Aberration-corrected scanning transmission electron microscopy for atomic-resolution studies of functional oxides

Electron microscopy has undergone a major revolution in the past few years because of the practical implementation of correctors for the parasitic lens aberrations that otherwise limit resolution. This has been particularly significant for scanning transmission electron microscopy (STEM) and now allows electron beams to be produced with a spot size of well below 1 Å, sufficient to resolve inter-atomic spacings in most crystal structures. This means that the advantages of STEM, relatively straightforward interpretation of images and highly localised analysis through electron energy-loss spectroscopy, can now be applied with atomic resolution to all kinds of materials and nanostructures. As this review shows, this is revolutionising our understanding of functional oxide ceramics, thin films, heterostructures and nanoparticles. This includes quantitative analysis of structures with picometre precision, mapping of electric polarisation at the unit cell scale, and mapping of chemistry and bonding on an atom-by-atom basis. This is also now providing the kind of high quality data that are very complementary to density functional theory (DFT) modelling, and combined DFT/microscopy studies are now providing deep insights into the structure and electronic structure of oxide nanostructures. Finally, some suggestions are made as to the prospects for further advances in our atomistic understanding of such materials as a consequence of recent technical advances in spectroscopy and imaging

Direct Experimental Evidence of Metal-Mediated Etching of Suspended Graphene

Atomic resolution high angle annular dark field imaging of suspended, single-layer graphene, onto which the metals Cr, Ti, Pd, Ni, Al and Au atoms had been deposited was carried out in an aberration corrected scanning transmission electron microscope. In combination with electron energy loss spectroscopy, employed to identify individual impurity atoms, it was shown that nano-scale holes were etched into graphene, initiated at sites where single atoms of all the metal species except for gold come into close contact with the graphene. The e-beam scanning process is instrumental in promoting metal atoms from clusters formed during the original metal deposition process onto the clean graphene surface, where they initiate the hole-forming process. Our observations are discussed in the light of calculations in the literature, predicting a much lowered vacancy formation in graphene when metal ad-atoms are present. The requirement and importance of oxygen atoms in this process, although not predicted by such previous calculations, is also discussed, following our observations of hole formation in pristine graphene in the presence of Si-impurity atoms, supported by new calculations which predict a dramatic decrease of the vacancy formation energy, when SiOx molecules are present.Comment: final version accepted in ACS Nano + supplementary info. 22+6 pages, 4+5 figure

The roles of Eu during the growth of eutectic Si in Al-Si alloys

Controlling the growth of eutectic Si and thereby modifying the eutectic Si from flake-like to fibrous is a key factor in improving the properties of Al-Si alloys. To date, it is generally accepted that the impurity-induced twinning (IIT) mechanism and the twin plane re-entrant edge (TPRE) mechanism as well as poisoning of the TPRE mechanism are valid under certain conditions. However, IIT, TPRE or poisoning of the TPRE mechanism cannot be used to interpret all observations. Here, we report an atomic-scale experimental and theoretical investigation on the roles of Eu during the growth of eutectic Si in Al-Si alloys. Both experimental and theoretical investigations reveal three different roles: (i) the adsorption at the intersection of Si facets, inducing IIT mechanism, (ii) the adsorption at the twin plane re-entrant edge, inducing TPRE mechanism or poisoning of the TPRE mechanism, and (iii) the segregation ahead of the growing Si twins, inducing a solute entrainment within eutectic Si. This investigation not only demonstrates a direct experimental support to the well-accepted poisoning of the TPRE and IIT mechanisms, but also provides a full picture about the roles of Eu atoms during the growth of eutectic Si, including the solute entrainment within eutectic Si

The atomic structure and chemistry of Fe-rich steps on antiphase boundaries in Ti-doped Bi_0.9Nd_0.15FeO3

Stepped antiphase boundaries are frequently observed in Ti-doped Bi<sub>0.85</sub>Nd<sub>0.15</sub>FeO<sub>3</sub>, related to the novel planar antiphase boundaries reported recently. The atomic structure and chemistry of these steps are determined by a combination of high angle annular dark field and bright field scanning transmission electron microscopy imaging, together with electron energy loss spectroscopy. The core of these steps is found to consist of 4 edge-sharing FeO<sub>6</sub> octahedra. The structure is confirmed by image simulations using a frozen phonon multislice approach. The steps are also found to be negatively charged and, like the planar boundaries studied previously, result in polarisation of the surrounding perovskite matrix

Self-Nano-Structuring in SrTiO₃: A Novel Strategy for Enhancement of Thermoelectric Response in Oxides

Nanostructuring is recognized as an efficient route for enhancing thermoelectric response. Here, we report a new synthesis strategy for nanostructuring oxide ceramics and demonstrate its effectiveness on an important n-type thermoelectric SrTiO3. Ceramics of Sr0.9La0.1TiO3 with additions of B2O3 were synthesized by the mixed oxide route. Samples were sintered in air followed by annealing in a reducing atmosphere. Crystallographic data from X-ray and electron diffraction showed Pm3̅m cubic symmetry for all the samples. High-resolution transmission electron microscopy (HRTEM) showed the formation of a core–shell type structure within the grains for the annealed ceramics. The cores contain nanosize features comprising pairs of nanosize voids and particles; the feature sizes depend on annealing time. Atomic-resolution, high-angle annular-dark-field imaging and electron energy loss spectroscopy in the scanning transmission electron microscopy (STEM-HAADF-EELS) showed the particles to be rich in Ti and the areas around the voids to contain high concentrations of Ti3+. Additionally, dislocations were observed, with significantly higher densities in the shell areas. The observed dislocations are combined (100) and (110) edge dislocations. The major impact of the core–shell type microstructures, with nanosize inclusions, is the reduction of the thermal conductivity. Sr0.9La0.1TiO3 ceramics containing grain boundary shells of size ≈ 1 μm and inclusions in the core of 60–80 nm exhibit a peak power factor of 1600 μW/m·K2 at 540 K; at 1000 K, they exhibit a low thermal conductivity (2.75 W/m·K) and a power factor of 1050 μW/m·K2 leading to a high of ZT of 0.39 ± 0.03. This is the highest ZT reported so far for Sr0.9La0.1TiO3 based-compositions. This nanostructuring strategy should be readily applicable to other functional oxides

Functionalization of graphene at the organic/water interface

A simple method for the deposition of noble metal (Pd, Au) nanoparticles on a free-standing chemical vapour deposited graphene (CVD GR) monolayer is reported. The method consists of assembling the high purity CVD GR, by transfer from poly (methyl methacrylate) (PMMA), at the organic/water interface. Metal deposition can then proceed using either spontaneous or electrochemically-controlled processes. The resultant graphene-based metal nanoclusters are characterized using atomic force and electron microscopy techniques, and the location of the nanostructures underneath the graphene layer is determined from the position and the intensity changes of the Raman bands (D, G, 2D). This novel process for decoration of a single-layer graphene sheet with metal nanoparticles using liquid/liquid interfaces opens an alternative and useful way to prepare low dimensional carbon-based nanocomposites and electrode materials