The exploitation of interface effects turned out to be a powerful tool for generating exciting material properties. Such properties include magnetism, electronic and ionic transport and even superconductivity. Here, instead of using conventional homogeneous doping to enhance the hole concentration in lanthanum cuprate and achieve superconductivity, we replace single LaO planes with SrO dopant planes using atomic-layer-by-layer molecular beam epitaxy (two-dimensional doping). Electron spectroscopy and microscopy, conductivity measurements and zinc tomography reveal such negatively charged interfaces to induce layer-dependent superconductivity (T_c up to 35 K) in the space-charge zone at the side of the planes facing the substrate, where the strontium (Sr) profile is abrupt. Owing to the growth conditions, the other side exhibits instead a Sr redistribution resulting in superconductivity due to conventional doping. The present study represents a successful example of two-dimensional doping of superconducting oxide systems and demonstrates its power in this field.

Complex oxides provide a versatile playground for many phenomena and possible applications, for instance, high-temperature superconductivity, magnetism, ferroelectricity, metal-to-insulator transition, colossal magnetoresistance, and piezoelectricity. The origin of these phenomena is the competition between different degrees of freedom such as charge, orbital, and spin, which are interrelated with the crystal structure, the oxygen stoichiometry, and the doping dependence. Recent developments not only in the epitaxial growth technologies, such as reactive molecular beam epitaxy, but also in the characterization techniques, as aberration-corrected scanning transmission electron microscopy with spectroscopic tools, allow synthesizing and identifying epitaxial systems at the atomic scale. Combination of different oxide layers opens access to interface physics and leads to engineering interface properties, where the degrees of freedom can be artificially modified. In this review, we present different homo- and hetero-epitaxial interfaces with extraordinary structural quality and different functionalities, including high-temperature superconductivity, thermoelectricity, and magnetism.

In this paper we present the atomic-layer-by-layer oxide molecular beam epitaxy (ALL-oxide MBE) which has been recently installed in the Max-Planck Institute for Solid State Research and we report on its present status, providing some examples that demonstrate its successful application in the synthesis of different layered oxides, with particular reference to superconducting La₂CuO₄ and insulator-to-metal La_2−xSr_xNiO₄. We briefly review the ALL-oxide MBE technique and its unique capabilities in the deposition of atomically smooth single-crystal thin films of various complex oxides, artificial compounds and heterostructures, introducing our goal of pursuing a deep investigation of such systems with particular emphasis on structural defects, with the aim of tailoring their functional properties by precise defects control.

The superconducting properties of high-$T_c$ materials are functions of the concentration of charge carriers, which is controlled by the concentration of defects including heterovalent cations, interstitial oxygen ions, and oxygen vacancies. Here we combine low-temperature thermal treatment of ${\mathrm{La}}_{2-x}{\mathrm{Sr}}_x{\mathrm{CuO}}_4$ epitaxial thin films and confocal Raman spectroscopy to control and investigate oxygen vacancies. We demonstrate that the apical site is the most favorable position to accommodate oxygen vacancies under low-temperature annealing conditions. Additionally we show that in high-quality films of overdoped ${\mathrm{La}}_{2-x}{\mathrm{Sr}}_x{\mathrm{CuO}}_4$, oxygen vacancies strongly deform the oxygen environment around the copper ions. This observation is consistent with previous defect-chemical studies, and calls for further investigation of the defect-induced properties in the overdoped regime of the hole-doped lanthanum cuprates.

The NdNiO₃ (NNO) system has attracted a considerable amount of attention owing to the discovery of superconductivity in Nd_0.8Sr_0.2NiO₂. In rare-earth nickelates, Ruddlesden–Popper (RP) faults play a significant role in functional properties, motivating our exploration of its microstructural characteristics and the electronic structure. Here, we employed aberration-corrected scanning transmission electron microscopy and spectroscopy to study a NdNiO₃ film grown by layer-by-layer molecular beam epitaxy (MBE). We found RP faults with multiple configurations in high-angle annular dark-field images. Elemental intermixing occurs at the SrTiO₃–NdNiO₃ interface and in the RP fault regions. Quantitative analysis of the variation in lattice constants indicates that large strains exist around the substrate–film interface. We demonstrate that the Ni valence change around RP faults is related to a strain and structure variation. This work provides insights into the microstructure and electronic-structure modifications around RP faults in nickelates.