Atom-by-atom observation of grain boundary migration in graphene

Grain boundary (GB) migration in polycrystalline solids is a materials science manifestation of survival of the fittest, with adjacent grains competing to add atoms to their outer surfaces at each other's expense. This process is thermodynamically favored when it lowers the total GB area in the sample, thereby reducing the excess free energy contributed by the boundaries. In this picture, a curved boundary is expected to migrate toward its center of curvature with a velocity proportional to the local radius of boundary curvature (R). Investigating the underlying mechanism of boundary migration in a 3D material, however, has been reserved for computer simulation or analytical theory, as capturing the dynamics of individual atoms in the core region of a GB is well beyond the spatial and temporal resolution limits of current characterization techniques. Here, we similarly overcome the conventional experimental limits by investigating a 2D material, polycrystalline graphene, in an aberration-corrected transmission electron microscope, exploiting the energy of the imaging electrons to stimulate individual bond rotations in the GB core region. The resulting morphological changes are followed in situ, atom-by-atom, revealing configurational fluctuations that take on a time-averaged preferential direction only in the presence of significant boundary curvature, as confirmed by Monte Carlo simulations. Remarkably, in the extreme case of a small graphene grain enclosed within a larger one, we follow its shrinkage to the point of complete disappearance.     

3D打印石墨烯制备技术及其在储能领域的应用研究进展

石墨烯优异的力学和物理性能使其成为理想的储能材料。因结构精确可控,易实现规模化制备,3D打印石墨烯材料有望在储能领域得到广泛应用。本文全面综述了3D打印石墨烯制备技术及其在储能领域的应用研究进展。石墨烯墨水的黏度和可打印性是实现石墨烯3D打印的制约因素。实现工艺简单、浓度可控、无黏结剂石墨烯墨水的规模化打印将成为3D打印石墨烯制备技术未来的研究热点。石墨烯超级电容器、锂硫电池、锂离子电池等储能元件一体化打印成型是3D打印石墨烯在储能领域应用的发展方向。     

Criteria for Realizing Room-Temperature Electrical Transport Applications of Topological Materials

The unusual electronic states found in topological materials can enable a new generation of devices and technologies, yet a long-standing challenge has been finding materials without deleterious parallel bulk conduction. This can arise either from defects or thermally activated carriers. Here, the criteria that materials need to meet to realize transport properties dominated by the topological states, a necessity for a topological device, are clarified. This is demonstrated for 3D topological insulators, 3D Dirac materials, and 1D quantum anomalous Hall insulators, though this can be applied to similar systems. The key parameters are electronic bandgap, dielectric constant, and carrier effective mass, which dictate under what circumstances (defect density, temperature, etc.) the unwanted bulk state will conduct in parallel to the topological states. As these are fundamentally determined by the basic atomic properties, simple chemical arguments can be used to navigate the phase space to ultimately find improved materials. This will enable rapid identification of new systems with improved properties, which is crucial to designing new material systems and push a new generation of topological technologies.     

Dirac Fermion Kinetics in 3D Curved Graphene

3D integration of graphene has attracted attention for realizing carbon-based electronic devices. While the 3D integration can amplify various excellent properties of graphene, the influence of 3D curved surfaces on the fundamental physical properties of graphene has not been clarified. The electronic properties of 3D nanoporous graphene with a curvature radius down to 25–50 nm are systematically investigated and the ambipolar electronic states of Dirac fermions are essentially preserved in the 3D graphene nanoarchitectures, while the 3D curvature can effectively suppress the slope of the linear density of states of Dirac fermion near the Fermi level are demonstrated. Importantly, the 3D curvature can be utilized to tune the back-scattering-suppressed electrical transport of Dirac fermions and enhance both electron localization and electron–electron interaction. As a result, nanoscale curvature provides a new degree of freedom to manipulate 3D graphene electrical properties, which may pave a new way to design new 3D graphene devices with preserved 2D electronic properties and novel functionalities.     

Cutting and controlled modification of graphene with ion beams

Using atomistic computer simulations, we study how ion irradiation can be used to alter the morphology of a graphene monolayer, by introducing defects of specific type, and to cut graphene sheets. Based on the results of our analytical potential molecular dynamics simulations, a kinetic Monte Carlo code is developed for modeling morphological changes in a graphene monolayer under irradiation at macroscopic time scales. Impacts of He, Ne, Ar, Kr, Xe, and Ga ions with kinetic energies ranging from tens of eV to 10?MeV and angles of incidence between 0° and 88° are studied. Our results provide microscopic insights into the response of graphene to ion irradiation and can directly be used for the optimization of graphene cutting and patterning with focused ion beams.     

Toward a predictive atomistic model of ion implantation and dopant diffusion in silicon

We review the development and application of kinetic Monte Carlo simulations to investigate defect and dopant diffusion in ion implanted silicon. In these types of Monte Carlo models, defects and dopants are treated at the atomic scale, and move according to reaction rates given as input parameters. These input parameters can be obtained from first principles calculations and/or empirical molecular dynamics (MD) simulations or can be extracted from fits to experimental data. Time and length scales differing several orders of magnitude can be followed with this method, allowing for direct comparison with experiments. The different approaches are explained and some results presented.     

多盲孔缺陷的超声兰姆波时域拓扑能量成像方法研究

传统超声成像方法受瑞利准则的约束，难以对缺陷间距小于成像分辨率阈值的多缺陷进行成像。提出了一种基于时域拓扑能量的超声兰姆波成像方法，将逆散射拓扑成像方法中的拓扑渐进过程转换成求解直接声场和伴随声场。然后通过将伴随声场进行时间反转，两个声场将具有在缺陷处聚焦，在非缺陷处不聚焦的特性。将直接声场和伴随声场进行融合，以时域拓扑能量值作为像素值进行成像，从而使表征缺陷的精度较高。建立了缺陷间距小于分辨率阈值的多盲孔缺陷有限元模型，通过“一发多收”的方式激发S0模式和采集缺陷散射信号，并进行时域拓扑能量成像。仿真结果表明：对于多盲孔缺陷，时域拓扑能量成像法能够获得比延时叠加法和时间反转成像法更高的分辨率，并且能在缺陷间距小于成像分辨率阈值时进行成像。     

Three dimensional simulation of microstructure evolution for ceramic tool materials

The observation and scientific quantitative characterization of three dimensional microstructure evolution during sintering process of ceramic tool materials is important to investigate the influence of nano-particles on mechanical properties. The relationship between microstructure and mechanical properties of ceramic tool materials can be established to direct the development of nano-composite ceramic tool materials by the research of the grain growth, grain boundary migration, distribution of nano-particles and microstructure densification at the different sintering temperature and pressure. In this paper, a 3D Monte Carlo model of three-phase nano-composite ceramic tool material is built and applied to simulate the microstructure evolution during sintering process. In this model, the grain boundary energy of each phase and interfacial energy between two phases are taken into consideration as the driving forces for grain growth. The sintering temperature and pressure are successfully coupled into the Monte Carlo simulation model. The microstructure evolution of defect free three-phase nano-composite ceramic tool materials is successfully simulated at different sintering temperature and pressure. The simulation results show that the higher the sintering temperature is, the faster the grain growth. However, the sintering pressure has little effect on the grain growth.     

低温一步制备氧化石墨烯及微波还原研究

以天然鳞片石墨为原料,通过低温一步氧化制备氧化石墨烯,经微波热还原得到低缺陷的还原氧化石墨烯。讨论了低温氧化过程中氧化剂用量、氧化时间对氧化石墨烯层间距、氧化程度的影响。结果表明:在高锰酸钾与天然鳞片石墨的质量比为1∶3,氧化温度为0℃,氧化时间为48h的条件下,制备出碳氧原子比为1.98、高C—O结构、低缺陷结构( I D∶ I G=0.63)的氧化石墨烯,避免了Hummers制备过程中由于CO 2的形成导致六元环断裂以及碳原子的缺失而使得氧化石墨烯的缺陷增加;经微波热还原后,得到的还原氧化石墨烯的两点平均缺陷距离 L D=12nm,缺陷密度 n D=2.21×10 11 cm -2 , I D∶ I G仅为0.85(Γ G=32.1cm -1 ),制备出低缺陷的还原氧化石墨烯。     

Photon migration in the presence of a single defect: a perturbation analysis

We present an analytical perturbation analysis for studying the sensitivity of diffusive photon flux to the addition of a small spherical defect object in multiple-scattering media such as human tissues. As a first simple application of our perturbation method, we derive analytically the photon migration path distributions and the shapes of the so-called banana regions in which the photon migration paths are concentrated. We then derive analytically the sensitivity of detected photon flux densities to the inclusion of small spherical defects in the multiple-scattering medium for both single-source and two-source configurations, at both steady-state (dc) and frequency-modulation conditions, and compare the results with Monte Carlo simulations.     

Structure of graphene and its disorders: a review

Monolayer graphene exhibits extraordinary properties owing to the unique, regular arrangement of atoms in it. However, graphene is usually modified for specific applications, which introduces disorder. This article presents details of graphene structure, including sp² hybridization, critical parameters of the unit cell, formation of σ and π bonds, electronic band structure, edge orientations, and the number and stacking order of graphene layers. We also discuss topics related to the creation and configuration of disorders in graphene, such as corrugations, topological defects, vacancies, adatoms and sp³-defects. The effects of these disorders on the electrical, thermal, chemical and mechanical properties of graphene are analyzed subsequently. Finally, we review previous work on the modulation of structural defects in graphene for specific applications.     

Inverse Design Strategies for 3D Surfaces Formed by Mechanically Guided Assembly

Deterministic transformations of 2D patterns of materials into well-controlled 3D mesostructures serve as the basis for manufacturing methods that can bypass limitations of conventional 3D micro/nanofabrication. Here, guided mechanical buckling processes provide access to a rich range of complex 3D mesostructures in high-performance materials, from inorganic and organic semiconductors, metals and dielectrics, to ceramics and even 2D materials (e.g., graphene, MoS₂). Previous studies demonstrate that iterative computational procedures can define design parameters for certain targeted 3D configurations, but without the ability to address complex shapes. A technical need is in efficient, generalized inverse design algorithms that directly yield sets of optimized parameters. Here, such schemes are introduced, where the distributions of thicknesses across arrays of separated or interconnected ribbons provide scalable routes to 3D surfaces with a broad range of targeted shapes. Specifically, discretizing desired shapes into 2D ribbon components allows for analytic solutions to the inverse design of centrally symmetric and even general surfaces, in an approximate manner. Combined theoretical, numerical, and experimental studies of ≈20 different 3D structures with characteristic sizes (e.g., ribbon width) ranging from ≈200 µm to ≈2 cm and with geometries that resemble hemispheres, fire balloons, flowers, concave lenses, saddle surfaces, waterdrops, and rodents, illustrate the essential ideas.     

Multiscale modelling of defect kinetics in irradiated iron.

Changes in microstructure and mechanical properties of nuclear materials are governed by the kinetics of defects produced by irradiation. The population of vacancies, interstitials and their clusters can however be followed only indirectly, for example by macroscopic resistivity measurements. The information on the mobility, recombination, clustering or dissociation of defects provided by such experiments is both extremely rich and difficult to interpret. By combining ab initio and kinetic Monte Carlo methods, we successfully reproduce the abrupt resistivity changes-so-called recovery stages-observed upon annealing at increasing temperatures after electron irradiation in alpha-iron. New features in the mechanisms responsible for these stages are revealed. We show that di-vacancies and tri-interstitials contribute to the stages attributed to mono-vacancy and di-interstitial migration respectively. We also predict the effect of the unexpected low migration barriers found for tri- and quadri-vacancies, and discuss the challenging questions raised by the mobility of larger defect clusters.     

The fatigue limit: An analytical solution to a Monte Carlo problem

A new extreme value distribution based on log-normally distributed defects is presented. From this, an analytical solution to the random defect Monte Carlo problem in form of a distribution function characterizing the fatigue limit of an arbitrary component is derived. Surface defects, defined as internal defects intersecting a free surface, are incorporated into the model through an original analytical approach. The presented model is physically based and simple to implement and apply.Furthermore, the model was applied to a series of fatigue limit experiments found in the literature. The fatigue limit predictions were in good agreement with experimental results.     

Stochastic fracture analysis of cracked structures with random field property using the scaled boundary finite element method

Fracture is one of the most prominent concerns for large scale applications of graphene. In this paper, we review some of the recent progresses in experimental and theoretical studies on the fracture behaviors of graphene, with discussions touching theoretical strength, mode I fracture toughness, mixed mode fracture, chemical fracture, irradiation fracture, dynamic fracture, impact fracture, and sonication fracture. In spite of rapid developments in experiments and simulations, there are still significant yet unresolved issues related to the fracture of graphene, examples including: (1) Can one enhance the toughness of graphene with designed topological defects? (2) How does grain size affect the strength of polycrystalline graphene? (3) How do the out-of-plane effects (e.g., wrinkle caused by external loading or curvature induced by topological defects) influence the fracture of graphene? (4) Can one develop a continuum model with the ability to capture graphene fracture with complicated modes, such as shear fracture coupled with wrinkling deformation and tear fracture? (5) How does fracture occur when tearing a polycrystalline graphene sheet? (6) Can one control the fracture behavior of graphene by combing the chemical, irradiation and stress effect? (7) How fast can cracks propagate in graphene? (8) What is the behavior of interfacial cracks in graphene, i.e., cracks along the grain boundaries or interfaces of heterogeneous structures? (9) How does a multilayer graphene membrane break under high speed impact and why such structures can absorb a large amount of kinetic energy? (10) Can one tailor/design the graphene structures with controlled fracture? The intention here is not to provide complete answers to such questions, but to draw attention from the mechanics community to them as potential research topics.     

Study of graphene device electronic properties with horizontal and vertical double vacancy defects

Abstract

Graphene device electronic properties with double vacancy (DV) defects for two cases, along the direction and perpendicular to the current pathways graphene device, were investigated by using the first principles calculations in combination with density functional theory. The bond lengths, density of states, transmission probability, and current-voltage curves are computed. For relaxed pristine graphene the bond length is around 1.43?Å. However, the bond lengths near the defects for relaxed graphene for DV case are modified to 1.40-1.49?Å. It is also observed that I???V graph is nonlinear based on the current-voltage curve of graphene device which contain DV defects. Furthermore, it has been shown that having the DV defects lead to reduce the current relative to the case of perfect graphene device. Moreover, we noted that when the voltage is increased from zero to one volt new peaks are created near Fermi level in the transmission spectrum graphs. In addition, we noted that the current for the vertical DV defect is smaller than the pristine and horizontal DV device because the number of blocked electrons current pathways in vertical DV defect is larger than the two other cases, namely the pristine and horizontal DV defect cases The obtained results can be useful for the construction of new nanoelectronic devices and may have practical applications.     

A kinetic Monte Carlo study of mixed 1D/3D defect migration

Defect clusters form readily in collision cascades in metals, and some of the self-interstitial atom clusters form as crowdion clusters that diffuse by one-dimensional migration along a close-packed direction. Defect interactions and thermal fluctuations can cause the direction of one-dimensional migration to change, resulting in a mixed one-dimensional/ three-dimensional migration. Kinetic Monte Carlo computer simulations applied to model systems are used to investigate the effects of one-dimensional, three-dimensional and mixed one-dimensional/ three-dimensional migration on defect reaction kinetics. The functional relationships between the sink strength, the size of sinks and the average distance between direction changes during mixed one-dimensional/three-dimensional migration are explored. This revised version was published online in July 2006 with corrections to the Cover Date.     

缺陷调控石墨烯复合催化剂在氧还原反应中的作用

电化学氧还原反应(ORR)在能源、催化等领域具有广阔的应用前景, 因此开发性能优异、选择性高的催化剂对于促进ORR发展具有重要意义。ORR反应按照反应过程可以分为二电子反应过程和四电子反应过程。本研究以化学修饰石墨烯为原料, 通过调控其表面缺陷并与银-对苯二琨二甲烷(Ag-TCNQ)纳米点复合, 合成了不同缺陷程度的复合催化剂, 在此基础上比较了Ag-TCNQ/高缺陷石墨烯和Ag-TCNQ/低缺陷石墨烯的ORR性能。研究结果显示Ag-TCNQ/高缺陷石墨烯催化ORR的电子转移数为2.4, 双氧水产率达0.62 mg/h, 法拉第效率为64.45%。相比之下, Ag-TCNQ/低缺陷石墨烯参与ORR的电子转移数为3.7, 氧还原半波电位约为0.7 V(vs. RHE)。因此, 高缺陷催化剂促进ORR的二电子过程, 而低缺陷的催化剂促进ORR的四电子过程。在复合材料中, Ag-TCNQ纳米颗粒和石墨烯发挥了各自的结构优势, 形成复合效应, 共同提高了催化活性。     

Vertically-aligned graphene flakes on nanoporous templates: morphology,thickness, and defect level control by pre-treatment

Various morphologies of the vertically-aligned graphene flakes were fabricated on the nanoporous templates treated with metal ions in solutions, as well as coated with a thin gold layer and activated in the low-temperature Ar plasma. The thickness and level of structural defects in the graphene flakes could be effectively controlled by a proper selection of the pre-treatment method. We have also demonstrated that various combinations of the flake thickness and defect levels can be obtained, and the morphology and density of the graphene pattern can be effectively controlled. The result obtained could be of interest for various applications requiring fabrication of large graphene networks with controllable properties.     

Assembly of Foldable 3D Microstructures Using Graphene Hinges

Origami/kirigami-inspired 3D assembly approaches have recently attracted attention for a variety of applications, such as advanced optoelectronic devices and biomedical sensors. The results reported here describe an approach to construct classes of multiple foldable 3D microstructures that involve deformations that typical conductive materials, such as conventional metal films, cannot tolerate. Atomically thin graphene sheets serve as folding hinges during a process of 2D to 3D conversion via a deterministic buckling process. The exceptional mechanical properties of graphene enable the controlled, geometric transformation of a 2D precursor bonded at selective sites on a prestretched elastomer into folded 3D microstructures, in a reversible manner without adverse effects on the electrical properties. Experimental and computational investigations of the folding mechanisms for such types of 3D objects reveal the underlying physics and the dependence of the process on the thickness of the graphene/supporting films that define the hinges.