Experimental measurements and theoretical calculations of the atomic structure of materials with subangstrom resolution and picometer precision

Lattice defects are unavoidable structural units in materials and play an important role in determining material properties. Compared with the periodic structure of crystals, the atomic configurations of the lattice defects are determined by the coordinates of a large number of atoms, making it difficult to experimentally investigate them. In computational materials science, multiparameter optimization is also a difficult problem and experimental verification is usually required to determine the possibility of obtaining the structure and properties predicted by cal- culations. Using our recent studies on oxide surfaces as examples, we introduce the method of integrated aberra- tion-corrected electron microscopy and the first-principles calculations to analyze the atomic structure of lattice defects. The atomic configurations of defects were mea- sured using quantitative high-resolution electron micros- copy at subangstrom resolution and picometer precision, and then the electronic structure and dynamic behavior of materials can be studied at the atomic scale using the first- principles calculations. The two methods complement each other and can be combined to increase the understanding of the atomic structure of materials in both the time and space dimensions, which will benefit materials design at the atomic scale.     

半氟化的石墨片电子和磁特性

通过密度泛函理论研究了半氟化石墨片的电子结构和磁性特点,结果发现它是带隙约为1.00 eV的反铁磁间接带隙半导体。由于氟原子对被氟化的碳原子的吸引作用,被氟化的碳原子与未氟化的碳原子分属于两个不同平面,面间距离达到0.286,C-C键长也增加到1.501。通过半氟化,实现了材料由无磁性向反铁磁的转变,并打开了带隙,这预示着在未来的纳米功能材料中可能的应用。     

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.     

Chemical identification of individual surface atoms by atomic force microscopy

Scanning probe microscopy is a versatile and powerful method that uses sharp tips to image, measure and manipulate matter at surfaces with atomic resolution. At cryogenic temperatures, scanning probe microscopy can even provide electron tunnelling spectra that serve as fingerprints of the vibrational properties of adsorbed molecules and of the electronic properties of magnetic impurity atoms, thereby allowing chemical identification. But in many instances, and particularly for insulating systems, determining the exact chemical composition of surfaces or nanostructures remains a considerable challenge. In principle, dynamic force microscopy should make it possible to overcome this problem: it can image insulator, semiconductor and metal surfaces with true atomic resolution, by detecting and precisely measuring the short-range forces that arise with the onset of chemical bonding between the tip and surface atoms and that depend sensitively on the chemical identity of the atoms involved. Here we report precise measurements of such short-range chemical forces, and show that their dependence on the force microscope tip used can be overcome through a normalization procedure. This allows us to use the chemical force measurements as the basis for atomic recognition, even at room temperature. We illustrate the performance of this approach by imaging the surface of a particularly challenging alloy system and successfully identifying the three constituent atomic species silicon, tin and lead, even though these exhibit very similar chemical properties and identical surface position preferences that render any discrimination attempt based on topographic measurements impossible.     

Grains and grain boundaries in single-layer graphene atomic patchwork quilts

The properties of polycrystalline materials are often dominated by the size of their grains and by the atomic structure of their grain boundaries. These effects should be especially pronounced in two-dimensional materials, where even a line defect can divide and disrupt a crystal. These issues take on practical significance in graphene, which is a hexagonal, two-dimensional crystal of carbon atoms. Single-atom-thick graphene sheets can now be produced by chemical vapour deposition on scales of up to metres, making their polycrystallinity almost unavoidable. Theoretically, graphene grain boundaries are predicted to have distinct electronic, magnetic, chemical and mechanical properties that strongly depend on their atomic arrangement. Yet because of the five-order-of-magnitude size difference between grains and the atoms at grain boundaries, few experiments have fully explored the graphene grain structure. Here we use a combination of old and new transmission electron microscopy techniques to bridge these length scales. Using atomic-resolution imaging, we determine the location and identity of every atom at a grain boundary and find that different grains stitch together predominantly through pentagon-heptagon pairs. Rather than individually imaging the several billion atoms in each grain, we use diffraction-filtered imaging to rapidly map the location, orientation and shape of several hundred grains and boundaries, where only a handful have been previously reported. The resulting images reveal an unexpectedly small and intricate patchwork of grains connected by tilt boundaries. By correlating grain imaging with scanning probe and transport measurements, we show that these grain boundaries severely weaken the mechanical strength of graphene membranes but do not as drastically alter their electrical properties. These techniques open a new window for studies on the structure, properties and control of grains and grain boundaries in graphene and other two-dimensional materials.     

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.     

高分辨率电子能量损失谱在半导体表面研究中的应用

低能电子与半导体表面的相互作用能激发带间电子跃迁和（或）表面振动,因而对背散射电子能量分布的高分辨率测量可望给出与这些激发相关的丰富信息,近年来的实验研究证实,进行这样的电子能量损失测量确能从各种不同半导体得到的诸发禁带宽度,表面电子态的能量,表面光学声子的特性,表面原子的成键方式,表面反应的产物等许多有关表面原子和电子结构的重要参数。     

量子化学从头计算法计算石墨微晶中碳原子的净电荷

采用从头计算法在RHF/STO-3G水平上对石墨微晶中不同位置碳原子的净电荷进行量化计算;研究碳原子的净电荷与炭材料的微观结构变化规律;根据石墨的结构与成键特征,将石墨表面的碳原子分为边缘碳原子与基平面碳原子.研究结果表明：在单碳层及含多层碳的石墨微晶中,不同位置碳原子的净电荷数差别较大;基平面碳原子的电子云密度较小,均带部分正电荷;部分边缘碳原子的电子云密度较大,净电荷为负.随着平行于碳层的微晶尺寸La及垂直于碳层的微晶尺寸Lc的增大,边缘碳原子中电子云密度最大的碳原子所带的负电荷增加.     

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.     

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.     

Orientation of molecular interface dipole on metal surface investigated by noncontact atomic force microscopy

We investigated the orientations of interface dipole moments of individual non-planar titanyl phthalocyanine(TiOPc)molecules on Cu(111)and Cu(100)substrates using scanning tunneling microscope(STM)and noncontact atomic force microscope(NC-AFM).The dipole moment orientations corresponding to two different configurations of individual TiOPc molecules were determined unambiguously.The correlation between the actual molecular structures and the corresponding STM topographies is proposed based on the sub-molecular resolution imaging and local contact potential difference(LCPD)measurements.Comparing with the pristine substrate,the LCPD shift due to the adsorption of non-planar molecule is dependent on the permanent molecular dipole,the charge transfer between the surface and the molecule,and the molecular configurations.This work would shed light on tailoring interfacial electronic properties and controlling local physical properties via polar molecule adsorption.     

Functionalized graphene oxide based on p-phenylenediamine as spacers and nitrogen dopants for high performance supercapacitors

p-Phenylenediamine （PPD） functionalized graphene oxide （GO） materials （PPDG） were prepared through a one-step solvothermal process and their appli-cation as supercapacitors （SCs） were studied. The PPD is not only as the spacers to prevent aggregating and re-stacking of the graphene sheets in the preparing process but also as nitrogen sources to obtain the nitrogen-doped graphene. The structures of PPDG were characterized by Fourier transformed infrared spectroscopy （FT-IR）, X-ray diffraction spectroscopy （XRD）, Raman spectroscopy and X-ray photoelectron spectroscopy （XPS） and the results show that the nitrogen-doped graphene was achieved with nitrogen content as high as 10.85 at.%. The field emission scanning electron microscopy （FE-SEM） and high resolu-tion transmission electron microscopy （HR-TEM） have confirmed that the morphologies of PPDG were looselayered with less aggregation, indicating that PPD mole-cules, as spacers, effectively prevent the graphene sheets from restacking during the solvothermal reaction. The special loose textures make PPDG materials exhibit excellent electrochemical performance for symmetric SCs with superior specific capacitance （313 F/g at 0.1 A/g）, rate capability and cycling stability. The present synthesis method is convenient and may have potential applications as ultrahigh performance SCs.     

Three-dimensional atomic imaging of crystalline nanoparticles

Determining the three-dimensional (3D) arrangement of atoms in crystalline nanoparticles is important for nanometre-scale device engineering and also for applications involving nanoparticles, such as optoelectronics or catalysis. A nanoparticle's physical and chemical properties are controlled by its exact 3D morphology, structure and composition. Electron tomography enables the recovery of the shape of a nanoparticle from a series of projection images. Although atomic-resolution electron microscopy has been feasible for nearly four decades, neither electron tomography nor any other experimental technique has yet demonstrated atomic resolution in three dimensions. Here we report the 3D reconstruction of a complex crystalline nanoparticle at atomic resolution. To achieve this, we combined aberration-corrected scanning transmission electron microscopy, statistical parameter estimation theory and discrete tomography. Unlike conventional electron tomography, only two images of the target--a silver nanoparticle embedded in an aluminium matrix--are sufficient for the reconstruction when combined with available knowledge about the particle's crystallographic structure. Additional projections confirm the reliability of the result. The results we present help close the gap between the atomic resolution achievable in two-dimensional electron micrographs and the coarser resolution that has hitherto been obtained by conventional electron tomography.     

合成硼,碳,氮体系化合物功能薄膜的结构性质

为探讨合成硼、碳、氮体系化合物功能薄膜结构性质，综合评述了Ｘ射线、电子衍射、高分辨电镜分析、红外光谱、拉曼光谱，以及俄歇电子谱和Ｘ射线光电子谱等方法对氮化硼、氮化碳和硼碳氮薄膜材料的结构性质的检测结果，指出以采用多种方法复合测定为宜；相互补充的成分、结构、特性等信息，会有助于薄膜结构研究的深化。     

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．     

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.     

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.     

Imaging and dynamics of light atoms and molecules on graphene

Observing the individual building blocks of matter is one of the primary goals of microscopy. The invention of the scanning tunnelling microscope revolutionized experimental surface science in that atomic-scale features on a solid-state surface could finally be readily imaged. However, scanning tunnelling microscopy has limited applicability due to restrictions in, for example, sample conductivity, cleanliness, and data acquisition rate. An older microscopy technique, that of transmission electron microscopy (TEM), has benefited tremendously in recent years from subtle instrumentation advances, and individual heavy (high-atomic-number) atoms can now be detected by TEM even when embedded within a semiconductor material. But detecting an individual low-atomic-number atom, for example carbon or even hydrogen, is still extremely challenging, if not impossible, via conventional TEM owing to the very low contrast of light elements. Here we demonstrate a means to observe, by conventional TEM, even the smallest atoms and molecules: on a clean single-layer graphene membrane, adsorbates such as atomic hydrogen and carbon can be seen as if they were suspended in free space. We directly image such individual adatoms, along with carbon chains and vacancies, and investigate their dynamics in real time. These techniques open a way to reveal dynamics of more complex chemical reactions or identify the atomic-scale structure of unknown adsorbates. In addition, the study of atomic-scale defects in graphene may provide insights for nanoelectronic applications of this interesting material.     

硼化氮-石墨烯杂化单原子层电学性质的第一原理

利用基于密度泛函理论的第一原理方法研究二维六方硼化氮片（h-BN） 石墨烯杂化单原子层的电学性质. 结果表明: 三角形h-BN嵌入石墨烯中或三角形石墨烯片嵌入二维h-BN中均会在能带结构导带和价带中间引入带间态, 带间态的形态与杂化方式有关; 半导体性与导体性质可相互转变, 即该杂化结构的电子结构可通过不同杂化形式调制.