Crystal Structure of the ZrO Phase at Zirconium/Zirconium Oxide Interfaces

Zirconium-based alloys are used in water-cooled nuclear reactors for both nuclear fuel cladding and structural components. Under this harsh environment, the main factor limiting the service life of zirconium cladding, and hence fuel burn-up efficiency, is water corrosion. This oxidation process has recently been linked to the presence of a sub-oxide phase with well-defined composition but unknown structure at the metal–oxide interface. In this paper, the combination of first-principles materials modeling and high-resolution electron microscopy is used to identify the structure of this sub-oxide phase, bringing us a step closer to developing strategies to mitigate aqueous oxidation in Zr alloys and prolong the operational lifetime of commercial fuel cladding alloys

Analytical transmission electron microscopy at organic interfaces

Organic materials are ubiquitous in all aspects of our daily lives. Increasingly there is a need to understand interactions between different organic phases, or between organic and inorganic materials (hybrid interfaces), in order to gain fundamental knowledge about the origin of their structural and functional properties. In order to understand the complex structure–property–processing relationships in (and between) these materials, we need tools that combine high chemical sensitivity with high spatial resolution to allow detailed interfacial characterisation. Analytical transmission electron microscopy (TEM) is a powerful and versatile technique that can fulfil both criteria. However, the application of analytical TEM to organic systems presents some unique challenges, such as low contrast between phases, and electron beam sensitivity. In this review recent analytical TEM approaches to the nanoscale characterisation of two systems will be discussed: the hybrid collagen/mineral interface in bone, and the all-organic donor/acceptor interface in OPV devices

High-resolution monochromated electron energy-loss spectroscopy of organic photovoltaic materials

Advances in electron monochromator technology are providing opportunities for high energy resolution (10 – 200 meV) electron energy-loss spectroscopy (EELS) to be performed in the scanning transmission electron microscope (STEM). The energy-loss near-edge structure in core-loss spectroscopy is often limited by core-hole lifetimes rather than the energy spread of the incident illumination. However, in the valence-loss region, the reduced width of the zero loss peak makes it possible to resolve clearly and unambiguously spectral features at very low energy-losses (<3 eV). In this contribution, high-resolution EELS was used to investigate four materials commonly used in organic photovoltaics (OPVs): poly(3-hexlythiophene) (P3HT), [6,6] phenyl-C61 butyric acid methyl ester (PCBM), copper phthalocyanine (CuPc), and fullerene (C60). Data was collected on two different monochromated instruments – a Nion UltraSTEM 100 MC ‘HERMES’ and a FEI Titan3 60–300 Image-Corrected S/TEM – using energy resolutions (as defined by the zero loss peak full-width at half-maximum) of 35 meV and 175 meV, respectively. The data was acquired to allow deconvolution of plural scattering, and Kramers–Kronig analysis was utilized to extract the complex dielectric functions. The real and imaginary parts of the complex dielectric functions obtained from the two instruments were compared to evaluate if the enhanced resolution in the Nion provides new opto-electronic information for these organic materials. The differences between the spectra are discussed, and the implications for STEM-EELS studies of advanced materials are considered

Electron Microscopy Reveals Structural and Chemical Changes at the Nanometer Scale in the Osteogenesis Imperfecta Murine Pathology

Alternations of collagen and mineral at the molecular level may have a significant impact on the strength and toughness of bone. In this study, scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) were employed to study structural and compositional changes in bone pathology at nanometer spatial resolution. Tail tendon and femoral bone of osteogenesis imperfecta murine (oim, brittle bone disease) and wild type (WT) mice were compared to reveal defects in the architecture and chemistry of the collagen and collagen-mineral composite in the oim tissue at the molecular level. There were marked differences in the substructure and organization of the collagen fibrils in the oim tail tendon; some regions have clear fibril banding and organization, while in other regions fibrils are disorganized. Malformed collagen fibrils were loosely packed, often bent and devoid of banding pattern. In bone, differences were detected in the chemical composition of mineral in oim and WT. While mineral present in WT and oim bone exhibited the major characteristics of apatite, examination in EELS of the fine structure of the carbon K ionization edge revealed a significant variation in the presence of carbonate in different regions of bone. Variations have been also observed in the fine structure and peak intensities of the nitrogen K-edge. These alterations are suggestive of differences in the maturation of collagen nucleation sites or cross-links. Future studies will aim to establish the scale and impact of the modifications observed in oim tissues. The compositional and structural alterations at the molecular level cause deficiencies at larger length scales. Understanding the effect of molecular alterations to pathologic bone is critical to the design of effective therapeutics

Room-Temperature Routes Toward the Creation of Zinc Oxide Films from Molecular Precursors

The fabrication of “flexible” electronics on plastic substrates with low melting points requires the development of thin-film deposition techniques that operate at low temperatures. This is easily achieved with vacuum- or solution-processed molecular or polymeric semiconductors, but oxide materials remain a significant challenge. Here, we show that zinc oxide (ZnO) can be prepared using only room-temperature processes, with the molecular thin-film precursor zinc phthalocyanine (ZnPc), followed by UV-light treatment in vacuum to elicit degradation of the organic components and transformation of the deposited film to the oxide material. The degradation mechanism was assessed by studying the influence of the atmosphere during the reaction: it was particularly sensitive to the oxygen pressure in the chamber and optimal degradation conditions were established as 3 mbar with 40% oxygen in nitrogen. The morphology of the film remained relatively unchanged during the reaction, but a detailed analysis of its composition using both scanning transmission electron microscopy and secondary ion mass spectrometry revealed that a 40 nm thick layer containing ZnO results from the 100 nm thick precursor after complete reaction. Our methodology represents a simple route for the fabrication of oxides and multilayer structures that can be easily integrated into current molecular thin-film growth setups, without the need for a high-temperature step

Chemical speciation of nanoparticles surrounding metal-on-metal hips.

Spectromicroscopy of tissue surrounding failed CoCr metal-on-metal hip replacements detected corroded nanoscale debris in periprosthetic tissue in two chemical states, with concomitant mitochondrial damage. The majority of debris contained Cr(3+), with trace amounts of oxidised cobalt. A minority phase containing a core of metallic chromium and cobalt was also observed

Felling of individual freestanding nanoobjects using focused-ion-beam milling for investigations of structural and transport properties

We report that, to enable studies of their compositional, structural and electrical properties, freestanding individual nanoobjects can be selectively felled in a controllable way by the technique of low-current focused-ion-beam (FIB) milling with the ion beam at a chosen angle of incidence to the nanoobject. To demonstrate the suitability of the technique, we report results zigzag/straight tungsten nanowires grown vertically on support substrates and then felled for characterization. We also describe a systematic investigation of the effect of the experimental geometry and parameters on the felling process and on the induced wire-bending phenomenon. The method of felling freestanding nanoobjects using FIB is an advantageous new technique for enabling investigations of the properties of selected individual nanoobjects

Electronic nature of the enhanced conductivity in YSZ-STO multilayers deposited by PLD

10 páginas, 8 figuras.-- et al.The search for new strategies to enhance the oxide ionic conductivity in oxide materials is a very active field of research. These materials are needed for application in a new generation of more efficient and durable solid state electrochemical devices such as reduced-temperature Solid Oxide Fuel Cells (SOFC's). Recently published results have claimed that sputtered yttria stabilised zirconia (YSZ)/SrTiO3 (STO) heterostructures show enhanced oxygen ion conductivity, by about eight orders of magnitude, with respect to that expected for YSZ and STO bulk values. The YSZ/STO heterostructures obtained in this work from Pulsed Laser Deposited (PLD) films, also show enhanced conductivity of a similar order. However, the fact that our structures show different relative orientations indicates that the conductivity enhancement may not be associated to a particular crystallographic arrangement at the interface. The combined characterisation of the conductivity dependence on oxygen partial pressure and direct oxygen diffusion by means of tracer experiments clearly demonstrate that the enhancement observed is related to the electronic rather than ionic conductivity.The authors also acknowledge the financial support of Spanish Government through projects: MAT2008-04931 and Consolider-Ingenio 2010-CSD2008-023. Two of the authors (A.C. and M.B.) acknowledge the support of their postdoctoral fellowships from the Spanish Ministry of Science and Innovation. DWM acknowledges the support of the Royal Academy of Engineering.Peer reviewe