Crystallization of heavy fermions via epitaxial strain in spinel LiV2O4 thin film.

The mixed-valent spinel LiV2O4 is known as the first oxide heavy-fermion system. There is a general consensus that a subtle interplay of charge, spin, and orbital degrees of freedom of correlated electrons plays a crucial role in the enhancement of quasi-particle mass, but the specific mechanism has remained yet elusive. A charge-ordering (CO) instability of V3+ and V4+ ions that is geometrically frustrated by the V pyrochlore sublattice from forming a long-range CO down to T = 0 K has been proposed as a prime candidate for the mechanism. Here, we uncover the hidden CO instability by applying epitaxial strain on single-crystalline LiV2O4 thin films. We find a crystallization of heavy fermions in a LiV2O4 film on MgO, where a charge-ordered insulator comprising of a stack of V3+ and V4+ layers along [001], the historical Verwey-type ordering, is stabilized by the in-plane tensile and out-of-plane compressive strains from the substrate. Our discovery of the [001] Verwey-type CO, together with previous realizations of a distinct [111] CO, evidence the close proximity of the heavy-fermion state to degenerate CO states mirroring the geometrical frustration of the V pyrochlore lattice, which supports the CO instability scenario for the mechanism behind the heavy-fermion formation.

Offcut Substrate-Induced Defect Trapping at Step Edges.

We report step edge-induced localized defects suppressing subsequent antiphase boundary formation in the bulk structure of a trilayer oxide heterostructure. The heterostructure encompasses a layer of La0.66Sr0.34MnO3 sandwiched between a superconducting La1.84Sr0.16CuO4 bottom layer and an insulating La2CuO4 top layer. The combination of a minor a-axis mismatch (0.11 Å) and a pronounced c-axis mismatch (2.73 Å) at the step edges leads to the emergence of localized defects exclusively forming at the step edge. Employing atomically resolved electron energy-loss spectroscopy maps, we discern the electronic state of those structures in the second La0.66Sr0.34MnO3 unit cell near the step edge. In particular, a reduction in the pre-edge region of the O-K edge indicates the formation of oxygen vacancies induced by the strained step edge. This study underscores our capability to control defects at the nanoscale.

Optical conductivity and superconductivity in highly overdoped La2-x Ca x CuO4 thin films.

We have used atomic layer-by-layer oxide molecular beam epitaxy to grow epitaxial thin films of [Formula: see text] with x up to 0.5, greatly exceeding the solubility limit of Ca in bulk systems ([Formula: see text]). A comparison of the optical conductivity measured by spectroscopic ellipsometry to prior predictions from dynamical mean-field theory demonstrates that the hole concentration p is approximately equal to x. We find superconductivity with [Formula: see text] of 15 to 20 K up to the highest doping levels and attribute the unusual stability of superconductivity in [Formula: see text] to the nearly identical radii of La and Ca ions, which minimizes the impact of structural disorder. We conclude that careful disorder management can greatly extend the "superconducting dome" in the phase diagram of the cuprates.

Thickness-Dependent Interface Polarity in Infinite-Layer Nickelate Superlattices.

The interface polarity plays a vital role in the physical properties of oxide heterointerfaces because it can cause specific modifications of the electronic and atomic structure. Reconstruction due to the strong polarity of the NdNiO2/SrTiO3 interface in recently discovered superconducting nickelate films may play an important role, as no superconductivity has been observed in the bulk. By employing four-dimensional scanning transmission electron microscopy and electron energy-loss spectroscopy, we studied effects of oxygen distribution, polyhedral distortion, elemental intermixing, and dimensionality in NdNiO2/SrTiO3 superlattices grown on SrTiO3 (001) substrates. Oxygen distribution maps show a gradual variation of the oxygen content in the nickelate layer. Remarkably, we demonstrate thickness-dependent interface reconstruction due to a polar discontinuity. An average cation displacement of ∼0.025 nm at interfaces in 8NdNiO2/4SrTiO3 superlattices is twice larger than that in 4NdNiO2/2SrTiO3 superlattices. Our results provide insights into the understanding of reconstructions at NdNiO2/SrTiO3 polar interfaces.

Preparation of High-Quality Samples for MEMS-Based In-Situ (S)TEM Experiments.

A novel focused ion beam (FIB)-based methodology for the preparation of clean and artifact-free specimens on micro-electro-mechanical-system (MEMS)-based chips for in-situ electrical and electro-thermal experiments in a (scanning) transmission electron microscope ((S)TEM) is introduced. Owing to an alternative geometry, the lamellae are attached to a MEMS-based chip directly after the lift-out procedure and afterward further treated or thinned to electron transparency. The quality of produced lamellae on a chip resembles the quality of a classical FIB-prepared sample that is here demonstrated by high-resolution STEM imaging and analytical techniques. Various sample preparation parameters and the performance of in-situ prepared samples have been evaluated through electrical-biasing experiments.

Electron Ptychographic Phase Imaging of Beam-sensitive All-inorganic Halide Perovskites Using Four-dimensional Scanning Transmission Electron Microscopy.

Halide perovskites (HPs) are promising candidates for optoelectronic devices, such as solar cells or light-emitting diodes. Despite recent progress in performance optimization and low-cost manufacturing, their commercialization remains hindered due to structural instabilities. While essential to the development of the technology, the relation between the microscopic properties of HPs and the relevant degradation mechanisms is still not well understood. The sensitivity of HPs toward electron-beam irradiation poses significant challenges for transmission electron microscopy (TEM) investigations of structure and degradation mechanisms at the atomic scale. However, technological advances and the development of direct electron cameras (DECs) have opened up a completely new field of electron microscopy: four-dimensional scanning TEM (4D-STEM). From a 4D-STEM dataset, it is possible to extract not only the intensity signal for any STEM detector geometry but also the phase information of the specimen. This work aims to show the potential of 4D-STEM, in particular, electron exit-wave phase reconstructions via focused probe ptychography as a low-dose and dose-efficient technique to image the atomic structure of beam-sensitive HPs. The damage mechanism under conventional irradiation is described and atomically resolved almost aberration-free phase images of three all-inorganic HPs, CsPbBr3, CsPbIBr2, and CsPbI3, are presented with a resolution down to the aperture-constrained diffraction limit.

Uncovering the Evolution of Low-Energy Plasmons in Nanopatterned Aluminum Plasmonics on Graphene.

We report adjusting the charge-transfer-plasmon (CTP) resonances of aluminum (Al) bowties on suspended monolayer graphene via controlled nanofabrication and focused electron-beam irradiation. CTP resonances of bowties with a conductive junction blue-shift with an increase in junction width, whereas their 3λ/2 and λ resonances barely red-shift. These plasmon modes are derived and confirmed by an LC circuit model and electromagnetic simulations performed with boundary-element and frequency-domain methods. A monotonic decay of the CTP lifetime is observed, while the junction width is extended. Instead, the lifetimes of 3λ/2 and λ resonances are nearly independent of junction width. When the junction is shrunk by electron-beam irradiation, all antenna resonances red-shift. Having created an electron-beam-induced sub 5 nm gap in bowties, we monitor the unambiguous transition of a CTP into a bonding-type gap mode, which is highly sensitive to the separation distance. Meanwhile, the 3λ/2 and λ resonances evolve into dipolar bright and dipolar dark modes.

Exfoliated 2D Layered and Nonlayered Metal Phosphorous Trichalcogenides Nanosheets as Promising Electrocatalysts for CO2 Reduction.

Two-dimensional (2D) materials catalysts provide an atomic-scale view on a fascinating arena for understanding the mechanism of electrocatalytic carbon dioxide reduction (CO2 ECR). Here, we successfully exfoliated both layered and nonlayered ultra-thin metal phosphorous trichalcogenides (MPCh3 ) nanosheets via wet grinding exfoliation (WGE), and systematically investigated the mechanism of MPCh3 as catalysts for CO2 ECR. Unlike the layered CoPS3 and NiPS3 nanosheets, the active Sn atoms tend to be exposed on the surfaces of nonlayered SnPS3 nanosheets. Correspondingly, the nonlayered SnPS3 nanosheets exhibit clearly improved catalytic activity, showing formic acid selectivity up to 31.6 % with -7.51 mA cm-2 at -0.65 V vs. RHE. The enhanced catalytic performance can be attributed to the formation of HCOO* via the first proton-electron pair addition on the SnPS3 surface. These results provide a new avenue to understand the novel CO2 ECR mechanism of Sn-based and MPCh3 -based catalysts.

Oxygen-evolving catalytic atoms on metal carbides.

Single-atom catalysts have shown promising performance in various catalytic reactions. Catalytic metal sites supported on oxides or carbonaceous materials are usually strongly coordinated by oxygen or heteroatoms, which naturally affects their electronic environment and consequently their catalytic activity. Here, we reveal the stabilization of single-atom catalysts on tungsten carbides without the aid of heteroatom coordination for efficient catalysis of the oxygen evolution reaction (OER). Benefiting from the unique structure of tungsten carbides, the atomic FeNi catalytic sites are weakly bonded with the surface W and C atoms. The reported catalyst shows a low overpotential of 237 mV at 10 mA cm-2, which can even be lowered to 211 mV when the FeNi content is increased, a high turnover frequency value of 4.96 s-1 (η = 300 mV) and good stability (1,000 h). Density functional theory calculations show that either metallic Fe/Ni atoms or (hydro)oxide FeNi species are responsible for the high OER activity. We suggest that the application of inexpensive and durable WCx supports opens up a promising pathway to develop further single-atom catalysts for electrochemical catalytic reactions.

Determination of Grain-Boundary Structure and Electrostatic Characteristics in a SrTiO3 Bicrystal by Four-Dimensional Electron Microscopy.

The grain boundary (GB) plays a critical role in a material's properties and device performance. Therefore, the characterization of a GB's atomic structure and electrostatic characteristics is a matter of great importance for materials science. Here, we report on the atomic structure and electrostatic analysis of a GB in a SrTiO3 bicrystal by four-dimensional scanning transmission electron microscopy (4D-STEM). We demonstrate that the Σ5 GB is Ti-rich and poor in Sr. We investigate possible effects on the variation in the atomic electrostatic field, including oxygen vacancies, Ti-valence change, and accumulation of cations. A negative charge resulting from a space-charge zone in SrTiO3 compensates a positive charge accumulated at the GB, which is in agreement with the double-Schottky-barrier model. It demonstrates the feasibility of characterizing the electrostatic properties at the nanometer scale by 4D-STEM, which provides comprehensive insights to understanding the GB structure and its concomitant effects on the electrostatic properties.

Assembling Metal Organic Layer Composites for High-Performance Electrocatalytic CO2 Reduction to Formate.

2D metal-organic-framework (MOF) based composites have emerged as promising candidates for electrocatalysis due to their high structural flexibility and fully exposed active sites. Herein, a freestanding metal-organic layer (MOL) with a 2D kgd (kagome dual) lattice was constructed with abundant surface oxygenate groups serving as anchoring sites to immobilize diverse guests. Taking Bi as an example, tetragonal Bi2 O3 nanowires can be uniformly grown on MOLs after solvothermal treatment, the structural evolution of which was followed by ex situ electron microscopy. The as-prepared Bi2 O3 /MOL exhibits excellent CO2 electroreduction activity towards formate reaching a specific current of 2.3 A mgBi -1 and Faradaic efficiencies of over 85 % with a wide potential range from -0.87 to -1.17 V, far surpassing Bi2 O3 /UiO (a 3D Zr6 -oxo based MOF) and Bi2 O3 /AB (Acetylene Black). Such a post-synthetic modification strategy can be flexibly extended to develop versatile MOL composites, highlighting the superiority of optimizing MOL-based composites for electrocatalysis.

Facile Preparation of MoS2 Nanocomposites for Efficient Potassium-Ion Batteries by Grinding-Promoted Intercalation Exfoliation.

Efficient exfoliations of bulk molybdenum disulfide (MoS2 ) into few-layered nanosheets in pure phase are highly attractive because of the promising applications of the resulted 2D materials in diversified optoelectronic devices. Here, a new exfoliation method is presented to prepare semiconductive 2D hexagonal phase (2H phase) MoS2 -cellulose nanocrystal (CNC) nanocomposites using grinding-promoted intercalation exfoliation (GPIE). This method with facile grinding of the bulk MoS2 and CNC powder followed by conventional liquid-phase exfoliation in water can not only efficiently exfoliate 2H-MoS2 nanosheets, but also produce the 2H-MoS2 /CNC 2D nanocomposites simultaneously. Interestingly, the intercalated CNC sandwiched in MoS2 nanosheets increases the interlayer spacing of 2H-MoS2 , providing perfect conditions to accommodate the large-sized ions. Therefore, these nanocomposites are good anode materials of potassium-ion batteries (KIBs), showing a high reversible capacity of 203 mAh g-1 at 200 mA g-1 after 300 cycles, a good reversible capacity of 114 mAh g-1 at 500 mA g-1 , and a low decay of 0.02% per cycle over 1500 cycles. With these impressive KIB performances, this efficient GPIE method will open up a new avenue to prepare pure-phase MoS2 and promising 2D nanocomposites for high-performance device applications.

Catalyzing Bond-Dissociation in Graphene via Alkali-Iodide Molecules.

Atomic design of a 2D-material such as graphene can be substantially influenced by etching, deliberately induced in a transmission electron microscope. It is achieved primarily by overcoming the threshold energy for defect formation by controlling the kinetic energy and current density of the fast electrons. Recent studies have demonstrated that the presence of certain species of atoms can catalyze atomic bond dissociation processes under the electron beam by reducing their threshold energy. Most of the reported catalytic atom species are single atoms, which have strong interaction with single-layer graphene (SLG). Yet, no such behavior has been reported for molecular species. This work shows by experimentally comparing the interaction of alkali and halide species separately and conjointly with SLG, that in the presence of electron irradiation, etching of SLG is drastically enhanced by the simultaneous presence of alkali and iodine atoms. Density functional theory and first principles molecular dynamics calculations reveal that due to charge-transfer phenomena the CC bonds weaken close to the alkali-iodide species, which increases the carbon displacement cross-section. This study ascribes pronounced etching activity observed in SLG to the catalytic behavior of the alkali-iodide species in the presence of electron irradiation.

Direct Observation of Huge Flexoelectric Polarization around Crack Tips.

Flexoelectricity is especially relevant for nanoscale structures, and it is expected to be largest at the tip of cracks. We demonstrate the presence of a huge flexoelectric polarization at crack tips in SrTiO3 by direct observation with scanning transmission electron microscopy. We observe an averaged polarization of 62 ± 16 µC cm-2 in the three unit cells adjacent to the crack tip, which is one of the largest flexoelectric polarizations ever reported. The polarization is screened by an electron density of 0.7 ± 0.1 e-/uc localized within one unit cell. These findings reveal the relevance of flexoelectricity for the science of crack formation and propagation.

Secondary-Phase-Assisted Grain Boundary Migration in CuInSe_{2}.

Significant structural evolution occurs during the deposition of CuInSe_{2} solar materials when the Cu content increases. We use in situ heating in a scanning transmission electron microscope to directly observe how grain boundaries migrate during heating, causing nondefected grains to consume highly defected grains. Cu substitutes for In in the near grain boundary regions, turning them into a Cu-Se phase topotactic with the CuInSe_{2} grain interiors. Together with density functional theory and molecular dynamics calculations, we reveal how this Cu-Se phase makes the grain boundaries highly mobile.

Probing plasmonic excitation mechanisms and far-field radiation of single-crystalline gold tapers with electrons.

Conical metallic tapers represent an intriguing subclass of metallic nanostructures, as their plasmonic properties show interesting characteristics in strong correlation to their geometrical properties. This is important for possible applications such as in the field of scanning optical microscopy, as favourable plasmonic resonance behaviour can be tailored by optimizing structural parameters like surface roughness or opening angle. Here, we review our recent studies, where single-crystalline gold tapers were investigated experimentally by means of electron energy-loss and cathodoluminescence spectroscopy techniques inside electron microscopes, supported by theoretical finite-difference time-domain calculations. Through the study of tapers with various opening angles, the underlying resonance mechanisms are discussed. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

Magnetic Properties of Epitaxially Grown SrRuO3 Nanodots.

We present the fabrication and exploration of arrays of nanodots of SrRuO3 with dot sizes between 500 and 15 nm. Down to the smallest dot size explored, the samples were found to be magnetic with a maximum Curie temperature TC achieved by dots of 30 nm diameter. This peak in TC is associated with a dot-size-induced relief of the epitaxial strain, as evidenced by scanning transmission electron microscopy.

Hierarchical Metal Sulfide/Carbon Spheres: A Generalized Synthesis and High Sodium-Storage Performance.

The development of suitable anode materials is far from satisfactory and is a major scientific challenge for a competitive sodium-ion battery technology. Metal sulfides have demonstrated encouraging results, but still suffer from sluggish kinetics and severe capacity decay associated with the phase change. Herein we show that rational electrode design, that is, building efficient electron/ion mixed-conducting networks, can overcome the problems resulting from conversion reactions. A general strategy for the preparation of hierarchical carbon-coated metal sulfide (MS⊂C) spheres through thermal sulfurization of metal glycerate has been developed. We demonstrate the concept by synthesizing highly uniform hierarchical carbon coated vanadium sulfide (V2 S3 ⊂C) spheres, which exhibit a highly reversibly sodium storage capacity of 777 mAh g-1 at 100 mA g-1 , excellent rate capability (410 mAh g-1 at 4000 mA g-1 ), and impressive cycling ability.