Angle-resolved Photoemission Spectroscopy Research Articles

Unraveling electronic origins for boosting thermoelectric performance of p-type (Bi,Sb)2Te3.

P-type Bi2-xSbxTe3 compounds are crucial for thermoelectric applications at room temperature, with Bi0.5Sb1.5Te3 demonstrating superior performance, attributed to its maximum density-of-states effective mass (m*). However, the underlying electronic origin remains obscure, impeding further performance optimization. Herein, we synthesized high-quality Bi2-xSbxTe3 (00 l) films and performed comprehensive angle-resolved photoemission spectroscopy (ARPES) measurements and band structure calculations to shed light on the electronic structures. ARPES results directly evidenced that the band convergence along the [Formula: see text]-[Formula: see text] direction contributes to the maximum m* of Bi0.5Sb1.5Te3. Moreover, strategic manipulation of intrinsic defects optimized the hole density of Bi0.5Sb1.5Te3, allowing the extra valence band along [Formula: see text]-[Formula: see text] to contribute to the electrical transport. The synergy of the above two aspects documented the electronic origins of the Bi0.5Sb1.5Te3's superior performance that resulted in an extraordinary power factor of ~5.5 milliwatts per meter per square kelvin. The study offers valuable guidance for further performance optimization of p-type Bi2-xSbxTe3.

Angle-resolved photoemission spectroscopy (ARPES): probing electronic structure and many-body interactions

Complex phenomenon in quantum materials is a major theme of physics today. As better controlled model systems, a sophisticated understanding of the universality and diversity of these solids may lead to revelations well beyond themselves. Angle-resolved photoemission spectroscopy (ARPES), formulated after Einstein’s photoelectric effect, has been a key tool to uncover the microscopic processes of the electrons that give rise to the rich physics in these solids. Over the last three decades, the improved resolution and carefully matched experiments have been the keys to turn this technique into a leading experimental probe of electronic structures and many-body effects. Drawing upon examples spanning from novel superconductors and topological materials to magnetic and one-dimensional materials, we illustrate ARPES's pivotal role in testing ideas, benchmarking theoretical frameworks, uncovering unexpected phenomena, and elucidating the fingerprints of many-body interactions. Moreover, we demonstrate how the integration of modern ultrafast UV lasers and spin polarimetry has empowered photoemission spectroscopy to capture essential microscopic quantities of electrons—energy, momentum, spin, and temporal dynamics—yielding invaluable insights from a wealth of rich and precise information.

Momentum-Resolved Electronic Structures and Strong Electronic Correlations in Graphene-like Nitride Superconductors.

Although transition-metal nitrides have been widely applied for several decades, experimental investigations of their high-resolution electronic band structures are rare due to the lack of high-quality single-crystalline samples. Here, we report on the first momentum-resolved electronic band structures of titanium nitride (TiN) films, which are remarkable nitride superconductors. The measurements of the crystal structures and electrical transport properties confirmed the high quality of these films. More importantly, from a combination of high-resolution angle-resolved photoelectron spectroscopy and first-principles calculations, the extracted Coulomb interaction strength of TiN films can be as large as 8.5 eV, whereas resonant photoemission spectroscopy yields a value of 6.26 eV. These large values of Coulomb interaction strength indicate that superconducting TiN is a strongly correlated system. Our results uncover the unexpected electronic correlations in transition-metal nitrides, potentially providing a perspective not only to understand their emergent quantum states but also to develop their applications in quantum devices.

Orbital-dependent electron correlation in double-layer nickelate La3Ni2O7

The latest discovery of high temperature superconductivity near 80 K in La3Ni2O7 under high pressure has attracted much attention. Many proposals are put forth to understand the origin of superconductivity. The determination of electronic structures is a prerequisite to establish theories to understand superconductivity in nickelates but is still lacking. Here we report our direct measurement of the electronic structures of La3Ni2O7 by high-resolution angle-resolved photoemission spectroscopy. The Fermi surface and band structures of La3Ni2O7 are observed and compared with the band structure calculations. Strong electron correlations are revealed which are orbital- and momentum-dependent. A flat band is formed from the Ni-3dz2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${}_{{z}^{2}}$$\\end{document} orbitals around the zone corner which is ~ 50 meV below the Fermi level and exhibits the strongest electron correlation. In many theoretical proposals, this band is expected to play the dominant role in generating superconductivity in La3Ni2O7. Our observations provide key experimental information to understand the electronic structure and origin of high temperature superconductivity in La3Ni2O7.

3D topological semimetal phases of strained [formula omitted]-Sn on insulating substrate

α-Sn is an elemental topological material, whose topological phases can be tuned by strain and magnetic field. Such tunability offers a substantial potential for topological electronics. However, InSb substrates, commonly used to stabilize α-Sn allotrope, suffer from parallel conduction, restricting transport investigations and potential applications. Here, the successful MBE growth of high-quality α-Sn layers on insulating, hybrid (001) CdTe/GaAs substrates, with bulk electron mobility approaching 20000 cm2V−1s−1 is reported. The electronic properties of the samples are systematically investigated by independent complementary techniques, enabling thorough characterization of the 3D Dirac (DSM) and Weyl (WSM) semimetal phases induced by the strains and magnetic field, respectively. Magneto-optical experiments, corroborated with band structure modelling, provide an exhaustive description of the bulk states in the DSM phase. The modelled electronic structure is directly observed in angle-resolved photoemission spectroscopy, which reveals linearly dispersing bands near the Fermi level. The first detailed study of negative longitudinal magnetoresistance relates this effect to the chiral anomaly and, consequently, to the presence of WSM. Observation of the π Berry phase in Shubnikov-de Haas oscillations agrees with the topologically non-trivial nature of the investigated samples. Our findings establish α-Sn as an attractive topological material for exploring relativistic physics and future applications.

Br-Vacancies Induced Variable Ranging Hopping Conduction in High-Order Topological Insulator Bi4Br4.

The defects have a remarkable influence on the electronic structures and the electric transport behaviors of the matter, providing the additional means to engineering their physical properties. In this work, a comprehensive study on the effect of Br-vacancies on the electronic structures and transport behaviors in the high-order topological insulator Bi4Br4 is performed by the combined techniques of the scanning tunneling microscopy (STM), angle-resolved photoemission spectroscopy (ARPES), and physical properties measurement system along with the first-principle calculations. The STM results show the defects on the cleaved surface of a single crystal and reveal that the defects are correlated to the Br-vacancies with the support of the simulated STM images. The role of the Br-vacancies in the modulation of the band structures has been identified by ARPES spectra and the calculated energy-momentum dispersion. The relationship between the Br-vacancies and the semiconducting-like transport behaviors at low temperature has been established, implying a Mott variable ranging hopping conduction in Bi4Br4. The work not only resolves the unclear transport behaviors in this matter, but also paves a way to modulate the electric conduction path by the defects engineering.

Preservation of Topological Surface States in Millimeter-Scale Transferred Membranes.

Ultrathin topological insulator membranes are building blocks of exotic quantum matter. However, traditional epitaxy of these materials does not facilitate stacking in arbitrary orders, while mechanical exfoliation from bulk crystals is also challenging due to the non-negligible interlayer coupling therein. Here we liberate millimeter-scale films of the topological insulator Bi2Se3, grown by molecular beam epitaxy, down to 3 quintuple layers. We characterize the preservation of the topological surface states and quantum well states in transferred Bi2Se3 films using angle-resolved photoemission spectroscopy. Leveraging the photon-energy-dependent surface sensitivity, the photoemission spectra taken with 6 and 21.2 eV photons reveal a transfer-induced migration of the topological surface states from the top to the inner layers. By establishing clear electronic structures of the transferred films and unveiling the wave function relocation of the topological surface states, our work lays the physics foundation crucial for the future fabrication of artificially stacked topological materials with single-layer precision.

Ultrafast Carrier Relaxation Dynamics in a Nodal-Line Semimetal PtSn4.

Topological Dirac nodal-line semimetals host topologically nontrivial electronic structure with nodal-line crossings around the Fermi level, which could affect the photocarrier dynamics and lead to novel relaxation mechanisms. Herein, by using time- and angle-resolved photoemission spectroscopy, we reveal the previously inaccessible linear dispersions of the bulk conduction bands above the Fermi level in a Dirac nodal-line semimetal PtSn4, as well as the momentum and temporal evolution of the gapless nodal lines. A surprisingly ultrafast relaxation dynamics within a few hundred femtoseconds is revealed for photoexcited carriers in the nodal line. Theoretical calculations suggest that such ultrafast carrier relaxation is attributed to the multichannel scatterings among the complex metallic bands of PtSn4 via electron-phonon coupling. In addition, a unique dynamic relaxation mechanism contributed by the highly anisotropic Dirac nodal-line electronic structure is also identified. Our work provides a comprehensive understanding of the ultrafast carrier dynamics in a Dirac nodal-line semimetal.

On-Surface Synthesis of Polyene-Linked Porphyrin Cooligomer.

π-Conjugated molecules are viewed as fundamental components in forthcoming molecular nanoelectronics in which semiconducting functional units are linked to each other via metallic molecular wires. However, it is still challenging to construct such block cooligomers on the surface. Here, we present a synthesis of [18]-polyene-linked Zn-porphyrin cooligomers via a two-step reaction of the alkyl groups on Cu(111) and Cu(110). Nonyl groups (-C9H19) substituted at the 5,15-meso positions of Zn-porphyrin were first transformed to alkenyl groups (-C9H10) by dehydrogenation. Subsequently, homocoupling of the terminal -CH2 groups resulted in the formation of extended [18]-polyene-linked porphyrin cooligomers. The structures of the products at each reaction step were investigated by bond-resolved scanning tunneling microscopy at low temperatures. A combination of angle-resolved photoemission spectroscopy and density functional theory calculations revealed the metallic property of the all trans [18]-polyene linker on Cu(110). This finding may provide an approach to fabricate complex nanocarbon structures on the surface.

Angle-resolved X-ray photoelectron spectroscopy intensity modeling of SiNx ultrathin layer grown on Si (100) and Si (111) substrates by N2 plasma treatment

In this work, we investigate the silicon nitridation process using a N2 plasma Glow Discharge Source (GDS) in an ultra-high vacuum chamber. In situ Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS) measurements were performed to determine various chemical environments of the surface species. The main goals of this study are determination of the film chemical composition, to estimate its thickness and identify various phenomena taking place during the nitridation process under different experimental conditions. To achieve these objectives, we developed an ARXPS intensity model for an ultrathin SiNx overlayer. Based on the ARXPS results, which indicate that the silicon nitride film is not homogenous, we adopted a bi-layer model composed of two SixNyOz layers with varying thickness and chemical composition. The model is built from analysis of photoelectron intensities, considering a comparison between experimental and theoretical data. This bi-layer model revealed that the silicon nitride layer consists of a surface layer composed of approximately equal amounts of silicon and nitrogen (50% each), and an interfacial layer containing varying amounts of oxygen depending on experimental parameters. The presence of oxygen is due to residual air contamination in the vacuum chamber and/or to Si native oxide. The estimated thickness of silicon nitride film is less than 9 nm, depending on the nitridation time and temperature.The model developed in this work enabled us to study the effects of initial surface state (as received or chemically cleaned), Si substrate crystallographic orientation (such as (100) and (111)), and the nitridation temperature (room temperature and 500°C). The diffusing species (N+, N2+, O+), which play a crucial role during nitridation, were found to be influenced by temperature, treatment time, and substrate orientation. The diffusion phenomenon competed with other processes such as NO desorption, leading to a significant impact on formation of the SiNx film. Furthermore, we compared the thickness obtained from the ARXPS model using cross-sectional High-Resolution Transmission Electron Microscopy (HR-TEM) images. Additional Low-Energy Electron Diffraction (LEED) measurements indicated that the SiNx film was amorphous.

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.

Ultrafast creation of a light-induced semimetallic state in strongly excited 1T-TiSe2.

Screening, a ubiquitous phenomenon associated with the shielding of electric fields by surrounding charges, has been widely adopted as a means to modify a material's properties. While most studies have relied on static changes of screening through doping or gating thus far, here we demonstrate that screening can also drive the onset of distinct quantum states on the ultrafast timescale. By using time- and angle-resolved photoemission spectroscopy, we show that intense optical excitation can drive 1T-TiSe2, a prototypical charge density wave material, almost instantly from a gapped into a semimetallic state. By systematically comparing changes in band structure over time and excitation strength with theoretical calculations, we find that the appearance of this state is likely caused by a dramatic reduction of the screening length. In summary, this work showcases how optical excitation enables the screening-driven design of a nonequilibrium semimetallic phase in TiSe2, possibly providing a general pathway into highly screened phases in other strongly correlated materials.

Manipulation of band gap in 1T-TiSe2 via rubidium-deposition

Abstract 1T-TiSe2 is a two-dimensional charge-density-wave (CDW) material that attracts great interest. A small band gap locates at the Fermi level separating the Ti d-bands and Se p-bands, which makes 1T-TiSe2 a promising candidate for realizing excitonic condensation. Here, we studied the band gap in 1T-TiSe2 using angle-resolved photoemission spectroscopy (ARPES). Instead of only focusing on the in-plane band dispersions, we obtained the detailed band dispersions of both conduction and valance bands along the out-of-plane direction. We found that, the conduction and valance bands split into multiple sub-bands in the CDW state due to band folding. As a result, the band gap between the Ti d-bands and Se p-bands reduces to ~25 meV and becomes a direct gap in the CDW state. More intriguingly, such band gap can be further reduced by the rubidium deposition. The band structure becomes semi-metallic in the rubidium-doped sample. Meanwhile, exotic gapless behaviors were observed at the p-d band crossing. Our result characterized the band gap of 1T-TiSe2 in three-dimensional Brillouin zone with unpreceded precision. It also suggests a closing of band gap or a potential band inversion in 1T-TiSe2 driven by rubidium-deposition.

Investigations towards nanoscale precise polishing of Nb3Sn thin films for SRF applications

The superconducting radio frequency performance of Nb3Sn is significantly impacted by its near-surface composition and nanostructure. In this study, an innovative polishing technique for Nb3Sn thin films with nanoscale precision is proposed. Systematic angle-resolved X-ray photoelectron spectroscopy (ARXPS) analysis reveal that the mechanism of this polishing process involves the formation of a few nanometer-thick oxide layer on the film's surface, followed by the uniform removal of the oxide layers with HF rinse. It is approximated that the polishing depth achieved in a single cycle can reach several nanometers. Advanced material characterization demonstrates that optimized polishing process effectively eliminates compulsive tin droplets and potential tin-rich phases with poor superconductivity generated on the surface during the preparation of Nb3Sn thin films. Simultaneously, no additional impurity phase will be formed on the surface, and the surface roughness will remain undamaged. Meanwhile, the results of magnetic and electrical analysis show that the superconducting properties of the polished films are not affected. This polishing technique is anticipated to ease the stringent coating conditions for the preparation of high-performance Nb3Sn thin film superconducting cavity, and will be a valuable addition to the post-treatment process of Nb3Sn thin films.

Observation of interlayer plasmon polaron in graphene/WS2 heterostructures

Harnessing electronic excitations involving coherent coupling to bosonic modes is essential for the design and control of emergent phenomena in quantum materials. In situations where charge carriers induce a lattice distortion due to the electron-phonon interaction, the conducting states get “dressed", which leads to the formation of polaronic quasiparticles. The exploration of polaronic effects on low-energy excitations is in its infancy in two-dimensional materials. Here, we present the discovery of an interlayer plasmon polaron in heterostructures composed of graphene on top of single-layer WS2. By using micro-focused angle-resolved photoemission spectroscopy during in situ doping of the top graphene layer, we observe a strong quasiparticle peak accompanied by several carrier density-dependent shake-off replicas around the single-layer WS2 conduction band minimum. Our results are explained by an effective many-body model in terms of a coupling between single-layer WS2 conduction electrons and an interlayer plasmon mode. It is important to take into account the presence of such interlayer collective modes, as they have profound consequences for the electronic and optical properties of heterostructures that are routinely explored in many device architectures involving 2D transition metal dichalcogenides.

Bias-Free Access to Orbital Angular Momentum in Two-Dimensional Quantum Materials.

The demonstration of a topological band inversion constitutes the most elementary proof of a quantum spin Hall insulator (QSHI). On a fundamental level, such an inverted band gap is intrinsically related to the bulk Berry curvature, a gauge-invariant fingerprint of the wave function's quantum geometric properties in Hilbert space. Intimately tied to orbital angular momentum (OAM), the Berry curvature can be, in principle, extracted from circular dichroism in angle-resolved photoemission spectroscopy (CD-ARPES), were it not for interfering final state photoelectron emission channels that obscure the initial state OAM signature. Here, we outline a full-experimental strategy to avoid such interference artifacts and isolate the clean OAM from the CD-ARPES response. Bench-marking this strategy for the recently discovered atomic monolayer system indenene, we demonstrate its distinct QSHI character and establish CD-ARPES as a scalable bulk probe to experimentally classify the topology of two-dimensional quantum materials with time reversal symmetry.

Observation of dichotomic field-tunable electronic structure in twisted monolayer-bilayer graphene

Twisted bilayer graphene (tBLG) provides a fascinating platform for engineering flat bands and inducing correlated phenomena. By designing the stacking architecture of graphene layers, twisted multilayer graphene can exhibit different symmetries with rich tunability. For example, in twisted monolayer-bilayer graphene (tMBG) which breaks the C2z symmetry, transport measurements reveal an asymmetric phase diagram under an out-of-plane electric field, exhibiting correlated insulating state and ferromagnetic state respectively when reversing the field direction. Revealing how the electronic structure evolves with electric field is critical for providing a better understanding of such asymmetric field-tunable properties. Here we report the experimental observation of field-tunable dichotomic electronic structure of tMBG by nanospot angle-resolved photoemission spectroscopy (NanoARPES) with operando gating. Interestingly, selective enhancement of the relative spectral weight contributions from monolayer and bilayer graphene is observed when switching the polarity of the bias voltage. Combining experimental results with theoretical calculations, the origin of such field-tunable electronic structure, resembling either tBLG or twisted double-bilayer graphene (tDBG), is attributed to the selectively enhanced contribution from different stacking graphene layers with a strong electron-hole asymmetry. Our work provides electronic structure insights for understanding the rich field-tunable physics of tMBG.

Weyl spin-momentum locking in a chiral topological semimetal

Spin-orbit coupling in noncentrosymmetric crystals leads to spin-momentum locking – a directional relationship between an electron’s spin angular momentum and its linear momentum. Isotropic orthogonal Rashba spin-momentum locking has been studied for decades, while its counterpart, isotropic parallel Weyl spin-momentum locking has remained elusive in experiments. Theory predicts that Weyl spin-momentum locking can only be realized in structurally chiral cubic crystals in the vicinity of Kramers-Weyl or multifold fermions. Here, we use spin- and angle-resolved photoemission spectroscopy to evidence Weyl spin-momentum locking of multifold fermions in the chiral topological semimetal PtGa. We find that the electron spin of the Fermi arc surface states is orthogonal to their Fermi surface contour for momenta close to the projection of the bulk multifold fermion at the Γ point, which is consistent with Weyl spin-momentum locking of the latter. The direct measurement of the bulk spin texture of the multifold fermion at the R point also displays Weyl spin-momentum locking. The discovery of Weyl spin-momentum locking may lead to energy-efficient memory devices and Josephson diodes based on chiral topological semimetals.

Autonomous micro-focus angle-resolved photoemission spectroscopy.

Angle-resolved photoemission spectroscopy (ARPES) is a technique used to map the occupied electronic structure of solids. Recent progress in x-ray focusing optics has led to the development of ARPES into a microscopic tool, permitting the electronic structure to be spatially mapped across the surface of a sample. This comes at the expense of a time-consuming scanning process to cover not only a three-dimensional energy-momentum (E, kx, ky) space but also the two-dimensional surface area. Here, we implement a protocol to autonomously search both k- and real-space in order to find positions of particular interest, either because of their high photoemission intensity or because of sharp spectral features. The search is based on the use of Gaussian process regression and can easily be expanded to include additional parameters or optimization criteria. This autonomous experimental control is implemented on the SGM4 micro-focus beamline of the synchrotron radiation source ASTRID2.

A compact approach to higher-resolution resonant inelastic x-ray scattering detection using photoelectrons

The detection of inelastically scattered soft x-rays with high energy resolution usually requires large grating spectrometers. Recently, photoelectron spectrometry for analysis of x-rays (PAX) has been rediscovered for modern spectroscopy experiments at synchrotron light sources. By converting scattered photons to electrons and using an electron energy analyser, the energy resolution for resonant inelastic x-ray scattering (RIXS) becomes decoupled from the x-ray spot size and instrument length. In this work, we develop PAX towards high energy resolution using a modern photoemission spectroscopy setup studying Ba2Cu3O4Cl2 at the Cu L 3-edge. We measure a momentum transfer range of 24% of the first Brillouin zone simultaneously. Our results hint at the observation of a magnon excitation below 100 meV energy transfer and show intensity variations related to the dispersion of dd-excitations. With dedicated setups, PAX can complement the best and largest RIXS instruments, while at the same time opening new opportunities to acquire RIXS at a range of momentum transfers simultaneously and combine it with angle-resolved photoemission spectroscopy in a single instrument.