Downsizing of robust Fe-triazole@SiO2 spin-crossover nanoparticles with ultrathin shells.

A chemical protocol to design robust hybrid [Fe(Htrz)2(trz)](BF4)@SiO2 nanoparticles (NPs) with sizes as small as 28 nm and ultrathin silica shells below 3 nm has been developed. These NPs present a characteristic abrupt spin transition with a subsequent decrease in the width of the thermal hysteresis upon reducing the NP size.

Impact of the atomic layer deposition precursors diffusion on solid-state carbon nanotube based supercapacitors performances.

A study on the impact of atomic layer deposition (ALD) precursors diffusion on the performance of solid-state miniaturized nanostructure capacitor array is presented. Three-dimensional nanostructured capacitor array based on double conformal coating of multiwalled carbon nanotubes (MWCNTs) bundles is realized using ALD to deposit Al2O3 as dielectric layer and TiN as high aspect-ratio conformal counter-electrode on 2 µm long MWCNT bundles. The devices have a small footprint (from 100 µm(2) to 2500 µm(2)) and are realized using an IC wafer-scale manufacturing process with high reproducibility (≤0.3E-12F deviation). To evaluate the enhancement of the electrode surface, the measured capacitance values are compared to a lumped circuital model. The observed discrepancies are explained with a partial coating of the CNT, that determine a limited use of the available electrode surface area. To analyze the CNT coating effectiveness, the ALD precursors diffusions inside the CNT bundle is studied using a Knudsen diffusion mechanism.

An electron microscopical study on the growth of TiO2-Ag antibacterial coatings on Ti6Al7Nb biomedical alloy.

This research was aimed at investigating the growth mechanism of TiO(2)-Ag antibacterial coatings during plasma electrolytic oxidation (PEO) of Ti6Al7Nb biomedical alloy in an electrolyte based on calcium acetate/calcium glycerophosphate bearing Ag nanoparticles. The focus was on the mechanism of incorporation of Ag nanoparticles, their distribution and chemical composition within the porous coatings using high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) imaging techniques combined with energy dispersive X-ray spectroscopy (EDX) for chemical analyses. The PEO coatings were grown using different oxidation times, 10, 30, 60, 90, 120, 180, 240 and 300 s. The electron microscopy results confirmed the formation of a porous coating with incorporated Ag nanoparticles from the initial stages of oxidation (i.e. 10 s), with further Ag incorporation as the PEO process was continued for longer durations. The Ag nanoparticles were embedded in the dense oxide layer, fused into the pore walls and on the surface of the coatings without any change in their morphology or chemistry as detected by HRTEM, SEM and EDX. Ag seems to be delivered to the sites of coating growth (where dielectric breakdown occurs) through different transport pathways, i.e. open pores, cracks and short-circuit channels.

Comparison of Si and Ge low-loss spectra to interpret the Ge contrast in EFTEM images of Si(1-x) Ge(x) nanostructures.

Recently, an EFTEM imaging method, exploiting the inelastically scattered electrons in the 60-90eV energy range, was proposed to visualise Ge in SiGe alloys [Pantel, R., Jullian, S., Delille, D., Dutartre, D., Chantre, A., Kermarrec, O., Campidelli, Y., Kwakman, L.F.T.Z., 2003. Inelastic electron scattering observation using Energy Filtered Transmission Electron Microscopy for silicon-germanium nanostructures imaging. Micron 34, 239-247]. This method was proven to be highly more efficient in terms of noise, drift and exposure time than the imaging of the weak and delayed ionization GeL2,3 edge at 1236eV. However, the physical phenomenon behind this Ge contrast was not clearly identified. In this work, we explain the origin of this Ge contrast, by comparing in details EELS low-loss spectra (<100eV) recorded from pure Si and Ge crystals. High resolved low-loss experiments are performed using analytical Field Emission Gun Transmission Electron Microscopes fitted or not with a monochromator. Low-loss spectra (LLS) are then deconvoluted from elastic/quasi-elastic and plural scattering effects. The deconvolution procedure is established from Si spectra recorded with the monochromated machine. The absence of second plasmon and the measurement of a band gap (1.12eV) on the Si single scattering distribution (SSD) spectrum allowed us to control the accuracy of the deconvolution procedure at high and low energy and to state that it could be reliably applied to Ge spectra. We show that the Ge-M4,5 ionisation edge located at 29eV, which is shadowed by the high second plasmon in the unprocessed Ge spectrum, can be clearly separated in the single scattering spectrum. We also show that the front edge of Ge-M4,5 is rather sharp which generates a high intensity post edge tail on several tens of eV. Due to this tail, the Si and Ge EELS signals in the 60 to 100eV energy window are very different and the monitoring of this signal gives information about the Ge concentration inside SiGe alloys. It is now evident that the EFTEM imaging technique proposed to quantify Ge (90eV/60eV image ratio) in Si-Ge nanostructures is valid and is a relevant way of exploiting the Ge-M4-5 ionisation edge.

Crystallographic analysis of thin specimens.

Electron backscattering diffraction (EBSD) is commonly used on bulk samples for crystallographic material characterization. In this work, the technique was applied on transmission electron microscopy (TEM)-type thin specimens, prepared with a focused ion beam. Orientation maps were successfully collected on specimens made of a Cu3Au copper-gold alloy. As compared to EBSD analysis on a bulk specimen, an improved pattern quality and a high spatial resolution (well below 10 nm) were obtained. Furthermore, a clear improvement of the signal-to-noise ratio with decreasing sample thickness was observed.

Application of the dual-beam FIB/SEM to metals research.

The dual-beam microscope is a combination of a focused ion beam with an electron beam. The instrument used in this work is also equipped with an energy-dispersive X-ray system for local elemental analysis. This powerful tool gives access to specific features inside a material. Two different applications are presented in this paper: (1) cross-sections and transmission electron microscope specimens cut in order to investigate the interface between an aluminium substrate and its epoxy coating; and (2) a grain boundary in a Cu(3)Au alloy. In both cases, the dual beam succeeded where other methods failed.

Materials science applications of HREELS in near edge structure analysis and low-energy loss spectroscopy.

New experiments made possible with a commercial transmission electron microscope (TEM) equipped with a high-resolution electron energy loss spectrometer (EELS) are presented. With this commercial system, a 100 meV energy resolution using a sub 2 nm probe or 500 meV at a 0.20 nm probe are possible, in combination with other modern techniques available for TEMs. In this paper a number of explorative examples of the first results are shown. The benefit of the increased resolution for detecting more details in near edge structures are shown for the Ti K edge in TiO(2) (brookite) and for the N K edge in cubic and hexagonal GaN. The bandgap of GaN is studied in both crystal structures, as well as the dependency of the low-loss spectrum on the momentum transfer direction in diffraction mode.

Effect of electron beam parameters on simulated CBED patterns from edge-on grain boundaries.

Convergent beam electron diffraction (CBED) at vertical grain boundaries (parallel to the electron beam) can be applied to determine the symmetry of bicrystals. It can also be used to investigate the structure of the boundary region itself when subnanometre probe sizes are employed. In this paper it is shown that (sub)nanometre-probe CBED patterns are largely influenced by the electron-beam geometry. In particular, simulations of coherent CBED patterns based on the multislice algorithm show that the CBED pattern of an edge-on interface depends on the defocus distance between the probe position and the specimen midplane, the probe size and the beam-convergence angle. The pattern symmetry may be lower than the theoretically predicted symmetry in case of large spherical aberration. This effect increases with smaller accelerating voltages. An increase in the beam-convergence angle also increases the possibility of a non-optimum symmetry due to spherical aberration of a coherent probe. Thus, for the determination of an interface structure using subnanometre (coherent) probes, the imaging conditions play an important role.