How the Complementarity at Vicinal Steps Enables Growth of 2D Monocrystals.

Large 2D monocrystals are highly sought after yet hard to achieve; unlike graphene, most dichalcogenides and h-BN possess low symmetry, which allows for nucleation of mutually inverted pieces, merging into polycrystals replete with grain boundaries. On vicinal substrate surfaces such growing pieces were observed to orient alike, and very recently this effect apparently enabled the growth of large single crystal h-BN. Addressing the compelling questions of how such a growth process can operate and what the key mechanisms are is crucial in guiding the substrate selection for optimal synthesis of perhaps many materials. To this end, the basic crystallography and atomistic-modeling theory presented here reveal (i) how the undulations of the ever-wandering steps do not, surprisingly, disturb the orientations of the attached 2D-nuclei, whose direction remains robust owing to complementarity between the meandering step and h-BN counterpart if their kinks have similar size of negligible misfit, δ k < 0.1 Å. (ii) Stronger chemical affinity of metal to the N atoms at the zigzag edge of h-BN singles out its particular orientation, without evidence of any epitaxy, at the edge or to the surface. (iii) The monocrystal integrity requires unhindered growth spillover across the steps and the seamless healing of the residual fissures, caused by the very same steps necessary for co-orientation. Molecular dynamics simulations show this happening for the steps not taller than the BN bond, s < 1.44 Å. These criteria point to [-1 1 2] steps on the Cu (110) surface, in accord with experimental results (Wang et al. Towards the growth of single-crystal boron nitride monolayer on Cu. arXiv:1811.06688 Cond. Mat. Mtrl. Sci., 2018), while other possibilities can also be predicted.

Evolutionary selection growth of two-dimensional materials on polycrystalline substrates.

There is a demand for the manufacture of two-dimensional (2D) materials with high-quality single crystals of large size. Usually, epitaxial growth is considered the method of choice 1 in preparing single-crystalline thin films, but it requires single-crystal substrates for deposition. Here we present a different approach and report the synthesis of single-crystal-like monolayer graphene films on polycrystalline substrates. The technological realization of the proposed method resembles the Czochralski process and is based on the evolutionary selection 2 approach, which is now realized in 2D geometry. The method relies on 'self-selection' of the fastest-growing domain orientation, which eventually overwhelms the slower-growing domains and yields a single-crystal continuous 2D film. Here we have used it to synthesize foot-long graphene films at rates up to 2.5 cm h-1 that possess the quality of a single crystal. We anticipate that the proposed approach could be readily adopted for the synthesis of other 2D materials and heterostructures.

Transient Kinetic Selectivity in Nanotubes Growth on Solid Co-W Catalyst.

Solid Co-W catalysts have been shown to yield single-walled carbon nanotubes (CNT) with high selectivity, simplistically attributed to CNT-catalyst symmetry match for certain chiral indices ( n, m). Here, based on large-scale first-principles calculations combined with kinetic Monte Carlo simulations, we show instead that such selectivity arises from a complex kinetics of growth. The solid Co7W6 catalyst strongly favors a restructured, asymmetric CNT edge which entails preferential nucleation of tubes with 2 m < n but much faster growth of chiral tubes with n ⩽ 2 m. We uncover a tendency of interface defects formation that, although rare, drive CNT type change from smaller to larger chiral angles (zigzag to armchair). Being both least prone to defects and fast growing, the (12,6) CNT appears as a transient, kinetics-selected type reaching highest abundance.

Computational Reverse Engineering Analysis of the Scattering Experiment Method for Interpretation of 2D Small-Angle Scattering Profiles (CREASE-2D).

Small-angle scattering (SAS) is a widely used characterization technique that provides structural information in soft materials at varying length scales (nanometers to microns). The output of an SAS measurement is the scattered intensity I(q) as a function of q, the scattered wavevector with respect to the incident wave; the latter is represented by its magnitude |q| ≡ q (in inverse distance units) and azimuthal angle θ. While isotropic structural arrangement can be interpreted by analysis of the azimuthally averaged one-dimensional (1D) scattering profile, to understand anisotropic arrangements, one has to interpret the two-dimensional (2D) scattering profile, I(q, θ). Manual interpretation of such 2D profiles usually involves fitting of approximate analytical models to azimuthally averaged sections of the 2D profile. In this paper, we present a new method called CREASE-2D that interprets, without any azimuthal averaging, the entire 2D scattering profile, I(q, θ), and outputs the relevant structural features. CREASE-2D is an extension of the "computational reverse engineering analysis for scattering experiments" (CREASE) method that has been used successfully to analyze 1D SAS profiles for a variety of soft materials. CREASE-2D goes beyond CREASE by enabling analysis of 2D scattering profiles, which is far more challenging to interpret than the azimuthally averaged 1D profiles. The CREASE-2D workflow identifies the structural features whose computed I(q, θ) profiles, calculated using a surrogate XGBoost machine learning model, match the input experimental I(q, θ). We expect that this CREASE-2D method will be a valuable tool for materials' researchers who need direct interpretation of the 2D scattering profiles in contrast to analyzing azimuthally averaged 1D I(q) vs q profiles that can lose important information related to structural anisotropy.

Computational approach for structure generation of anisotropic particles (CASGAP) with targeted distributions of particle design and orientational order.

The macroscopic properties of materials are governed by their microscopic structure which depends on the materials' composition (i.e., building blocks) and processing conditions. In many classes of synthetic, bioinspired, or natural soft and/or nanomaterials, one can find structural anisotropy in the microscopic structure due to anisotropic building blocks and/or anisotropic domains formed through the processing conditions. Experimental characterization and complementary physics-based or data-driven modeling of materials' structural anisotropy are critical for understanding structure-property relationships and enabling targeted design of materials with desired macroscopic properties. In this pursuit, to interpret experimentally obtained characterization results (e.g., scattering profiles) of soft materials with structural anisotropy using data-driven computational approaches, there is a need for creating real space three-dimensional structures of the designer soft materials with realistic physical features (e.g., dispersity in building block sizes) and anisotropy (i.e., aspect ratios of the building blocks, their orientational and positional order). These real space structures can then be used to compute and complement experimentally obtained characterization results or be used as initial configurations for physics-based simulations/calculations that can then provide training data for machine learning models. To address this need, we present a new computational approach called CASGAP - Computational Approach for Structure Generation of Anisotropic Particles - for generating any desired three dimensional real-space structure of anisotropic building blocks (modeled as particles) adhering to target distributions of particle shape, size, and positional and orientational order.

Fatigue in assemblies of indefatigable carbon nanotubes.

Despite being one of the most consequential processes in the utilization of structural materials, fatigue at the nano- and mesoscale has been marginally explored or understood even for the most promising nanocarbon forms­nanotubes and graphene. By combining atomistic models with kinetic Monte Carlo simulations, we show that a pristine carbon nanotube under ambient working conditions is essentially indefatigable­accumulating no structural memory of prior load; over time, it probabilistically breaks, abruptly. In contrast, by using coarse-grained modeling, we demonstrate that any practical assemblies of nanotubes, e.g., bundles and fibers, display a clear gradual strength degradation in cyclic tensile loading due to recurrence and ratchet-up of slip at the tube-tube interfaces, not occurring under static load even of equal amplitude.

Universal Strength Scaling in Carbon Nanotube Bundles with Frictional Load Transfer.

Carbon nanotubes (CNTs) individually display exceptional mechanical properties, but the strength of their mesoscale assemblies such as bundles has a fundamental disconnect, with limited understanding of its scaling. Here we use coarse-grained implementation of a CNT interface with prescribed length distributions and parametrized cross-link density, providing two essential control parameters. It is shown that a linear relationship between strength of the bundles and these control parameters exists, across multiple hierarchies of nanotube interfaces. Furthermore, all geometrical perturbations caused by length distribution and bundle dimensions result in a net stress concentration effect, without influencing the scaling behavior.

Strain tolerance of two-dimensional crystal growth on curved surfaces.

Two-dimensional (2D) crystal growth over substrate features is fundamentally guided by the Gauss-Bonnet theorem, which mandates that rigid, planar crystals cannot conform to surfaces with nonzero Gaussian curvature. Here, we reveal how topographic curvature of lithographically designed substrate features govern the strain and growth dynamics of triangular WS2 monolayer single crystals. Single crystals grow conformally without strain over deep trenches and other features with zero Gaussian curvature; however, features with nonzero Gaussian curvature can easily impart sufficient strain to initiate grain boundaries and fractured growth in different directions. Within a strain-tolerant regime, however, triangular single crystals can accommodate considerable (<1.1%) localized strain exerted by surface features that shift the bandgap up to 150 meV. Within this regime, the crystal growth accelerates in specific directions, which we describe using a growth model. These results present a previously unexplored strategy to strain-engineer the growth directions and optoelectronic properties of 2D crystals.

Tilt Grain Boundary Topology Induced by Substrate Topography.

Synthesis of two-dimensional (2D) crystals is a topic of great current interest, since their chemical makeup, electronic, mechanical, catalytic, and optical properties are so diverse. A universal challenge, however, is the generally random formation of defects caused by various growth factors on flat surfaces. Here we show through theoretical analysis and experimental demonstration that nonplanar, curved-topography substrates permit the intentional and controllable creation of topological defects within 2D materials. We augment a common phase-field method by adding a geometric phase to track the crystal misorientation on a curved surface and to detect the formation of grain boundaries, especially when a growing monocrystal "catches its own tail" on a nontrivial topographical feature. It is specifically illustrated by simulated growth of a trigonal symmetry crystal on a conical-planar substrate, to match the experimental synthesis of WS2 on silicon template, with satisfactory and in some cases remarkable agreement of theory predictions and experimental evidence.

Carbonization with Misfusion: Fundamental Limits of Carbon-Fiber Strength Revisited.

D-loops, a new type of structural defect in carbon fibers, are presented, which have highly detrimental effect on their mechanical properties and can define a new fundamental upper limit to their strength. These defects form exclusively during polyacrylonitrile carbonization, act as stress concentrators in the graphitic basal plane, and cannot be removed by local annealing.

Thermally stable plasmonic nanocermets grown on microengineered surfaces as versatile surface enhanced Raman spectroscopy sensors for multianalyte detection.

Noble metal nanoparticle-based plasmonic sensors, fabricated by top-down and colloidal routes, are widely used for high sensitivity detection of diverse analyte molecules using surface enhanced Raman spectroscopy (SERS). However, most of these sensors do not show stability under harsh environments, which limits their use as versatile SERS substrates. In this work, we report the first use of plasmonic nanocermets, grown on microengineered Si surfaces, as potential candidates for a highly robust SERS sensor. The robustness of the sensor is attributed to the anchoring of the nanoparticles in the nanocermet, which is an important factor for exploiting its reusability. The fairly uniform distribution of nanoparticles in the sensor led to high enhancement factors (10(6)-10(7)) and enabled the detection of low concentrations of a wide range of analytes, including differently charged biomolecules, which is extremely difficult for other SERS sensors. With more precise control over the particle geometry and distribution, plasmonic nanocermets may play an important role in ultrasensitive SERS measurements in adverse conditions such as high temperature.