Image matching between experimental and simulated high-resolution electron micrographs of sapphire on the [0110] orientation.

The effects of imaging parameters have been studied on their roles of the severe mismatches between experimental and simulated high-resolution transmission electron micrographs of sapphire along the direction. Image simulation and convergent-beam electron diffraction techniques have been performed on misalignments of the electron beam and the crystal specimen. Based on this study, we have introduced an approach to achieve reliable simulation for experimental images of sapphire on the projection by the use of iterative digital image matching.

Specific twin junctions in doped zirconia.

The effect of different dopant cations on the phase transformations of the initially stabilized supersaturated tetragonal ZrO(2) phase during various heat treatments has been studied. The obtained fraction of monoclinic grains develop twinned structures, but there is still a lack of information about the character of grain boundaries formed in doped monoclinic solid solutions. The inspection of particular selected-area electron diffraction patterns provides an alternative method with respect to high-resolution electron microscopy or electron back-scattered diffraction for characterizing different twin junctions in various doped zirconia systems. The classification of these special twins is based on the coincidence site lattice concept.

Dispersion of carbon nanotubes using organic solvents.

Phenyl ethyl alcohol was used for fast and stable dispersion of carbon nanotubes. This solvent, more effective than ethanol and toluene, allows easy dispersion of carbon nanotubes for TEM characterization. For TEM grids prepared at high dilution, it is possible to observe each tube separately. Applying that solvent, it was possible to measure the length, the diameter and the solubility of different carbon nanotubes samples.

Aspects regarding measurement of thickness of intergranular glassy films.

Materials such as Si(3)N(4), SiC and SrTiO(3) can have grain boundaries characterized by the presence of a thin intergranular amorphous film of nearly constant thickness, in some cases (e.g. Si(3)N(4)) almost independent of the orientation of the bounding grains, but dependent on the composition of the ceramic. Microscopy techniques such as high-resolution lattice fringe imaging, Fresnel fringe imaging and diffuse dark field imaging have been applied to the study of intergranular glassy films. The theme of the current investigation is the use of Fresnel fringes and Fourier filtering for the measurement of the thickness of intergranular glassy films. Fresnel fringes hidden in high-resolution micrographs can be used to objectively demarcate the glass-crystal interface and to measure the thickness of intergranular glassy films. Image line profiles obtained from Fourier filtering the high-resolution micrographs can yield better estimates of the thickness. Using image simulation, various kinds of deviation from an ideal square-well potential profile and their effects on the Fresnel image contrast are considered. A method is also put forth to objectively retrieve Fresnel fringe spacing data by Fourier filtering Fresnel contrast images. Difficulties arising from the use of the standard Fresnel fringe extrapolation technique are outlined and an alternative method for the measurement of the thickness of intergranular glassy films, based on zero-defocus (in-focus) Fresnel contrast images is suggested. The experimental work is from two ceramic systems: Lu-Mg-doped Si(3)N(4) and SrTiO(3) (stoichiometric and nonstoichiometric). Further, a comparison is made between the standard high-resolution lattice fringe technique, the standard Fresnel fringe extrapolation technique and the methods of analyses introduced in the current work, to illustrate their utility and merits. Taking experimental difficulties into account, this work is intended to be a practical tool kit for the study of intergranular glassy films.

Ordered liquid aluminum at the interface with sapphire.

Understanding the nature of solid-liquid interfaces is important for many processes of technological interest, such as solidification, liquid-phase epitaxial growth, wetting, liquid-phase joining, crystal growth, and lubrication. Recent studies have reported on indirect evidence of density fluctuations at solid-liquid interfaces on the basis of x-ray scattering methods that have been complemented by atomistic simulations. We provide evidence for ordering of liquid atoms adjacent to an interface with a crystal, based on real-time high-temperature observations of alumina-aluminum solid-liquid interfaces at the atomic-length scale. In addition, crystal growth of alumina into liquid aluminum, facilitated by interfacial transport of oxygen from the microscope column, was observed in situ with the use of high-resolution transmission electron microscopy.

Structures of BaF2-CaF2 heterolayers and their influences on ionic conductivity.

Recently, artificial ion conductors have been prepared by growing epitaxial heterolayers consisting of BaF2-CaF2 using molecular beam epitaxy. The ionic conductivity of these heterolayers shows a strong dependence on the layer thickness [N. Sata, S. Eberman, K. Eberl, and J. Maier, Nature 408, 996 (2000)]. In this paper three such heterolayers with different spacings (sample A: 80 nm, sample B: 10 nm, sample C: 1 nm) are investigated by conventional transmission electron microscopy and high-resolution transmission electron microscopy. The spacings are chosen such that they fall into the three conductivity regimes observed in N. Sata et al. (l > 50 nm; 8 < l < 50 nm; l < 8 nm). In accordance with conductivity studies, the samples with spacings of 10 nm or greater (A,B) are epitaxial and continuous, whereas in the case of extremely small spacing (C) the continuity of the layers is destroyed by formation of a column-like structure. Analytical electron microscopy reveals that, instead of forming multilayers, Ca and Ba separate in different columns in sample C. The structure properties of sample A (large l) are quite ideal: Planar interfaces with regular arrays of misfit dislocations with their Burgers vectors on the interface are observed. In the case of sample B (medium l) the lattice misfit is accommodated, in addition, by wavy interfaces associated with dislocations characterized by a Burgers vector that makes a large angle to the interfaces. The (111) lattice spacing very close to the interfaces is markedly changed due to this novel relaxation mechanism in the multilayer. The influences of the crystallographic defects on the ionic conductivity are also discussed.

Core-hole effects on the ELNES of absorption edges in SrTiO3.

Near-edge structures of absorption edges in electron energy-loss spectra (ELNES) of SrTiO(3) were calculated and compared to experimental inelastic electron scattering data. The goal of this study was to investigate final-state effects on the electronic structure. Two theoretical approaches were applied: density-functional theory with a band-structure supercell method and a real-space multiple-scattering cluster approach. Within both techniques, the Z+1 approximation was used to model the core hole generated by the inelastic scattering process. For the band-structure calculations, supercells of (SrTiO(3))(n)(n=1,4,8,16) composition with three-dimensional periodic boundary conditions were applied. The influence of supercell size and shape on calculated site- and symmetry-projected local densities of unoccupied states is assessed quantitatively. Relevant convergence criteria are the length scale set by the spatial extension of the valence-electron screening cloud around the core hole, and the interaction energy of neighbouring core hole centres. For a sufficiently large supercell size, the Z+1 approximation yields a reasonable description of the local densities of unoccupied states probed by the energy losses of inelastically scattered electrons of the Ti L(3)-, O K- and Sr L(3)-absorption edges. The quantitative equivalence of ELNES information extracted from the multiple-scattering cluster calculations and the band-structure supercell calculations is demonstrated. Discrepancies between theoretical and experimental results are discussed.

Plasmon energy mapping in energy-filtering transmission electron microscopy.

In this paper, we demonstrate the two-dimensional mapping of plasmon energies by energy-filtering transmission electron microscopy. The maps are obtained from a series of energy-filtered images in the plasmon energy region. Examples are shown for a nano-crystalline Si-B-C-N ceramic. This material contains SiC and Si(3)N(4) grains as well as intergranular regions composed of hexagonal BN (h-BN) and turbostratic carbon (t-C). The different phases can be clearly identified by their specific plasmon energies. An energy resolution of < or =0.1eV is achieved. In addition, the plasmon map of an amorphous carbon film is used to visualize the non-isochromaticity of the Corrected Omega filter (90 degrees filter) of the SESAM2. A procedure is proposed for the correction of the non-isochromaticity.

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 degrees C. High-resolution transmission electron microscopy revealed that the interfaces were atomically abrupt with the (110)Mo plane parallel to the substrate surface. Ti-L2,3 ( approximately 460 eV), O-K ( approximately 530 eV), Sr-L2,3 ( approximately 1950 eV) and Mo-L2,3 ( approximately 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-L2,3 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-L2,3 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-L2,3, 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.

Chemical reactions and morphological stability at the Cu/Al2O3 interface.

The microstructures of diffusion-bonded Cu/(0001)Al2O3 bicrystals annealed at 1000 degrees C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high-resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20-35 nm thick interfacial CuAlO2 layer formed, which crystallises in the rhombohedral structure. However, the CuAlO2 layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle-like structure was observed. The needles are several millimetres long, approximately 10 microm wide and approximately 1 microm thick. They consist of CuAlO2 with alternating rhombohedral and hexagonal structures. Solid-state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as-bonded sample.

Nanotube composites: novel SiO2 coated carbon nanotubes.

A novel route to nanocomposites consisting of multi-walled carbon nanotubes (MWNTs) embedded in amorphous SiOx is reported; the material has been characterised by high resolution transmission electron microscopy (HRTEM) and high resolution electron energy loss spectroscopy (HREELS); for the first time, and based on our observations, we propose theoretical models accounting for stable SiOx/tube interfaces using density functional based tight binding (DFTB).

Validity of the dipole-selection rule for the Al-L2,3 edge of alpha-Al2O3 under channeling conditions.

The validity of the dipole-selection rule for the Al-L2,3 electron energy-loss edge of alpha-Al2O3 is investigated. Dipole forbidden transitions can be observed in a transmission electron microscope operated with large collection apertures. In addition, it is shown that channeling along a highly symmetrical zone axis in alpha-Al2O3 can lead to the detection of dipole forbidden transitions even with small collection apertures. For an incident electron direction parallel to the <0001> orientation it is observed experimentally that the fine structure of the Al-L2,3 edge shows additional features compared to measurements with the electron beam parallel to <1100>. This effect is due to the occurrence of channeling conditions, indicated by the dependence of the additional dipole forbidden features on the sample thickness. These additional features disappear when tilting the crystal by 1.8 degrees (0.84 A(-1)) or even into the less-symmetrical <1100> zone axis. It is suggested that these observations are explained by differences in local symmetry at the excited center with respect to the incident beam directions.

Plasticity and an inverse brittle-to-ductile transition in strontium titanate.

The use of ceramic materials is often restricted by a transition from ductile behavior to brittle fracture with decreasing temperature. For example, strontium titanate ( SrTiO3) is known to be extremely fragile and brittle below 1300 K. It is therefore surprising to find that SrTiO3 single crystals can be deformed in compression below 1050 K again. Extensive plastic deformation up to 7% strain at low yield stresses of the order of only 120 MPa is possible at room temperature. Low temperature plasticity is carried by the same [110] [110] dislocations as the high temperature deformation along the [001] axis. From this we conclude that these dislocations must exist in two different core configurations.

Quantitative atomic-scale analysis of interface structures: transmission electron microscopy and local density functional theory.

Transmission electron microscopy (TEM) and local density functional theory (LDFT) are combined to analyze the microscopic structure of the rhombohedral twin interface in alpha-Al2O3. LDFT provides interfacial energetics and atomic and electronic structures for three competing models. With high-resolution TEM the atomic structure at the interface is imaged quantitatively along two orthogonal zone axes. Electron energy loss spectroscopy in TEM with nanoscale spatial resolution yields the interfacial electronic structure. Both experiments confirm the theoretically preferred model quantitatively.

Valence electron energy loss study of Fe-doped SrTiO3 and a sigma13 boundary: electronic structure and dispersion forces.

Valence electron energy loss spectroscopy in a dedicated scanning transmission electron microscope has been used to obtain the interband transition strength of a sigma13 tilt grain boundary in SrTiO3. In a first step the electronic structure of bulk SrTiO3 has been analysed quantitatively by comparing VEELS spectra with vacuum ultraviolet spectra and with ab initio density of states calculations. The electronic structure of a near sigma13 grain boundary and the corresponding dispersion forces were then determined by spatially resolved VEELS. Also the effects of delocalization of the inelastic scattering processes were estimated and compared with results from the literature.

Core-hole effect in the ELNES of alpha-Al2O3: experiment and theory.

The occurrence of the core-hole effect at the Al-K and Al-L1 edge in alpha-Al2O3 was studied by comparing experimental electron energy-loss near-edge structures (ELNES) and results of band-structure calculations with and without accounting for core-hole effects by the Z + 1 approximation. It was found that the theoretically calculated unoccupied p-like projected densities of states (PDOS) without Z + 1 approximation matches better to the experimental Al-L1 ELNES, whereas the PDOS with Z + 1 approximation matches better to the experimental Al-K ELNES. We conclude that the localisation of the initial state is an important prerequisite for the observability of the core-hole effect in the ELNES.

Advances in energy-filtering transmission electron microscopy.

First experiments using a new energy-filtering microscope (Sub-eV-Sub-A microscope, or SESAM) are shown. They make use of the high transmissivity of the 90 degree filter. This allows the mapping of chemical bonding of large specimen areas, even if narrow energy selecting slits are used. Because large scattering angles are accepted by this filter, energy-filtered diffraction patterns extending to 150 mrad can be recorded by a single exposure. This can be used to determine the reduced density function of amorphous materials and reduces the exposure time of the investigated area by three orders of magnitude as compared with previous approaches.

Selective specimen preparation for TEM observation of the cross-section of individual carbon nanotube/metal junctions

We present here an efficient method to prepare a transmission electron microscopy (TEM) specimen for selective observation of the cross-section of individual nanoscale structures. As a typical example, the cross-sectional TEM observation of a quasi-one-dimensional material - a nano-electronic component based on an individual carbon nanotube - is presented.

Analysis of local strain in aluminium interconnects by energy filtered CBED

Energy filtered convergent beam electron diffraction (CBED) was used to investigate localised strain in aluminium interconnects. The quantitative analysis of the experimental patterns is based on a multi-step evaluation procedure which is the main subject of the present paper. The improvements which were made to the analysis method aim at increasing both the automation and the accuracy. The detection of the higher order Laue zone (HOLZ) line positions is performed by means of the Hough transform. The required sub-pixel resolution can be achieved routinely and the achievable accuracy is only limited by the line width and the amount of noise in the patterns. The determination of the strain state is performed via a refinement algorithm which is based on varying the strain state in the sample coordinate system and simulating the patterns for the individual grains until a best fit with the experiment is obtained. For the simulation we have developed a new correction scheme in which the dynamical effects are treated separately for each individual HOLZ line. The results show that the main source of the observed strains is the difference in thermal expansion coefficients. The strain is substantially reduced underneath a hillock in the interconnect. Asymmetries in the strain distribution around the hillock show that the unidirectional diffusion during electromigration tests causes peak strains in areas next to the hillock which may be possible failure sites.