Vibrational properties of disordered stealthy hyperuniform 1D atomic chains.

Disorder hyperuniformity is a recently discovered exotic state of many-body systems that possess a hidden order in between that of a perfect crystal and a completely disordered system. Recently, this novel disordered state has been observed in a number of quantum materials including amorphous 2D graphene and silica, which are endowed with unexpected electronic transport properties. Here, we numerically investigate 1D atomic chain models, including perfect crystalline, disordered stealthy hyperuniform (SHU) as well as randomly perturbed atom packing configurations to obtain a quantitative understanding of how the unique SHU disorder affects the vibrational properties of these low-dimensional materials. We find that the disordered SHU chains possess lower cohesive energies compared to the randomly perturbed chains, implying their potential reliability in experiments. Our inverse partition ratio (IPR) calculations indicate that the SHU chains can support fully delocalized states just like perfect crystalline chains over a wide range of frequencies, i.e.ω∈(0,100)cm-1, suggesting superior phonon transport behaviors within these frequencies, which was traditionally considered impossible in disordered systems. Interestingly, we observe the emergence of a group of highly localized states associated withω∼200cm-1, which is characterized by a significant peak in the IPR and a peak in phonon density of states at the corresponding frequency, and is potentially useful for decoupling electron and phonon degrees of freedom. These unique properties of disordered SHU chains have implications in the design and engineering of novel quantum materials for thermal and phononic applications.

Scalable nanomanufacturing of holey graphene via chemical etching: an investigation into process mechanisms.

Graphene with in-plane nanoholes, named holey graphene, shows great potential in electrochemical applications due to its fast mass transport and improved electrochemical activity. Scalable nanomanufacturing of holey graphene is generally based on chemical etching using hydrogen peroxide to form through-the-thickness nanoholes on the basal plane of graphene. In this study, we probe into the fundamental mechanisms of nanohole formation under peroxide etching via an integrated experimental and computational effort. The research results show that the growth of nanoholes during the etching of graphene oxide is achieved by a three-stage reduction-oxidation-reduction procedure. First, it is demonstrated that vacancy defects are formed via a partial reduction-based pretreatment. Second, hydrogen peroxide reacts preferentially with the edge-sites of defect areas on graphene oxide sheets, leading to the formation of various oxygen-containing functional groups. Third, the carbon atoms around the defects are removed along with the neighboring carbon atoms via reduction. By advancing the understanding of process mechanisms, we further demonstrate an improved nanomanufacturing strategy, in which graphene oxide with a high density of defects is introduced for peroxide etching, leading to enhanced nanohole formation.

A percolation theory for designing corrosion-resistant alloys.

Iron-chromium and nickel-chromium binary alloys containing sufficient quantities of chromium serve as the prototypical corrosion-resistant metals owing to the presence of a nanometre-thick protective passive oxide film1-8. Should this film be compromised by a scratch or abrasive wear, it reforms with little accompanying metal dissolution, a key criterion for good passive behaviour. This is a principal reason that stainless steels and other chromium-containing alloys are used in critical applications ranging from biomedical implants to nuclear reactor components9,10. Unravelling the compositional dependence of this electrochemical behaviour is a long-standing unanswered question in corrosion science. Herein, we develop a percolation theory of alloy passivation based on two-dimensional to three-dimensional crossover effects that accounts for selective dissolution and the quantity of metal dissolved during the initial stage of passive film formation. We validate this theory both experimentally and by kinetic Monte Carlo simulation. Our results reveal a path forward for the design of corrosion-resistant metallic alloys.

Stone-Wales defects preserve hyperuniformity in amorphous two-dimensional networks.

Disordered hyperuniformity (DHU) is a recently discovered novel state of many-body systems that possesses vanishing normalized infinite-wavelength density fluctuations similar to a perfect crystal and an amorphous structure like a liquid or glass. Here, we discover a hyperuniformity-preserving topological transformation in two-dimensional (2D) network structures that involves continuous introduction of Stone-Wales (SW) defects. Specifically, the static structure factor [Formula: see text] of the resulting defected networks possesses the scaling [Formula: see text] for small wave number k, where [Formula: see text] monotonically decreases as the SW defect concentration p increases, reaches [Formula: see text] at [Formula: see text], and remains almost flat beyond this p. Our findings have important implications for amorphous 2D materials since the SW defects are well known to capture the salient feature of disorder in these materials. Verified by recently synthesized single-layer amorphous graphene, our network models reveal unique electronic transport mechanisms and mechanical behaviors associated with distinct classes of disorder in 2D materials.

Room-Temperature Synthesis of 2D Janus Crystals and their Heterostructures.

Janus crystals represent an exciting class of 2D materials with different atomic species on their upper and lower facets. Theories have predicted that this symmetry breaking induces an electric field and leads to a wealth of novel properties, such as large Rashba spin-orbit coupling and formation of strongly correlated electronic states. Monolayer MoSSe Janus crystals have been synthesized by two methods, via controlled sulfurization of monolayer MoSe2 and via plasma stripping followed thermal annealing of MoS2 . However, the high processing temperatures prevent growth of other Janus materials and their heterostructures. Here, a room-temperature technique for the synthesis of a variety of Janus monolayers with high structural and optical quality is reported. This process involves low-energy reactive radical precursors, which enables selective removal and replacement of the uppermost chalcogen layer, thus transforming classical transition metal dichalcogenides into a Janus structure. The resulting materials show clear mixed character for their excitonic transitions, and more importantly, the presented room-temperature method enables the demonstration of first vertical and lateral heterojunctions of 2D Janus TMDs. The results present significant and pioneering advances in the synthesis of new classes of 2D materials, and pave the way for the creation of heterostructures from 2D Janus layers.

Anomalous Behavior of 2D Janus Excitonic Layers under Extreme Pressures.

Newly discovered 2D Janus transition metal dichalcogenides layers have gained much attention from a theory perspective owing to their unique atomic structure and exotic materials properties, but little to no experimental data are available on these materials. Here, experimental and theoretical studies establish the vibrational and optical behavior of 2D Janus S-W-Se and S-Mo-Se monolayers under high pressures for the first time. Chemical vapor deposition (CVD)-grown classical transition metal dichalcogenides (TMD) monolayers are first transferred onto van der Waals (vdW) mica substrates and converted to 2D Janus sheets by surface plasma technique, and then integrated into a 500 µm size diamond anvil cell for high-pressure studies. The results show that 2D Janus layers do not undergo phase transition up to 15 GPa, and in this pressure regime, their vibrational modes exhibit a nonmonotonic response to the applied pressures (dω/dP). Interestingly, these 2D Janus monolayers exhibit unique blueshift in photoluminescence (PL) upon compression, which is in contrast to many other traditional semiconductor materials. Overall theoretical simulations offer in-depth insights and reveal that the overall optical response is a result of competition between the ab-plane (blueshift) and c-axis (redshift) compression. The overall findings shed the very first light on how 2D Janus monolayers respond under extreme pressures and expand the fundamental understanding of these materials.

Disordered hyperuniformity in two-dimensional amorphous silica.

Disordered hyperuniformity (DHU) is a recently proposed new state of matter, which has been observed in a variety of classical and quantum many-body systems. DHU systems are characterized by vanishing infinite-wavelength normalized density fluctuations and are endowed with unique novel physical properties. Here, we report the discovery of disordered hyperuniformity in atomic-scale two-dimensional materials, i.e., amorphous silica composed of a single layer of atoms, based on spectral-density analysis of high-resolution transmission electron microscopy images. Moreover, we show via large-scale density functional theory calculations that DHU leads to almost complete closure of the electronic bandgap compared to the crystalline counterpart, making the material effectively a metal. This is in contrast to the conventional wisdom that disorder generally diminishes electronic transport and is due to the unique electron wave localization induced by the topological defects in the DHU state.

Phase Transition across Anisotropic NbS3 and Direct Gap Semiconductor TiS3 at Nominal Titanium Alloying Limit.

Alloying selected layered transitional metal trichalcogenides (TMTCs) with unique chain-like structures offers the opportunities for structural, optical, and electrical engineering thus expands the regime of this class of pseudo-one-dimensional materials. Here, the novel phase transition in anisotropic Nb(1- x ) Tix S3 alloys is demonstrated for the first time. Results show that Nb(1- x ) Tix S3 can be fully alloyed across the entire composition range from triclinic-phase NbS3 to monoclinic-phase TiS3 . Surprisingly, incorporation of a small concentration of Ti (x ≈ 0.05-0.18) into NbS3 host matrix is sufficient to induce triclinic to monoclinic transition. Theoretical studies suggest that Ti atoms effectively introduce hole doping, thus rapidly decreases the total energy of monoclinic phase and induces the phase transition. When alloyed, crystalline and optical anisotropy are largely preserved as evidenced by high resolution transmission electron microscopy and angle-resolved Raman spectroscopy. Further Raman measurements identify Raman modes to determine crystalline anisotropy direction and offer insights into the degree of anisotropy. Overall results introduce Nb(1- x ) Tix S3 as a new and easy phase change material and mark the first phase engineering in anisotropic van der Waals (vdW) trichalcogenide systems for their potential applications in two-dimensional superconductivity, electronics, photonics, and information technologies.

Electrochemical surface passivation of LiCoO2 particles at ultrahigh voltage and its applications in lithium-based batteries.

Lithium cobalt oxide, as a popular cathode in portable devices, delivers only half of its theoretical capacity in commercial lithium-ion batteries. When increasing the cut-off voltage to release more capacity, solubilization of cobalt in the electrolyte and structural disorders of lithium cobalt oxide particles are severe, leading to rapid capacity fading and limited cycle life. Here, we show a class of ternary lithium, aluminum, fluorine-modified lithium cobalt oxide with a stable and conductive layer using a facile and scalable hydrothermal-assisted, hybrid surface treatment. Such surface treatment hinders direct contact between liquid electrolytes and lithium cobalt oxide particles, which reduces the loss of active cobalt. It also forms a thin doping layer that consists of a lithium-aluminum-cobalt-oxide-fluorine solid solution, which suppresses the phase transition of lithium cobalt oxide when operated at voltages >4.55 V.

Ultimate Control over Hydrogen Bond Formation and Reaction Rates for Scalable Synthesis of Highly Crystalline vdW MOF Nanosheets with Large Aspect Ratio.

Large-scale synthesis of van der Waals (vdW) metal-organic framework (MOF) nanosheets with controlled crystallinity and interlayer coupling strength is one of the bottlenecks in 2D materials that has limited its successful transition to large-scale applications. Here, scalable synthesis of mBDC (m = Zn and Cu) 2D MOFs at large scales through a biphase method is demonstrated. The results show replacing water molecules with pyridine eliminates hydrogen bond formation at metal cluster sites. This prohibits tight coupling across adjacent MOF layers and sustains controllable 2D vdW MOF growth. It is further shown that control over the growth speed, crystallinity, and thickness can be achieved by addition of a controlled amount of triethylamine and formic acid to achieve highly crystalline vdW MOF nanosheets with extraordinarily high aspect ratio. The described synthesis route can easily be scaled up for large-scale production either by deposition onto desired substrates or in crystalline layered powder form. Owing to its large lateral size, vdW nature, and high crystallinity, it is possible to perform atomic force microscopy, Kelvin probe force microscopy, and Raman measurements on the 2D MOFs. The results not only establish their vibrational properties and layer-dependent responses but also show striking differences from other 2D inorganic materials.

Anomalous isoelectronic chalcogen rejection in 2D anisotropic vdW TiS3(1-x)Se3x trichalcogenides.

Alloying in semiconductors has enabled many civilian technologies in electronics, optoelectronics, photonics, and others. While the alloying phenomenon is well established in traditional bulk semiconductors owing to a vast array of available ternary phase diagrams, alloying in 2D materials still remains at its seminal stages. This is especially true for transition metal trichalcogenides (TMTCs) such as TiS3 which has been recently predicted to be a direct gap, high carrier mobility, pseudo-1D semiconductor. In this work, we report on an unusual alloying rejection behavior in TiS3(1-x)Se3x vdW crystals. TEM, SEM, EDS, and angle-resolved Raman measurements show that only a miniscule amount (8%) of selenium can be successfully alloyed into a TiS3 host matrix despite vastly different precursor amounts as well as growth temperatures. This unusual behavior contrasts with other vdW systems such as TiS2(1-x)Se2x, MoS2(1-x)Se2x, Mo1-xWxS2, WS2(1-x)Se2x, where continuous alloying can be attained. Angle-resolved Raman and kelvin probe force microscopy measurements offer insights into how selenium alloying influences in-plane structural anisotropy as well as electron affinity values of exfoliated sheets. Our cluster expansion theory calculations show that only the alloys with a small amount of Se can be attained due to energetic instability above/below a certain selenium concentration threshold in the ternary phase diagrams. The overall findings highlight potential challenges in achieving stable Ti based TMTCs alloys.

Abnormal band bowing effects in phase instability crossover region of GaSe1-xTe x nanomaterials.

Akin to the enormous number of discoveries made through traditional semiconductor alloys, alloying selected 2D semiconductors enables engineering of their electronic structure for a wide range of new applications. 2D alloys have been demonstrated when two components crystallized in the same phase, and their bandgaps displayed predictable monotonic variation. By stabilizing previously unobserved compositions and phases of GaSe1-xTe x at nanoscales on GaAs(111), we demonstrate abnormal band bowing effects and phase instability region when components crystallize in different phases. Advanced microscopy and spectroscopy measurements show as tellurium is alloyed into GaSe, nanostructures undergo hexagonal to monoclinic and isotropic to anisotropic transition. There exists an instability region (0.56 < x < 0.67) where both phases compete and coexist, and two different bandgap values can be found at the same composition leading to anomalous band bowing effects. Results highlight unique alloying effects, not existing in single-phase alloys, and phase engineering routes for potential applications in photonic and electronics.

A "cation-anion regulation" synergistic anode host for dendrite-free lithium metal batteries.

Dendritic Li deposition has been "a Gordian knot" for almost half a century, which significantly hinders the practical use of high-energy lithium metal batteries (LMBs). The underlying mechanisms of this dendrite formation are related to the preferential lithium deposition on the tips of the protuberances of the anode surface and also associated with the concentration gradient or even depletion of anions during cycling. Therefore, a synergistic regulation of cations and anions at the interface is vital to promoting dendrite-free Li anodes. An ingenious molecular structure is designed to realize the "cation-anion regulation" with strong interactions between adsorption sites and ions at the molecular level. A quaternized polyethylene terephthalate interlayer with a "lithiophilic" ester building block and an "anionphilic" quaternary ammonium functional block can guide ions to form dendrite-free Li metal deposits at an ultrahigh current density of 10 mA cm-2, enabling stable LMBs.

Layered tetragonal zinc chalcogenides for energy-related applications: from photocatalysts for water splitting to cathode materials for Li-ion batteries.

Two-dimensional (2D) materials with tunable direct bandgaps are attractive for energy-related applications such as visible-light optical devices and cathode materials in metal-ion batteries. Here we perform first-principles calculations to investigate the structural, electrical, optical, and electrochemical properties of 2D tetragonal (t-) ZnX (X = S, Se) with layered structures and we also explore their applications in photocatalysts and Li-ion batteries. We find that t-ZnX layers prefer the AA stacking pattern when forming multi-layer (ML) structures. We also show that t-ZnX MLs and 3D bulks are all stable according to phonon calculations and ab initio molecular dynamics (MD) simulations. The band edge positions of these layered materials can be tuned by modifying the number of layers to transform them into being more suitable for photocatalysis. We further show that the t-ZnX layered structures, in particular t-ZnS single-layer (SL), are promising cathode materials for Li-ion batteries exhibiting a strong adsorption of Li atoms without reducing the Li mobility. Finally, we find that the most favorable adsorption configuration of Li atoms on t-ZnX SL strongly depends on the Li concentration. It is worth pointing out that the almost barrierless feature of Li diffusion on t-ZnS SLs makes t-ZnS SL a good candidate for a fast-charging device. Our work opens a promising avenue for the modulation of novel t-ZnX layered structures for a wealth of potential applications in energy conversion and storage.

Chloride-Reinforced Carbon Nanofiber Host as Effective Polysulfide Traps in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) battery is one of the most promising alternatives for the current state-of-the-art lithium-ion batteries due to its high theoretical energy density and low production cost from the use of sulfur. However, the commercialization of Li-S batteries has been so far limited to the cyclability and the retention of active sulfur materials. Using co-electrospinning and physical vapor deposition procedures, we created a class of chloride-carbon nanofiber composites, and studied their effectiveness on polysulfides sequestration. By trapping sulfur reduction products in the modified cathode through both chemical and physical confinements, these chloride-coated cathodes are shown to remarkably suppress the polysulfide dissolution and shuttling between lithium and sulfur electrodes. From adsorption experiments and theoretical calculations, it is shown that not only the sulfide-adsorption effect but also the diffusivity in the vicinity of these chlorides materials plays an important role on the reversibility of sulfur-based cathode upon repeated cycles. Balancing the adsorption and diffusion effects of these nonconductive materials could lead to the enhanced cycling performance of an Li-S cell. Electrochemical analyses over hundreds of cycles indicate that cells containing indium chloride-modified carbon nanofiber outperform cells with other halogenated salts, delivering an average specific capacity of above 1200 mAh g-1 at 0.2 C.

Tunable one-dimensional electron gas carrier densities at nanostructured oxide interfaces.

The emergence of two-dimensional metallic states at the LaAlO3/SrTiO3 (LAO/STO) heterostructure interface is known to occur at a critical thickness of four LAO layers. This insulator to-metal transition can be explained through the "polar catastrophe" mechanism arising from the divergence of the electrostatic potential at the LAO surface. Here, we demonstrate that nanostructuring can be effective in reducing or eliminating this critical thickness. Employing a modified "polar catastrophe" model, we demonstrate that the nanowire heterostructure electrostatic potential diverges more rapidly as a function of layer thickness than in a regular heterostructure. Our first-principles calculations indicate that for nanowire heterostructures a robust one-dimensional electron gas (1DEG) can be induced, consistent with recent experimental observations of 1D conductivity at LAO/STO steps. Similar to LAO/STO 2DEGs, we predict that the 1D charge density decays laterally within a few unit cells away from the nanowire; thus providing a mechanism for tuning the carrier dimensionality between 1D and 2D conductivity. Our work provides insight into the creation and manipulation of charge density at an oxide heterostructure interface and therefore may be beneficial for future nanoelectronic devices and for the engineering of novel quantum phases.

Petascale Orbital-Free Density Functional Theory Enabled by Small-Box Algorithms.

Orbital-free density functional theory (OFDFT) is a quantum-mechanics-based method that utilizes electron density as its sole variable. The main computational cost in OFDFT is the ubiquitous use of the fast Fourier transform (FFT), which is mainly adopted to evaluate the kinetic energy density functional (KEDF) and electron-electron Coulomb interaction terms. We design and implement a small-box FFT (SBFFT) algorithm to overcome the parallelization limitations of conventional FFT algorithms. We also propose real-space truncation of the nonlocal Wang-Teter KEDF kernel. The scalability of the SBFFT is demonstrated by efficiently simulating one full optimization step (electron density, energies, forces, and stresses) of 1,024,000 lithium (Li) atoms on up to 65,536 cores. We perform other tests using Li as a test material, including calculations of physical properties of different phases of bulk Li, geometry optimizations of nanocrystalline Li, and molecular dynamics simulations of liquid Li. All of the tests yield excellent agreement with the original OFDFT results, suggesting that the OFDFT-SBFFT algorithm opens the door to efficient first-principles simulations of materials containing millions of atoms.

Enhanced Li-S Batteries Using Amine-Functionalized Carbon Nanotubes in the Cathode.

The rechargeable lithium-sulfur (Li-S) battery is an attractive platform for high-energy, low-cost electrochemical energy storage. Practical Li-S cells are limited by several fundamental issues, including the low conductivity of sulfur and its reduction compounds with Li and the dissolution of long-chain lithium polysulfides (LiPS) into the electrolyte. We report on an approach that allows high-performance sulfur-carbon cathodes to be designed based on tethering polyethylenimine (PEI) polymers bearing large numbers of amine groups in every molecular unit to hydroxyl- and carboxyl-functionalized multiwall carbon nanotubes. Significantly, for the first time we show by means of direct dissolution kinetics measurements that the incorporation of CNT-PEI hybrids in a sulfur cathode stabilizes the cathode by both kinetic and thermodynamic processes. Composite sulfur cathodes based the CNT-PEI hybrids display high capacity at both low and high current rates, with capacity retention rates exceeding 90%. The attractive electrochemical performance of the materials is shown by means of DFT calculations and physical analysis to originate from three principal sources: (i) specific and strong interaction between sulfur species and amine groups in PEI; (ii) an interconnected conductive CNT substrate; and (iii) the combination of physical and thermal sequestration of LiPS provided by the CNT=PEI composite.