Understanding and manipulating complex spin texture in multiferroics can offer new perspectives for electric field-controlled spin manipulation. In BiFeO 3 , a well-known room temperature multiferroic, the competition between various exchange interactions manifests itself as non-collinear spin order, i.e., an incommensurate spin cycloid with period 64 nm. We report on the stability and systematic expansion of the length of the spin cycloid in (110)-oriented epitaxial Co-doped BiFeO 3 thin films. Neutron diffraction shows (i) this cycloid, despite its partly out-of-plane canted propagation vector, can be stabilized in thinnest films; (ii) the cycloid length expands significantly with decreasing film thickness; (iii) theory confirms a unique [112] cycloid propagation direction; and (iv) in the temperature dependence the cycloid length expands significantly close to T N. These observations are supported by Monte Carlo simulations based on a first-principles effective Hamiltonian method. Our results therefore offer new opportunities for nanoscale magnonic devices based on complex spin textures.

Piezoelectrics interconvert mechanical energy and electric charge and are widely used in actuators and sensors. The best performing materials are ferroelectrics at a morphotropic phase boundary (MPB), where several phases can intimately coexist. Switching between these phases by electric field produces a large electromechanical response. In the ferroelectric BiFeO3, strain can be used to create an MPB-like phase mixture and thus to generate large electric field dependent strains. However, this enhanced response occurs at localized, randomly positioned regions of the film, which potentially complicates nanodevice design. Here, we use epitaxial strain and orientation engineering in tandem -anisotropic epitaxy -to craft a hitherto unavailable low-symmetry phase of BiFeO3 which acts as a structural bridge between the rhombohedral-like and tetragonal-like polymorphs. Interferometric displacement sensor measurements and first-principle calculations reveal that under external electric bias, this phase undergoes a transition to the tetragonal-like polymorph, generating a piezoelectric response enhanced by over 200%, and associated giant field-induced reversible strain. These results offer a new route to engineer giant electromechanical properties in thin films, with broader perspectives for other functional oxide systems.

Domain switching pathways fundamentally control performance in ferroelectric thin film devices. In epitaxial bismuth ferrite (BiFeO 3 ) films, the domain morphology is known to influence the multiferroic orders. While both striped and mosaic domains have been observed, the origins of the latter have remained unclear. Here, it is shown that domain morphology is defined by the strain profile across the film-substrate interface. In samples with mosaic domains, X-ray diffraction analysis reveals strong strain gradients, while geometric phase analysis using scanning transmission electron microscopy finds that within 5 nm of the film-substrate interface, the out-of-plane strain shows an anomalous dip while the in-plane strain is constant. Conversely, if uniform strain is maintained across the interface with zero strain gradient, striped domains are formed. Critically, an ex situ thermal treatment, which eliminates the interfacial strain gradient, converts the domains from mosaic to striped. The antiferromagnetic state of the BiFeO 3 is also influenced by the domain structure, whereby the mosaic domains disrupt the long-range spin cycloid. This work demonstrates that atomic scale tuning of interfacial strain gradients is a powerful route to manipulate the global multiferroic orders in epitaxial films.

Bismuth ferrite (BiFeO3) is one of the most widely studied multiferroics. The coexistence of ferroelectricity and antiferromagnetism in this compound has driven an intense search for electric‐field control of the magnetic order. Such efforts require a complete understanding of the various exchange interactions that underpin the magnetic behavior. An important characteristic of BiFeO3 is its noncollinear magnetic order; namely, a long‐period incommensurate spin cycloid. Here, the progress in understanding this fascinating aspect of BiFeO3 is reviewed, with a focus on epitaxial films. The advances made in developing the theory used to capture the complexities of the cycloid are first chronicled, followed by a description of the various experimental techniques employed to probe the magnetic order. To help the reader fully grasp the nuances associated with thin films, a detailed description of the spin cycloid in the bulk is provided. The effects of various perturbations on the cycloid are then described: magnetic and electric fields, doping, epitaxial strain, finite size effects, and temperature. To conclude, an outlook on possible device applications exploiting noncollinear magnetism in BiFeO3 films is presented. It is hoped that this work will act as a comprehensive experimentalist's guide to the spin cycloid in BiFeO3 thin films.

BiFeO 3 thin films have attracted considerable attention by virtue of their potential application in low-energy spintronic and magnonic devices. BiFeO 3 possesses an intricate magnetic structure, characterized by a spin cycloid with period $62 nm that governs the functional magnonic response, and which can be modulated or even destroyed by strain, magnetic and electric fields, or chemical doping. The literature on (110)-oriented BiFeO 3 films is not explicit in defining the conditions under which this cycloid persists, as its presence depends on synthesis method and thin-film boundary conditions, especially in the sub-100 nm thickness regime. This report aims to end "trial and error" approaches in determining the conditions under which this cycloid and its associated functional magnonic response exist. We show that in specific crystallographic orientations of epitaxial BiFeO 3 , an unexplored strain parameter-the distortion in the ab plane of the monoclinic unit cell-significantly influences the spin structure. Combining M€ ossbauer spectroscopy and low-energy Raman spectroscopy with first-principles-based effective Hamiltonian calculations, we show that both average strain and this distortion destroy the cycloid. For films grown on (110)-oriented SrTiO 3 substrates, if the BiFeO 3 lattice parameters a and b differ by more than about 1.2%, the cycloid is destabilized, resulting in a pseudocollinear magnetic order ground state. We are thereby able to construct a phase diagram of the spin structure for nanoscale epitaxial BiFeO 3 films, which aims to resolve long-standing literature inconsistencies and provide powerful guidelines for the design of future magnonic and spintronic devices.

The interaction between superconductivity and magnetism in spatially confined heterostructures of thin film multilayers is investigated in the ferromagnetic manganite La2/3Ca1/3MnO3 (LCMO) and the high-temperature superconductor YBa2Cu3O7-δ (YBCO) mediated by an intermediate insulating SrTiO3 (STO) layer. The STO layer is used to mediate and tune the range of interactions between the ferromagnet and superconductor. A magnetically depleted layer with zero-magnetisation within the LCMO layer is shown by polarised neutron reflectometry measurements. This zero-magnetisation layer is caused by the onset of superconductivity in YBCO despite being separated by an insulating layer with a thickness much larger than the superconducting coherence length. The magnetic field dependence of this interaction is also explored. We show that the magnetism of the depleted layer can be restored by applying a magnetic field that partially destroys the superconductivity in YBCO, restricting the electronic interaction between the materials.

Topological defects in ferroelectric materials have attracted much attention due to the emergence of conductive, ferroic, and magnetic functionalities. However, many topological configurations dynamically evolve during the switching processes, making them a challenge to characterize via traditional techniques. Here, we implement an automated experimentation approach for the exploration of functional properties in BiFeO3 thin films. Specifically, we visualize the ferroelectric domain structures via single frequency piezoresponse force microscopy and implement a computer vision-based algorithm to discover features of interest at which spectroscopic measurements are taken. Subsequently, we employ dimensionality reduction techniques to reveal characteristic polarization behaviors at these features. This approach can be extended to other spectroscopies and modalities to probe only specific features of interest, ultimately enabling dynamical processes in ferroelectrics to be studied.

Multi-dimensional spectral-imaging is a mainstay of the scanning probe and electron microscopies, micro-Raman, and various forms of chemical imaging. In many cases, individual spectra can be fit to a specific functional form, with the model parameter maps, providing direct insight into material properties. Since spectra are often acquired across a spatial grid of points, spatially adjacent spectra are likely to be similar to one another; yet, this fact is almost never used when considering parameter estimation for functional fits. On datasets tried here, we show that by utilizing proximal information, whether it be in the spatial or spectral domains, it is possible to improve the reliability and increase the speed of such functional fits by ∼2–3×, as compared to random priors. We explore and compare three distinct new methods: (a) spatially averaging neighborhood spectra, and propagating priors based on functional fits to the averaged case, (b) hierarchical clustering-based methods where spectra are grouped hierarchically based on response, with the priors propagated progressively down the hierarchy, and (c) regular clustering without hierarchical methods with priors propagated from fits to cluster means. Our results highlight that utilizing spatial and spectral neighborhood information is often critical for accurate parameter estimation in noisy environments, which we show for ferroelectric hysteresis loops acquired on a prototypical PbTiO3 thin film with piezoresponse spectroscopy. This method is general and applicable to any spatially measured spectra where functional forms are available. Examples include exploring the superconducting gap with tunneling spectroscopy, using the Dynes formula, or current–voltage curve fits in conductive atomic force microscopy mapping. Here we explore the problem for ferroelectric hysteresis, which, given its large parameter space, constitutes a more difficult task than, for example, fitting current–voltage curves with a Schottky emission formula (Chiu 2014 Adv. Mater. Sci. Eng. 2014 578168).