Electric-field-induced multiferroic topological solitons.

Topologically protected spin whirls in ferromagnets are foreseen as the cart-horse of solitonic information technologies. Nevertheless, the future of skyrmionics may rely on antiferromagnets due to their immunity to dipolar fields, straight motion along the driving force and ultrafast dynamics. While complex topological objects were recently discovered in intrinsic antiferromagnets, mastering their nucleation, stabilization and manipulation with energy-efficient means remains an outstanding challenge. Designing topological polar states in magnetoelectric antiferromagnetic multiferroics would allow one to electrically write, detect and erase topological antiferromagnetic entities. Here we stabilize ferroelectric centre states using a radial electric field in multiferroic BiFeO3 thin films. We show that such polar textures contain flux closures of antiferromagnetic spin cycloids, with distinct antiferromagnetic entities at their cores depending on the electric field polarity. By tuning the epitaxial strain, quadrants of canted antiferromagnetic domains can also be electrically designed. These results open the path to reconfigurable topological states in multiferroic antiferromagnets.

Onset of Multiferroicity in Prototypical Single-Spin Cycloid BiFeO3 Thin Films.

In the room-temperature magnetoelectric multiferroic BiFeO3, the noncollinear antiferromagnetic state is coupled to the ferroelectric order, opening applications for low-power electric-field-controlled magnetic devices. While several strategies have been explored to simplify the ferroelectric landscape, here we directly stabilize a single-domain ferroelectric and spin cycloid state in epitaxial BiFeO3 (111) thin films grown on orthorhombic DyScO3 (011). Comparing them with films grown on SrTiO3 (111), we identify anisotropic in-plane strain as a powerful handle for tailoring the single antiferromagnetic state. In this single-domain multiferroic state, we establish the thickness limit of the coexisting electric and magnetic orders and directly visualize the suppression of the spin cycloid induced by the magnetoelectric interaction below the ultrathin limit of 1.4 nm. This as-grown single-domain multiferroic configuration in BiFeO3 thin films opens an avenue both for fundamental investigations and for electrically controlled noncollinear antiferromagnetic spintronics.

Revisiting the Ferroelectric Photovoltaic Properties of Vertical BiFeO3 Capacitors: A Comprehensive Study.

The ferroelectric photovoltaic effect has been extensively studied for possible applications in energy conversion and photo-electrics. The reversible spontaneous polarization gives rise to a switchable photovoltaic behavior. However, despite its long history, the origin of the ferroelectric photovoltaic effect still lacks a full understanding since multiple mechanisms such as bulk and Schottky-barrier-related interface effects are involved. Herein, we report a comprehensive study on the photovoltaic response of BiFeO3-based vertical heterostructures, using multiple strategies to clarify its origin. We found that, under white light illumination, polarization-modulated Schottky barrier at the interface is the dominating mechanism. By varying the top metal contacts, only the photovoltaic effect of the polarization downward state is strongly modulated, suggesting selective interface contribution in different polarization states. A Schottky-barrier-free device shows negligible photovoltaic effect, suggesting the lack of bulk photovoltaic effect in vertical heterostructures under white light illumination.

Effect of polarization rotation on the optical and photovoltaic properties of BiFeO3thin films.

Visible-light-active ferroelectric materials are gaining increasing attention due to the unique ferroelectric photovoltaic effect. To boost the light harvesting capability, vast research is devoted to band gap engineering by chemical substitutions, regardless of the side effect on ferroelectric polarization. Here, we focus on how polar order affects the optical and photovoltaic properties. Using BiFeO3as the model system, we induce the polarization rotation by A-site La substitution, which results in continuous reduction of optical anisotropy of the samples, as revealed by the concerted optical characterizations. This further causes the decrease of angular dependence of ferroelectric photovoltaic effect on the light polarization. The results demonstrate the inner connection of the ferroelectric polarization and optical anisotropy via the lattice degree of freedom.

Continuously controllable photoconductance in freestanding BiFeO3 by the macroscopic flexoelectric effect.

Flexoelectricity induced by the strain gradient is attracting much attention due to its potential applications in electronic devices. Here, by combining a tunable flexoelectric effect and the ferroelectric photovoltaic effect, we demonstrate the continuous tunability of photoconductance in BiFeO3 films. The BiFeO3 film epitaxially grown on SrTiO3 is transferred to a flexible substrate by dissolving a sacrificing layer. The tunable flexoelectricity is achieved by bending the flexible substrate which induces a nonuniform lattice distortion in BiFeO3 and thus influences the inversion asymmetry of the film. Multilevel conductance is thus realized through the coupling between flexoelectric and ferroelectric photovoltaic effect in freestanding BiFeO3. The strain gradient induced multilevel photoconductance shows very good reproducibility by bending the flexible BiFeO3 device. This control strategy offers an alternative degree of freedom to tailor the physical properties of flexible devices and thus provides a compelling toolbox for flexible materials in a wide range of applications.

Tuning Photovoltaic Performance of Perovskite Nickelates Heterostructures by Changing the A-Site Rare-Earth Element.

Perovskite rare-earth nickelates (RNiO3) have attracted much attention because of their exotic physical properties and rich potential applications. Here, we report systematic tuning of the electronic structures of RNiO3 (R = Nd, Sm, Gd, and Lu) by isovalent A-site substitution. By integrating RNiO3 thin films with Nb-doped SrTiO3 (NSTO), p-n heterojunction photovoltaic cells have been prepared and their performance has been investigated. The open-circuit voltage increases monotonically with decreasing A-site cation radius. This change results in a downward shift of the Fermi level and induces an increase in the built-in potential at the RNiO3/NSTO heterojunction, with LuNiO3/NSTO showing the largest open-circuit voltage. At the same time, the short-circuit current initially increases upon changing the A-site element from Nd to Sm. However, the larger bandgaps of GdNiO3 and LuNiO3 reduce light absorption which in turn induces a decrease in the short-circuit current. A power conversion efficiency of 1.13% has been achieved by inserting an ultrathin insulating SrTiO3 layer at the SmNiO3/NSTO interface. Our study illustrates how changing the A-site cation is an effective strategy for tuning photovoltaic performance and sheds light on which A-site element is the best for photovoltaic applications, which can significantly increase the applicability of nickelates in optoelectric devices.

Strain Effect on Oxygen Evolution Reaction Activity of Epitaxial NdNiO3 Thin Films.

Epitaxial strain can cause both lattice distortion and oxygen nonstoichiometry, effects that are strongly coupled at heterojunctions of complex nickelate oxides. Here we decouple these structural and chemical effects on the oxygen evolution reaction (OER) by using a set of coherently strained epitaxial NdNiO3 films. We show that within the regime where oxygen vacancies (VO) are negligible, compressive strain is favorable for the OER whereas tensile strain is unfavorable; the former induces orbital splitting, resulting in a higher occupancy in the d3 z2- r2 orbital and weaker Ni-O chemisorption. However, when the tensile strain is sufficiently large to promote VO formation, an increase in the OER is also observed. The partial reduction of Ni3+ to Ni2+ due to VO makes the eg occupancy slightly larger than unity, which is thought to account for the increased OER activity. Our work highlights that epitaxial-strain-induced lattice distortion and VO generation can be individually or collectively exploited to tune OER activity, which is important for the predictive synthesis of high-performance electrocatalysts.