Broken Screw Rotational Symmetry in the Near-Surface Electronic Structure of AB-Stacked Crystals.

We investigate the electronic structure of 2H-NbS_{2} and h-BN by angle-resolved photoemission spectroscopy (ARPES) and photoemission intensity calculations. Although in bulk form, these materials are expected to exhibit band degeneracy in the k_{z}=π/c plane due to screw rotation and time-reversal symmetries, we observe gapped band dispersion near the surface. We extract from first-principles calculations the near-surface electronic structure probed by ARPES and find that the calculated photoemission spectra from the near-surface region reproduce the gapped ARPES spectra. Our results show that the near-surface electronic structure can be qualitatively different from the bulk electronic structure due to partially broken nonsymmorphic symmetries.

Symmetry Engineering in Twisted Bilayer WTe2.

The fabrication of artificial structures using a twisted van der Waals assembly has been a key technique for recent advancements in the research of two-dimensional (2D) materials. To date, various exotic phenomena have been observed thanks to the modified electron correlation or moiré structure controlled by the twist angle. However, the twisted van der Waals assembly has further potential to modulate the physical properties by controlling the symmetry. In this study, we fabricated twisted bilayer WTe2 and demonstrated that the twist angle successfully controls the spatial inversion symmetry and hence the spin splitting in the band structure. Our results reveal the further potential of a twisted van der Waals assembly, suggesting the feasibility of pursuing new physical phenomena in 2D materials based on the control of symmetry.

Resonant Tunneling between Quantized Subbands in van der Waals Double Quantum Well Structure Based on Few-Layer WSe2.

We demonstrate van der Waals double quantum well (vDQW) devices based on few-layer WSe2 quantum wells and a few-layer h-BN tunnel barrier. Due to the strong out-of-plane confinement, an exfoliated WSe2 exhibits quantized subband states at the Γ point in its valence band. Here, we report resonant tunneling and negative differential resistance in vDQW at room temperature owing to momentum- and energy-conserved tunneling between the quantized subbands in each well. Compared to single quantum well (QW) devices with only one QW layer possessing quantized subbands, superior current peak-to-valley ratios were obtained for the DQWs. Our findings suggest a new direction for utilizing few-layer-thick transition metal dichalcogenides in subband QW devices, bridging the gap between two-dimensional materials and state-of-the-art semiconductor QW electronics.

Evidence for a higher-order topological insulator in a three-dimensional material built from van der Waals stacking of bismuth-halide chains.

Low-dimensional van der Waals materials have been extensively studied as a platform with which to generate quantum effects. Advancing this research, topological quantum materials with van der Waals structures are currently receiving a great deal of attention. Here, we use the concept of designing topological materials by the van der Waals stacking of quantum spin Hall insulators. Most interestingly, we find that a slight shift of inversion centre in the unit cell caused by a modification of stacking induces a transition from a trivial insulator to a higher-order topological insulator. Based on this, we present angle-resolved photoemission spectroscopy results showing that the real three-dimensional material Bi4Br4 is a higher-order topological insulator. Our demonstration that various topological states can be selected by stacking chains differently, combined with the advantages of van der Waals materials, offers a playground for engineering topologically non-trivial edge states towards future spintronics applications.

Pressure-induced topological phase transition in noncentrosymmetric elemental tellurium.

Recent progress in understanding the electronic band topology and emergent topological properties encourage us to reconsider the band structure of well-known materials including elemental substances. Controlling such a band topology by external field is of particular interest from both fundamental and technological viewpoints. Here we report possible signatures of the pressure-induced topological phase transition from a semiconductor to a Weyl semimetal in elemental tellurium probed by transport measurements. Pressure variation of the periods of Shubnikov-de Haas oscillations, as well as oscillation phases, shows an anomaly around the pressure theoretically predicted for topological phase transition. This behavior is consistent with the pressure-induced band deformation and resultant band-crossing effect. Moreover, effective cyclotron mass is reduced toward the critical pressure, potentially reflecting the emergence of massless linear dispersion. The present result paves the way for studying the electronic band topology in well-known compounds and topological phase transition by the external field.

Resonant Tunneling Due to van der Waals Quantum-Well States of Few-Layer WSe2 in WSe2/h-BN/p+-MoS2 Junction.

Few-layer transition metal dichalcogenides (TMDs) exhibit out-of-plane wave function confinement with subband quantization. This phenomenon is totally absent in monolayer crystals and is regarded as resulting from a naturally existing van der Waals quantum-well state. Because the energy separation between the subbands corresponds to the infrared wavelength range, few-layer TMDs are attractive for their potential to facilitate the application of TMD semiconductors as infrared photodetectors and emitters. Here, we report a few-layer WSe2/h-BN tunnel barrier/multilayer p+-MoS2 tunnel junction to access the quantized subbands of few-layer WSe2 via tunneling spectroscopy measurements. Resonant tunneling and a negative differential resistance were observed when the top of the valence band Γ-point of p+-MoS2 was energetically aligned with one of the empty subbands at the Γ-point of few-layer WSe2. These results demonstrate a critical step toward the utilization of subband quantization in few-layer TMD materials for infrared optoelectronics applications.

Observation of Bogoliubov Band Hybridization in the Optimally Doped Trilayer Bi_{2}Sr_{2}Ca_{2}Cu_{3}O_{10+δ}.

Using a laser-excited angle-resolved photoemission spectroscopy capable of bulk sensitive and high-energy resolution measurements, we reveal a new phenomenon of superconductors in the optimally doped trilayer Bi_{2}Sr_{2}Ca_{2}Cu_{3}O_{10+δ}. We observe a hybridization of the Bogoliubov bands derived from the inner and outer CuO_{2} planes with different magnitudes of energy gaps. Our data clearly exhibit the splitting of coherent peaks and the consequent enhancement of spectral gaps. These features are reproduced by model calculations, which indicate that the gap enhancement extends over a wide range of Fermi surface up to the antinode. The significant modulation of electron pairing uncovered here might be a crucial factor to achieve the highest critical temperature in the trilayer cuprates.

Direct spectroscopic evidence for phase competition between the pseudogap and superconductivity in Bi2Sr2CaCu2O(8+δ).

In the high-temperature (T(c)) cuprate superconductors, a growing body of evidence suggests that the pseudogap phase, existing below the pseudogap temperature T*, is characterized by some broken electronic symmetries distinct from those associated with superconductivity. In particular, recent scattering experiments have suggested that charge ordering competes with superconductivity. However, no direct link of an interplay between the two phases has been identified from the important low-energy excitations. Here, we report an antagonistic singularity at T(c) in the spectral weight of Bi2Sr2CaCu2O(8+δ) as compelling evidence for phase competition, which persists up to a high hole concentration p ~ 0.22. Comparison with theoretical calculations confirms that the singularity is a signature of competition between the order parameters for the pseudogap and superconductivity. The observation of the spectroscopic singularity at finite temperatures over a wide doping range provides new insights into the nature of the competitive interplay between the two orders and the complex phase diagram near the pseudogap critical point.

Bandgap modulation in photoexcited topological insulator Bi2Te3 via atomic displacements.

The atomic and electronic dynamics in the topological insulator (TI) Bi2Te3 under strong photoexcitation were characterized with time-resolved electron diffraction and time-resolved mid-infrared spectroscopy. Three-dimensional TIs characterized as bulk insulators with an electronic conduction surface band have shown a variety of exotic responses in terms of electronic transport when observed under conditions of applied pressure, magnetic field, or circularly polarized light. However, the atomic motions and their correlation between electronic systems in TIs under strong photoexcitation have not been explored. The artificial and transient modification of the electronic structures in TIs via photoinduced atomic motions represents a novel mechanism for providing a comparable level of bandgap control. The results of time-domain crystallography indicate that photoexcitation induces two-step atomic motions: first bismuth and then tellurium center-symmetric displacements. These atomic motions in Bi2Te3 trigger 10% bulk bandgap narrowing, which is consistent with the time-resolved mid-infrared spectroscopy results.

Crossover between rigid and reconstructed moiré lattice in h-BN-encapsulated twisted bilayer WSe2 with different twist angles.

A moiré lattice in a twisted-bilayer transition metal dichalcogenide (tBL-TMD) exhibits a complex atomic reconstruction effect when its twist angle is less than a few degrees. The influence of the atomic reconstruction on material properties of the tBL-TMD has been of particular interest. In this study, we performed scanning transmission electron microscopy (STEM) imaging of a moiré lattice in h-BN-encapsulated twisted bilayer WSe2 with various twist angles. Atomic-resolution imaging of the moiré lattice revealed a reconstructed moiré lattice below a crossover twist angle of ∼4° and a rigid moiré lattice above this angle. Our findings indicate that h-BN encapsulation has a considerable influence on lattice reconstruction, as the crossover twist angle was larger in h-BN-encapsulated devices compared to non-encapsulated devices. We believe that this difference is due to the improved flatness and uniformity of the twisted bilayers with h-BN encapsulation. Our results provide a foundation for a deeper understanding of the lattice reconstruction in twisted TMD materials with h-BN encapsulation.

Gate-Defined Josephson Weak-Links in Monolayer WTe2.

Systems combining superconductors with topological insulators offer a platform for the study of Majorana bound states and a possible route to realize fault tolerant topological quantum computation. Among the systems being considered in this field, monolayers of tungsten ditelluride (WTe2 ) have a rare combination of properties. Notably, it has been demonstrated to be a quantum spin Hall insulator (QSHI) and can easily be gated into a superconducting state. Measurements on gate-defined Josephson weak-link devices fabricated using monolayer WTe2 are reported. It is found that consideration of the 2D superconducting leads are critical in the interpretation of magnetic interference in the resulting junctions. The reported fabrication procedures suggest a facile way to produce further devices from this technically challenging material and the results mark the first step toward realizing versatile all-in-one topological Josephson weak-links using monolayer WTe2 .

Giant second harmonic transport under time-reversal symmetry in a trigonal superconductor.

Nonreciprocal or even-order nonlinear responses in symmetry-broken systems are powerful probes of emergent properties in quantum materials, including superconductors, magnets, and topological materials. Recently, vortex matter has been recognized as a key ingredient of giant nonlinear responses in superconductors with broken inversion symmetry. However, nonlinear effects have been probed as excess voltage only under broken time-reversal symmetry. In this study, we report second harmonic transport under time-reversal symmetry in the noncentrosymmetric trigonal superconductor PbTaSe2. The magnitude of anomalous nonlinear transport is two orders of magnitude larger than those in the normal state, and the directional dependence of nonlinear signals are fully consistent with crystal symmetry. The enhanced nonlinearity is semiquantitatively explained by the asymmetric Hall effect of vortex-antivortex string pairs in noncentrosymmetric systems. This study enriches the literature on nonlinear phenomena by elucidating quantum transport in noncentrosymmetric superconductors.

Dry pick-and-flip assembly of van der Waals heterostructures for microfocus angle-resolved photoemission spectroscopy.

We present a dry pick-and-flip assembly technique for angle-resolved photoemission spectroscopy (ARPES) of van der Waals heterostructures. By combining Elvacite2552C acrylic resin and 1-ethyl-3-methylimidazolium ionic liquid, we prepared polymers with glass transition temperatures (Tg) ranging from 37 to 100 â„ƒ. The adhesion of the polymer to the 2D crystals was enhanced at [Formula: see text]. By utilizing the difference in [Formula: see text], a 2D heterostructure can be transferred from a high-[Formula: see text] polymer to a lower-[Formula: see text] polymer, which enables flipping its surface upside down. This process is suitable for assembling heterostructures for ARPES, where the top capping layer should be monolayer graphene. The laser-based micro-focused ARPES measurements of 5-layer WTe2, 3-layer MoTe2, 2-layer WTe2/few-layer Cr2Ge2Te6, and twisted double bilayer WTe2 demonstrate that this process can be utilized as a versatile sample fabrication method for investigating the energy spectra of 2D heterostructures.

An Efficient ab Initio Scheme for Discovering Organic-Inorganic Hybrid Materials by Using Genetic Algorithms.

Organic-inorganic hybrid materials (OIHMs), such as methylammonium lead triiodide (MAPbI3), have a wide composition space because of the various potential combinations of organic molecules and inorganic cages. However, for unknown OHIMs, it is difficult to predict what kind of crystal structure will be stable without any experimental data. In this work, we report an efficient scheme for predicting crystal structures and phase diagrams of MA-Pb-I systems from first-principles calculations and genetic algorithms. In our scheme, OIHMs are divided into organic molecules and inorganic clusters. A pseudobinary phase diagram of MAI-PbI2 was obtained by predicting structures at each composition. These results indicated that only MAPbI3 and MA2PbI4 are stable phases, consistent with the experiments. In addition, the electronic and optical properties of the predicted structures were calculated and the solar cell performance was evaluated. Thus, our method allowed us to search for unknown OIHMs without any experimental data.

Chirality-Dependent Circular Photogalvanic Effect in Enantiomorphic 2D Organic-Inorganic Hybrid Perovskites.

The control of the optoelectronic properties of 2D organic-inorganic hybrid perovskite (2D-OIHP) lead halides is an increasingly prevalent topic. Herein, the observation of the circular photogalvanic effect (CPGE) in new enantiomorphic 2D-OIHP lead iodides is reported, which are synthesized as a first OIHP-related system belonging to a chiral space group by incorporating organic chiral cations into the inorganic layers of lead iodides. The CPGE is an optoelectronic phenomenon associated with the spin-orbit coupling of heavy atoms in noncentrosymmetric systems. Owing to the CPGE, light-helicity-dependent steady photocurrents are generated without an external bias voltage under the irradiation of circularly polarized light. Furthermore, the sign reversal of the CPGE photocurrent depending on the chirality of the designed 2D-OIHP lead iodides is observed. This result indicates formation of the theoretically predicted radial spin-polarized texture in k-space of chiral systems owing to spin-momentum locking. Hence, chiral 2D-OIHP lead halides can be a promising platform for engineering opto-spintronic functionalities.

Magnetic Gap of Fe-Doped BiSbTe2Se Bulk Single Crystals Detected by Tunneling Spectroscopy and Gate-Controlled Transports.

Topological insulators with broken time-reversal symmetry and the Fermi level within the magnetic gap at the Dirac cone provides exotic topological magneto-electronic phenomena. Here, we introduce an improved magnetically doped topological insulator, Fe-doped BiSbTe2Se (Fe-BSTS) bulk single crystal, with an ideal Fermi level. Scanning tunneling microscopy and spectroscopy (STM/STS) measurements revealed that the surface state possesses a Dirac cone with the Dirac point just below the Fermi level by 12 meV. The normalized dI/dV spectra suggest a gap opening with Δmag ∼55 meV, resulting in the Fermi level within the opened gap. Ionic-liquid gated-transport measurements also support the Dirac point just below the Fermi level and the presence of the magnetic gap. The chemical potential of the surface state can be fully tuned by ionic-liquid gating, and thus the Fe-doped BSTS provides an ideal platform to investigate exotic quantum topological phenomena.

Dual-gate control of the surface carriers of the highly-bulk-resistive topological insulator Sn0.02Bi1.08Sb0.9Te2S.

Exotic surface states of topological insulators have long attracted the attention of researchers. Recently, surface-dominant electrical transport in topological insulators has been observed; however, surface conduction in topological insulators is still not fully understood. To address this knowledge gap, we measured the transport properties of a thin flake of a highly bulk-resistive topological insulator, Sn0.02Bi1.08Sb0.9Te2S (Sn-BSTS), whose carrier density was controlled with the field effect. Single crystals of Sn-BSTS were synthesized by the Bridgman method, and Hall devices were fabricated with exfoliated flakes. The bottom gate structure was used to control the bottom surface of a Sn-BSTS flake. The measured Hall resistance was analyzed using the two-band model, which quantitatively showed that ambipolar conduction was achieved. In addition, the carriers on the top surface were controlled by the formation of an electrical double layer by an ionic liquid. With a top-gate voltage of -1.5 V, a massive number of p-type carriers were induced on the top surface of the Sn-BSTS flake, as also confirmed with the two-band model. The longitudinal resistance was also found to be affected by the carrier density. The magnetoresistance was enhanced when n- and p-type carriers coexisted on the top and bottom surfaces. In particular, the magnetoresistance was quantitatively shown to increase when the densities of n- and p-type carriers were similar. This study is the first to quantitatively analyze the conduction in Sn-BSTS in the presence of multiple types of carriers. Our findings pave the way for a quantitative understanding of transport phenomena in topological insulators.

Emergence of superconductivity in the cuprates via a universal percolation process.

A pivotal step toward understanding unconventional superconductors would be to decipher how superconductivity emerges from the unusual normal state. In the cuprates, traces of superconducting pairing appear above the macroscopic transition temperature Tc, yet extensive investigation has led to disparate conclusions. The main difficulty has been to separate superconducting contributions from complex normal-state behaviour. Here we avoid this problem by measuring nonlinear conductivity, an observable that is zero in the normal state. We uncover for several representative cuprates that the nonlinear conductivity vanishes exponentially above Tc, both with temperature and magnetic field, and exhibits temperature-scaling characterized by a universal scale Ξ0. Attempts to model the response with standard Ginzburg-Landau theory are systematically unsuccessful. Instead, our findings are captured by a simple percolation model that also explains other properties of the cuprates. We thus resolve a long-standing conundrum by showing that the superconducting precursor in the cuprates is strongly affected by intrinsic inhomogeneity.

Ultrafast dynamics of vibrational symmetry breaking in a charge-ordered nickelate.

The ability to probe symmetry-breaking transitions on their natural time scales is one of the key challenges in nonequilibrium physics. Stripe ordering represents an intriguing type of broken symmetry, where complex interactions result in atomic-scale lines of charge and spin density. Although phonon anomalies and periodic distortions attest the importance of electron-phonon coupling in the formation of stripe phases, a direct time-domain view of vibrational symmetry breaking is lacking. We report experiments that track the transient multi-terahertz response of the model stripe compound La1.75Sr0.25NiO4, yielding novel insight into its electronic and structural dynamics following an ultrafast optical quench. We find that although electronic carriers are immediately delocalized, the crystal symmetry remains initially frozen-as witnessed by time-delayed suppression of zone-folded Ni-O bending modes acting as a fingerprint of lattice symmetry. Longitudinal and transverse vibrations react with different speeds, indicating a strong directionality and an important role of polar interactions. The hidden complexity of electronic and structural coupling during stripe melting and formation, captured here within a single terahertz spectrum, opens new paths to understanding symmetry-breaking dynamics in solids.

Facile preparation of YAG:Ce nanoparticles by laser irradiation in water and their optical properties.

Yttrium aluminum oxide Y3Al5O12 (YAG:Ce) nanoparticles were prepared by laser ablation in liquid, and the photoluminescence (PL) properties of the nanoparticles were investigated. A pellet of YAG:Ce synthesized by co-precipitation in deionized water was irradiated with a focused laser beam to obtain a solution containing dispersed nanoparticles. The compositions and morphologies of the nanoparticles were investigated by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray analysis, and dynamic light scattering. PL and photoluminescence excitation (PLE) spectra at room temperature and low temperature were measured using a fluorescence spectrophotometer. Nanoparticles of YAG single phase as a matrix were obtained by irradiation at high laser energy density. The average particle size was approximately 9 nm, although the nanoparticles were slightly aggregated. The broad peak centered at 540 nm in the PL spectrum was asymmetrically broadened at shorter wavelength. The intensity of the PLE peak centered at 340 nm decreased with increasing energy density of the laser beam. These phenomena were related to the nanosize effect of the YAG:Ce phosphor.