Perovskites with the generic composition ABO3 exhibit an enormous variety of quantum states, such as orbital order, magnetism and superconductivity. Their flexible and comparatively simple structure allows for straightforward chemical substitution and cube-on-cube combination of different compounds in atomically sharp epitaxial heterostructures. Many of the diverse physical properties of perovskites are determined by small deviations from the ideal cubic perovskite structure, which are challenging to control. Here we show that directional imprinting of atomic displacements in the antiferromagnetic Mott insulator YVO3 can be achieved by depositing epitaxial films on different facets of the same isostructural substrate. These facets were chosen such that other well-known control parameters, including lattice and polarity mismatch with the overlayer, remain nearly unchanged. We observe signatures of staggered orbital and magnetic order and demonstrate distinct spin–orbital ordering patterns on different facets. We attribute these results to the influence of specific octahedral rotation and cation displacement patterns, which are imprinted by the substrate facet, on the covalency of the bonds and the superexchange interactions in YVO3. Our results show that substrate-induced templating of lattice distortion patterns constitutes a pathway for materials design beyond established strain-engineering strategies. Different facets of an orthorhombic substrate can stabilize different ordering patterns in a perovskite oxide, even in the absence of differences in strain and polarity mismatches.

The nondestructive investigation of electronic and magnetic modifications at buried interfaces contributes significantly to the understanding of the underlying interactions. This knowledge is essential for the design of electronic devices based on complex quantum materials. Herein, the application of resonant X‐ray and neutron reflectometry for the study of perovskite transition metal oxide heterostructures is reviewed. Both methods are well suited for the nondestructive study of interfacial reconstructions and interactions of spin, charge, and orbitals at the nanoscale. Herein, cases are highlighted in which both methods are complementary and thus provide unique insights into the physics of oxide heterostructures.

Heterostructuring provides different ways to manipulate the orbital degrees of freedom and to tailor orbital occupations in transition-metal oxides. However, the reliable prediction of these modifications remains a challenge. Here we present a detailed investigation of the relationship between the crystal and electronic structure in YVO3-LaAlO3 superlattices by combining ab initio theory, scanning transmission electron microscopy, and x-ray diffraction. Density functional theory simulations including an on-site Coulomb repulsion term accurately predict the crystal structure and, in conjunction with x-ray diffraction, provide an explanation for the lifting of degeneracy of the vanadium dxz and dyz orbitals that was recently observed in this system. In addition, we unravel the combined effects of electronic confinement and octahedral connectivity by disentangling their impact from that of epitaxial strain. Our results demonstrate that the specific orientation of the substrate and the thickness of the YVO3 slabs in the multilayer can be utilized to reliably engineer orbital polarization.

Oxide heterostructures provide unique opportunities to modify the properties of quantum materials through a targeted manipulation of spin, charge, and orbital states. Here, we use resonant x-ray reflectometry to probe the electronic structure of thin slabs of YVO3 embedded in a superlattice with LaAlO3. We extend the previously established methods of reflectometry analysis to a general form applicable to t(2g) electron systems and extract quantitative depth-dependent x-ray linear dichroism profiles. Our data reveal an artificial, layered orbital polarization, where the average occupation of xz and yz orbitals in the interface planes next to LaAlO3 is inverted compared to the central part of the YVO3 slab. This phase is stable down to 30 K and the bulklike orbital ordering transitions are absent. We identify the key mechanism for the electronic reconstruction to be a combination of epitaxial strain and spatial confinement by the LaAlO3 layers, in good agreement with predictions from ab initio theory.

We have used atomic layer-by-layer molecular beam epitaxy to synthesize coherently lattice-matched thin films of the high-temperature superconductor DyBa2Cu3O7−x with minimal defect density. A systematic set of x-ray reciprocal-space maps reveals tetragonal and orthorhombic structures with different twinning patterns and elucidates their evolution with the thickness, the oxygenation state, and the epitaxial relationship with the substrate. We also show that films with more pronounced orthorhombicity exhibit lower normal-state resistivities and higher superconducting transition temperatures. These findings provide guidance for the synthesis of optimized superconducting heterostructures and devices.

The explanation and control of phase transitions remain cornerstones of contemporary physics. Landau provided an invaluable insight into the thermodynamics of complex systems by formulating their phase transitions in terms of an order parameter. Within this formulation, continuous evolution of the order parameter away from zero classifies the phase transition as second-order, whereas a discontinuous change signals a first-order transition. Here we show that the temperature-tuned insulator–metal transition in the prototypical correlated electron system NdNiO3 defies this established binary classification. By harnessing a nanoscale optical probe of the local electronic conductivity, we reveal two physically distinct yet concurrent phase transitions in epitaxial NdNiO3 films. Whereas the sample bulk exhibits a first-order transition between metal and insulator phases, we resolve anomalous nanoscale domain walls in the insulating state that undergo a distinctly continuous insulator–metal transition, with hallmarks of second-order behaviour. We ascribe these domain walls to boundaries between antiferromagnetically ordered domains within the charge ordered bulk. The close correspondence of these observations to predictions from a Landau theory of coupled charge and magnetic orders highlights the importance of coupled order parameters in driving the complex phase transition in NdNiO3. A phase transition between metallic and insulating states is observed to simultaneously happen in two ways at once. The bulk of the sample shows an instantaneous jump in the conductivity, while 1D domain walls show a slow switching into a metallic state.