Tuning commensurability in twisted van der Waals bilayers.

Moiré superlattices based on van der Waals bilayers1-4 created at small twist angles lead to a long wavelength pattern with approximate translational symmetry. At large twist angles (θt), moiré patterns are, in general, incommensurate except for a few discrete angles. Here we show that large-angle twisted bilayers offer distinctly different platforms. More specifically, by using twisted tungsten diselenide bilayers, we create the incommensurate dodecagon quasicrystals at θt = 30° and the commensurate moiré crystals at θt = 21.8° and 38.2°. Valley-resolved scanning tunnelling spectroscopy shows disparate behaviours between moiré crystals (with translational symmetry) and quasicrystals (with broken translational symmetry). In particular, the K valley shows rich electronic structures exemplified by the formation of mini-gaps near the valence band maximum. These discoveries demonstrate that bilayers with large twist angles offer a design platform to explore moiré physics beyond those formed with small twist angles.

Comparative Electronic Structures of the Chiral Helimagnets Cr1/3NbS2 and Cr1/3TaS2.

Magnetic materials with noncollinear spin textures are promising for spintronic applications. To realize practical devices, control over the length and energy scales of such spin textures is imperative. The chiral helimagnets Cr1/3NbS2 and Cr1/3TaS2 exhibit analogous magnetic-phase diagrams with different real-space periodicities and field dependence, positioning them as model systems for studying the relative strengths of the microscopic mechanisms giving rise to exotic spin textures. Although the electronic structure of the Nb analogue has been experimentally investigated, the Ta analogue has received far less attention. Here, we present a comprehensive suite of electronic structure studies on both Cr1/3NbS2 and Cr1/3TaS2 using angle-resolved photoemission spectroscopy and density functional theory. We show that bands in Cr1/3TaS2 are more dispersive than their counterparts in Cr1/3NbS2, resulting in markedly different Fermi wavevectors. The fact that their qualitative magnetic phase diagrams are nevertheless identical shows that hybridization between the intercalant and host lattice mediates the magnetic exchange interactions in both of these materials. We ultimately find that ferromagnetic coupling is stronger in Cr1/3TaS2, but larger spin-orbit coupling (and a stronger Dzyaloshinskii-Moriya interaction) from the heavier host lattice ultimately gives rise to shorter spin textures.

Order-disorder phase transition driven by interlayer sliding in lead iodides.

A variety of phase transitions have been found in two-dimensional layered materials, but some of their atomic-scale mechanisms are hard to clearly understand. Here, we report the discovery of a phase transition whose mechanism is identified as interlayer sliding in lead iodides, a layered material widely used to synthesize lead halide perovskites. The low-temperature crystal structure of lead iodides is found not 2H polytype as known before, but non-centrosymmetric 4H polytype. This undergoes the order-disorder phase transition characterized by the abrupt spectral broadening of valence bands, taken by angle-resolved photoemission, at the critical temperature of 120 K. It is accompanied by drastic changes in simultaneously taken photocurrent and photoluminescence. The transmission electron microscopy is used to reveal that lead iodide layers stacked in the form of 4H polytype at low temperatures irregularly slide over each other above 120 K, which can be explained by the low energy barrier of only 10.6 meV/atom estimated by first principles calculations. Our findings suggest that interlayer sliding is a key mechanism of the phase transitions in layered materials, which can significantly affect optoelectronic and optical characteristics.

Charge order landscape and competition with superconductivity in kagome metals.

In the kagome metals AV3Sb5 (A = K, Rb, Cs), three-dimensional charge order is the primary instability that sets the stage for other collective orders to emerge, including unidirectional stripe order, orbital flux order, electronic nematicity and superconductivity. Here, we use high-resolution angle-resolved photoemission spectroscopy to determine the microscopic structure of three-dimensional charge order in AV3Sb5 and its interplay with superconductivity. Our approach is based on identifying an unusual splitting of kagome bands induced by three-dimensional charge order, which provides a sensitive way to refine the spatial charge patterns in neighbouring kagome planes. We found a marked dependence of the three-dimensional charge order structure on composition and doping. The observed difference between CsV3Sb5 and the other compounds potentially underpins the double-dome superconductivity in CsV3(Sb,Sn)5 and the suppression of Tc in KV3Sb5 and RbV3Sb5. Our results provide fresh insights into the rich phase diagram of AV3Sb5.

Pseudogap in a crystalline insulator doped by disordered metals.

Key to our understanding of how electrons behave in crystalline solids is the band structure that connects the energy of electron waves to their wavenumber. Even in phases of matter with only short-range order (liquid or amorphous solid), the coherent part of electron waves still has a band structure. Theoretical models for the band structure of liquid metals were formulated more than five decades ago1-15, but, so far, band-structure renormalization and the pseudogap induced by resonance scattering have remained unobserved. Here we report the observation of the unusual band structure at the interface of a crystalline insulator (black phosphorus) and disordered dopants (alkali metals). We find that a conventional parabolic band structure of free electrons bends back towards zero wavenumber with a pseudogap of 30-240 millielectronvolts from the Fermi level. This is wavenumber renormalization caused by resonance scattering, leading to the formation of quasi-bound states in the scattering potential of alkali-metal ions. The depth of this potential tuned by different kinds of disordered alkali metal (sodium, potassium, rubidium and caesium) allows the classification of the pseudogap of p-wave and d-wave resonance. Our results may provide a clue to the puzzling spectrum of various crystalline insulators doped by disordered dopants16-20, such as the waterfall dispersion observed in copper oxides.

Black phosphorus as a bipolar pseudospin semiconductor.

Semiconductor devices rely on the charge and spin of electrons, but there is another electronic degree of freedom called pseudospin in a two-level quantum system1 such as a crystal consisting of two sublattices2. A potential way to exploit the pseudospin of electrons in pseudospintronics3-5 is to find quantum matter with tunable and sizeable pseudospin polarization. Here, we propose a bipolar pseudospin semiconductor, where the electron and hole states have opposite net pseudospin polarization. We experimentally identify such states in anisotropic honeycomb crystal-black phosphorus. By sublattice interference of photoelectrons, we find bipolar pseudospin polarization greater than 95% that is stable at room temperature. This pseudospin polarization is identified as a consequence of Dirac cones merged in the highly anisotropic honeycomb system6,7. The bipolar pseudospin semiconductor, which is a pseudospin analogue of magnetic semiconductors, is not only interesting in itself, but also might be useful for pseudospintronics.

Holstein polaron in a valley-degenerate two-dimensional semiconductor.

Two-dimensional (2D) crystals have emerged as a class of materials with tunable carrier density1. Carrier doping to 2D semiconductors can be used to modulate many-body interactions2 and to explore novel composite particles. The Holstein polaron is a small composite particle of an electron that carries a cloud of self-induced lattice deformation (or phonons)3-5, which has been proposed to play a key role in high-temperature superconductivity6 and carrier mobility in devices7. Here we report the discovery of Holstein polarons in a surface-doped layered semiconductor, MoS2, in which a puzzling 2D superconducting dome with the critical temperature of 12 K was found recently8-11. Using a high-resolution band mapping of charge carriers, we found strong band renormalizations collectively identified as a hitherto unobserved spectral function of Holstein polarons12-18. The short-range nature of electron-phonon (e-ph) coupling in MoS2 can be explained by its valley degeneracy, which enables strong intervalley coupling mediated by acoustic phonons. The coupling strength is found to increase gradually along the superconducting dome up to the intermediate regime, which suggests a bipolaronic pairing in the 2D superconductivity.

Two-Dimensional Dirac Fermions Protected by Space-Time Inversion Symmetry in Black Phosphorus.

We report the realization of novel symmetry-protected Dirac fermions in a surface-doped two-dimensional (2D) semiconductor, black phosphorus. The widely tunable band gap of black phosphorus by the surface Stark effect is employed to achieve a surprisingly large band inversion up to ∼0.6 eV. High-resolution angle-resolved photoemission spectra directly reveal the pair creation of Dirac points and their movement along the axis of the glide-mirror symmetry. Unlike graphene, the Dirac point of black phosphorus is stable, as protected by space-time inversion symmetry, even in the presence of spin-orbit coupling. Our results establish black phosphorus in the inverted regime as a simple model system of 2D symmetry-protected (topological) Dirac semimetals, offering an unprecedented opportunity for the discovery of 2D Weyl semimetals.

Universal Mechanism of Band-Gap Engineering in Transition-Metal Dichalcogenides.

van der Waals two-dimensional (2D) semiconductors have emerged as a class of materials with promising device characteristics owing to the intrinsic band gap. For realistic applications, the ideal is to modify the band gap in a controlled manner by a mechanism that can be generally applied to this class of materials. Here, we report the observation of a universally tunable band gap in the family of bulk 2H transition metal dichalcogenides (TMDs) by in situ surface doping of Rb atoms. A series of angle-resolved photoemission spectra unexceptionally shows that the band gap of TMDs at the zone corners is modulated in the range of 0.8-2.0 eV, which covers a wide spectral range from visible to near-infrared, with a tendency from indirect to direct band gap. A key clue to understanding the mechanism of this band-gap engineering is provided by the spectroscopic signature of symmetry breaking and resultant spin-splitting, which can be explained by the formation of 2D electric dipole layers within the surface bilayer of TMDs. Our results establish the surface Stark effect as a universal mechanism of band-gap engineering on the basis of the strong 2D nature of van der Waals semiconductors.

Band-Tail Transport of CuSCN: Origin of Hole Extraction Enhancement in Organic Photovoltaics.

Copper thiocyanate (CuSCN) is known as a promising hole transport layer in organic photovoltaics (OPVs) due to its good hole conduction and exciton blocking abilities with high transparency. Despite its successful device applications, the origin of its hole extraction enhancement in OPVs has not yet been understood. Here, we investigated the electronic structure of CuSCN and the energy level alignment at the poly(3-hexylthiophene-2,5-diyl) (P3HT)/CuSCN/ITO interfaces using ultraviolet photoelectron spectroscopy. The band-tail states of CuSCN close to the Fermi level (EF) were observed at 0.25 eV below the EF, leading to good hole transport. The CuSCN interlayer significantly reduces the hole transport barrier between ITO and P3HT due to its high work function and band-tail states. The barrier reduction leads to enhanced current density-voltage characteristics of hole-dominated devices. These results provide the origin of hole-extraction enhancement by CuSCN and insights for further application.

2D MATERIALS. Observation of tunable band gap and anisotropic Dirac semimetal state in black phosphorus.

Black phosphorus consists of stacked layers of phosphorene, a two-dimensional semiconductor with promising device characteristics. We report the realization of a widely tunable band gap in few-layer black phosphorus doped with potassium using an in situ surface doping technique. Through band structure measurements and calculations, we demonstrate that a vertical electric field from dopants modulates the band gap, owing to the giant Stark effect, and tunes the material from a moderate-gap semiconductor to a band-inverted semimetal. At the critical field of this band inversion, the material becomes a Dirac semimetal with anisotropic dispersion, linear in armchair and quadratic in zigzag directions. The tunable band structure of black phosphorus may allow great flexibility in design and optimization of electronic and optoelectronic devices.