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.     

Measurement of the displacement field of dislocations to 0.03 A by electron microscopy

Defects and their associated long-range strain fields are of considerable importance in many areas of materials science. For example, a major challenge facing the semiconductor industry is to understand the influence of defects on device operation, a task made difficult by the fact that their interactions with charge carriers can occur far from defect cores, where the influence of the defect is subtle and difficult to quantify. The accurate measurement of strain around defects would therefore allow more detailed understanding of how strain fields affect small structures-in particular their electronic, mechanical and chemical properties--and how such fields are modified when confined to nanometre-sized volumes. Here we report the measurement of displacements around an edge dislocation in silicon using a combination of high-resolution electron microscopy and image analysis inherited from optical interferometry. The agreement of our observations with anisotropic elastic theory calculations is better than 0.03 A. Indeed, the results can be considered as an experimental verification of anisotropic theory at the near-atomic scale. With the development of nanostructured materials and devices, we expect the use of electron microscopy as a metrological tool for strain analysis to become of increasing importance.     

Au／MgO（001）界面上Au原子与点缺陷相互作用的第一性原理研究

采用基于密度泛函理论的第一性原理平面波赝势方法,系统地研究了Au／MgO（001）界面中8种晶格匹配方式的电子结构和化学键特征．界面处原子间距、界面能以及电子密度分布显示不同点缺陷与Au原子层相互作用的微观机制存在明显差异,并且界面体系稳定性和Au原子生长模式与界面原子排列方式密切相关．     

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.     

Direct observation of a local thermal vibration anomaly in a quasicrystal

Quasicrystals have long-range order with symmetries that are incompatible with periodicity, and are often described with reference to a higher-dimensional analogue of a periodic lattice. Within the context of this 'hyperspace' crystallography, lattice dynamics of quasicrystals can be described by a combination of lattice vibrations and atomic fluctuations--phonons and phasons. However, it is difficult to see localized fluctuations in a real-space quasicrystal structure, and so the nature of phason-related fluctuations and their contribution to thermodynamic stability are still not fully understood. Here we use atomic-resolution annular dark-field scanning transmission electron microscopy to map directly the change in thermal diffuse scattering intensity distribution in the quasicrystal, through in situ high-temperature observation of decagonal Al72Ni20Co8. We find that, at 1,100 K, a local anomaly of atomic vibrations becomes significant at specific atomic sites in the structure. The distribution of these localized vibrations is not random but well-correlated, with a quasiperiodic length scale of 2 nm. We are able to explain this feature by an anomalous temperature (Debye-Waller) factor for the Al atoms that sit at the phason-related sites defined within the framework of hyperspace crystallography. The present results therefore provide a direct observation of local thermal vibration anomalies in a solid.     

Atomic-scale imaging of insulating diamond through resonant electron injection

The electronic properties of insulators such as diamond are of interest not only for their passive dielectric capabilities for use in electronic devices, but also for their strong electron confinement on atomic scales. However, the inherent lack of electrical conductivity in insulators usually prevents the investigation of their surfaces by atomic-scale characterization techniques such as scanning tunnelling microscopy (STM). And although atomic force microscopy could in principle be used, imaging diamond surfaces has not yet been possible. Here, we demonstrate that STM can be used in an unconventional resonant electron injection mode to image insulating diamond surfaces and to probe their electronic properties at the atomic scale. Our results reveal striking electronic features in high-purity diamond single crystals, such as the existence of one-dimensional fully delocalized electronic states and a very long diffusion length for conduction-band electrons. We expect that our method can be applied to investigate the electronic properties of other insulating materials and so help in the design of atomic-scale electronic devices.     

Interplay of electron-lattice interactions and superconductivity in superconductivity in Bi2Sr2CaCu2O8+delta

Formation of electron pairs is essential to superconductivity. For conventional superconductors, tunnelling spectroscopy has established that pairing is mediated by bosonic modes (phonons); a peak in the second derivative of tunnel current d2I/dV2 corresponds to each phonon mode. For high-transition-temperature (high-T(c)) superconductivity, however, no boson mediating electron pairing has been identified. One explanation could be that electron pair formation and related electron-boson interactions are heterogeneous at the atomic scale and therefore challenging to characterize. However, with the latest advances in d2I/dV2 spectroscopy using scanning tunnelling microscopy, it has become possible to study bosonic modes directly at the atomic scale. Here we report d2I/dV2 imaging studies of the high-T(c) superconductor Bi2Sr2CaCu2O8+delta. We find intense disorder of electron-boson interaction energies at the nanometre scale, along with the expected modulations in d2I/dV2 (refs 9, 10). Changing the density of holes has minimal effects on both the average mode energies and the modulations, indicating that the bosonic modes are unrelated to electronic or magnetic structure. Instead, the modes appear to be local lattice vibrations, as substitution of 18O for 16O throughout the material reduces the average mode energy by approximately 6 per cent--the expected effect of this isotope substitution on lattice vibration frequencies. Significantly, the mode energies are always spatially anticorrelated with the superconducting pairing-gap energies, suggesting an interplay between these lattice vibration modes and the superconductivity.     

BaVS_3化合物电子结构、晶格动力学、热力学研究

采用基于第一性原理计算的平面波赝势方法,在局域密度近似下对六角结构的BaVS3电子结构进行计算,接着采用线性响应的密度泛函微扰理论研究了BaVS3化合物的晶格动力学性质以及热力学性质.获得了自力常数、原子间力常数以及定容比热.     

Electron tomography at 2.4-ångström resolution

Transmission electron microscopy is a powerful imaging tool that has found broad application in materials science, nanoscience and biology. With the introduction of aberration-corrected electron lenses, both the spatial resolution and the image quality in transmission electron microscopy have been significantly improved and resolution below 0.5??ngstr?ms has been demonstrated. To reveal the three-dimensional (3D) structure of thin samples, electron tomography is the method of choice, with cubic-nanometre resolution currently achievable. Discrete tomography has recently been used to generate a 3D atomic reconstruction of a silver nanoparticle two to three nanometres in diameter, but this statistical method assumes prior knowledge of the particle's lattice structure and requires that the atoms fit rigidly on that lattice. Here we report the experimental demonstration of a general electron tomography method that achieves atomic-scale resolution without initial assumptions about the sample structure. By combining a novel projection alignment and tomographic reconstruction method with scanning transmission electron microscopy, we have determined the 3D structure of an approximately ten-nanometre gold nanoparticle at 2.4-?ngstr?m resolution. Although we cannot definitively locate all of the atoms inside the nanoparticle, individual atoms are observed in some regions of the particle and several grains are identified in three dimensions. The 3D surface morphology and internal lattice structure revealed are consistent with a distorted icosahedral multiply twinned particle. We anticipate that this general method can be applied not only to determine the 3D structure of nanomaterials at atomic-scale resolution, but also to improve the spatial resolution and image quality in other tomography fields.     

First-principles calculation of crystalline materials genome: a preliminary study

The US President Obama launched the Materials Genome Initiative on June 24,2011,aimed at speeding up the pace of discovering,developing,manufacturing,and deploying advanced materials by at least twice as fast as is possible at present,at a fraction of the cost with the help of existing advanced computer technology.According to the authors’understanding to the event,this article will first give a brief discussion on the origin of material genome,its scientific implication,research significance,and the far-reaching influence of materials genome study to the developments of materials science and human society.Then,the subsequent contents will introduce the research progresses of the related works carried out by the authors’research group over the last decade,on the first-principles studies of crystalline materials genome.The highlights are focused on the method implementations for configuration optimization of lattice structure,first-principles calculations of various physical parameters on elastic,electronic,dielectric,and thermodynamic properties,and simulations of phase transition and particle transport in solids.The technical details for extending these methods to low-dimensional crystalline materials are also discussed.The article concludes with an outlook on the prospect of materials genome research.     

Atomic-scale imaging of nanoengineered oxygen vacancy profiles in SrTiO3

At the heart of modern oxide chemistry lies the recognition that beneficial (as well as deleterious) materials properties can be obtained by deliberate deviations of oxygen atom occupancy from the ideal stoichiometry. Conversely, the capability to control and confine oxygen vacancies will be important to realize the full potential of perovskite ferroelectric materials, varistors and field-effect devices. In transition metal oxides, oxygen vacancies are generally electron donors, and in strontium titanate (SrTiO3) thin films, oxygen vacancies (unlike impurity dopants) are particularly important because they tend to retain high carrier mobilities, even at high carrier densities. Here we report the successful fabrication, using a pulsed laser deposition technique, of SrTiO3 superlattice films with oxygen doping profiles that exhibit subnanometre abruptness. We profile the vacancy concentrations on an atomic scale using annular-dark-field electron microscopy and core-level spectroscopy, and demonstrate absolute detection sensitivities of one to four oxygen vacancies. Our findings open a pathway to the microscopic study of individual vacancies and their clustering, not only in oxides, but in crystalline materials more generally.     

Effect of rare earth elements on the structures and mechanical properties of magnesium alloys

By means of first-principles calculations,we have investigated the effects of rare earth elements (REEs) on the structures and mechanical properties of magnesium.The lattice parameters,elastic constants,bulk moduli,shear moduli,Young’s moduli and anisotropic parameter of these solid solutions have been calculated and analyzed.The nearest-neighbor distance between Mg and the REEs is also analyzed to explore the correlation with the bulk moduli.The results show that the 4f-electrons and atomic radii play an important role in the strengthening process.The anomalies of the lattice parameters and mechanical properties at Eu and Yb are due to the half-filled and full-filled 4f-electron orbital states.Finally,the increase of directional bonding character near the alloying elements may account for the anisotropy and brittleness of these magnesium alloys.     

LiCoO2的体态几何与电子结构的理论研究

采用基于局域密度泛函理论和第一性原理赝势法，选择GGA交换关联势，使用自洽投影缀加平面波方法，对锂离子电池正极材料LiCO2的原子几何结构与电子结构进行了理论研究．给出了其结构——总体态密度与分波态密度、电荷密度分布以及能带结构等，并对三种超晶胞模型进行了简要对比研究,计算结果表明：三种模型在计算上是等价的；完全驰豫后所得的晶体结构、晶格常数、电子结构及能带结构等都与其他方法的计算结果以及实验值符合良好。     

Bi,Se和Te吸附n/p型石墨烯电子结构研究

本文采用基于密度泛函理论的第一性原理方法研究了Bi,Se,Te在缺陷(单空位,B掺杂和N掺杂)石墨烯上的吸附结构及电子和磁性质.研究表明:在能量稳定的Bi(Se)/石墨烯吸附体系中,Bi吸附诱导产生磁性;在空位缺陷石墨烯上的吸附会改变费米能级处态密度分布,影响体系的导电性质;在B(N)掺杂吸附体系中,B比N对吸附原子的影响大;除Se在B掺杂石墨烯上吸附外,Bi,Se,Te在其它n/p型掺杂吸附体系中均显示磁性.缺陷增强了Bi,Se,Te与石墨烯之间的相互作用,对吸附体系的电子结构和电荷分布有较大的影响.     

Three-dimensional mapping of a deformation field inside a nanocrystal

Coherent X-ray diffraction imaging is a rapidly advancing form of microscopy: diffraction patterns, measured using the latest third-generation synchrotron radiation sources, can be inverted to obtain full three-dimensional images of the interior density within nanocrystals. Diffraction from an ideal crystal lattice results in an identical copy of this continuous diffraction pattern at every Bragg peak. This symmetry is broken by the presence of strain fields, which arise from the epitaxial contact forces that are inevitable whenever nanocrystals are prepared on a substrate. When strain is present, the diffraction copies at different Bragg peaks are no longer identical and contain additional information, appearing as broken local inversion symmetry about each Bragg point. Here we show that one such pattern can nevertheless be inverted to obtain a 'complex' crystal density, whose phase encodes a projection of the lattice deformation. A lead nanocrystal was crystallized in ultrahigh vacuum from a droplet on a silica substrate and equilibrated close to its melting point. A three-dimensional image of the density, obtained by inversion of the coherent X-ray diffraction, shows the expected facetted morphology, but in addition reveals a real-space phase that is consistent with the three-dimensional evolution of a deformation field arising from interfacial contact forces. Quantitative three-dimensional imaging of lattice strain on the nanometre scale will have profound consequences for our fundamental understanding of grain interactions and defects in crystalline materials. Our method of measuring and inverting diffraction patterns from nanocrystals represents a vital step towards the ultimate goal of atomic resolution single-molecule imaging that is a prominent justification for development of X-ray free-electron lasers.     

Cr原子链的几何结构与电子性质研究

基于第一性原理方法研究Cr原子链可能形成的几何结构与电子性质.计算表明:Cr原子链可形成线性型、二聚化型、平面之字型和梯型等一维原子链.梯型结构的原子链结合能最大,稳定性最好,二聚化型结构次之,然后是大角度的之字型结构、小角度的之字型结构,线性结构的结合能最小.其中二聚化结构原子链的能带表现出间接带隙的特征,大角度之字型结构原子链为半金属性,小角度之字型结构原子链的能带则表现为较强的金属性.同时还讨论了这些结构的相对稳定性以及各链式结构的电子能带、电荷密度等性质.     

Tix-Nb1-x合金结构及弹性性质的第一性原理研究

本文基于密度泛函理论的第一性原理计算方法详细地计算了高温高压下不同铌含量对Tix-Nb1-x (x=0, 025, 05, 075,1)二元合金的能量和结构的影响。结果表明,零温零压下不同铌含量下的三种稳定的合金组成结构分别为六角密堆结构Nb025Ti075,体心立方结构 Nb05Ti05和体心立方结构Nb075Ti025,所得的稳定的合金结构晶格参数与相关的实验值和理论值符合的很好。这样, 分别计算了在压强60GPa范围内的稳定的合金结构的弹性性质和弹性模量。     

Si在Au(111)面的电子结构和光学性质的第一性原理研究

基于第一性原理,对Si原子在Au(111)表面和体内掺杂的电子结构和光学性质进行了比较研究。结果表明,在Au(111)体内掺杂时,Si原子与周围六个Au原子成键,p电子更局域。电荷密度分析表明,掺杂Si后,Au原子周围的电子密度明显减少,而SiAu原子之间的电子密度明显增加,电子由Au原子向SiAu原子之间转移。通过计算Mul-liken键级表明,SiAu原子之间形成共价键,表面掺杂时的SiAu键级比体内大。吸收谱的计算表明,在体内掺杂Si原子时的吸收谱明显增强。     

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.     

Half-metallic graphene nanoribbons

Electrical current can be completely spin polarized in a class of materials known as half-metals, as a result of the coexistence of metallic nature for electrons with one spin orientation and insulating nature for electrons with the other. Such asymmetric electronic states for the different spins have been predicted for some ferromagnetic metals--for example, the Heusler compounds--and were first observed in a manganese perovskite. In view of the potential for use of this property in realizing spin-based electronics, substantial efforts have been made to search for half-metallic materials. However, organic materials have hardly been investigated in this context even though carbon-based nanostructures hold significant promise for future electronic devices. Here we predict half-metallicity in nanometre-scale graphene ribbons by using first-principles calculations. We show that this phenomenon is realizable if in-plane homogeneous electric fields are applied across the zigzag-shaped edges of the graphene nanoribbons, and that their magnetic properties can be controlled by the external electric fields. The results are not only of scientific interest in the interplay between electric fields and electronic spin degree of freedom in solids but may also open a new path to explore spintronics at the nanometre scale, based on graphene.