Atom-resolved imaging of ordered defect superstructures at individual grain boundaries

The ability to resolve spatially and identify chemically atoms in defects would greatly advance our understanding of the correlation between structure and property in materials. This is particularly important in polycrystalline materials, in which the grain boundaries have profound implications for the properties and applications of the final material. However, such atomic resolution is still extremely difficult to achieve, partly because grain boundaries are effective sinks for atomic defects and impurities, which may drive structural transformation of grain boundaries and consequently modify material properties. Regardless of the origin of these sinks, the interplay between defects and grain boundaries complicates our efforts to pinpoint the exact sites and chemistries of the entities present in the defective regions, thereby limiting our understanding of how specific defects mediate property changes. Here we show that the combination of advanced electron microscopy, spectroscopy and first-principles calculations can provide three-dimensional images of complex, multicomponent grain boundaries with both atomic resolution and chemical sensitivity. The high resolution of these techniques allows us to demonstrate that even for magnesium oxide, which has a simple rock-salt structure, grain boundaries can accommodate complex ordered defect superstructures that induce significant electron trapping in the bandgap of the oxide. These results offer insights into interactions between defects and grain boundaries in ceramics and demonstrate that atomic-scale analysis of complex multicomponent structures in materials is now becoming possible.     

Atom-by-atom spectroscopy at graphene edge

The properties of many nanoscale devices are sensitive to local atomic configurations, and so elemental identification and electronic state analysis at the scale of individual atoms is becoming increasingly important. For example, graphene is regarded as a promising candidate for future devices, and the electronic properties of nanodevices constructed from this material are in large part governed by the edge structures. The atomic configurations at graphene boundaries have been investigated by transmission electron microscopy and scanning tunnelling microscopy, but the electronic properties of these edge states have not yet been determined with atomic resolution. Whereas simple elemental analysis at the level of single atoms can now be achieved by means of annular dark field imaging or electron energy-loss spectroscopy, obtaining fine-structure spectroscopic information about individual light atoms such as those of carbon has been hampered by a combination of extremely weak signals and specimen damage by the electron beam. Here we overcome these difficulties to demonstrate site-specific single-atom spectroscopy at a graphene boundary, enabling direct investigation of the electronic and bonding structures of the edge atoms-in particular, discrimination of single-, double- and triple-coordinated carbon atoms is achieved with atomic resolution. By demonstrating how rich chemical information can be obtained from single atoms through energy-loss near-edge fine-structure analysis, our results should open the way to exploring the local electronic structures of various nanodevices and individual molecules.     

Observation of rare-earth segregation in silicon nitride ceramics at subnanometre dimensions

Silicon nitride (Si3N4) ceramics are used in numerous applications because of their superior mechanical properties. Their intrinsically brittle nature is a critical issue, but can be overcome by introducing whisker-like microstructural features. However, the formation of such anisotropic grains is very sensitive to the type of cations used as the sintering additives. Understanding the origin of dopant effects, central to the design of high-performance Si3N4 ceramics, has been sought for many years. Here we show direct images of dopant atoms (La) within the nanometre-scale intergranular amorphous films typically found at grain boundaries, using aberration corrected Z-contrast scanning transmission electron microscopy. It is clearly shown that the La atoms preferentially segregate to the amorphous/crystal interfaces. First-principles calculations confirm the strong preference of La for the crystalline surfaces, which is essential for forming elongated grains and a toughened microstructure. Whereas principles of micrometre-scale structural design are currently used to improve the mechanical properties of ceramics, this work represents a step towards the atomic-level structural engineering required for the next generation of ceramics.     

二维功能材料的生物学效应

继石墨烯被发现以来,因其稳定的二维结构和独特的物理化学性质,在材料、能源、环境、生物等领域展现出广泛应用前景,也已成为纳米生物医学的研究热点,被用于生物传感、细胞成像、药物运输、组织工程等领域.随后,具有类似结构的相关二维功能材料的研究也层出不穷、备受关注.本文综述了以石墨烯为代表的二维功能材料的生物学效应,并作出展望.     

Experimental observation of the quantum Hall effect and Berry's phase in graphene

When electrons are confined in two-dimensional materials, quantum-mechanically enhanced transport phenomena such as the quantum Hall effect can be observed. Graphene, consisting of an isolated single atomic layer of graphite, is an ideal realization of such a two-dimensional system. However, its behaviour is expected to differ markedly from the well-studied case of quantum wells in conventional semiconductor interfaces. This difference arises from the unique electronic properties of graphene, which exhibits electron-hole degeneracy and vanishing carrier mass near the point of charge neutrality. Indeed, a distinctive half-integer quantum Hall effect has been predicted theoretically, as has the existence of a non-zero Berry's phase (a geometric quantum phase) of the electron wavefunction--a consequence of the exceptional topology of the graphene band structure. Recent advances in micromechanical extraction and fabrication techniques for graphite structures now permit such exotic two-dimensional electron systems to be probed experimentally. Here we report an experimental investigation of magneto-transport in a high-mobility single layer of graphene. Adjusting the chemical potential with the use of the electric field effect, we observe an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene. The relevance of Berry's phase to these experiments is confirmed by magneto-oscillations. In addition to their purely scientific interest, these unusual quantum transport phenomena may lead to new applications in carbon-based electronic and magneto-electronic devices.     

低压烧结制备石墨烯增强WC-Co硬质合金

采用机械搅拌和静电吸附2种工艺制备氧化石墨烯增强WC-Co复合粉末,对复合粉末的微观形貌进行表征,并利用低压烧结工艺制备石墨烯增强WC-Co硬质合金,对硬质合金力学性能进行测试分析。静电吸附工艺和低压烧结相结合所制备的石墨烯增强WC-Co硬质合金抗弯强度和维氏硬度分别为3 250 MPa和1 846,比不添加石墨烯的WC-Co硬质合金抗弯强度和硬度分别提高了38.92%和7.93%;比机械搅拌工艺和低压烧结相结合所制备的石墨烯增强WC-Co硬质合金抗弯强度提高了8.33%,硬度略有提高。石墨烯通过静电吸附工艺均匀地分散在WC-Co基体中,高温烧结时通过阻碍晶界的扩散和位错的滑移来细化晶粒,有裂纹产生时会阻碍裂纹扩展,从而增强材料力学性能。     

高温预熔化晶界位错的结构组态转变的探究

晶体材料的性能受其内部晶界特性的影响。在高温下，晶体材料在晶界上易发生预熔化。本研究采用晶体相场(PFC)方法模拟高温二维六角晶体的晶界预熔化区在双轴加载作用下的结构演化情况。结果显示，晶界位错会发生配对，形成具有对称结构的位错团，一对位错上下排列，另一对位错左右排列，构成4个位错的组合。随着施加的应变增大，晶界位错预熔化区域横向扩展，其形状最初为棒状，逐渐转化为六边形，再转变成“V”形，最后又收缩为六边形。晶界预熔化区的形状变化伴随着内部位错结构的转变，从而发生位错芯扩展，原来上下配对的位错转变为并行排列的位错，左右排列的位错发生扩展滑移，并在左右两端萌生出一对新的位错。当预熔化区域扩展达到横向最宽时，该区域发射一对位错，随后预熔化区域开始收缩，最后又恢复到初始的形状。上述结果表明，位错结构的组态转变对晶体材料的高温变形机制能产生强烈的影响。     

Designer Dirac fermions and topological phases in molecular graphene

The observation of massless Dirac fermions in monolayer graphene has generated a new area of science and technology seeking to harness charge carriers that behave relativistically within solid-state materials. Both massless and massive Dirac fermions have been studied and proposed in a growing class of Dirac materials that includes bilayer graphene, surface states of topological insulators and iron-based high-temperature superconductors. Because the accessibility of this physics is predicated on the synthesis of new materials, the quest for Dirac quasi-particles has expanded to artificial systems such as lattices comprising ultracold atoms. Here we report the emergence of Dirac fermions in a fully tunable condensed-matter system-molecular graphene-assembled by atomic manipulation of carbon monoxide molecules over a conventional two-dimensional electron system at a copper surface. Using low-temperature scanning tunnelling microscopy and spectroscopy, we embed the symmetries underlying the two-dimensional Dirac equation into electron lattices, and then visualize and shape the resulting ground states. These experiments show the existence within the system of linearly dispersing, massless quasi-particles accompanied by a density of states characteristic of graphene. We then tune the quantum tunnelling between lattice sites locally to adjust the phase accrual of propagating electrons. Spatial texturing of lattice distortions produces atomically sharp p-n and p-n-p junction devices with two-dimensional control of Dirac fermion density and the power to endow Dirac particles with mass. Moreover, we apply scalar and vector potentials locally and globally to engender topologically distinct ground states and, ultimately, embedded gauge fields, wherein Dirac electrons react to 'pseudo' electric and magnetic fields present in their reference frame but absent from the laboratory frame. We demonstrate that Landau levels created by these gauge fields can be taken to the relativistic magnetic quantum limit, which has so far been inaccessible in natural graphene. Molecular graphene provides a versatile means of synthesizing exotic topological electronic phases in condensed matter using tailored nanostructures.     

Element-selective imaging of atomic columns in a crystal using STEM and EELS

Microstructure characterization has become indispensable to the study of complex materials, such as strongly correlated oxides, and can obtain useful information about the origin of their physical properties. Although atomically resolved measurements have long been possible, an important goal in microstructure characterization is to achieve element-selective imaging at atomic resolution. A combination of scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) is a promising technique for atomic-column analysis. However, two-dimensional analysis has not yet been performed owing to several difficulties, such as delocalization in inelastic scattering or instrumentation instabilities. Here we demonstrate atomic-column imaging of a crystal specimen using localized inelastic scattering and a stabilized scanning transmission electron microscope. The atomic columns of La, Mn and O in the layered manganite La1.2Sr1.8Mn2O7 are visualized as two-dimensional images.     

单层石墨烯温度效应的分子动力学模拟

在不同温度条件（0 K-3000K）下,采用AIREBO势函数对单层石墨烯薄膜的弛豫性能和拉伸性能进行分子动力学模拟,研究单层石墨烯在弛豫过程中温度效应对其原子结构的影响以及单层石墨烯在拉伸过程中力学性能与温度效应的关系.研究结果表明：单层石墨烯的弛豫性能和拉伸性能均对温度具有很强的依赖性.理想状态下,单层石墨烯的弛豫是一个原子结构的动态平衡过程,随着温度升高,石墨烯稳定性降低,弛豫过程中原子的波动起伏变得不规则和剧烈起来.在温度从0K上升到3000K的过程中,单层石墨烯的拉伸强度、拉伸极限应变和弹性模量值均呈现下降趋势,且锯齿型石墨烯的弹性模量对温度的依赖程度比扶手椅型大,薄膜的拉伸随温度变化表现出不同的破坏形态.     

A brief review of graphene-based material synthesis and its application in environmental pollution management

Graphene is an interesting two-dimensional carbon allotrope that has attracted considerable research interest because of its unique structure and physicochemical properties. Studies have been conducted on graphene-based nanomaterials including modified graphene, graphene/semiconductor hybrids, graphene/metal nanoparticle composites, and graphene-complex oxide composites. These nanomaterials inherit the unique properties of graphene, and the addition of functional groups or the nanoparticle composites on their surfaces improves their performance. Applications of these materials in pollutant removal and environmental remediation have been explored. From the viewpoint of environmental chemistry and materials, this paper reviews recent important advances in synthesis of graphene-related materials and their application in treatment of environmental pollution. The roles of graphene-based materials in pollutant removal and potential research are discussed.     

Monte Carlo study on abnormal growth of Goss grains in Fe-3%Si steel induced by second-phase particles

The selective abnormal growth of Goss grains in magnetic sheets of Fe-3%Si (grade Hi-B) induced by second-phase particles (AlN and MnS) was studied using a modified Monte Carlo Potts model. The starting microstructures for the simulations were generated from electron backscatter diffraction (EBSD) orientation imaging maps of recrystallized samples. In the simulation, second-phase particles were assumed to be randomly distributed in the initial microstructures and the Zener drag effect of particles on Goss grain boundaries was assumed to be selectively invalid because of the unique properties of Goss grain boundaries. The simulation results suggest that normal growth of the matrix grains stagnates because of the pinning effect of particles on their boundaries. During the onset of abnormal grain growth, some Goss grains with concave boundaries in the initial microstructure grow fast abnormally and other Goss grains with convex boundaries shrink and eventually disappear.     

The structure of suspended graphene sheets

The recent discovery of graphene has sparked much interest, thus far focused on the peculiar electronic structure of this material, in which charge carriers mimic massless relativistic particles. However, the physical structure of graphene--a single layer of carbon atoms densely packed in a honeycomb crystal lattice--is also puzzling. On the one hand, graphene appears to be a strictly two-dimensional material, exhibiting such a high crystal quality that electrons can travel submicrometre distances without scattering. On the other hand, perfect two-dimensional crystals cannot exist in the free state, according to both theory and experiment. This incompatibility can be avoided by arguing that all the graphene structures studied so far were an integral part of larger three-dimensional structures, either supported by a bulk substrate or embedded in a three-dimensional matrix. Here we report on individual graphene sheets freely suspended on a microfabricated scaffold in vacuum or air. These membranes are only one atom thick, yet they still display long-range crystalline order. However, our studies by transmission electron microscopy also reveal that these suspended graphene sheets are not perfectly flat: they exhibit intrinsic microscopic roughening such that the surface normal varies by several degrees and out-of-plane deformations reach 1 nm. The atomically thin single-crystal membranes offer ample scope for fundamental research and new technologies, whereas the observed corrugations in the third dimension may provide subtle reasons for the stability of two-dimensional crystals.     

石墨烯银纳米线透明导电薄膜的制备进展

透明导电薄膜是触摸器件以及液晶显示器等的重要组成部分,制备透明导电薄膜的材料主要有金属氧化物、导电聚合物、碳材料、金属材料和复合材料等。其中,一维银纳米线和二维石墨烯材料制备透明导电薄膜具有光电性能优异、化学性能稳定和柔韧性好等特点,有望应用于柔性电子设备中。介绍了石墨烯银纳米线透明导电薄膜常用的制备方法：旋涂法、真空抽滤法、棒涂法、喷涂法、滴涂法等5种以及各种制备方法的优缺点;总结了石墨烯银纳米线复合薄膜的应用领域;展望了石墨烯银纳米线透明导电薄膜的发展前景。     

晶体结构预测的新方法和典型应用

物质的微观结构直接或间接决定了材料的几乎所有物理和化学性质.这也是后续材料设计的重要基础.近年来,随着多种晶体结构预测方法的发展和改进,仅根据化学组分就从理论上确定物质结构的研究已经取得了长足进步.本文概述了当前主流的晶体结构理论预测方法,并对基于自适应遗传算法(AGA)以及利用"结构单元(Motifs)"(XMsearch)的新型结构预测方法做了重点介绍.近年来,基于不同算法的AGA,XMsearch等程序包得到了开发与完善,只需给定化学组分和压力等条件,便能对材料的稳态、亚稳态结构进行预测研究.目前,这些新工具已在高压材料、电池材料、磁性材料、界面材料等凝聚态物质结构研究中得到了广泛应用.     

Three-dimensional X-ray structural microscopy with submicrometre resolution

Advanced materials and processing techniques are based largely on the generation and control of non-homogeneous microstructures, such as precipitates and grain boundaries. X-ray tomography can provide three-dimensional density and chemical distributions of such structures with submicrometre resolution; structural methods exist that give submicrometre resolution in two dimensions; and techniques are available for obtaining grain-centroid positions and grain-average strains in three dimensions. But non-destructive point-to-point three-dimensional structural probes have not hitherto been available for investigations at the critical mesoscopic length scales (tenths to hundreds of micrometres). As a result, investigations of three-dimensional mesoscale phenomena--such as grain growth, deformation, crumpling and strain-gradient effects--rely increasingly on computation and modelling without direct experimental input. Here we describe a three-dimensional X-ray microscopy technique that uses polychromatic synchrotron X-ray microbeams to probe local crystal structure, orientation and strain tensors with submicrometre spatial resolution. We demonstrate the utility of this approach with micrometre-resolution three-dimensional measurements of grain orientations and sizes in polycrystalline aluminium, and with micrometre depth-resolved measurements of elastic strain tensors in cylindrically bent silicon. This technique is applicable to single-crystal, polycrystalline, composite and functionally graded materials.     

丝材3D打印2024/7055铝合金梯度结构组织与性能分析

大型高强度轻质铝合金整体结构件在航空航天装备结构中应用广泛。为充分发挥不同材料的性能优势,可将两种以上的铝合金材料通过增材制造技术整体成型,从而制造出兼顾功能与减重要求的整体梯度结构件。为此,提出了一种多丝材电弧增材制造铝合金梯度结构件的制备方法,实现了航空结构常用的2024/7055铝合金梯度结构的3D打印,并对梯度结构进行了宏/微观组织、气孔缺陷、过渡区元素含量以及力学性能等进行了全面的分析。研究结果表明：通过多丝材增材制造打印的2024/7055铝合金梯度结构连接良好、过渡区域连续;梯度区域两种材料的晶粒组成不同,2024铝合金由等轴晶粒组成,而7055由短柱状晶粒组成;气孔在空间分布中呈条状分布,并且两种合金Zn元素含量不同,导致力学性能差异较大;当材料组分占比为2024(25%)/7055(75%)时,力学性能最好,材料折损率最低。     

MXene材料储能应用研究进展

MXene是一种新型的二维过渡金属碳化物或碳氮化物,具有类似石墨烯的二维结构.MXene因其独特的物理和化学特性,以及在储能、催化、电子与光电子等领域中的良好应用前景而受到广泛关注.介绍了MXene材料的制备、表征以及在锂离子电池、钠离子电池、锂硫电池和超级电容器等储能器件上的最新研究成果.最后,对MXene材料的未来发展和挑战进行了介绍.     

AlMgB_（14）三元超硬硼化物的实验制备与理论研究

三元硼化物AlMgB14材料具有高硬度,高韧性,低密度,低摩擦系数以及抗高温氧化腐蚀等众多优异性能,在工具、模具、微机械制造及航空航天关键零部件等领域具有重要的应用前景.本文采用多靶射频磁控共溅射技术,以高纯度Al（99.99%）,Mg（99.95%）,B（99.9%）材料为溅射靶源,在单晶Si（100）衬底上溅射沉积得到了表面均匀致密,不同化学组分的Al-Mg-B三元非晶态薄膜,通过调控溅射参数,可以实现原子比接近Al：Mg：B=1：1：14.对于所制备的薄膜样品,在三元相图上沿Al-Mg等含量线,Al-Mg-B材料的硬度,随着B元素含量增加由13GPa增大到32GPa,其中AlMgB14附近成分点的硬度达到25~32GPa.同时,采用第一性原理计算,得到AlMgB14晶体的维氏硬度为27.6GPa,与实验值接近.通过电子结构分析,我们进一步探讨了AlMgB14晶体和其他相似结构富B三元化合物硬度的起源,发现他们共同具有的B12二十面体骨架是决定硬度的主要因素.Al,Mg等金属元素主要通过向B12的电荷转移对材料硬度进行微调,Al-B之间形成了弱的共价键而Mg-B之间形成离子键,这点同时也为XPS实验谱图所证实.采用准简谐近似德拜模型,我们还研究了AlMgB14晶体的热学性质以及温度对体弹性模量的影响,发现体模量随温度增加明显的减小,同实验上提高衬底温度对硬度的增强呈现了相反的变化趋势.这从侧面说明了衬底温度提高导致的硬度增强并不是改变了材料的本征硬度,而可能由于加强了薄膜同衬底间附着力.