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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.

ACS applied materials & interfaces 11(28), 25378 - 25387 (2019). doi:10.1021/acsami.9b04449, Published by ACS, Washington, DC

Advanced electronic materials 0, 2001069 (2021). doi:10.1002/aelm.202001069, Published by Wiley-VCH Verlag GmbH & Co. KG, Weinheim

Significant structural evolution occurs during the deposition of ${\mathrm{CuInSe}}_{2}$ 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 ${\mathrm{CuInSe}}_{2}$ grain interiors. Together with density functional theory and molecular dynamics calculations, we reveal how this Cu-Se phase makes the grain boundaries highly mobile.

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 scanning transmission electron microscopy spectrum/diffraction imaging data., 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.

The initial interfacial reactions of crystalline nickel and amorphous silicon carbide (Ni/a-SiC) thin films were investigated by means of X-ray diffraction (XRD) analysis, high-resolution transmission electron microscopy [(HR)TEM], Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). Upon annealing at 500 °C, in the initial stage (

The utilization of interface effects in epitaxial systems at the nanoscale has emerged as a very powerful approach for engineering functional properties of oxides. Here we present a novel structure fabricated by a state-of-the-art oxide molecular beam epitaxy method and consisting of lanthanum cuprate and strontium (Sr)-doped lanthanum nickelate, in which interfacial high-temperature superconductivity (Tc up to 40 K) occurs at the contact between the two phases. In such a system, we are able to tune the superconducting properties simply by changing the structural parameters. By employing electron spectroscopy and microscopy combined with dedicated conductivity measurements, we show that decoupling occurs between the electronic charge carrier and the cation (Sr) concentration profiles at the interface and that a hole accumulation layer forms, which dictates the resulting superconducting properties. Such effects are rationalized in the light of a generalized space-charge theory for oxide systems that takes account of both ionic and electronic redistribution effects.

In the present study, the dielectric function of freestanding GaN nanomembranes was described using valence electron energy loss spectroscopy coupled to a monochromated electron probe in a Sub-Electron-volt Sub-Angstrom transmission electron Microscope. Such a technique has proven to be very efficient in handling nanometer-scale freestanding nanomembranes and provided local and direct measurements of optical characteristics. Indeed, core-state along with outer-shell electrons transitions were first measured in the configuration where the GaN c → -axis was normal to the transferred momentum q → . With the help of Kramers-Kroning analyses and density functional theory, critical points energies were extracted and assigned. Finally, optical data such as the real refractive index n, extinction coefficient k, absorption coefficient α and reflectivity R were numerically deduced from the real and imaginary parts of the dielectric function.

This work investigates the conductivity and structure of nanocrystalline CaF2 films grown at 200 °C by thermal evaporation. The in-plane conductivity is enhanced by several orders of magnitude compared to lightly doped bulk samples of CaF2, which independently confirms the finding of a previous work [Modine et al., J. Appl. Phys. 74, 2658 (1993)]. Upon heating above 200 °C, the enhancement is partially annealed out, and the activation energy increases continuously from 0.7 to 1.0 eV, which contradicts the annealing model proposed previously. The enhancement is seen only in an ∼20-nm thick region adjacent to the substrate, but this may be because the films show substantial porosity outside this region. A 5–10 nm grain size and a high density of grain boundaries are observed by high-resolution transmission electron microscopy. A 2–4 nm interfacial amorphous layer is seen in films grown on Al2O3, but such a layer is absent on MgO and evidently not responsible for the enhanced conduction. Overall, the evidence points to grain boundaries and/or dislocations as providing fast transport pathways. These results help to reconcile previous reports of enhanced ion transport in CaF2, and they are also relevant for understanding the enhancement mechanism in CaF2-based composites and antifluorite-structured materials such as Li2O.

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.

Significant structural evolution occurs during the deposition of CuInSe2 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 CuInSe2 grain interiors. Together with density functional theory and molecular dynamics calculations, we reveal how this Cu-Se phase makes the grain boundaries highly mobile.

In the present study, monochromated low-loss electron energy-loss spectroscopy in a scanning transmission electron microscope, confronted with ab-initio calculations, is used to investigate the bandgap and excitons energies of black phosphorus flakes in the near infrared region. Due to the monochromation of the electron beam and to a spectrometer with an energy resolution of 20 meV, a direct measurement of the narrow bandgap energy, E0, of about 0.33 eV was successful, along with an intraband electronic transition E1 at around 0.75 eV. Interestingly, additional transitions, excitonic in nature, are identified at 0.42 eV and 0.55 eV, the intensity of which increases with decreasing thickness. All these findings demonstrate the ability of monochromated low-loss electron energy loss spectroscopy to reveal unprecedented electronic and excitonic transitions in very narrow bandgap semiconductors.

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.

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.

Electron energy loss spectroscopy (EELS) in a monochromated transmission electron microscope is applied to probe standing-wave-like cavity modes hybridized with surface plasmon polaritons (SPP) in rectangular submicron slits in a thin gold film. Coupling of hybridized SPP-cavity modes between two adjacent slits is studied by systematically varying the width of the metal bar d that separates the identical slits in a two-slit system. Measurements on two-slit systems with different slit lengths L and fixed width reveal energy shifts and mode splitting of the fundamental SPP cavity mode which can be generally described as a function of a dimensionless scaling parameter L/d. Numerical simulations with the Discontinuous Galerkin Time-Domain (DGTD) method confirm the experimental data and reveal insights into the underlying complex coupling mechanisms.

The delafossite compound PdCoO${}_{2}$ is composed of highly conducting Pd and insulating CoO${}_{2}$ layers. As a consequence of this lattice architecture, the thermopower of PdCoO${}_{2}$ was predicted to be extremely anisotropic. Because of the limited size of available single crystals, however, these predictions had not been tested experimentally. The authors of this paper show that the electric and thermoelectric transport parameters of PdCoO${}_{2}$ along the main crystallographic directions can be determined from measurements on thin films grown on substrates with different offcut angles. The method is applicable to a wide range of thermoelectric materials. The experimental results confirm the predicted thermopower anisotropy of PdCoO${}_{2}$ and thus provide interesting perspectives for thermoelectric device applications.

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.

Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) has enabled atomically resolved imaging of molecules adsorbed on low-dimensional materials like carbon nanotubes, graphene oxide and few-layer-graphene. However, conventional methods for depositing molecules onto such supports lack selectivity and specificity. Here, we describe the chemically selective preparation and deposition of molecules-like polyoxometalate (POM) anions [PW12O40]3− using electrospray ion-beam deposition (ES-IBD) along with high-resolution TEM imaging. This approach provides access to sub-monolayer coatings of intact molecules on freestanding graphene, which enables their atomically resolved ex situ characterization by low-voltage AC-HRTEM. The capability to tune the deposition parameters in either soft or reactive landing mode, combined with the well-defined high-vacuum deposition conditions, renders the ES-IBD based method advantageous over alternative methods such as drop-casting. Furthermore, it might be expanded towards depositing and imaging large and nonvolatile molecules with complex structures.

We present the use of (1) dark-field inline electron holography for measuring the structural strain, and indirectly obtaining the composition, in a wurtzite, 4-nm-thick InAlGaN epilayer on a AlN/GaN/AlN/GaN multinano-layer heterosystem, and (2) valence electron energy-loss spectroscopy to study the bandgap value of five different, also hexagonal, 20-50-nm-thick InAlGaN layers. The measured strain values were almost identical to the ones obtained by other techniques for similarly grown materials. We found that the biaxial strain in the III-N alloys lowers the bandgap energy as compared to the value calculated with different known expressions and bowing parameters for unstrained layers. By contrast, calculated and experimental values agreed in the case of lattice-matched (almost unstrained) heterostructures.

The determination of atom positions from atomically resolved transmission electron micrographs is fundamental for the analysis of crystal defects and strain. In recent years annular bright-field (ABF) imaging has become a popular imaging technique owing to its ability to map both light and heavy elements. Contrast formation in ABF is partially governed by the phase of the electron wave, which renders the technique more sensitive to the tilt of the electron beam with respect to the crystal zone axis than high-angle annular dark-field imaging. Here we show this sensitivity experimentally and use image simulations to quantify this effect. This is essential for error estimation in future quantitative ABF studies.

To investigate the physical properties of Bi nanowires and to explore their possible implementation in thermoelectric devices, it is essential to understand their chemical and thermal stability in air both at room and moderate temperatures. In this work, we study the influence of low temperature annealing processes on the morphology and composition of the wires by scanning and transmission electron microscopy and by Raman spectroscopy, revealing the formation of a metal oxide phase. This oxidation process initiates an increase of the nanowires surface roughness at low annealing temperatures, while clear protuberances are formed at 250 °C. Difficulties to electrically contact single Bi nanowires, as well as the high resistance values measured and reported by other groups, are attributed to this oxidation process, which constitutes a clear challenge for the reliable characterization of Bi nanowires and the investigation of their performance.

The fabrication of nanowires by electrodeposition of Au−Ag alloy into the pores of etched ion track polymer membrane is presented. The crystallinity, morphology, and composition of wires with diameters of 85, 45, and 30 nm are investigated by means of X-ray diffraction, high-resolution scanning transmission electron microscopy, and energy-dispersive X-ray analysis. Energy-dispersive X-ray analysis with very high spatial resolution (below 1 nm) reveals the presence of surface enrichment. A Ag-rich layer in Au40Ag60 wires and a Au-rich layer in Au60Ag40 wires with thicknesses between 1 and 4 nm are observed. After dealloying in nitric acid, Ag-rich wires exhibit porous morphologies whereas Au-rich wires remain solid cylinders. The results clearly indicate that the analyzed AuAg alloy nanowires do not consist of homogeneous solid solution, but surface effects before and during the dealloying play an important role for the final morphology of dealloyed nanowires.

Nanomaterials 8(9), 693 - (2018). doi:10.3390/nano8090693, Published by MDPI, Basel

The systematic study of the ionic transport properties of epitaxial Y

Cu(In,Ga)Se₂ (CIGS)-based solar cells reach high power-conversion efficiencies of above 22%. In this work, a three-stage co-evaporation method was used for their fabrication. During the growth stages, the stoichiometry of the absorbers changes from Cu-poor ([Cu]/([In] + [Ga]) 1) and finally becomes Cu-poor again when the growth process is completed. It is known that, according to the Cu-In-Ga-Se phase diagram, a Cu-rich growth leads to the presence of Cu₂–ₓSe (x = 0–0.25), which is assumed to assist in recrystallization, grain growth, and defect annihilation in the CIGS layer. So far, Cu₂–ₓSe precipitates with spatial extensions on the order of 10–100 nm have been detected only in Cu-rich CIGS layers. In the present work, we report Cu₂–ₓSe platelets with widths of only a few atomic planes at grain boundaries and as inclusions within grains in a polycrystalline, Cu-poor CIGS layer, as evidenced by high-resolution scanning transmission electron microscopy (STEM). The chemistry of the Cu–Se secondary phase was analyzed by electron energy-loss spectroscopy, and STEM image simulation confirmed the identification of the detected phase. These results represent additional experimental evidence for the proposed topotactical growth model for Cu–Se–assisted CIGS thin-film formation under Cu-rich conditions.

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. SrTiO 3 bulk material and Sr-doped La 2 CuO 4 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.

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.

A nanoscale study of combined strain/size effects has been performed using monochromated valence electron energy-loss spectroscopy and density functional theory (DFT) calculations to locally explore the valence and conduction bands of a strained 2 nm GaN quantum well inserted between two fully relaxed AlN thick layers. Two main electronic transitions from the valence to the conduction band were experimentally detected and interpreted. The first transition was shown to be a collective oscillation (or plasmon), which was significantly blue-shifted in energy mainly due to the widening of the valence-band top-part. The second, however, had a single-particle character, that is: Ga-3d → Ga-4p, and was weakly affected by strain and size. In addition, our DFT calculations showed that strain and size can be adjusted separately to tune the GaN band-gap energy.

This paper deals with the synthesis of Pt and Pt/Pb nanoparticles via oil-in-water microemulsions. Studying systematically the phase behavior of microemulsions which contain metal precursors, it was possible to determine the influence of the metal precursors on the phase behavior of the base microemulsion. It was found that the addition of Pb(ethylhexanoate)2 to the microemulsion shifts the phase boundaries to slightly lower temperatures, while adding dimethyl-(cyclooctadiene) platinum has no effect on the phase boundaries. SAXS measurements confirmed that the addition of the metal precursors does not influence the size of the microemulsion droplets along the emulsification failure boundary. Using transmission electron microscopy (TEM) we found that by increasing the oil content w B in the microemulsion from 0.04 to 0.08 the size of the resulting mono- and bimetallic Pt and Pt/Pb nanoparticles changes from 3 to 4.4 nm.

A second type of cation (Mg2+, Ca2+) was introduced into BaF2 by low-temperature atomic beam deposition. The structure evolution from low-temperature (–150 °C) amorphous deposits to high-temperature (< 1000 °C) annealed crystalline phases was studied by in-situ transmission electron microscopy and X-ray diffraction. Amorphous (Ba0.5, Ca0.5)F2 crystallizes in a first step to metastable solid solution phase (fluorite-type), which then decomposes into the pure phases of CaF2 and BaF2 at higher temperature. The crystallization behavior of amorphous (BaxMg1–x)F2 is completely different. When the Mg/Ba atomic ratio is around 1:1, the mixture transforms to the ternary compound BaMgF4 at annealing, and no decomposition occurs by further heating up to 1000 °C. When the Ba concentration is below 15 % in atomic ratio (x < 0.15), the mixture forms a solid solution phase (rutile type) with the lattice expanded by +1 % compared to rutile type MgF2. The difference between the phase evolutions of the two mixture systems is discussed.

In the present study, we report on the synthesis of nano-porous perovskite-type lanthanum iron oxide, LaFeO3, using the ascorbic-acid assisted sol-gel method. The as-synthesized powders are characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), electron energy-loss spectroscopy (EELS), and ultra-violet visible (UV–Vis) spectrophotometry. Experimental results are systematically discussed by Density Functional Theory modeling analysis. Our XRD findings show that the as-synthesized powders have an excellent crystallinity. These powders are found to be composed of particles around 60 nm in size, as revealed by TEM results, inside which there exist a high density of pores. Each nanoparticle exhibits a good chemical homogeneity as determined from core-loss EELS mapping analysis. Our low-loss EELS analysis, in addition, shows that the optical bandgap as measured on a single particle is close to 2.38 eV, which is larger than that of its bulk counterpart (2.1 eV). This result is also confirmed with the help of UV–Vis McLean analysis on a macroscopic scale, where the inter-pore spacing (22 nm) is found to be responsible for the observed increase in the bandgap. We believe that this increase in the bandgap, combined with the fine inter-particles porosity, make our as-synthesize nanoporous LaFeO3 powders a promising candidate for solar photocatalytic activities.

Structural disorder and distortion play a significant role in phase transformations. Experimentally, electron diffraction in the transmission electron microscope offers the ability to characterize disorderviathe pair distribution function (PDF) at high spatial resolution. In this work, energy-filteredin situelectron diffraction is applied to measure PDFs of different phases of MgF2from the amorphous deposit through metastable modifications to the thermodynamically stable phase. Despite the restriction of thick specimens resulting in multiple electron scattering, elaborate data analysis enabled experimental and molecular dynamics simulation data to be matched, thus allowing analysis of the evolution of short-range ordering. In particular, it is possible to explain the theoretically not predicted existence of a metastable phase by the presence of atomic disorder and distortion. The short-range ordering in the amorphous and crystalline phases is elucidated as three steps: (i) an initial amorphous phase exhibiting CaCl2-type short-range order which acts as a crystallization nucleus to guide the phase transformation to the metastable CaCl2-type phase and thus suppresses the direct appearance of the rutile-type phase; (ii) a metastable CaCl2-type phase containing short-range structural features of the stable rutile type; and (iii) the formation of a large volume fraction of disordered intergranular regions which stabilize the CaCl2-type phase. The structure evolution is described within the energy landscape concept.

Variations in growth conditions associated with different deposition techniques can greatly affect the phase stability and defect structure of complex oxide heterostructures. We synthesized superlattices of the paramagnetic metal LaNiO3 and the large band gap insulator LaAlO3 by atomic layer-by-layer molecular beam epitaxy (MBE) and pulsed laser deposition (PLD) and compared their crystallinity, microstructure as revealed by high-resolution transmission electron microscopy images and resistivity. The MBE samples show a higher density of stacking faults, but smoother interfaces and generally higher electrical conductivity. Our study identifies the opportunities and challenges of MBE and PLD growth and serves as a general guide for the choice of deposition technique for perovskite oxides., Comment: APL in press