Tungsten Nitride (W5N6): An Ultraresilient 2D Semimetal.

Two-dimensional transition metal nitrides offer intriguing possibilities for achieving novel electronic and mechanical functionality owing to their distinctive and tunable bonding characteristics compared to other 2D materials. We demonstrate here the enabling effects of strong bonding on the morphology and functionality of 2D tungsten nitrides. The employed bottom-up synthesis experienced a unique substrate stabilization effect beyond van-der-Waals epitaxy that favored W5N6 over lower metal nitrides. Comprehensive structural and electronic characterization reveals that monolayer W5N6 can be synthesized at large scale and shows semimetallic behavior with an intriguing indirect band structure. Moreover, the material exhibits exceptional resilience against mechanical damage and chemical reactions. Leveraging these electronic properties and robustness, we demonstrate the application of W5N6 as atomic-scale dry etch stops that allow the integration of high-performance 2D materials contacts. These findings highlight the potential of 2D transition metal nitrides for realizing advanced electronic devices and functional interfaces.

High-Performance Monolithic 3D Integrated Complementary Inverters Based on Monolayer n-MoS2 and p-WSe2.

Herein, the structure of integrated M3D inverters are successfully demonstrated where a chemical vapor deposition (CVD) synthesized monolayer WSe2 p-type nanosheet FET is vertically integrated on top of CVD synthesized monolayer MoS2 n-type film FET arrays (2.5 × 2.5 cm) by semiconductor industry techniques, such as transfer, e-beam evaporation (EBV), and plasma etching processes. A low temperature (below 250 °C) is employed to protect the WSe2 and MoS2 channel materials from thermal decomposition during the whole fabrication process. The MoS2 NMOS and WSe2 PMOS device fabricated show an on/off current ratio exceeding 106 and the integrated M3D inverters indicate an average voltage gain of ≈9 at VDD = 2 V. In addition, the integrated M3D inverter demonstrates an ultra-low power consumption of 0.112 nW at a VDD of 1 V. Statistical analysis of the fabricated inverters devices shows their high reliability, rendering them suitable for large-area applications. The successful demonstration of M3D inverters based on large-scale 2D monolayer TMDs indicate their high potential for advancing the application of 2D TMDs in future integrated circuits.

Tailoring long-range superlattice chirality in molecular self-assemblies via weak fluorine-mediated interactions.

Controllable fabrication of enantiospecific molecular superlattices is a matter of imminent scientific and technological interest. Herein, we demonstrate that long-range superlattice chirality in molecular self-assemblies can be tailored by tuning the interplay of weak intermolecular non-covalent interactions between hexaphenylbenzene-based enantiomers. By means of high-resolution scanning tunneling microscopy measurements, we demonstrate that the functionalization of a hexaphenylbenzene-based molecule with fluorine (F) atoms leads to the formation of molecular self-assemblies with distinct long-range chiral recognition patterns. We employed density functional theory calculations to quantify F-mediated lone pair F⋯π, C-H⋯F, and F⋯F interactions attributed to the distinct enantiospecific molecular self-organizations. Our findings underpin a viable route to fabricate long-range chiral recognition patterns in supramolecular assemblies by engineering the weak non-covalent intermolecular interactions.

Hybridizing Plasmonic Materials with 2D-Transition Metal Dichalcogenides toward Functional Applications.

Recently, 2D transition metal dichalcogenides (TMDs) have become intriguing materials in the versatile field of photonics and optoelectronics because of their strong light-matter interaction that stems from the atomic layer thickness, broadband optical response, controllable optoelectronic properties, and high nonlinearity, as well as compatibility. Nevertheless, the low optical cross-section of 2D-TMDs inhibits the light-matter interaction, resulting in lower quantum yield. Therefore, hybridizing the 2D-TMDs with plasmonic nanomaterials has become one of the promising strategies to boost the optical absorption of thin 2D-TMDs. The appeal of plasmonics is based on their capability to localize and enhance the electromagnetic field and increase the optical path length of light by scattering and injecting hot electrons to TMDs. In this regard, recent achievements with respect to hybridization of the plasmonic effect in 2D-TMDs systems and its augmented optical and optoelectronic properties are reviewed. The phenomenon of plasmon-enhanced interaction in 2D-TMDs is briefly described and state-of-the-art hybrid device applications are comprehensively discussed. Finally, an outlook on future applications of these hybrid devices is provided.

Dimensionality-Mediated Semimetal-Semiconductor Transition in Ultrathin PtTe_{2} Films.

Platinum ditelluride (PtTe_{2}), a type-II Dirac semimetal, remains semimetallic in ultrathin films down to just two triatomic layers (TLs) with a negative gap of -0.36 eV. Further reduction of the film thickness to a single TL induces a Lifshitz electronic transition to a semiconductor with a large positive gap of +0.79 eV. This transition is evidenced by experimental band structure mapping of films prepared by layer-resolved molecular beam epitaxy, and by comparing the data to first-principles calculations using a hybrid functional. The results demonstrate a novel electronic transition at the two-dimensional limit through film thickness control.

Giant Emission Enhancement of Solid-State Gold Nanoclusters by Surface Engineering.

Ligand-induced surface restructuring with heteroatomic doping is used to precisely modify the surface of a prototypical [Au25 (SR1 )18 ]- cluster (1) while maintaining its icosahedral Au13 core for the synthesis of a new bimetallic [Au19 Cd3 (SR2 )18 ]- cluster (2). Single-crystal X-ray diffraction studies reveal that six bidentate Au2 (SR1 )3 motifs (L2) attached to the Au13 core of 1 were replaced by three quadridentate Au2 Cd(SR2 )6 motifs (L4) to create a bimetallic cluster 2. Experimental and theoretical results demonstrate a stronger electronic interaction between the surface motifs (Au2 Cd(SR2 )6 ) and the Au13 core, attributed to a more compact cluster structure and a larger energy gap of 2 compared to that of 1. These factors dramatically enhance the photoluminescence quantum efficiency and lifetime of crystal of the cluster 2. This work provides a new route for the design of a wide range of bimetallic/alloy metal nanoclusters with superior optoelectronic properties and functionality.

Quantum Phase Transition of Correlated Iron-Based Superconductivity in LiFe_{1-x}Co_{x}As.

The interplay between unconventional Cooper pairing and quantum states associated with atomic scale defects is a frontier of research with many open questions. So far, only a few of the high-temperature superconductors allow this intricate physics to be studied in a widely tunable way. We use scanning tunneling microscopy to image the electronic impact of Co atoms on the ground state of the LiFe_{1-x}Co_{x}As system. We observe that impurities progressively suppress the global superconducting gap and introduce low energy states near the gap edge, with the superconductivity remaining in the strong-coupling limit. Unexpectedly, the fully opened gap evolves into a nodal state before the Cooper pair coherence is fully destroyed. Our systematic theoretical analysis shows that these new observations can be quantitatively understood by the nonmagnetic Born-limit scattering effect in an s±-wave superconductor, unveiling the driving force of the superconductor to metal quantum phase transition.

Direct evidence of interaction-induced Dirac cones in a monolayer silicene/Ag(111) system.

Silicene, analogous to graphene, is a one-atom-thick 2D crystal of silicon, which is expected to share many of the remarkable properties of graphene. The buckled honeycomb structure of silicene, along with enhanced spin-orbit coupling, endows silicene with considerable advantages over graphene in that the spin-split states in silicene are tunable with external fields. Although the low-energy Dirac cone states lie at the heart of all novel quantum phenomena in a pristine sheet of silicene, a hotly debated question is whether these key states can survive when silicene is grown or supported on a substrate. Here we report our direct observation of Dirac cones in monolayer silicene grown on a Ag(111) substrate. By performing angle-resolved photoemission measurements on silicene(3 × 3)/Ag(111), we reveal the presence of six pairs of Dirac cones located on the edges of the first Brillouin zone of Ag(111), which is in sharp contrast to the expected six Dirac cones centered at the K points of the primary silicene(1 × 1) Brillouin zone. Our analysis shows clearly that the unusual Dirac cone structure we have observed is not tied to pristine silicene alone but originates from the combined effects of silicene(3 × 3) and the Ag(111) substrate. Our study thus identifies the case of a unique type of Dirac cone generated through the interaction of two different constituents. The observation of Dirac cones in silicene/Ag(111) opens a unique materials platform for investigating unusual quantum phenomena and for applications based on 2D silicon systems.

Phase-Engineered PtSe2 -Layered Films by a Plasma-Assisted Selenization Process toward All PtSe2 -Based Field Effect Transistor to Highly Sensitive, Flexible, and Wide-Spectrum Photoresponse Photodetectors.

The formation of PtSe2 -layered films is reported in a large area by the direct plasma-assisted selenization of Pt films at a low temperature, where temperatures, as low as 100 °C at the applied plasma power of 400 W can be achieved. As the thickness of the Pt film exceeds 5 nm, the PtSe2 -layered film (five monolayers) exhibits a metallic behavior. A clear p-type semiconducting behavior of the PtSe2 -layered film (≈trilayers) is observed with the average field effective mobility of 0.7 cm2 V-1 s-1 from back-gated transistor measurements as the thickness of the Pt film reaches below 2.5 nm. A full PtSe2 field effect transistor is demonstrated where the thinner PtSe2 , exhibiting a semiconducting behavior, is used as the channel material, and the thicker PtSe2 , exhibiting a metallic behavior, is used as an electrode, yielding an ohmic contact. Furthermore, photodetectors using a few PtSe2 -layered films as an adsorption layer synthesized at the low temperature on a flexible substrate exhibit a wide range of absorption and photoresponse with the highest photocurrent of 9 µA under the laser wavelength of 408 nm. In addition, the device can maintain a high photoresponse under a large bending stress and 1000 bending cycles.

Robust Large Gap Two-Dimensional Topological Insulators in Hydrogenated III-V Buckled Honeycombs.

A large gap two-dimensional (2D) topological insulator (TI), also known as a quantum spin Hall (QSH) insulator, is highly desirable for low-power-consuming electronic devices owing to its spin-polarized backscattering-free edge conducting channels. Although many freestanding films have been predicted to harbor the QSH phase, band topology of a film can be modified substantially when it is placed or grown on a substrate, making the materials realization of a 2D TI challenging. Here we report a first-principles study of possible QSH phases in 75 binary combinations of group III (B, Al, Ga, In, and Tl) and group V (N, P, As, Sb, and Bi) elements in the 2D buckled honeycomb structure, including hydrogenation on one or both sides of the films to simulate substrate effects. A total of six compounds (GaBi, InBi, TlBi, TlAs, TlSb, and TlN) are identified to be nontrivial in unhydrogenated case; whereas for hydrogenated case, only four (GaBi, InBi, TlBi, and TlSb) remains nontrivial. The band gap is found to be as large as 855 meV for the hydrogenated TlBi film, making this class of III-V materials suitable for room temperature applications. TlBi remains topologically nontrivial with a large band gap at various hydrogen coverages, indicating the robustness of its band topology against bonding effects of substrates.

Prediction of large-gap two-dimensional topological insulators consisting of bilayers of group III elements with Bi.

We use first-principles electronic structure calculations to predict a new class of two-dimensional (2D) topological insulators (TIs) in binary compositions of group III elements (B, Al, Ga, In, and Tl) and bismuth (Bi) in a buckled honeycomb structure. We identify band inversions in pristine GaBi, InBi, and TlBi bilayers, with gaps as large as 560 meV, making these materials suitable for room-temperature applications. Furthermore, we demonstrate the possibility of strain engineering in that the topological phase transition in BBi and AlBi could be driven at ∼6.6% strain. The buckled structure allows the formation of two different topological edge states in the zigzag and armchair edges. More importantly, isolated Dirac-cone edge states are predicted for armchair edges with the Dirac point lying in the middle of the 2D bulk gap. A room-temperature bulk band gap and an isolated Dirac cone allow these states to reach the long-sought topological spin-transport regime. Our findings suggest that the buckled honeycomb structure is a versatile platform for hosting nontrivial topological states and spin-polarized Dirac fermions with the flexibility of chemical and mechanical tunability.

Confined VLS Growth of Single-Layer 2D Tungsten Nitrides.

Two-dimensional (2D) metal nitrides have garnered significant interest due to their potential applications in future electronics and quantum systems. However, the synthesis of such materials with sufficient uniformity and at relevant scales remains an unaddressed challenge. This study demonstrates the potential of confined growth to control and enhance the morphology of 2D metal nitrides. By restricting the reaction volume of vapor-liquid-solid reactions, an enhanced precursor concentration was achieved that reduces the nucleation density, resulting in larger grain sizes and suppression of multilayer growth. Detailed characterization reveals the importance of balancing the energetic and kinetic aspects of tungsten nitride formation toward this ability. The introduction of a promoter enabled the realization of large-scale, single-layer tungsten nitride with a uniform and high interfacial quality. Finally, our advance in morphology control was applied to the production of edge-enriched 2D tungsten nitrides with significantly enhanced hydrogen evolution ability, as indicated by an unprecedented Tafel slope of 55 mV/dec.

Rational Design of Phase-Engineered WS2/WSe2 Heterostructures by Low-Temperature Plasma-Assisted Sulfurization and Selenization toward Enhanced HER Performance.

Efficient hydrogen generation from water splitting underpins chemistry to realize hydrogen economy. The electrocatalytic activity can be effectively modified by two-dimensional (2D) heterostructures, which offer great flexibility. Furthermore, they are useful in enhancing the exposure of the active sites for the hydrogen evolution reaction. Although the 1T-metallic phase of the transition metal dichalcogenides (TMDs) is important for the hydrogen evolution reaction (HER) catalyst, its practical application has not yet been much utilized because of the lack of stability of the 1T phase. Here, we introduce a novel approach to create a 1T-WS2/1T-WSe2 heterostructure using a low-temperature plasma-assisted chemical vapor reaction (PACVR), namely plasma-assisted sulfurization and plasma-assisted selenization processes. This heterostructure exhibits superior electrocatalytic performance due to the presence of the metallic 1T phase and the beneficial synergistic effect at the interface, which is attributed to the transfer of electrons from the underlying WS2 layer to the overlying WSe2 layer. The WS2/WSe2 heterostructure catalyst demonstrates remarkable performance in the HER as evidenced by its small Tafel slope of 57 mV dec-1 and exceptional durability. The usage of plasma helps in replacing the top S atoms with Se atoms, and this ion bombardment also increases the roughness of the thin film, thus adding another factor to enhance the HER performance. This plasma-synthesized low-temperature metallic-phase heterostructure brings out a novel method for the discovery of other catalysts.

Integrated Graphene Heterostructures in Optical Sensing.

Graphene-an outstanding low-dimensional material-exhibited many physics behaviors that are unknown over the past two decades, e.g., exceptional matter-light interaction, large light absorption band, and high charge carrier mobility, which can be adjusted on arbitrary surfaces. The deposition approaches of graphene on silicon to form the heterostructure Schottky junctions was studied, unveiling new roadmaps to detect the light at wider-ranged absorption spectrums, e.g., far-infrared via excited photoemission. In addition, heterojunction-assisted optical sensing systems enable the active carriers' lifetime and, thereby, accelerate the separation speed and transport, and then they pave new strategies to tune high-performance optoelectronics. In this mini-review, an overview is considered concerning recent advancements in graphene heterostructure devices and their optical sensing ability in multiple applications (ultrafast optical sensing system, plasmonic system, optical waveguide system, optical spectrometer, or optical synaptic system) is discussed, in which the prominent studies for the improvement of performance and stability, based on the integrated graphene heterostructures, have been reported and are also addressed again. Moreover, the pros and cons of graphene heterostructures are revealed along with the syntheses and nanofabrication sequences in optoelectronics. Thereby, this gives a variety of promising solutions beyond the ones presently used. Eventually, the development roadmap of futuristic modern optoelectronic systems is predicted.

Widely Tunable Berry Curvature in the Magnetic Semimetal Cr1+ δ Te2.

Magnetic semimetals have increasingly emerged as lucrative platforms hosting spin-based topological phenomena in real and momentum spaces. Cr1+ δ Te2 is a self-intercalated magnetic transition metal dichalcogenide (TMD), which exhibits topological magnetism and tunable electron filling. While recent studies have explored real-space Berry curvature effects, similar considerations of momentum-space Berry curvature are lacking. Here, the electronic structure and transport properties of epitaxial Cr1+ δ Te2 thin films are systematically investigated over a range of doping, δ (0.33 - 0.71). Spectroscopic experiments reveal the presence of a characteristic semi-metallic band region, which shows a rigid like energy shift with δ. Transport experiments show that the intrinsic component of the anomalous Hall effect (AHE) is sizable and undergoes a sign flip across δ. Finally, density functional theory calculations establish a link between the doping evolution of the band structure and AHE: the AHE sign flip is shown to emerge from the sign change of the Berry curvature, as the semi-metallic band region crosses the Fermi energy. These findings underscore the increasing relevance of momentum-space Berry curvature in magnetic TMDs and provide a unique platform for intertwining topological physics in real and momentum spaces.

Causal structure of interacting Weyl fermions in condensed matter systems.

The spacetime light cone is central to the definition of causality in the theory of relativity. Recently, links between relativistic and condensed matter physics have been uncovered, where relativistic particles can emerge as quasiparticles in the energy-momentum space of matter. Here, we unveil an energy-momentum analogue of the spacetime light cone by mapping time to energy, space to momentum, and the light cone to the Weyl cone. We show that two Weyl quasiparticles can only interact to open a global energy gap if they lie in each other's energy-momentum dispersion cones-analogous to two events that can only have a causal connection if they lie in each other's light cones. Moreover, we demonstrate that the causality of surface chiral modes in quantum matter is entangled with the causality of bulk Weyl fermions. Furthermore, we identify a unique quantum horizon region and an associated 'thick horizon' in the emergent causal structure.

Robust Tunable Large-Gap Quantum Spin Hall States in Monolayer Cu2S on Insulating Substrates.

Quantum spin Hall (QSH) insulators with large band gaps and dissipationless edge states are of both technological and scientific interest. Although numerous two-dimensional (2D) systems have been predicted to host the QSH phase, very few of them harbor large band gaps and retain their nontrivial band topology when they are deposited on substrates. Here, based on a first-principles analysis with hybrid functional calculations, we investigated the electronic and topological properties of inversion-asymmetric monolayer copper sulfide (Cu2S). Interestingly, we found that monolayer Cu2S possesses an intrinsic QSH phase, Rashba spin splitting, and a large band gap of 220 meV that is suitable for room-temperature applications. Most importantly, we constructed heterostructures of a Cu2S film on PtTe2, h-BN, and Cu(111) substrates and found that the topological properties remain preserved upon an interface with these substrates. Our findings suggest Cu2S as a possible platform to realize inversion-asymmetric QSH insulators with potential applications in low-dissipation electronic devices.

Prediction of topological Dirac semimetal in Ca-based Zintl layered compounds CaM2X2 (M = Zn or Cd; X = N, P, As, Sb, or Bi).

Topological Dirac materials are attracting a lot of attention because they offer exotic physical phenomena. An exhaustive search coupled with first-principles calculations was implemented to investigate 10 Zintl compounds with a chemical formula of CaM2X2 (M = Zn or Cd, X = N, P, As, Sb, or Bi) under three crystal structures: CaAl2Si2-, ThCr2Si2-, and BaCu2S2-type crystal phases. All of the materials were found to energetically prefer the CaAl2Si2-type structure based on total ground state energy calculations. Symmetry-based indicators are used to evaluate their topological properties. Interestingly, we found that CaM2Bi2 (M = Zn or Cd) are topological crystalline insulators. Further calculations under the hybrid functional approach and analysis using k · p model reveal that they exhibit topological Dirac semimetal (TDSM) states, where the four-fold degenerate Dirac points are located along the high symmetry line in-between Г to A points. These findings are verified through Green's function surface state calculations under HSE06. Finally, phonon spectra calculations revealed that CaCd2Bi2 is thermodynamically stable. The Zintl phase of AM2X2 compounds have not been identified in any topological material databases, thus can be a new playground in the search for new topological materials.

Proximity-Effect-Induced Anisotropic Superconductivity in a Monolayer Ni-Pb Binary Alloy.

A proximity effect facilitates the penetration of Cooper pairs that permits superconductivity in a normal metal, offering a promising approach to turn heterogeneous materials into superconductors and develop exceptional quantum phenomena. Here, we have systematically investigated proximity-induced anisotropic superconductivity in a monolayer Ni-Pb binary alloy by combining scanning tunneling microscopy/spectroscopy (STM/STS) with theoretical calculations. By means of high-temperature growth, the (33×33)R30o Ni-Pb surface alloy has been fabricated on Pb(111) and the appearance of a domain boundary as well as a structural phase transition can be deduced from a half-unit-cell lattice displacement. Given the high spatial and energy resolution, tunneling conductance (dI/dU) spectra have resolved the reduced but anisotropic superconducting gap ΔNiPb ≈ 1.0 meV, in stark contrast to the isotropic ΔPb ≈ 1.3 meV. In addition, the higher density of states at the Fermi energy (D(EF)) of the Ni-Pb surface alloy results in an enhancement of coherence peak height. According to the same Tc ≈ 7.1 K with Pb(111) from the temperature-dependent ΔNiPb and the short decay length Ld ≈ 3.55 nm from the spatially monotonic decrease of ΔNiPb, both results are supportive of a proximity-induced superconductivity. Despite a lack of a bulk counterpart, the atomically thick Ni-Pb bimetallic compound opens a pathway to engineer superconducting properties down to the two-dimensional limit, giving rise to the emergence of anisotropic superconductivity via a proximity effect.

Structural and electronic properties of hydrogen adsorptions on BC3 sheet and graphene: a comparative study.

We have systematically investigated the effect of hydrogen adsorption on a single BC3 sheet as well as graphene using first-principles calculations. Specifically, a comparative study of the energetically favorable atomic configurations for both H-adsorbed BC3 sheets and graphene at different hydrogen concentrations ranging from 1/32 to 4/32 ML and 1/8 to 1 ML was undertaken. The preferred hydrogen arrangement on the single BC3 sheet and graphene was found to have the same property as that of the adsorbed H atoms on the neighboring C atoms on the opposite sides of the sheet. Moreover, at low coverage of H, the pattern of hydrogen adsorption on the BC3 shows a proclivity toward formation on the same ring, contrasting their behavior on graphene where they tend to form the elongated zigzag chains instead. Lastly, both the hydrogenated BC3 sheet and graphene exhibit alternation of semiconducting and metallic properties as the H concentration is increased. These results suggest the possibility of manipulating the bandgaps in a single BC3 sheet and graphene by controlling the H concentrations on the BC3 sheet and graphene.