Atomic-scale Resolution Research Articles

Sliding History-Dependent Adhesion of Nanoscale Silicon Contacts Revealed by in Situ Transmission Electron Microscopy.

Nanoscale asperity-on-asperity sliding experiments were conducted using a nanoindentation apparatus inside a transmission electron microscope, allowing for atomic-scale resolution of contact formation, sliding, and adhesive separation of two silicon nanoasperities in real time. The formation and separation of the contacts without sliding revealed adhesion forces often below detectable limits (ca. 5 nN) or at most equal to values expected from van der Waals forces. Lateral sliding during contact by distances ranging from 3.7 μm down to as little as 20 nm resulted in an average 19× increase in the adhesive pull-off force, with increases as large as 32× seen. Adhesion after sliding increased with both the sliding speed and the applied normal contact stress. Unlike cold welding, where irreversible material changes like flow occur, these effects were repeatable and reversible multiple times, for multiple pairs of asperities. We hypothesize that sliding removes passivating surface terminal species, most likely hydrogen or hydroxyl groups, making sites available to form strong covalent bonds across the interface that increase adhesion. Upon separation, repassivation occurs within the experimentally limited lower bound time frame of 5 s, with full recovery of low adhesion. The results demonstrate the strong sliding history-dependence of adhesion, which hinges on the interplay between tribologically induced removal of adsorbed species and repassivation of unsaturated bonds on freshly separated surfaces by dissociative chemisorption.

The Light Years: Combined optical and environmental electron microscopy to visualize photonic processes with atomic-scale resolution

The Light Years: Combined optical and environmental electron microscopy to visualize photonic processes with atomic-scale resolution

Spatial Distribution of Silica-Bound Catalytic Organic Functional Groups Can Now Be Revealed by Conventional and DNP-Enhanced Solid-State NMR Methods

Understanding the spatial distribution of functionalities on surfaces with atomic-scale resolution is very important for catalytic applications, yet very challenging for analytical inquiry. Recent ...

Crystals from the Powellite-Scheelite Series at the Nanoscale: A Case Study from the Zhibula Cu Skarn, Gangdese Belt, Tibet

Scheelite (CaWO4) and powellite (CaMoO4) are isostructural minerals considered as a non-ideal solid solution series. Micron- to nanoscale investigation of a specimen of skarnoid from Zhibula, Gangdese Belt, Tibet, China, was carried out to assess the identity of the phases within a broad scheelite-powellite (Sch-Pow) compositional range, and to place additional constraints on redox changes during ore formation. An electron probe microanalysis shows that Mo-rich domains within complex oscillatory-zoned single crystals, and as thin sliver-like domains, have a compositional range from 20 mol.% to 80 mol.% Pow. These occur within a matrix of unzoned, close-to-end-member scheelite aggregates (87 mol.%–95 mol.% Sch). Laser-ablation inductively coupled plasma mass spectrometry spot analysis and element mapping reveal systematic partitioning behaviour of trace elements in skarn minerals (grossular50, diopside80, anorthite, and retrograde clinozoisite) and scheelite-powellite aggregates. The Mo-rich domains feature higher concentrations of As, Nb, and light rare earth elements LREE, whereas W-rich domains are comparatively enriched in Y and Sr. Transmission electron microscopy (TEM) was carried out on focused-ion-beam-prepared foils extracted in situ from domains with oscillatory zoning occurring as slivers of 20 mol.%–40 mol.% Pow and 48 mol.%–80 mol.% Pow composition within an unzoned low-Mo matrix (20 mol.% Pow). Electron diffractions, high-angular annular dark field (HAADF) scanning-TEM (STEM) imaging, and energy-dispersive spectroscopy STEM mapping show chemical oscillatory zoning with interfaces that have continuity in crystal orientation throughout each defined structure, zoned grain or sliver. Non-linear thermodynamics likely govern the patterning and presence of compositionally and texturally distinct domains, in agreement with a non-ideal solid solution. We show that the sharpest compositional contrasts are also recognisable by variation in growth direction. Atomic-scale resolution imaging and STEM simulation confirm the presence of scheelite-powellite within the analysed range (20 mol.%–80 mol.% Pow). Xenotime-(Y) inclusions occur as nm-wide needles with epitaxial orientation to the host scheelite-powellite matrix throughout both types of patterns, but no discrete Mo- or W-bearing inclusions are observed. The observed geochemical and petrographic features can be reconciled with a redox model involving prograde deposition of a scheelite+molybdenite assemblage (reduced), followed by interaction with low-T fluids, leading to molybdenite dissolution and reprecipitation of Mo as powellite-rich domains (retrograde stage, oxidised). The observation of nanoscale inclusions of xenotime-(Y) within scheelite carries implications for the meaningful interpretation of petrogenesis based on rare earth element (REE) concentrations and fractionation patterns. This research demonstrates that HAADF-STEM is a versatile technique to address issues of solid solution and compositional heterogeneity.

Alloy theory with atomic resolution for Rashba or topological systems

Interest in substitutional disordered alloys has recently reemerged with focus on the symmetry-sensitive properties in the alloy such as topological insulation and Rashba effect. A substitutional random alloy manifests a distribution of local environments, creating a polymorphous network. While the macroscopic average (monomorphous) structure may have the original high symmetry of the constituent compounds, many observable physical properties are sensitive to local symmetry, and are hence $<P(S_i)>$ rather than $P(S_0)$=$P(<S_i>)$. The fundamental difference between polymorphous $<P(S_i)>$ and monomorphous $P(S_0)$ led to the often-diverging results and the missing the atomic-scale resolution needed to discern symmetry-related physics. A natural approach capturing the polymorphous aspect is supercell model, which however suffers the difficulty of band folding ('spaghetti bands'), rendering the E vs k dispersion needed in topology and Rashba physics and seen in experiments, practically inaccessible. A solution that retains the polymorphous nature but restores the E vs k relation is to unfold the supercell bands. This yields alloy Effective Band Structure (EBS), providing a 3D picture of spectral density consisting of E- and k-dependent spectral weight with coherent and incoherent features, all created naturally by the polymorphous distribution of many local environments. We illustrate this EBS approach for CdTe-HgTe, PbSe-SnSe and PbS-PbTe alloys. We found properties that are critical for e.g. topological phase transition and Rashba splitting but totally absent in conventional monomorphous approaches, including (1) co-existing, wavevector- and energy-dependent coherent band splitting and incoherent band broadening, (2) coherent-incoherent transition along different k space directions, and (3) Rashba-like band splitting having both coherent and incoherent features.

Difference frequency generation of ultraviolet from x-ray pulses in opaque materials

We suggest a new approach for observing x-ray nonlinear wave mixing in opaque materials. We focus on difference frequency generation of ultraviolet radiation from two short x-ray pulses by measuring the depletion of the pumping pulses. Like other processes involving nonlinear interactions between x-rays and longer wavelengths, our method can lead to the development of a probe for spectroscopy of valence electrons at the atomic scale resolution. The two main advantages of the method we propose over the direct observation of the generated signal are the ability to probe the properties of materials at wavelengths where they are opaque and the higher predicted efficiency in the ultraviolet regime. We describe a possible experimental setup with realistic specifications optimized with respect to the characteristics of the input pulses. We expect that experimental observations of the effect will be feasible with the new emerging high-repetition-rate x-ray free-electron lasers.

(Keynote) Designing Lithium Metal Anodes: Host Materials and Solid Electrolyte Interphase

Lithium metal anode is critical for new generation of high energy batteries. We identified that the two root causes of Li metal problems are high chemical reactivity and infinite relative volume change during Li metal plating and stripping. Nanoscale materials design represents a new powerful paradigm shift and offers new solutions to address these challenges. Here I will present our understanding and progress on: 1) Nanoscale design of host and interface for Li metal anodes; examples of host materials include graphene oxides, hollow carbon spheres, metal fluoride and oxide. We also developed robust interfacial layer materials and synthesis process for BN, Li3N and LiF. 2) Demonstration of cryogenic electron microscopy applied to battery materials research, leading atomic scale resolution of Li metal dendrite and solid electrolyte interphase. We also established the correlation of the SEI structure with battery performance.

Interfaces Between Cathode and Electrolyte in Solid State Lithium Batteries: Challenges and Perspectives.

Solid state lithium batteries are widely accepted as promising candidates for next generation of various energy storage devices with the probability to realize improved energy density and superior safety performances. However, the interface between electrode and solid electrolyte remain a key issue that hinders practical development of solid state lithium batteries. In this review, we specifically focus on the interface between solid electrolytes and prevailing cathodes. The basic principles of interface layer formation are summarized and three kinds of interface layers can be categorized. For typical solid state lithium batteries, a most common and daunting challenge is to achieve and sustain intimate solid-solid contact. Meanwhile, different specific issues occur on various types of solid electrolytes, depending on the intrinsic properties of adjacent solid components. Our discussion mostly involves following electrolytes, including solid polymer electrolyte, inorganic solid oxide and sulfide electrolytes as well as composite electrolytes. The effective strategies to overcome the interface instabilities are also summarized. In order to clarify interfacial behaviors fundamentally, advanced characterization techniques with time, and atomic-scale resolution are required to gain more insights from different perspectives. And recent progresses achieved from advanced characterization are also reviewed here. We highlight that the cooperative characterization of diverse advanced characterization techniques is necessary to gain the final clarification of interface behavior, and stress that the combination of diverse interfacial modification strategies is required to build up decent cathode-electrolyte interface for superior solid state lithium batteries.

RECENT ADVANCES IN ULTRAFAST TIME-RESOLVED SCANNING TUNNELING MICROSCOPY

Making smaller and faster functional devices has led to an increasing demand for a microscopic technique that allows the investigation of carrier and phonon dynamics with both high spatial and temporal resolutions. Traditional optical pump–probe methods can achieve femtosecond temporal resolution but fall short in the spatial resolution due to the diffraction limit. Scanning tunneling microscopy (STM), on the contrary, has realized atomic-scale spatial resolution relying on the high sensitivity of the tunneling current to the tip-sample distance. However, limited by the electronics bandwidth, STM can only push the temporal resolution to the microseconds scale, restricting its applications to probe various ultrafast dynamic processes. The combination of these two methods takes advantages of optical pump–probe techniques and highly localized tunneling currents of STM, providing one viable solution to track atomic-scale ultrafast dynamics in single molecules and low-dimensional materials. In this review, we will focus on several ultrafast time-resolved STM methods by coupling the tunneling junctions with pulsed electric waves, THz, near-infrared and visible laser. Their applications to probe the carrier dynamics, spin dynamics, and molecular motion will be highlighted. In the end, we will present an outlook on the challenges and new opportunities in this field.

STM STUDIES ON MOLECULAR ROTORS AND MOTORS

Molecular motor is a nanoscale machine that consumes energy to produce work via the unidirectional and controlled movement. They are universal in nature and essential to numerous processes of life. When mounted onto solid surfaces, scanning tunneling microscopy (STM) is a powerful technique to characterize the molecular rotors and motors due to the atomic-scale resolution coupled with its ability to track the motion of molecular rotor and motor over time. Moreover, the molecular rotors and motors can be powered by STM tip through injecting tunneling electrons. This review addresses recent advances in the STM studies of the structure, motion, and manipulation of molecular rotors and motors. The developments of surface-mounted azimuthal and altitudinal rotor and motors, large-scale array of molecular rotors, as well as the molecular motors with translational motion will be addressed.

Probing one-dimensional systems via noise magnetometry with single spin qubits

The study of exotic one-dimensional states, particularly those at the edges of topological materials, demand new experimental probes that can access the interplay between charge and spin degrees of freedom. One potential approach is to use a single spin probe, such as a Nitrogen Vacancy center in diamond, which has recently emerged as a versatile tool to probe nanoscale systems in a non-invasive fashion. Here we present a theory describing how noise magnetometry with spin probes can directly address several questions that have emerged in experimental studies of 1D systems, including those in topological materials. We show that by controlling the spin degree of freedom of the probe, it is possible to measure locally and independently local charge and spin correlations of 1D systems. Visualization of 1D edge states, as well as sampling correlations with wavevector resolution can be achieved by tuning the probe-to-sample distance. Furthermore, temperature-dependent measurements of magnetic noise can clearly delineate the dominant scattering mechanism (impurities vs. interactions) -- this is of particular relevance to quantum spin Hall measurements where conductance quantization is not perfect. The possibility to probe both charge and spin excitations in a wide range of length scales opens new pathways to bridging the large gap between atomic scale resolution of scanning probes and global transport measurements.

Cavity-Correlated Electron-Nuclear Dynamics from First Principles.

The rapidly developing and converging fields of polaritonic chemistry and quantum optics necessitate a unified approach to predict strongly correlated light-matter interactions with atomic-scale resolution. Toward this overarching goal, we introduce a general time-dependent density-functional theory to study correlated electron, nuclear, and photon interactions on the same quantized footing. We complement our theoretical formulation with the first abinitio calculation of a correlated electron-nuclear-photon system. For a CO_{2} molecule in an optical cavity, we construct the infrared spectra exhibiting Rabi splitting between the upper and lower polaritonic branches, time-dependent quantum-electrodynamical observables such as the electric displacement field, and observe cavity-modulated molecular motion. Our work opens an important new avenue in introducing abinitio methods to the nascent field of collective strong vibrational light-matter interactions.

Characterization of Membrane Proteins Using Cryo-Electron Microscopy.

The steep increase of atomic scale structures determined by 3D cryo-electron microscopy (EM) deposited in the EMDataBank documents progress of a methodology that was frustratingly slow ten years ago. While sample vitrification on grids has been successfully used in all EM laboratories for decades, beam damage remains a road block. Developments in instrumentation and software to exploit the information carried by elastically scattered electrons made the task to achieve atomic scale resolution easier. This together with the development of fast single electron detecting cameras has resulted in unprecedented possibilities for structure determination by 3D cryo-EM. With such technologies in place, the purification of membrane protein complexes in a functional state is key to collecting atomic scale structural information and insight into the chemistry of physiological processes. Therefore, we focus here on the preparation of membrane proteins for structural analyses by 3D cryo-EM and the data acquisition of such vitrified samples. © 2018 by John Wiley & Sons, Inc.

Scanning Seebeck tunneling microscopy

The tunneling Seebeck effect in a metal-vacuum-metal junction is studied experimentally in a scanning tunneling microscopy setup. Selective heating of the tip with a laser generates a well-defined temperature difference at the tunnel junction. The thermovoltage between the tip and the sample is measured with atomic-scale lateral resolution and related to the band structure of the junction, as revealed by local tunneling spectroscopy. Tunnel current rectification experiments in compensated conditions allow for a direct measurement of the Seebeck coefficient without the need for tip heating, thereby realizing Seebeck mapping on the atomic scale.

Electron radiation-induced material diffusion and nanocrystallization in nanostructured amorphous CoFeB thin film

Transmission electron microscopy (TEM) is widely used for physical characterization of CoFeB based magnetic tunneling junctions (MTJ) with its atomic-scale resolution. However, highly energetic electron radiation during TEM analysis may cause phase and microstructure modification of CoFeB and its associated MTJ layers. It is the intention of this work to address the issues of the electron-beam sensitivity of CoFeB material. With in-situ TEM, we investigated the electron beam radiation-induced material diffusion and the nanocrystallization behaviors in nanostructured amorphous CowFexByOz/Co60Fe20B20/SiO2 thin films. It was found that electron radiation with different electron dose led to massive diffusion of Co, Fe, B and O atoms across the whole thin film layers, which directly resulted in the modification of the phase and composition of the thin film layers, i.e. the oxidation of Co, Fe, B with O diffusion and the formation of pure Si phase from SiO2. Two stages of material diffusion were observed. While Stage-I material diffusion proceeded with a high diffusion speed, Stage-II had a relatively low diffusion rate accompanying with the nanocrystallization at the bottom of the CoFeB layer. A detailed kinetic study by in-situ TEM revealed the electron-beam radiation induced massive diffusion was a non-thermal process, and the underlying driving force arose from radiation-enhanced diffusion (RED) effects. Nanocrystallization during Stage-II electron-radiation experiment showed unique phase transformation phenomena, repeated nanocrystallization, amorphization, and nanocrystallization processes in the sequence before a stable grain growth could be achieved. A detailed TEM analysis revealed that RED-enhanced B diffusion was responsible for such unique repeated phase transformation processes. B diffusion and the associated structure distortion and the local short-range re-ordering may also account for the phase transformation from fcc-CoxFe23-xB6 to B-rich orthorhombic- CoxFe3-xB phase.

Development of Local Analysis Technique of Electric Double Layer at Electrode Interfaces and Its Application to Ionic Liquid Interfaces

Abstract Local analyses of electrolyte/solid electrode interfaces at controlled electrode potentials are of fundamental importance to understanding the origin and properties of the electric double layer (EDL) at the interfaces, which is necessary for their application to electrochemical devices. This award account summarizes our recent achievements of such analyses by using the novel analytical tools of electrochemical frequency modulation AFM (EC-FM-AFM), which enables acquisition of information from the liquid molecules’ structuring as well as the atomic scale resolution of the solid side, both are often affected by the electrode potential. Potential and electrolyte dependent EDL structures at aqueous solution/graphite interfaces and strong substrate dependency on the structuring of interfacial ionic liquid are mainly discussed.

Reorganization energy upon charging a single molecule on an insulator measured by atomic force microscopy.

Intermolecular single-electron transfer on electrically insulating films is a key process in molecular electronics1-4 and an important example of a redox reaction5,6. Electron-transfer rates in molecular systems depend on a few fundamental parameters, such as interadsorbate distance, temperature and, in particular, the Marcus reorganization energy 7 . This crucial parameter is the energy gain that results from the distortion of the equilibrium nuclear geometry in the molecule and its environment on charging8,9. The substrate, especially ionic films 10 , can have an important influence on the reorganization energy11,12. Reorganization energies are measured in electrochemistry 13 as well as with optical14,15 and photoemission spectroscopies16,17, but not at the single-molecule limit and nor on insulating surfaces. Atomic force microscopy (AFM), with single-charge sensitivity18-22, atomic-scale spatial resolution 20 and operable on insulating films, overcomes these challenges. Here, we investigate redox reactions of single naphthalocyanine (NPc) molecules on multilayered NaCl films. Employing the atomic force microscope as an ultralow current meter allows us to measure the differential conductance related to transitions between two charge states in both directions. Thereby, the reorganization energy of NPc on NaCl is determined as (0.8 ± 0.2) eV, and density functional theory (DFT) calculations provide the atomistic picture of the nuclear relaxations on charging. Our approach presents a route to perform tunnelling spectroscopy of single adsorbates on insulating substrates and provides insight into single-electron intermolecular transport.

Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions.

Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with insitu mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

Atomic scale imaging of magnetic circular dichroism by achromatic electron microscopy.

In order to obtain a fundamental understanding of the interplay between charge, spin, orbital and lattice degrees of freedom in magnetic materials and to predict and control their physical properties1-3, experimental techniques are required that are capable of accessing local magnetic information with atomic-scale spatial resolution. Here, we show that a combination of electron energy-loss magnetic chiral dichroism 4 and chromatic-aberration-corrected transmission electron microscopy, which reduces the focal spread of inelastically scattered electrons by orders of magnitude when compared with the use of spherical aberration correction alone, can achieve atomic-scale imaging of magnetic circular dichroism and provide element-selective orbital and spin magnetic moments atomic plane by atomic plane. This unique capability, which we demonstrate for Sr2FeMoO6, opens the door to local atomic-level studies of spin configurations in a multitude of materials that exhibit different types of magnetic coupling, thereby contributing to a detailed understanding of the physical origins of magnetic properties of materials at the highest spatial resolution.

Parametric Down-Conversion of X Rays into the Optical Regime.

We report the observation of parametrically down-converted x-ray signal photons at photon energies that correspond to idler photons at optical wavelengths. The count-rate dependence on the angles of the input beam and of the detector and on the slit sizes agrees with theory within the experimental uncertainties. The nonlinear susceptibility, which we calculated from the measured efficiencies, is comparable to the nonlinear susceptibility evaluated from the measurements of x-ray and optical wave mixing. The results of the present Letter advance the development of a spectroscopy method for probing valence-electron charges and the microscopic optical response of crystals with atomic-scale resolution.