Li iontronics in single-crystalline T-Nb2O5 thin films with vertical ionic transport channels.

The niobium oxide polymorph T-Nb2O5 has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure, which has two-dimensional (2D) layers with very low steric hindrance, allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, probably due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T-Nb2O5 thin films, critically with the ionic transport channels oriented perpendicular to the film's surface. These vertical 2D channels enable fast Li-ion migration, which we show gives rise to a colossal insulator-metal transition, where the resistivity drops by 11 orders of magnitude due to the population of the initially empty Nb 4d0 states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, which allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way for the exploration of novel thin films with ionic channels and their potential applications.

Long-range supercurrents through a chiral non-collinear antiferromagnet in lateral Josephson junctions.

The proximity-coupling of a chiral non-collinear antiferromagnet (AFM)1-5 with a singlet superconductor allows spin-unpolarized singlet Cooper pairs to be converted into spin-polarized triplet pairs6-8, thereby enabling non-dissipative, long-range spin correlations9-14. The mechanism of this conversion derives from fictitious magnetic fields that are created by a non-zero Berry phase15 in AFMs with non-collinear atomic-scale spin arrangements1-5. Here we report long-ranged lateral Josephson supercurrents through an epitaxial thin film of the triangular chiral AFM Mn3Ge (refs. 3-5). The Josephson supercurrents in this chiral AFM decay by approximately one to two orders of magnitude slower than would be expected for singlet pair correlations9-14 and their response to an external magnetic field reflects a clear spatial quantum interference. Given the long-range supercurrents present in both single- and mixed-phase Mn3Ge, but absent in a collinear AFM IrMn16, our results pave a way for the topological generation of spin-polarized triplet pairs6-8 via Berry phase engineering15 of the chiral AFMs.

Thickness-Tunable Zoology of Magnetic Spin Textures Observed in Fe5GeTe2.

The family of two-dimensional (2D) van der Waals (vdW) materials provides a playground for tuning structural and magnetic interactions to create a wide variety of spin textures. Of particular interest is the ferromagnetic compound Fe5GeTe2 that we show displays a range of complex spin textures as well as complex crystal structures. Here, using a high-brailliance laboratory X-ray source, we show that the majority (1 × 1) Fe5GeTe2 (FGT5) phase exhibits a structure that was previously considered as being centrosymmetric but rather lacks inversion symmetry. In addition, FGT5 exhibits a minority phase that exhibits a long-range ordered (√3 × âˆš3)-R30° superstructure. This superstructure is highly interesting in that it is innately 2D without any lattice periodicity perpendicular to the vdW layers, and furthermore, the superstructure is a result of ordered Te vacancies in one of the topmost layers of the FGT5 sheets rather than being a result of vertical Fe ordering as earlier suggested. We show, from direct real-space magnetic imaging, evidence for three distinct magnetic ground states in lamellae of FGT5 that are stabilized with increasing lamella thickness, namely, a multidomain state, a stripe phase, and an unusual fractal state. In the stripe phase we also observe unconventional type-I and type-II bubbles where the spin texture in the central region of the bubbles is nonuniform, unlike conventional bubbles. In addition, we find a bobber or a cocoon-like spin texture in thick (∼170 µm) FGT5 that emerges from the fractal state in the presence of a magnetic field. Among all the 2D vdW magnets we have thus demonstrated that FGT5 hosts perhaps the richest variety of magnetic phases that, thereby, make it a highly interesting platform for the subtle tuning of magnetic interactions.

Chiral antiferromagnetic Josephson junctions as spin-triplet supercurrent spin valves and d.c. SQUIDs.

Spin-triplet supercurrent spin valves are of practical importance for the realization of superconducting spintronic logic circuits. In ferromagnetic Josephson junctions, the magnetic-field-controlled non-collinearity between the spin-mixer and spin-rotator magnetizations switches the spin-polarized triplet supercurrents on and off. Here we report an antiferromagnetic equivalent of such spin-triplet supercurrent spin valves in chiral antiferromagnetic Josephson junctions as well as a direct-current superconducting quantum interference device. We employ the topological chiral antiferromagnet Mn3Ge, in which the Berry curvature of the band structure produces fictitious magnetic fields, and the non-collinear atomic-scale spin arrangement accommodates triplet Cooper pairing over long distances (>150 nm). We theoretically verify the observed supercurrent spin-valve behaviours under a small magnetic field of <2 mT for current-biased junctions and the direct-current superconducting quantum interference device functionality. Our calculations reproduce the observed hysteretic field interference of the Josephson critical current and link these to the magnetic-field-modulated antiferromagnetic texture that alters the Berry curvature. Our work employs band topology to control the pairing amplitude of spin-triplet Cooper pairs in a single chiral antiferromagnet.

Atomic Displacements Enabling the Observation of the Anomalous Hall Effect in a Non-Collinear Antiferromagnet.

Antiferromagnets with non-collinear spin structures display various properties that make them attractive for spintronic devices. Some of the most interesting examples are an anomalous Hall effect despite negligible magnetization and a spin Hall effect with unusual spin polarization directions. However, these effects can only be observed when the sample is set predominantly into a single antiferromagnetic domain state. This can only be achieved when the compensated spin structure is perturbed and displays weak moments due to spin canting that allows for external domain control. In thin films of cubic non-collinear antiferromagnets, this imbalance is previously assumed to require tetragonal distortions induced by substrate strain. Here, it is shown that in Mn3 SnN and Mn3 GaN, spin canting is due to structural symmetry lowering induced by large displacements of the magnetic manganese atoms away from high-symmetry positions. These displacements remain hidden in X-ray diffraction when only probing the lattice metric and require measurement of a large set of scattering vectors to resolve the local atomic positions. In Mn3 SnN, the induced net moments enable the observation of the anomalous Hall effect with an unusual temperature dependence, which is conjectured to result from a bulk-like temperature-dependent coherent spin rotation within the kagome plane.

2D honeycomb transformation into dodecagonal quasicrystals driven by electrostatic forces.

Dodecagonal oxide quasicrystals are well established as examples of long-range aperiodic order in two dimensions. However, despite investigations by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), low-energy electron microscopy (LEEM), photoemission spectroscopy as well as density functional theory (DFT), their structure is still controversial. Furthermore, the principles that guide the formation of quasicrystals (QCs) in oxides are elusive since the principles that are known to drive metallic QCs are expected to fail for oxides. Here we demonstrate the solution of the oxide QC structure by synchrotron-radiation based surface x-ray diffraction (SXRD) refinement of its largest-known approximant. The oxide QC formation is forced by large alkaline earth metal atoms and the reduction of their mutual electrostatic repulsion. It drives the n = 6 structure of the 2D Ti2O3 honeycomb arrangement via Stone-Wales transformations into an ordered structure with empty n = 4, singly occupied n = 7 and doubly occupied n = 10 rings, as supported by DFT.

Crystal-field mediated electronic transitions of EuS up to 35 GPa.

An advanced experimental and theoretical model to explain the correlation between the electronic and local structure of Eu[Formula: see text] in two different environments within a same compound, EuS, is presented. EuX monochalcogenides (X: O, S, Se, Te) exhibit anomalies in all their properties around 14 GPa with a semiconductor to metal transition. Although it is known that these changes are related to the [Formula: see text] [Formula: see text] [Formula: see text] electronic transition, no consistent model of the pressure-induced modifications of the electronic structure currently exists. We show, by optical and x-ray absorption spectroscopy, and by ab initio calculations up to 35 GPa, that the pressure evolution of the crystal field plays a major role in triggering the observed electronic transitions from semiconductor to the half-metal and finally to the metallic state.

Magnetic Skyrmions in a Thickness Tunable 2D Ferromagnet from a Defect Driven Dzyaloshinskii-Moriya Interaction.

There is considerable interest in van der Waals (vdW) materials as potential hosts for chiral skyrmionic spin textures. Of particular interest is the ferromagnetic, metallic compound Fe3 GeTe2 (FGT), which has a comparatively high Curie temperature (150-220 K). Several recent studies have reported the observation of chiral Néel skyrmions in this compound, which is inconsistent with its presumed centrosymmetric structure. Here the observation of Néel type skyrmions in single crystals of FGT via Lorentz transmission electron microscopy (LTEM) is reported. It is shown from detailed X-ray diffraction structure analysis that FGT lacks an inversion symmetry as a result of an asymmetric distribution of Fe vacancies. This vacancy-induced breaking of the inversion symmetry of this compound is a surprising and novel observation and is a prerequisite for a Dzyaloshinskii-Moriya vector exchange interaction which accounts for the chiral Néel skyrmion phase. This phenomenon is likely to be common to many 2D vdW materials and suggests a path to the preparation of many such acentric compounds. Furthermore, it is found that the skyrmion size in FGT is strongly dependent on its thickness: the skyrmion size increases from ≈100 to ≈750 nm as the thickness of the lamella is increased from ≈90 nm to ≈2 µm. This extreme size tunability is a feature common to many low symmetry ferro- and ferri-magnetic compounds.

Observation of Néel-type skyrmions in acentric self-intercalated Cr1+δTe2.

Transition-metal dichalcogenides intercalated with 3d-transition metals within the van der Waals (vdW) gaps have been the focus of intense investigations owing to their fascinating structural and magnetic properties. At certain concentrations the intercalated atoms form ordered superstructures that exhibit ferromagnetic or anti-ferromagnetic ordering. Here we show that the self-intercalated compound Cr1+δTe2 with δ ≈ 0.3 exhibits a new, so far unseen, three-dimensionally ordered (2×2×2) superstructure. Furthermore, high resolution X-ray diffraction reveals that there is an asymmetric occupation of the two inequivalent vdW gaps in the unit cell. The structure thus lacks inversion symmetry, which, thereby, allows for chiral non-collinear magnetic nanostructures. Indeed, Néel-type skyrmions are directly observed using Lorentz transmission electron microscopy. The skyrmions are stable within the accessible temperature range (100-200 K) as well as in zero magnetic field. The diameter of the Néel skyrmions increases with lamella thickness and varies with applied magnetic field, indicating the role of long-range dipole fields. Our studies show that self-intercalation in vdW materials is a novel route to the formation of synthetic non-collinear spin textures.

Control of Oxygen Vacancy Ordering in Brownmillerite Thin Films via Ionic Liquid Gating.

Oxygen defects and their atomic arrangements play a significant role in the physical properties of many transition metal oxides. The exemplary perovskite SrCoO3-δ (P-SCO) is metallic and ferromagnetic. However, its daughter phase, the brownmillerite SrCoO2.5 (BM-SCO), is insulating and an antiferromagnet. Moreover, BM-SCO exhibits oxygen vacancy channels (OVCs) that in thin films can be oriented either horizontally (H-SCO) or vertically (V-SCO) to the film's surface. To date, the orientation of these OVCs has been manipulated by control of the thin film deposition parameters or by using a substrate-induced strain. Here, we present a method to electrically control the OVC ordering in thin layers via ionic liquid gating (ILG). We show that H-SCO (antiferromagnetic insulator, AFI) can be converted to P-SCO (ferromagnetic metal, FM) and subsequently to V-SCO (AFI) by the insertion and subtraction of oxygen throughout thick films via ILG. Moreover, these processes are independent of substrate-induced strain which favors formation of H-SCO in the as-deposited film. The electric-field control of the OVC channels is a path toward the creation of oxitronic devices.

Fermi surface chirality induced in a TaSe2 monosheet formed by a Ta/Bi2Se3 interface reaction.

Spin-momentum locking in topological insulators and materials with Rashba-type interactions is an extremely attractive feature for novel spintronic devices and is therefore under intense investigation. Significant efforts are underway to identify new material systems with spin-momentum locking, but also to create heterostructures with new spintronic functionalities. In the present study we address both subjects and investigate a van der Waals-type heterostructure consisting of the topological insulator Bi2Se3 and a single Se-Ta-Se triple-layer (TL) of H-type TaSe2 grown by a method which exploits an interface reaction between the adsorbed metal and selenium. We then show, using surface x-ray diffraction, that the symmetry of the TaSe2-like TL is reduced from D3h to C3v resulting from a vertical atomic shift of the tantalum atom. Spin- and momentum-resolved photoemission indicates that, owing to the symmetry lowering, the states at the Fermi surface acquire an in-plane spin component forming a surface contour with a helical Rashba-like spin texture, which is coupled to the Dirac cone of the substrate. Our approach provides a route to realize chiral two-dimensional electron systems via interface engineering in van der Waals epitaxy that do not exist in the corresponding bulk materials.

Nanoscale Noncollinear Spin Textures in Thin Films of a D2d Heusler Compound.

Magnetic nano-objects, namely antiskyrmions and Bloch skyrmions, have been found to coexist in single-crystalline lamellae formed from bulk crystals of inverse tetragonal Heusler compounds with D2d symmetry. Here evidence is shown for magnetic nano-objects in epitaxial thin films of Mn2 RhSn formed by magnetron sputtering. These nano-objects exhibit a wide range of sizes with stability with respect to magnetic field and temperature that is similar to single-crystalline lamellae. However, the nano-objects do not form well-defined arrays, nor is any evidence found for helical spin textures. This is speculated to likely be a consequence of the poorer homogeneity of chemical ordering in the thin films. However, evidence is found for elliptically distorted nano-objects along perpendicular crystallographic directions within the epitaxial films, which is consistent with elliptical Bloch skyrmions observed in single-crystalline lamellae. Thus, these measurements provide strong evidence for the formation of noncollinear spin textures in thin films of Mn2 RhSn. Using these films, it is shown that individual nano-objects can be deleted using a local magnetic field from a magnetic tip and collections of nano-objects can be similarly written. These observations suggest a path toward the use of these objects in thin films with D2d symmetry as magnetic memory elements.

Observation of Robust Néel Skyrmions in Metallic PtMnGa.

Over the past decade the family of chiral noncollinear spin textures has continued to expand with the observation in metallic compounds of Bloch-like skyrmions in several B20 compounds, and antiskyrmions in a tetragonal inverse Heusler. Néel like skyrmions in bulk crystals with broken inversion symmetry have recently been seen in two distinct nonmetallic compounds, GaV4 S8 and VOSe2 O5 at low temperatures (below ≈13 K) only. Here, the first observation of bulk Néel skyrmions in a metallic compound PtMnGa and, moreover, at high temperatures up to ≈220 K is reported. Lorentz transmission electron microscopy reveals the chiral Néel character of the skyrmions. A strong variation is reported of the size of the skyrmions on the thickness of the lamella in which they are confined, varying by a factor of 7 as the thickness is varied from ≈90 nm to ≈4 µm. Moreover, the skyrmions are highly robust to in-plane magnetic fields and can be stabilized in a zero magnetic field using suitable field-cooling protocols over a very broad temperature range to as low as 5 K. These properties, together with the possibility of manipulating skyrmions in metallic PtMnGa via current induced spin-orbit torques, make them extremely exciting for future spintronic applications.

A bismuth triiodide monosheet on Bi2Se3(0001).

A stable BiI3 monosheet has been grown for the first time on the (0001) surface of the topological insulator Bi2Se3 as confirmed by scanning tunnelling microscopy, surface X-ray diffraction, and X-ray photoemision spectroscopy. BiI3 is deposited by molecular beam epitaxy from the crystalline BiTeI precursor that undergoes decomposition sublimation. The key fragment of the bulk BiI3 structure, [Formula: see text][I-Bi-I] layer of edge-sharing BiI6 octahedra, is preserved in the ultra-thin film limit, but exhibits large atomic relaxations. The stacking sequence of the trilayers and alternations of the Bi-I distances in the monosheet are the same as in the bulk BiI3 structure. Momentum resolved photoemission spectroscopy indicates a direct band gap of 1.2 eV. The Dirac surface state is completely destroyed and a new flat band appears in the band gap of the BiI3 film that could be interpreted as an interface state.

Reversible Formation of 2D Electron Gas at the LaFeO3 /SrTiO3 Interface via Control of Oxygen Vacancies.

A conducting 2D electron gas (2DEG) is formed at the interface between epitaxial LaFeO3 layers >3 unit cells thick and the surface of SrTiO3 single crystals. The 2DEG is exquisitely sensitive to cation intermixing and oxygen nonstoichiometry. It is shown that the latter thus allows the controllable formation of the 2DEG via ionic liquid gating, thereby forming a nonvolatile switch.