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Bismuth ferrite (BiFeO₃) is a multiferroic material that exhibits both ferroelectricity and canted antiferromagnetism at room temperature, making it a unique candidate in the development of electric-field controllable magnetic devices. The magnetic moments in BiFeO₃are arranged into a spin cycloid, resulting in unique magnetic properties which are tied to the ferroelectric order. Previous understanding of this coupling has relied on average, mesoscale measurements. Using nitrogen vacancy-based diamond magnetometry, we observe the magnetic spin cycloid structure of BiFeO₃in real space. This structure is magnetoelectrically coupled through symmetry to the ferroelectric polarization and this relationship is maintained through electric field switching. Through a combination of in-plane and out-of-plane electrical switching, coupled with ab initio studies, we have discovered that the epitaxy from the substrate imposes a magnetoelastic anisotropy on the spin cycloid, which establishes preferred cycloid propagation directions. The energy landscape of the cycloid is shaped by both the ferroelectric degree of freedom and strain-induced anisotropy, restricting the spin spiral propagation vector to changes to specific switching events.

 

There is an increasing desire to utilize complex functional electronic materials such as ferroelectrics in next-generation microelectronics. As new materials are considered or introduced in this capacity, an understanding of how we can process these materials into those devices must be developed. Here, the effect of different fabrication processes on the ferroelectric and related properties of prototypical metal oxide (SrRuO3)/ferroelectric (BaTiO3)/metal oxide (SrRuO3) heterostructures is explored. Two different types of etching processes are studied, namely, wet etching of the top SrRuO3 using a NaIO4 solution and dry etching using an Ar+-ion beam (i.e., ion milling). Polarization-electric-field hysteresis loops for capacitors produced using both methods are compared. For the ion-milling process, it is found that the Ar+ beam can introduce defects into the SrRuO3/BaTiO3/SrRuO3 devices and that the milling depth strongly influences the defect level and can induce a voltage imprint on the function. Realizing that such processing approaches may be necessary, work is performed to ameliorate the imprint of the hysteresis loops via ex situ “healing” of the process-induced defects by annealing the ferroelectric material in a barium-and-oxygen-rich environment via a chemical-vapor-deposition-style process. This work provides a pathway for the nanoscale fabrication of these candidate materials for next-generation memory and logic applications.

 

Understanding the microscopic origin of the superior electromechanical response in relaxor ferroelectrics requires knowledge not only of the atomic-scale formation of polar nanodomains (PNDs) but also the rules governing the arrangements and stimulated response of PNDs over longer distances. Using x-ray coherent nanodiffraction, we show the staggered self-assembly of PNDs into unidirectional mesostructures that we refer to as polar laminates in the relaxor ferroelectric 0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃(PMN-0.32PT). We reveal the highly heterogeneous electric-field–driven responses of intra- and interlaminate PNDs and establish their correlation with the local strain and the nature of the PND walls. Our observations highlight the critical role of hierarchical lattice organizations on macroscopic material properties and provide guiding principles for the understanding and design of relaxors and a wide range of quantum and functional materials.

 

The bulk photovoltaic effect (BPE) has drawn considerable attention due to its ability to generate photovoltages above the bandgap and reports of highly enhanced photovoltaic current when using nanoscale absorbers or nanoscale electrodes, which, however, do not lend themselves to practical, scalable implementation. Herein, it is shown that a strikingly high BPE photoresponse can be achieved in an ordinary thin‐film configuration merely by tuning fundamental ferroelectric properties. Nonmonotonic dependence of the responsivity (R_SC) on the ferroelectric polarization is observed and at the optimal value of the film polarization, a more than three orders of magnitude increase in theR_SCfrom the bulk BaTiO₃value is obtained, reachingR_SCclose to 10⁻² A W⁻¹, the highest value reported to date for the archetypical ferroelectric BaTiO₃films. Results challenge the applicability of standard first‐principles‐based descriptions of BPE to thin films and the inherent weakness of BPE in ferroelectric thin films.

 

Further miniaturization of electronic devices necessitates the introduction of new materials, including piezoelectric thin films, that exhibit electromechanical functionalities without significant degradation in response due to substrate-induced clamping. To identify material systems with superior piezoelectric properties as thin films, simplified and quantitative electromechanical characterization techniques are required. Here, single-beam, laser Doppler vibrometry is used to detect ac electric-field-induced surface displacement in the frequency range 1–100 kHz with low error (around 6% at 10 kHz) and resolution of 0.0003 nm. The technique is used to quantify both electrostriction and piezoelectric responses (surface displacement values <0.05 nm) of various thin films. Requirements for sample geometry and device structures are established and measurement accuracy and resolution are validated against measurements from the literature via synchrotron-based diffraction measurements. A general methodology to measure and extract the piezoelectric coefficients for thin-film samples using finite-element modeling is presented and applied to determine the d33 coefficient and visualize the response in substrate-clamped 50–400-nm-thick PbZr0.52Ti0.48O3 films, especially as compared to bulk versions with the same sample geometry. 

Bismuth ferrite has garnered considerable attention as a promising candidate for magnetoelectric spin-orbit coupled logic-in-memory. As model systems, epitaxial BiFeO₃thin films have typically been deposited at relatively high temperatures (650–800 °C), higher than allowed for direct integration with silicon-CMOS platforms. Here, we circumvent this problem by growing lanthanum-substituted BiFeO₃at 450 °C (which is reasonably compatible with silicon-CMOS integration) on epitaxial BaPb_0.75Bi_0.25O₃electrodes. Notwithstanding the large lattice mismatch between the La-BiFeO₃, BaPb_0.75Bi_0.25O₃, and SrTiO₃(001) substrates, all the layers in the heterostructures are well ordered with a [001] texture. Polarization mapping using atomic resolution STEM imaging and vector mapping established the short-range polarization ordering in the low temperature grown La-BiFeO₃. Current-voltage, pulsed-switching, fatigue, and retention measurements follow the characteristic behavior of high-temperature grown La-BiFeO₃, where SrRuO₃typically serves as the metallic electrode. These results provide a possible route for realizing epitaxial multiferroics on complex-oxide buffer layers at low temperatures and opens the door for potential silicon-CMOS integration.

 

In ferroelectric heterostructures, the interaction between intrinsic polarization and the electric field generates a rich set of localized electrical properties. The local electric field is determined by several connected factors, including the charge distribution of individual unit cells, the interfacial electromechanical boundary conditions, and chemical composition of the interfaces. However, especially in ferroelectric perovskites, a complete description of the local electric field across micro-, nano-, and atomic-length scales is missing. Here, by applying four-dimensional scanning transmission electron microscopy (4D STEM) with multiple probe sizes matching the size of structural features, we directly image the electric field of polarization vortices in (PbTiO3)16/(SrTiO3)16 superlattices and reveal different electric field configurations corresponding to the atomic scale electronic ordering and the nanoscale boundary conditions. The separability of two different fields probed by 4D STEM offers the possibility to reveal how each contributes to the electronic properties of the film.

 

Abstract Complex oxides show a vast range of functional responses, unparalleled within the inorganic solids realm, making them promising materials for applications as varied as next-generation field-effect transistors, spintronic devices, electro-optic modulators, pyroelectric detectors, or oxygen reduction catalysts. Their stability in ambient conditions, chemical versatility, and large susceptibility to minute structural and electronic modifications make them ideal subjects of study to discover emergent phenomena and to generate novel functionalities for next-generation devices. Recent advances in the synthesis of single-crystal, freestanding complex oxide membranes provide an unprecedented opportunity to study these materials in a nearly-ideal system (e.g. free of mechanical/thermal interaction with substrates) as well as expanding the range of tools for tweaking their order parameters (i.e. (anti-)ferromagnetic, (anti-)ferroelectric, ferroelastic), and increasing the possibility of achieving novel heterointegration approaches (including interfacing dissimilar materials) by avoiding the chemical, structural, or thermal constraints in synthesis processes. Here, we review the recent developments in the fabrication and characterization of complex-oxide membranes and discuss their potential for unraveling novel physicochemical phenomena at the nanoscale and for further exploiting their functionalities in technologically relevant devices.