The electronic structure of the prototypical quasi-one dimensional (1D) conductor K03MoO3 has been studied using high resolution photoemission spectroscopy. In particular, the electronic structure of defects was investigated in order to understand the mechanism for charge density wave pinning and destruction of the Peierls transition. Defects were found to radically alter the electronic structure close to the Fermi level (EF), thus strongly modifying the structure of the Fermi surface. While a low emission intensity at EF has been interpreted as evidence for a Luttinger liquid ground state in a ID metal, we show that non-stoichiometric surfaces lead to similar effects. The nature of the ground state is discussed in the context of these results.

Experimental surface core-level shifts (SCLSs) aid in understanding the roles of altered electronic and screening properties at reconstructed semiconductor surfaces.1 Because of unresolved theoretical issues, the assignment of SCLSs has often remained controversial even though the surface geometry has been completely determined with traditional probes.

Angular- and energy-dependent x-ray photoelectron diffraction (XPD) of each chemically resolved surface core-level electron can be used to discriminate the structure around each chemically shifted species. However, this technique requires tunability, high energy resolution to separate the SCLSs from the bulk core-levels, and high photon flux in order to gather large amounts of data in a reasonable time. Using the newly commissioned spectromicroscopy beamline 7.0 at the Advanced Light Source, we have acquired chemically-resolved XPD data for Si(111) 7×7 for several photon energies, and by examination of forward-focusing peaks we can draw tentative conclusions about the atomic origins of each core-level shifted peak.

We present simulated photoelectron angular distributions (PAD's) for LiF and graphite. The results describe electron photocurrent versus photon energy, electron initial-state energy, and emission angles (leading to identification of two, or three, components of a valence electron's initial crystal momentum). Results are displayed in a fashion greatly facilitated by display analyzers. Earlier experimental results for LiF are confirmed in great detail. We discuss statistical comparison of theoretical and experimental PAD's. Effects of Bragg- diffraction on outgoing photoelectrons and uncertainty in crystal momentum normal to a surface are analyzed. In graphite, the observed lowering of symmetry, from that in a periodic-zone band structure to that seen in the PAD's, is modeled and explained.

In the exploration of the nano-world of semiconductors there is a strong focus on low-dimensional structures and ultra-small devices. Two fundamental problems, which challenge progress in this field are: (i) large ensembles of nano-objects, like Quantum Dots (QDs), do not have identical geometrical shapes and electronic properties, and, (ii) the properties of a low-dimensional structure can be dominated by a few impurity atoms, whereas the properties of a macroscopic structure is determined by the quasi-continuous background of dopant impurities. To allow QDs and discrete impurities to be studied, novel experimental techniques are required. In this paper we describe how local luminescence has been excited from single QDs using electrons injected from a Scanning Electron Microscope (SEM), from the tip of a Scanning Tunneling Microscope (STM) or using highly focused photons for excitation. We present images of QDs as well as characteristic spectra of individual QDs. We finally show how the local character of the excitation enables us to excite and image individual impurities in low-dimensional structures, including the measurement of characteristic emission spectra from a single impurity atom in GaAs.

Interfacial microstructures in 100-period InxGa1−xAs(15Å)/GaAs(100Å) superlattices grown on GaAs (100) substrates by molecular beam epitaxy were studied by using large angle x-ray scattering techniques. Unusual satellite peaks in the lateral direction parallel to the sample surface were observed in a sample with x = 0.535 grown at 480°C, indicating an in-plane structural ordering. This result is confirmed by high resolution transmission electron microscopy observations that thickness modulation in the InxGa1−xAs layers gives rise to long-range lateral periodic arrays of cluster-like microstructures with spacing on the order of a few hundred Ångstroms. This thickness modulation is found to occur only in [110] direction, thus the material can be viewed as a somewhat disordered array of grown-in parallel quantum wires.

Ge δ-layers on Si(111) and Si(001), grown by molecular beam epitaxy (MBE) and solid phase epitaxy (SPE) were characterized in-situ by high-resolution low-energy electrondiffraction and post-growth by x-ray standing waves. LEED intensity oscillations are used to determine the growth mode of Ge on Si which is found to proceed in a double bilayer fashion for Ge on Si(111). X-ray standing waves are employed to investigate crystal quality of the Ge layer. SPE on Si(111) requires high annealing temperatures (600°C) for sufficient recrystallization of defects in the Ge δ-layer. On Si(001), Ge δ-layers of surprisingly high crystalline quality are grown by solid phase epitaxy at room temperature.

Synchrotron X-ray scattering techniques provide a powerful tool for the in situ study of atomic scale processes occurring at solid-liquid interfaces. We have applied these techniques to characterize and study reactions at mineral-water interfaces. Here we present two examples. The first is the characterization of the calcite (CaCO3) (1014) cleavage surface, in equilibrium with deionized water, by crystal truncation rod measurements. The second is the in situ study of the heteroepitaxial growth of otavite (CdCO3) on the calcite (1014) cleavage surface. The results of such studies will lead to significant progress in understanding mineral-water interface geochemistry.

The molecular structure and phase diagram of relaxed monolayer films of methyl eicosanoate at the air/water interface were studied using x-ray diffraction and Brewster Angle Microscopy. Six phases have been identified in relaxed films in a temperature range of 5 to 28 degrees Celsius.

In-situ elastic light scattering is used to measure the evolution of the surface morphology of InxGa1−xAs films during molecular beam epitaxy growth on GaAs substrates. The in-situ measurements are compared with ex-situ measurements of the surface morphology on quenched films by optical scatterometry and atomic force microscopy (AFM). The AFM results are in good agreement with the rms roughness obtained from light scattering and both techniques detect the onset of misfit dislocation formation in this system.

High-resolution x-ray diffraction is an excellent probe of strain relaxation in complex SiGe structures. The high flux provided by synchrotron sources enables us to make extensive reciprocal space map measurements and evaluate many samples. The diffraction peak positions of each layer in a step-graded structure, measured for two different reflections, yield quantitative values for the relaxation and alloy composition in the layer. Grazing-incidence diffraction allows us to determine the in-plane structure of very thin layers, which have thickness-broadened peaks at conventional diffraction geometries. We demonstrate the power of these techniques with two examples.

EXAFS data are used to probe the local structure of Co/Cu multilayers having comparable dimensions but prepared by two different techniques, MBE and sputtering. Significant differences are found. The nearest neighbor distance in all Co layers increases about the same amount relative to the bulk value and MBE Co layers are less disordered than sputtered Co layers. Nearest neighbor distances in thinner Cu layers are less than bulk values but approach bulk value for thicker Cu layers. Nearest neighbor distances in thin MBE Cu layers are more contracted and have a more rapid thickness dependence than in sputtered Cu layers.

Measurement of diffuse x-ray scattering from binary crystalline solid solutions at more than one x-ray energy is a sensitive probe of the average interatomic distance between neighboring pairs of atoms. Deviations of these bond distances by as little as 0.001Å are easily detected in the diffuse scattering from binary alloys consisting of atoms nearby in the periodic table and/or where x-ray energies chosen near their absorption edges can change the scattering contrast. Individual bond distances (AA, AB and BB) are recovered out to several near neighbor shells by combining three scattering measurements at x-ray energies chosen for maximum and minimum contrast. Average bond distances recovered from four metal alloys Fe77.5Ni22.5, Fe46.5Ni53.5Cr47Fe53and Cr20Ni80 are discussed. We find that the interatomic distances measured for these alloys give interesting insights to atomic displacements in solid solutions. Nearest neighbor bond distances are not well represented by phenomenological models based on pure element atomic size and concentration dependence of the lattice constants. Radial and nonradial displacements are recovered from these measurements of diffuse scattering.

We have measured the magnetic Compton profile (MCP) of ordered and disordered Fe 3Pt samples both above and below their Curie temperature. From these measurements, we have determined the average moment per atom at room temperature to be 2.81μB ± 0.04μB for disordered Fe3Pt and 1.78μB ± 0.05μB for ordered Fe3Pt. At temperatures above Tc, we measured a substantial reduction in the moment (0.6μB ± 0.10μB for disordered Fe3Pt and 0.64μB ± 0.13μB ± for ordered Fe3Pt) and a change in the shape of the MCP. This suggests that the mechanism behind the Invar effect in Fe3Pt can be described by a high-spin to low-spin magnetic phase transition. The experimental MCPs for both ordered and disordered Fe3 Pt are analyzed within the framework of the Weiss 2γ model.

Hydroxylated alumina films have been synthesized by water oxidation of single crystal Al(110) surfaces. Thermal dehydroxylation results in anion vacancies which produce an Al(3s) defect state 3.5 eV below the conduction band edge. The defect-DOS exhibits a maximum for oxides heated to 648±25 K, which is just where the materials exhibit maximum Lewis acidity with respect to C2H4 Adsorbed C2H4 produces thermally reactive C2 species which interact covalently with the defect-DOS and nonbonding O(2p) states from the top of the valence band. C(1s) binding energies suggest significant charge transfer which is consistent with a carbenium ion. Ni deposits behave similarly but transfer charge directly to Al species and do not interact with O atoms at the defect site. The defect-DOS is regenerated when the C2 species decomposes or when Ni migrates thermally through the oxide layer.

Uranium L3-edge x-ray absorption spectra have been measured for uranium-mineral sorption systems. An expansible layer silicate, vermiculite, was treated to obtain a collapsed phase, thereby limiting access to the interior cation exchange sites. Samples were prepared by exposing the finely powdered mineral, in the natural and modified form, to aqueous solutions of uranyl chloride. EXAFS spectra of the encapsulated samples were measured at the Stanford Synchrotron Radiation Laboratory. Results indicate that the uranyl ion possesses a more symmetric local structure for the natural vermiculite than for the collapsed form, suggesting structural differences between uranyl species within the interlayer regions of vermiculite and on the external surfaces.

Cerium activated glasses of composition 20Li2O·15MO·64.4SiO2·0.6Ce2O3 (where M is Mg, Ca, Sr, or Ba) exhibit scintillation efficiencies that vary by more than a factor of 2.5 with the alkaline earth. Previous work has suggested a correlation between the microstructure of these glasses and scintillation efficiency. Measurements of the Ce LIII x-ray absorption edge in the Mg, Ca and Sr glasses display a feature near the absorption edge that is suggestive of the presence of Ce4+. The area of this peak is, in fact, correlated with the scintillation efficiency of the glass. The amount of Ce4+ indicated by the intensity of this feature is, however, too high to be a permanent population. We suspect that the feature is a transient phenomenon related to creation of Ce4+ and trapped electrons due to photoionization by the x-ray beam.

We describe a system being developed to use x-rays for spatially resolved measurements of strain, microstructure and composition in thin films. These capabilities are particularly important for improved understanding of electromigration, stress relaxation, and associated reliability issues in microelectronics. The system uses white radiation collimated and focused with a tapered glass capillary, an area CCD detector for measuring Laue patterns, and an energy sensitive Si detector for measuring lattice spacings. Examples are shown of strain measurements for a 4 μm thick Al film on a Si substrate with 300 μm and 30 μm x-ray beams; of Laue diffraction from a single grain for a 40 μm thick Al foil with a 0.3 μm x-ray beam; and of x-ray fluorescence mapping for a patterned Cu film with a 30 μm x-ray beam.

It has been demonstrated, using synchrotron radiation, that at rapid thermal annealing rates (3°C/s) the formation of CoSi2 shifts to higher temperatures when a thin Ti interlayer is placed between Co and polycrystalline Si. It has also been shown that the Ti interlayer reduces the temperature range between the start of CoSi formation and CoSi2 formation (i.e. the range over which CoSi is present). 13 nm of Co deposited by physical vapor deposition on polycrystalline Si with and without either a 2 nm or 3.4 nm interlayer of Ti was analyzed in-situ by monitoring x-ray diffraction (XRD) peak intensity as a function of temperature using monochromatic radiation from a synchrotron beam line and by monitoring resistivity as a function of temperature in a rapid thermal annealing (RTA) system. The XRD analysis indicates that the phase formation proceeds from CoSi to CoSi2 in a temperature range that decreases from about 200°C to 140°C to 115°C with pure Co, Co/2 nm Ti and Co/3.4 nm Ti films respectively. The onset of the CoSi formation increases by about 135°C and 160° for Co/ 2 nm Ti and Co/3.4 nm Ti compared to pure Co. The CoSi temperature range decreases from about 75°C in pure Co to less than 50°C in Co/Ti. In-situ RTA resistance along with in-situ XRD analysis indicates that the onset formation temperatures for CoSi are about 440°C, 575°C and 600°C and the temperatures for the completion of CoSi2 formation are about 640°C, 715°C and 715°C for Co, Co / 2 nm Ti and Co / 3.4 nm Ti films respectively. The results are consistent with the Ti interlayer acting as a diffusion barrier during the initial stages of the Co-Si reaction.

The overall crystalline lattice uniformity in recently available, highly purified mercuric iodide single crystals has been shown to be impacted by crystal handling techniques that were previously satisfactory. High resolution diffraction imaging of the surface regularity of crystals of various levels of purity and growth orientation shows: 1) that the newer materials have a generally lower level of precipitates, 2) that the incidence of these precipitates is now closely correlated with growth direction, and 3) that the deformation resistance and resulting sensitivity to crystal handling procedures are also closely correlated with these factors in this soft material.

As a result, gentler cutting and polishing procedures have been developed and are shown to be effective in preserving overall lattice regularity in the new material. The polishing required to remove residual surface scratches affects the lattice orientation of the softer, precipitate-free regions, while not affecting those regions with detectible levels of precipitates. These results correlate closely with the electrical properties of devices made from these crystals.

Resonant (anomalous) x-ray scattering is used to alter the contrast between atoms nearby in the periodic table to recover local pair correlations. Both Warren-Cowley short-range order parameters and chemically specific interatomic distances are recovered from diffusely scattered x-ray intensities measured at three different x-ray energies (3λ method). Analysis of the statistical and systematic errors shows that the average values for the number and kinds of first nearest neighbors are recovered to about one atom in one hundred and their interatomic distances to about ±0.002 Å.