Significantly enhanced superconductivity in monolayer FeSe films on SrTiO3(001) via metallic δ-doping.

Superconductivity transition temperature (Tc) marks the inception of a macroscopic quantum phase-coherent paired state in fermionic systems. For 2D superconductivity, the paired electrons condense into a coherent superfluid state at Tc, which is usually lower than the pairing temperature, between which intrinsic physics including Berezinskii-Kosterlitz-Thouless transition and pseudogap state are hotly debated. In the case of monolayer FeSe superconducting films on SrTiO3(001), although the pairing temperature (Tp) is revealed to be 65-83 K by using spectroscopy characterization, the measured zero-resistance temperature ([Formula: see text]) is limited to 20 K. Here, we report significantly enhanced superconductivity in monolayer FeSe films by δ-doping of Eu or Al on SrTiO3(001) surface, in which [Formula: see text] is enhanced by 12 K with a narrowed transition width ΔTc ∼ 8 K, compared with non-doped samples. Using scanning tunneling microscopy/spectroscopy measurements, we demonstrate lowered work function of the δ-doped SrTiO3(001) surface and enlarged superconducting gaps in the monolayer FeSe with improved morphology/electronic homogeneity. Our work provides a practical route to enhance 2D superconductivity by using interface engineering.

Robust Two-Dimensional Ferromagnetism in Cr5Te8/CrTe2 Heterostructure with Curie Temperature above 400 K.

The discovery of ferromagnetism in two-dimensional (2D) van der Waals crystals has generated widespread interest. The seeking of robust 2D ferromagnets with high Curie temperature (Tc) is vitally important for next-generation spintronic devices. However, owing to the enhanced spin fluctuation and weak exchange interaction upon the reduced dimensionalities, the exploring of robust 2D ferromagnets with Tc > 300 K is highly demanded but remains challenging. In this work, we fabricated air-stable 2D Cr5Te8/CrTe2 vertical heterojunctions with Tc above 400 K by the chemical vapor deposition method. Transmission electron microscopy demonstrates a high-quality-crystalline epitaxial structure between tri-Cr5Te8 and 1T-CrTe2 with striped moiré patterns and a superior ambient stability over six months. A built-in dual-axis strain together with strong interfacial coupling cooperatively leads to a record-high Tc for the CrxTey family. A temperature-dependent spin-flip process induces the easy axis of magnetization to rotate from the out-of-plane to the in-plane direction, indicating a phase-dependent proximity coupling effect, rationally interpreted by first-principles calculations of the magnetic anisotropy of a tri-Cr5Te8 and 1T-CrTe2 monolayer. Our results provide a material realization of effectively enhancing the transition temperature of 2D ferromagnetism and manipulating the spin-flip of the easy axis, which will facilitate future spintronic applications.

Intrinsic surface p-wave superconductivity in layered AuSn4.

The search for topological superconductivity (TSC) is currently an exciting pursuit, since non-trivial topological superconducting phases could host exotic Majorana modes. However, the difficulty in fabricating proximity-induced TSC heterostructures, the sensitivity to disorder and stringent topological restrictions of intrinsic TSC place serious limitations and formidable challenges on the materials and related applications. Here, we report a new type of intrinsic TSC, namely intrinsic surface topological superconductivity (IS-TSC) and demonstrate it in layered AuSn4 with Tc of 2.4 K. Different in-plane and out-of-plane upper critical fields reflect a two-dimensional (2D) character of superconductivity. The two-fold symmetric angular dependences of both magneto-transport and the zero-bias conductance peak (ZBCP) in point-contact spectroscopy (PCS) in the superconducting regime indicate an unconventional pairing symmetry of AuSn4. The superconducting gap and surface multi-bands with Rashba splitting at the Fermi level (EF), in conjunction with first-principle calculations, strongly suggest that 2D unconventional SC in AuSn4 originates from the mixture of p-wave surface and s-wave bulk contributions, which leads to a two-fold symmetric superconductivity. Our results provide an exciting paradigm to realize TSC via Rashba effect on surface superconducting bands in layered materials.

Growth of Mesoscale Ordered Two-Dimensional Hydrogen-Bond Organic Framework with the Observation of Flat Band.

Flat bands (FBs), presenting a strongly interacting quantum system, have drawn increasing interest recently. However, experimental growth and synthesis of FB materials have been challenging and have remained elusive for the ideal form of monolayer materials where the FB arises from destructive quantum interference as predicted in 2D lattice models. Here, we report surface growth of a self-assembled monolayer of 2D hydrogen-bond (H-bond) organic frameworks (HOFs) of 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) on Au(111) substrate and the observation of FB. High-resolution scanning tunneling microscopy or spectroscopy shows mesoscale, highly ordered, and uniform THPB HOF domains, while angle-resolved photoemission spectroscopy highlights a FB over the whole Brillouin zone. Density-functional-theory calculations and analyses reveal that the observed topological FB arises from a hidden electronic breathing-kagome lattice without atomically breathing bonds. Our findings demonstrate that self-assembly of HOFs provides a viable approach for synthesis of 2D organic topological materials, paving the way to explore many-body quantum states of topological FBs.

Kinetic Controlled Chirality Transfer and Induction in 2D Hydrogen-Bonding Assemblies of Glycylglycine on Au(111).

Chirality transfer is of vital importance that dominates the structure and functionality of biological systems and living matters. External physical stimulations, e.g. polarized light and mechanical forces, can trigger the chirality symmetry breaking, leading to the appearance of the enantiomeric entities created from a chiral self-assembly of achiral molecule. Here, several 2D assemblies with different chirality, synthesized on Au(111) surface by using achiral building blocks - glycylglycine (digly), the simplest polypeptide are reported. By delicately tuning the kinetic factors, i.e., one-step slow/rapid deposition, or stepwise slow deposition with mild annealing, achiral square hydrogen-bond organic frameworks (HOF), homochiral rhombic HOF and racemic rectangular assembly are achieved, respectively. Chirality induction and related symmetry broken in assemblies are introduced by the handedness (H-bond configurations in principle) of the assembled motifs and then amplified to the entire assemblies via the interaction between motifs. The results show that the chirality transfer and induction of biological assemblies can be tuned by altering the kinetic factors instead of applying external forces, which may offer an in-depth understanding and practical approach to peptide chiral assembly on the surfaces and can further facilitate the design of desired complex biomolecular superstructures.

Discrete scale invariance of the quasi-bound states at atomic vacancies in a topological material.

Recently, log-periodic quantum oscillations have been detected in the topological materials zirconium pentatelluride (ZrTe5) and hafnium pentatelluride (HfTe5), displaying an intriguing discrete scale invariance (DSI) characteristic. In condensed materials, the DSI is considered to be related to the quasi-bound states formed by massless Dirac fermions with strong Coulomb attraction, offering a feasible platform to study the long-pursued atomic-collapse phenomenon. Here, we demonstrate that a variety of atomic vacancies in the topological material HfTe5 can host the geometric quasi-bound states with a DSI feature, resembling an artificial supercritical atom collapse. The density of states of these quasi-bound states is enhanced, and the quasi-bound states are spatially distributed in the "orbitals" surrounding the vacancy sites, which are detected and visualized by low-temperature scanning tunneling microscope/spectroscopy. By applying the perpendicular magnetic fields, the quasi-bound states at lower energies become wider and eventually invisible; meanwhile, the energies of quasi-bound states move gradually toward the Fermi energy (EF). These features are consistent with the theoretical prediction of a magnetic field-induced transition from supercritical to subcritical states. The direct observation of geometric quasi-bound states sheds light on the deep understanding of the DSI in quantum materials.

A Fullerene-Platinum Complex for Direct Functional Patterning of Single Metal Atom-Embedded Carbon Nanostructures.

The development of patterning materials ("resists") at the nanoscale involves two distinct trends: one is toward high sensitivity and resolution for miniaturization, the other aims at functionalization of the resists to realize bottom-up construction of distinct nanoarchitectures. Patterning of carbon nanostructures, a seemingly ideal application for organic functional resists, has been highly reliant on complicated pattern transfer processes because of a lack of patternable precursors. Herein, we present a fullerene-metal coordination complex as a fabrication material for direct functional patterning of sub-10 nm metal-containing carbon structures. The attachment of one platinum atom per fullerene molecule not only leads to significant improvement of sensitivity and resolution but also enables stable atomic dispersion of the platinum ions within the carbon matrix, which may gain fundamentally new interest in functional patterning of hierarchical carbon nanostructures.

Complex supramolecular tessellations with on-surface self-synthesized C60 tiles through van der Waals interaction.

Supramolecular tessellation with self-synthesized (C60)7 tiles is achieved based on a cooperative interaction between co-adsorbed C60 and octanethiol (OT) molecules. Tile synthesis and tiling take place simultaneously on a gold substrate leading to a two-dimensional lattice of (C60)7 tiles with OT as the binder molecule filling the gaps between the tiles. This supramolecular tessellation is featured with simultaneous on-site synthesis of tiles and self-organized tiling. In the absence of specific functional groups, the key to ordered tiling for the C60/OT system is the collective van der Waals (vdW) interaction among a large number of molecules. This bicomponent system herein offers a way for the artificial synthesis of 2D complex vdW supramolecular tessellations.

Magnetic Doping Induced Superconductivity-to-Incommensurate Density Waves Transition in a 2D Ultrathin Cr-Doped Mo2C Crystal.

In the vicinity of a competing electronic order, superconductivity emerges within a superconducting dome in the phase diagram, which has been demonstrated in unconventional superconductors and transition-metal dichalcogenides (TMDs), suggesting a scenario where fluctuations or a partial melting of a parent order are essential for inducing superconductivity. Here, we present a contrary example, the two-dimensional (2D) superconductivity in transition-metal carbide can be readily turned into charge density wave (CDW) phases via dilute magnetic doping. Low temperature scanning tunneling microscopy/spectroscopy (STM/STS), transport measurements, and density functional theory (DFT) calculations were employed to investigate Cr-doped superconducting Mo2C crystals in the 2D limit. With ultralow Cr doping (2.7 atom %), the superconductivity of Mo2C is heavily suppressed. Strikingly, an incommensurate density wave (IDW) and a related partially opened gap are observed at a temperature above the superconducting regime. The wave vector of IDW agrees well with the calculated Fermi surface nesting vectors. By further increasing the Cr doping level to 9.4 atom %, a stronger IDW with a smaller periodicity and a larger partial gap appear concurrently. The resistance anomaly implies the onset of the CDW phase. Spatial-resolved and temperature-dependent spectroscopy reveals that such CDW phases exist only in a nonsuperconducting regime and could form long-range orders uniformly. The results provide the understanding for the interplay between charge ordered states and superconductivity in 2D transition-metal carbide.

Constructing and Transferring Two-Dimensional Tessellation Kagome Lattices via Chemical Reactions on Cu(111) Surface.

Two-dimensional (2D) tessellation of organic species acquired increased interests recently because of their potential applications in physics, biology, and chemistry. 2D tessellations have been successfully constructed on surfaces via various intermolecular interactions. However, the transformation between 2D tessellation lattices has been rarely reported. Herein, we successfully fabricated two types of Kagome lattices on Cu(111). The former phase exhibits (3,6,3,6) Kagome lattices, which are stabilized via the intermolecular hydrogen bond interactions. The latter phase is formed through direct chemical transferring from the former one maintaining almost the same Kagome lattices, except for that the unit cell rotates for 4°. Detailed scanning tunneling microscopy and density functional calculation studies reveal that the chemical transformation is achieved by the formation of the N-Cu-N metal-organic bonds via dehydrogenation reactions of the amines.

Computational Search for Better Thermoelectric Performance in Nickel-Based Half-Heusler Compounds.

Half-Heusler alloys have recently received extensive attention because of their promising thermoelectric (TE) properties and great potential for applications requiring efficient thermoelectricity. Although the conversion efficiency of these materials can be greatly improved by doping, it is still far away from the real-life applications. Therefore, search for better parent TE compounds is deemed urgent. Using a high-throughput search method based on first-principles calculations in newly proposed 378 half-Heusler alloys, we identify nine nickel-based half-Heusler semiconductors as candidates and systematically study their mechanical, electronic, and transport properties. Their mechanical and dynamical stabilities are verified based on the calculated elastic constants and phonon spectra. The electronic structure calculations indicate the existence of direct energy gaps in the NiVZ (Z = Al, Ga, and In) and indirect energy gaps in the NiTiZ (Z = Si, Ge, and Sn) and NiScZ (Z = P, As, and Sb) compounds. Among them, NiVAl, NiVGa, and NiVIn exhibit a sharp slope of density of states near the Fermi level, which is predicted to be essential for a high TE performance. Further investigation on carrier concentration and temperature dependence of TE properties shows the high power factors of NiVAl, NiVGa, and NiVIn, which are responsible for their high figure of merit values. The highest maximum power factor of 5.152 mW m-1 K-2 and figure of merit of 0.309 are predicted for pristine half-Heusler NiVIn, which are larger than the values of some known pristine and doped half-Heusler TE materials. Our work opens up new avenues for rationally searching better TE materials among half-Heusler alloys for applications in fields requiring efficient thermoelectricity.

Immunogenicity and persistence of high-dose recombinant hepatitis B vaccine in adults infected with human immunodeficiency virus in China: A randomized, double-blind, parallel controlled trial.

OBJECTIVES: To explore the immunogenicity and persistence of the 60 µg hepatitis B vaccine in adults infected with human immunodeficiency virus (HIV). METHODS: We conducted a randomised controlled trial for adults infected with HIV. A total of 182 patients were randomly allocated to receive 20 µg (IM20 group) or 60 µg (IM60 group) of recombinant hepatitis B vaccine at months 0, 1, and 6 to assess the immunogenicity and were followed-up from month 7 to 42 to assess long-term immunogenicity. RESULTS: Our data showed that the response rate and geometric mean concentration (GMC) of antibodies to hepatitis B surface antigen (anti-HBs) in the IM60 group at month 7 were higher than those in the IM20 group (P > 0.05). The GMC of anti-HBs among the two groups decreased rapidly during the follow-up period (P > 0.05). Survival analysis showed that 25% of patients with anti-HBs ≥ 10 mIU/mL were 20 months in the IM60 group and 9.3 months in the IM20 group. CONCLUSION: The three-dose 60 µg hepatitis B vaccine showed partially better immunogenicity and persistence than the three-dose 20 µg vaccine. TRIAL REGISTRATION: The trial was registered on clinicaltrials.gov, NCT03316807.

In Situ Observation of Stepwise C-H Bond Scission: Deciphering the Catalytic Selectivity of Ethylbenzene-to-Styrene Conversion on TiO2.

The conversion of light alkanes to olefins is crucial to the chemical industry. The quest for improved catalytic performance for this conversion is motivated by current drawbacks including: expensive noble metal catalysts, poor conversion, low selectivity, and fast decay of efficiency. The in situ visualization of complex catalysis at the atomic level is therefore a major advance in the rational framework upon building the future catalysts. Herein, the catalytic C-H bond activations of ethylbenzene on TiO2(110)-(1 × 1) were explored with high-resolution scanning tunneling microscopy and first-principles calculations. We report that the first C-H bond scission is a two-step process that can be triggered by either heat or ultraviolet light at 80 K, with near 100% selectivity of ß-CH bond cleavage. This work provides fundamental understanding of C-H bonds cleavage of ethylbenzene on metal oxides, and it may promote the design of new catalysts for selective styrene production under mild conditions.

Superhigh Uniform Magnetic Cr Substitution in a 2D Mo2 C Superconductor for a Macroscopic-Scale Kondo Effect.

Substitutional doping provides an effective strategy to tailor the properties of 2D materials, but it remains an open challenge to achieve tunable uniform doping, especially at high doping level. Here, uniform lattice substitution of a 2D Mo2 C superconductor by magnetic Cr atoms with controlled concentration up to ≈46.9 at% by chemical vapor deposition and a specifically designed Cu/Cr/Mo trilayer growth substrate is reported. The concentration of Cr atoms can be easily tuned by simply changing the thickness of the Cr layer, and the samples retain the original structure of 2D Mo2 C even at a very high Cr concentration. The controlled uniform Cr doping enables the tuning of the competition of the 2D superconductor and the Kondo effect across the whole sample. Transport measurements show that with increasing Cr concentration, the superconductivity of the 2D Cr-doped Mo2 C crystals disappears along with the emergence of the Kondo effect, and the Kondo temperature increases monotonously. Using scanning tunneling microscopy/spectroscopy, the mechanism of the doping level effect on the interplay and evolution between superconductivity and the Kondo effect is revealed. This work paves a new way for the synthesis of 2D materials with widely tunable doping levels, and provides new understandings on the interplay between superconductivity and magnetism in the 2D limit.

Surface superconductivity in the type II Weyl semimetal TaIrTe4.

The search for unconventional superconductivity in Weyl semimetal materials is currently an exciting pursuit, since such superconducting phases could potentially be topologically non-trivial and host exotic Majorana modes. The layered material TaIrTe4 is a newly predicted time-reversal invariant type II Weyl semimetal with the minimum number of Weyl points. Here, we report the discovery of surface superconductivity in Weyl semimetal TaIrTe4. Our scanning tunneling microscopy/spectroscopy (STM/STS) visualizes Fermi arc surface states of TaIrTe4 that are consistent with the previous angle-resolved photoemission spectroscopy results. By a systematic study based on STS at ultralow temperature, we observe uniform superconducting gaps on the sample surface. The superconductivity is further confirmed by electrical transport measurements at ultralow temperature, with an onset transition temperature (T c) up to 1.54 K being observed. The normalized upper critical field h*(T/T c) behavior and the stability of the superconductivity against the ferromagnet indicate that the discovered superconductivity is unconventional with the p-wave pairing. The systematic STS, and thickness- and angular-dependent transport measurements reveal that the detected superconductivity is quasi-1D and occurs in the surface states. The discovery of the surface superconductivity in TaIrTe4 provides a new novel platform to explore topological superconductivity and Majorana modes.

Strongly Compressed Few-Layered SnSe2 Films Grown on a SrTiO3 Substrate: The Coexistence of Charge Ordering and Enhanced Interfacial Superconductivity.

High pressure has been demonstrated to be a powerful approach of producing novel condensed-matter states, particularly in tuning the superconducting transition temperature (Tc) of the superconductivity in a clean fashion without involving the complexity of chemical doping. However, the challenge of high-pressure experiment hinders further in-depth research for underlying mechanisms. Here, we have successfully synthesized continuous layer-controllable SnSe2 films on SrTiO3 substrate using molecular beam epitaxy. By means of scanning tunneling microscopy/spectroscopy (STM/S) and Raman spectroscopy, we found that the strong compressive strain is intrinsically built in few-layers films, with a largest equivalent pressure up to 23 GPa in the monolayer. Upon this, unusual 2 × 2 charge ordering is induced at the occupied states in the monolayer, accompanied by prominent decrease in the density of states (DOS) near the Fermi energy (EF), resembling the gap states of CDW reported in transition metal dichalcogenide (TMD) materials. Subsequently, the coexistence of charge ordering and the interfacial superconductivity is observed in bilayer films as a result of releasing the compressive strain. In conjunction with spatially resolved spectroscopic study and first-principles calculation, we find that the enhanced interfacial superconductivity with an estimated Tc of 8.3 K is observed only in the 1 × 1 region. Such superconductivity can be ascribed to a combined effect of interfacial charge transfer and compressive strain, which leads to a considerable downshift of the conduction band minimum and an increase in the DOS at EF. Our results provide an attractive platform for further in-depth investigation of compression-induced charge ordering (monolayer) and the interplay between charge ordering and superconductivity (bilayer). Meanwhile, it has opened up a pathway to prepare strongly compressed two-dimensional materials by growing onto a SrTiO3 substrate, which is promising to induce superconductivity with a higher Tc.

Layer-Stacking, Defects, and Robust Superconductivity on the Mo-Terminated Surface of Ultrathin Mo2C Flakes Grown by CVD.

Materials can exhibit exotic properties when they approach the two-dimensional (2D) limit. Because of promising applications in catalysis and energy storage, 2D transition-metal carbides (TMCs) have attracted considerable attention in recent years. Among these TMCs, ultrathin crystalline α-Mo2C flakes have been fabricated by chemical vapor deposition on Cu/Mo bilayer foils, and their 2D superconducting property was revealed by transport measurements. Herein, we studied the ultrathin α-Mo2C flakes by atomic-resolved scanning tunneling microscopy/spectroscopy (STM/S). Strain-related structural modulation and the coexistence of different layer-stacking modes are observed on the Mo-terminated surface of α-Mo2C flakes as well as various lattice defects. Furthermore, an enhanced superconductivity with shorter correlation length was observed by STS technique, and such superconductivity is very robust despite the appearance of the defects. A mechanism of superconducting enhancement is proposed based on the strain-induced strong coupling and the increased disordering originated from lattice defects. Our results provide a comprehensive understanding of the correlations between atomic structure, defects, and enhanced superconductivity of this emerging 2D material.

Sodium bismuth dichalcogenides: candidates for ferroelectric high-mobility semiconductors for multifunctional applications.

The combination of ferroelectricity with narrow-gap high-mobility semiconductors may not only entail both functions of nonvolatile memory and efficient manipulation of signals, but may also facilitate efficient ferroelectric photovoltaics and thermoelectrics. However, these applications are hindered by the wide gap and poor mobility of current ferroelectrics. A recent study (J. Am. Chem. Soc., 2018, 140, 3736) reported a facile, general, low-temperature, and size tunable solution phase synthesis of NaBiS2 and NaBiSe2 that are made of relatively abundant or biocompatible elements, which enables their large-scale practical applications. Herein we show first-principles evidence of their ferroelectricity with a large polarization (∼33 µC cm-2), a moderate bandgap (∼1.6 eV) and a high electron-mobility (∼104 cm2 V-1 s-1). Although they have a relatively small switching barrier, their ferroelectricity can be robust under ambient conditions with enhanced polarization upon either application of a small tensile strain or ion doping, where distortion can be increased and multiferroics may also be obtained, despite reduced mobility. Considering previous reports on photovoltaics and thermoelectrics of similar compounds, sodium bismuth dichalcogenides might be tuned for higher performance with the coexistence of these desirable properties.

Epitaxial Growth of PbSe Few-Layers on SrTiO3: The Effect of Compressive Strain and Potential Two-Dimensional Topological Crystalline Insulator.

The freestanding PbSe monolayer has been predicted as a candidate of the two-dimensional topological crystalline insulator, which possesses the Dirac-cone-like edge states resided at the edge. Up to now, however, direct experimental evidence of topological PbSe monolayer has not yet been reported. Here, we report the epitaxial growth and scanning tunneling microscopy study of few-layers PbSe islands grown on SrTiO3 substrate. From the investigation of different thickness, we discover the release of compressive strain and the reduction of bandgap as the thickness becomes thick. Following detailed spectroscopic measurements, a signature of Dirac-like edge states is observed at the edge of seventh-layer PbSe. In conjunction with first-principle calculations, we find that compressive-strain-induced buckling adjusts the topological band inversion and eventually leads to a phase transition from nontrivial two-dimensional topological crystalline insulator to trivial insulator, which match well with our experimental observations. Therefore, both theoretical calculations and experimental observations reveal that the strain can effectively affect the property of epitaxial PbSe, meanwhile demonstrate seventh-layer PbSe as a potential candidate of 2D TCI.

Locally Induced Spin States on Graphene by Chemical Attachment of Boron Atoms.

Pristine graphene is known to be nonmagnetic due to its π-conjugated electron system. However, we find that localized magnetic moments can be generated by chemically attaching boron atoms to the graphene sheets. Such spin-polarized states are evidenced by the spin-split of the density of states (DOS) peaks near the Fermi level in scanning tunneling spectroscopy (STS). In the vicinity of several coadsorbed boron atoms, the Coulomb repulsion between multiple spins leads to antiferromagnetic coupling for the induced spin states in the graphene lattice, manifesting itself as an increment of spin-down state at specific regions. Experimental observations and interpretations are rationalized by extensive density functional theory (DFT) simulations.