Scintillator-based Timepix3 detector for neutron spin-echo techniques using intensity modulation.

A scintillator-based Timepix3 (TPX3) detector was developed to resolve the high-frequency modulation of a neutron beam in both spatial and temporal domains, as required for neutron spin-echo experiments. In this system, light from a scintillator is manipulated with an optical lens and is intensified using an image intensifier, making it detectable with the TPX3 chip. Two different scintillators, namely, 6LiF:ZnS(Ag) and 6LiI:Eu, were investigated to achieve the high resolution needed for spin-echo modulated small-angle neutron scattering (SEMSANS) and modulation of intensity with zero effort (MIEZE). The methodology for conducting event-mode analysis is described, including the optimization of clustering parameters for both scintillators. The detector with both scintillators was characterized with respect to detection efficiency, spatial resolution, count rate, uniformity, and γ-sensitivity. The 6LiF:ZnS(Ag) scintillator-based detector achieved a spatial resolution of 200 µm and a count rate capability of 1.1 × 105 cps, while the 6LiI:Eu scintillator-based detector demonstrated a spatial resolution of 250 µm and a count rate capability exceeding 2.9 × 105 cps. Furthermore, high-frequency intensity modulations in both spatial and temporal domains were successfully observed, confirming the suitability of this detector for SEMSANS and MIEZE techniques, respectively.

Skyrmion-Excited Spin-Wave Fractal Networks.

Magnetic skyrmions exhibit unique, technologically relevant pseudo-particle behaviors which arise from their topological protection, including well-defined, 3D dynamic modes that occur at microwave frequencies. During dynamic excitation, spin waves are ejected into the interstitial regions between skyrmions, creating the magnetic equivalent of a turbulent sea. However, since the spin waves in these systems have a well-defined length scale, and the skyrmions are on an ordered lattice, ordered structures from spin-wave interference can precipitate from the chaos. This work uses small-angle neutron scattering (SANS) to capture the dynamics in hybrid skyrmions and investigate the spin-wave structure. Performing simultaneous ferromagnetic resonance and SANS, the diffraction pattern shows a large increase in low-angle scattering intensity, which is present only in the resonance condition. This scattering pattern is best fit using a mass fractal model, which suggests the spin waves form a long-range fractal network. The fractal structure is constructed of fundamental units with a size that encodes the spin-wave emissions and are constrained by the skyrmion lattice. These results offer critical insights into the nanoscale dynamics of skyrmions, identify a new dynamic spin-wave fractal structure, and demonstrate SANS as a unique tool to probe high-speed dynamics.

Emergent Magnetic States and Tunable Exchange Bias at 3d Nitride Heterointerfaces.

Interfacial magnetism stimulates the discovery of giant magnetoresistance (MR) and spin-orbital coupling across the heterointerfaces, facilitating the intimate correlation between spin transport and complex magnetic structures. Over decades, functional heterointerfaces composed of nitrides have seldom been explored due to the difficulty in synthesizing high-quality nitride films with correct compositions. Here, the fabrication of single-crystalline ferromagnetic Fe3 N thin films with precisely controlled thicknesses is reported. As film thickness decreases, the magnetization dramatically deteriorates, and the electronic state changes from metallic to insulating. Strikingly, the high-temperature ferromagnetism is maintained in a Fe3 N layer with a thickness down to 2 u.c. (≈8 Å). The MR exhibits a strong in-plane anisotropy; meanwhile, the anomalous Hall resistivity reverses its sign when the Fe3 N layer thickness exceeds 5 u.c. Furthermore, a sizable exchange bias is observed at the interfaces between a ferromagnetic Fe3 N and an antiferromagnetic CrN. The exchange bias field and saturation moment strongly depend on the controllable bending curvature using the cylinder diameter engineering technique, implying the tunable magnetic states under lattice deformation. This work provides a guideline for exploring functional nitride films and applying their interfacial phenomena for innovative perspectives toward practical applications.

Room-temperature valence transition in a strain-tuned perovskite oxide.

Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films.

Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO2 ) as a model system, in this work, the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO2 . It is found that UO2+ x thin films are hypostoichiometric (x<0) with in-plane tensile strain, while they are hyperstoichiometric (x>0) with in-plane compressive strain. Different from strain engineering in non-actinide oxide thin films, the epitaxial strain in UO2 is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defects and ferromagnetism in strain engineered UO2+ x thin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films.

Atomically engineered cobaltite layers for robust ferromagnetism.

Emergent phenomena at heterointerfaces are directly associated with the bonding geometry of adjacent layers. Effective control of accessible parameters, such as the bond length and bonding angles, offers an elegant method to tailor competing energies of the electronic and magnetic ground states. In this study, we construct unit-thick syntactic layers of cobaltites within a strongly tilted octahedral matrix via atomically precise synthesis. The octahedral tilt patterns of adjacent layers propagate into cobaltites, leading to a continuation of octahedral tilting while maintaining substantial misfit tensile strain. These effects induce severe rumpling within an atomic plane of neighboring layers, further triggering the electronic reconstruction between the splitting orbitals. First-principles calculations reveal that the cobalt ions transit to a higher spin state level upon octahedral tilting, resulting in robust ferromagnetism in ultrathin cobaltites. This work demonstrates a design methodology for fine-tuning the lattice and spin degrees of freedom in correlated quantum heterostructures by exploiting epitaxial geometric engineering.

Room-Temperature Ferromagnetism at an Oxide-Nitride Interface.

Heterointerfaces have led to the discovery of novel electronic and magnetic states because of their strongly entangled electronic degrees of freedom. Single-phase chromium compounds always exhibit antiferromagnetism following the prediction of the Goodenough-Kanamori rules. So far, exchange coupling between chromium ions via heteroanions has not been explored and the associated quantum states are unknown. Here, we report the successful epitaxial synthesis and characterization of chromium oxide (Cr_{2}O_{3})-chromium nitride (CrN) superlattices. Room-temperature ferromagnetic spin ordering is achieved at the interfaces between these two antiferromagnets, and the magnitude of the effect decays with increasing layer thickness. First-principles calculations indicate that robust ferromagnetic spin interaction between Cr^{3+} ions via anion-hybridization across the interface yields the lowest total energy. This work opens the door to fundamental understanding of the unexpected and exceptional properties of oxide-nitride interfaces and provides access to hidden phases at low-dimensional quantum heterostructures.

Ferroelectric Self-Polarization Controlled Magnetic Stratification and Magnetic Coupling in Ultrathin La0.67Sr0.33MnO3 Films.

Multiferroic oxide heterostructures consisting of ferromagnetic and ferroelectric components hold the promise for nonvolatile magnetic control via ferroelectric polarization, advantageous for the low-dissipation spintronics. Modern understanding of the magnetoelectric coupling in these systems involves structural, orbital, and magnetic reconstructions at interfaces. Previous works have long proposed polarization-dependent interfacial magnetic structures; however, direct evidence is still missing, which requires advanced characterization tools with near-atomic-scale spatial resolutions. Here, extensive polarized neutron reflectometry (PNR) studies have determined the magnetic depth profiles of PbZr0.2Ti0.8O3/La0.67Sr0.33MnO3 (PZT/LSMO) bilayers with opposite self-polarizations. When the LSMO is 2-3 nm thick, the bilayers show two magnetic transitions on cooling. However, temperature-dependent magnetization is different below the lower-temperature transition for opposite polarizations. PNR finds that the LSMO splits into two magnetic sublayers, but the inter-sublayer magnetic couplings are of opposite signs for the two polarizations. Near-edge X-ray absorption spectroscopy further shows contrasts in both the Mn valences and the Mn-O bond anisotropy between the two polarizations. This work completes the puzzle for the magnetoelectric coupling model at the PZT/LSMO interface, showing a synergic interplay among multiple degrees of freedom toward emergent functionalities at complex oxide interfaces.

Dimensional Control of Octahedral Tilt in SrRuO3 via Infinite-Layered Oxides.

Manipulation of octahedral distortion at atomic scale is an effective means to tune the ground states of functional oxides. Previous work demonstrates that strain and film thickness are variable parameters to modify the octahedral parameters. However, selective control of bonding geometry by structural propagation from adjacent layers is rarely studied. Here we propose a new route to tune the ferromagnetism in SrRuO3 (SRO) ultrathin layers by oxygen coordination of adjacent SrCuO2 (SCO) layers. The infinite-layered CuO2 exhibits a structural transformation from "planar-type" to "chain-type" with reduced film thickness. Two orientations dramatically modify the polyhedral connectivity at the interface, thus altering the octahedral distortion of SRO. The local structural variation changes the spin state of Ru and orbital hybridization strength, leading to a significant change in the magnetoresistance and anomalous Hall resistivity. These findings could launch investigations into adaptive control of functionalities in quantum oxide heterostructures using oxygen coordination.

Vertically Aligned Single-Crystalline CoFe2O4 Nanobrush Architectures with High Magnetization and Tailored Magnetic Anisotropy.

Micrometer-tall vertically aligned single-crystalline CoFe2O4 nanobrush architectures with extraordinarily large aspect ratio have been achieved by the precise control of a kinetic and thermodynamic non-equilibrium pulsed laser epitaxy process. Direct observations by scanning transmission electron microscopy reveal that the nanobrush crystal is mostly defect-free by nature, and epitaxially connected to the substrate through a continuous 2D interface layer. In contrast, periodic dislocations and lattice defects such as anti-phase boundaries and twin boundaries are frequently observed in the 2D interface layer, suggesting that interface misfit strain relaxation under a non-equilibrium growth condition plays a critical role in the self-assembly of such artificial architectures. Magnetic property measurements have found that the nanobrushes exhibit a saturation magnetization value of 6.16 B/f.u., which is much higher than the bulk value. The discovery not only enables insights into an effective route for fabricating unconventional high-quality nanostructures, but also demonstrates a novel magnetic architecture with potential applications in nanomagnetic devices.

Colossal oxygen vacancy formation at a fluorite-bixbyite interface.

Oxygen vacancies in complex oxides are indispensable for information and energy technologies. There are several means to create oxygen vacancies in bulk materials. However, the use of ionic interfaces to create oxygen vacancies has not been fully explored. Herein, we report an oxide nanobrush architecture designed to create high-density interfacial oxygen vacancies. An atomically well-defined (111) heterointerface between the fluorite CeO2 and the bixbyite Y2O3 is found to induce a charge modulation between Y3+ and Ce4+ ions enabled by the chemical valence mismatch between the two elements. Local structure and chemical analyses, along with theoretical calculations, suggest that more than 10% of oxygen atoms are spontaneously removed without deteriorating the lattice structure. Our fluorite-bixbyite nanobrush provides an excellent platform for the rational design of interfacial oxide architectures to precisely create, control, and transport oxygen vacancies critical for developing ionotronic and memristive devices for advanced energy and neuromorphic computing technologies.

Exploiting Symmetry Mismatch to Control Magnetism in a Ferroelastic Heterostructure.

In the bulk, LaCoO_{3} (LCO) is a paramagnet, yet the low-temperature ferromagnetism (FM) is observed in tensile strained thin films, and its origin remains unresolved. Here, we quantitatively measured the distribution of atomic density and magnetization in LCO films by polarized neutron reflectometry (PNR) and found that the LCO layers near the heterointerfaces exhibit a reduced magnetization but an enhanced atomic density, whereas the film's interior (i.e., its film bulk) shows the opposite trend. We attribute the nonuniformity to the symmetry mismatch at the interface, which induces a structural distortion related to the ferroelasticity of LCO. This assertion is tested by systematic application of hydrostatic pressure during the PNR experiments. The magnetization can be controlled at a rate of -20.4% per GPa. These results provide unique insights into mechanisms driving FM in strained LCO films while offering a tantalizing observation that tunable deformation of the CoO_{6} octahedra in combination with the ferroelastic order parameter.

Nanoscale ferroelastic twins formed in strained LaCoO3 films.

The coexistence and coupling of ferroelasticity and magnetic ordering in a single material offers a great opportunity to realize novel devices with multiple tuning knobs. Complex oxides are a particularly promising class of materials to find multiferroic interactions due to their rich phase diagrams, and are sensitive to external perturbations. Still, there are very few examples of these systems. Here, we report the observation of twin domains in ferroelastic LaCoO3 epitaxial films and their geometric control of structural symmetry intimately linked to the material's electronic and magnetic states. A unidirectional structural modulation is achieved by selective choice of substrates having twofold rotational symmetry. This modulation perturbs the crystal field-splitting energy, leading to unexpected in-plane anisotropy of orbital configuration and magnetization. These findings demonstrate the use of structural modulation to control multiferroic interactions and may enable a great potential for stimulation of exotic phenomena through artificial domain engineering.

Large orbital polarization in nickelate-cuprate heterostructures by dimensional control of oxygen coordination.

Artificial heterostructures composed of dissimilar transition metal oxides provide unprecedented opportunities to create remarkable physical phenomena. Here, we report a means to deliberately control the orbital polarization in LaNiO3 (LNO) through interfacing with SrCuO2 (SCO), which has an infinite-layer structure for CuO2. Dimensional control of SCO results in a planar-type (P-SCO) to chain-type (C-SCO) structure transition depending on the SCO thickness. This transition is exploited to induce either a NiO5 pyramidal or a NiO6 octahedral structure at the SCO/LNO interface. Consequently, a large change in the Ni d orbital occupation up to ~30% is achieved in P-SCO/LNO superlattices, whereas the Ni eg orbital splitting is negligible in C-SCO/LNO superlattices. The engineered oxygen coordination triggers a metal-to-insulator transition in SCO/LNO superlattices. Our results demonstrate that interfacial oxygen coordination engineering provides an effective means to manipulate the orbital configuration and associated physical properties, paving a pathway towards the advancement of oxide electronics.

Oxygen Diode Formed in Nickelate Heterostructures by Chemical Potential Mismatch.

Deliberate control of oxygen vacancy formation and migration in perovskite oxide thin films is important for developing novel electronic and iontronic devices. Here, it is found that the concentration of oxygen vacancies (VO ) formed in LaNiO3 (LNO) during pulsed laser deposition is strongly affected by the chemical potential mismatch between the LNO film and its proximal layers. Increasing the VO concentration in LNO significantly modifies the degree of orbital polarization and drives the metal-insulator transition. Changes in the nickel oxidization state and carrier concentration in the films are confirmed by soft X-ray absorption spectroscopy and optical spectroscopy. The ability to unidirectional-control the oxygen flow across the heterointerface, e.g., a so-called "oxygen diode", by exploiting chemical potential mismatch at interfaces provides a new avenue to tune the physical and electrochemical properties of complex oxides.

Spatially Resolved Large Magnetization in Ultrathin BiFeO3.

Here, a quantitative magnetic depth profile across the planar interfaces in BiFeO3 /La0.7 Sr0.3 MnO3 (BFO/LSMO) superlattices using polarized neutron reflectometry is obtained. An enhanced magnetization of 1.83 ± 0.16 µB /Fe in BFO layers is observed when they are interleaved between two manganite layers. The enhanced magnetic order in BFO persists up to 200 K. The depth dependence of magnetic moments in BFO/LSMO superlattices as a function of the BFO layer thickness is also explored. The results show the enhanced net magnetic moment in BFO from the LSMO/BFO interface extends 3-4 unit cells into BFO. The interior part of a thicker BFO layer has a much smaller magnetization, suggesting it still keeps the small canted AFM state. The results exclude charge transfer, intermixing, epitaxial strain, and octahedral rotations/tilts as dominating mechanisms for the large net magnetization in BFO. An explanation-one suggested by others previously and consistent with the observations-attributes the temperature dependence of the net magnetization of BFO to strong orbital hybridization between Fe and Mn across the interfaces. Such orbital reconstruction would establish an upper temperature limit for magnetic ordering of BFO.

Orientation Control of Interfacial Magnetism at La0.67Sr0.33MnO3/SrTiO3 Interfaces.

Understanding the magnetism at the interface between a ferromagnet and an insulator is essential because the commonly posited magnetic "dead" layer close to an interface can be problematic in magnetic tunnel junctions. Previously, degradation of the magnetic interface was attributed to charge discontinuity across the interface. Here, the interfacial magnetism was investigated using three identically prepared La0.67Sr0.33MnO3 (LSMO) thin films grown on different oriented SrTiO3 (STO) substrates by polarized neutron reflectometry. In all cases the magnetization at the LSMO/STO interface is larger than the film bulk. We show that the interfacial magnetization is largest across the LSMO/STO interfaces with (001) and (111) orientations, which have the largest net charge discontinuities across the interfaces. In contrast, the magnetization of LSMO/STO across the (110) interface, the orientation with no net charge discontinuity, is the smallest of the three orientations. We show that a magnetically degraded interface is not intrinsic to LSMO/STO heterostructures. The approach to use different crystallographic orientations provides a means to investigate the influence of charge discontinuity on the interfacial magnetization.

Hidden Interface Driven Exchange Coupling in Oxide Heterostructures.

A variety of emergent phenomena have been enabled by interface engineering in complex oxides. The existence of an intrinsic interfacial layer has often been found at oxide heterointerfaces. However, the role of such an interlayerin controlling functionalities is not fully explored. Here, we report the control of the exchange bias (EB) in single-phase manganite thin films with nominallyuniform chemical composition across the interfaces. The sign of EB depends on the magnitude of the cooling field. A pinned layer, confirmed by polarized neutron reflectometry, provides the source of unidirectional anisotropy. The origin of the exchange bias coupling is discussed in terms of magnetic interactions between the interfacial ferromagnetically reduced layer and the bulk ferromagnetic region. The sign of EB is related to the frustration of antiferromagnetic coupling between the ferromagnetic region and the pinned layer. Our results shed new light on using oxide interfaces to design functional spintronic devices.

Reversible Control of Interfacial Magnetism through Ionic-Liquid-Assisted Polarization Switching.

The ability to control magnetism of materials via electric field enables a myriad of technological innovations in information storage, sensing, and computing. We use ionic-liquid-assisted ferroelectric switching to demonstrate reversible modulation of interfacial magnetism in a multiferroic heterostructure composed of ferromagnetic (FM) La0.8Sr0.2MnO3 and ferroelectric (FE) PbZr0.2Ti0.8O3. It is shown that ionic liquids can be used to persistently and reversibly switch a large area of a FE film. This is a prerequisite for polarized neutron reflectometry (PNR) studies that are conducted to directly probe magnetoelectric coupling of the FE polarization to the interfacial magnetization.