A novel approach to on-demand improvement of electronic properties in complex-oxide ferroelectrics is demonstrated whereby ion bombardment - commonly used in classic semiconductor materials - is applied to the PbTiO₃ system. The result is deterministic reduction in leakage currents by 5 orders of magnitude, improved ferroelectric switching, and unprecedented insights into the nature of defects and intergap state evolution in these materials.

Interface materials offer a means to achieve electrical control of ferrimagnetism at room temperature as was recently demonstrated in (LuFeO₃)_m/(LuFe₂O₄)₁ superlattices. A challenge to understanding the inner workings of these complex magnetoelectric multiferroics is the multitude of distinct Fe centres and their associated environments. This is because macroscopic techniques characterize average responses rather than the role of individual iron centres. Here, we combine optical absorption, magnetic circular dichroism and first-principles calculations to uncover the origin of high-temperature magnetism in these superlattices and the charge-ordering pattern in the m = 3 member. In a significant conceptual advance, interface spectra establish how Lu-layer distortion selectively enhances the Fe²⁺ →  Fe³⁺ charge-transfer contribution in the spin-up channel, strengthens the exchange interactions and increases the Curie temperature. Comparison of predicted and measured spectra also identifies a non-polar charge ordering arrangement in the LuFe₂O₄ layer. This site-specific spectroscopic approach opens the door to understanding engineered materials with multiple metal centres and strong entanglement.

Antiferroelectric materials have seen a resurgence of interest because of proposed applications in a number of energy-efficient technologies. Unfortunately, relatively few families of antiferroelectric materials have been identified, precluding many proposed applications. Here, we propose a design strategy for the construction of antiferroelectric materials using interfacial electrostatic engineering. We begin with a ferroelectric material with one of the highest known bulk polarizations, BiFeO3. By confining thin layers of BiFeO3 in a dielectric matrix, we show that a metastable antiferroelectric structure can be induced. Application of an electric field reversibly switches between this new phase and a ferroelectric state. The use of electrostatic confinement provides an untapped pathway for the design of engineered antiferroelectric materials with large and potentially coupled responses.

The layered square-planar nickelates, Nd_n+1Ni_nO_2n+2, are an appealing system to tune the electronic properties of square-planar nickelates via dimensionality; indeed, superconductivity was recently observed in Nd₆Ni₅O₁₂ thin films. Here, we investigate the role of epitaxial strain in the competing requirements for the synthesis of the n = 3 Ruddlesden-Popper compound, Nd₄Ni₃O₁₀, and subsequent reduction to the square-planar phase, Nd₄Ni₃O₈. We synthesize our highest quality Nd₄Ni₃O₁₀ films under compressive strain on LaAlO₃ (001), while Nd₄Ni₃O₁₀ on NdGaO₃ (110) exhibits tensile strain-induced rock salt faults but retains bulk-like transport properties. A high density of extended defects forms in Nd₄Ni₃O₁₀ on SrTiO₃ (001). Films reduced on LaAlO₃ become insulating and form compressive strain-induced c-axis canting defects, while Nd₄Ni₃O₈ films on NdGaO₃ are metallic. This work provides a pathway to the synthesis of Nd_n+1Ni_nO_2n+2 thin films and sets limits on the ability to strain engineer these compounds via epitaxy.

A key open question in the study of layered superconducting nickelate films is the role that hydrogen incorporation into the lattice plays in the appearance of the superconducting state. Due to the challenges of stabilizing highly crystalline square planar nickelate films, films are prepared by the deposition of a more stable parent compound which is then transformed into the target phase via a topotactic reaction with a strongly reducing agent such as CaH2. Recent studies, both experimental and theoretical, have introduced the possibility that the incorporation of hydrogen from the reducing agent into the nickelate lattice may be critical for the superconductivity. In this work, we use secondary ion mass spectrometry to examine superconducting La1-xXxNiO2 / SrTiO3 (X = Ca and Sr) and Nd6Ni5O12 / NdGaO3 films, along with non-superconducting NdNiO2 / SrTiO3 and (Nd,Sr)NiO2 / SrTiO3. We find no evidence for extensive hydrogen incorporation across a broad range of samples, including both superconducting and non-superconducting films. Theoretical calculations indicate that hydrogen incorporation is broadly energetically unfavorable in these systems, supporting our conclusion that extensive hydrogen incorporation is not generally required to achieve a superconducting state in layered square-planar nickelates.

Correction to: Nature Communicationshttps://doi.org/10.1038/s41467-023-37117-4, published online 16 March 2023 In the Acknowledgements section of this article the grant number relating to NSF was incorrectly given as DMR 2045826 and should have been DMR-2045826. The original article has been corrected.

The rare-earth nickelates possess a diverse set of collective phenomena including metal-to-insulator transitions, magnetic phase transitions, and upon chemical reduction, superconductivity. Here, we demonstrate epitaxial stabilization of layered nickelates in the Ruddlesden-Popper form Ndn+1NinO3n+1 using molecular beam epitaxy. By optimizing the stoichiometry of the parent perovskite NdNiO3, we can reproducibly synthesize the n=1-5 member compounds. X-ray absorption spectroscopy at the O K and Ni L edges indicate systematic changes in both the nickel-oxygen hybridization level and nominal nickel filling from 3d8 to 3d7 as we move across the series from n=1 to ∞. The n=3-5 compounds exhibit weakly hysteretic metal-to-insulator transitions with transition temperatures that depress with increasing order toward NdNiO3 (n=∞).