Characterising the surface and interior chemistry of core-shell nanoparticles using scanning transmission electron microscopy

A method for extracting core and shell spectra from core-shell particles with varying core to shell volume fractions is described. The method extracts the information from a single EELS spectrum image of the particle. The distribution of O and N was correctly reproduced for a nanoparticle with a TiN core and Ti-oxide shell. In addition, the O distribution from a nanoparticle with a Cu core and a Cu-oxide shell was obtained, and the extracted Cu L_2,3-core and shell spectra showed the required change in EELS near edge fine structure. The extracted spectra can be used for multiple linear least squares fitting to the raw data in the spectrum image. The effect of certain approximations on numerical accuracy, such as treating the nanoparticle as a perfect sphere, as well as the intrinsic detection limits of the technique have also been explored. The technique is most suitable for qualitative, rather than quantitative, work.     

Successful application of spatial difference technique to electron energy-loss spectroscopy studies of Mo/SrTiO3 interfaces

The electron energy‐loss near‐edge structure (ELNES) of Mo/SrTiO₃ interfaces has been studied using high spatial resolution electron energy‐loss spectroscopy (EELS) in a dedicated scanning transmission electron microscope. Thin films of Mo with a thickness of 50 nm were grown on (001)‐orientated SrTiO₃ surfaces by molecular beam epitaxy at 600 °C. High‐resolution transmission electron microscopy revealed that the interfaces were atomically abrupt with the (110)_Mo plane parallel to the substrate surface. Ti‐L_2,3 (～460 eV), O‐K (～530 eV), Sr‐L_2,3 (～1950 eV) and Mo‐L_2,3 (～2500 eV) absorption edges were acquired by using the Gatan Enfina parallel EELS system with a CCD detector. The interface‐specific components of the ELNES were extracted by employing the spatial difference method. The interfacial Ti‐L_2,3 edge shifted to lower energy values and the splitting due to crystal field became less pronounced compared to bulk SrTiO₃, which indicated that the Ti atoms at the interface were in a reduced oxidation state and that the symmetry of the TiO₆ octahedra was disturbed. No interfacial Sr‐L_2,3 edge was observed, which may demonstrate that Sr atoms do not participate in the interfacial bonding. An evident interface‐specific O‐K edge was found, which differs from that of the bulk in both position (0.8 ± 0.2 eV positive shift) and shape. In addition, a positive shift (0.9 ± 0.3 eV) occurred for the interfacial Mo‐L_2,3, revealing an oxidized state of Mo at the interface. Our results indicated that at the interface SrTiO₃ was terminated with TiO₂. The validity of the spatial difference technique is discussed and examined by introducing subchannel drift intentionally.     

A method for the characterization of surface-modified asbestos fibres by electron energy-loss spectroscopy and electron spectroscopic imaging

A method for the characterization of surface-treated asbestos fibres with electron microscopy is presented. Electron spectroscopic imaging (ESI) of organosilane-treated chrysotile asbestos fibres has been carried out. Initially, the region below the carbon edge was inspected in ESI mode for its effectiveness as a background correction. Elemental mapping was performed on standard untreated fibres to take into account non-characteristic signals from extrapolation errors and camera artefacts. The highest resulting pixel value that results from non-characteristic signals was used as a threshold for further background correction in the net images. Samples for electron energy-loss spectroscopy were prepared in two different ways, either by gluing on grids, or by using perforated carbon foils. The results show that the use of a conducting carbon film is necessary for the analysis of such electrically insulating asbestos fibres. Focusing of the electron beam on the individual fibres results in a thermal effect promoting the evaporation of the organosilane reaction products.     

A high-speed area detector for novel imaging techniques in a scanning transmission electron microscope

A scanning transmission electron microscope (STEM) produces a convergent beam electron diffraction pattern at each position of a raster scan with a focused electron beam, but recording this information poses major challenges for gathering and storing such large data sets in a timely manner and with sufficient dynamic range. To investigate the crystalline structure of materials, a 16×16 analog pixel array detector (PAD) is used to replace the traditional detectors and retain the diffraction information at every STEM raster position. The PAD, unlike a charge-coupled device (CCD) or photomultiplier tube (PMT), directly images 120–200 keV electrons with relatively little radiation damage, exhibits no afterglow and limits crosstalk between adjacent pixels. Traditional STEM imaging modes can still be performed by the PAD with a 1.1 kHz frame rate, which allows post-acquisition control over imaging conditions and enables novel imaging techniques based on the retained crystalline information. Techniques for rapid, semi-automatic crystal grain segmentation with sub-nanometer resolution are described using cross-correlation, sub-region integration, and other post-processing methods.     

Development of a new analytical electron microscopy technique to quantify the chemistry of planar defects and to measure accurately solute segregation to grain boundaries

A new technique of analytical transmission electron microscopy called ConceptEM has been developed for determining highly accurately small amounts of solute or dopant atoms incorporated into well‐defined planar defects such as stacking faults, grain boundaries or interfaces. The method is based on recording series of analytical spectra taken with different electron beam diameters on the same position centred above a defect that is orientated either edge‐on or slightly inclined with respect to the electron beam. It can be applied to energy‐dispersive X‐ray spectroscopy or electron energy‐loss spectroscopy and necessitates only a nano‐probe modus but no scanning unit. Reliability and accuracy have been tested numerically under various conditions using simulations for a specific geometry, as a function of specimen thickness, material, acceleration voltage, collection angle, random beam displacements and solid solubility. The accuracy has been found to be substantially better (by factors of 5–10) than that of any other current standard technique based on single measurements. Our calculations suggest an accuracy in the determination of the Gibbsian solute excess at a special grain boundary down to ±1% of a monolayer, i.e. around ±0.1 atoms nm^?2 under typical experimental conditions, with a maximum error about twice as large. The parameter limiting a straightforward analysis is found to be the solid solubility, which itself, however, can be measured accurately by the technique so that it can be taken into account quantitatively and the above‐stated precision is retained.     

A new method of scanning tunneling spectroscopy for study of the energy structure of semiconductors and free electron gas in metals

In this study, anew method for the scanning tunneling spectroscopy (STS) of direct and indirect gap semiconductors and free electron gas in metals is proposed. Band structures of Si, porous Si, and Ge were studied. The tunneling current-voltage characteristics of Si and porous Si surfaces were measured over different voltage intervals from tens of mV to 20 V under incident light from an Xe lamp and those of a Ge surface in the dark. The correlation between the shapes of the I-V curves and band structure of the materials was calculated. It was found that the curves are linear if measured in the voltage range V₀ E_g/(2e) and nonlinear when V₀ α E_g/(2e) (in the measurements the applied voltage was changed from -V₀ to V₀). The method was used for the observation of a new effect of tunneling of free electron gas having thermal energies from a metal tip to a band gap state of the semiconductor. The energy spectrum of free electron gas was measured.