Carbon–metal interfaces analyzed by aberration-corrected TEM: How copper and nickel nanoparticles interact with MWCNTs

Experimental confirmation for the stronger interaction of Ni with multi-walled carbon nanotubes (MWCNTs) compared to Cu with MWCNTs is presented. The interfaces between Cu (Ni) nanoparticles side-on oriented onto MWCNTs are analyzed with high spatial resolution electron energy-loss spectroscopy (EELS) of the carbon K-edge. The EEL spectra reveal a rehybridization from sp² to sp³ hybridized carbon of the outermost MWCNT layer at the Ni interface, but no such rehybridization can be observed at the Cu interface. The EELS results are supported by transmission electron microscopy (TEM) images, which show a better wetting behavior of Ni and a smaller gap at the Ni–MWCNT interface, as compared to the corresponding Cu interfaces. The different behavior of Cu and Ni can be explained in terms of differing valence d-orbital occupancy. For the successful experimental demonstration of this effect the use of a soft chemical metal deposition technique is crucial.     

TEM preparation methods and influence of radiation damage on the beam sensitive CaCO3 shell of Emiliania huxleyi

The ultrastructure of biologically formed calcium carbonate crystals like the shell of Emiliania huxleyi depends on the environmental conditions such as pH value, temperature and salinity. Therefore, they can be used as indicator for climate changes. However, for this a detailed understanding of their crystal structure and chemical composition is required. High resolution methods like transmission electron microscopy can provide those information on the nanoscale, given that sufficiently thin samples can be prepared. In our study, we developed sample preparation techniques for cross-section and plan-view investigations and studied the sample stability under electron bombardment. In addition to the biological material (Emiliania huxleyi) we also prepared mineralogical samples (Iceland spar) for comparison. High resolution transmission electron microscopy imaging, electron diffraction and electron energy-loss spectroscopy studies revealed that all prepared samples are relatively stable under electron bombardment at an acceleration voltage of 300 kV when using a parallel illumination. Above an accumulated dose of ∼10⁵ e/nm² the material – independent whether its origin is biological or geological – transformed to poly-crystalline calcium oxide.     

Electron energy loss spectroscopy of ultrathin pentacene field effect transistors

Electron energy loss spectra of ultrathin pentacene field effect transistors were measured by applying gate bias voltages. Tailing and shouldering of the primary peak on the energy loss side was observed for 1.5 nm thick films when a negative gate bias was applied. The energy loss spectra obtained from the deconvolution of the primary electron profile showed peaks, and the peak energies increased as a function of the gate bias voltage. This is consistent with the behavior of two-dimensional plasmons of field-induced carriers. The thickness dependence is explained by the thickness of the accumulation layer and the probing depth of the spectroscopy.     

The sp2 and sp3 fractions of unknown carbon materials: electron energy-loss near-edge structure analysis of C-K spectra acquired under the magic-angle condition by the electron nanobeam technique

A method is described for the quantification of the sp², sp³ and intermediate hybridizations in several carbon (C) material samples. Electron energy-loss near-edge spectra were acquired using fast electrons (120 keV) in an electron microscope in nanobeam configuration under the so-called ”magic-angle” condition, and were analysed to extract the sp² and sp³ fractions, and identify the possible mixed sp^2+ε hybridizations. The method consists in projecting the unknown spectra on a basis made up of pure sp² and sp³ spectra, obtained under the same experimental conditions from graphite and diamond crystals, respectively. The residual spectra contain information about the intermediate hybridizations sp^2+ε occurring in the samples. The method was successfully tested on “ab initio” numerically generated spectra relative to amorphous C materials. Finally, it was applied to actual C amorphous and pyrolytic samples, and results were compared to those obtained by the most commonly used, conventional ”three-Gaussian” method. The combined application of electron diffraction and spectroscopy, in the nanobeam configuration, yielded useful information about the atomic and electronic structure from very small volumes of the unknown C material.     

Structural characterization of ultrathin Cr and Sc films for soft X-ray mirrors

The structure of multilayers of ultrathin scandium (Sc) and chromium (Cr) films has been characterized by means of transmission electron microscopy (TEM). Face centered cubic Sc was found both in magnetron sputtered thin Sc layers on Si(0 0 1) and in Cr/Sc multilayers for soft X-ray mirrors. The single Sc and Cr layers are polycrystalline with randomly oriented grains, while Sc and Cr within the Cr/Sc multilayer show a strong [0 0 1] texture in the deposition direction. From high-resolution images the orientation-relationship at the Cr/Sc interfaces could be deduced as: Sc_[110]//Cr_[100] and Sc_[010]//Cr_[110], which was confirmed by image simulations.     

Electron energy-loss spectroscopy in the low-loss region as a characterization tool of electrode materials

Energy losses below 100 eV are by far less exploited than higher losses in electron energy-loss spectroscopy. Two new examples are given to illustrate the characterization possibilities offered by spectra in this energy range. Typical materials that could be used as electrodes in electrochemical cells were chosen as application cases. Through the use of calculations based on density functional theory, we first demonstrate that the first peak present at the lithium K edge in Li _x TiP₄ can give access to the precise localisation of inserted Li atoms in the f.c.c. structure. In particular, different tetrahedral sites could be differentiated according to their distance to the Ti site. Secondly, calculations of valence electron energy-loss spectra of perovskite materials indicate that a characteristic peak for regular perovskite (Pm m space group) exists in the 10–15 eV range. The high sensitivity of this peak to the distortion of the octahedron arrangements is also demonstrated. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Catalytic activity of Fe, Co and Fe-Co-MCM-41 for the growth of carbon nanotubes by chemical vapour deposition method

Iron, cobalt and a mixture of iron and cobalt incorporated mesoporous MCM-41 molecular sieves were synthesised by hydrothermal method and used to investigate the rules governing their nanotube producing activity. The catalysts were characterised by XRD and N₂ sorption studies. The effect of the catalysts has been investigated for the production of carbon nanotubes at an optimised temperature 750 °C with flow rate of N₂ and C₂H₂ is 140 and 60 ml/min, respectively for a reaction time 10 min. Fe-Co-MCM-41 catalyst was selective for carbon nanotubes with low amount of amorphous carbon with increase in single-walled carbon nanotubes (SWNTs) yield at 750 °C. Formation of nanotubes was studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy. Transmission electron microscope and Raman spectrum was used to follow the quality and nature of carbon nanotubes formed and the graphitic layers and disordered band, which shows the clear evidence for the formation of SWNTs, respectively. The result propose that the diameter of the nanotubes in the range of 0.78-1.35 nm. Using our optimised conditions for this system, Fe-Co-MCM-41 showed the best results for selective SWNTs with high yield when compared with Fe-MCM-41 and Co-MCM-41.     

Measuring the aspect ratios of ZnO nanobelts

Nanobelts are new materials that have a rectangular cross-section and are characterized by widths and width-to-thickness aspect ratios. In this paper, the thickness and aspect ratios of ZnO nanobelts are measured by a conjunction application of convergent beam electron diffraction (CBED) and electron energy-loss spectroscopy (EELS). The thicknesses of thicker nanobelts are first determined by CBED under two-beam diffracting condition, then they are used to determine the electron inelastic mean-free-path (MFP) length, which is 161±15 nm for ZnO at 200 kV. The thicknesses of the thinner nanobelts are then determined by EELS using the calibrated MFP. The results show that the aspect ratio depends on conditions under which the sample was synthesized.     

Frenkel exciton model of electron energy loss spectroscopy in -PTCDA

Recent experimental findings concerning electron energy loss spectroscopy in -Perylene-tetracarboxylic-dianhydride are analysed in terms of a Frenkel exciton model. Taking into account the energy dispersion of excitations with finite momentum transfer, the k-dependence of the dielectric tensor and the corresponding electron energy loss functions can be calculated. The exciton dispersion with a minimum at k≠0 yields a red shift of the lineshape of loss functions at large k, as observed experimentally.     

Decisive factors for realizing atomic-column resolution using STEM and EELS

We demonstrate atomic-column imaging by scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). The silicon atomic-columns of a β-Si₃N₄ (0 0 1) specimen are clearly resolved. The atomic-site dependence and the energy-loss dependence of the spatial resolution are elucidated on the basis of the experimental results and multislice calculations. We describe two decisive factors for realizing atomic-column imaging in terms of localization in elastic and inelastic scattering. One is the channeling of the incident probe due to dynamical diffraction, which has atomic-site dependence. The other is the localization in inelastic scattering; in addition to the energy-loss dependence of delocalization, we point out its dependence on the offset energy from the ionization energy, i.e., an additional localization factor concerning the Bethe surface. The present atomic-column observation of the Si-L core-loss image indicates that the local approximation, which can be interpreted intuitively, is achievable under appropriate experimental conditions, such as high-energy-loss, a small convergence angle and a large collection angle (e.g., 400 eV, 15 and 30 mrad, respectively).     

Synthesis and characterization of Cr doped CdS nanoparticles stabilized with polyvinylpyrrolidone

Undoped and Cr (2 and 4 at.%) doped CdS nanoparticles were synthesized in aqueous solution by simple chemical co-precipitation method using polyvinylpyrrolidone (PVP) as stabilizer. The prepared nanoparticles were examined using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDAX), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and Fourier transform infrared spectroscopy (FTIR). XRD pattern of the nanoparticles showed cubic zincblende phase with the particle size of the order of 3-4 nm, which was in good agreement with the results obtained from TEM studies. The EDAX analysis confirmed that Cd, Cr and S elements were present in the samples and the variations between the target and actual compositions were microscopic. UV-vis DRS spectra of the samples exhibited decrease in the band gap which further attests the incorporation of Cr into CdS nanoparticles. FTIR studies revealed that the undoped as well as Cr doped CdS nanoparticles were capped by polyvinylpyrrolidone.     

Microspectroscopy and spectromicroscopy with photoemission electron microscopy using a new kind of imaging energy filter

The use of an imaging retarding field analyser attached to the FOCUS IS-PEEM is described. This kind of energy filter is a simple, powerful tool to obtain microspectra from areas of down to about 1 μm using (V)UV and X-ray excitation sources. First results of microspectroscopy measured by excitation with a laboratory as well as a synchrotron X-ray source are presented.     

Electron diffraction on graphite nanocrystals in the walls of carbon nanotubes

The structure and defects in the walls and cavities of carbon nanotubes were examined by electron diffraction, transmission electron microscopy, energy dispersive X-ray analysis and Raman spectroscopy. The predominating defects in the walls of the nanotubes are graphite nanocrystals having a preferential orientation in the direction of the nanotube axis, and another significant type of defects are particles of the catalyst in the nanotube cavities. In the cavities, also the presence of molybdenum was proved having its origin in the catalyst.     

Metal interface formation studied by high-energy reflection energy loss spectroscopy and electron Rutherford backscattering

We demonstrate that high-energy, high-resolution reflection electron energy loss spectroscopy can provide unique insights into interface formation, especially for the case where an extended interface is formed. By changing the geometry and/or electron energy the electronic structure can be probed over a range of thicknesses (from 10s of Å to more than 1000 Å). At the same time one resolves the elastically scattered electrons into different components, corresponding to scattering of atoms with different mass (so-called ‘electron Rutherford backscattering’). Thus these high-energy REELS/elastic scattering experiments obtain information on both the electronic structure and the atomic composition of the overlayer formed.     

Initial oxidation of MgO-supported Rh nanoparticles studied by TEM

The formation of ultrathin oxide layers on the facets of MgO(0 0 1) supported Rh nanoparticles is revealed by high-resolution transmission electron microscopy (HRTEM) and spatially-resolved electron energy-loss spectroscopy (EELS). An O–Rh–O trilayer surface oxide has been observed on both {1 1 1} and (0 0 1) facets, which is confirmed by image simulation using the atomic model of a two-dimensional surface oxide obtained by density functional theory (DFT). The spacing between the oxide layer and the Rh {1 1 1} facet is however markedly smaller, indicating a variation of interface bonding in the case of nanoparticles. When the oxide layer is slightly thicker with two Rh planes, the structure of the surface oxide is different from corundum Rh₂O₃ bulk oxide, and the trilayer surface oxide persists as terminating layer. The spacing between the oxide layer and the Rh(1 1 1) facet is found to vary, being smaller in the middle of the oxide layer. It is also found that oxidation is more pronounced at the intersections of the nanoparticles’ facets.     

Electron energy loss spectroscopy (eels) of organic molecules in vapour phase: Design and fabrication of an indigenouseel spectrometer

An indigenous electron energy loss spectrometer has been designed and fabricated for the study of free molecules. The spectrometer enables the recording of low-resolution electronic spectra of molecules in the vapour phase with ready access to the vacuum ultraviolet region. Electron energy loss spectra of aliphatic alcohols and carbonyl compounds as well as of benzene derivatives have been recorded with the indigenous spectrometer and the electronic transitions in these molecules discussed. Contribution No. 274 from the Solid State and Structural Chemistry Unit, dedicated to Dr. Raja Ramanna on his 60th birthday.     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical properties and electronic transitions of SnO2 thin films by reflection electron energy loss spectroscopy

Optical properties of SnO₂ thin films in the 4–60 eV energy range are determined by reflection electron energy loss spectroscopy. Bulk and surface electron loss functions, real and imaginary parts of the dielectric function, refraction index, extinction and absorption coefficients are obtained from the analysis of the electron energy loss spectra. Electronic transitions are identified through the interpretation of the optical data. The samples (250–500 nm thick) were produced by ion beam-induced chemical vapor deposition. It is found that the compacity of the SnO₂ thin films affects their optical properties and therefore the relative intensity of the observed electronic transitions. The advantages of this method to determine optical properties of thin films are discussed. Inelastic mean free paths (6.2, 17 and 41 Å for electrons traveling in SnO₂ with kinetic energies of 300, 800 and 2000 eV, respectively) are obtained from the corresponding inelastic electron scattering cross-sections.     

Cytochemical localization of calcium and X-ray microanalysis of Catharanthus roseus L. infected with phytoplasmas

The potassium pyroantimonate (KPA) Ca²⁺ precipitation technique, X-ray microanalysis and Electron Energy Loss Spectroscopy carried out by transmission electron microscopy were used to analyze the Ca²⁺ distribution in Catharanthus roseus L. leaves infected with phytoplasmas belonging to different taxonomic groups, and in phytoplasma cells. The analysis revealed that the distribution of Ca²⁺ was different in healthy and diseased plants (where the KPA deposits were numerous) and no differences were observed in the tissues of the three types of infected C. roseus L. Since no KPA precipitates were visible in the phloem and on phytoplasma cells, it is likely that Ca²⁺ ions are not directly involved in phytoplasma replication, but, in infected cells is a response to the pathogen indicative of a higher Ca²⁺ in the plasmalemma.     

Growth of single wall carbon nanotubes using PECVD technique: An efficient chemiresistor gas sensor

In this work, the uniform and vertically aligned single wall carbon nanotubes (SWCNTs) have been grown on Iron (Fe) deposited Silicon (Si) substrate by plasma enhanced chemical vapor deposition (PECVD) technique at very low temperature of 550 °C. The as-grown samples of SWCNTS were characterized by field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM) and Raman spectrometer. SWCNT based chemiresistor gas sensing device was fabricated by making the proper gold contacts on the as-grown SWCNTs. The electrical conductance and sensor response of grown SWCNTs have been investigated. The fabricated SWCNT sensor was exposed to ammonia (NH₃) gas at 200 ppm in a self assembled apparatus. The sensor response was measured at room temperature which was discussed in terms of adsorption of NH₃ gas molecules on the surface of SWCNTs. The achieved results are used to develope a miniaturized gas sensor device for monitoring and control of environment pollutants.