Magnetic vortices in superconductors have become directly and dynamically observable[l] by Lorentz microscopy in our 300 kV field-emission TEM[2]. Since material defects can also be observed simultaneously though the images are defocused, the microscopic flux pinning mechanism can be directly observed. Using this technique, we observed when and how vortices trapped at artificial defects were depinned.

Artificial point defects were produced by the irradiation of a focused Ga ion beam. Electron microscopy revealed that the defect consisted of a pit 300 Å in radius surrounded by entangled dislocations. The depth of a pit increased with the ion dose.

We first investigated the pinning force of individual defect: by observing the depinning of vortices from defects produced with various ion-doses. When a force was exerted on vortices trapped at the defects by changing the magnetic field and increased, we found that the pinning force of defects increased with the ion doses.

Due to the extemely short coherence lengths of the high-Tc superconductors (around 30 Å in the a-b plane), defects such as grain boundaries are obvious barriers to the flow of supercurrent. Within a few months of the discovery of these materials, it was shown how the critical current dropped four orders of magnitude as the grain boundary misorientaion increased from zero to 45°. Even today, there is no quantitative understanding of this behavior. A qualitative understanding is however possible through atomic resolution Z-contrast imaging on YBa2cu3O7-δ and SrTiO3 bicrystal grain boundaries, combined with bond-valence-sum analysis.

The Z-contrast image of a YBa2cu3O7-δ low angle grain boundary in Fig. 1 shows the same kind of reconstructed dislocation cores as seen in SrTiO3, containing reconstructions on both the Cu and Y/Ba sublattices.

Developing an atomic scale study of the structure-property relationships of grain boundaries in high-Tc superconductors is essential to understand their current dissipation mechanism and for incorporating these materials into viable devices. Thin YBa2Cu3O7-δ films have been deposited by pulsed laser deposition (PLD) on SrTiO3 symmetric bicrystals. Transport measurements in a magnetic field have been conducted across the grain boundaries through a wide bridge. The data obtained are consistent with microstructural observation in a VG Microscopes HB603 U and a VG HB501 UX dedicated STEM. Of particular interest in the study of high-Tc materials is the use of EELS, which can highlight the presence of non-superconducting regions through interpretation of the onset positions and finestructure (ELNES) of characteristic core-edge features.

The V(I) curves recorded across a 24° boundary for several magnetic fields (fig. 1 - left) show an onset critical current density followed by a linear differential ohmic behavior which gives a negative intercept.

High temperature superconductivity in cuprates has become a fairly mature field now that more than a decade has passed by since its discovery. While scientific appeal of the field continues, the technological implications have faced harsh realities. Although the transition temperatures are high, the coherence length in oxide superconductors is awfully short and thus inhomegeneity or perturbation at the length scale of a few nanometers proves extremely detrimental to their properties, especially transport. Further, slight changes in the oxygen stoichiometry in cuprates have a profound effect on their superconducting properties and it is often not clear whether the nonstoichiometry at defect sites (e.g. grain boundaries- GBs) is intrinsic or extrinsic.

The anisotropy of electronic structure is well reflected in low loss EELS spectra of these materials. Figure 1 shows low loss EELS spectra from Y124: one taken with momentum transfer confined to the Cu-02 planes, and the other normal to them. These observations are in accord with the fact that conduction is predominantly along the ab-planes, within single crystals.

A cubic millimeter (10-9 m3) of condensed matter contains typically ∼1020 atoms, and a complete solution to the general structure problem requires finding ∼3 ×l020 atom coordinates. For crystals, long-range translational periodicity immensely simplifies the structure elucidation problem to something like a 101-102 problem (further reduced by the symmetry accompanying orientational order), because only the contents of the unit cell (< 100 atoms for most inorganic structures) and the unit cell geometry need be determined. Amorphous is the epithet traditionally bestowed on structures with neither orientation nor translational order, a more precise term for which is topologically disordered [1], A structural average for an amorphous solid can be established with a good many fewer than 1020 atoms, because many atom-atom correlations nevertheless exist in topologically-disordered structures due to bonding, packing and associated topological constraints. In fact, assemblies with less than 200 atoms can usually adequately represent characteristic structural topologies [1].

Covalently bonded materials of the light elements B, C, N, O and Al form an interesting series of structures which are readily prepared by physical vapour deposition methods. The most important structural issues are the degree of positional order (that is, whether the material is amorphous or nano phase crystalline) and for alloys, the degree of site occupancy order (that is, the extent of ‘chemical’ order). We propose that the degree of positional order is dependent on the bond angle stiffness of the covalent bonding and the degree of chemical order is dependent on the energy difference of bonds between like and unlike atoms (see figure 1).

The observation of structure in these materials is conveniently carried out by electron optical techniques in an electron microscope. The techniques of value are (a) Energy Filtered Electron Diffraction, and (b) Electron Energy Loss Spectroscopy (EELS).

Observations made more than ten years ago1 showed that SiC could be made amorphous at cryogenic temperatures by in-situ 300kV electron irradiation. However, high-voltage electron microscope (HVEM) results indicate a threshold voltage of 725 kV for amorphization of SiC at 140 K. In addition, a recent review exposes the considerable uncertainty in the literature regarding displacement energies for SiC. Therefore, further experiments have been performed in a Philips CM30 (LaB6 cathode) with a Gatan double-tilt cooling holder in an attempt to determine the threshold voltage for amorphization at ∼ 140 K. Sintered α-SiC (defected 6H polytype), beam direction B=< 1120 >, and probes containing ∽ 75 nA in ∽0.5 μm, were used. Amorphization occurred in <10 min at 300 kV and after ∽60 min at 180 kV (Fig. 1); visible darkening occurred at lower voltages and doses. Similar behavior occurred for B=[0001]. The critical dose for amorphization was measured as a function of accelerating voltage.

Abstract

Fast electrons are a particularly useful chemical and structural probe for the small sample volumes associated with ion- or fast electron-irradiation-induced amorphization, because of their much stronger interaction with matter than for X-rays or neutrons, and also because they can be readily focused to small probes. Three derivative signals are particularly rich in information: the angular distribution of scattered electrons (which is utilized in both diffraction and imaging studies); the energy loss spectrum of scattered electrons (electron energy loss spectroscopy, or EELS); and the emission spectrum of characteristic X-rays resulting from ionization energy losses (energy dispersive X-ray spectroscopy, or EDXS). We have applied the first two to the study of three amorphized compounds (AIPO4, SiO2, SiC) using MIT's Vacuum Generators HB603 field-emission (FEG) scanning transmission electron microscope (STEM), operating at 250 kV and equipped with a Gatan digital parallel-detection electron energy-loss spectrometer (digiPEELS).

Amorphous materials are devoid of periodic long range order, but at the nearest-neighbor level they possess a high degree of short-range order. In amorphous tetrahedral semiconductors, such as Si and Ge, this short-range order arises because each atom attempts to satisfy four bonds arranged as a regular tetrahedron. It is the rotations about each bond, from the second-nearest-neighbor outwards, that result in the loss of long-range order. It is apparent from modeling of amorphous materials, that there is considerable flexibility as to how rapidly the medium-range-order diminishes. The continuous random network (CRN) is a hypothetical tetrahedral extended structure wherein the atoms possess full four-connected coordination, but have minimal medium-range order. However, real amorphous materials infrequently exhibit true CRN-like topologies. Traditionally, diffraction has been used to study short- and medium-range order in amorphous materials. Assuming kinematical scattering, and that every atom has a similar environment, a radial distribution function (RDF) can be extracted which is sensitive only to the averaged atom pair-correlations out to ∼1 nm.

The electron microscope provides an ideal environment for the structural analysis of small volumes of amorphous and polycrystalline materials by collecting scattering information as a function of energy loss and momentum transfer. The scattering intensity at zero energy loss can be readily processed to a reduced density function G(r), providing information on nearest neighbour distances and bond angles[l]. Figure 1(a) shows the G(r) for glassy carbon, a turbostratic form of graphite. The three nearest neighbours in glassy carbon (labelled 1-3 in figure 1) are at 1.42 Å, 2.44 Å and 3.75 Å respectively. These distances correspond to the first three nearest neighbours in a graphite sheet and are expected in glassy carbon which is know to have good in-plane graphitic order. In figure 1(b) the G(r) of cathodic arc deposited tetrahedral amorphous carbon is shown. This material contains a high fraction of diamond-like bonding[2] and has a 1st nearest neighbour peak at 1.52 Å.

The recent availability of Gatan's imaging filter (GIF) has improved detail in electron energy loss spectroscopy (EELS) owing to the greatly reduced channel-to-channel gain variation. In particular, extended electron loss fine structure (EXELFS) can be rapidly obtained with relatively low beam exposures to the sample. Previous studies using EXELFS (of which there are relatively few) have been limited to rather beam-insensitive samples and have required extensive effort to correct detector gain variation. [1,2] We will discuss here some of our ongoing work on use of EXELFS as a complement to other analytical microscopy techniques to study changes in materials caused by radiation damage (ion and alpha) and transmutation. Using an imaging filter as a spectrometer, we have obtained EXELFS from a rather beam-sensitive alkali aluminosilicate, pollucite (CsAlSi2O6).

The recent discovery of graphite cones [1,2] has raised some interesting questions about the nucleation and growth of curved graphitic structures. Here we report the structural peculiarities of one member of the ensemble, i.e. the flat graphite disks. Unlike graphite flakes seen in carbon soot which are irregularly shaped, the disks in this sample often show regular faceting which might give us additional insight into the growth mechanisms.

The samples were examined in a Hitachi H9000 NAR TEM. Samples were sonicated in high purity methanol and dispersed on a 300 mesh Cu grid coated with a 20 nm thick amorphous carbon layer. Typical disk diameters range from 0.5 to 3.0 μm, with thickness ranging from 10 nm to 50 nm.

A close examination reveals that the edges of the disks are faceted and typically have 12 sides. In most cases, the edges show a long facet alternating with a shorter facet.

Boron-based thin film materials have numerous uses ranging from application as hard and refractory protective coatings to potential employment in wide-band gap semiconductor electronics. Of particular interest are the boron carbides, nitrides, oxides, and phosphides. These compounds exhibit a broad range of structural and bonding variations. The crystalline form of elemental boron is based on an arrangement of 12-atom boron icosahedra positioned at the vertices of a rhombohedral lattice. Related materials, such as B4C, and B12P, also possess structures closely related to this icosahedrally coordinated prototype. However, the structural coordination of the boron carbides and phosphides will vary with composition. For instance, BP possesses a tetrahedrally coordinated zinc-blende structure, and the carbon-rich boron carbides will form in a graphitic structure. Boron nitride has the added complication that for the same composition (BN) multiple bonding and polytypic variations are possible: both soft, graphitic sp2-rich (e.g., hexagonal and rhombohedral BN) and hard, diamond-like sp3-rich phases (e.g., cubic and wurtzitic BN) can be formed.

In 1992, researchers at Mobil Research and Development created a new class of porous silicates, most notably mesoporous MCM-41.2-3 This material features a hexagonal arrangement of linear pores and surface areas in excess of 1000 m2 g-1. MCM-41 exhibits narrow pore size distributions in the nanometer range. The walls of MCM-41 are essentially amorphous silica, but its porous nature makes it about 3 kJ mol-1 less stable than the collapsed form. Particles of MCM-41 are beam sensitive and it appears that they cannot withstand the large current densities required to obtain reliable analytical data at the nanometer scale in the transmission electron microscope (TEM). For example, low beam currents were used to preserve the pore structure but resulted in energy-filtered TEM elemental maps of oxygen K and Ti L2,3 edge intensities that were too noisy to reveal structure at 5 nm resolution.

Amorphous chalcogenides films coated with certain metals are known to possess a remarkable sensitivity to radiation. Based on these effects they have found several important applications in the production of microcircuits, e.g. as resists in photo- and electron beam lithography. A variety of chalcogenides in combination with a range of metals has been extensively investigated with regard to potential applications in the fabrication of semiconductor devices.

The objectives of the present project are to extend knowledge of the behaviour of amorphous chalcogenides in contact with metals. This includes studying the metal diffusion process, understanding the film-electron beam interaction process and evaluating the potential of the metal lines formed by the electron beam in fabrication of photomasks for the production of higher densities of silicon microcircuits.

A recent development in the study of nanocrystalline materials has been the self-assembly of passivated nanometer scale building blocks into larger, well ordered structures reaching the micron scale. Nanocrystal supercrystals (NCS) have been observed in metallic, semiconductor, and magnetic materials. In most cases the nanocrystals (NXs) are encapsulated in some inert medium that effectively protects the nanocrystal core and its unique electronic and optical properties. Here we describe the self-assembly of gold nanocrystals (∼4.5 nm core diameter), passivated with hexanethiol self-assembled-monolayers into ordered regions exhibiting a body-centered-cubic (bcc) superstructure. Transmission Electron Microscopy (TEM) imaging and Electron Diffraction (ED) experiments were used to characterize the NCSs and their resulting superstructures.

A large agglomeration of NCSs can be seen in figure 1. One can clearly see regions of periodicity within the nanocrystal aggregation.

ZnS particles consisting of nanocrystallites have potential applications as light emitters for displays. The possibility of encapsulating chemicals into porous particles and the temperature-controlled release of them could also be of interest in chemical engineering. The objective of this study is to determine the size distribution, shape and morphology of ZnS particles synthesized under different conditions, since they strongly influence the optical and electric properties.

The ZnS powders were prepared by precipitation from homogeneous aqueous solutions, following a procedure described elsewhere1-3 The initial solution consists of a zincsalt precursor dissolved in ultrapure water under acidic pH conditions. Adding Thioacetamide (TAA: CH3C(S)NH2) to this acidic solution at elevated temperature leads to the precipitation of ZnS nanocrystals. Four different types of zincsalt precursors were used to study their influence on the precipitation process and the final powder morphology: acetate (CH3COO), chloride (Cl-), trifluoromethanesulfonate (tFMS: CF3SO3-) and dimethyldithiocarbamate (dMdTC: S4N2C6H12-). The dried powder were subjected to 350°C and 700°C heat treatments, respectively.

NiAl is an important high temperature structural material, with a high melting point (1640°C), low density and excellent high temperature oxidation resistance. The room temperature ductility of NiAl may potentially be improved with the use of nanocrystalline grain size. However, a key question concerning the application of nanostructured NiAl is about its structural stability at high temperature. The current study is thus focused on the investigation of the structural stability of nanocrystalline NiAl using in-situ transmission electron microscopy (TEM) and differential thermal analysis (DTA).

Nanocrystalline B2-NiAl was prepared by ball milling (24 hrs) from elemental Ni and Al powders. Subsequent consolidation into bulk form was performed using dynamic consolidation employing a 3-capsule plate-impact fixture at approximately 400 m/s [1-3]. Powder nanocrystalline NiAl was dispersed on a holey carbon film for TEM observation. TEM specimens of shock compacted bulk NiAl nanocrystals were prepared by cutting, polishing, dimpling and ion milling.

A description of the microstructure of heterogeneous catalysts is important in understanding the mechanisms for catalysis and may result in improvements in catalyst performance. Many commercial catalysts consist of small metal particles and/or metal oxide particles dispersed on a porous support. For bimetallic catalysts, the metals may be in the form of alloys, metal mixtures or completely phase separated. HREM has been demonstrated to be a powerful technique for determining the lattice spacing from small particles[l]. In many studies of catalysts it is necessary to prepare TEM samples by microtomy so that the particle location relative to the porous support is preserved. However, such samples show a reduction in particle visibility and signal-to-noise ratio of lattice fringes. In spite of these difficulties, we have been able to routinely use HREM to rapidly determine the relative distributions of metal and metal oxides in many systems because of the large difference in spacing between strong reflections from the metal and metal oxide (typically 20 %).

High-temperature catalysts containing Pd supported on high-surface area ceria-zirconia are optimum materials for fuel economy when automotive engines operate under high speed or load conditions. A prerequisite for developing such thermally stable catalysts is to gain a good understanding of the thermal deactivation modes contributing to the aging and degradation of catalysts in harsh thermal environments. It was discovered by X-ray diffraction that upon hightemperature aging, Pd may sinter into large (about 10 nm diameter) particles and become encapsulated in the ceria-zirconia. To confirm this conclusion, a prototype high-temperature catalyst containing Pd supported on high-surface area ceria-zirconia, aged at temperature above 1100 °C is studied by transmission electron microscopy (TEM).

The ceria-zirconia supported Pd (0.25 wt%) catalyst was aged at 1105 °C and calcined at 700 °C for 2 h. For TEM sample preparations, first of all, a large-size aggregate with diameter about 1 mm was selected and sandwiched between by two pieces of silicon crystal.