Atomistic Mechanics of Torn Back Folded Edges of Triangular Voids in Monolayer WS2.

Triangular nanovoids in 2D materials transition metal dichalcogenides have vertex points that cause stress concentration and lead to sharp crack propagation and failure. Here, the atomistic mechanics of back folding around triangular nanovoids in monolayer WS2 sheets is examined. Combining atomic-resolution images from annular dark-field scanning transmission electron microscopy with reactive molecular modelling, it is revealed that the folding edge formation has statistical preferences under geometric conditions based on the orientation mismatch. It is further investigated how loading directions and strong interlayer friction, interplay with WS2 lattice's crack preference, govern the deformation and fracture pattern around folding edges. These results provide fundamental insights into the combination of fracture and folding in flexible monolayer crystals and the resultant Moiré lattices.

Atomically Sharp Dual Grain Boundaries in 2D WS2 Bilayers.

It is shown that tilt grain boundaries (GBs) in bilayer 2D crystals of the transition metal dichalcogenide WS2 can be atomically sharp, where top and bottom layer GBs are located within sub-nanometer distances of each other. This expands the current knowledge of GBs in 2D bilayer crystals, beyond the established large overlapping GB types typically formed in chemical vapor deposition growth, to now include atomically sharp dual bilayer GBs. By using atomic-resolution annular dark-field scanning transmission electron microscopy (ADF-STEM) imaging, different atomic structures in the dual GBs are distinguished considering bilayers with a 3R (AB stacking)/2H (AA' stacking) interface as well as bilayers with 2H/2H boundaries. An in situ heating holder is used in ADF-STEM and the GBs are stable to at least 800 °C, with negligible thermally induced reconstructions observed. Normal dislocation cores are seen in one WS2 layer, but the second WS2 layer has different dislocation structures not seen in freestanding monolayers, which have metal-rich clusters to accommodate the stacking mismatch of the 2H:3R interface. These results reveal the competition between maintaining van der Waals bilayer stacking uniformity and dislocation cores required to stitch tilted bilayer GBs together.

Sub-nanometre channels embedded in two-dimensional materials.

Two-dimensional (2D) materials are among the most promising candidates for next-generation electronics due to their atomic thinness, allowing for flexible transparent electronics and ultimate length scaling. Thus far, atomically thin p-n junctions, metal-semiconductor contacts, and metal-insulator barriers have been demonstrated. Although 2D materials achieve the thinnest possible devices, precise nanoscale control over the lateral dimensions is also necessary. Here, we report the direct synthesis of sub-nanometre-wide one-dimensional (1D) MoS2 channels embedded within WSe2 monolayers, using a dislocation-catalysed approach. The 1D channels have edges free of misfit dislocations and dangling bonds, forming a coherent interface with the embedding 2D matrix. Periodic dislocation arrays produce 2D superlattices of coherent MoS2 1D channels in WSe2. Using molecular dynamics simulations, we have identified other combinations of 2D materials where 1D channels can also be formed. The electronic band structure of these 1D channels offers the promise of carrier confinement in a direct-gap material and the charge separation needed to access the ultimate length scales necessary for future electronic applications.

Multiscale Mechanics of Triply Periodic Minimal Surfaces of Three-Dimensional Graphene Foams.

The mechanics of triply periodic minimal surfaces (TPMSs) with three-dimensional (3D) graphene foams are systematically studied to understand the effects of structure and size on the mechanical properties, for example, elasticity, strength, and fracture. The design of lightweight open-shell porous solid materials with TPMSs has shown excellent and tunable load-bearing properties. However, fracture properties and their relations with surface topologies are largely unknown. Utilizing reactive molecular dynamics simulations, here we investigate the elastic and fracture properties of three different surface topologies with 3D graphene foams: P (primitive), D (diamond), and G (gyroid), called Schwarzites. Models with different lattice sizes are utilized to derive power laws, which can connect the properties along different sizes to shed light on the multiscale mechanics of TPMSs. Our study provides a systematic understanding of the relation between TPMS topologies and their mechanical properties, including failure mechanisms of graphene foams, opening opportunities to explore designable structures with tailored properties.

Multiscale Modeling of Muscular-Skeletal Systems.

Multiscale modeling of muscular-skeletal systems-the materials and structures that help organisms support themselves and move-is a rapidly growing field of study that has contributed key elements to the understanding of these systems, especially from a multiscale perspective. The systems, including materials such as bone and muscle, have hierarchical structures ranging from the nano- to the macroscale, and it is difficult to understand their macroscopic behaviors, both physiological and pathological, without knowledge of their hierarchical structures and properties. In this review, we discuss the methods of multiscale modeling. Through a series of case studies about key materials in muscular-skeletal systems, we describe how different methods can bridge the gap between hierarchical structures and their roles in the systems' mechanical properties. In particular, we emphasize the importance of the quality of minerals in bone. Finally, we discuss biomimetic material designs facilitated by additive manufacturing technology.

Materials-by-Design: Computation, Synthesis, and Characterization from Atoms to Structures.

In the 50 years that succeeded Richard Feynman's exposition of the idea that there is "plenty of room at the bottom" for manipulating individual atoms for the synthesis and manufacturing processing of materials, the materials-by-design paradigm is being developed gradually through synergistic integration of experimental material synthesis and characterization with predictive computational modeling and optimization. This paper reviews how this paradigm creates the possibility to develop materials according to specific, rational designs from the molecular to the macroscopic scale. We discuss promising techniques in experimental small-scale material synthesis and large-scale fabrication methods to manipulate atomistic or macroscale structures, which can be designed by computational modeling. These include recombinant protein technology to produce peptides and proteins with tailored sequences encoded by recombinant DNA, self-assembly processes induced by conformational transition of proteins, additive manufacturing for designing complex structures, and qualitative and quantitative characterization of materials at different length scales. We describe important material characterization techniques using numerous methods of spectroscopy and microscopy. We detail numerous multi-scale computational modeling techniques that complements these experimental techniques: DFT at the atomistic scale; fully atomistic and coarse-grain molecular dynamics at the molecular to mesoscale; continuum modeling at the macroscale. Additionally, we present case studies that utilize experimental and computational approaches in an integrated manner to broaden our understanding of the properties of two-dimensional materials and materials based on silk and silk-elastin-like proteins.

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.

Low-thermal-budget synthesis of monolayer molybdenum disulfide for silicon back-end-of-line integration on a 200 mm platform.

Two-dimensional (2D) materials are promising candidates for future electronics due to their excellent electrical and photonic properties. Although promising results on the wafer-scale synthesis (≤150 mm diameter) of monolayer molybdenum disulfide (MoS2) have already been reported, the high-quality synthesis of 2D materials on wafers of 200 mm or larger, which are typically used in commercial silicon foundries, remains difficult. The back-end-of-line (BEOL) integration of directly grown 2D materials on silicon complementary metal-oxide-semiconductor (CMOS) circuits is also unavailable due to the high thermal budget required, which far exceeds the limits of silicon BEOL integration (<400 °C). This high temperature forces the use of challenging transfer processes, which tend to introduce defects and contamination to both the 2D materials and the BEOL circuits. Here we report a low-thermal-budget synthesis method (growth temperature < 300 °C, growth time ≤ 60 min) for monolayer MoS2 films, which enables the 2D material to be synthesized at a temperature below the precursor decomposition temperature and grown directly on silicon CMOS circuits without requiring any transfer process. We designed a metal-organic chemical vapour deposition reactor to separate the low-temperature growth region from the high-temperature chalcogenide-precursor-decomposition region. We obtain monolayer MoS2 with electrical uniformity on 200 mm wafers, as well as a high material quality with an electron mobility of ~35.9 cm2 V-1 s-1. Finally, we demonstrate a silicon-CMOS-compatible BEOL fabrication process flow for MoS2 transistors; the performance of these silicon devices shows negligible degradation (current variation < 0.5%, threshold voltage shift < 20 mV). We believe that this is an important step towards monolithic 3D integration for future electronics.

Atomic-Scale Insights into the Lateral and Vertical Epitaxial Growth in Two-Dimensional Pd2Se3-MoS2 Heterostructures.

Two-dimensional (2D) materials form heterostructures in both the lateral and vertical directions when two different materials are interfaced, but with totally different bonding mechanisms of covalent in-plane to van der Waal's layered interactions. Understanding how the competition between lateral and vertical forces influences the epitaxial growth is important for future materials development of complex mixed layered heterostructures. Here, we use atomic-resolution annular dark-field scanning transmission electron microscopy to study the detailed atomic arrangements at mixed 2D heterostructure interfaces composed of two semiconductors with distinctly different crystal symmetry and elemental composition, Pd2Se3:MoS2, in order to understand the role of different chemical bonds on the resultant epitaxy. Pd2Se3 is grown off the step edge in bilayer MoS2, and the vertical and lateral epitaxial relationships of the Pd2Se3-MoS2 heterostructures are investigated. We find that the similarity of geometry at the interface with one metal (Pd or Mo) atoms bonded with two chalcogens (S or Se) are the crucial factors to make the atomically stitched lateral junction of 2D heterostructures. In addition, the vertical van der Waal interactions that are normally dominant in layered materials can be overcome by in-plane forces if the interfacial atomic stitching is high in quality and low in defect density. This knowledge should help guide the approaches for improving the epitaxy in mixed 2D heterostructures and seamless stitching of in-plane 2D heterostructures with various complex monolayer structures.

Molecular origin of viscoelasticity in mineralized collagen fibrils.

Bone is mineralized tissue constituting the skeletal system, supporting and protecting the body's organs and tissues. In addition to such fundamental mechanical functions, bone also plays a remarkable role in sound conduction. From a mechanical standpoint, bone is a composite material consisting of minerals and collagen arranged in multiple hierarchical structures, with a complex anisotropic viscoelastic response, capable of transmitting and dissipating energy. At the molecular level, mineralized collagen fibrils are the basic building blocks of bone tissue, and hence, understanding bone properties down to fundamental tissue structures enables better identification of the mechanisms of structural failures and damage. While efforts have focused on the study of micro- and macro-scale viscoelasticity related to bone damage and healing based on creep, mineralized collagen has not been explored at the molecular level. We report a study that aims at systematically exploring the viscoelasticity of collagenous fibrils with different mineralization levels. We investigate the dynamic mechanical response upon cyclic and impulsive loads to observe the viscoelastic phenomena from either shear or extensional strains via molecular dynamics. We perform a sensitivity analysis with several key benchmarks: intrafibrillar mineralization percentage, hydration state, and external load amplitude. Our results show an increase of the dynamic moduli with an increase of the mineral percentage, pronounced at low strains. When intrafibrillar water is present, the material softens the elastic component, but considerably increases its viscosity, especially at high frequencies. This behavior is confirmed from the material response upon impulsive loads, in which water drastically reduces the relaxation times throughout the input velocity range by one order of magnitude, with respect to the dehydrated counterparts. We find that, upon transient loads, water has a major impact on the mechanics of mineralized fibrillar collagen, being able to improve the capability of the tissue to passively and effectively dissipate energy, especially after fast and high-amplitude external loads. Our study provides knowledge of bone mechanics in relation to pathologies deriving from dehydration or traumas. Moreover, these findings show the potential for being used in designing new bioinspired materials not limited to tissue engineering applications, in which passive mechanisms for dissipating energy can prevent structural failures.

Strain-Induced Growth of Twisted Bilayers during the Coalescence of Monolayer MoS2 Crystals.

Tailoring the grain boundaries (GBs) and twist angles between two-dimensional (2D) crystals are two crucial synthetic challenges to deterministically enable envisioned applications such as moiré excitons, emerging magnetism, or single-photon emission. Here, we reveal how twisted 2D bilayers can be synthesized from the collision and coalescence of two growing monolayer MoS2 crystals during chemical vapor deposition. The twisted bilayer (TB) moiré angles are found to preserve the misorientation angle (θ) of the colliding crystals. The shapes of the TB regions are rationalized by a kink propagation model that predicts the GB formed by the coalescing crystals. Optical spectroscopy measurements reveal a θ-dependent long-range strain in crystals with stitched grain boundaries and a sharp (θ > 20°) threshold for the appearance of TBs, which relieves this strain. Reactive molecular dynamics simulations explain this strain from the continued growth of the crystals during coalescence due to the insertion of atoms at unsaturated defects along the GB, a process that self-terminates when the defects become saturated. The simulations also reproduce atomic-resolution electron microscopy observations of faceting along the GB, which is shown to arise from the growth-induced long-range strain. These facets align with the axes of the colliding crystals to provide favorable nucleation sites for second-layer growth of a TB with twist angles that preserve the misorientation angle θ. This interplay between strain generation and aligned nucleation provides a synthetic pathway for the growth of TBs with deterministic angles.

Wave Propagation and Energy Dissipation in Collagen Molecules.

Collagen is the key protein of connective tissue (i.e., skin, tendons and ligaments, and cartilage, among others), accounting for 25-35% of the whole-body protein content and conferring mechanical stability. This protein is also a fundamental building block of bone because of its excellent mechanical properties together with carbonated hydroxyapatite minerals. Although the mechanical resilience and viscoelasticity have been studied both in vitro and in vivo from the molecular to tissue level, wave propagation properties and energy dissipation have not yet been deeply explored, in spite of being crucial to understanding the vibration dynamics of collagenous structures (e.g., eardrum, cochlear membranes) upon impulsive loads. By using a bottom-up atomistic modeling approach, here we study a collagen peptide under two distinct impulsive displacement loads, including longitudinal and transversal inputs. Using a one-dimensional string model as a model system, we investigate the roles of hydration and load direction on wave propagation along the collagen peptide and the related energy dissipation. We find that wave transmission and energy-dissipation strongly depend on the loading direction. Also, the hydrated collagen peptide can dissipate five times more energy than dehydrated one. Our work suggests a distinct role of collagen in term of wave transmission of different tissues such as tendon and eardrum. This study can step toward understanding the mechanical behavior of collagen upon transient loads, impact loading and fatigue, and designing biomimetic and bioinspired materials to replace specific native tissues such as the tympanic membrane.

Mechanics of Mineralized Collagen Fibrils upon Transient Loads.

Collagen is a key structural protein in the human body, which undergoes mineralization during the formation of hard tissues. Earlier studies have described the mechanical behavior of bone at different scales, highlighting material features across hierarchical structures. Here we present a study that aims to understand the mechanical properties of mineralized collagen fibrils upon tensile/compressive transient loads, investigating how the kinetic energy propagates and it is dissipated at the molecular scale, thus filling a gap of knowledge in this area. These specific features are the mechanisms that nature has developed to passively dissipate stress and prevent structural failures. In addition to the mechanical properties of the mineralized fibrils, we observe distinct nanomechanical behaviors for the two regions (i.e., overlap and gap) of the D-period to highlight the effect of the mineralization. We notice decreasing trends for both wave speeds and Young's moduli over input velocity with a marked strengthening effect in the gap region due to the accumulation of the hydroxyapatite. In contrast, the dissipative behavior is not affected by either loading conditions or the mineral percentage, showing a stronger damping effect upon faster inputs compatible to the bone behavior at the macroscale. Our results offer insights into the dissipative behavior of mineralized collagen composites to design and characterize bioinspired composites for replacement devices (e.g., prostheses for sound transmission or conduction) or optimized structures able to bear transient loads, for example, impact, fatigue, in structural applications.

Adverse effects of Alport syndrome-related Gly missense mutations on collagen type IV: Insights from molecular simulations and experiments.

Patients with Alport syndrome (AS) exhibit blood and elevated protein levels in their urine, inflamed kidneys, and many other abnormalities. AS is attributed to mutations in type IV collagen genes, particularly glycine missense mutations in the collagenous domain of COL4A5 that disrupt common structural motifs in collagen from the repeat (Gly-Xaa-Yaa)n amino acid sequence. To characterize and elucidate the molecular mechanisms underlying how AS-related mutations perturb the structure and function of type IV collagen, experimental studies and molecular simulations were integrated to investigate the structure, stability, protease sensitivity, and integrin binding affinity of collagen-like proteins containing amino acid sequences from the α5(IV) chain and AS-related Gly missense mutations. We show adverse effects where (i) three AS-related Gly missense mutations significantly reduced the structural stability of the collagen in terms of decreased melting temperatures and calorimetric enthalpies, in conjunction with a collective drop in the external work needed to unfold the peptides containing mutation sequences; (ii) due to local unwinding around the sites of mutations, these triple helical peptides were also degraded more rapidly by trypsin and chymotrypsin, as these enzymes could access the collagenous triple helix more easily and increase the number of contacts; (iii) the mutations further abolished the ability of the recombinant collagens to bind to integrins and greatly reduced the binding affinities between collagen and integrins, thus preventing cells from adhering to these mutants. Our unified experimental and computational approach provided underlying insights needed to guide potential therapies for AS that ameliorate the adverse effects from AS disease onset and progression.

Accumulation of collagen molecular unfolding is the mechanism of cyclic fatigue damage and failure in collagenous tissues.

Overuse injuries to dense collagenous tissues are common, but their etiology is poorly understood. The predominant hypothesis that micro-damage accumulation exceeds the rate of biological repair is missing a mechanistic explanation. Here, we used collagen hybridizing peptides to measure collagen molecular damage during tendon cyclic fatigue loading and computational simulations to identify potential explanations for our findings. Our results revealed that triple-helical collagen denaturation accumulates with increasing cycles of fatigue loading, and damage is correlated with creep strain independent of the cyclic strain rate. Finite-element simulations demonstrated that biphasic fluid flow is a possible fascicle-level mechanism to explain the rate dependence of the number of cycles and time to failure. Molecular dynamics simulations demonstrated that triple-helical unfolding is rate dependent, revealing rate-dependent mechanisms at multiple length scales in the tissue. The accumulation of collagen molecular denaturation during cyclic loading provides a long-sought "micro-damage" mechanism for the development of overuse injuries.

Chirality-Dependent Second Harmonic Generation of MoS2 Nanoscroll with Enhanced Efficiency.

Materials with high second harmonic generation (SHG) efficiency and reduced dimensions are favorable for integrated photonics and nonlinear optical applications. Here, we fabricate MoS2 nanoscrolls with different chiralities and study their SHG performances. As a 1D material, MoS2 nanoscroll shows reduced symmetry and strong chirality dependency in the polarization-resolved SHG characterizations. This SHG performance can be well explained by the superposition theory of second harmonic field of the nanoscroll walls. MoS2 nanoscrolls with certain chiralities and diameters in our experiment can have SHG intensity up to 95 times stronger than that of monolayer MoS2, and the full potential can still be further exploited. The same chirality-dependent SHG can be expected for nanoscrolls or nanotubes composed of other noncentrosymmetric 2D materials, such as WS2, WSe2, and hBN. The characterization and analysis results presented here can also be exploited as a nondestructive technique to determine the chiralities of these nanoscrolls and nanotubes.

Multiscale Design of Graphyne-Based Materials for High-Performance Separation Membranes.

By varying the number of acetylenic linkages connecting aromatic rings, a new family of atomically thin graph-n-yne materials can be designed and synthesized. Generating immense scientific interest due to its structural diversity and excellent physical properties, graph-n-yne has opened new avenues toward numerous promising engineering applications, especially for separation membranes with precise pore sizes. Having these tunable pore sizes in combination with their excellent mechanical strength to withstand high pressures, free-standing graph-n-yne is theoretically posited to be an outstanding membrane material for separating or purifying mixtures of either gases or liquids, rivaling or even dramatically exceeding the capabilities of current, state-of-art separation membranes. Computational modeling and simulations play an integral role in the bottom-up design and characterization of these graph-n-yne materials. Thus, here, the state of the art in modeling α-, ß-, γ-, δ-, and 6,6,12-graphyne nanosheets for synthesizing graph-2-yne materials and 3D architectures thereof is discussed. Different synthesis methods are described and a broad overview of computational characterizations of graph-n-yne's electrical, chemical, and thermal properties is provided. Furthermore, a series of in-depth computational studies that delve into the specifics of graph-n-yne's mechanical strength and porosity, which confer superior performance for separation and desalination membranes, are reviewed.

Grain Boundaries as Electrical Conduction Channels in Polycrystalline Monolayer WS2.

We show that grain boundaries (GBs) in polycrystalline monolayer WS2 can act as conduction channels with a lower gate onset potential for field-effect transistors made parallel, compared to devices made in pristine areas and perpendicular to GBs. Localized doping at the GB causes photoluminescence quenching and a reduced Schottky barrier with the metal electrodes, resulting in higher conductivity at lower applied bias values. Samples are grown by chemical vapor deposition with large domains of ∼100 µm, enabling numerous devices to be made within single domains, across GBs and at many similar sites across the substrate to reveal similar behaviors. We corroborate our electrical measurements with Kelvin probe microscopy, highlighting the nature of the doping-type in the material to change at the grain boundaries. Molecular dynamics simulations of the GB are used to predict the atomic structure of the dislocations and meandering tilt GB behavior on the nanoscale. These results show that GBs can be used to provide conduction pathways that are different to transport across GBs and in pristine area for potential electronic applications.

Anisotropic Fracture Dynamics Due to Local Lattice Distortions.

A brittle material under loading fails by the nucleation and propagation of a sharp crack. In monatomic crystals, such as silicon, the lattice geometries front to the crack-tip changes the way of propagation even with the same cleavage surface. In general, however, crystals have multiple kinds of atoms and how the deformation of each atom affects the failure is still elusive. Here, we show that local atomic distortions from the different types of atoms causes a propagation anisotropy in suspended WS2 monolayers by combining annular dark-field scanning transmission electron microscopy and empirical molecular dynamics that are validated by first-principles calculations. Conventional conditions for brittle failure such as surface energy, elasticity, and crack geometry cannot account for this anisotropy. Further simulations predict the enhancement of the strengths and fracture toughness of the materials by designing void shapes and edge structures.