Crystalline C_60 is a molecular solid whose electronic properties emerge from the interplay of intermolecular hopping, electron correlations, and electron-vibration coupling. Unlike moiré van der Waals heterostructures, where interaction strength is commonly tuned by twist angle, molecular materials offer a complementary route in which layer number, molecular orientation, and substrate registry provide experimentally accessible control parameters. Here we present a systematic thickness-dependent angle-resolved photoemission study of C_60 films, spanning the monolayer to the bulk limit. The HOMO-derived band exhibits a non-monotonic evolution: the intermediate-thickness film shows larger bandwidth, reduced effective mass, and pronounced gap-like and sub-band features. The experimental trends, together with Holstein-model simulations, point to strengthened effective intermolecular electronic coupling and enhanced electron-phonon-induced spectral renormalization in the intermediate-thickness regime. These results identify a dimensional crossover in C_60 films and establish layer number as an effective knob for engineering electronic structure and many-body interactions in molecular thin films.

Competing electronic instabilities lie at the heart of emergent phenomena in quantum materials. In low-dimensional metals, Fermi-surface nesting can drive charge density wave (CDW) formation through a Peierls-like mechanism, while in strongly correlated systems, Kondo hybridization reconstructs the electronic structure by entangling localized moments with itinerant electrons. How these two fundamentally different instabilities interact-whether they coexist, compete, or mutually exclude each other-remains an open question. Here, we present suppression of charge density wave via the Kondo interaction in van der Waals material UTe_3. The angle-resolved photoemission spectroscopy (ARPES) data reveals Fermi surface nesting under similar conditions as seen in RETe_3 compounds. Despite that, no CDW is found in UTe_3 after an extensive search. We demonstrate that strong hybridization between U 5f electrons and Te p states reconstructs the low-energy electronic structure, removes the instability, and preempts CDW formation. Our results reveal a rare example where Kondo hybridization preempts density wave formation, offering a new route to controlling ordering phenomena in correlated 2D materials.

Spontaneous symmetry breaking in kagome metals has prompted intense debate, particularly regarding the charge density wave (CDW) phase in CsV3Sb5 and whether time-reversal symmetry (TRS) is broken, and if so, when it occurs. Here, we try to resolve this issue by performing circular dichroism measurements in angle-resolved photoemission spectroscopy (ARPES) on CsV3Sb5 across an extended temperature range. We observe clear signatures of chiral symmetry breaking emerging at T* ≈ 145 K well above the conventional CDW temperature, manifested by a pronounced dichroic response in the photoemission intensity. Importantly, this phenomenon is unlikely to arise solely from structural distortions or domain effects, and rather indicates the presence of such an intriguing phase as loop current order that breaks time-reversal symmetry. Upon entering the CDW phase at TCDW ≈ 90K, the dichroic response evolves in a complex manner, reflecting the mixed nature of charge bonding and current order. These observations are supported by first-principles calculations and atomic orbital angular momentum (OAM) analysis, which together identify the dichroism as a characteristic of orbital polarization resulting from time-reversal symmetry breaking. Our findings indicate that CD-ARPES is an effective tool for investigating certain types of hidden orders, and provide insight into the symmetry-breaking characteristics of the CDW phase in kagome metals.

High-resolution angle- and spin-resolved photoemission spectroscopy (ARPES) of the triple-layered ruthenate Sr4Ru3O10 reveals features of the electronic structure that extend our understanding of the layered strontium ruthenates. The spectra near the Fermi energy are very different from the nonmagnetic analogues Sr2RuO4 and Sr3Ru2O7 with distinct Fermi surfaces for wide electronlike minority spin bands around the zone center and narrow holelike majority spin Fermi surface contours around the zone corners. The most dramatic results are two narrow spectral peaks similar to 30 meV below the Fermi level, a spin-minority holelike band at the Brillouin zone center, and a spin-majority saddle-band van Hove singularity at the zone edge, which exhibits almost 100% spin polarization at low temperature, and a strong temperature dependent coherence-incoherence crossover attributed to Hund metal correlations. Quantitative comparison of the ARPES to spin-polarized density functional theory (DFT) calculations identify the specific antibonding and nonbonding orbital origins of the narrow bands, with a prediction of different spatial localization in the central and outer layers. This is shown to be consistent with experimental ARPES multizone matrix element intensity variations, and implicates outer-layer-specific control of the in-plane metamagnetism. The renormalization of the bands relative to the mean-field DFT, the demonstration of spin-polarized oxygen bands, and of spin-minority and spin-majority band-crossing hybridization provide a more complete picture of the magnetism which displays aspects of both delocalized and local moment behavior.

Correlated topological materials often maintain a delicate balance among physical symmetries. Many topological orders are symmetry protected, whereas most correlated phenomena arise from spontaneous symmetry breaking. Cases where symmetry breaking induces a non-trivial topological phase are rare. Here we demonstrate the presence of two such phases in Ta2Pd3Te5, where Coulomb interactions form excitons that condense below 100 K, one with zero and the other with finite momentum. We observed a full spectral bulk gap, which stems from exciton condensation. This topological excitonic insulator state spontaneously breaks mirror symmetries but involves a weak structural coupling. Scanning tunnelling microscopy shows gapless boundary modes in the bulk insulating phase. Their magnetic field response, together with theoretical modelling, indicates a topological origin. These observations establish Ta2Pd3Te5 as a topological excitonic insulator in a three-dimensional crystal. Thus, our results manifest a unique sequence of topological exciton condensations in a bulk crystal, offering exciting opportunities to study critical behaviour and excitations.

To explore how anion substitution modifies the existing magnetism in strongly correlated oxides, we investigate local electronic states and magnetic ordering in nickel oxide (NiO) induced by substituting oxygen (O) with nitrogen (N). Each N introduces an additional N 2p hole and modifies the magnetic moment of a neighboring nickel (Ni) cation site, as the exchange interaction between this hole and the Ni eg electrons exceeds the Ni-O-Ni superexchange interaction. This leads to the formation of Ni-N-Ni centers consisting of five spins, without perturbing the antiferromagnetic NiO lattice. These centers are studied using density functional theory and confirmed through high-resolution spectroscopy on N-substituted NiO thin films grown by molecular beam epitaxy. This type of magnetic design may enable future advances in quantum technologies based on strongly correlated materials, such as quantum sensors and spin-based qubits.

A Berry phase of odd multiples of pi inferred from quantum oscillations (QOs) has often been treated as evidence for nontrivial reciprocal space topology. However, disentangling the Berry phase values from the Zeeman effect and the orbital magnetic moment is often challenging. In centrosymmetric compounds, the case is simpler as the orbital magnetic moment contribution is negligible. Although the Zeeman effect can be significant, it is usually overlooked in most studies of QOs in centrosymmetric compounds. Here, we present a detailed study on the nonmagnetic centrosymmetric SrGa2 and BaGa2, which are predicted to be Dirac nodal line semimetals based on density functional theory (DFT) calculations. Evidence of the nontrivial topology is found in magnetotransport measurements. The Fermi surface topology and band structure are carefully studied through a combination of angle-dependent QOs, angle-resolved photoemission spectroscopy (ARPES), and DFT calculations, where the nodal line is observed in the vicinity of the Fermi level. Strong de Haas-van Alphen fundamental oscillations associated with higher harmonics are observed in both compounds, which are well fitted by the Lifshitz-Kosevich (LK) formula. However, even with the inclusion of higher harmonics in the fitting, we found that the Berry phases cannot be unambiguously determined when the Zeeman effect is included. We revisit the LK formula and analyze the phenomena and outcomes that were associated with the Zeeman effect in previous studies. Our experimental results confirm that SrGa2 and BaGa2 are Dirac nodal line semimetals. Additionally, we highlight the often overlooked role of spin-damping terms in Berry phase analysis.

Recent reports on a family of kagome metals of the form LnTi3Bi4 (Ln = Lanthanide) has stoked interest due to the combination of highly anisotropic magnetism and a rich electronic structure. The electronic structure near the Fermi level is proposed to exhibit Dirac points and van Hove singularities. In this manuscript, we use angle resolved photoemission spectroscopy measurements in combination with density functional theory calculations to investigate the electronic structure of a newly discovered kagome metal LaTi3Bi4. Our results reveal multiple van Hove singularities (VHSs) with one VHS located in the vicinity of the Fermi level. We clearly observe two flat bands, which originate from the destructive interference of wave functions within the Ti kagome motif. These flat bands and VHSs originate from Ti d orbitals and are very responsive to the polarization of the incident beam. We notice a significant anisotropy in the electronic structure, resulting from the breaking of six fold rotational symmetry in this material. Our findings demonstrate this new family of Ti based kagome material as a promising platform to explore novel emerging phenomena in the wider LnTi3Bi4 (Ln= lanthanide) family of materials.

Spin moiré superlattices (SMSs) have been proposed as a magnetic analog of crystallographic moiré systems and a source of electron minibands offering vector-field moiré tunability and Berry curvature effects. However, it has proven challenging to realize an SMS in which a large exchange coupling J is transmitted between conduction electrons and localized spins. Furthermore, most systems have carrier mean free paths l mfp shorter than their spin moiré lattice constant a spin , inhibiting miniband formation. Here, we discover that the layered magnetic semimetal EuAg 4 Sb 2 overcomes these challenges by forming an interface with J ~ 100 milli–electron volts transferred between a Eu triangular lattice and anionic Ag 2 Sb bilayers hosting a two-dimensional electron band in the ballistic regime ( l mfp >> a spin ). The system realizes an SMS with a spin commensurate with the Fermi momentum, leading to a marked quenching of the transport response from miniband formation. Our findings demonstrate an approach to magnetically engineering moiré superlattices and a potential route to an emergent spin-driven quantum Hall state.

Received 26 February 2024DOI:https://doi.org/10.1103/PhysRevB.109.199901©2024 American Physical SocietyPhysics Subject Headings (PhySH)Research AreasCharge orderDirac fermionsSymmetry protected topological statesPhysical SystemsChalcogenidesDirac semimetalTopological materialsTechniquesAngle-resolved photoemission spectroscopyDensity functional calculationsCondensed Matter, Materials & Applied Physics

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.

Emergent phases often appear when the electronic kinetic energy is comparable to the Coulomb interactions. One approach to seek material systems as hosts of such emergent phases is to realize localization of electronic wavefunctions due to the geometric frustration inherent in the crystal structure, resulting in flat electronic bands. Recently, such efforts have found a wide range of exotic phases in the two-dimensional kagome lattice, including magnetic order, time-reversal symmetry breaking charge order, nematicity, and superconductivity. However, the interlayer coupling of the kagome layers disrupts the destructive interference needed to completely quench the kinetic energy. Here we demonstrate that an interwoven kagome network-a pyrochlore lattice-can host a three dimensional (3D) localization of electron wavefunctions. Meanwhile, the nonsymmorphic symmetry of the pyrochlore lattice guarantees all band crossings at the Brillouin zone X point to be 3D gapless Dirac points, which was predicted theoretically but never yet observed experimentally. Through a combination of angle-resolved photoemission spectroscopy, fundamental lattice model and density functional theory calculations, we investigate the novel electronic structure of a Laves phase superconductor with a pyrochlore sublattice, CeRu$_2$. We observe flat bands originating from both the Ce 4$f$ orbitals as well as from the 3D destructive interference of the Ru 4$d$ orbitals. We further observe the nonsymmorphic symmetry-protected 3D gapless Dirac cones at the X point. Our work establishes the pyrochlore structure as a promising lattice platform to realize and tune novel emergent phases intertwining topology and many-body interactions.

PtTe2 and PdTe2 are among the first transition metal dichalcogenides that were predicted to host type-II Dirac fermions, exotic particles prohibited in free space. These materials are layered and air stable, which makes them top candidates for technological applications that take advantage of their anisotropic magnetotransport properties. Here, we provide a detailed characterization of the electronic structure of PtTe2 and PdTe2 using angle-resolved photoemission spectroscopy (ARPES) and density functional theory calculations, offering an alternative interpretation for one of the Dirac-like dispersions in these materials. Through the use of circularly polarized light, we report a different behavior of such dispersion in PdTe2 compared to PtTe2, that we relate to a symmetry analysis of the dipole matrix element. Such analysis reveals a link between the observed circular dichroism and the different momentum-dependent terms in the dispersion of these two compounds, despite their close similarity in crystal structure. Additionally, our data show a clear difference in the circular dichroic signal for the type-II Dirac cones characteristic of these materials, compared to their topologically protected surface states. Our paper provides a useful reference for the ARPES characterization of other transition metal dichalcogenides with topological properties and illustrates the use of circular dichroism as a guide to identify the topological character and attributes of two otherwise equivalent band dispersions.

A quantum state of matter that is forbidden to interact with photons and is therefore undetectable by spectroscopic means is called a dark state. This basic concept can be applied to condensed matter where it suggests that a whole band of quantum states could be undetectable across a full Brillouin zone. Here we report the discovery of such condensed-matter dark states in palladium diselenide as a model system that has two pairs of sublattices in the primitive cell. By using angle-resolved photoemission spectroscopy, we find valence bands that are practically unobservable over the whole Brillouin zone at any photon energy, polarization and scattering plane. Our model shows that two pairs of sublattices located at half-translation positions and related by multiple glide-mirror symmetries make their relative quantum phases polarized into only four kinds, three of which become dark due to double destructive interference. This mechanism is generic to other systems with two pairs of sublattices, and we show how the phenomena observed in cuprates, lead halide perovskites and density wave systems can be resolved by the mechanism of dark states. Our results suggest that the sublattice degree of freedom, which has been overlooked so far, should be considered in the study of correlated phenomena and optoelectronic characteristics. The identification of dark states-quantum states that do not interact with photons-in real materials may help to address many unsolved issues in condensed-matter physics. Now, they have been identified in palladium diselenide.

Abstract 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−δ GeTe2. 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.

In 2D noble metals like copper, the carrier scattering at grain boundaries has obscured the intrinsic nature of electronic transport. However, it is demonstrated that the intrinsic nature of transport by hole carriers in 2D copper can be revealed by growing thin films without grain boundaries. As even a slight deviation from the twin boundary is perceived as grain boundaries by electrons, it is only through the thorough elimination of grain boundaries that the hidden hole-like attribute of 2D single-crystal copper can be unmasked. Two types of Fermi surfaces, a large hexagonal Fermi surface centered at the zone center and the triangular Fermi surface around the zone corner, tightly matching to the calculated Fermi surface topology, confirmed by angle-resolved photoemission spectroscopy (ARPES) measurements and vivid nonlinear Hall effects of the 2D single-crystal copper account for the presence of hole carriers experimentally. This breakthrough suggests the potential to manipulate the majority carrier polarity in metals by means of grain boundary engineering in a 2D geometry.

Since the initial discovery of 2D van der Waals (vdW) materials, significant effort has been made to incorporate the three properties of magnetism, band structure topology, and strong electron correlations-to leverage emergent quantum phenomena and expand their potential applications. However, the discovery of a single vdW material that intrinsically hosts all three ingredients has remained an outstanding challenge. Here, the discovery of a Kondo-interacting topological antiferromagnet is reported in the vdW 5f electron system UOTe. It has a high antiferromagnetic (AFM) transition temperature of 150 K, with a unique AFM configuration that breaks the combined parity and time reversal (PT) symmetry in an even number of layers while maintaining zero net magnetic moment. This angle-resolved photoemission spectroscopy (ARPES) measurements reveal Dirac bands near the Fermi level, which combined with the theoretical calculations demonstrate UOTe as an AFM Dirac semimetal. Within the AFM order, the presence of the Kondo interaction is observed, as evidenced by the emergence of a 5f flat band near the Fermi level below 100 K and hybridization between the Kondo band and the Dirac band. The density functional theory calculations in its bilayer form predict UOTe as a rare example of a fully-compensated AFM Chern insulator.

Flat bands and nontrivial topological physics are two important topics of condensed matter physics. With a unique stacking configuration analogous to the Su-Schrieffer-Heeger model, rhombohedral graphite (RG) is a potential candidate for realizing both flat bands and nontrivial topological physics. Here, we report experimental evidence of topological flat bands (TFBs) on the surface of bulk RG, which are topologically protected by bulk helical Dirac nodal lines via the bulk-boundary correspondence. Moreover, upon in situ electron doping, the surface TFBs show a splitting with exotic doping evolution, with an order-of-magnitude increase in the bandwidth of the lower split band, and pinning of the upper band near the Fermi level. These experimental observations together with Hartree-Fock calculations suggest that correlation effects are important in this system. Our results demonstrate RG as a platform for investigating the rich interplay between nontrivial band topology, correlation effects, and interaction-driven symmetry-broken states.

In this and the two following papers, we present the results of a combined study by density-functional band theory and angle-resolved photoemission spectroscopy (ARPES) of lithium purple bronze, ${\mathrm{Li}}_{1x}{\mathrm{Mo}}_{6}{\mathrm{O}}_{17}$. This material is particularly notable for its unusually robust quasi-one-dimensional (quasi-1D) behavior. The band structure, in a large energy window around the Fermi energy, is basically two-dimensional and formed by three Mo ${t}_{2g}$-like extended Wannier orbitals (WOs), each one giving rise to a 1D band running at a ${120}^{\ensuremath{\circ}}$ angle to the two others. A structural ``dimerization'' from $\mathbf{c}/2$ to $\mathbf{c}$ gaps the $xz$ and $yz$ bands while leaving the $xy$ bands metallic in the gap but resonantly coupled to the gap edges and, hence, to the two other directions. The resulting complex shape of the quasi-1D Fermi surface (FS), verified by our ARPES, thus depends strongly on the Fermi energy position in the gap, implying a great sensitivity to Li stoichiometry of properties dependent on the FS, such as FS nesting or superconductivity. The theory is verified in detail by the recognition and application of an ARPES selection rule that enables the separation in ARPES spectra of the two barely split $xy$ bands and the observation of their complex split FS. The strong resonances prevent either a two-band tight-binding model or a related real-space ladder picture from giving a valid description of the low-energy electronic structure. Down to a temperature of 6 K we find no evidence for a theoretically expected downward renormalization of perpendicular single-particle hopping due to LL fluctuations in the quasi-1D chains. This paper I introduces the material, motivates our study, summarizes the $N\mathrm{th}$-order muffin-tin orbital (NMTO) method that we use, analyzes the crystal structure and the basic electronic structure, and presents our NMTO calculation of the ${t}_{2g}$ low-energy WOs and the resulting tight-binding Hamiltonian for the six lowest energy bands, only the four lowest being occupied. Thus this paper sets the theoretical framework and nomenclature for the following two papers.