Thickness-Dependent Interface Polarity in Infinite-Layer Nickelate Superlattices.

The interface polarity plays a vital role in the physical properties of oxide heterointerfaces because it can cause specific modifications of the electronic and atomic structure. Reconstruction due to the strong polarity of the NdNiO2/SrTiO3 interface in recently discovered superconducting nickelate films may play an important role, as no superconductivity has been observed in the bulk. By employing four-dimensional scanning transmission electron microscopy and electron energy-loss spectroscopy, we studied effects of oxygen distribution, polyhedral distortion, elemental intermixing, and dimensionality in NdNiO2/SrTiO3 superlattices grown on SrTiO3 (001) substrates. Oxygen distribution maps show a gradual variation of the oxygen content in the nickelate layer. Remarkably, we demonstrate thickness-dependent interface reconstruction due to a polar discontinuity. An average cation displacement of ∼0.025 nm at interfaces in 8NdNiO2/4SrTiO3 superlattices is twice larger than that in 4NdNiO2/2SrTiO3 superlattices. Our results provide insights into the understanding of reconstructions at NdNiO2/SrTiO3 polar interfaces.

Direct observation of strong surface reconstruction in partially reduced nickelate films.

The polarity of a surface can affect the electronic and structural properties of oxide thin films through electrostatic effects. Understanding the mechanism behind these effects requires knowledge of the atomic structure and electrostatic characteristics at the surface. In this study, we use annular bright-field imaging to investigate the surface structure of a Pr0.8Sr0.2NiO2+x (0 < x < 1) film. We observe a polar distortion coupled with octahedral rotations in a fully oxidized Pr0.8Sr0.2NiO3 sample, and a stronger polar distortion in a partially reduced sample. Its spatial depth extent is about three unit cells from the surface. Additionally, we use four-dimensional scanning transmission electron microscopy (4D-STEM) to directly image the local atomic electric field surrounding Ni atoms near the surface and discover distinct valence variations of Ni atoms, which are confirmed by atomic-resolution electron energy-loss spectroscopy (EELS). Our results suggest that the strong surface reconstruction in the reduced sample is closely related to the formation of oxygen vacancies from topochemical reduction. These findings provide insights into the understanding and evolution of surface polarity at the atomic level.

Orbital reflectometry of oxide heterostructures.

The occupation of d orbitals controls the magnitude and anisotropy of the inter-atomic electron transfer in transition-metal oxides and hence exerts a key influence on their chemical bonding and physical properties. Atomic-scale modulations of the orbital occupation at surfaces and interfaces are believed to be responsible for massive variations of the magnetic and transport properties, but could not thus far be probed in a quantitative manner. Here we show that it is possible to derive quantitative, spatially resolved orbital polarization profiles from soft-X-ray reflectivity data, without resorting to model calculations. We demonstrate that the method is sensitive enough to resolve differences of ~3% in the occupation of Ni e(g) orbitals in adjacent atomic layers of a LaNiO(3)-LaAlO(3) superlattice, in good agreement with ab initio electronic-structure calculations. The possibility to quantitatively correlate theory and experiment on the atomic scale opens up many new perspectives for orbital physics in transition-metal oxides.

Imaging mesoscopic antiferromagnetic spin textures in the dilute limit from single-geometry resonant coherent x-ray diffraction.

The detection and manipulation of antiferromagnetic domains and topological antiferromagnetic textures are of central interest to solid-state physics. A fundamental step is identifying tools to probe the mesoscopic texture of an antiferromagnetic order parameter. In this work, we demonstrate that Bragg coherent diffractive imaging can be extended to study the mesoscopic texture of an antiferromagnetic order parameter using resonant magnetic x-ray scattering. We study the onset of the antiferromagnet transition in PrNiO3, focusing on a temperature regime in which the antiferromagnetic domains are dilute in the beam spot and the coherent diffraction pattern modulating the antiferromagnetic peak is greatly simplified. We demonstrate that it is possible to extract the arrangements and sizes of these domains from single diffraction patterns and show that the approach could be extended to a time-structured light source to study the motion of dilute domains or the motion of topological defects in an antiferromagnetic spin texture.

Formation mechanism of Ruddlesden-Popper faults in compressive-strained ABO3 perovskite superlattices.

Ruddlesden-Popper (RP) faults have emerged as a promising candidate for defect engineering in epitaxial ABO3 perovskites. Functionalities could be fine-tuned by incorporating RP faults into ABO3 thin films and superlattices. However, due to the lattice expansion at AO-AO interfaces, it is generally believed that RP faults are only energetically favorable under tensile strain. Contrary to this common cognition, here we present that compressive strain must be regarded as an alternative driving force for creating RP faults. Unlike the conventional perovskite-to-rock-salt transition, the RP faults originated from Shockley partial dislocations bounded by stacking faults on the basal plane. The edge-type partials gave rise to strain relaxation, facilitating the formation of RP faults under compressive strain. We envisage that our results will give new insights into the rational design and defect engineering in epitaxial-strained ABO3 perovskites.

High-Temperature Thermoelectricity in LaNiO3-La2CuO4 Heterostructures.

Transition metal oxides exhibit a high potential for application in the field of electronic devices, energy storage, and energy conversion. The ability of building these types of materials by atomic layer-by-layer techniques provides a possibility to design novel systems with favored functionalities. In this study, by means of the atomic layer-by-layer oxide molecular beam epitaxy technique, we designed oxide heterostructures consisting of tetragonal K2NiF4-type insulating La2CuO4 (LCO) and perovskite-type conductive metallic LaNiO3 (LNO) layers with different thicknesses to assess the heterostructure-thermoelectric property-relationship at high temperatures. We observed that the transport properties depend on the constituent layer thickness, interface intermixing, and oxygen-exchange dynamics in the LCO layers, which occurs at high temperatures. As the thickness of the individual layers was reduced, the electrical conductivity decreased and the sign of the Seebeck coefficient changed, revealing the contribution of the individual layers where possible interfacial contributions cannot be ruled out. High-resolution scanning transmission electron microscopy investigations showed that a substitutional solid solution of La2(CuNi)O4 was formed when the thickness of the constituent layers was decreased.

Layer selective control of the lattice structure in oxide superlattices.

A combined synchrotron X-ray diffraction and transmission electron microscopy study reveals a structural phase transition controlled by the overall thickness of epitaxial nickelate-aluminate superlattices. The transition between uniform and twin-domain states is confined to the nickelate layers and leaves the aluminate layers unaffected.

Element specific monolayer depth profiling.

The electronic phase behavior and functionality of interfaces and surfaces in complex materials are strongly correlated to chemical composition profiles, stoichiometry and intermixing. Here a novel analysis scheme for resonant X-ray reflectivity maps is introduced to determine such profiles, which is element specific and non-destructive, and which exhibits atomic-layer resolution and a probing depth of hundreds of nanometers.