an out‐of‐plane deformation of the crystal at the H‐H and T‐T domain walls occurs even in the absence of the out‐of‐plane polarization component due to a specific form of the piezoelectric tensor. In spite of their different symmetry, in all studied materials, the dominant contribution comes from the counteracting shear strains on both sides of the H‐H and T‐T domain walls. The finite element analysis approach that takes into account a contribution of all elements in the piezoelectric tensor, is applicable to any ferroelectric material and can be instrumental for getting a new insight into the coupling between the electromechanical and electronic properties of the charged ferroelectric domain walls. 

Abstract Ferroelectric domain walls, topological entities separating domains of uniform polarization, are promising candidates as active elements for nanoscale memories. In such applications, controlled nucleation and stabilization of domain walls are critical. Here, using in situ transmission electron microscopy and phase‐field simulations, a controlled nucleation of vertically oriented 109° domain walls in (110)‐oriented BiFeO₃(BFO) thin films is reported. In the switching experiment, reversed domains that are nucleated preferentially at the nanoscale edges of the “crest and sag” pattern‐like electrode under external bias subsequently grow into a stable stripe configuration. In addition, when triangular pockets (with an in‐plane polarization component) are present, these domain walls are pinned to form stable flux‐closure domains. Phase field simulations show that i) field enhancement at the edges of the electrode causes site‐specific domain nucleation, and ii) the local electrostatics at the domain walls drives the formation of flux closure domains, thus stabilizing the striped pattern, irrespective of the initial configuration. The results demonstrate how flux closure pinning can be exploited in conjunction with electrode patterning and substrate orientation to achieve a desired topological defect configuration. These insights constitute critical advancements in exploiting domain walls in next generation ferroelectronic devices. 

Abstract A domain wall‐enabled memristor is created, in thin film lithium niobate capacitors, which shows up to twelve orders of magnitude variation in resistance. Such dramatic changes are caused by the injection of strongly inclined conducting ferroelectric domain walls, which provide conduits for current flow between electrodes. Varying the magnitude of the applied electric‐field pulse, used to induce switching, alters the extent to which polarization reversal occurs; this systematically changes the density of the injected conducting domain walls in the ferroelectric layer and hence the resistivity of the capacitor structure as a whole. Hundreds of distinct conductance states can be produced, with current maxima achieved around the coercive voltage, where domain wall density is greatest, and minima associated with the almost fully switched ferroelectric (few domain walls). Significantly, this “domain wall memristor” demonstrates a plasticity effect: when a succession of voltage pulses of constant magnitude is applied, the resistance changes. Resistance plasticity opens the way for the domain wall memristor to be considered for artificial synapse applications in neuromorphic circuits.