Hexagonal Hybrid Bismuthene by Molecular Interface Engineering.

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of "electronic grade" structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.

Combining Freestanding Ferroelectric Perovskite Oxides with Two-Dimensional Semiconductors for High Performance Transistors.

We demonstrate the fabrication of field-effect transistors based on single-layer MoS2 and a thin layer of BaTiO3 (BTO) dielectric, isolated from its parent epitaxial template substrate. Thin BTO provides an ultrahigh-κ gate dielectric effectively screening Coulomb scattering centers. These devices show mobilities substantially larger than those obtained with standard SiO2 dielectrics and comparable with values obtained with hexagonal boron nitride, a dielectric employed for fabrication of high-performance two-dimensional (2D) based devices. Moreover, the ferroelectric character of BTO induces a robust hysteresis of the current vs gate voltage characteristics, attributed to its polarization switching. This hysteresis is strongly suppressed when the device is warmed up above the tetragonal-to-cubic transition temperature of BTO that leads to a ferroelectric-to-paraelectric transition. This hysteretic behavior is attractive for applications in memory storage devices. Our results open the door to the integration of a large family of complex oxides exhibiting strongly correlated physics in 2D-based devices.

Atomistic Origin of Li-Ion Conductivity Reduction at (Li3xLa2/3-x)TiO3 Grain Boundary.

Lithium lanthanum titanate (LLTO) is one of the excellent candidates for an electrolyte in the all-solid-state Li-ion battery, owing to the high Li-ion conductivity in the bulk. However, the Li-ion conductivity at the grain boundary (GB) is largely reduced, and it is therefore important to reveal the origin of Li-ion conductivity reduction at the GB. Here, by using atomic-resolution scanning transmission electron microscopy combined with atomic force microscopy, we investigate the charge states, Li-ion conductivities, atomic and electronic structures at the LLTO Σ5 and Σ13 GBs. Although the Σ5 GB has no significant influence on Li-ion conductivity, the Σ13 GB shows the evident reduction of Li-ion conductivity. We further elucidate that the Σ13 GB is positively charged by the formation of oxygen vacancies at the GB. Such a positive charge would form the Li-ion depletion layers adjacent to the GB, which causes the significant reduction of Li-ion conductivity.

Franckeite as an Exfoliable Naturally Occurring Topological Insulator.

Franckeite is a natural superlattice composed of two alternating layers of different composition which has shown potential for optoelectronic applications. In part, the interest in franckeite lies in its layered nature which makes it easy to exfoliate into very thin heterostructures. Not surprisingly, its chemical composition and lattice structure are so complex that franckeite has escaped screening protocols and high-throughput searches of materials with nontrivial topological properties. On the basis of density functional theory calculations, we predict a quantum phase transition originating from stoichiometric changes in one of franckeite composing layers (the quasihexagonal one). While for a large concentration of Sb, franckeite is a sequence of type-II semiconductor heterojunctions, for a large concentration of Sn, these turn into type-III, much alike InAs/GaSb artificial heterojunctions, and franckeite becomes a strong topological insulator. Transmission electron microscopy observations confirm that such a phase transition may actually occur in nature.

Symmetry Breakdown in Franckeite: Spontaneous Strain, Rippling, and Interlayer Moiré.

Franckeite is a naturally occurring layered mineral with a structure composed of alternating stacks of SnS2-like and PbS-like layers. Although this superlattice is composed of a sequence of isotropic two-dimensional layers, it exhibits a spontaneous rippling that makes the material structurally anisotropic. We demonstrate that this rippling comes hand in hand with an inhomogeneous in-plane strain profile and anisotropic electrical, vibrational, and optical properties. We argue that this symmetry breakdown results from a spatial modulation of the van der Waals interaction between layers due to the SnS2-like and PbS-like lattices incommensurability.

Direct Visualization of Local Electromagnetic Field Structures by Scanning Transmission Electron Microscopy.

The functional properties of materials and devices are critically determined by the electromagnetic field structures formed inside them, especially at nanointerface and surface regions, because such structures are strongly associated with the dynamics of electrons, holes and ions. To understand the fundamental origin of many exotic properties in modern materials and devices, it is essential to directly characterize local electromagnetic field structures at such defect regions, even down to atomic dimensions. In recent years, rapid progress in the development of high-speed area detectors for aberration-corrected scanning transmission electron microscopy (STEM) with sub-angstrom spatial resolution has opened new possibilities to directly image such electromagnetic field structures at very high-resolution. In this Account, we give an overview of our recent development of differential phase contrast (DPC) microscopy for aberration-corrected STEM and its application to many materials problems. In recent years, we have developed segmented-type STEM detectors which divide the detector plane into 16 segments and enable simultaneous imaging of 16 STEM images which are sensitive to the positions and angles of transmitted/scattered electrons on the detector plane. These detectors also have atomic-resolution imaging capability. Using these segmented-type STEM detectors, we show DPC STEM imaging to be a very powerful tool for directly imaging local electromagnetic field structures in materials and devices in real space. For example, DPC STEM can clearly visualize the local electric field variation due to the abrupt potential change across a p-n junction in a GaAs semiconductor, which cannot be observed by normal in-focus bright-field or annular type dark-field STEM imaging modes. DPC STEM is also very effective for imaging magnetic field structures in magnetic materials, such as magnetic domains and skyrmions. Moreover, real-time imaging of electromagnetic field structures can now be realized through very fast data acquisition, processing, and reconstruction algorithms. If we use DPC STEM for atomic-resolution imaging using a sub-angstrom size electron probe, it has been shown that we can directly observe the atomic electric field inside atoms within crystals and even inside single atoms, the field between the atomic nucleus and the surrounding electron cloud, which possesses information about the atomic species, local chemical bonding and charge redistribution between bonded atoms. This possibility may open an alternative way for directly visualizing atoms and nanostructures, that is, seeing atoms as an entity of electromagnetic fields that reflect the intra- and interatomic electronic structures. In this Account, the current status of aberration-corrected DPC STEM is highlighted, along with some applications in real material and device studies.

Oxygen octahedral distortions in LaMO3/SrTiO3 superlattices.

In this work we study the interfaces between the Mott insulator LaMnO3 (LMO) and the band insulator SrTiO3 (STO) in epitaxially grown superlattices with different thickness ratios and different transport and magnetic behaviors. Using atomic resolution electron energy-loss spectral imaging, we analyze simultaneously the structural and chemical properties of these interfaces. We find changes in the oxygen octahedral tilts within the LaMnO3 layers when the thickness ratio between the manganite and the titanate layers is varied. Superlattices with thick LMO and ultrathin STO layers present unexpected octahedral tilts in the STO, along with a small amount of oxygen vacancies. On the other hand, thick STO layers exhibit undistorted octahedra while the LMO layers present reduced O octahedral distortions near the interfaces. These findings are discussed in view of the transport and magnetic differences found in previous studies.

Hydrogen-Induced Reduction Improves the Photoelectrocatalytic Performance of Titania.

One of the main challenges to expand the use of titanium dioxide (titania) as a photocatalyst is related to its large band gap energy and the lack of an atomic scale description of the reduction mechanisms that may tailor the photocatalytic properties. We show that rutile TiO2 single crystals annealed in the presence of atomic hydrogen experience a strong reduction and structural rearrangement, yielding a material that exhibits enhanced light absorption, which extends from the ultraviolet to the near-infrared (NIR) spectral range, and improved photoelectrocatalytic performance. We demonstrate that both magnitudes behave oppositely: heavy/mild plasma reduction treatments lead to large/negligible spectral absorption changes and poor/enhanced (×10) photoelectrocatalytic performance, as judged from the higher photocurrent. To correlate the photoelectrochemical performance with the atomic and chemical structures of the hydrogen-reduced materials, we have modeled the process with in situ scanning tunneling microscopy measurements, which allow us to determine the initial stages of oxygen desorption and the desorption/diffusion of Ti atoms from the surface. This multiscale study opens a door toward improved materials for diverse applications such as more efficient rutile TiO2-based photoelectrocatalysts, green photothermal absorbers for solar energy applications, or NIR-sensing materials.

Bimodal ionic photomemristor based on a high-temperature oxide superconductor/semiconductor junction.

Memristors, a cornerstone for neuromorphic electronics, respond to the history of electrical stimuli by varying their electrical resistance across a continuum of states. Much effort has been recently devoted to developing an analogous response to optical excitation. Here we realize a novel tunnelling photo-memristor whose behaviour is bimodal: its resistance is determined by the dual electrical-optical history. This is obtained in a device of ultimate simplicity: an interface between a high-temperature superconductor and a transparent semiconductor. The exploited mechanism is a reversible nanoscale redox reaction between both materials, whose oxygen content determines the electron tunnelling rate across their interface. The redox reaction is optically driven via an interplay between electrochemistry, photovoltaic effects and photo-assisted ion migration. Besides their fundamental interest, the unveiled electro-optic memory effects have considerable technological potential. Especially in combination with high-temperature superconductivity which, in addition to facilitating low-dissipation connectivity, brings photo-memristive effects to the realm of superconducting electronics.

Strongly Anisotropic Strain-Tunability of Excitons in Exfoliated ZrSe3.

The effect of uniaxial strain on the band structure of ZrSe3 , a semiconducting material with a marked in-plane structural anisotropy, is studied. By using a modified three-point bending test apparatus, thin ZrSe3 flakes are subjected to uniaxial strain along different crystalline orientations monitoring the effect of strain on their optical properties through micro-reflectance spectroscopy. The obtained spectra show excitonic features that blueshift upon uniaxial tension. This shift is strongly dependent on the direction along which the strain is being applied. When the flakes are strained along the b-axis, the exciton peak shifts at ≈60-95 meV %-1 , while along the a-axis, the shift only reaches ≈0-15 meV %-1 . Ab initio calculations are conducted to study the influence of uniaxial strain, applied along different crystal directions, on the band structure and reflectance spectra of ZrSe3 , exhibiting a remarkable agreement with the experimental results.

An Oxygen Vacancy Memristor Ruled by Electron Correlations.

Resistive switching effects offer new opportunities in the field of conventional memories as well as in the booming area of neuromorphic computing. Here the authors demonstrate memristive switching effects produced by a redox-driven oxygen exchange in tunnel junctions based on NdNiO3 , a strongly correlated electron system characterized by the presence of a metal-to-insulator transition (MIT). Strikingly, a strong interplay exists between the MIT and the redox mechanism, which on the one hand modifies the MIT itself, and on the other hand radically affects the tunnel resistance switching and the resistance states' lifetime. That results in a very unique temperature behavior and endows the junctions with multiple degrees of freedom. The obtained results bring up fundamental questions on the interplay between electronic correlations and the creation and mobility of oxygen vacancies in nickelates, opening a new avenue toward mimicking neuromorphic functions by exploiting the electric-field control of correlated states.

Linear imaging theory for differential phase contrast and other phase imaging modes in scanning transmission electron microscopy.

We propose a linear imaging theory for differential phase contrast under the weak-phase-weak-amplitude object approximation. Contrast transfer functions are defined for thin and thick weak objects, and they successfully describe several imaging characteristics of differential phase contrast. We discuss the defocus dependence of the contrast for several examples: atomic resolution, a p-n junction, a heterointerface, and grain boundaries. Understanding the imaging characteristics helps in adjusting aberrations in DPC STEM.

Direct Transformation of Crystalline MoO3 into Few-Layers MoS2.

We fabricated large-area atomically thin MoS2 layers through the direct transformation of crystalline molybdenum trioxide (MoO3) by sulfurization at relatively low temperatures. The obtained MoS2 sheets are polycrystalline (~10-20 nm single-crystal domain size) with areas of up to 300 × 300 µm2, 2-4 layers in thickness and show a marked p-type behavior. The synthesized films are characterized by a combination of complementary techniques: Raman spectroscopy, X-ray diffraction, transmission electron microscopy and electronic transport measurements.

Direct electric field imaging of graphene defects.

Material properties are sensitive to atomistic structure defects such as vacancies or impurities, and it is therefore important to determine not only the local atomic configuration but also their chemical bonding state. Annular dark-field scanning transmission electron microscopy (STEM) combined with electron energy-loss spectroscopy has been utilized to investigate the local electronic structures of such defects down to the level of single atoms. However, it is still challenging to two-dimensionally map the local bonding states, because the electronic fine-structure signal from a single atom is extremely weak. Here, we show that atomic-resolution differential phase-contrast STEM imaging can directly visualize the anisotropy of single Si atomic electric fields in monolayer graphene. We also visualize the atomic electric fields of Stone-Wales defects and nanopores in graphene. Our results open the way to directly examine the local chemistry of the defective structures in materials at atomistic dimensions.

Direct Determination of Atomic Structure and Magnetic Coupling of Magnetite Twin Boundaries.

Clarifying how the atomic structure of interfaces/boundaries in materials affects the magnetic coupling nature across them is of significant academic value and will facilitate the development of state-of-the-art magnetic devices. Here, by combining atomic-resolution transmission electron microscopy, atomistic spin-polarized first-principles calculations, and differential phase contrast imaging, we conduct a systematic investigation of the atomic and electronic structures of individual Fe3O4 twin boundaries (TBs) and determine their concomitant magnetic couplings. We demonstrate that the magnetic coupling across the Fe3O4 TBs can be either antiferromagnetic or ferromagnetic, which directly depends on the TB atomic core structures and resultant electronic structures within a few atomic layers. Revealing the one-to-one correspondence between local atomic structures and magnetic properties of individual grain boundaries will shed light on in-depth understanding of many interesting magnetic behaviors of widely used polycrystalline magnetic materials, which will surely promote the development of advanced magnetic materials and devices.

Probing the Internal Atomic Charge Density Distributions in Real Space.

Probing the charge density distributions in materials at atomic scale remains an extremely demanding task, particularly in real space. However, recent advances in differential phase contrast-scanning transmission electron microscopy (DPC-STEM) bring this possibility closer by directly visualizing the atomic electric field. DPC-STEM at atomic resolutions measures how a sub-angstrom electron probe passing through a material is affected by the atomic electric field, the field between the nucleus and the surrounding electrons. Here, we perform a fully quantitative analysis which allows us to probe the charge density distributions inside atoms, including both the positive nuclear and the screening electronic charges, with subatomic resolution and in real space. By combining state-of-the-art DPC-STEM experiments with advanced electron scattering simulations we are able to map the spatial distribution of the electron cloud within individual atomic columns. This work constitutes a crucial step toward the direct atomic scale determination of the local charge redistributions and modulations taking place in materials systems.

Electric field imaging of single atoms.

In scanning transmission electron microscopy (STEM), single atoms can be imaged by detecting electrons scattered through high angles using post-specimen, annular-type detectors. Recently, it has been shown that the atomic-scale electric field of both the positive atomic nuclei and the surrounding negative electrons within crystalline materials can be probed by atomic-resolution differential phase contrast STEM. Here we demonstrate the real-space imaging of the (projected) atomic electric field distribution inside single Au atoms, using sub-Å spatial resolution STEM combined with a high-speed segmented detector. We directly visualize that the electric field distribution (blurred by the sub-Å size electron probe) drastically changes within the single Au atom in a shape that relates to the spatial variation of total charge density within the atom. Atomic-resolution electric field mapping with single-atom sensitivity enables us to examine their detailed internal and boundary structures.

Quantitative electric field mapping in thin specimens using a segmented detector: Revisiting the transfer function for differential phase contrast.

Differential phase contrast in scanning transmission electron microscopy can visualize local electromagnetic fields inside specimens. The contrast derived from first moments, the so-called center of mass, of the diffraction patterns for each probe position can be quantitatively related to the local electromagnetic field under the phase object approximation. While only approximate first moments can be obtained with a segmented detector, in weak phase objects the fields can be accurately quantified on the basis of a phase contrast transfer function. Through systematic image simulations we further show that the quantification based on the approximated first moment is a good approximation also for strong phase objects.

Resonant electron tunnelling assisted by charged domain walls in multiferroic tunnel junctions.

The peculiar features of domain walls observed in ferroelectrics make them promising active elements for next-generation non-volatile memories, logic gates and energy-harvesting devices. Although extensive research activity has been devoted recently to making full use of this technological potential, concrete realizations of working nanodevices exploiting these functional properties are yet to be demonstrated. Here, we fabricate a multiferroic tunnel junction based on ferromagnetic La0.7Sr0.3MnO3 electrodes separated by an ultrathin ferroelectric BaTiO3 tunnel barrier, where a head-to-head domain wall is constrained. An electron gas stabilized by oxygen vacancies is confined within the domain wall, displaying discrete quantum-well energy levels. These states assist resonant electron tunnelling processes across the barrier, leading to strong quantum oscillations of the electrical conductance.

An artificial photosynthesis anode electrode composed of a nanoparticulate photocatalyst film in a visible light responsive GaN-ZnO solid solution system.

The artificial photosynthesis technology known as the Honda-Fujishima effect, which produces oxygen and hydrogen or organic energy from sunlight, water, and carbon dioxide, is an effective energy and environmental technology. The key component for the higher efficiency of this reaction system is the anode electrode, generally composed of a photocatalyst formed on a glass substrate from electrically conductive fluorine-doped tin oxide (FTO). To obtain a highly efficient electrode, a dense film composed of a nanoparticulate visible light responsive photocatalyst that usually has a complicated multi-element composition needs to be deposited and adhered onto the FTO. In this study, we discovered a method for controlling the electronic structure of a film by controlling the aerosol-type nanoparticle deposition (NPD) condition and thereby forming films of materials with a band gap smaller than that of the prepared raw material powder, and we succeeded in extracting a higher current from the anode electrode. As a result, we confirmed that a current approximately 100 times larger than those produced by conventional processes could be obtained using the same material. This effect can be expected not only from the materials discussed (GaN-ZnO) in this paper but also from any photocatalyst, particularly materials of solid solution compositions.