Chiral twisted van der Waals nanowires.

Van der Waals heterostructures with small misalignment between adjacent layers ('interlayer twist') are of interest because of electronic structure and correlation phenomena (such as superconductivity) that are determined by both the atomic lattice and long-range superlattice potentials arising in interlayer moiré patterns1-7. Previously, such twisted heterostructures have involved a single planar interface between layers isolated by exfoliation and micromechanically stacked in the desired relative orientation1,8-12. Here we demonstrate a class of materials-van der Waals nanowires of layered crystals-in which a tunable interlayer twist evolves naturally during synthesis. In vapour-liquid-solid growth, nanowires of germanium(II) sulfide, an anisotropic layered semiconductor, crystallize with layering along the wire axis13 and have a strong propensity for forming axial screw dislocations. Nanometre-resolved electron diffraction shows that Eshelby twist, induced by a torque on the ends of a cylindrical solid due to the stress field of an axial dislocation14,15, causes a chiral structure in the van der Waals nanowires. The in-plane germanium sulfide crystal axes progressively rotate along the wire, and germanium sulfide layers in adjacent turns of the helix naturally form a moiré pattern because of their interlayer twist. The axial rotation and the twist are tunable by varying the nanowire thickness. Combined electron diffraction and cathodoluminescence spectroscopy show the correlation between the interlayer twist and locally excited light emission that is due to progressive changes in the lattice orientation and in the interlayer moiré registry along the nanowires. The findings demonstrate a step towards scalable fabrication of van der Waals structures with defined twist angles, in which interlayer moiré patterns are realized along a helical path on a nanowire instead of a planar interface.

Tunable 1D van der Waals Nanostructures by Vapor-Liquid-Solid Growth.

ConspectusVapor-liquid-solid (VLS) growth using molten metal catalysts has traditionally been used to synthesize nanowires from different 3D-crystalline semiconductors. With their anisotropic structure and properties, 2D/layered semiconductors create additional opportunities for materials design when shaped into 1D nanostructures. In contrast to hexagonal 2D crystals such as graphene, h-BN, and transition metal dichalcogenides, which tend to roll up into nanotubes, VLS growth of layered group III and group IV monochalcogenides produces diverse nanowire and nanoribbon morphologies that crystallize in a bulk-like layered structure with nanometer-scale footprint and lengths exceeding tens of micrometers. In this Account, we discuss the achievable morphologies, the mechanisms governing key structural features, and the emerging functional properties of these 1D van der Waals (vdW) architectures. Recent results highlight rich sets of phenomena that qualify these materials as a distinct class of nanostructures, far beyond a mere extension of 3D-crystalline VLS nanowires to vdW crystals.The main difference between 3D- and vdW crystals, the pronounced in-plane/cross-plane anisotropy of layered materials, motivates investigating the factors governing the layer orientation. Recent research suggests that the VLS catalyst plays a key role, and that its modification via the choice of chalcogens or through modifiers added to the growth precursor can switch both the nanostructure morphology and vdW layering. In many instances, ordinary layered structures are not formed but VLS growth is dominated by morphologies─often containing a crystal defect─that present reduced or vanishing layer nucleation barriers, thus achieving fast growth and emerging as the principal synthesis product. Prominent defect morphologies include vdW bicrystals growing by a twin-plane reentrant process and chiral nanowires formed by spiral growth around an axial screw dislocation. The latter carry particular promise, e.g., for twistronics. In vdW nanowires, Eshelby twist─a progressive crystal rotation caused by the dislocation stress field─translates into interlayer twist that is precisely tunable via the wire diameter. Projected onto a helicoid vdW interface, the resulting twist moirés not only modify the electronic structure but also realize configurations without equivalent in planar systems, such as continuously variable twist and twist homojunctions.1D vdW nanostructures derive distinct functionality from both their layered structure and embedded defects. Correlated electron microscopy methods including imaging, nanobeam diffraction, as well as electron-stimulated local absorption and luminescence spectroscopies combine to an exceptionally powerful probe of this emerging functionality, identifying twist-moiré induced electronic modulations and chiral photonic modes, demonstrating the benign nature of defects in optoelectronics, and uncovering ferroelectricity via symmetry-breaking by single-layer stacking faults in vdW nanowires. Far-reaching possibilities for tuning crystal structure, morphology, and defects create a rich playground for the discovery of new functional nanomaterials based on vdW crystals. Given the prominence of defects and extensive prospects for controlling their character and placement during synthesis, 1D vdW nanostructures have the potential to cause a paradigm shift in the science of electronic materials, replacing the traditional strategy of suppressing crystal imperfections with an alternative philosophy that embraces the use of individual defects with designed properties as drivers of technology.

Tuning of Single Mixed (Helical) Dislocations in Core-Shell van der Waals Nanowires.

Linear defects (dislocations) not only govern the mechanical properties of crystalline solids but they can also produce distinct electronic, thermal, and topological effects. Accessing this functionality requires control over the placement and geometry of single dislocations embedded in a small host volume to maximize emerging effects. Here we identify a synthetic route for rational dislocation placement and tuning in van der Waals nanowires, where the layered crystal limits the possible defect configurations and the nanowire architecture puts single dislocations in close proximity to the entire host volume. While homogeneous layered nanowires host single screw dislocations, the synthesis of radial nanowire heterostructures (here exemplified by GeS-Ge1-xSnxS monochalcogenide core-shell nanowires) transforms the defect into a mixed (helical) dislocation whose edge/screw ratio is tunable via the core-shell lattice mismatch. The ability to design nanomaterials with control over individual mixed dislocations paves the way for identifying the functional properties of dislocations and harnessing them in technology.

Self-Assembly of Mixed-Dimensional GeS1- x Sex (1D Nanowire)-(2D Plate) Van der Waals Heterostructures.

The integration of dissimilar materials into heterostructures is a mainstay of modern materials science and technology. An alternative strategy of joining components with different electronic structure involves mixed-dimensional heterostructures, that is, architectures consisting of elements with different dimensionality, for example, 1D nanowires and 2D plates. Combining the two approaches can result in hybrid architectures in which both the dimensionality and composition vary between the components, potentially offering even larger contrast between their electronic structures. To date, realizing such heteromaterials mixed-dimensional heterostructures has required sequential multi-step growth processes. Here, it is shown that differences in precursor incorporation rates between vapor-liquid-solid growth of 1D nanowires and direct vapor-solid growth of 2D plates attached to the wires can be harnessed to synthesize heteromaterials mixed-dimensional heterostructures in a single-step growth process. Exposure to mixed GeS and GeSe vapors produces GeS1- x Sex van der Waals nanowires whose S:Se ratio is considerably larger than that of attached layered plates. Cathodoluminescence spectroscopy on single heterostructures confirms that the bandgap contrast between the components is determined by both composition and carrier confinement. These results demonstrate an avenue toward complex heteroarchitectures using single-step synthesis processes.

Photonics in Multimaterial Lateral Heterostructures Combining Group IV Chalcogenide van der Waals Semiconductors.

Lateral heterostructures combining two multilayer group IV chalcogenide van der Waals semiconductors have attracted interest for optoelectronics, twistronics, and valleytronics, owing to their structural anisotropy, bulk-like electronic properties, enhanced optical thickness, and vertical interfaces enabling in-plane charge manipulation/separation, perpendicular to the trajectory of incident light. Group IV monochalcogenides support propagating photonic waveguide modes, but their interference gives rise to complex light emission patterns throughout the visible/near-infrared range both in uniform flakes and single-interface lateral heterostructures. Here, this work demonstrates the judicious integration of pure and alloyed monochalcogenide crystals into multimaterial heterostructures with unique photonic properties, notably the ability to select photonic modes with targeted discrete energies through geometric factors rather than band engineering. SnS-GeS1-x Sex -GeSe-GeS1-x Sex heterostructures with a GeS1-x Sex active layer sandwiched laterally between GeSe and SnS, semiconductors with similar optical constants but smaller bandgaps, were designed and realized via sequential vapor transport synthesis. Raman spectroscopy, electron microscopy/diffraction, and energy-dispersive X-ray spectroscopy confirm a high crystal quality of the laterally stitched components with sharp interfaces. Nanometer-scale cathodoluminescence spectroscopy provides evidence for a facile transfer of electron-hole pairs across the lateral interfaces and demonstrates the selection of photon emission at discrete energies in the laterally embedded active (GeS1- x Sex ) part of the heterostructure.

Germanium Diselenide Ribbons with Orthorhombic Crystal Structure.

Many materials are known to exist in several stable polymorphs, but synthesis only provides access to a subset. This situation is exemplified by the dichalcogenide semiconductor GeSe2. Besides the amorphous form, which attracted intense interest, crystalline GeSe2 in the bulk and in nanostructures such as flakes and nanobelts invariably adopts the 2D/layered monoclinic ß-phase. Hence, the properties of other polymorphs such as the orthorhombic 3D GeSe2 phase remain unknown. Here, we report the high-yield synthesis of orthorhombic GeSe2 nanoribbons by GeSe/Se vapor transport over Au catalysts. Access to air-stable monocrystalline, single-phase ribbons enabled investigating the properties of orthorhombic GeSe2 including its characteristic Raman spectrum. Optical absorption on ensembles and cathodoluminescence spectroscopy on individual ribbons show a wide bandgap and intense band-to-band emission in the visible, with a broad sub-bandgap emission tail. Our results establish orthorhombic GeSe2 ribbons as a promising wide-bandgap semiconductor nanostructure for applications in optoelectronics and energy conversion.

Imaging Anisotropic Waveguide Exciton Polaritons in Tin Sulfide.

In recent years, novel materials supporting in-plane anisotropic polaritons have attracted a great deal of research interest due to their capability of shaping nanoscale field distributions and controlling nanophotonic energy flows. Here we report a nano-optical imaging study of waveguide exciton polaritons (EPs) in tin sulfide (SnS) in the near-infrared (near-IR) region using scattering-type scanning near-field optical microscopy (s-SNOM). With s-SNOM, we mapped in real space the propagative EPs in SnS, which show sensitive dependence on the excitation energy and sample thickness. Moreover, we found that both the polariton wavelength and propagation length are anisotropic in the sample plane. In particular, in a narrow spectral range from 1.32 to 1.44 eV, the EPs demonstrate quasi-one-dimensional propagation, which is rarely seen in natural polaritonic materials. A further analysis indicates that the observed polariton anisotropy originates from the different optical band gaps and exciton binding energies along the two principal crystal axes of SnS.

Real-Time Electron Microscopy of Nanocrystal Synthesis, Transformations, and Self-Assembly in Solution.

Solution-phase processes such as colloidal synthesis and transformations have enabled the formation of nanocrystals with exquisite control over size, shape, and composition. Self-assembly, in solution or at phase boundaries, can arrange such nanocrystal building blocks into ordered superlattices and dynamically reconfigurable "smart" materials. Ultimately, continued improvements in our ability to direct nanocrystal matter depend on progress in understanding colloidal chemistry and self-assembly in solution. The traditional approach for investigating the underlying, inherently dynamic processes involves sampling at different stages combined with ex situ characterization, for example, using electron microscopy. In situ studies have been restricted to a few methods capable of measuring in bulk liquids, either in reciprocal space by diffraction or scattering or using spatially averaging (e.g., optical) measurements. These strategies face clear limitations in obtaining mechanistic information, and they are unable to address heterogeneous systems that may harbor rich sets of configurations with different local properties. The development of microfabricated cells that hermetically encapsulate bulk solutions between ultrathin (electron transparent) membranes has paved the way for studying processes in liquids in real time by electron microscopy at resolution down to the atomic scale. Electrons interact much more strongly with matter than other probes, for example, X-rays. In ordinary inorganic samples, the main effects are atom displacements and defect formation via knock-on and ionization damage. In liquid-cell electron microscopy, the interaction of the beam with both the suspended nanostructures and the solution creates more diverse effects, so the straightforward scenario of imaging unperturbed nanocrystal chemistry in solution is rarely realized.In this Account, we discuss applications of real-time electron microscopy to the analysis of nanocrystal synthesis, transformations, and self-assembly in solution. While in the simplest case the effects of the electron beam are negligible, the interaction with high-energy electrons often provides excitation or stimulus for solution-phase processes or opens up competing chemical pathways. Real-time observations of self-assembly demonstrate particularly clearly the power of in situ microscopy in identifying key nucleation and growth mechanisms and providing information about preferred structural motifs that can be analyzed to quantify the balance of forces and the role of entropy in stabilizing ordered assemblies. Modifications of the solution by the electron beam can provide stimuli for on-demand self-assembly, for example, via an acid spike due to water radiolysis that locally lowers the pH in the imaged area. While in this and other cases (e.g., colloidal synthesis), beam-induced radicals become part of the experimental design, in imaging redox reactions such as galvanic transformations of nanocrystal templates, radicals need to be managed and if possible eliminated by suitable scavengers. Finally, excitation by the imaging electron beam can transfer energy to individual nanocrystals in solution, thus driving nonthermal (e.g., plasmon-mediated) synthesis or other chemistry while following the reaction progress with high resolution. Overall, with validation by ex situ control experiments, the unique ability of observing processes in solution at the nanometer scale should make liquid-cell electron microscopy an integral part of the toolkit for designing novel inorganic nanocrystal architectures.

Optoelectronics and Nanophotonics of Vapor-Liquid-Solid Grown GaSe van der Waals Nanoribbons.

2D/layered semiconductors are of interest for fundamental studies and for applications in optoelectronics and photonics. Work to date focused on extended crystals, produced by exfoliation or growth and investigated by diffraction-limited spectroscopy. Processes such as vapor-liquid-solid (VLS) growth carry potential for mass-producing nanostructured van der Waals semiconductors with exceptionally high crystal quality and optoelectronic/photonic properties at least on par with those of extended flakes. Here, we demonstrate the synthesis, structure, morphology, and optoelectronics/photonics of GaSe van der Waals nanoribbons obtained by Au- and Ag-catalyzed VLS growth. Although all GaSe ribbons are high-quality basal-plane oriented single crystals, those grown at lower temperatures stand out with their remarkably uniform morphology and low edge roughness. Photoluminescence spectroscopy shows intense, narrow light emission at the GaSe bandgap energy. Nanophotonic experiments demonstrate traveling waveguide modes at visible/near-infrared energies and illustrate approaches for locally exciting and probing such photonic modes by cathodoluminescence in transmission electron microscopy.

Ultrathin Twisted Germanium Sulfide van der Waals Nanowires by Bismuth Catalyzed Vapor-Liquid-Solid Growth.

1D nanowires of 2D layered crystals are emerging nanostructures synthesized by combining van der Waals (vdW) epitaxy and vapor-liquid-solid (VLS) growth. Nanowires of the group IV monochalcogenide germanium sulfide (GeS) are of particular interest for twistronics due to axial screw dislocations giving rise to Eshelby twist and precision interlayer twist at helical vdW interfaces. Ultrathin vdW nanowires have not been realized, and it is not clear if confining layered crystals into extremely thin wires is even possible. If axial screw dislocations are still stable, ultrathin vdW nanowires can reach large twists and should display significant quantum confinement. Here it is shown that VLS growth over Bi catalysts yields vdW nanowires down to ≈15 nm diameter while maintaining tens of µm length. Combined electron microscopy and diffraction demonstrate that ultrathin GeS nanowires crystallize in the orthorhombic bulk structure but can realize nonequilibrium stacking that may lead to 1D ferroelectricity. Ultrathin nanowires carry screw dislocations, remain chiral, and achieve very high twist rates. Whenever the dislocation extends to the nanowire tip, it continues into the Bi catalyst. Eshelby twist analysis demonstrates that the ultrathin nanowires follow continuum predictions. Cathodoluminescence on individual nanowires, finally, shows pronounced emission blue shifts consistent with quantum confinement.

Plasmonic Effects on the Growth of Ag Nanocrystals in Solution.

The light-stimulated transformation of ensembles of spherical nanoparticles into anisotropic metal nanostructures mediated by localized surface plasmon resonance (LSPR) excitation is an elegant way of synthesizing triangular silver nanoprisms with extraordinary control over size and shape. Generally, the transformation occurs in oxidizing environments along a pathway that involves the oxidative etching of small preexisting Ag seeds, followed by plasmon-mediated reduction of the resulting Ag ions and Ag0 incorporation into the anisotropic nanocrystals. Here, we investigate pathways toward Ag nanoprisms from initially homogeneous AgNO3 solutions held under reducing conditions. Observations using in situ electron microscopy show that reducing environments and high Ag precursor concentrations in the presence of sodium citrate favor two alternative transformation routes of initial spherical nuclei into anisotropic nanoprisms: (i) the aggregation of spherical nanoparticles and plasmon-mediated conversion of small clusters into triangular prisms; (ii) shape fluctuations of individual small nanoparticles. Simulated field distributions confirm that the coupling of the LSPR excitation between closely spaced nanoparticles causes significant field enhancements near the local plasmonic hot spots, which facilitates accelerated Ag incorporation and thus supports the transformation into nanoprisms.

Single-Crystalline γ-Ga2S3 Nanotubes via Epitaxial Conversion of GaAs Nanowires.

The chemical transformation of nanowire templates into nanotubes is a promising avenue toward hollow one-dimensional (1D) nanostructures. To date, high-quality single crystalline tubes of nonlayered inorganic crystals have been obtained by solid-state reactions in diffusion couples of nanowires with deposited thin film shells, but this approach presents issues in achieving single-phase tubes with a desired stoichiometry. Chemical transformations with reactants supplied from the gas- or vapor-phase can avoid these complications, allowing single-phase nanotubes to be obtained through self-termination of the reaction once the sacrificial template has been consumed. Here, we demonstrate the realization of this scenario with the transformation of zincblende GaAs nanowires into single-crystalline cubic γ-Ga2S3 nanotubes by reaction with sulfur vapor. The conversion proceeds via the formation of epitaxial GaAs-Ga2S3 core-shell structures, vacancy injection and aggregation into Kirkendall voids, elastic relaxation of the detached Ga2S3 shell, and finally complete incorporation of Ga in a crystalline chalcogenide tube. Absorption and luminescence spectroscopy on individual nanotubes show optoelectronic properties, notably a ∼3.1 eV bandgap and intense band-edge and near band-edge emission consistent with high-quality single crystals, along with transitions between gap-states due to the inherent cation-vacancy defect structure of Ga2S3. Our work establishes the transformation of nanowires via vapor-phase reactions as a viable approach for forming single-crystalline hollow 1D nanostructures with promising properties.

Germanium Sulfide Nano-Optics Probed by STEM-Cathodoluminescence Spectroscopy.

Nano-optical studies of confined modes in planar waveguides have attracted significant interest as a means to probe exciton-polaritons and other hybrid light-matter quasiparticles in layered semiconductors, such as transition metal dichalcogenides or boron nitride. There is a need to broaden such studies to other materials and to identify alternatives to scanning near-field optical microscopy for exciting and measuring confined waveguide modes. Here, we establish an approach for probing the dispersion of traveling waveguide modes by cathodoluminescence spectroscopy excited by the focused electron beam in scanning transmission electron microscopy (STEM-CL) and apply it to solid-state resonators consisting of mesoscale monocrystalline prisms and plates composed of GeS, an anisotropic layered semiconductor with direct bandgap in the near-infrared spectral range. Structure, crystallography, and chemical composition of the mesostructures are analyzed by analytical electron microscopy. STEM-CL maps and spectra show pronounced interference effects and sharp emission peaks at photon energies below the fundamental bandgap of GeS. Our analysis demonstrates that locally excited light emission in STEM-CL launches in-plane waveguide modes in the mesoscale GeS structures, which are internally reflected by highly specular GeS edges to cause interference of the waveguide modes. Reabsorption and secondary luminescence give rise to the intensity modulations detected in the far field. Our results highlight avenues for probing light-matter interactions below the diffraction limit in a wide range of quantum materials and open up the possibility of tuning light emission geometrically using interference rather than by the conventional bandgap engineering.

Oxidation-driven surface dynamics on NiAl(100).

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling up of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). By comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.

Defect-Laden MoSe2 Quantum Dots Made by Turbulent Shear Mixing as Enhanced Electrocatalysts.

A high density of edge sites and other defects can significantly improve the catalytic activity of layered 2D materials. Herein, this study demonstrates a novel top-down strategy to maximize catalytic edge sites of MoSe2 by breaking up bulk MoSe2 into quantum dots (QDs) via "turbulent shear mixing" (TSM). The ultrasmall size of the MoSe2 QDs provides a high fraction of atoms in reactive edge sites, thus significantly improving the catalytic activities. The violent TSM further introduces abundant defects as additional active sites for electrocatalytic reactions. These edge-proliferated and defect-laden MoSe2 QDs are found to be efficient electrocatalysts for the hydrogen evolution reaction, and useful as counter electrodes in dye-sensitized solar cells. The work provides a new paradigm for creating edge-proliferated and defect-rich QDs from bulk layered materials.

Two-color field enhancement at an STM junction for spatiotemporally resolved photoemission.

We report measurements and numerical simulations of ultrafast laser-excited carrier flow across a scanning tunneling microscope (STM) junction. The current from a nanoscopic tungsten tip across a ∼1 nm vacuum gap to a silver surface is driven by a two-color excitation scheme that uses an optical delay-modulation technique to extract the two-color signal from background contributions. The role of optical field enhancements in driving the current is investigated using density functional theory and full three-dimensional finite-difference time-domain computations. We find that simulated field-enhanced two-photon photoemission (2PPE) currents are in excellent agreement with the observed exponential decay of the two-color photoexcited current with increasing tip-surface separation, as well as its optical-delay dependence. The results suggest an approach to 2PPE with simultaneous subpicosecond temporal and nanometer spatial resolution.

Termination of Ge surfaces with ultrathin GeS and GeS2 layers via solid-state sulfurization.

Reactions of Ge with S vapor, of interest as a potential approach for forming thin passivation layers on Ge surfaces, have been studied by photoelectron spectroscopy and Raman spectroscopy. Exposure of Ge(100) and Ge(111) to S drives the formation of Ge sulfide near-surface layers. At low temperatures, the reaction products comprise a thin GeS interlayer terminated by near-surface GeS2. Above 400 °C, exposure to sulfur gives rise to single-phase GeS2 layers whose thickness increases with temperature. Arrhenius analysis of the GeS2 thickness yields an activation energy (0.63 ± 0.08) eV, close to the barrier that controls Ge oxidation by O radicals. XPS measurements after extended ambient exposure show a stable, ultrathin near-surface GeS2 without significant oxidation, indicating that Ge-sulfides may provide an effective surface passivation for Ge surfaces.

Direct Measurement of the Tunable Electronic Structure of Bilayer MoS2 by Interlayer Twist.

Using angle-resolved photoemission on micrometer-scale sample areas, we directly measure the interlayer twist angle-dependent electronic band structure of bilayer molybdenum-disulfide (MoS2). Our measurements, performed on arbitrarily stacked bilayer MoS2 flakes prepared by chemical vapor deposition, provide direct evidence for a downshift of the quasiparticle energy of the valence band at the Brillouin zone center (Γ̅ point) with the interlayer twist angle, up to a maximum of 120 meV at a twist angle of ∼40°. Our direct measurements of the valence band structure enable the extraction of the hole effective mass as a function of the interlayer twist angle. While our results at Γ̅ agree with recently published photoluminescence data, our measurements of the quasiparticle spectrum over the full 2D Brillouin zone reveal a richer and more complicated change in the electronic structure than previously theoretically predicted. The electronic structure measurements reported here, including the evolution of the effective mass with twist-angle, provide new insight into the physics of twisted transition-metal dichalcogenide bilayers and serve as a guide for the practical design of MoS2 optoelectronic and spin-/valley-tronic devices.

High-Resolution Tracking Asymmetric Lithium Insertion and Extraction and Local Structure Ordering in SnS2.

In the rechargeable lithium ion batteries, the rate capability and energy efficiency are largely governed by the lithium ion transport dynamics and phase transition pathways in electrodes. Real-time and atomic-scale tracking of fully reversible lithium insertion and extraction processes in electrodes, which would ultimately lead to mechanistic understanding of how the electrodes function and why they fail, is highly desirable but very challenging. Here, we track lithium insertion and extraction in the van der Waals interactions dominated SnS2 by in situ high-resolution TEM method. We find that the lithium insertion occurs via a fast two-phase reaction to form expanded and defective LiSnS2, while the lithium extraction initially involves heterogeneous nucleation of intermediate superstructure Li0.5SnS2 domains with a 1-4 nm size. Density functional theory calculations indicate that the Li0.5SnS2 is kinetically favored and structurally stable. The asymmetric reaction pathways may supply enlightening insights into the mechanistic understanding of the underlying electrochemistry in the layered electrode materials and also suggest possible alternatives to the accepted explanation of the origins of voltage hysteresis in the intercalation electrode materials.

Role of RuO2(100) in surface oxidation and CO oxidation catalysis on Ru(0001).

We have studied the oxidation of the Ru(0001) surface by in situ microscopy during exposure to NO2, an efficient source of atomic oxygen, at elevated temperatures. In a previous investigation [Flege et al., Phys. Rev. B: Condens. Matter Mater. Phys., 2008, 78, 165407], at O coverages exceeding 1 monolayer, using the combination of intensity-voltage (I(V)) low-energy electron microscopy (LEEM) and multiple scattering calculations for the (00) beam in the very-low-energy range (E≤ 50 eV) we identified three surface components during the initial Ru oxidation: a (1 × 1)-O chemisorption phase, the RuO2(110) oxide phase, and a surface oxide structure characterized by a trilayer O-Ru-O stacking. Here, we use dark-field LEEM imaging and micro-illumination low-energy electron diffraction in the range of 100 to 400 eV to show that this trilayer phase is actually a RuO2(100)-(1 × 1) phase with possibly mixed O and Ru surface terminations. This identification rationalizes the thermodynamic stability of this phase at elevated temperatures and is consistent with the observation of catalytic activity of the phase in CO oxidation.