Hidden non-collinear spin-order induced topological surface states.

Rare-earth monopnictides are a family of materials simultaneously displaying complex magnetism, strong electronic correlation, and topological band structure. The recently discovered emergent arc-like surface states in these materials have been attributed to the multi-wave-vector antiferromagnetic order, yet the direct experimental evidence has been elusive. Here we report observation of non-collinear antiferromagnetic order with multiple modulations using spin-polarized scanning tunneling microscopy. Moreover, we discover a hidden spin-rotation transition of single-to-multiple modulations 2 K below the Néel temperature. The hidden transition coincides with the onset of the surface states splitting observed by our angle-resolved photoemission spectroscopy measurements. Single modulation gives rise to a band inversion with induced topological surface states in a local momentum region while the full Brillouin zone carries trivial topological indices, and multiple modulation further splits the surface bands via non-collinear spin tilting, as revealed by our calculations. The direct evidence of the non-collinear spin order in NdSb not only clarifies the mechanism of the emergent topological surface states, but also opens up a new paradigm of control and manipulation of band topology with magnetism.

Atomistic Origin of Diverse Charge Density Wave States in CsV_{3}Sb_{5}.

Kagome metals AV_{3}Sb_{5} (A=K, Rb, or Cs) exhibit intriguing charge density wave (CDW) instabilities, which interplay with superconductivity and band topology. However, despite firm observations, the atomistic origins of the CDW phases, as well as hidden instabilities, remain elusive. Here, we adopt our newly developed symmetry-adapted cluster expansion method to construct a first-principles-based effective Hamiltonian of CsV_{3}Sb_{5}, which not only reproduces the established inverse star of David (ISD) phase, but also predict a series of D_{3h}-n states under mild tensile strains. With such atomistic Hamiltonians, the microscopic origins of different CDW states are revealed as the competition of the second-nearest neighbor V-V pairs versus the first-nearest neighbor V-V and V-Sb couplings. Interestingly, the effective Hamiltonians also reveal the existence of ionic Dzyaloshinskii-Moriya interaction in the high-symmetry phase of CsV_{3}Sb_{5} and drives the formation of noncollinear CDW patterns. Our work thus not only deepens the understanding of the CDW formation in AV_{3}Sb_{5}, but also demonstrates that the effective Hamiltonian is a suitable approach for investigating CDW mechanisms, which can be extended to various CDW systems.

Atomically precise engineering of spin-orbit polarons in a kagome magnetic Weyl semimetal.

Atomically precise defect engineering is essential to manipulate the properties of emerging topological quantum materials for practical quantum applications. However, this remains challenging due to the obstacles in modifying the typically complex crystal lattice with atomic precision. Here, we report the atomically precise engineering of the vacancy-localized spin-orbit polarons in a kagome magnetic Weyl semimetal Co3Sn2S2, using scanning tunneling microscope. We achieve the step-by-step repair of the selected vacancies, leading to the formation of artificial sulfur vacancies with elaborate geometry. We find that that the bound states localized around these vacancies undergo a symmetry dependent energy shift towards Fermi level with increasing vacancy size. As the vacancy size increases, the localized magnetic moments of spin-orbit polarons become tunable and eventually become itinerantly negative due to spin-orbit coupling in the kagome flat band. These findings provide a platform for engineering atomic quantum states in topological quantum materials at the atomic scale.

Competing itinerant and local spin interactions in kagome metal FeGe.

The combination of a geometrically frustrated lattice, and similar energy scales between degrees of freedom endows two-dimensional Kagome metals with a rich array of quantum phases and renders them ideal for studying strong electron correlations and band topology. The Kagome metal, FeGe is a noted example of this, exhibiting A-type collinear antiferromagnetic (AFM) order at TN ≈ 400 K, then establishes a charge density wave (CDW) phase coupled with AFM ordered moment below TCDW ≈ 110 K, and finally forms a c-axis double cone AFM structure around TCanting ≈ 60 K. Here we use neutron scattering to demonstrate the presence of gapless incommensurate spin excitations associated with the double cone AFM structure of FeGe at temperatures well above TCanting and TCDW that merge into gapped commensurate spin waves from the A-type AFM order. Commensurate spin waves follow the Bose factor and fit the Heisenberg Hamiltonian, while the incommensurate spin excitations, emerging below TN where AFM order is commensurate, start to deviate from the Bose factor around TCDW, and peaks at TCanting. This is consistent with a critical scattering of a second order magnetic phase transition with decreasing temperature. By comparing these results with density functional theory calculations, we conclude that the incommensurate magnetic structure arises from the nested Fermi surfaces of itinerant electrons and the formation of a spin density wave order.

Tunable vortex bound states in multiband CsV3Sb5-derived kagome superconductors.

Vortices and bound states offer an effective means of comprehending the electronic properties of superconductors. Recently, surface-dependent vortex core states have been observed in the newly discovered kagome superconductors CsV3Sb5. Although the spatial distribution of the sharp zero energy conductance peak appears similar to Majorana bound states arising from the superconducting Dirac surface states, its origin remains elusive. In this study, we present observations of tunable vortex bound states (VBSs) in two chemically-doped kagome superconductors Cs(V1-xTrx)3Sb5 (Tr = Ta or Ti), using low-temperature scanning tunneling microscopy/spectroscopy. The CsV3Sb5-derived kagome superconductors exhibit full-gap-pairing superconductivity accompanied by the absence of long-range charge orders, in contrast to pristine CsV3Sb5. Zero-energy conductance maps demonstrate a field-driven continuous reorientation transition of the vortex lattice, suggesting multiband superconductivity. The Ta-doped CsV3Sb5 displays the conventional cross-shaped spatial evolution of Caroli-de Gennes-Matricon bound states, while the Ti-doped CsV3Sb5 exhibits a sharp, non-split zero-bias conductance peak (ZBCP) that persists over a long distance across the vortex. The spatial evolution of the non-split ZBCP is robust against surface effects and external magnetic field but is related to the doping concentrations. Our study reveals the tunable VBSs in multiband chemically-doped CsV3Sb5 system and offers fresh insights into previously reported Y-shaped ZBCP in a non-quantum-limit condition at the surface of kagome superconductor.

Direct observation of the collective modes of the charge density wave in the kagome metal CsV3Sb5.

A recently discovered group of kagome metals AV[Formula: see text]Sb[Formula: see text] (A = K, Rb, Cs) exhibit a variety of intertwined unconventional electronic phases, which emerge from a puzzling charge density wave phase. Understanding of this charge-ordered parent phase is crucial for deciphering the entire phase diagram. However, the mechanism of the charge density wave is still controversial, and its primary source of fluctuations-the collective modes-has not been experimentally observed. Here, we use ultrashort laser pulses to melt the charge order in CsV[Formula: see text]Sb[Formula: see text] and record the resulting dynamics using femtosecond angle-resolved photoemission. We resolve the melting time of the charge order and directly observe its amplitude mode, imposing a fundamental limit for the fastest possible lattice rearrangement time. These observations together with ab initio calculations provide clear evidence for a structural rather than electronic mechanism of the charge density wave. Our findings pave the way for a better understanding of the unconventional phases hosted on the kagome lattice.

Abundant Lattice Instability in Kagome Metal ScV_{6}Sn_{6}.

Kagome materials are emerging platforms for studying charge and spin orders. In this Letter, we have revealed a rich lattice instability in a Z_{2} kagome metal ScV_{6}Sn_{6} by first-principles calculations. Beyond verifying the sqrt[3]×sqrt[3]×3 charge density wave (CDW) order observed by the recent experiment, we further identified three more possible CDW structures, i.e., sqrt[3]×sqrt[3]×2 CDW with P6/mmm symmetry, 2×2×2 CDW with Immm symmetry, and 2×2×2 CDW with P6/mmm symmetry. The former two are more energetically favored than the sqrt[3]×sqrt[3]×3 phase, while the third one is comparable in energy. These CDW distortions involve mainly out-of-plane motions of Sc and Sn atoms, while V atoms constituting the kagome net are almost unchanged. We attribute the lattice instability to the smallness of Sc atomic radius. In contrast, such instability disappears in its sister compounds RV_{6}Sn_{6} (R is Y, or a rare-earth element), which exhibit quite similar electronic band structures to the Sc compound, because R has a larger atomic radius. Our work indicates that ScV_{6}Sn_{6} might exhibit varied CDW phases in different experimental conditions and provides insights to explore rich charge orders in kagome materials.

Distinct Magnetic Gaps between Antiferromagnetic and Ferromagnetic Orders Driven by Surface Defects in the Topological Magnet MnBi_{2}Te_{4}.

Many experiments observed a metallic behavior at zero magnetic fields (antiferromagnetic phase, AFM) in MnBi_{2}Te_{4} thin film transport, which coincides with gapless surface states observed by angle-resolved photoemission spectroscopy, while it can become a Chern insulator at field larger than 6 T (ferromagnetic phase, FM). Thus, the zero-field surface magnetism was once speculated to be different from the bulk AFM phase. However, recent magnetic force microscopy refutes this assumption by detecting persistent AFM order on the surface. In this Letter, we propose a mechanism related to surface defects that can rationalize these contradicting observations in different experiments. We find that co-antisites (exchanging Mn and Bi atoms in the surface van der Waals layer) can strongly suppress the magnetic gap down to several meV in the AFM phase without violating the magnetic order but preserve the magnetic gap in the FM phase. The different gap sizes between AFM and FM phases are caused by the exchange interaction cancellation or collaboration of the top two van der Waals layers manifested by defect-induced surface charge redistribution among the top two van der Waals layers. This theory can be validated by the position- and field-dependent gap in future surface spectroscopy measurements. Our work suggests suppressing related defects in samples to realize the quantum anomalous Hall insulator or axion insulator at zero fields.

Strong room-temperature bulk nonlinear Hall effect in a spin-valley locked Dirac material.

Nonlinear Hall effect (NLHE) is a new type of Hall effect with wide application prospects. Practical device applications require strong NLHE at room temperature (RT). However, previously reported NLHEs are all low-temperature phenomena except for the surface NLHE of TaIrTe4. Bulk RT NLHE is highly desired due to its ability to generate large photocurrent. Here, we show the spin-valley locked Dirac state in BaMnSb2 can generate a strong bulk NLHE at RT. In the microscale devices, we observe the typical signature of an intrinsic NLHE, i.e. the transverse Hall voltage quadratically scales with the longitudinal current as the current is applied to the Berry curvature dipole direction. Furthermore, we also demonstrate our nonlinear Hall device's functionality in wireless microwave detection and frequency doubling. These findings broaden the coupled spin and valley physics from 2D systems into a 3D system and lay a foundation for exploring bulk NLHE's applications.

Emergent topological quantum orbits in the charge density wave phase of kagome metal CsV3Sb5.

The recently discovered kagome materials AV3Sb5 (A = K, Rb, Cs) attract intense research interest in intertwined topology, superconductivity, and charge density waves (CDW). Although the in-plane 2 × 2 CDW is well studied, its out-of-plane structural correlation with the Fermi surface properties is less understood. In this work, we advance the theoretical description of quantum oscillations and investigate the Fermi surface properties in the three-dimensional CDW phase of CsV3Sb5. We derived Fermi-energy-resolved and layer-resolved quantum orbits that agree quantitatively with recent experiments in the fundamental frequency, cyclotron mass, and topology. We reveal a complex Dirac nodal network that would lead to a π Berry phase of a quantum orbit in the spinless case. However, the phase shift of topological quantum orbits is contributed by the orbital moment and Zeeman effect besides the Berry phase in the presence of spin-orbital coupling (SOC). Therefore, we can observe topological quantum orbits with a π phase shift in otherwise trivial orbits without SOC, contrary to common perception. Our work reveals the rich topological nature of kagome materials and paves a path to resolve different topological origins of quantum orbits.

Titanium doped kagome superconductor CsV3-xTixSb5 and two distinct phases.

The vanadium-based kagome superconductor CsV3Sb5 has attracted tremendous attention due to its unexcepted anomalous Hall effect (AHE), charge density waves (CDWs), nematicity, and a pseudogap pair density wave (PDW) coexisting with unconventional strong-coupling superconductivity. The origins of CDWs, unconventional superconductivity, and their correlation with different electronic states in this kagome system are of great significance, but so far, are still under debate. Chemical doping in the kagome layer provides one of the most direct ways to reveal the intrinsic physics, but remains unexplored. Here, we report, for the first time, the synthesis of Ti-substituted CsV3Sb5 single crystals and its rich phase diagram mapping the evolution of intertwining electronic states. The Ti atoms directly substitute for V in the kagome layers. CsV3-xTixSb5 shows two distinct superconductivity phases upon substitution. The Ti slightly-substituted phase displays an unconventional V-shaped superconductivity gap, coexisting with weakening CDW, PDW, AHE, and nematicity. The Ti highly-substituted phase has a U-shaped superconductivity gap concomitant with a short-range rotation symmetry breaking CDW, while long-range CDW, twofold symmetry of in-plane resistivity, AHE, and PDW are absent. Furthermore, we also demonstrate the chemical substitution of V atoms with other elements such as Cr and Nb, showing a different modulation on the superconductivity phases and CDWs. These findings open up a way to synthesise a new family of doped CsV3Sb5 materials, and further represent a new platform for tuning the different correlated electronic states and superconducting pairing in kagome superconductors.

[Spatial and Temporal Distribution and Source Variation of Heavy Metals in Cultivated Land Soil of Xiangzhou District Based on EBK Interpolation Prediction and GDM Model].

In order to explore the spatial and temporal changes in spatial patterns and source changes in heavy metals in Xiangzhou District, 395 and 326 soil samples were collected from cultivated soil in Xiangzhou District in November 2009 and November 2019, respectively. The contents of Cr, Pb, As, Hg, and Cd during these two years were measured. The spatial pattern and variation distribution of five types of heavy metals during these two years were obtained by using the empirical Bayesian Kriging (EBK) method. The effect (q-statistic) of 19 environmental factors and 5 types of heavy metals was calculated by using the geographical detector model (GDM), and the changes over the two years were compared. The results showed that compared with that in 2009, the heavy metal contents of Cr, Pb, Hg, and As in Xiangzhou District were decreased as a whole in 2019, whereas the Cd content increased overall. The spatial differentiation of heavy metals in the soil in Xiangzhou District in 2019 was more complicated than that in 2009. Pb, Hg, and Cd in the south and Hg in the central urban area and surrounding areas also increased. The content of each element decreased to the north and northwest. Compared with that in 2009, the explanatory power of natural factors and the distance between pollution enterprises on the single factor of the five soil heavy metal contents in 2019 decreased, and the influence on the contents under the control of single factors decreased significantly. The superposition influence of human activity factors increased, especially the distance between residential land, road, and land for pollution enterprises and environmental factors on soil heavy metal elements. These results indicated that the changes in soil heavy metal sources in 2019 tended to be complex, with structural factors as the main influencing factor. The influence of the emission of polluting enterprises on heavy metal elements decreased, whereas the influence of human activities on heavy metal content increased.

Delicate Ferromagnetism in MnBi6Te10.

Tailoring magnetic orders in topological insulators is critical to the realization of topological quantum phenomena. An outstanding challenge is to find a material where atomic defects lead to tunable magnetic orders while maintaining a nontrivial topology. Here, by combining magnetization measurements, angle-resolved photoemission spectroscopy, and transmission electron microscopy, we reveal disorder-enabled, tunable magnetic ground states in MnBi6Te10. In the ferromagnetic phase, an energy gap of 15 meV is resolved at the Dirac point on the MnBi2Te4 termination. In contrast, antiferromagnetic MnBi6Te10 exhibits gapless topological surface states on all terminations. Transmission electron microscopy and magnetization measurements reveal substantial Mn vacancies and Mn migration in ferromagnetic MnBi6Te10. We provide a conceptual framework where a cooperative interplay of these defects drives a delicate change of overall magnetic ground state energies and leads to tunable magnetic topological orders. Our work provides a clear pathway for nanoscale defect-engineering toward the realization of topological quantum phases.

Observation of anomalous amplitude modes in the kagome metal CsV3Sb5.

The kagome lattice provides a fertile platform to explore novel symmetry-breaking states. Charge-density wave (CDW) instabilities have been recently discovered in a new kagome metal family, commonly considered to arise from Fermi-surface instabilities. Here we report the observation of Raman-active CDW amplitude modes in CsV3Sb5, which are collective excitations typically thought to emerge out of frozen soft phonons, although phonon softening is elusive experimentally. The amplitude modes strongly hybridize with other superlattice modes, imparting them with clear temperature-dependent frequency shift and broadening, rarely seen in other known CDW materials. Both the mode mixing and the large amplitude mode frequencies suggest that the CDW exhibits the character of strong electron-phonon coupling, a regime in which phonon softening can cease to exist. Our work highlights the importance of the lattice degree of freedom in the CDW formation and points to the complex nature of the mechanism.

Roton pair density wave in a strong-coupling kagome superconductor.

The transition metal kagome lattice materials host frustrated, correlated and topological quantum states of matter1-9. Recently, a new family of vanadium-based kagome metals, AV3Sb5 (A = K, Rb or Cs), with topological band structures has been discovered10,11. These layered compounds are nonmagnetic and undergo charge density wave transitions before developing superconductivity at low temperatures11-19. Here we report the observation of unconventional superconductivity and a pair density wave (PDW) in CsV3Sb5 using scanning tunnelling microscope/spectroscopy and Josephson scanning tunnelling spectroscopy. We find that CsV3Sb5 exhibits a V-shaped pairing gap Δ ~ 0.5 meV and is a strong-coupling superconductor (2Δ/kBTc ~ 5) that coexists with 4a0 unidirectional and 2a0 × 2a0 charge order. Remarkably, we discover a 3Q PDW accompanied by bidirectional 4a0/3 spatial modulations of the superconducting gap, coherence peak and gap depth in the tunnelling conductance. We term this novel quantum state a roton PDW associated with an underlying vortex-antivortex lattice that can account for the observed conductance modulations. Probing the electronic states in the vortex halo in an applied magnetic field, in strong field that suppresses superconductivity and in zero field above Tc, reveals that the PDW is a primary state responsible for an emergent pseudogap and intertwined electronic order. Our findings show striking analogies and distinctions to the phenomenology of high-Tc cuprate superconductors, and provide groundwork for understanding the microscopic origin of correlated electronic states and superconductivity in vanadium-based kagome metals.

Charge Density Waves and Electronic Properties of Superconducting Kagome Metals.

Kagome metals AV_{3}Sb_{5} (A=K, Rb, and Cs) exhibit intriguing superconductivity below 0.9∼2.5 K, a charge density wave (CDW) transition around 80∼100 K, and Z_{2} topological surface states. The nature of the CDW phase and its relation to superconductivity remains elusive. In this work, we investigate the electronic and structural properties of CDW by first-principles calculations. We reveal an inverse Star of David deformation as the 2×2×2 CDW ground state of the kagome lattice. The kagome lattice shows softening breathing-phonon modes, indicating the structural instability. However, electrons play an essential role in the CDW transition via Fermi surface nesting and van Hove singularity. The inverse Star of David structure agrees with recent experiments by scanning tunneling microscopy (STM). The CDW phase inherits the nontrivial Z_{2}-type topological band structure. Further, we find that the electron-phonon coupling is too weak to account for the superconductivity T_{c} in all three materials. It implies the existence of unconventional pairing of these kagome metals. Our results provide essential knowledge toward understanding the superconductivity and topology in kagome metals.

Large Fermi-Energy Shift and Suppression of Trivial Surface States in NbP Weyl Semimetal Thin Films.

Weyl semimetals, a class of 3D topological materials, exhibit a unique electronic structure featuring linear band crossings and disjoint surface states (Fermi-arcs). While first demonstrations of topologically driven phenomena have been realized in bulk crystals, efficient routes to control the electronic structure have remained largely unexplored. Here, a dramatic modification of the electronic structure in epitaxially grown NbP Weyl semimetal thin films is reported, using in situ surface engineering and chemical doping strategies that do not alter the NbP lattice structure and symmetry, retaining its topological nature. Through the preparation of a dangling-bond-free, P-terminated surface which manifests in a surface reconstruction, all the well-known trivial surface states of NbP are fully suppressed, resulting in a purely topological Fermi-arc dispersion. In addition, a substantial Fermi-energy shift from -0.2 to 0.3 eV across the Weyl points is achieved by surface chemical doping, unlocking access to the hitherto unexplored n-type region of the Weyl spectrum. These findings constitute a milestone toward surface-state and Fermi-level engineering of topological bands in Weyl semimetals, and, while there are still challenges in minimizing doping-driven disorder and grain boundary density in the films, they do represent a major advance to realize device heterostructures based on Weyl physics.

Accuracy trade-off between one-electron and excitonic spectra of cuprous halides in first-principles calculations.

Because of the sophisticated error cancellation in the density functional theory (DFT)-based calculations, a theoretically more accurate input would not guarantee a better output. In this work, our first-principles GW plus Bethe-Salpeter equation calculations using pseudopotentials show that cuprous halides (CuCl and CuBr) are such extreme cases for which a better one-electron band is not accompanied with a better exciton binding energy. Moreover, we find that the exchange interaction of Cu core electrons plays a crucial role in their ground-state electronic properties, especially in the energy gap and macroscopic dielectric constant. Our work provides new insights into the understanding of the electronic structure of cuprous halides from the DFT perspective.

Electric-Field Switching of Magnetic Topological Charge in Type-I Multiferroics.

Applying electric field to control magnetic properties is a very efficient way for spintronics devices. However, the control of magnetic characteristics by electric fields is not straightforward, due to the time-reversal symmetry of magnetism versus spatial inversion symmetry of electricity. Such fundamental difficulty makes it challenging to modify the topology of magnetic skyrmionic states with electric field. Here, we propose a novel mechanism that realizes the electric-field (E) switching of magnetic topological charge (Q) in a controllable and reversible fashion, through the mediation of electric polarization (P) and Dzyaloshinskii-Moriya interaction (D). Such a mechanism is coined here EPDQ. Its validity is demonstrated in a multiferroic VOI_{2} monolayer, which is predicted to host magnetic bimerons. The change in magnetic anisotropy is found to play a crucial role in realizing the EPDQ process and its microscopic origin is discussed. Our study thus provides a new approach toward the highly desired electric-field control of magnetism.

Hexagonal rare-earth manganites and ferrites: a review of improper ferroelectricity, magnetoelectric coupling, and unusual domain walls.

Hexagonal rare-earth manganites and ferrites are well-known improper ferroelectrics with low-temperature antiferromagnetism/weak ferromagnetism. In recent decades, new multi-functional device concepts and applications have provoked the exploration for multiferroics which simultaneously possess ferroelectric and magnetic orders. As a promising platform for multiferroicity, hexagonal manganites and ferrites are attracting great research interest among the fundamental scientific and technological communities. Moreover, the novel type of vortex-like ferroelectric domain walls are locked to the antiphase structural domain walls, providing an extra degree of freedom to tune the magnetoelectric coupling and other properties such as conductance. Here, we summarize the main experimental achievements and up-to-date theoretical understanding of the ferroelectric, magnetic, and magnetoelectric properties, as well as the intriguing domain patterns in hexagonal rare-earth manganites and ferrites. Recent work on non-stoichiometric compounds will also be briefly introduced.