Two-dimensional ferroelectricity in a single-element bismuth monolayer.

Ferroelectric materials are fascinating for their non-volatile switchable electric polarizations induced by the spontaneous inversion-symmetry breaking. However, in all of the conventional ferroelectric compounds, at least two constituent ions are required to support the polarization switching1,2. Here, we report the observation of a single-element ferroelectric state in a black phosphorus-like bismuth layer3, in which the ordered charge transfer and the regular atom distortion between sublattices happen simultaneously. Instead of a homogenous orbital configuration that ordinarily occurs in elementary substances, we found the Bi atoms in a black phosphorous-like Bi monolayer maintain a weak and anisotropic sp orbital hybridization, giving rise to the inversion-symmetry-broken buckled structure accompanied with charge redistribution in the unit cell. As a result, the in-plane electric polarization emerges in the Bi monolayer. Using the in-plane electric field produced by scanning probe microscopy, ferroelectric switching is further visualized experimentally. Owing to the conjugative locking between the charge transfer and atom displacement, we also observe the anomalous electric potential profile at the 180° tail-to-tail domain wall induced by competition between the electronic structure and electric polarization. This emergent single-element ferroelectricity broadens the mechanism of ferroelectrics and may enrich the applications of ferroelectronics in the future.

Decision trees within a molecular memristor.

Profuse dendritic-synaptic interconnections among neurons in the neocortex embed intricate logic structures enabling sophisticated decision-making that vastly outperforms any artificial electronic analogues1-3. The physical complexity is far beyond existing circuit fabrication technologies: moreover, the network in a brain is dynamically reconfigurable, which provides flexibility and adaptability to changing environments4-6. In contrast, state-of-the-art semiconductor logic circuits are based on threshold switches that are hard-wired to perform predefined logic functions. To advance the performance of logic circuits, we are re-imagining fundamental electronic circuit elements by expressing complex logic in nanometre-scale material properties. Here we use voltage-driven conditional logic interconnectivity among five distinct molecular redox states of a metal-organic complex to embed a 'thicket' of decision trees (composed of multiple if-then-else conditional statements) having 71 nodes within a single memristor. The resultant current-voltage characteristic of this molecular memristor (a 'memory resistor', a globally passive resistive-switch circuit element that axiomatically complements the set of capacitor, inductor and resistor) exhibits eight recurrent and history-dependent non-volatile switching transitions between two conductance levels in a single sweep cycle. The identity of each molecular redox state was determined with in situ Raman spectroscopy and confirmed by quantum chemical calculations, revealing the electron transport mechanism. Using simple circuits of only these elements, we experimentally demonstrate dynamically reconfigurable, commutative and non-commutative stateful logic in multivariable decision trees that execute in a single time step and can, for example, be applied as local intelligence in edge computing7-9.

Antiferromagnetic half-skyrmions and bimerons at room temperature.

In the quest for post-CMOS (complementary metal-oxide-semiconductor) technologies, driven by the need for improved efficiency and performance, topologically protected ferromagnetic 'whirls' such as skyrmions1-8 and their anti-particles have shown great promise as solitonic information carriers in racetrack memory-in-logic or neuromorphic devices1,9-11. However, the presence of dipolar fields in ferromagnets, which restricts the formation of ultrasmall topological textures3,6,8,9,12, and the deleterious skyrmion Hall effect, when skyrmions are driven by spin torques9,10,12, have thus far inhibited their practical implementation. Antiferromagnetic analogues, which are predicted to demonstrate relativistic dynamics, fast deflection-free motion and size scaling, have recently become the subject of intense focus9,13-19, but they have yet to be experimentally demonstrated in natural antiferromagnetic systems. Here we realize a family of topological antiferromagnetic spin textures in α-Fe2O3-an Earth-abundant oxide insulator-capped with a platinum overlayer. By exploiting a first-order analogue of the Kibble-Zurek mechanism20,21, we stabilize exotic merons and antimerons (half-skyrmions)8 and their pairs (bimerons)16,22, which can be erased by magnetic fields and regenerated by temperature cycling. These structures have characteristic sizes of the order of 100 nanometres and can be chemically controlled via precise tuning of the exchange and anisotropy, with pathways through which further scaling may be achieved. Driven by current-based spin torques from the heavy-metal overlayer, some of these antiferromagnetic textures could emerge as prime candidates for low-energy antiferromagnetic spintronics at room temperature1,9-11,23.

Spatially reconfigurable antiferromagnetic states in topologically rich free-standing nanomembranes.

Antiferromagnets hosting real-space topological textures are promising platforms to model fundamental ultrafast phenomena and explore spintronics. However, they have only been epitaxially fabricated on specific symmetry-matched substrates, thereby preserving their intrinsic magneto-crystalline order. This curtails their integration with dissimilar supports, restricting the scope of fundamental and applied investigations. Here we circumvent this limitation by designing detachable crystalline antiferromagnetic nanomembranes of α-Fe2O3. First, we show-via transmission-based antiferromagnetic vector mapping-that flat nanomembranes host a spin-reorientation transition and rich topological phenomenology. Second, we exploit their extreme flexibility to demonstrate the reconfiguration of antiferromagnetic states across three-dimensional membrane folds resulting from flexure-induced strains. Finally, we combine these developments using a controlled manipulator to realize the strain-driven non-thermal generation of topological textures at room temperature. The integration of such free-standing antiferromagnetic layers with flat/curved nanostructures could enable spin texture designs via magnetoelastic/geometric effects in the quasi-static and dynamical regimes, opening new explorations into curvilinear antiferromagnetism and unconventional computing.

Holographic imaging of antiferromagnetic domains with in-situ magnetic field.

Lensless coherent x-ray imaging techniques have great potential for high-resolution imaging of magnetic systems with a variety of in-situ perturbations. Despite many investigations of ferromagnets, extending these techniques to the study of other magnetic materials, primarily antiferromagnets, is lacking. Here, we demonstrate the first (to our knowledge) study of an antiferromagnet using holographic imaging through the 'holography with extended reference by autocorrelation linear differential operation' technique. Energy-dependent contrast with both linearly and circularly polarized x-rays are demonstrated. Antiferromagnetic domains and topological textures are studied in the presence of applied magnetic fields, demonstrating quasi-cyclic domain reconfiguration up to 500 mT.

Origin of a Topotactic Reduction Effect for Superconductivity in Infinite-Layer Nickelates.

Topotactic reduction utilizing metal hydrides as reagents has emerged as an effective approach to achieve exceptionally low oxidization states of metal ions and unconventional coordination networks. This method opens avenues to the development of entirely new functional materials, with one notable example being the infinite-layer nickelate superconductors. However, the reduction effect on the atomic reconstruction and electronic structures-crucial for superconductivity-remains largely unresolved. We designed two sets of control Nd_{0.8}Sr_{0.2}NiO_{2} thin films and used secondary ion mass spectroscopy to highlight the absence of reduction-induced hydrogen intercalation. X-ray absorption spectroscopy revealed a significant linear dichroism with dominant Ni 3d_{x2-y2} orbitals on superconducting samples, indicating a Ni single-band nature of infinite-layer nickelates. Consistent with the superconducting T_{c}, the Ni 3d orbitals asymmetry manifests a domelike dependence on the reduction duration. Our results unveil the critical role of reduction in modulating the Ni-3d orbital polarization and its impact on the superconducting properties.

Charge and Spin Order Dichotomy in NdNiO_{2} Driven by the Capping Layer.

Superconductivity in infinite-layer nickelates holds exciting analogies with that of cuprates, with similar structures and 3d-electron count. Using resonant inelastic x-ray scattering, we studied electronic and magnetic excitations and charge density correlations in Nd_{1-x}Sr_{x}NiO_{2} thin films with and without an SrTiO_{3} capping layer. We observe dispersing magnons only in the capped samples, progressively dampened at higher doping. We detect an elastic resonant scattering peak in the uncapped x=0 compound at wave vector (∼⅓,0), remindful of the charge order signal in hole doped cuprates. The peak weakens at x=0.05 and disappears in the superconducting x=0.20 film. The role of the capping on the electronic reconstruction far from the interface remains to be understood.

Experimental Evidence of t_{2g} Electron-Gas Rashba Interaction Induced by Asymmetric Orbital Hybridization.

We report the control of Rashba spin-orbit interaction by tuning asymmetric hybridization between Ti orbitals at the LaAlO_{3}/SrTiO_{3} interface. This asymmetric orbital hybridization is modulated by introducing a LaFeO_{3} layer between LaAlO_{3} and SrTiO_{3}, which alters the Ti-O lattice polarization and traps interfacial charge carriers, resulting in a large Rashba spin-orbit effect at the interface in the absence of an external bias. This observation is verified through high-resolution electron microscopy, magnetotransport and first-principles calculations. Our results open hitherto unexplored avenues of controlling Rashba interaction to design next-generation spin orbitronics.

Oxygen Electromigration and Energy Band Reconstruction Induced by Electrolyte Field Effect at Oxide Interfaces.

Electrolyte gating is a powerful means for tuning the carrier density and exploring the resultant modulation of novel properties on solid surfaces. However, the mechanism, especially its effect on the oxygen migration and electrostatic charging at the oxide heterostructures, is still unclear. Here we explore the electrolyte gating on oxygen-deficient interfaces between SrTiO_{3} (STO) crystals and LaAlO_{3} (LAO) overlayer through the measurements of electrical transport, x-ray absorption spectroscopy, and photoluminescence spectra. We found that oxygen vacancies (O_{vac}) were filled selectively and irreversibly after gating due to oxygen electromigration at the amorphous LAO/STO interface, resulting in a reconstruction of its interfacial band structure. Because of the filling of O_{vac}, the amorphous interface also showed an enhanced electron mobility and quantum oscillation of the conductance. Further, the filling effect could be controlled by the degree of the crystallinity of the LAO overlayer by varying the growth temperatures. Our results reveal the different effects induced by electrolyte gating, providing further clues to understand the mechanism of electrolyte gating on buried interfaces and also opening a new avenue for constructing high-mobility oxide interfaces.

Tunable Spin-Polarized States in Graphene on a Ferrimagnetic Oxide Insulator.

Spin-polarized two-dimensional (2D) materials with large and tunable spin-splitting energy promise the field of 2D spintronics. While graphene has been a canonical 2D material, its spin properties and tunability are limited. Here, this work demonstrates the emergence of robust spin-polarization in graphene with large and tunable spin-splitting energy of up to 132 meV at zero applied magnetic fields. The spin polarization is induced through a magnetic exchange interaction between graphene and the underlying ferrimagnetic oxide insulating layer, Tm3 Fe5 O12 , as confirmed by its X-ray magnetic circular dichroism (XMCD). The spin-splitting energies are directly measured and visualized by the shift in their Landau-fan diagram mapped by analyzing the measured Shubnikov-de-Haas (SdH) oscillations as a function of applied electric fields, showing consistent fit with the first-principles and machine learning calculations. Further, the observed spin-splitting energies can be tuned over a broad range between 98 and 166 meV by field cooling. The methods and results are applicable to other 2D (magnetic) materials and heterostructures, and offer great potential for developing next-generation spin logic and memory devices.

Extensive hydrogen incorporation is not necessary for superconductivity in topotactically reduced nickelates.

A key open question in the study of layered superconducting nickelate films is the role that hydrogen incorporation into the lattice plays in the appearance of the superconducting state. Due to the challenges of stabilizing highly crystalline square planar nickelate films, films are prepared by the deposition of a more stable parent compound which is then transformed into the target phase via a topotactic reaction with a strongly reducing agent such as CaH2. Recent studies, both experimental and theoretical, have introduced the possibility that the incorporation of hydrogen from the reducing agent into the nickelate lattice may be critical for the superconductivity. In this work, we use secondary ion mass spectrometry to examine superconducting La1-xXxNiO2 / SrTiO3 (X = Ca and Sr) and Nd6Ni5O12 / NdGaO3 films, along with non-superconducting NdNiO2 / SrTiO3 and (Nd,Sr)NiO2 / SrTiO3. We find no evidence for extensive hydrogen incorporation across a broad range of samples, including both superconducting and non-superconducting films. Theoretical calculations indicate that hydrogen incorporation is broadly energetically unfavorable in these systems, supporting our conclusion that extensive hydrogen incorporation is not generally required to achieve a superconducting state in layered square-planar nickelates.

Controlled alignment of supermoiré lattice in double-aligned graphene heterostructures.

The supermoiré lattice, built by stacking two moiré patterns, provides a platform for creating flat mini-bands and studying electron correlations. An ultimate challenge in assembling a graphene supermoiré lattice is in the deterministic control of its rotational alignment, which is made highly aleatory due to the random nature of the edge chirality and crystal symmetry. Employing the so-called "golden rule of three", here we present an experimental strategy to overcome this challenge and realize the controlled alignment of double-aligned hBN/graphene/hBN supermoiré lattice, where the twist angles between graphene and top/bottom hBN are both close to zero. Remarkably, we find that the crystallographic edge of neighboring graphite can be used to better guide the stacking alignment, as demonstrated by the controlled production of 20 moiré samples with an accuracy better than ~ 0.2°. Finally, we extend our technique to low-angle twisted bilayer graphene and ABC-stacked trilayer graphene, providing a strategy for flat-band engineering in these moiré materials.

Scanning SQUID-on-tip microscope in a top-loading cryogen-free dilution refrigerator.

The scanning superconducting quantum interference device (SQUID) fabricated on the tip of a sharp quartz pipette (SQUID-on-tip) has emerged as a versatile tool for the nanoscale imaging of magnetic, thermal, and transport properties of microscopic devices of quantum materials. We present the design and performance of a scanning SQUID-on-tip microscope in a top-loading probe of a cryogen-free dilution refrigerator. The microscope is enclosed in a custom-made vacuum-tight cell mounted at the bottom of the probe and is suspended by springs to suppress vibrations caused by the pulse tube cryocooler. Two capillaries allow for the in situ control of helium exchange gas pressure in the cell that is required for thermal imaging. A nanoscale heater is used to create local temperature gradients in the sample, which enables quantitative characterization of relative vibrations between the tip and the sample. The spectrum of the vibrations shows distinct resonant peaks with a maximal power density of about 27 nm/Hz1/2 in the in-plane direction. The performance of the SQUID-on-tip microscope is demonstrated by magnetic imaging of the MnBi2Te4 magnetic topological insulator, magnetization and current distribution imaging in a SrRuO3 ferromagnetic oxide thin film, and thermal imaging of dissipation in graphene.

Observation of perfect diamagnetism and interfacial effect on the electronic structures in infinite layer Nd0.8Sr0.2NiO2 superconductors.

Nickel-based complex oxides have served as a playground for decades in the quest for a copper-oxide analog of the high-temperature superconductivity. They may provide clues towards understanding the mechanism and an alternative route for high-temperature superconductors. The recent discovery of superconductivity in the infinite-layer nickelate thin films has fulfilled this pursuit. However, material synthesis remains challenging, direct demonstration of perfect diamagnetism is still missing, and understanding of the role of the interface and bulk to the superconducting properties is still lacking. Here, we show high-quality Nd0.8Sr0.2NiO2 thin films with different thicknesses and demonstrate the interface and strain effects on the electrical, magnetic and optical properties. Perfect diamagnetism is achieved, confirming the occurrence of superconductivity in the films. Unlike the thick films in which the normal-state Hall-coefficient changes signs as the temperature decreases, the Hall-coefficient of films thinner than 5.5 nm remains negative, suggesting a thickness-driven band structure modification. Moreover, X-ray absorption spectroscopy reveals the Ni-O hybridization nature in doped infinite-layer nickelates, and the hybridization is enhanced as the thickness decreases. Consistent with band structure calculations on the nickelate/SrTiO3 heterostructure, the interface and strain effect induce a dominating electron-like band in the ultrathin film, thus causing the sign-change of the Hall-coefficient.

Reversible hydrogen control of antiferromagnetic anisotropy in α-Fe2O3.

Antiferromagnetic insulators are a ubiquitous class of magnetic materials, holding the promise of low-dissipation spin-based computing devices that can display ultra-fast switching and are robust against stray fields. However, their imperviousness to magnetic fields also makes them difficult to control in a reversible and scalable manner. Here we demonstrate a novel proof-of-principle ionic approach to control the spin reorientation (Morin) transition reversibly in the common antiferromagnetic insulator α-Fe2O3 (haematite) - now an emerging spintronic material that hosts topological antiferromagnetic spin-textures and long magnon-diffusion lengths. We use a low-temperature catalytic-spillover process involving the post-growth incorporation or removal of hydrogen from α-Fe2O3 thin films. Hydrogenation drives pronounced changes in its magnetic anisotropy, Néel vector orientation and canted magnetism via electron injection and local distortions. We explain these effects with a detailed magnetic anisotropy model and first-principles calculations. Tailoring our work for future applications, we demonstrate reversible control of the room-temperature spin-state by doping/expelling hydrogen in Rh-substituted α-Fe2O3.

Origin and Quenching of Novel ultraviolet and blue emission in NdGaO3: Concept of Super-Hydrogenic Dopants.

In this study we report the existence of novel ultraviolet (UV) and blue emission in rare-earth based perovskite NdGaO3 (NGO) and the systematic quench of the NGO photoluminescence (PL) by Ce doping. Study of room temperature PL was performed in both single-crystal and polycrystalline NGO (substrates and pellets) respectively. Several NGO pellets were prepared with varying Ce concentration and their room temperature PL was studied using 325 nm laser. It was found that the PL intensity shows a systematic quench with increasing Ce concentration. XPS measurements indicated that nearly 50% of Ce atoms are in the 4+ state. The PL quench was attributed to the novel concept of super hydrogenic dopant (SHD)", where each Ce4+ ion contributes an electron which forms a super hydrogenic atom with an enhanced Bohr radius, due to the large dielectric constant of the host. Based on the critical Ce concentration for complete quenching this SHD radius was estimated to be within a range of 0.85 nm and 1.15 nm whereas the predicted theoretical value of SHD radius for NdGaO3 is ~1.01 nm.