Spectroscopic evidence of spin-state excitation in d-electron correlated semiconductor FeSb2.

Iron antimonide (FeSb2) has been investigated for decades due to its puzzling electronic properties. It undergoes the temperature-controlled transition from an insulator to an ill-defined metal, with a cross-over from diamagnetism to paramagnetism. Extensive efforts have been made to uncover the underlying mechanism, but a consensus has yet to be reached. While macroscopic transport and magnetic measurements can be explained by different theoretical proposals, the essential spectroscopic evidence required to distinguish the physical origin is missing. In this paper, through the use of X-ray absorption spectroscopy and atomic multiplet simulations, we have observed the mixed spin states of 3d 6 configuration in FeSb2. Furthermore, we reveal that the enhancement of the conductivity, whether induced by temperature or doping, is characterized by populating the high-spin state from the low-spin state. Our work constitutes vital spectroscopic evidence that the electrical/magnetical transition in FeSb2 is directly associated with the spin-state excitation.

Band-selective gap opening by a C 4-symmetric order in a proximity-coupled heterostructure Sr2VO3FeAs.

Complex electronic phases in strongly correlated electron systems are manifested by broken symmetries in the low-energy electronic states. Some mysterious phases, however, exhibit intriguing energy gap opening without an apparent signature of symmetry breaking (e.g., high-TC cuprates and heavy fermion superconductors). Here, we report an unconventional gap opening in a heterostructured, iron-based superconductor Sr2VO3FeAs across a phase transition at T 0 ∼150 K. Using angle-resolved photoemission spectroscopy, we identify that a fully isotropic gap opens selectively on one of the Fermi surfaces with finite warping along the interlayer direction. This band selectivity is incompatible with conventional gap opening mechanisms associated with symmetry breaking. These findings, together with the unusual field-dependent magnetoresistance, suggest that the Kondo-type proximity coupling of itinerant Fe electrons to localized V spin plays a role in stabilizing the exotic phase, which may serve as a distinct precursor state for unconventional superconductivity.

Robust Luttinger Liquid State of 1D Dirac Fermions in a Van der Waals System Nb9Si4Te18.

We report on the Tomonaga-Luttinger liquid (TLL) behavior in fully degenerate 1D Dirac Fermions. A ternary van der Waals material Nb9Si4Te18 incorporates in-plane NbTe2 chains, which produce a 1D Dirac band crossing Fermi energy. Tunneling conductance of electrons confined within NbTe2 chains 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.

Electronic Structure of Above-Room-Temperature van der Waals Ferromagnet Fe3GaTe2.

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 Fe3GaTe2 in 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-TC ferromagnetic 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-TC ferromagnetic ordering in Fe3GaTe2.

Dirac Nodal Line in Hourglass Semimetal Nb3SiTe6.

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 Nb3SiTe6 observed in our results helps unveil linear band crossings that could be missed. In situ alkali-metal doping of Nb3SiTe6 also 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.

Converting the Bulk Transition Metal Dichalcogenides Crystal into Stacked Monolayers via Ethylenediamine Intercalation.

We report the synthesis of ethylenediamine-intercalated NbSe2 and Li-ethylenediamine-intercalated MoSe2 single 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 NbSe2 shows an electronic structure almost identical to that of monolayer NbSe2. Intercalated MoSe2 also 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.

Quantum electron liquid and its possible phase transition.

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.

Visualizing Higher-Fold Topology in Chiral Crystals.

Novel topological phases of matter are fruitful platforms for the discovery of unconventional electromagnetic phenomena. Higher-fold topology is one example, where the low-energy description goes beyond standard model analogs. Despite intensive experimental studies, conclusive evidence remains elusive for the multigap topological nature of higher-fold chiral fermions. In this Letter, we leverage a combination of fine-tuned chemical engineering and photoemission spectroscopy with photon energy contrast to discover the higher-fold topology of a chiral crystal. We identify all bulk branches of a higher-fold chiral fermion for the first time, critically important for allowing us to explore unique Fermi arc surface states in multiple interband gaps, which exhibit an emergent ladder structure. Through designer chemical gating of the samples in combination with our measurements, we uncover an unprecedented multigap bulk boundary correspondence. Our demonstration of multigap electronic topology will propel future research on unconventional topological responses.

Sign-tunable anomalous Hall effect induced by two-dimensional symmetry-protected nodal structures in ferromagnetic perovskite thin films.

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.

Anisotropic c-f Hybridization in the Ferromagnetic Quantum Critical Metal CeRh_{6}Ge_{4}.

Heavy fermion compounds exhibiting a ferromagnetic quantum critical point have attracted considerable interest. Common to two known cases, i.e., CeRh_{6}Ge_{4} and YbNi_{4}P_{2}, is that the 4f moments reside along chains with a large interchain distance, exhibiting strong magnetic anisotropy that was proposed to be vital for the ferromagnetic quantum criticality. Here, we report an angle-resolved photoemission study on CeRh_{6}Ge_{4} in which we observe sharp momentum-dependent 4f bands and clear bending of the conduction bands near the Fermi level, indicating considerable hybridization between conduction and 4f electrons. The extracted hybridization strength is anisotropic in momentum space and is obviously stronger along the Ce chain direction.The hybridized 4f bands persist up to high temperatures, and the evolution of their intensity shows clear band dependence. Our results provide spectroscopic evidence for anisotropic hybridization between conduction and 4f electrons in CeRh_{6}Ge_{4}, which could be important for understanding the electronic origin of the ferromagnetic quantum criticality.

Robust Surface States and Coherence Phenomena in Magnetically Alloyed SmB_{6}.

Samarium hexaboride is a candidate for the topological Kondo insulator state, in which Kondo coherence is predicted to give rise to an insulating gap spanned by topological surface states. Here we investigate the surface and bulk electronic properties of magnetically alloyed Sm_{1-x}M_{x}B_{6} (M=Ce, Eu), using angle-resolved photoemission spectroscopy and complementary characterization techniques. Remarkably, topologically nontrivial bulk and surface band structures are found to persist in highly modified samples with up to 30% Sm substitution and with an antiferromagnetic ground state in the case of Eu doping. The results are interpreted in terms of a hierarchy of energy scales, in which surface state emergence is linked to the formation of a direct Kondo gap, while low-temperature transport trends depend on the indirect gap.

Low Energy Band Structure and Symmetries of UTe_{2} from Angle-Resolved Photoemission Spectroscopy.

The compound UTe_{2} has recently been shown to realize spin triplet superconductivity from a nonmagnetic normal state. This has sparked intense research activity, including theoretical analyses that suggest the superconducting order parameter to be topologically nontrivial. However, the underlying electronic band structure is a critical factor for these analyses, and remains poorly understood. Here, we present high resolution angle-resolved photoemission measurements covering multiple planes in the 3D Brillouin zone of UTe_{2}, revealing distinct Fermi-level features from two orthogonal quasi-one-dimensional light electron bands and one heavy band. The electronic symmetries are evaluated in comparison with numerical simulations, and the resulting picture is discussed as a platform for unconventional many-body order.

In Situ Strain Tuning of the Dirac Surface States in Bi2Se3 Films.

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 Bi2Se3 can 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 Bi2Se3 films 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 Bi2Se3 and, more generally, demonstrates a new route toward momentum-resolved mapping of strain-induced band structure changes.

Evidence for a Quasi-One-Dimensional Charge Density Wave in CuTe by Angle-Resolved Photoemission Spectroscopy.

We report the electronic structure of CuTe with a high charge density wave (CDW) transition temperature T_{c}=335 K by angle-resolved photoemission spectroscopy. An anisotropic charge density wave gap with a maximum value of 190 meV is observed in the quasi-one-dimensional band formed by Te p_{x} orbitals. The CDW gap can be filled by increasing the temperature or electron doping through in situ potassium deposition. Combining the experimental results with calculated electron scattering susceptibility and phonon dispersion, we suggest that both Fermi surface nesting and electron-phonon coupling play important roles in the emergence of the CDW.

Electronic-dimensionality reduction of bulk MoS2 by hydrogen treatment.

A reduction in the electronic-dimensionality of materials is one method for achieving improvements in material properties. Here, a reduction in electronic-dimensionality is demonstrated using a simple hydrogen treatment technique. Quantum well states from hydrogen-treated bulk 2H-MoS2 are observed using angle resolved photoemission spectroscopy (ARPES). The electronic states are confined within a few MoS2 layers after the hydrogen treatment. A significant reduction in the band-gap can also be achieved after the hydrogen treatment, and both phenomena can be explained by the formation of sulfur vacancies generated by the chemical reaction between sulfur and hydrogen.

A novel quasi-one-dimensional topological insulator in bismuth iodide ß-Bi4I4.

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 Z2 classification of TIs as well as their structural and compositional diversity are far from being fully exploited. Here, a new Z2 topological insulator is theoretically predicted and experimentally confirmed in the ß-phase of quasi-one-dimensional bismuth iodide Bi4I4. The electronic structure of ß-Bi4I4, characterized by Z2 invariants (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.

Soft X-ray angle-resolved photoemission with micro-positioning techniques for metallic V2O3.

Soft X-ray angle-resolved photoemission has been performed for metallic V2O3. By combining a microfocus beam (40 µm × 65 µm) and micro-positioning techniques with a long-working-distance microscope, it has been possible to observe band dispersions from tiny cleavage surfaces with a typical size of several tens of µm. The photoemission spectra show a clear position dependence, reflecting the morphology of the cleaved sample surface. By selecting high-quality flat regions on the sample surface, it has been possible to perform band mapping using both photon-energy and polar-angle dependences, opening the door to three-dimensional angle-resolved photoemission spectroscopy for typical three-dimensional correlated materials where large cleavage planes are rarely obtained.

Topological Fermi-arc surface state covered by floating electrons on a two-dimensional electride.

Two-dimensional electrides can acquire topologically non-trivial phases due to intriguing interplay between the cationic atomic layers and anionic electron layers. However, experimental evidence of topological surface states has yet to be verified. Here, via angle-resolved photoemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM), we probe the magnetic Weyl states of the ferromagnetic electride [Gd2C]2+·2e-. In particular, the presence of Weyl cones and Fermi-arc states is demonstrated through photon energy-dependent ARPES measurements, agreeing with theoretical band structure calculations. Notably, the STM measurements reveal that the Fermi-arc states exist underneath a floating quantum electron liquid on the top Gd layer, forming double-stacked surface states in a heterostructure. Our work thus not only unveils the non-trivial topology of the [Gd2C]2+·2e- electride but also realizes a surface heterostructure that can host phenomena distinct from the bulk.

Reversible non-volatile electronic switching in a near-room-temperature van der Waals ferromagnet.

Non-volatile phase-change memory devices utilize local heating to toggle between crystalline and amorphous states with distinct electrical properties. Expanding on this kind of switching to two topologically distinct phases requires controlled non-volatile switching between two crystalline phases with distinct symmetries. Here, we report the observation of reversible and non-volatile switching between two stable and closely related crystal structures, with remarkably distinct electronic structures, in the near-room-temperature van der Waals ferromagnet Fe5-δGeTe2. We show that the switching is enabled by the ordering and disordering of Fe site vacancies that results in distinct crystalline symmetries of the two phases, which can be controlled by a thermal annealing and quenching method. The two phases are distinguished by the presence of topological nodal lines due to the preserved global inversion symmetry in the site-disordered phase, flat bands resulting from quantum destructive interference on a bipartite lattice, and broken inversion symmetry in the site-ordered phase.

Satellite-Dominated Sulfur L2,3 X-ray Emission of Alkaline Earth Metal Sulfides.

The sulfur L2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L2,3 emission and only observed for the L2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.