Interplay between Topological States and Rashba States as Manifested on Surface Steps at Room Temperature.

The unique spin texture of quantum states in topological materials underpins many proposed spintronic applications. However, realizations of such great potential are stymied by perturbations, such as temperature and local fields imposed by impurities and defects, that can render a promising quantum state uncontrollable. Here, we report room-temperature scanning tunneling microscopy/spectroscopy observation of interaction between Rashba states and topological surface states, which manifests local electronic structure along step edges controllable by the layer thickness of thin films. The first-principles theoretical calculation elucidates the robust Rashba states coexisting with topological surface states along the surface steps with characteristic spin textures in momentum space. Furthermore, the Rashba edge states can be switched off by reducing the thickness of a topological insulator Bi2Se3 to bolster their interaction with the hybridized topological surface states. The study unveils a manipulating mechanism of the spin textures at room temperature, reinforcing the necessity of thin film technology in controlling the quantum states.

Distance-Dependent Evolution of Electronic States in Kagome-Honeycomb Lateral Heterostructures in FeSn.

In this work, we demonstrate the formation and electronic influence of lateral heterointerfaces in FeSn containing Kagome and honeycomb layers. Lateral heterostructures offer spatially resolved property control, enabling the integration of dissimilar materials and promoting phenomena not typically observed in vertical heterostructures. Using the molecular beam epitaxy technique, we achieve a controllable synthesis of lateral heterostructures in the Kagome metal FeSn. With scanning tunneling microscopy/spectroscopy in conjunction with first-principles calculations, we provide a comprehensive understanding of the bonding motif connecting the Fe3Sn-terminated Kagome and Sn2-terminated honeycomb surfaces. More importantly, we reveal a distance-dependent evolution of the electronic states in the vicinity of the heterointerfaces. This evolution is significantly influenced by the orbital character of the flat bands. Our findings suggest an approach to modulate the electronic properties of the Kagome lattice, which should be beneficial for the development of future quantum devices.

Predictions of delafossite-hosted honeycomb and kagome phases.

Delafossites, typically denoted by the formula ABO2, are a class of layered materials that exhibit a wide range of electronic and optical properties. Recently, the idea of modifying these delafossites into ordered kagome or honeycomb phases via strategic doping has emerged as a potential way to tailor these properties. In this study, we use high-throughput density functional theory calculations to explore many possible candidate kagome and honeycomb phases by considering dopants selected from the parent compounds of known ternary delafossite oxides from the inorganic crystal structure database. Our results indicate that while A-site in existing delafossites can host a limited range of elemental specifies, and display a low propensity for mixing or ordering, the oxide sub-units in the BO2 much more readily admit guest species. Our study identifies four candidate B-site kagome and fifteen candidate B-site honeycombs with a formation energy more than 50 meV f.u.-1 below other competing phases. The ability to predict and control the formation of these unique structures offers exciting opportunities in materials design, where innovative properties can be engineered through the selection of specific dopants. A number of these constitute novel correlated metals, which may be of interest for subsequent efforts in synthesis. These novel correlated metals may have significant implications for quantum computing, spintronics, and high-temperature superconductivity, thus inspiring future experimental synthesis and characterization of these proposed materials.

Low Ohmic contact resistance and high on/off ratio in transition metal dichalcogenides field-effect transistors via residue-free transfer.

Beyond-silicon technology demands ultrahigh performance field-effect transistors. Transition metal dichalcogenides provide an ideal material platform, but the device performances such as the contact resistance, on/off ratio and mobility are often limited by the presence of interfacial residues caused by transfer procedures. Here, we show an ideal residue-free transfer approach using polypropylene carbonate with a negligible residue coverage of ~0.08% for monolayer MoS2 at the centimetre scale. By incorporating a bismuth semimetal contact with an atomically clean monolayer MoS2 field-effect transistor on hexagonal boron nitride substrate, we obtain an ultralow Ohmic contact resistance of ~78 Ω µm, approaching the quantum limit, and a record-high on/off ratio of ~1011 at 15 K. Such an ultra-clean fabrication approach could be the ideal platform for high-performance electrical devices using large-area semiconducting transition metal dichalcogenides.

Tailoring Chemical Absorption-Precipitation to Lower the Regeneration Energy of a CO2 Capture Solvent.

Solvent-based CO2 capture consumes significant amounts of energy for solvent regeneration. To improve energy efficiency, this study investigates CO2 fixation in a solid form through solvation, followed by ionic self-assembly-aided precipitation. Based on the hypothesis that CO3 2- ions may bind with monovalent metal ions, we introduced Na+ into an aqueous hexane-1,6-diamine solution where CO2 forms carbamate and bicarbonate. Then, Na+ ions in the solvent act as a seed for ionic self-assembly with diamine carbamate to form an intermediate ionic complex. The recurring chemical reactions lead to the formation of an ionic solid from a mixture of organic carbamate/carbonate and inorganic sodium bicarbonate (NaHCO3 ), which can be easily removed from the aqueous solvent through sedimentation or centrifugation and heated to release the captured CO2 . Mild-temperature heating of the solids at 80-150 °C causes decomposition of the solid CO2 -diamine-Na molecular aggregates and discharge of CO2 . This sorbent regeneration process requires 6.5-8.6 GJ/t CO2 . It was also found that the organic carbamate/carbonate solid, without NaHCO3 , contains a significant amount of CO2 , up to 6.2 mmol CO2 /g-sorbent, requiring as low as 2.9-5.8 GJ/t CO2 . Molecular dynamic simulations support the hypothesis of using Na+ to form relatively less stable, yet sufficiently solid, complexes for the least energy-intensive recovery of diamine solvents compared to bivalent carbonate-forming ions.

Role of Curvature in Stabilizing Boron-Doped Nanocorrugated Graphene.

Boron-doped carbon nanostructures have attracted great interest recently because of their remarkable electrocatalytic performance comparable to or better than that of conventional metal catalysts. In a previous work (Carbon 123, 605 (2017)), we reported that along with significant performance improvement, B doping enhances the oxidation resistance of few-layer graphene (FLG) that provides increased structural stability for intermediate-temperature fuel-cell electrodes. In general, detailed characterization of the atomic and electronic structure transformations that occur in B-doped carbon nanostructures during fuel-cell operation is lacking. In this work, we use aberration-corrected scanning transmission electron microscopy, nanobeam electron diffraction, and electron energy-loss spectroscopy (EELS) to characterize the atomic and electronic structures of B-doped FLG before and after fuel-cell operation. These data point to the nanoscale corrugation of B-doped FLGs as the key factor responsible for increased stability and high corrosion resistance. The similarity of the 1s to π* and σ* transition features in the B K-edge EELS to those in B-doped carbon nanotubes provides an estimate for the curvature of nanocorrugation in B-FLG.

More Than 30 000-fold Field Enhancement of Terahertz Nanoresonators Enabled by Rapid Inverse Design.

The rapid development of 6G communications using terahertz (THz) electromagnetic waves has created a demand for highly sensitive THz nanoresonators capable of detecting these waves. Among the potential candidates, THz nanogap loop arrays show promising characteristics but require significant computational resources for accurate simulation. This requirement arises because their unit cells are 10 times smaller than millimeter wavelengths, with nanogap regions that are 1 000 000 times smaller. To address this challenge, we propose a rapid inverse design method using physics-informed machine learning, employing double deep Q-learning with an analytical model of the THz nanogap loop array. In ∼39 h on a middle-level personal computer, our approach identifies the optimal structure through 200 000 iterations, achieving an experimental electric field enhancement of 32 000 at 0.2 THz, 300% stronger than prior results. Our analytical model-based approach significantly reduces the amount of computational resources required, offering a practical alternative to numerical simulation-based inverse design for THz nanodevices.

Theoretical Investigation of Delafossite-Cu2ZnSnO4 as a Promising Photovoltaic Absorber.

In the quest for efficient and cost-effective photovoltaic absorber materials beyond silicon, considerable attention has been directed toward exploring alternatives. One such material, zincblende-derived Cu2ZnSnS4 (CZTS), has shown promise due to its ideal band gap size and high absorption coefficient. However, challenges such as structural defects and secondary phase formation have hindered its development. In this study, we examine the potential of another compound, Cu2ZnSnO4 (CZTO), with a similar composition to CZTS as a promising alternative. Employing ab initio density function theory (DFT) calculations in combination with an evolutionary structure prediction algorithm, we identify that the crystalline phase of delafossite structure is the most stable among the 900 (meta)stable CZTO. Its thermodynamic stability at room temperature is also confirmed by the molecular dynamics study. Excitingly, this new phase of CZTO displays a direct band gap where the dipole-allowed transition occurs, making it a strong candidate for efficient light absorptions. Furthermore, the estimation of spectroscopic limited maximum efficiency (SLME) directly demonstrates the high potential of delafossite-CZTO as a photovoltaic absorber. Our numerical results suggest that delafossite-CZTO holds promise for future photovoltaic applications.

Stacking Faults and Topological Properties in MnBi2Te4: Reconciling Gapped and Gapless States.

Despite theoretical predictions of a gapped surface state for the magnetic topological insulator MnBi2Te4 (MBT), there has been a series of experimental evidence pointing toward gapless states. Here, we theoretically explore how stacking faults could influence the topological characteristics of MBT. We envisage a scenario that a stacking fault exists at the surface of MBT, causing the uppermost layer to deviate from the ground state and its interlayer separation to be expanded. This stacking fault with modulated interlayer couplings hosts a nearly gapless state within the topmost layer due to charge redistribution as the outermost layer recedes. Furthermore, we find evidence of spin-momentum locking and preservation of weak band inversion in the gapless surface state, suggesting the nontrivial topological surface states in the presence of the stacking fault. Our findings provide a plausible elucidation to the long-standing conundrum of reconciling the observation of gapped and gapless states on MBT surfaces.

Top-Down Fabrication of Atomic Patterns in Twisted Bilayer Graphene.

Atomic-scale engineering typically involves bottom-up approaches, leveraging parameters such as temperature, partial pressures, and chemical affinity to promote spontaneous arrangement of atoms. These parameters are applied globally, resulting in atomic-scale features scattered probabilistically throughout the material. In a top-down approach, different regions of the material are exposed to different parameters, resulting in structural changes varying on the scale of the resolution. In this work, the application of global and local parameters is combined in an aberration-corrected scanning transmission electron microscope (STEM) to demonstrate atomic-scale precision patterning of atoms in twisted bilayer graphene. The focused electron beam is used to define attachment points for foreign atoms through the controlled ejection of carbon atoms from the graphene lattice. The sample environment is staged with nearby source materials such that the sample temperature can induce migration of the source atoms across the sample surface. Under these conditions, the electron-beam (top-down) enables carbon atoms in the graphene to be replaced spontaneously by diffusing adatoms (bottom-up). Using image-based feedback control, arbitrary patterns of atoms and atom clusters are attached to the twisted bilayer graphene with limited human interaction. The role of substrate temperature on adatom and vacancy diffusion is explored by first-principles simulations.

Understanding Heterogeneities in Quantum Materials.

Quantum materials are usually heterogeneous, with structural defects, impurities, surfaces, edges, interfaces, and disorder. These heterogeneities are sometimes viewed as liabilities within conventional systems; however, their electronic and magnetic structures often define and affect the quantum phenomena such as coherence, interaction, entanglement, and topological effects in the host system. Therefore, a critical need is to understand the roles of heterogeneities in order to endow materials with new quantum functions for energy and quantum information science applications. In this article, several representative examples are reviewed on the recent progress in connecting the heterogeneities to the quantum behaviors of real materials. Specifically, three intertwined topic areas are assessed: i) Reveal the structural, electronic, magnetic, vibrational, and optical degrees of freedom of heterogeneities. ii) Understand the effect of heterogeneities on the behaviors of quantum states in host material systems. iii) Control heterogeneities for new quantum functions. This progress is achieved by establishing the atomistic-level structure-property relationships associated with heterogeneities in quantum materials. The understanding of the interactions between electronic, magnetic, photonic, and vibrational states of heterogeneities enables the design of new quantum materials, including topological matter and quantum light emitters based on heterogenous 2D materials.

Role of Sr doping and external strain on relieving bottleneck of oxygen diffusion in La2-xSrxCuO4-δ.

In many complex oxides, the oxygen vacancy formation is a promising route to modify the material properties such as a superconductivity and an oxygen diffusivity. Cation substitutions and external strain have been utilized to control the concentration and diffusion of oxygen vacancies, but the mechanisms behind the controls are not fully understood. Using first-principles calculations, we find how Sr doping and external strain greatly enhances the diffusivity of oxygen vacancies in La2-xSrxCuO4-δ (LSCO) in the atomic level. In hole-doped case (2x > δ), the formation energy of an apical vacancy in the LaO layer is larger than its equatorial counterpart by 0.2 eV that the bottleneck of diffusion process is for oxygen vacancies to escape equatorial sites. Such an energy difference can be reduced and even reversed by either small strain (< 1.5%) or short-range attraction between Sr and oxygen vacancy, and in turn, the oxygen diffusivity is greatly enhanced. For fully compensated hole case (2x ≦ δ), the formation energy of an apical vacancy becomes too high that most oxygen vacancies cannot move but would be trapped at equatorial sites. From our electronic structure analysis, we found that the contrasting change in the formation energy by Sr doping and external strain is originated from the different localization natures of electron carrier from both types of oxygen vacancies.

Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe2 Crystals with High Mobility and In-Plane Optical and Electrical Anisotropy.

PdSe2 has a layered structure with an unusual, puckered Cairo pentagonal tiling. Its atomic bond configuration features planar 4-fold-coordinated Pd atoms and intralayer Se-Se bonds that enable polymorphic phases with distinct electronic and quantum properties, especially when atomically thin. PdSe2 is conventionally orthorhombic, and direct synthesis of its metastable polymorphic phases is still a challenge. Here, we report an ambient-pressure chemical vapor deposition approach to synthesize metastable monoclinic PdSe2. Monoclinic PdSe2 is shown to be synthesized selectively under Se-deficient conditions that induce Se vacancies. These defects are shown by first-principles density functional theory calculations to reduce the free energy of the metastable monoclinic phase, thereby stabilizing it during synthesis. The structure and composition of the monoclinic PdSe2 crystals are identified and characterized by scanning transmission electron microscopy imaging, convergent beam electron diffraction, and electron energy loss spectroscopy. Polarized Raman spectroscopy of the monoclinic PdSe2 flakes reveals their strong in-plane optical anisotropy. Electrical transport measurements show that the monoclinic PdSe2 exhibits n-type charge carrier conduction with electron mobilities up to ∼298 cm2 V-1 s-1 and a strong in-plane electron mobility anisotropy of ∼1.9. The defect-mediated growth pathway identified in this work is promising for phase-selective direct synthesis of other 2D transition metal dichalcogenides.

Topography inversion in scanning tunneling microscopy of single-atom-thick materials from penetrating substrate states.

Scanning tunneling microscopy (STM) is one of the indispensable tools to characterize surface structures, but the distinction between atomic geometry and electronic effects based on the measured tunneling current is not always straightforward. In particular, for single-atomic-thick materials (graphene or boron nitride) on metallic substrates, counterintuitive phenomena such as a larger tunneling current for insulators than for metal and a topography opposite to the atomic geometry are reported. Using first-principles density functional theory calculations combined with analytical modeling, we reveal the critical role of penetrating states of metallic substrates that surpass 2D material states, hindering the measurement of intrinsic 2D materials states and leading to topography inversion. Our finding should be instrumental in the interpretation of STM topographies of atomic-thick materials and in the development of 2D material for (opto)electronic and various quantum applications.

Selective Antisite Defect Formation in WS2 Monolayers via Reactive Growth on Dilute W-Au Alloy Substrates.

Defects are ubiquitous in 2D materials and can affect the structure and properties of the materials and also introduce new functionalities. Methods to adjust the structure and density of defects during bottom-up synthesis are required to control the growth of 2D materials with tailored optical and electronic properties. Here, the authors present an Au-assisted chemical vapor deposition approach to selectively form SW and S2W antisite defects, whereby one or two sulfur atoms substitute for a tungsten atom in WS2 monolayers. Guided by first-principles calculations, they describe a new method that can maintain tungsten-poor growth conditions relative to sulfur via the low solubility of W atoms in a gold/W alloy, thereby significantly reducing the formation energy of the antisite defects during the growth of WS2 . The atomic structure and composition of the antisite defects are unambiguously identified by Z-contrast scanning transmission electron microscopy and electron energy-loss spectroscopy, and their total concentration is statistically determined, with levels up to ≈5.0%. Scanning tunneling microscopy/spectroscopy measurements and first-principles calculations further verified these antisite defects and revealed the localized defect states in the bandgap of WS2 monolayers. This bottom-up synthesis method to form antisite defects should apply in the synthesis of other 2D materials.

Revealing the Chemical Bonding in Adatom Arrays via Machine Learning of Hyperspectral Scanning Tunneling Spectroscopy Data.

The adatom arrays on surfaces offer an ideal playground to explore the mechanisms of chemical bonding via changes in the local electronic tunneling spectra. While this information is readily available in hyperspectral scanning tunneling spectroscopy data, its analysis has been considerably impeded by a lack of suitable analytical tools. Here we develop a machine learning based workflow combining supervised feature identification in the spatial domain and unsupervised clustering in the energy domain to reveal the details of structure-dependent changes of the electronic structure in adatom arrays on the Co3Sn2S2 cleaved surface. This approach, in combination with first-principles calculations, provides insight for using artificial neural networks to detect adatoms and classifies each based on their local neighborhood comprised of other adatoms. These structurally classified adatoms are further spectrally deconvolved. The unexpected inhomogeneity of electronic structures among adatoms in similar configurations is unveiled using this method, suggesting there is not a single atomic species of adatoms, but rather multiple types of adatoms on the Co3Sn2S2 surface. This is further supported by a slight contrast difference in the images (or slight size variation) of the topography of the adatoms.

Understanding Substrate-Guided Assembly in van der Waals Epitaxy by in Situ Laser Crystallization within a Transmission Electron Microscope.

Understanding the bottom-up synthesis of atomically thin two-dimensional (2D) crystals and heterostructures is important for the development of new processing strategies to assemble 2D heterostructures with desired functional properties. Here, we utilize in situ laser-heating within a transmission electron microscope (TEM) to understand the stages of crystallization and coalescence of amorphous precursors deposited by pulsed laser deposition (PLD) as they are guided by 2D crystalline substrates into van der Waals (vdW) epitaxial heterostructures. Amorphous clusters of tungsten selenide were deposited by PLD at room temperature onto graphene or MoSe2 monolayer crystals that were suspended on TEM grids. The precursors were then stepwise evolved into 2D heterostructures with pulsed laser heating treatments within the TEM. The lattice-matching provided by the MoSe2 substrate is shown to guide the formation of large-domain, heteroepitaxial vdW WSe2/MoSe2 bilayers both during the crystallization process via direct templating and after crystallization by assisting the coalescence of nanosized domains through nonclassical particle attachment processes including domain rotation and grain boundary migration. The favorable energetics for domain rotation induced by lattice matching with the substrate were understood from first-principles calculations. These in situ TEM studies of pulsed laser-driven nonequilibrium crystallization phenomena represent a transformational tool for the rapid exploration of synthesis and processing pathways that may occur on extremely different length and time scales and lend insight into the growth of 2D crystals by PLD and laser crystallization.