Atomic‐Scale Mechanism of Unidirectional Oxide Growth

A fundamental knowledge of the unidirectional growth mechanisms is required for precise control on size, shape, and thereby functionalities of nanostructures. The oxidation of many metals results in oxide nanowire growth with a bicrystal grain boundary along the axial direction. Using transmission electron microscopy that spatially and temporally resolves CuO nanowire growth during the oxidation of copper, herein, direct evidence of the correlation between unidirectional crystal growth and bicrystal grain boundary diffusion is provided. Based on atomic scale observations of the upward growth at the nanowire tip, oscillatory downward growth of atomic layers on the nanowire sidewall and the parabolic kinetics of lengthening, it is shown that bicrystal grain boundary diffusion is the mechanism by which Cu ions are delivered from the nanowire root to the tip. Together with density‐functional theory calculations, it is further shown that the asymmetry in the corner‐crossing barriers promotes the unidirectional oxide growth by hindering the transport of Cu ions from the nanowire tip to the sidewall facets. The broader applicability of these results in manipulating the growth of nanostructured oxides by controlling the bicrystal grain boundary structure that favors anisotropic diffusion for unidirectional, 1D crystal growth for nanowires or isotropic diffusion for 2D platelet growth is expected.     

Novel Nanorod Precipitate Formation in Neodymium and Titanium Codoped Bismuth Ferrite

The discovery of unusual nanorod precipitates in bismuth ferrite doped with Nd and Ti is reported. The atomic structure and chemistry of the nanorods are determined using a combination of high angle annular dark field imaging, electron energy loss spectroscopy, and density functional calculations. It is found that the structure of the BiFeO₃ matrix is strongly modified adjacent to the precipitates; the readiness of BiFeO₃ to adopt different structural allotropes in turn explains why such a large axial ratio, uncommon in precipitates, is stabilized. In addition, a correlation is found between the alignment of the rods and the orientation of ferroelastic domains in the matrix, which is consistent with the system's attempt to minimize its internal strain. Density functional calculations indicate a finite density of electronic states at the Fermi energy within the rods, suggesting enhanced electrical conductivity along the rod axes, and motivating future investigations of nanorod functionalities.     

石墨烯带长度变化与电子结构和电子输运的关系

利用基于非平衡格林函数的密度泛函方法,对长度变化石墨烯带的电子结构和输运特性进行了研究,得出在同一长度的石墨烯带内,系统态密度的峰值与电子传输概率的峰值具有较好的对应关系,但是电子传输概率的大小与电子态密度值的大小没有明显的正比关系。随着长度的增加,电子的传输更倾向于集中在某几个能量态,传输曲线呈现梳齿状,这是由于石墨烯带越长,电子态呈现越稳定的分布。研究还得出不同长度的石墨烯带的电导值和HOM O-LUM O差值成反比,且随着石墨烯带长度增大,其电导出现非线性变化,且呈现规则的振荡状态。     

Revealing the Atomic Defects of WS2 Governing Its Distinct Optical Emissions

Defects and their spatial distribution are crucial factors in controlling the electronic and optical properties of semiconductors. By using scanning transmission electron microscopy and electron energy loss spectroscopy, the type of impurities/defects in WS₂ subdomains with different optical properties is successfully assigned. A higher population of Cr impurities is found in the W‐terminated edge domain, while the S‐terminated domain contains more Fe impurities, in accordance with the luminescence characteristics of chemical‐vapor‐grown WS₂ of a hexagonal shape. In agreement with the first‐principles calculations, the domains with Cr substitutional dopants exhibit strong trion emission. Fe atoms tend to gather into trimer configuration and introduce deep acceptor levels which compensate the n‐type doping and suppress trion emission. It is also discovered that the domain with higher luminescence but smaller defect concentration tends to get oxidized more rapidly and degrade the 2D structure with many triangular holes. Excitons tend to accumulate at the edges of the oxidized triangular holes and results in enhanced PL emission. The findings indicate that choosing stable elements as dopant and controlling the number of specific edge structures within a crystal domain of 2D transitional metal dichalcogenides can be a new route to improve the optical properties of these materials.     

Process Pathway Controlled Evolution of Phase and Van‐der‐Waals Epitaxy in In/In2O3 on Graphene Heterostructures

Many applications of 2D materials require deposition of non‐2D metals and metal‐oxides onto the 2D materials. Little is however known about the mechanisms of such non‐2D/2D interfacing, particularly at the atomic scale. Here, atomically resolved scanning transmission electron microscopy (STEM) is used to follow the entire physical vapor deposition (PVD) cycle of application‐relevant non‐2D In/In₂O₃ nanostructures on graphene. First, a “quasi‐in‐situ” approach with indium being in situ evaporated onto graphene in oxygen‐/water‐free ultra‐high‐vacuum (UHV) is employed, followed by STEM imaging without vacuum break and then repeated controlled ambient air exposures and reloading into STEM. This allows stepwise monitoring of the oxidation of specific In particles toward In₂O₃ on graphene. This is then compared with conventional, scalable ex situ In PVD onto graphene in high vacuum (HV) with significant residual oxygen/water traces. The data shows that the process pathway difference of oxygen/water feeding between UHV/ambient and HV fabrication drastically impacts not only non‐2D In/In₂O₃ phase evolution but also In₂O₃/graphene out‐of‐plane texture and in‐plane rotational van‐der‐Waals epitaxy. Since non‐2D/2D heterostructures' properties are intimately linked to their structure and since influences like oxygen/water traces are often hard to control in scalable fabrication, this is a key finding for non‐2D/2D integration process design.     

Boosting the Electrical Double‐Layer Capacitance of Graphene by Self‐Doped Defects through Ball‐Milling

Improving the capacitance of carbon materials for supercapacitors without sacrificing their rate performance, especially volumetric capacitance at high mass loadings, is a big challenge because of the limited assessable surface area and sluggish electrochemical kinetics of the pseudocapacitive reactions. Here, it is demonstrated that “self‐doping” defects in carbon materials can contribute to additional capacitance with an electrical double‐layer behavior, thus promoting a significant increase in the specific capacitance. As an exemplification, a novel defect‐enriched graphene block with a low specific surface area of 29.7 m² g^?1 and high packing density of 0.917 g cm^?3 performs high gravimetric, volumetric, and areal capacitances of 235 F g^?1, 215 F cm^?3, and 3.95 F cm^?2 (mass loading of 22 mg cm^?2) at 1 A g^?1, respectively, as well as outstanding rate performance. The resulting specific areal capacitance reaches an ultrahigh value of 7.91 F m^?2 including a “self‐doping” defect contribution of 4.81 F m^?2, which is dramatically higher than the theoretical capacitance of graphene (0.21 F m^?2) and most of the reported carbon‐based materials. Therefore, the defect engineering route broadens the avenue to further improve the capacitive performance of carbon materials, especially for compact energy storage under limited surface areas.     

Impact of Bonding on the Stacking Defects in Layered Chalcogenides

Phase‐change materials for high‐density data storage traditionally exploit the amorphous‐to‐crystalline phase transition. A number of these compounds are organized in blocks, separated by van der Waals‐like gaps. Such layered chalcogenides are attracting interest due to their unique material properties and the possibility to change their properties upon local rearrangements at the gap, giving rise to novel applications. To better understand the behavior of layered chalcogenides, the connection between structural defects, physical properties, and the bonding situation is highlighted here using electron microscopy, X‐ray diffraction, and density functional theory. In particular, stacking defects in hexagonal Ge₄Se₃Te, GaSe, and Sb₂Te₃ are characterized experimentally, followed by an investigation of the influence of observed and hypothetical stacking defects on optical and electronic properties by theoretical means. Then, a connection between observed defects and the bonding situation in these materials is drawn and related to the presence of van der Waals and metavalent bonding in chalcogenides. Finally, additional experiments are performed to validate the conclusions for other metavalently bonded layered chalcogenides. Transmission electron microscopy provides a powerful tool for direct detection of defects and, when combined with diffraction experiments and ab initio theory, it facilitates the precise investigation of the bonding mechanisms in layered chalcogenides.     

Atomic‐Scale Imaging and Quantification of Electrical Polarisation in Incommensurate Antiferroelectric Lanthanum‐Doped Lead Zirconate Titanate

Lanthanum doping of zirconium rich lead zirconate titanate gives rise to incommensurate, long‐period antiferroelectric structures. The structure of two stacking sequences in this incommensurate phase is determined using quantitative analysis of high‐resolution scanning transmission electron microscopy images, with the lead atom positions located with an exceptional precision of about 6 pm. This allows the estimation of local polarisation variations across the stacking units, and the polarisation varies in an approximately sinusoidal fashion along the stacking direction. The measured peak Pb atom displacements of about 28 pm and peak polarisation values of about 60 μC cm^?2 match extremely well to reported values for the commensurate antiferroelectric PbZrO₃ phase.     

Structural Changes of 2D FexMn1−xO2 Nanosheets for Low‐Temperature Growth of Carbon Nanotubes

The synthesis of carbon nanotubes (CNTs) is usually done by metallic catalysts with a gaseous carbon precursor at high temperature. Yet, mild synthesis conditions can broaden the application of CNTs and their composites. In the present work, it is unraveled why partially substituted Fe ions in 2D MnO₂ nanosheets lead to the growth of CNTs at low temperatures of 400?500 °C. The local formation of Fe₃C by carbon precursor explains the unusually high catalytic activity of 2D Fe_xMn_1?xO₂ nanosheets for preparing CNTs. Finally, Fe₃C is oxidized to Fe₃C/FeO_x yolk/shell morphology in ambient atmosphere after the CNT formation reaction. These results shed light on the development of novel catalyst materials that allow for efficiently prepare CNTs under mild conditions for their wider use in energy‐harvesting applications.     

Modification of the Gallium‐Doped Zinc Oxide Surface with Self‐Assembled Monolayers of Phosphonic Acids: A Joint Theoretical and Experimental Study

Gallium‐doped zinc oxide (GZO) surfaces, both bare and modified with chemisorbed phosphonic acid (PA) molecules, are studied using a combination of density functional theory calculations and ultraviolet and X‐ray photoelectron spectroscopy measurements. Excellent agreement between theory and experiment is obtained, which leads to an understanding of: i) the core‐level binding energy shifts of the various oxygen atoms belonging to different surface sites and to the phosphonic acid molecules; ii) the GZO work‐function change upon surface modification, and; iii) the energy level alignments of the frontier molecular orbitals of the PA molecules with respect to the valence band edge and Fermi level of the GZO surface. Importantly, both density of states calculations and experimental measurements of the valence band features demonstrate an increase in the density of states and changes in the characteristics of the valence band edge of GZO upon deposition of the phosphonic acid molecules. The new valence band features are associated with contributions from surface oxygen atoms near a defect site on the oxide surface and from the highest occupied molecular orbitals of the phosphonic acid molecules.     

New Apatite‐Type Oxide Ion Conductor,Bi2La8[(GeO4)6]O3: Structure,Properties, and Direct Imaging of Low‐Level Interstitial Oxygen Atoms Using Aberration‐Corrected Scanning Transmission Electron Microscopy

The new solid electrolyte Bi₂La₈[(GeO₄)₆]O₃ is prepared and characterized by variable‐temperature synchrotron X‐ray and neutron diffraction, aberration‐corrected scanning transmission electron microscopy, and physical property measurements (impedance spectroscopy and second harmonic generation). The material is a triclinic variant of the apatite structure type and owes its ionic conductivity to the presence of oxide ion interstitials. A combination of annular bright‐field scanning transmission electron microscopy experiments and frozen‐phonon multislice simulations enables direct imaging of the crucial interstitial oxygen atoms present at a level of 8 out of 1030 electrons per formula unit of the material, and crystallographically disordered, in the unit cell. Scanning transmission electron microscopy also leads to a direct observation of the local departures from the centrosymmetric average structure determined by diffraction. As no second harmonic generation signal is observed, these displacements are non‐cooperative on the longer length scales probed by optical methods.     

The Exfoliation of Graphene in Liquids by Electrochemical,Chemical, and Sonication‐Assisted Techniques: A Nanoscale Study

The different exfoliation routes of graphite to produce graphene by sonication in solvent, chemical oxidation and electrochemical oxidation are compared. The exfoliation process and roughening of a flat graphite substrate is directly visualized at the nanoscale by scanning probe and electron microscopy. The etching damage in graphite and the properties of the exfoliated sheets are compared by Raman spectroscopy and X‐ray diffraction analysis. The results show the trade‐off between exfoliation speed and preservation of graphene quality. A key step to achieve efficient exfoliation is to couple gas production and mechanical exfoliation on a macroscale with non‐covalent exfoliation and preservation of graphene properties on a molecular scale.     

Wetting‐Assisted Crack‐ and Wrinkle‐Free Transfer of Wafer‐Scale Graphene onto Arbitrary Substrates over a Wide Range of Surface Energies

The polymer‐supported wet transfer of chemical vapor deposition‐grown graphene provides high‐quality large‐area graphene on a target substrate. The transfer‐induced defects that result from these processes, such as micrometer‐scale folds and cracks, have been regarded as an inevitable problem. Here, the transfer processes are thoroughly examined stage‐by‐stage and it is found that lamination wrinkles, which cause defects in the graphene, are generated as a result of the high contact angles of the trapped transfer medium liquids. Systematic theoretical and experimental studies demonstrate that a liquid droplet with a low surface tension trapped between the polymer/graphene film and the substrate minimizes lamination wrinkles during the transfer process by completely wetting the target substrate, regardless of the surface energy. In connection with these results, a simple and broadly applicable transfer method is developed using an organic liquid with a low surface tension to uniformly transfer high‐quality graphene onto arbitrary substrates, even onto superhydrophobic substrate. The graphene obtained using the proposed organic liquid transfer method displays better electrical and mechanical properties than the graphene transferred by the conventional method using water. This effective and practical transfer method provides an approach to obtaining high‐quality graphene for use in graphene‐based devices.     

Probing Functional Structures,Defects, and Interfaces of 2D Transition Metal Dichalcogenides by Electron Microscopy

2D transition metal dichalcogenides (TMDs) exhibit remarkable properties that are strongly influenced by their atomic structures, as well as by various types of defects and interfaces that can be precisely engineered and controlled. These features make 2D TMDs and TMD-based materials highly promising for a wide range of applications in electronics, optoelectronics, magnetism, spintronics, catalysis, energy, etc. By providing a comprehensive approach to understand the structure–property–functionality relationship in materials at the atomic scale, electron microscopy, and spectroscopy techniques have emerged as invaluable tools for studying both the static characteristics and dynamic evolutions of 2D TMDs. In this review, the primary focus lies in exploring intrinsic and artificial structures in TMDs and their heterostructures, along with their corresponding properties, through cutting-edge aberration-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS). Additionally, recent advancements in the field of in situ visualization and manipulation of 2D TMDs using electron beams are highlighted. It is anticipated that the up-to-date overview provided, along with a glimpse into the future development of STEM-based techniques, will make a substantial contribution to advancing research on 2D materials.     

Probing Local Electronic Transitions in Organic Semiconductors through Energy‐Loss Spectrum Imaging in the Transmission Electron Microscope

Improving the performance of organic electronic devices depends on exploiting the complex nanostructures formed in the active layer. Current imaging methods based on transmission electron microscopy provide limited chemical sensitivity, and thus the application to materials with compositionally similar phases or complicated multicomponent systems is challenging. Here, it is demonstrated that monochromated transmission electron microscopes can generate contrast in organic thin films based on differences in the valence electronic structure at energy losses below 10 eV. In this energy range, electronic fingerprints corresponding to interband excitations in organic semiconductors can be utilized to generate significant spectral contrast between phases. Based on differences in chemical bonding of organic materials, high‐contrast images are thus obtained revealing the phase separation in polymer/fullerene mixtures. By applying principal component analysis to the spectroscopic image series, further details about phase compositions and local electronic transitions in the active layer of organic semiconductor mixtures can be explored.     

Surface Reduced Manganese States as a Source of Oxygen Reduction Activity in BaMnO3

In relation to perovskites, tweaking the oxidation state of the B-site cation is fundamental to controlling the catalytic activity of these materials, thus necessitating a complete characterization of surface oxidation states. Herein, using a combination of atomic-scale imaging and spectroscopic techniques, structure-property correlation in barium manganese oxide (BaMnO₃) is established for the oxygen reduction reaction (ORR). Electron energy loss spectroscopy (EELS) on the synthesized BaMnO₃ find the rods to contain an amorphous surface layer with reduced Mn³⁺ states compared to Mn⁴⁺ states in the bulk. Consequently, the BaMnO₃ rods show electrocatalytic activity for the ORR, which originates from the presence of Mn³⁺ at the rod surface. Furthermore, heating of the samples in air at 300 and 800 °C results in a decrease in the number of Mn³⁺ states, and thus lowering of the ORR activity. This study represents a step-stone study in understanding the mechanism of ORR activity and its association to the Mn³⁺ state at the perovskite's surface, opening up possibilities for further surface engineering and tuning catalytic properties.