Direct observation of strong surface reconstruction in partially reduced nickelate films.

The polarity of a surface can affect the electronic and structural properties of oxide thin films through electrostatic effects. Understanding the mechanism behind these effects requires knowledge of the atomic structure and electrostatic characteristics at the surface. In this study, we use annular bright-field imaging to investigate the surface structure of a Pr0.8Sr0.2NiO2+x (0 < x < 1) film. We observe a polar distortion coupled with octahedral rotations in a fully oxidized Pr0.8Sr0.2NiO3 sample, and a stronger polar distortion in a partially reduced sample. Its spatial depth extent is about three unit cells from the surface. Additionally, we use four-dimensional scanning transmission electron microscopy (4D-STEM) to directly image the local atomic electric field surrounding Ni atoms near the surface and discover distinct valence variations of Ni atoms, which are confirmed by atomic-resolution electron energy-loss spectroscopy (EELS). Our results suggest that the strong surface reconstruction in the reduced sample is closely related to the formation of oxygen vacancies from topochemical reduction. These findings provide insights into the understanding and evolution of surface polarity at the atomic level.

Experimental evidence of a size-dependent sign change of the Seebeck coefficient of Bi nanowire arrays.

The electrical transport in bismuth nanowires is strongly influenced by both sample geometry and crystallinity. Compared to bulk bismuth, the electrical transport in nanowires is dominated by size effects and influenced by surface states, which gain increasing relevance with increasing surface-to-volume ratios, i.e. with decreasing wire diameter. Bismuth nanowires with tailored diameter and crystallinity constitute, therefore, excellent model systems, allowing to study the interplay of the different transport phenomena. Here, we present temperature-dependent Seebeck coefficient and relative electrical resistance measurements of parallel bismuth nanowire arrays with diameters between 40 and 400 nm synthesized by pulsed electroplating in polymer templates. Both electrical resistance and Seebeck coefficient exhibit a non-monotonic temperature dependence, with the sign of the Seebeck coefficient changing from negative to positive with decreasing temperature. The observed behavior is size-dependent and is attributed to limitations of the mean free path of the charge carriers within the nanowires. The observed size-dependent Seebeck coefficient and in particular the size-dependent sign change opens a promising avenue for single-material thermocouples with p- and n-legs made from nanowires with different diameters.

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.

Three-dimensional free-standing gold nanowire networks as a platform for catalytic applications.

We report the catalytic performance of networks of highly interconnected Au nanowires with diameters tailored between 80 and 170 nm. The networks were synthesized by electrodeposition in etched ion-track polymer templates, and the synthesis conditions were developed for optimal wire crystallinity and network homogeneity. The nanowire networks were self-supporting and could be easily handled as electrodes in electrochemical cells or other devices. The electrochemically active surface area of the networks increased systematically with increasing the wire diameter. They showed a very stable performance during 200 CV cycles of methanol oxidation reactions, with the peak current density reaching up to 200 times higher than that of a flat reference electrode, with only a 5% drop in the peak current density. The Au nanowire networks proved to be excellent model systems for investigation of the performance of porous catalysts and very promising nanosystems for application in direct alcohol fuel cell catalysts.

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.

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.

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'.

Substrate-Selective Morphology of Cesium Iodide Clusters on Graphene.

Formation and characterization of low-dimensional nanostructures is crucial for controlling the properties of two-dimensional (2D) materials such as graphene. Here, we study the structure of low-dimensional adsorbates of cesium iodide (CsI) on free-standing graphene using aberration-corrected transmission electron microscopy at atomic resolution. CsI is deposited onto graphene as charged clusters by electrospray ion-beam deposition. The interaction with the electron beam forms two-dimensional CsI crystals only on bilayer graphene, while CsI clusters consisting of 4, 6, 7, and 8 ions are exclusively observed on single-layer graphene. Chemical characterization by electron energy-loss spectroscopy imaging and precise structural measurements evidence the possible influence of charge transfer on the structure formation of the CsI clusters and layers, leading to different distances of the Cs and I to the graphene.

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.

Far-Field Radiation of Three-Dimensional Plasmonic Gold Tapers near Apexes.

Three-dimensional plasmonic gold tapers are widely used structures in nano-optics for achieving imaging at the nanometer scale, enhanced spectroscopy, confined light sources, and ultrafast photoelectron emission. To understand their radiation properties further, especially in the proximity of the apex at the nanoscale, we employ cathodoluminescence spectroscopy with high spatial and energy resolution. The plasmon-induced radiation in the visible spectral range from three-dimensional gold tapers with opening angles of 13° and 47° is investigated under local electron excitation. We observe a much weaker radiation from the apex of the 13° taper than from that of the 47° taper. By means of finite-difference time-domain simulations we show that for small opening angles plasmon modes that are created at the apex are efficiently guided along the taper shaft. In contrast for tapers with larger opening angles, generated plasmon polaritons experience larger radiation damping. Interestingly, we find for both tapers that the most intense radiation comes from locations a few hundreds of nanometers behind the apexes, instead of exactly at the apexes. Our findings provide useful details for the design of plasmonic gold tapers as confined light sources or light absorbers.

Tuning the Size and Shape of NanoMOFs via Templated Electrodeposition and Subsequent Electrochemical Oxidation.

The control over the size and shape of nanoMOFs is essential for their exploitation in integrated devices such as sensors, membranes for gas separation, photoelectrodes, etc. Here, we demonstrate the synthesis of nanowires and three-dimensionally interconnected nanowire networks of Cu-based metal-organic frameworks (MOFs) by a combination of ion-track technology and electrochemical methods. In particular, Cu nanowires and nanowire networks were electrodeposited inside polymeric etched ion-track membranes and subsequently converted by electrochemical oxidation into different Cu-based MOFs such as the well-known Cu3(BTC)2 (also known as HKUST-1) and the lesser-known MOF Cu(INA)2. The MOFs are formed inside the template, therefore adopting the shape of the host nanochannels. The synthesized MOF nanowires exhibit tunable diameters between 80 and 260 nm. Characterization by X-ray diffraction, thermogravimetric analysis/differential scanning calorimetry, scanning electron microscopy, and transmission electron microscopy indicates that the employed electrochemical conversion includes the formation of Cu2O as an intermediate, as well as the initial formation of an amorphous MOF phase, which crystallizes upon longer reaction times.

Silver nanowires with optimized silica coating as versatile plasmonic resonators.

Metal nanoparticles are the most frequently used nanostructures in plasmonics. However, besides nanoparticles, metal nanowires feature several advantages for applications. Their elongation offers a larger interaction volume, their resonances can reach higher quality factors, and their mode structure provides better coupling into integrated hybrid dielectric-plasmonic circuits. It is crucial though, to control the distance of the wire to a supporting substrate, to another metal layer or to active materials with sub-nanometer precision. A dielectric coating can be utilized for distance control, but it must not degrade the plasmonic properties. In this paper, we introduce a controlled synthesis and coating approach for silver nanowires to fulfill these demands. We synthesize and characterize silver nanowires of around 70 nm in diameter. These nanowires are coated with nm-sized silica shells using a modified Stöber method to achieve a homogeneous and smooth surface quality. We use transmission electron microscopy, dark-field microscopy and electron-energy loss spectroscopy to study morphology and plasmonic resonances of individual nanowires and quantify the influence of the silica coating. Thorough numerical simulations support the experimental findings showing that the coating does not deteriorate the plasmonic properties and thus introduce silver nanowires as usable building blocks for integrated hybrid plasmonic systems.

ZnO Nanowire Networks as Photoanode Model Systems for Photoelectrochemical Applications.

In this work, the fabrication of zinc oxide (ZnO) nanowire networks is presented. By combining ion-track technology, electrochemical deposition, and atomic layer deposition, hierarchical and self-supporting three-dimensional (3D) networks of pure ZnO- and TiO2-coated ZnO nanowires were synthesized. Analysis by means of high-resolution transmission electron microscopy revealed a highly crystalline structure of the electrodeposited ZnO wires and the anatase phase of the TiO2 coating. In photoelectrochemical measurements, the ZnO and ZnO/TiO2 nanowire networks, used as anodes, generated higher photocurrents compared to those produced by their film counterparts. The ZnO/TiO2 nanowire network exhibited the highest photocurrents. However, the protection by the TiO2 coatings against chemical corrosion still needs improvement. The one-dimensionality of the nanowires and the large electrolyte-accessible area make these 3D networks promising photoelectrodes, due to the improved transport properties of photogenerated charge carriers and faster redox reactions at the surface. Moreover, they can find further applications in e.g., sensing, catalytical, and piezoelectric devices.

Correcting the linear and nonlinear distortions for atomically resolved STEM spectrum and diffraction imaging.

Specimen and stage drift as well as scan distortions can lead to a mismatch between true and desired electron probe positions in scanning transmission electron microscopy (STEM) which can result in both linear and nonlinear distortions in the subsequent experimental images. This problem is intensified in STEM spectrum and diffraction imaging techniques owing to the extended dwell times (pixel exposure time) as compared to conventional STEM imaging. As a consequence, these image distortions become more severe in STEM spectrum/diffraction imaging. This becomes visible as expansion, compression and/or shearing of the crystal lattice, and can even prohibit atomic resolution and thus limits the interpretability of the results. Here, we report a software tool for post-correcting the linear and nonlinear image distortions of atomically resolved 3D spectrum imaging as well as 4D diffraction imaging. This tool improves the interpretability of distorted STEM spectrum/diffraction imaging data.

Towards atomically resolved EELS elemental and fine structure mapping via multi-frame and energy-offset correction spectroscopy.

Electron energy-loss spectroscopy and energy-dispersive X-ray spectroscopy are two of the most common means for chemical analysis in the scanning transmission electron microscope. The marked progress of the instrumentation hardware has made chemical analysis at atomic resolution readily possible nowadays. However, the acquisition and interpretation of atomically resolved spectra can still be problematic due to image distortions and poor signal-to-noise ratio of the spectra, especially for investigation of energy-loss near-edge fine structures. By combining multi-frame spectrum imaging and automatic energy-offset correction, we developed a spectrum imaging technique implemented into customized DigitalMicrograph scripts for suppressing image distortions and improving the signal-to-noise ratio. With practical examples, i.e. SrTiO3 bulk material and Sr-doped La2CuO4 superlattices, we demonstrate the improvement of elemental mapping and the EELS spectrum quality, which opens up new possibilities for atomically resolved EELS fine structure mapping.

Interface Effects on the Ion Transport of Epitaxial Y2Zr2O7 Films.

The systematic study of the ionic transport properties of epitaxial Y2Zr2O7 films with defective fluorite structure reveals an enhanced oxygen vacancy conductivity at the interface between the films and the MgO(110) substrate, which is characterized by a high density of misfit dislocations. This beneficial effect is discussed in terms of space-charge and mobility effects.

Dopant size effects on novel functionalities: High-temperature interfacial superconductivity.

Among the range of complex interactions, especially at the interfaces of epitaxial oxide systems, contributing to the occurrence of intriguing effects, a predominant role is played by the local structural parameters. In this study, oxide molecular beam epitaxy grown lanthanum cuprate-based bilayers (consisting of a metallic (M) and an insulating phase (I)), in which high-temperature superconductivity arises as a consequence of interface effects, are considered. With the aim of assessing the role of the dopant size on local crystal structure and chemistry, and on the interface functionalities, different dopants (Ca2+, Sr2+ and, Ba2+) are employed in the M-phase, and the M-I bilayers are investigated by complementary techniques, including spherical-aberration-corrected scanning transmission electron microscopy. A series of exciting outcomes are found: (i) the average out-of-plane lattice parameter of the bilayers is linearly dependent on the dopant ion size, (ii) each dopant redistributes at the interface with a characteristic diffusion length, and (iii) the superconductivity properties are highly dependent on the dopant of choice. Hence, this study highlights the profound impact of the dopant size and related interface chemistry on the functionalities of superconducting oxide systems.

Reflection and Phase Matching in Plasmonic Gold Tapers.

We investigate different dynamic mechanisms, reflection and phase matching, of surface plasmons in a three-dimensional single-crystalline gold taper excited by relativistic electrons. Plasmonic modes of gold tapers with various opening angles from 5° to 47° are studied both experimentally and theoretically, by means of electron energy-loss spectroscopy and finite-difference time-domain numerical calculations, respectively. Distinct resonances along the taper shaft are observed in tapers independent of opening angles. We show that, despite their similarity, the origin of these resonances is different at different opening angles and results from a competition between two coexisting mechanisms. For gold tapers with large opening angles (above ∼20°), phase matching between the electron field and that of higher-order angular momentum modes of the taper is the dominant contribution to the electron energy-loss because of the increasing interaction length between electron and the taper near-field. In contrast, reflection from the taper apex dominates the EELS contrast in gold tapers with small opening angles (below ∼10°). For intermediate opening angles, a gradual transition of these two mechanisms was observed.

Electron-Beam-Induced Antiphase Boundary Reconstructions in a ZrO2-LSMO Pillar-Matrix System.

The availability of aberration correctors for the probe-forming lenses makes simultaneous modification and characterization of materials down to atomic scale inside a transmission electron microscopy (TEM) realizable. In this work, we report on the electron-beam-induced reconstructions of three types of antiphase boundaries (APBs) in a probe-aberration-corrected TEM. With the utilization of high-angle annular dark-field scanning transmission electron microscopy (STEM), annular bright-field STEM, and electron energy-loss spectroscopy, the motion of both heavy element Mn and light element O atomic columns under moderate electron beam irradiation are revealed at atomic resolution. Besides, Mn segregated in the APBs was observed to have reduced valence states which can be directly correlated with oxygen loss. Charge states of the APBs are finally discussed on the basis of these experimental results. This study provides support for the design of radiation-engineering solid-oxide fuel cell materials.