Charge Distribution across Capped and Uncapped Infinite-Layer Neodymium Nickelate Thin Films.

Charge ordering (CO) phenomena have been widely debated in strongly-correlated electron systems mainly regarding their role in high-temperature superconductivity. Here, the structural and charge distribution in NdNiO2 thin films prepared with and without capping layers, and characterized by the absence and presence of CO are elucidated. The microstructural and spectroscopic analysis is done by scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) and hard X-ray photoemission spectroscopy (HAXPES). Capped samples show Ni1+ , with an out-of-plane (o-o-p) lattice parameter of around 3.30 Å indicating good stabilization of the infinite-layer structure. Bulk-sensitive HAXPES on Ni-2p shows weak satellite features indicating large charge-transfer energy. The uncapped samples evidence an increase of the o-o-p parameter up to 3.65 Å on the thin film top with a valence toward Ni2+ in this region. Here, 4D-STEM demonstrates (303)-oriented stripes which emerge from partially occupied apical oxygen. Those stripes form quasi-2D coherent domains viewed as rods in the reciprocal space with Δqz ≈ 0.24 reciprocal lattice units (r.l.u.) extension located at Q = ( ± 1 3 , 0 , ± 1 3 $\pm \frac{1}{3},0,\pm \frac{1}{3}$ ) and ( ± 2 3 , 0 , ± 2 3 $\pm \frac{2}{3},0,\pm \frac{2}{3}$ ) r.l.u. The stripes associated with oxygen re-intercalation concomitant with hole doping suggest a possible link to the previously reported CO in infinite-layer nickelate thin films.

Tunability of silicon clathrate film properties by controlled guest-occupation of their cages.

Type I and type II silicon clathrates are guest-host structures made of silicon polyhedral cages large enough to contain atoms that can be either inserted or evacuated with only a slight volume change of the structure. This feature is of interest not only for batteries or storage applications but also for tuning the properties of the silicon clathrate films. The thermal decomposition process can be tuned to obtain Na8Si46 and Na2

An Oxygen Vacancy Memristor Ruled by Electron Correlations.

Resistive switching effects offer new opportunities in the field of conventional memories as well as in the booming area of neuromorphic computing. Here the authors demonstrate memristive switching effects produced by a redox-driven oxygen exchange in tunnel junctions based on NdNiO3 , a strongly correlated electron system characterized by the presence of a metal-to-insulator transition (MIT). Strikingly, a strong interplay exists between the MIT and the redox mechanism, which on the one hand modifies the MIT itself, and on the other hand radically affects the tunnel resistance switching and the resistance states' lifetime. That results in a very unique temperature behavior and endows the junctions with multiple degrees of freedom. The obtained results bring up fundamental questions on the interplay between electronic correlations and the creation and mobility of oxygen vacancies in nickelates, opening a new avenue toward mimicking neuromorphic functions by exploiting the electric-field control of correlated states.

Imaging and Harnessing Percolation at the Metal-Insulator Transition of NdNiO3 Nanogaps.

Competition between coexisting electronic phases in first-order phase transitions can lead to a sharp change in the resistivity as the material is subjected to small variations in the driving parameter, for example, the temperature. One example of this phenomenon is the metal-insulator transition (MIT) in perovskite rare-earth nickelates. In such systems, reducing the transport measurement area to dimensions comparable to the domain size of insulating and metallic phases around the MIT should strongly influence the shape of the resistance-temperature curve. Here we measure the temperature dependence of the local resistance and the nanoscale domain distribution of NdNiO3 areas between Au contacts gapped by 40-260 nm. We find that a sharp resistance drop appears below the bulk MIT temperature at ∼105 K, with an amplitude inversely scaling with the nanogap width. By using X-ray photoemission electron microscopy, we directly correlate the resistance drop to the emergence and distribution of individual metallic domains at the nanogap. Our observation provides useful insight into percolation at the MIT of rare-earth nickelates.

A Living-Dead Magnetic Layer at the Surface of Ferrimagnetic DyTiO3 Thin Films.

When ferromagnetic films become ultrathin, key properties such as the Curie temperature and the saturation magnetization are usually depressed. This effect is thoroughly investigated in magnetic oxides such as half-metallic manganites, but much less in ferrimagnetic insulating perovskites such as rare-earth titanates RTiO3 , despite their appeal to design correlated 2D electron gases. Here, the magnetic properties of epitaxial DyTiO3 thin films are reported. While films thicker than about 50 nm show a bulk-like response, at low thickness a surprising increase of the saturation magnetization is observed. This behavior is described using a classical model of a "dead layer" but assuming that this layer is actually "living," that is, it responds to the magnetic field with a strong paramagnetic susceptibility. Through depth-dependent X-ray absorption and photoemission spectroscopy, it is shown that the "living-dead layer" corresponds to surface regions where magnetic (S = 1/2) Ti3+ ions are replaced by nonmagnetic Ti4+ ions. Hysteresis cycles at the Dy M 5 and Ti L 3 edges indicate that the surface Ti4+ ions decouple the Dy3+ ions, thus unleashing their strong paramagnetic response. Finally, it is shown how capping the DyTiO3 film can help increase the Ti3+ content near the surface and thus recover a better ferrimagnetic behavior.

Direct Mapping of Phase Separation across the Metal-Insulator Transition of NdNiO3.

Perovskite rare-earth nickelates RNiO3 are prototype correlated oxides displaying a metal-insulator transition (MIT) at a temperature tunable by the ionic radius of the rare-earth R. Although its precise origin remains a debated topic, the MIT can be exploited in various types of applications, notably for resistive switching and neuromorphic computation. So far, the MIT has been mostly studied by macroscopic techniques, and insights into its nanoscale mechanisms were only provided recently by X-ray photoemission electron microscopy through absorption line shifts, used as an indirect proxy to the resistive state. Here, we directly image the local resistance of NdNiO3 thin films across their first-order MIT using conductive-atomic force microscopy. Our resistance maps reveal the nucleation of ∼100-300 nm metallic domains in the insulating state that grow and percolate as temperature increases. We discuss the resistance contrast mechanism, analyze the microscopy and transport data within a percolation model, and propose experiments to harness this mesoscopic electronic texture in devices.

Electric-Field Control of the Orbital Occupancy and Magnetic Moment of a Transition-Metal Oxide.

By using soft-x-ray linear and magnetic dichroism on La_{0.825}Sr_{0.175}MnO_{3}/PbZr_{0.2}Ti_{0.8}O_{3} ferromagnetic-ferroelectric heterostructures we demonstrate a nonvolatile modulation of the Mn 3d orbital anisotropy and magnetic moment. X-ray absorption spectroscopy at the Mn L_{2,3} edges shows that the ferroelectric polarization direction modifies the carrier density, the spin moment, and the orbital splitting of t_{2g} and e_{g} Mn 3d states. These results are consistent with polar distortions of the oxygen octahedra surrounding the Mn ions induced by the switching of the ferroelectric polarization.

In-plane tunnelling field-effect transistor integrated on Silicon.

Silicon has persevered as the primary substrate of microelectronics during last decades. During last years, it has been gradually embracing the integration of ferroelectricity and ferromagnetism. The successful incorporation of these two functionalities to silicon has delivered the desired non-volatility via charge-effects and giant magneto-resistance. On the other hand, there has been a numerous demonstrations of the so-called magnetoelectric effect (coupling between ferroelectric and ferromagnetic order) using nearly-perfect heterostructures. However, the scrutiny of the ingredients that lead to magnetoelectric coupling, namely magnetic moment and a conducting channel, does not necessarily require structural perfection. In this work, we circumvent the stringent requirements for epilayers while preserving the magnetoelectric functionality in a silicon-integrated device. Additionally, we have identified an in-plane tunnelling mechanism which responds to a vertical electric field. This genuine electroresistance effect is distinct from known resistive-switching or tunnel electro resistance.