The metal–insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal–insulator transition in terms of bond disproportionation.

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Thickness-driven electronic phase transitions are broadly observed in different types of functional perovskite heterostructures. However, uncertainty remains whether these effects are solely due to spatial confinement, broken symmetry, or rather to a change of structure with varying film thickness. Here, this study presents direct evidence for the relaxation of oxygen-2p and Mn-3d orbital (p-d) hybridization coupled to the layer-dependent octahedral tilts within a La2/3Sr1/3MnO3 film driven by interfacial octahedral coupling. An enhanced Curie temperature is achieved by reducing the octahedral tilting via interface structure engineering. Atomically resolved lattice, electronic, and magnetic structures together with X-ray absorption spectroscopy demonstrate the central role of thickness-dependent p-d hybridization in the widely observed dimensionality effects present in correlated oxide heterostructures

SignificanceCorrelated transition metal oxide perovskites receive a lot of attention due to their unique physical properties, which are largely driven by distortion of the BO6 octahedral network. In bulk, the control of the octahedral network is normally obtained by cation substitutions in a random alloy. Similar to the charge donors in semiconductors, cation substitutions will introduce scattering and disorder. The development of artificial heterostructures offers unprecedented opportunities to lattice engineering to achieve desired properties. In this work, we demonstrated a structural analogue of modulation doping in nickelate heterostructures through the interfacial transfer of tilt patterns. Modulation tilt control was used to remotely control the Ni–O bonds in the compound SmNiO3 and thereby its critical temperature for optimal optical switching application.

The tuning of semiconductor band gaps can often provide significant performance increases and new applications for electronic, optoelectronic, and photocatalytic devices. Here, we study the band gaps of pure and nickeldoped zinc oxide thin films synthesized using the low-cost spray pyrolysis deposition method. Nickel concentration is varied from 0 to 15%, and the effects that this doping has on the electronic structure are analyzed. Using optical and synchrotron X-ray techniques, two regimes of band gap reduction via Ni doping are uncovered. For doping up to 4% Ni, there is a strong reduction in the gap, while continued doping up to 15% further reduces the gap, but to a lesser extent. The results are explained using X-ray spectroscopy and an Anderson impurity model. These tools show that the low doping case is driven by the interaction of the Ni 3d and O 2p states in both the valence and conduction bands. At high doping, the removal of Zn 3d states from the valence band and the change in Ni coordination from T d to O h both contribute to counteract the gap reduction. These results show how Ni can be used to tune the ZnO band gap over a large range useful for many applications.

Previously, researchers have used circular contours with sinusoidal deformations of the radius (radial frequency [RF] patterns) to investigate the underlying processing involved in simple shape perception. On finding that the rapid improvement in sensitivity to deformation as more cycles of modulation were added was greater than expected from probability summation across sets of local independent detectors, they concluded that global integration of contour information was occurring. More recently, this conclusion has been questioned by researchers using a method of calculating probability summation derived from signal detection theory (Baldwin, Schmidtmann, Kingdom, & Hess, 2016). They could not distinguish between global integration and probability summation. Furthermore, it has been argued that RF patterns and lines are processed in a similar manner (Mullen, Beaudot, & Ivanov, 2011; Schmidtmann & Kingdom, 2017). The current study investigates these claims using fixed-phase (in which the local elements have spatial certainty) and random-phase (in which the local elements have spatial uncertainty) RF patterns and modulated lines. Thresholds were collected from eight naïve observers and compared to probability summation estimates calculated using methods derived from both high threshold theory and signal detection theory. The results indicate global processing of random-phase RF patterns and evidence for an interaction between local and global cues for fixed-phase RF patterns. They also show no evidence of global integration with modulated line stimuli. The results provide further evidence for the global processing of random-phase RF patterns and indicate that RF patterns and modulated lines are processed differently.

We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe electron valence undergoes no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ∼5-10% in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.

Polar discontinuities and redox reactions provide alternative paths to create two-dimensional electron liquids (2DELs) at oxide interfaces. Herein, we report high mobility 2DELs at interfaces involving SrTiO3 (STO) achieved using polar La7/8Sr1/8MnO3 (LSMO) buffer layers to manipulate both polarities and redox reactions from disordered * Corresponding Authors.