Single-atom vibrational spectroscopy in the scanning transmission electron microscope

Vibrational spectroscopy can achieve high energy resolution, but spatial resolution of unperturbed vibrations is more difficult to realize. Hage et al. show that a single-atom impurity in a solid (a silicon atom in graphene) can give rise to distinctive localized vibrational signatures. They used high-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope to detect this signal. An experimental geometry was chosen that reduced the relative elastic scattering contribution, and repeated scanning near the silicon impurity enhanced the signal. The experimental vibration frequencies are in agreement with ab initio calculations.Science, this issue p. 1124Single-atom impurities and other atomic-scale defects can notably alter the local vibrational responses of solids and, ultimately, their macroscopic properties. Using high-resolution electron energy-loss spectroscopy in the electron microscope, we show that a single substitutional silicon impurity in graphene induces a characteristic, localized modification of the vibrational response. Extensive ab initio calculations reveal that the measured spectroscopic signature arises from defect-induced pseudo-localized phonon modestextemdashthat is, resonant states resulting from the hybridization of the defect modes and the bulk continuumtextemdashwith energies that can be directly matched to the experiments. This finding realizes the promise of vibrational spectroscopy in the electron microscope with single-atom sensitivity and has broad implications across the fields of physics, chemistry, and materials science

Observation of complete inversion of the hysteresis loop in a bimodal magnetic thin film

The existence of inverted hysteresis loops (IHLs) in magnetic materials is still in debate due to the lack of direct evidence and convincing theoretical explanations. Here we report the direct observation and physical interpretation of complete IHL in Ni45Fe55 films with 1 to 2 nm thin Ni3Fe secondary phases at the grain boundaries. The origin of the inverted loop, however, is shown to be due to the exchange bias coupling between Ni45Fe55 and Ni3Fe, which can be broken by the application of a high magnetic field. A large positive exchange bias (HEB=14×HC) is observed in the NiFe composite material giving novel insight into the formation of a noninverted hysteresis loop (non-IHL) and IHL, which depend on the loop tracing field range (HR). The crossover from non-IHL to IHL is found to be at 688 Oe

Towards atomically precise manipulation of 2D nanostructures in the electron microscope

Despite decades of research, the ultimate goal of nanotechnology—top-down manipulation of individual atoms—has been directly achieved with only one technique: scanning probe microscopy. In this review, we demonstrate that scanning transmission electron microscopy (STEM) is emerging as an alternative method for the direct assembly of nanostructures, with possible applications in plasmonics, quantum technologies, and materials science. Atomically precise manipulation with STEM relies on recent advances in instrumentation that have enabled non-destructive atomicresolution imaging at lower electron energies. While momentum transfer from highly energetic electrons often leads to atom ejection, interesting dynamics can be induced when the transferable kinetic energies are comparable to bond strengths in the material. Operating in this regime, very recent experiments have revealed the potential for single-atom manipulation using the Ångströmsized electron beam. To truly enable control, however, it is vital to understand the relevant atomicscale phenomena through accurate dynamical simulations. Although excellent agreement between experiment and theory for the specific case of atomic displacements from graphene has been recently achieved using density functional theory molecular dynamics, in many other cases quantitative accuracy remains a challenge. We provide a comprehensive reanalysis of available experimental data on beam-driven dynamics in light of the state-of-the-art in simulations, and identify important targets for improvement. Overall, the modern electron microscope has great potential to become an atom-scale fabrication platform, especially for covalently bonded 2D nanostructures. We review the developments that have made this possible, argue that graphene is an ideal starting material, and assess the main challenges moving forward

Stability of Schottky and Ohmic Au Nanocatalysts to ZnO Nanowires

Manufacturable nanodevices must now be the predominant goal of nanotechnological research to ensure the enhanced properties of nanomaterials can be fully exploited and fulfill the promise that fundamental science has exposed. Here, we test the electrical stability of Au nanocatalyst-ZnO nanowire contacts to determine the limits of the electrical transport properties and the metal-semiconductor interfaces. While the transport properties of as-grown Au nanocatalyst contacts to ZnO nanowires have been well-defined, the stability of the interfaces over lengthy time periods and the electrical limits of the ohmic or Schottky function have not been studied. In this work, we use a recently developed iterative analytical process that directly correlates multiprobe transport measurements with subsequent aberration-corrected scanning transmission electron microscopy to study the electrical, structural, and chemical properties when the nanowires are pushed to their electrical limits and show structural changes occur at the metal-nanowire interface or at the nanowire midshaft. The ohmic contacts exhibit enhanced quantum-mechanical edge-tunneling transport behavior because of additional native semiconductor material at the contact edge due to a strong metal-support interaction. The low-resistance nature of the ohmic contacts leads to catastrophic breakdown at the middle of the nanowire span where the maximum heating effect occurs. Schottky-type Au-nanowire contacts are observed when the nanowires are in the as-grown pristine state and display entirely different breakdown characteristics. The higher-resistance rectifying I-V behavior degrades as the current is increased which leads to a permanent weakening of the rectifying effect and atomic-scale structural changes at the edge of the Au interface where the tunneling current is concentrated. Furthermore, to study modified nanowires such as might be used in devices the nanoscale tunneling path at the interface edge of the ohmic nanowire contacts is removed with a simple etch treatment and the nanowires show similar I-V characteristics during breakdown as the Schottky pristine contacts. Breakdown is shown to occur either at the nanowire midshaft or at the Au contact depending on the initial conductivity of the Au contact interface. These results demonstrate the Au-nanowire structures are capable of withstanding long periods of electrical stress and are stable at high current densities ensuring they are ideal components for nanowire-device designs while providing the flexibility of choosing the electrical transport properties which other Au-nanowire systems cannot presently deliver

A Multi-objective Network Design Model for Post-disaster Transportation Network Management

Despite their inherent vulnerability to structural and functional degradation, transportation networks play a vital role in the aftermath of disasters by ensuring physical access to the affected communities and providing services according to the generated needs. In this setting of operational conditions and service needs which deviate from normal, a restructuring of network functions is deemed to be beneficial for overall network serviceability. In such context, this paper explores the planning of post-disaster operations on a network following a hazardous event on one of the network’s nodes. Lane reversal, demand regulation and path activation are applied to provide an optimally reconfigured network with reallocated demand, so that the network performance is maximized. The problem is formulated as a bi-level optimization model; the upper level determines the optimal network management strategy implementation scheme while the lower level assigns traffic on the network. Three performance indices are used for that purpose: the total network travel time (TNTT), the total network flow (TNF) and the special origin-destination pair (OD pair) accessibility. A genetic algorithm coupled with a traffic assignment process is used as a solution methodology. Application of the model on a real urban network proves the computational efficiency of the algorithm; the model systematically produces robust results of enhanced network performance, indicating its value as an operation planning tool

Atomically resolved chemical ordering at the nm-thick TiO precipitate/matrix interface in V-4Ti-4Cr alloy

We have used advanced analytical electron microscopy to characterise the local structure and chemistry at the interface between nm-thick TiO precipitates and the V-based matrix in a V-4Ti-4Cr alloy. Our results reveal the presence of an intergrowth between the fcc TiO and bcc vanadium structures, with a repeat lattice distance that equals 2.5 times the vanadium lattice parameter along the c-axis. Our atomic resolution analysis of the interface will impact the mechanistic understanding of its interaction with interstitials and radiation-induced lattice defects, and consequently trigger the development of improved alloy structures with interfaces engineered for enhanced radiation tolerance

Phonon Spectroscopy at Atomic Resolution

Advances in source monochromation in transmission electron microscopy have opened up new possibilities for investigations of condensed matter using the phonon-loss sector of the energy-loss spectrum. Here, we explore the spatial variations of the spectrum as an atomic-sized probe is scanned across a thin flake of hexagonal boron nitride. We demonstrate that phonon spectral mapping of atomic structure is possible. These results are consistent with a model for the quantum excitation of phonons and confirm that Z-contrast imaging is based on inelastic scattering associated with phonon excitation