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Directed self-assembly uses different stimuli to initiate and control the interaction between nanocrystals. Protonation at reduced pH represents a convenient stimulus for initiating self-assembly. Prior work has focused on protonation-induced hydrogen bonding between peptide or amino acid functionalized nanocrystals for reversible cycling between dispersed and aggregated states. Here, we discuss a fundamentally different approach, in which changes in pH modify the nonspecific interparticle interaction between Au nanorods conjugated with single-stranded (ss) DNA. While electrostatic repulsion stabilizes dispersed suspensions at neutral pH, protonation in acidic solution modifies the DNA corona, turning the interaction between the rods attractive and triggering their self-assembly. Analysis of in-situ electron microscopy of ssDNA-Au nanorods in solution is consistent with a van der Waals attraction of charge-neutral monomers at acidic pH. The results demonstrate ssDNA-conjugated anisotropic nanostructures as versatile building blocks with stimuli-programmable interactions for on-demand self-assembly., Competing Interests: Declaration of Competing Interest The authors declare that they have no conflicts of interest., (Copyright © 2020 Elsevier Inc. All rights reserved.)

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.

Ultrathin van der Waals semiconductors have shown extraordinary optoelectronic and photonic properties. Propagating photonic modes make layered crystal waveguides attractive for photonic circuitry and for studying hybrid light-matter states. Accessing guided modes by conventional optics is challenging due to the limited spatial resolution and poor out-of-plane far-field coupling. Scanning near-field optical microscopy can overcome these issues and can characterize waveguide modes down to a resolution of tens of nanometers, albeit for planar samples or nanostructures with moderate height variations. Electron microscopy provides atomic-scale localization also for more complex geometries, and recent advances have extended the accessible excitations from interband transitions to phonons. Here, bottom-up synthesized layered semiconductor (Ge 1- x Sn x S) nanoribbons with an axial twist and deep subwavelength thickness are demonstrated as a platform for realizing waveguide modes, and cathodoluminescence spectroscopy is introduced as a tool to characterize them. Combined experiments and simulations show the excitation of guided modes by the electron beam and their efficient detection via photons emitted in the ribbon plane, which enables the measurement of key properties such as the evanescent field into the vacuum cladding with nanometer resolution. The results identify van der Waals waveguides operating in the infrared and highlight an electron-microscopy-based approach for probing complex-shaped nanophotonic structures., (© 2020 Wiley-VCH GmbH.)

Engineered heterostructures derive distinct properties from materials integration and interface formation. Two-dimensional crystals have been combined to form vertical stacks and lateral heterostuctures with covalent line interfaces. While thicker vertical stacks have been realized, lateral heterostructures from multilayer van der Waals crystals, which could bring the benefits of high-quality interfaces to bulk-like layered materials, have remained much less explored. Here, we demonstrate the integration of anisotropic layered Sn and Ge monosulfides into complex heterostructures with seamless lateral interfaces and tunable vertical design using a two-step growth process. The anisotropic lattice mismatch at the lateral interfaces between GeS and SnS is relaxed via dislocations and interfacial alloying. Nanoscale optoelectronic measurements by cathodoluminescence spectroscopy show the characteristic light emission of joined high-quality van der Waals crystals. Spectroscopy across the lateral interface indicates valley-selective luminescence in the bulk SnS component that arises due to anisotropic electron transfer across the interface. The results demonstrate the ability to realize high-quality lateral heterostructures of multilayer van der Waals crystals for diverse applications, e.g. , in optoelectronics or valleytronics.

Nanowires of layered van der Waals (vdW) crystals are of interest due to structural characteristics and emerging properties that have no equivalent in conventional 3D crystalline nanostructures. Here, vapor-liquid-solid growth, optoelectronics, and photonics of GaS vdW nanowires are studied. Electron microscopy and diffraction demonstrate the formation of high-quality layered nanostructures with different vdW layer orientation. GaS nanowires with vdW stacking perpendicular to the wire axis have ribbon-like morphologies with lengths up to 100 μm and uniform width. Wires with axial layer stacking show tapered morphologies and a corrugated surface due to twinning between successive few-layer GaS sheets. Layered GaS nanowires are excellent wide-bandgap optoelectronic materials with E g = 2.65 eV determined by single-nanowire absorption measurements. Nanometer-scale spectroscopy on individual nanowires shows intense blue band-edge luminescence along with longer wavelength emissions due to transitions between gap states and photonic properties such as interference of confined waveguide modes propagating within the nanowires. The combined results show promise for applications in electronics, optoelectronics, and photonics, as well as photo- or electrocatalysis owing to a high density of reactive edge sites, and intercalation-type energy storage benefiting from facile access to the interlayer vdW gaps.

Two-dimensional materials provide extraordinary opportunities for exploring phenomena arising in atomically thin crystals. Beginning with the first isolation of graphene, mechanical exfoliation has been a key to provide high-quality two-dimensional materials, but despite improvements it is still limited in yield, lateral size and contamination. Here we introduce a contamination-free, one-step and universal Au-assisted mechanical exfoliation method and demonstrate its effectiveness by isolating 40 types of single-crystalline monolayers, including elemental two-dimensional crystals, metal-dichalcogenides, magnets and superconductors. Most of them are of millimeter-size and high-quality, as shown by transfer-free measurements of electron microscopy, photo spectroscopies and electrical transport. Large suspended two-dimensional crystals and heterojunctions were also prepared with high-yield. Enhanced adhesion between the crystals and the substrates enables such efficient exfoliation, for which we identify a gold-assisted exfoliation method that underpins a universal route for producing large-area monolayers and thus supports studies of fundamental properties and potential application of two-dimensional materials.

The physical properties of two-dimensional (2D) materials depend strongly on the number of layers. Hence, methods for controlling their thickness with atomic layer precision are highly desirable, yet still too rare, and demonstrated for only a limited number of 2D materials. Here, we present a simple and scalable method for the continuous layer-by-layer thinning that works for a large class of 2D materials, notably layered germanium pnictides and chalcogenides. It is based on a simple oxidation/etching process, which selectively occurs on the topmost layers. Through a combination of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray diffraction experiments we demonstrate the thinning method on germanium arsenide (GeAs), germanium sulfide (GeS), and germanium disulfide (GeS 2 ). We use first-principles simulation to provide insights into the oxidation mechanism. Our strategy, which could be applied to other classes of 2D materials upon proper choice of the oxidation/etching reagent, supports 2D material-based device applications, e.g. , in electronics or optoelectronics, where a precise control over the number of layers (hence over the material's physical properties) is needed. Finally, we also show that when used in combination with lithography, our method can be used to make precise patterns in the 2D materials.

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 Ag 0 incorporation into the anisotropic nanocrystals. Here, we investigate pathways toward Ag nanoprisms from initially homogeneous AgNO 3 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.

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-Ga 2 S 3 nanotubes by reaction with sulfur vapor. The conversion proceeds via the formation of epitaxial GaAs-Ga 2 S 3 core-shell structures, vacancy injection and aggregation into Kirkendall voids, elastic relaxation of the detached Ga 2 S 3 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 Ga 2 S 3 . 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.

Vertical van der Waals (vdW) heterostructures of 2D crystals with defined interlayer twist are of interest for band-structure engineering via twist moiré superlattice potentials. To date, twist-heterostructures have been realized by micromechanical stacking. Direct synthesis is hindered by the tendency toward equilibrium stacking without interlayer twist. Here, we demonstrate that growing a 2D crystal with fixed azimuthal alignment to the substrate followed by transformation of this intermediate enables a potentially scalable synthesis of twisted heterostructures. Microscopy during growth of ultrathin orthorhombic SnS on trigonal SnS 2 shows that vdW epitaxy yields azimuthal order even for non-isotypic 2D crystals. Excess sulfur drives a spontaneous transformation of the few-layer SnS to SnS 2 , whose orientation - rotated 30° against the underlying SnS 2 crystal - is defined by the SnS intermediate rather than the substrate. Preferential nucleation of additional SnS on such twisted domains repeats the process, promising the realization of complex twisted stacks by bottom-up synthesis.

Among 2D/layered semiconductors, group IV monochalcogenides such as SnS(e) and GeS(e) have attracted attention as phosphorene/black phosphorus analogues with anisotropic structures and predicted unusual properties. In contrast to SnS, for which bottom-up synthesis has been reported, few-layer GeS has been realized primarily via exfoliation from bulk crystals. Here, we report the synthesis of large (up to >20 μm), faceted single crystalline GeS flakes with anisotropic properties using a vapor transport process. In situ electron microscopy is used to identify the thermal stability and sublimation pathways, and demonstrates that the GeS flakes are self-encapsulated in a thin, sulfur-rich amorphous GeS x shell during growth. The shell provides exceptional chemical stability to the layered GeS core. In contrast to exfoliated GeS, which rapidly degrades during exposure to air, the synthesized GeS-GeS x core-shell structures show no signs of chemical attack and remain unchanged in air for extended time periods. Measurements of the optoelectronic properties by photoluminescence spectroscopy show a tunable bandgap due to out-of-plane quantum confinement in flakes with thickness below 100 nm. Cathodoluminescence (CL) spectroscopy with nanoscale excitation provides evidence for interfacial charge transfer due to a type II heterojunction between the crystalline core and amorphous shell. Measurements by locally excited CL yield a minority carrier (electron) diffusion length in the p -type GeS core l diff = 0.27 μm, on par with diffusion lengths in the highest-quality layered chalcogenide semiconductors.

Engineered heterostructures create new functionality by integrating dissimilar materials. Combining different 2D crystals naturally produces two distinct classes of heterostructures, vertical van der Waals (vdW) stacks or 2D sheets bonded laterally by covalent line interfaces. When joining thicker layered crystals, the arising structural and topological conflicts can result in more complex geometries. Phase separation during one-pot synthesis of layered tin chalcogenides spontaneously creates core-shell structures in which large orthorhombic SnS crystals are enclosed in a wrap-around shell of trigonal SnS 2 , forcing the coexistence of parallel vdW layering along with unconventional, orthogonally layered core-shell interfaces. Measurements of the optoelectronic properties establish anisotropic carrier separation near type II core-shell interfaces and extended long-wavelength light harvesting via spatially indirect interfacial absorption, making multifunctional layered core-shell structures attractive for energy-conversion applications., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 patterns 1-7 . Previously, such twisted heterostructures have involved a single planar interface between layers isolated by exfoliation and micromechanically stacked in the desired relative orientation 1,8-12 . 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 axis 13 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 dislocation 14,15 , 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.

Solution-phase self-assembly of DNA-functionalized nanoparticles into mesoscale structures is a promising strategy for creating functional materials from nanocrystal building blocks. The predominant approach has been the use of Watson-Crick base pairing between complementary bases in designated 'sticky ends' to trigger programmable self-assembly into ordered superlattices. Here we demonstrate the ordered self-assembly of Au nanoparticles conjugated with single-stranded (ss) DNA in acidic solutions. Au nanoparticles functionalized with thiolated ssDNA are protected against coalescence and the DNA conformation undergoes significant modifications at low pH, which can be associated with the protonation of adenine bases and the formation of a parallel poly-adenine duplex, which govern the interaction between ssDNA-Au nanoparticle conjugates. In situ liquid cell electron microscopy enables real-time imaging of the self-assembly process and the identification of key characteristics, such as the preferred structural motifs and interparticle separations in the native solution environment. Our results highlight alternatives to conventional base-pairing interactions for building DNA-directed nanoparticle superlattices.

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.

Layered semiconductors show promise as channel materials for field-effect transistors (FETs). Usually, such devices incorporate solid back or top gate dielectrics. Here, we explore deionized (DI) water as a solution top-gate for field-effect switching of layered semiconductors including SnS 2 , MoS 2 , and black phosphorus. The DI water gate is easily fabricated, can sustain rapid bias changes, and its efficient coupling to layered materials provides high on-off current ratios, near-ideal subthreshold swing, and enhanced short-channel behavior even for FETs with thick, bulk-like channels, where such  control is difficult to realize with conventional back gating. Screening by the high-k solution gate eliminates hysteresis due to surface and interface trap states and substantially enhances the field-effect mobility. The onset of water electrolysis sets the ultimate limit to DI water gating at large negative gate bias. Measurements in this regime show promise for aqueous sensing, demonstrated here by the amperometric detection of glucose in aqueous solution. DI water gating of layered semiconductors can be harnessed in research on novel materials and devices, and it may with further development find broad applications in microelectronics and sensing.

Oligonucleotide-nanoparticle conjugates, also called programmable atom equivalents, carry promise as building blocks for self-assembled colloidal crystals, reconfigurable or stimuli responsive functional materials, as well as bio-inspired hierarchical architectures in wet environments. In situ studies of the DNA-mediated self-assembly of nanoparticles have so far been limited to reciprocal space techniques. Liquid-cell electron microscopy could enable imaging such systems with high resolution in their native environment but to realize this potential, radiation damage to the oligonucleotide linkages needs to be understood and conditions for damage-free electron microscopy identified. Here, we analyze in situ observations of DNA-linked two-dimensional nanoparticle arrays, along with control experiments for different oligonucleotide configurations, to identify the mechanisms of radiation damage for ordered superlattices of DNA-nanoparticle conjugates. In a biological context, the results point to new avenues for studying direct and indirect radiation effects for small ensembles of DNA in solution by tracking conjugated nanoparticles. By establishing low-dose conditions suitable for extended in situ imaging of programmable atom equivalents, our work paves the way for real-space observations of DNA-mediated self-assembly processes.

The rutile TiO 2 (110) surface has long-served as a well-characterized, prototypical transition-metal oxide surface used in heterogeneous catalysis and photocatalytic water splitting. Naturally occurring defects on this surface, called bridging-oxygen (BO) vacancies, are important as they determine the overall reactivity of the surface. Herein, we report a bias-dependent, scanning tunneling microscopy (STM) signature of the BO vacancies on TiO 2 (110): for sample bias voltages past a threshold of +3 V, the bright vacancies are flanked on either side (along the oxygen row) by two dark spots approximately shaped like half-moons. The BO vacancies have a bright aspect below the threshold bias also but are not surrounded by half-moon dark depressions. Using generalized gradient approximation calculations with Hubbard correction (GGA + U ) for projected density of states (DOS) and simulated STM images, we find that the bias-dependent STM signature originates from (i) local DOS maxima of all BOs (lighter background that occurs above the threshold bias) and (ii) the increased separation between the first and second BO atoms neighboring the vacancy which leads to an apparent dip between these neighboring oxygens. These results offer a new striking example of the STM signature that appears without switching the polarity of the bias. Similar approaches can be employed for seeking distinguishing features on the surfaces of other large band gap semiconductors and insulators., Competing Interests: The authors declare no competing financial interest.

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 GeS 2 . Above 400 °C, exposure to sulfur gives rise to single-phase GeS 2 layers whose thickness increases with temperature. Arrhenius analysis of the GeS 2 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 GeS 2 without significant oxidation, indicating that Ge-sulfides may provide an effective surface passivation for Ge surfaces.

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 MoSe 2 by breaking up bulk MoSe 2 into quantum dots (QDs) via "turbulent shear mixing" (TSM). The ultrasmall size of the MoSe 2 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 MoSe 2 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., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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.

Switching the magnetic properties of organic semiconductors on a metal surface has thus far largely been limited to molecule-by-molecule tip-induced transformations in scanned probe experiments. Here we demonstrate with molecular resolution that collective control of activated Kondo screening can be achieved in thin-films of the organic semiconductor titanyl phthalocyanine on Cu(110) to obtain tunable concentrations of Kondo impurities. Using low-temperature scanning tunneling microscopy and spectroscopy, we show that a thermally activated molecular distortion dramatically shifts surface-molecule coupling and enables ensemble-level control of Kondo screening in the interfacial spin system. This is accompanied by the formation of a temperature-dependent Abrikosov-Suhl-Kondo resonance in the local density of states of the activated molecules. This enables coverage-dependent control over activation to the Kondo screening state. Our study thus advances the versatility of molecular switching for Kondo physics and opens new avenues for scalable bottom-up tailoring of the electronic structure and magnetic texture of organic semiconductor interfaces at the nanoscale.

Galvanic replacement reactions are important as they transform nanoparticle templates into complex porous and hollow metal or alloy nanostructures with interesting properties for a variety of applications. Real-time liquid cell electron microscopy (LCEM) observations of the transformation of solid nanoparticles into hollow shell and cage bimetallic nanostructures are challenging because the high-energy electron beam strongly affects the galvanic process via species such as aqueous electrons and hydroxyl radicals generated through the radiolysis of water in the liquid cell. As a result the galvanic reactions are modified by the introduction of additional pathways that can decouple the oxidation of the nanoparticles from the reduction of the metal ion complexes in solution. Here we demonstrate that changing the pH of the solution provides an effective approach to alter the balance of radiolysis products. In situ observations of the transformation of Ag nanocubes in Au salt containing neutral and acidic aqueous solutions demonstrate that a lowering of the pH by addition of H 2 SO 4 significantly lessens radical-induced modifications of redox reactions by avoiding the excessive reduction of metal-chloro complexes by aqueous electrons (e aq - ) and making the process sufficiently slow to be observed. As a result, the different stages of galvanic replacement reactions on nanoparticles can be imaged in real-time by LCEM.

The combination of zero-dimensional (0D) colloidal CdSe/ZnS quantum dots with tin disulfide (SnS2), a two-dimensional (2D)-layered metal dichalcogenide, results in 0D-2D hybrids with enhanced light absorption properties. These 0D-2D hybrids, when exposed to light, exhibit intrahybrid nonradiative energy transfer from photoexcited CdSe/ZnS quantum dots to SnS2. Using single nanocrystal spectroscopy, we find that the rate for energy transfer in 0D-2D hybrids increases with added number of SnS2 layers, a positive manifestation toward the potential functionality of such 2D-based hybrids in applications such as photovoltaics and photon sensing.

Solution-phase self-assembly of nanocrystals into mesoscale structures is a promising strategy for constructing functional materials from nanoscale components. Liquid environments are key to self-assembly since they allow suspended nanocrystals to diffuse and interact freely, but they also complicate experiments. Real-time observations with single-particle resolution could have transformative impact on our understanding of nanocrystal self-assembly. Here we use real-time in situ imaging by liquid-cell electron microscopy to elucidate the nucleation and growth mechanism and properties of linear chains of octapod-shaped nanocrystals in their native solution environment. Statistical mechanics modelling based on these observations and using the measured chain-length distribution clarifies the relative importance of dipolar and entropic forces in the assembly process and gives direct access to the interparticle interaction. Our results suggest that monomer-resolved in situ imaging combined with modelling can provide unprecedented quantitative insight into the microscopic processes and interactions that govern nanocrystal self-assembly in solution.

We use in situ observations during high-temperature transmission electron microscopy to quantify the exchange of semiconductor material between Au-Ge vapor--liquid--solid seed drops and Ge nanowires (NWs). By performing simultaneous measurements under identical conditions on arrays with systematic variations in NW diameter, we establish the nanoscale size dependence of the temperature-dependent equilibrium composition of the Au-Ge binary alloy. We find a significantly enhanced Ge solubility for drops on thin NWs compared to thicker ones. The controlled modification of the surface of the NW by an ordered carbon shell leads to drastic changes in the solubility.

Intercalation of metal atoms is an established route for tuning the coupling of graphene to a substrate. The extension to reactive species such as oxygen would set the stage for a wide spectrum of interfacial chemistry. Here we demonstrate the controlled modification of a macroscopic graphene-metal interface by oxygen intercalation. The selective oxidation of a ruthenium surface beneath graphene lifts the strong metal-carbon coupling and restores the characteristic Dirac cones of isolated monolayer graphene. Our experiments establish the competition between low-temperature oxygen intercalation and graphene etching at higher temperatures and suggest that small molecules can populate the space between graphene and metals, with the adsorbate-metal interaction being modified significantly by the presence of graphene. These findings open up new avenues for the processing of graphene for device applications and for performing chemical reactions in the confined space between a metal surface and a graphene sheet.

We use transmission electron microscopy observations to establish the parts of the phase diagram of nanometer sized Au-Ge alloy drops at the tips of Ge nanowires (NWs) that determine their temperature-dependent equilibrium composition and, hence, their exchange of semiconductor material with the NWs. We find that the phase diagram of the nanoscale drop deviates significantly from that of the bulk alloy, which explains discrepancies between actual growth results and predictions on the basis of the bulk-phase equilibria. Our findings provide the basis for tailoring vapor-liquid-solid growth to achieve complex one-dimensional materials geometries.

Using transmission electron microscopy, we identify the temperature-dependent interaction pathway of carbon-supported Au nanoparticles. At low temperature (room temp. to 400 degrees C), Au nanoparticles predominantly interact by coalescence initiated by an atomic Au bridge. At high temperature (400-800 degrees C), the particles assemble into Au/C core-shell nanostructures. C-shells around individual nanoparticles passivate their surface and prevent coalescence. Ultimately coalescence does occur via rupture of the passivating shells, which invariably follows the assembly of C sheets enveloping and compressing multiple closely spaced Au/C nanoparticles.