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Rashba states have been actively revisited as a platform for advanced applications such as spintronics and topological quantum computation. Yet, access to the Rashba state is restricted to the specific material sets, and the methodology to control the Rashba state is not established. Here, we report the Rashba states on the (001) surface of KZnBi, a 3D Dirac semimetal. Using angle-resolved photoemission spectroscopy and first-principles calculations, we investigated the evolution of Rashba states under different surface conditions controlled by alkali metal deposition. We observed that restoring surface ordering enables a Rashba state, which is absent in freshly cleaved surfaces. Interestingly, we were able to modify the dispersion of the Rashba state from an ordinary parabolic dispersion to a linearly dispersing Dirac-like state by additional alkali-metal deposition. Our findings provide a methodology for engineering the properties of Rashba states for advanced applications and redefine topological systems as generic hosts of Rashba states.

Fe3GaTe2, a recently discovered van der Waals ferromagnet, demonstrates intrinsic ferromagnetism above room temperature, necessitating a comprehensive investigation of the microscopic origins of its high Curie temperature (TC). In this study, we reveal the electronic structure of Fe3GaTe2in its ferromagnetic ground state using angle-resolved photoemission spectroscopy and density functional theory calculations. Our results establish a consistent correspondence between the measured band structure and theoretical calculations, underscoring the significant contributions of the Heisenberg exchange interaction (Jex) and magnetic anisotropy energy to the development of the high-TCferromagnetic ordering in Fe3GaTe2. Intriguingly, we observe substantial modifications to these crucial driving factors through doping, which we attribute to alterations in multiple spin-splitting bands near the Fermi level. These findings provide valuable insights into the underlying electronic structure and its correlation with the emergence of high-TCferromagnetic ordering in Fe3GaTe2.

The classification scheme of electronic phases uses two prominent paradigms: correlations and topology. Electron correlations give rise to superconductivity and charge density waves, while the quantum geometric Berry phase gives rise to electronic topology. The intersection of these two paradigms has initiated an effort to discover electronic instabilities at or near the Fermi level of topological materials. Here we identify the electronic topology of chiral fermions as the driving mechanism for creating van Hove singularities that host electronic instabilities in the surface band structure. We observe that the chiral fermion conductors RhSi and CoSi possess two types of helicoid arc van Hove singularities that we call type I and type II. In RhSi, the type I variety drives a switching of the connectivity of the helicoid arcs at different energies. In CoSi, we measure a type II intra-helicoid arc van Hove singularity near the Fermi level. Chemical engineering methods are able to tune the energy of these singularities. Finally, electronic susceptibility calculations allow us to visualize the dominant Fermi surface nesting vectors of the helicoid arc singularities, consistent with recent observations of surface charge density wave ordering in CoSi. This suggests a connection between helicoid arc singularities and surface charge density waves.

Purely quantum electron systems exhibit intriguing correlated electronic phases by virtue of quantum fluctuations in addition to electron–electron interactions. To realize such quantum electron systems, a key ingredient is dense electrons decoupled from other degrees of freedom. Here, we report the discovery of a pure quantum electron liquid that spreads up to ~3 Å in a vacuum on the surface of an electride crystal. Its extremely high electron density and weak hybridization with buried atomic orbitals show the quantum and pure nature of the electrons, which exhibit a polarized liquid phase, as demonstrated by our spin-dependent measurement. Furthermore, upon enhancing the electron correlation strength, the dynamics of the quantum electrons change to that of a non-Fermi liquid along with an anomalous band deformation, suggestive of a transition to a hexatic liquid crystal phase. Our findings develop the frontier of quantum electron systems and serve as a platform for exploring correlated electronic phases in a pure fashion.

Magnetism and spin–orbit coupling are two quintessential ingredients underlying topological transport phenomena in itinerant ferromagnets. When spin-polarized bands support nodal points/lines with band degeneracy that can be lifted by spin–orbit coupling, the nodal structures become a source of Berry curvature, leading to a large anomalous Hall effect. However, two-dimensional systems can possess stable nodal structures only when proper crystalline symmetry exists. Here we show that two-dimensional spin-polarized band structures of perovskite oxides generally support symmetry-protected nodal lines and points that govern both the sign and the magnitude of the anomalous Hall effect. To demonstrate this, we performed angle-resolved photoemission studies of ultrathin films of SrRuO3, a representative metallic ferromagnet with spin–orbit coupling. We show that the sign-changing anomalous Hall effect upon variation in the film thickness, magnetization and chemical potential can be well explained by theoretical models. Our work may facilitate new switchable devices based on ferromagnetic ultrathin films.

Recent direct experimental observation of multiple highly dispersive C60valence bands has allowed for a detailed analysis of the unusual photoemission traits of these features through photon energy- and polarization-dependent measurements. Previously obscured dispersions and strong photoemission traits are now revealed by specific light polarizations. The observed intensity effects prove the locking in place of the C60molecules at low temperatures and the existence of an orientational order imposed by the substrate chosen. Most importantly, photon energy- and polarization-dependent effects are shown to be intimately linked with the orbital character of the C60band manifolds which allow for a more precise determination of the orbital character within the third highest occupied molecular orbital (HOMO–2). Our observations and analysis provide important considerations for the connection between molecular and crystalline C60electronic structure, past and future band structure studies, and for increasingly popular C60electronic device applications, especially those making use of heterostructures.

Elastic strain has the potential for a controlled manipulation of the band gap and spin-polarized Dirac states of topological materials, which can lead to pseudomagnetic field effects, helical flat bands, and topological phase transitions. However, practical realization of these exotic phenomena is challenging and yet to be achieved. Here we show that the Dirac surface states of the topological insulator Bi2Se3can be reversibly tuned by an externally applied elastic strain. Performing in situ X-ray diffraction and in situ angle-resolved photoemission spectroscopy measurements during tensile testing of epitaxial Bi2Se3films bonded onto a flexible substrate, we demonstrate elastic strains of up to 2.1% and quantify the resulting changes in the topological surface state. Our study establishes the functional relationship between the lattice and electronic structures of Bi2Se3and, more generally, demonstrates a new route toward momentum-resolved mapping of strain-induced band structure changes.

We report the synthesis of ethylenediamine-intercalated NbSe2and Li-ethylenediamine-intercalated MoSe2single crystals with increased interlayer distances and their electronic structures measured by means of angle-resolved photoemission spectroscopy (ARPES). X-ray diffraction patterns and transmission electron microscopy images confirm the successful intercalation and an increase in the interlayer distance. ARPES measurement reveals that intercalated NbSe2shows an electronic structure almost identical to that of monolayer NbSe2. Intercalated MoSe2also returns the characteristic feature of the monolayer electronic structure, a direct band gap, which generates sizable photoluminescence even in the bulk form. Our results demonstrate that the properties and phenomena of the monolayer transition metal dichalcogenides can be achieved with large-scale bulk samples by blocking the interlayer interaction through intercalation.

We report on the Tomonaga-Luttinger liquid (TLL) behavior in fully degenerate 1D Dirac Fermions. A ternary van der Waals material Nb9Si4Te18incorporates in-plane NbTe2chains, which produce a 1D Dirac band crossing Fermi energy. Tunneling conductance of electrons confined within NbTe2chains is found to be substantially suppressed at Fermi energy, which follows a power law with a universal temperature scaling, hallmarking a TLL state. The obtained Luttinger parameter of ∼0.15 indicates a strong electron–electron interaction. The TLL behavior is found to be robust against atomic-scale defects, which might be related to the Dirac electron nature. These findings, combined with the tunability of the compound and the merit of a van der Waals material, offer a robust, tunable, and integrable platform to exploit non-Fermi liquid physics.

Recent progress in the field of topological states of matter has largely been initiated by the discovery of bismuth and antimony chalcogenide bulk topological insulators (TIs; refs ,,,), followed by closely related ternary compounds and predictions of several weak TIs (refs ,,). However, both the conceptual richness of Z2classification of TIs as well as their structural and compositional diversity are far from being fully exploited. Here, a new Z2topological insulator is theoretically predicted and experimentally confirmed in the β-phase of quasi-one-dimensional bismuth iodide Bi4I4. The electronic structure of β-Bi4I4, characterized by Z2invariants (1;110), is in proximity of both the weak TI phase (0;001) and the trivial insulator phase (0;000). Our angle-resolved photoemission spectroscopy measurements performed on the (001) surface reveal a highly anisotropic band-crossing feature located at the  point of the surface Brillouin zone and showing no dispersion with the photon energy, thus being fully consistent with the theoretical prediction.

No single material or materials system today is a clear choice for photoelectrochemical electrode applications. Generally, materials with narrow, well-aligned band gaps are unstable in solution and stable materials have band gaps that are too wide to efficiently absorb sunlight. Here, we demonstrate the narrowing of the ZnO band gap and combine a variety of electrical, spectroscopic, and photoelectrochemical methods to explore the opportunities for this so-called highly mismatched alloy in photoelectrochemical water splitting applications. We find that the conduction band edge of ZnO1–xSexis located at 4.95 eV below the vacuum level (0.5 V below the hydrogen evolution potential). Soft X-ray emission and absorption spectroscopies confirm that the previously observed ∼1 eV reduction in the ZnO band gap with the addition of selenium result from the formation of a narrow Se-derived band. We observe that this narrow band contributes to photocurrent production using applied bias incident photon to current efficiency measurements at an electrochemical junction. Electrical measurements, electrochemical flat band, and photocurrent measurements as a function of xin ZnO1–xSexalloys indicate that this alloy is a good candidate for an oxide/silicon tandem photoelectrochemical device because of the natural band alignment between the silicon valence band and the ZnO1–xSexconduction band. We observe that the photocurrent onset in preliminary ZnO1–xSex/silicon diode tandem devices is shifted toward spontaneous hydrogen production compared to ZnO1–xSexfilms grown on sapphire. With these findings, we hope that our method of band gap engineering oxides for photoelectrodes can be extended to devise better materials systems for spontaneous solar water splitting.

The chemical state of nitrogen in nitrogen-entrapped carbon nanohorns (N-CNHs) synthesized by submerged arc discharge in liquid nitrogen was determined by soft X-ray emission and absorption spectroscopy using synchrotron radiation. X-ray absorption spectra (XAS) and X-ray emission spectra (XES) in the CKand NKregions of the N-CNHs were measured at the Advanced Light Source. From fingerprintanalysis in NK-XAS and by referring to nitrogen-containing aromatic compounds, the suggested chemical state of nitrogen in N-CNHs is imine. Theoretical analysis of NK-XES using the discrete variational Xα molecular orbital calculations elucidated that the local structure of N-CNHs is chemisorption of N2, forming pentagonal and/or hexagonal rings with carbon atoms at the graphitic layer edges, which assume an imine structure. Therefore, the entrapped nitrogen in N-CNHs is chemisorbed at the edges of the graphitic layers.

Abstract

The crystal structure of magnetite nanoparticles may be transformed to maghemite by complete oxidation, but under many relevant conditions the oxidation is partial, creating a mixed-valence material with structural and electronic properties that are poorly characterized. We used X-ray diffraction, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy, and soft X-ray absorption and emission spectroscopy to characterize the products of oxidizing uncoated and oleic acid-coated magnetite nanoparticles in air. The oxidization of uncoated magnetite nanoparticles creates a material that is structurally and electronically indistinguishable from maghemite. By contrast, while oxidized oleic acid-coated nanoparticles are also structurally indistinguishable from maghemite, Fe L-edge spectroscopy revealed the presence of interior reduced iron sites even after a 2-year period. We used X-ray emission spectroscopy at the O K-edge to study the valence bands (VB) of the iron oxide nanoparticles, using resonant excitation to remove the contributions from oxygen atoms in the ligands and from low-energy excitations that obscured the VB edge. The bonding in all nanoparticles was typical of maghemite, with no detectable VB states introduced by the long-lived, reduced-iron sites in the oleic acid-coated sample. However, O K-edge absorption spectroscopy observed a ∼0.2 eV shift in the position of the lowest unoccupied states in the coated sample, indicating an increase in the semiconductor band gap relative to bulk stoichiometric maghemite that was also observed by optical absorption spectroscopy. The results show that the ferrous iron sites within ferric iron oxide nanoparticles coated by an organic ligand can persist under ambient conditions with no evidence of a distinct interior phase and can exert an effect on the global electronic and optical properties of the material. This phenomenon resembles the band gap enlargement caused by electron accumulation in the conduction band of TiO2.

Glide-mirror symmetry in nonsymmorphic crystals can foster the emergence of novel hourglass nodal loop states. Here, we present spectroscopic signatures from angle-resolved photoemission of a predicted topological hourglass semimetal phase in Nb3SiTe6. Linear band crossings are observed at the zone boundary of Nb3SiTe6, which could be the origin of the nontrivial Berry phase and are consistent with a predicted glide quantum spin Hall effect; such linear band crossings connect to form a nodal loop. Furthermore, the saddle-like Fermi surface of Nb3SiTe6observed in our results helps unveil linear band crossings that could be missed. In situalkali-metal doping of Nb3SiTe6also facilitated the observation of other band crossings and parabolic bands at the zone center correlated with accidental nodal loop states. Overall, our results complete the system’s band structure, help explain prior Hall measurements, and suggest the existence of a nodal loop at the zone center of Nb3SiTe6.

To analyze the local structure and/or chemical states of boron atoms in boron-doped diamond, which can be synthesized by the microwave plasma-assisted chemical vapor deposition method (CVD-B-diamond) and the temperature gradient method at high pressure and high temperature (HPT-B-diamond), we measured the soft X-ray emission spectra in the CKand BKregions of B-diamonds using synchrotron radiation at the Advanced Light Source (ALS). X-ray spectral analyses using the fingerprint method and molecular orbital calculations confirm that boron atoms in CVD-B-diamond substitute for carbon atoms in the diamond lattice to form covalent B–C bonds, while boron atoms in HPT-B-diamond react with the impurity nitrogen atoms to form hexagonal boron nitride. This suggests that the high purity diamond without nitrogen impurities is necessary to synthesize p-type B-diamond semiconductors.