Effect of Surface Oxidation and Crystal Thickness on the Magnetic Properties and Magnetic Domain Structures of Cr2Ge2Te6.

van der Waals (vdW) magnetic materials, such as Cr2Ge2Te6 (CGT), show promise for memory and logic applications. This is due to their broadly tunable magnetic properties and the presence of topological magnetic features such as skyrmionic bubbles. A systematic study of thickness and oxidation effects on magnetic domain structures is important for designing devices and vdW heterostructures for practical applications. Here, we investigate thickness effects on magnetic properties, magnetic domains, and bubbles in oxidation-controlled CGT crystals. We find that CGT exposed to ambient conditions for 5 days forms an oxide layer approximately 5 nm thick. This oxidation leads to a significant increase in the oxidation state of the Cr ions, indicating a change in local magnetic properties. This is supported by real-space magnetic texture imaging through Lorentz transmission electron microscopy. By comparing the thickness-dependent saturation field of oxidized and pristine crystals, we find that oxidation leads to a nonmagnetic surface layer that is thicker than the oxide layer alone. We also find that the stripe domain width and skyrmionic bubble size are strongly affected by the crystal thickness in pristine crystals. These findings underscore the impact of thickness and surface oxidation on the properties of CGT, such as saturation field and domain/skyrmionic bubble size, and suggest a pathway for manipulating magnetic properties through a controlled oxidation process.

Spin-orbit-splitting-driven nonlinear Hall effect in NbIrTe4.

The Berry curvature dipole (BCD) serves as a one of the fundamental contributors to emergence of the nonlinear Hall effect (NLHE). Despite intense interest due to its potential for new technologies reaching beyond the quantum efficiency limit, the interplay between BCD and NLHE has been barely understood yet in the absence of a systematic study on the electronic band structure. Here, we report NLHE realized in NbIrTe4 that persists above room temperature coupled with a sign change in the Hall conductivity at 150 K. First-principles calculations combined with angle-resolved photoemission spectroscopy (ARPES) measurements show that BCD tuned by the partial occupancy of spin-orbit split bands via temperature is responsible for the temperature-dependent NLHE. Our findings highlight the correlation between BCD and the electronic band structure, providing a viable route to create and engineer the non-trivial Hall effect by tuning the geometric properties of quasiparticles in transition-metal chalcogen compounds.

Proton-fluence dependent magnetic properties of exfoliable quasi-2D van der Waals Cr2Si2Te6magnet.

The discovery of long-range magnetic ordering in atomically thin materials catapulted the van der Waals (vdW) family of compounds into an unprecedented popularity, leading to potentially important technological applications in magnetic storage and magneto-transport devices, as well as photoelectric sensors. With the potential for the use of vdW materials in space exploration technologies it is critical to understand how the properties of such materials are affected by ionizing proton irradiation. Owing to their robust intra-layer stability and sensitivity to external perturbations, these materials also provide excellent opportunities for studying proton irradiation as a non-destructive tool for controlling their magnetic properties. Specifically, the exfoliable Cr2Si2Te6(CST) is a ferromagnetic semiconductor with the Curie temperature (TC) of ∼32 K. Here, we have investigated the magnetic properties of CST upon proton irradiation as a function of fluence (1 × 1015, 5 × 1015, 1 × 1016, 5 × 1016, and 1 × 1018H+/cm-2) by employing variable-temperature, variable-field magnetization measurements, and detail how the magnetization, magnetic anisotropy vary as a function of proton fluence across the magnetic phase transition. While theTCremains constant as a function of proton fluence, we observed that the saturation magnetization and magnetic anisotropy diverge at the proton fluence of 5 × 1016H+/cm-2, which is prominent in the ferromagnetic phase, in particular.This work demonstrates that proton irradiation is a feasible method for modifying the magnetic properties and local magnetic interactions of vdWs crystals, which represents a significant step forward in the design of future spintronic and magneto-electronic applications.

Nanoscale inhomogeneity and the evolution of correlation strength in FeSe[Formula: see text]S[Formula: see text].

We report a comprehensive study of the nanoscale inhomogeneity and disorder on the thermoelectric properties of FeSe[Formula: see text]S[Formula: see text] ([Formula: see text]) single crystals and the evolution of correlation strength with S substitution. A hump-like feature in temperature-dependent thermpower is enhanced for x = 0.12 and 0.14 in the nematic region with increasing in orbital-selective electronic correlations, which is strongly suppressed across the nematic critical point and for higher S content. Nanoscale Se/S atom disorder in the tetrahedral surroundings of Fe atoms is confirmed by scanning transmission electron microscopy measurements, providing an insight into the nanostructural details and the evolution of correlation strength in FeSe[Formula: see text]S[Formula: see text].

Voltage control of magnetism in Fe3-xGeTe2/In2Se3 van der Waals ferromagnetic/ferroelectric heterostructures.

We investigate the voltage control of magnetism in a van der Waals (vdW) heterostructure device consisting of two distinct vdW materials, the ferromagnetic Fe3-xGeTe2 and the ferroelectric In2Se3. It is observed that gate voltages applied to the Fe3-xGeTe2/In2Se3 heterostructure device modulate the magnetic properties of Fe3-xGeTe2 with significant decrease in coercive field for both positive and negative voltages. Raman spectroscopy on the heterostructure device shows voltage-dependent increase in the in-plane In2Se3 and Fe3-xGeTe2 lattice constants for both voltage polarities. Thus, the voltage-dependent decrease in the Fe3-xGeTe2 coercive field, regardless of the gate voltage polarity, can be attributed to the presence of in-plane tensile strain. This is supported by density functional theory calculations showing tensile-strain-induced reduction of the magnetocrystalline anisotropy, which in turn decreases the coercive field. Our results demonstrate an effective method to realize low-power voltage-controlled vdW spintronic devices utilizing the magnetoelectric effect in vdW ferromagnetic/ferroelectric heterostructures.

Interplay of hidden orbital order and superconductivity in CeCoIn5.

Visualizing atomic-orbital degrees of freedom is a frontier challenge in scanned microscopy. Some types of orbital order are virtually imperceptible to normal scattering techniques because they do not reduce the overall crystal lattice symmetry. A good example is dxz/dyz (π,π) orbital order in tetragonal lattices. For enhanced detectability, here we consider the quasiparticle scattering interference (QPI) signature of such (π,π) orbital order in both normal and superconducting phases. The theory reveals that sublattice-specific QPI signatures generated by the orbital order should emerge strongly in the superconducting phase. Sublattice-resolved QPI visualization in superconducting CeCoIn5 then reveals two orthogonal QPI patterns at lattice-substitutional impurity atoms. We analyze the energy dependence of these two orthogonal QPI patterns and find the intensity peaked near E = 0, as predicted when such (π,π) orbital order is intertwined with d-wave superconductivity. Sublattice-resolved superconductive QPI techniques thus represent a new approach for study of hidden orbital order.

Robust three-dimensional type-II Dirac semimetal state in SrAgBi.

Topological semimetals such as Dirac, Weyl or nodal line semimetals are widely studied for their peculiar properties including high Fermi velocities, small effective masses and high magnetoresistance. When the Dirac cone is tilted, exotic phenomena could emerge whereas materials hosting such states are promising for photonics and plasmonics applications. Here we present evidence that SrAgBi is a spin-orbit coupling-induced type-II three-dimensional Dirac semimetal featuring tilted Dirac cone at the Fermi energy. Near charge compensation and Fermi surface characteristics are not much perturbed by 7% of vacancy defects on the Ag atomic site, suggesting that SrAgBi could be a material of interest for observation of robust optical and spintronic topological quantum phenomena.

On single-crystal total scattering data reduction and correction protocols for analysis in direct space. Corrigendum.

The name of the third author of the article by Koch et al. [Acta Cryst. (2021). A77, 611-636] is corrected.

Mooij Law Violation from Nanoscale Disorder.

Nanoscale inhomogeneity can profoundly impact properties of two-dimensional van der Waals materials. Here, we reveal how sulfur substitution on the selenium atomic sites in Fe1-ySe1-xSx (0 ≤ x ≤ 1, y ≤ 0.1) causes Fe-Ch (Ch = Se, S) bond length differences and strong disorder for 0.4 ≤ x ≤ 0.8. There, the superconducting transition temperature Tc is suppressed and disorder-related scattering is enhanced. The high-temperature metallic resistivity in the presence of strong disorder exceeds the Mott limit and provides an example of the violation of Matthiessen's rule and the Mooij law, a dominant effect when adding moderate disorder past the Drude/Matthiessen's regime in all materials. The scattering mechanism responsible for the resistivity above the Mott limit is unrelated to phonons and arises for strong Se/S atom disorder in the tetrahedral surrounding of Fe. Our findings shed light on the intricate connection between the nanostructural details and the unconventional scattering mechanism, which is possibly related to charge-nematic or magnetic spin fluctuations.

Giant Thermoelectric Power Factor Anisotropy in PtSb1.4Sn0.6.

We report on the giant anisotropy found in the thermoelectric power factor (S2σ) of marcasite structure-type PtSb1.4Sn0.6 single crystal. PtSb1.4Sn0.6, synthesized using an ambient pressure flux growth method upon mixing Sb and Sn on the same atomic site, is a new phase different from both PtSb2 and PtSn2, which crystallize in the cubic Pa3̅ pyrite and Fm3̅m fluorite unit cell symmetry, respectively. The large difference in S2σ for heat flow applied along different principal directions of the orthorhombic unit cell stems mostly from anisotropic Seebeck coefficients.

Short-Range Crystalline Order-Tuned Conductivity in Cr2Si2Te6 van der Waals Magnetic Crystals.

Two-dimensional magnetic materials (2DMMs) are significant not only for studies on the nature of 2D long-range magnetic order but also for future spintronic devices. Of particular interest are 2DMMs where spins can be manipulated by electrical conduction. Whereas Cr2Si2Te6 exhibits magnetic order in few-layer crystals, its large band gap inhibits electronic conduction. Here we show that the defect-induced short-range crystal order in Cr2Si2Te6, on the length scale below 0.6 nm, induces a substantially reduced band gap and robust semiconducting behavior down to 2 K that turns to metallic above 10 GPa. Our results will be helpful in designing conducting states in 2DMMs and call for spin-resolved measurement of the electronic structure in exfoliated ultrathin crystals.

Suppression of Superconductivity and Nematic Order in Fe1-ySe1-xSx (0 ≤ x ≤ 1; y ≤ 0.1) Crystals by Anion Height Disorder.

Connections between crystal chemistry and critical temperature Tc have been in the focus of superconductivity, one of the most widely studied phenomena in physics, chemistry, and materials science alike. In most Fe-based superconductors, materials chemistry and physics conspire so that Tc correlates with the average anion height above the Fe plane, i.e., with the geometry of the FeAs4 or FeCh4 (Ch = Te, Se, or S) tetrahedron. By synthesizing Fe1-ySe1-xSx (0 ≤ x ≤ 1; y ≤ 0.1), we find that in alloyed crystals Tc is not correlated with the anion height like it is for most other Fe superconductors. Instead, changes in Tc(x) and tetragonal-to-orthorhombic (nematic) transition Ts(x) upon cooling are correlated with disorder in Fe vibrations in the direction orthogonal to Fe planes, along the crystallographic c-axis. The disorder stems from the random nature of S substitution, causing deformed Fe(Se,S)4 tetrahedra with different Fe-Se and Fe-S bond distances. Our results provide evidence of Tc and Ts suppression by disorder in anion height. The connection to local crystal chemistry may be exploited in computational prediction of new superconducting materials with FeSe/S building blocks.

The Magnetic Genome of Two-Dimensional van der Waals Materials.

Magnetism in two-dimensional (2D) van der Waals (vdW) materials has recently emerged as one of the most promising areas in condensed matter research, with many exciting emerging properties and significant potential for applications ranging from topological magnonics to low-power spintronics, quantum computing, and optical communications. In the brief time after their discovery, 2D magnets have blossomed into a rich area for investigation, where fundamental concepts in magnetism are challenged by the behavior of spins that can develop at the single layer limit. However, much effort is still needed in multiple fronts before 2D magnets can be routinely used for practical implementations. In this comprehensive review, prominent authors with expertise in complementary fields of 2D magnetism (i.e., synthesis, device engineering, magneto-optics, imaging, transport, mechanics, spin excitations, and theory and simulations) have joined together to provide a genome of current knowledge and a guideline for future developments in 2D magnetic materials research.

On single-crystal total scattering data reduction and correction protocols for analysis in direct space.

Data reduction and correction steps and processed data reproducibility in the emerging single-crystal total-scattering-based technique of three-dimensional differential atomic pair distribution function (3D-ΔPDF) analysis are explored. All steps from sample measurement to data processing are outlined using a crystal of CuIr2S4 as an example, studied in a setup equipped with a high-energy X-ray beam and a flat-panel area detector. Computational overhead as pertains to data sampling and the associated data-processing steps is also discussed. Various aspects of the final 3D-ΔPDF reproducibility are explicitly tested by varying the data-processing order and included steps, and by carrying out a crystal-to-crystal data comparison. Situations in which the 3D-ΔPDF is robust are identified, and caution against a few particular cases which can lead to inconsistent 3D-ΔPDFs is noted. Although not all the approaches applied herein will be valid across all systems, and a more in-depth analysis of some of the effects of the data-processing steps may still needed, the methods collected herein represent the start of a more systematic discussion about data processing and corrections in this field.

Coexistence and Coupling of Multiple Charge Orderings and Spin States in Hexagonal Ferrite.

The coupling between charge and spin orderings in strongly correlated systems plays a crucial role in fundamental physics and device applications. As a candidate of multiferroic materials, LuFe2O4 with a nominal Fe2.5+ valence state has the potential for strong charge-spin interactions; however, these interactions have not been fully understood until now. Here, combining complementary characterization methods with theoretical calculations, two types of charge orderings with distinct magnetic properties are revealed. The ground states of LuFe2O4 are decided by the parallel/antiparallel coupling of both charge and spin orderings in the adjacent FeO double layers. Whereas the ferroelectric charge ordering remains ferrimagnetic below 230 K, the antiferroelectric ordering undergoes antiferromagnetic-ferrimagnetic-paramagnetic transitions from 2 K to room temperature. This study demonstrates the unique aspects of strong spin-charge coupling within LuFe2O4. Our results shed light on the coexistence and competing nature of orderings in quantum materials.

Synthesis and Characterization of Ultrathin FeTe2 Nanocrystals.

Ultrathin crystals including monolayers have been reported for various transition-metal dichalcogenides (TMDCs) with van der Waals bonds in the crystal structure. Herein, we report a detailed synthesis procedure and characterization of ultrathin iron ditelluride crystals. This material crystallizes in an orthorhombic marcasite Pnnm crystal structure whose bonding is dominantly covalent and without loosely connected van der Waals (vdW) bonds, making monolayer FeTe2 synthesis less straightforward than other TMDC monolayer syntheses. The chemical vapor deposition synthesis process described is simple, effective, and results in a range of crystal thicknesses from approximately 400 nm down to the FeTe2 monolayer.

Electronic properties of the bulk and surface states of Fe1+yTe1-xSex.

The idea of employing non-Abelian statistics for error-free quantum computing ignited interest in reports of topological surface superconductivity and Majorana zero modes (MZMs) in FeTe0.55Se0.45. However, the topological features and superconducting properties are not observed uniformly across the sample surface. The understanding and practical control of these electronic inhomogeneities present a prominent challenge for potential applications. Here, we combine neutron scattering, scanning angle-resolved photoemission spectroscopy, and microprobe composition and resistivity measurements to characterize the electronic state of Fe1+yTe1-xSex. We establish a phase diagram in which the superconductivity is observed only at sufficiently low Fe concentration, in association with distinct antiferromagnetic correlations, whereas the coexisting topological surface state occurs only at sufficiently high Te concentration. We find that FeTe0.55Se0.45 is located very close to both phase boundaries, which explains the inhomogeneity of superconducting and topological states. Our results demonstrate the compositional control required for use of topological MZMs in practical applications.

Short-Range Order in VI3.

We present a detailed investigation of the crystal structure of VI3, a two-dimensional van der Waals material of interest for studies of low-dimensional magnetism. As opposed to the average crystal structure that features R3̅ symmetry of the unit cell, our Raman scattering and X-ray atomic pair distribution function analysis supported by density functional theory calculations point to the coexistence of short-range ordered P3̅1c and long-range ordered R3̅ phases. The highest-intensity peak, A1g3, exhibits a moderate asymmetry that might be traced back to the spin-phonon interactions, as in the case of CrI3.

Author Correction: Anisotropic magnetocaloric effect in Fe3-xGeTe2.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Controlling the Magnetic Anisotropy of the van der Waals Ferromagnet Fe3GeTe2 through Hole Doping.

Identifying material parameters affecting properties of ferromagnets is key to optimized materials that are better suited for spintronics. Magnetic anisotropy is of particular importance in van der Waals magnets, since it not only influences magnetic and spin transport properties, but also is essential to stabilizing magnetic order in the two-dimensional limit. Here, we report that hole doping effectively modulates the magnetic anisotropy of a van der Waals ferromagnet and explore the physical origin of this effect. Fe3-xGeTe2 nanoflakes show a significant suppression of the magnetic anisotropy with hole doping. Electronic structure measurements and calculations reveal that the chemical potential shift associated with hole doping is responsible for the reduced magnetic anisotropy by decreasing the energy gain from the spin-orbit induced band splitting. Our findings provide an understanding of the intricate connection between electronic structures and magnetic properties in two-dimensional magnets and propose a method to engineer magnetic properties through doping.