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Structure and properties of solid surfaces

Difficulties in experimental studies of crystalline surfaces are related to the fact that surface atoms have an intrinsic tendency to react with their environment. A second problem is connected with the effective thickness of surfaces, which ranges from one to several atom layers. The phenomenology of surface interactions with gases are considered, taking into account physical adsorption, chemisorption, and the oxidation of surfaces. Studies of the surface structure are discussed, giving attention to field emission microscopy, field-ion microscopy, electron diffraction techniques, Auger spectroscopy, scanning electron microscopy, electron probe microanalysis, ion microprobe methods, and low-energy backscattering spectroscopy. Investigations of semiconductor surfaces are also described.

Gatos, H. C.

Electrode surface studies by LEED-Auger

The role the electronic and geometric structures of the metal surface play in electrochemical surface reactions remains as yet an unknown factor. In order to investigate these surface contributions to electrochemical reactions, a low-energy-electron diffraction (LEED) and an Auger electron spectrometer (AES) have been combined with an electrochemical thin-layer cell. The surface to be studied electrochemically is first characterized by LEED-AES and then transferred into a second chamber where it becomes part of the electrochemical thin-layer cell. Electrochemical reactions are then run on this surface. The sample may then be transferred back to the LEED-AES chamber for further characterization. Data on Pt (111) will be presented.

Ogrady, W. E.

The nature of chemisorbed oxygen on Ni(100) and Cu(100)

Model calculations indicate two low-lying states for the interaction of O with Ni and Cu(100). The oxide state is approximately 1 eV more stable and its R(perpendicular) for Ni(100) is consistent with the experimental value for Ni(100), indicating only one type of stable chemisorption bond. This agrees with XPS (X-ray photoemission spectroscopy) and EXAFS (extended X-ray absorption fine structure) data for the observed LEED (low energy electron diffraction) structures. Interpretations of EELS (electron energy loss spectroscopy) data in terms of a radical state forthe p(2x2) and the oxide state for the c(2x2) structure must be seriously questioned.

Bauschlicher, C. W., Jr.

Alkali layered compounds interfaces for energy conversion and energy storage

During year one a new ultra-high vacuum, an Ar(+) ion sputterer, a low energy electron diffraction (LEED) system, an Auger electron spectrometer (AES), a work function measurement device with a Kelvin probe, and related accessories were used. The study found a focus in the adsorption of chalcogenides on Si and III-V compound semiconductors. In the second year, a scanning tunneling microscope was obtained along with a quadrapole mass spectrometer, power supplies, a computer, a chart recorder, etc. We started the systematic study on the adsorption of chalcogenides on the compound semiconductor surfaces. The third year saw the mounting of the scanning tunneling microscope (STM) on the existing UHV system. The investigation continued with the adsorption of Cs (alkali) on S-covered Si(100)2x1 surfaces. Then the adsorption of S on Cs-covered Si(100) surfaces was studied.

Papageorgopoulos, Chris A.

Thermoelectric Inhomogeneities in (Ag(sub 1-y)SbTe2)(sub x)(PbTe)(sub 1-x)

A document presents a study of why materials of composition (Ag1 ySbTe2)0.05 (PbTe)0.95 [0< or = y < or = 1] were previously reported to have values of the thermoelectric figure of merit [ZT (where Z = alpha(sup 2)/rk, alpha is the Seebeck coefficient, r is electrical resistivity, k is thermal conductivity, and T is absolute temperature)] ranging from <1 to >2. In the study, samples of (AgSbTe2)0.05(PbTe)0.95, (Ag0.67SbTe2)0.05 (PbTe)0.95, and (Ag0.55SbTe2)0.05(PbTe)0.95 were prepared by melting followed, variously, by slow or rapid cooling. Analyses of these samples by x-ray diffraction, electron microscopy, and scanning-microprobe measurements of the Seebeck coefficient led to the conclusion that these materials have a multiphase character on a scale of the order of millimeters, even though they appear homogeneous in x-ray diffraction and electron microscopy. The Seebeck measurements showed significant variations, including both n-type and p-type behavior in the same sample. These variations were found to be consistent with observed variations of ZT. The rapidly quenched samples were found to be less inhomogeneous than were the furnace-cooled ones; hence, rapid quenching was suggested as a basis of research on synthesizing more nearly uniform high-ZT samples.

Snyder, G. Jeffrey

Electron microscopy and diffraction of layered, superconducting intercalation complexes.

Several layered, transition metal dichalcogenide intercalation complexes with unique superconducting properties have been examined by high-resolution electron microscopy and electron diffraction. Details of the crystalline lattice and of the lattice imperfections have been directly resolved. The results can be correlated with the available X-ray diffraction and chemical data, and they confirm and extend the postulated models.

Fernandez-Moran, H.

Geometry and Unoccupied Electronic States of Ba and BaO on W(001)

A study aimed at understanding the geometrical and electronic properties of barium and oxygen coadsorbed on the tungsten(001) surface has been carried out by means of work-function measurements (Delta-phi), Auger-electron spectroscopy, low-energy electron diffraction, inverse photoelectron spectroscopy, and relativistic-electronic-structure calculations. A report of the experimental measurements and a comparison with theoretical results from embedded-cluster-model calculations are presented. Our experimental studies show that the work function of the W(001) surface (phi = 4.63 eV) is lowered to approximately 2.3-2.4 eV by coadsorption of 1 ML of Ba and O regardless of the order of deposition of these two species. The technique of IPS in the isochromat mode was used to determine the unoccupied electronic-energy band structure for ordered c (2 X 2) Ba and O layers on W(001). Several spectral features are observed above the Fermi level (E(F)), which we assign to transitions into Ba and W d-states. The measured two-dimensional electronic band structure is independent of the order of Ba and O deposition. Using embedded-cluster-model calculations, we investigated two possible adsorption configurations of an ordered c(2 X 2) adlayer of Ba and O on W(001): 'tilted,' where Ba and O are placed on alternate fourfold-hollow sites, and 'upright,' where the adsorbed atoms lay above the same site with Ba outer-most. The calculated densities of states for the tilted geometry show distinct peaks above E(F) originating from Ba and W d-orbitals and are in good agreement with the experimental results.

Lamouri, A.

Measurement of lattice damage caused by ion-implantation doping of semiconductors.

Discussion of two new techniques used to measure the lattice damage produced in GaAs by the implantation of 60 keV cadmium ions. In the first method, optical reflection spectra of the ion-implanted samples were measured in the wavelength range from 2000 to 4600 A. The decrease in reflectivity resulting from ion-implantation was used to determine the relative amount of lattice damage as a function of ion dose. The second technique employed the scanning electron microscope. Patterns very similar in appearance to Kikuchi electron diffraction patterns are obtained when the secondary and/or backscattered electron intensity is displayed as a function of the angle of incidence of the electron beam on a single crystal surface. The results of measurements made by both methods are compared with each other and with data obtained by the method of measuring lattice damage by Rutherford scattering of 1 MeV helium ions.

Hunsperger, R. G.

Water-Rock Interactions in Outer Solar System Bodies: Evidence from the Coordinated Analysis of Interplanetary Dust

NASA has an ongoing program of collecting interplanetary dust particles (IDPs) in the stratosphere using high altitude research aircraft. The collected IDPs are derived from asteroids and comets and here we report studies of a subset of hydrated IDPs rich in carbonaceous matter that are proposed to have a cometary origin. Our studies are aimed at understanding the evolution of oxygen reservoirs in the Solar System and their interaction with cometary minerals and organic matter. The small size (<20 μm) and fragility of these IDPs present a number of analytical challenges. We have pioneered techniques for performing chemical, mineralogical, isotopic, and spectroscopic measurements on the same sample in a carefully coordinated sequence. Coordinated analyses of nanogram-size samples is made possible by several delicate sample preparation techniques. To avoid organic contamination, we embed IDPs in elemental sulfur and use ultramicrotomy to partly section the particles (the first few micrometers). Multiple thin sections (50-70 nm thick) are placed on different substrates depending on the analysis technique. We use a JEOL 2500SE scanning, transmission electron microscope (STEM) to determine the mineralogy, microstructure, and elemental compositions of constituent minerals in the thin sections through a combination of high resolution imaging, electron diffraction, quantitative energy-dispersive x-ray mapping, and electron energy-loss spectroscopy. Following the STEM analyses, we use a NanoSIMS 50L for high spatial resolution isotopic measurements of H, C, N, and O to search for presolar grains and to understand the origin of the indigenous organic matter. The isotopic analyses are performed on the same sections analyzed in the STEM in order to correlate isotopic properties with the elemental and mineralogical data. We reserve other thin sections for non-destructive analyses utilizing synchrotron-based techniques including Fourier-transform infrared (FTIR) micro-spectroscopy and X-ray absorption near-edge structure (XANES) analyses, especially for functional group analysis of organic matter in the particles. The remainder of the IDP is extracted from the sulfur bead that was used for microtomy and is pressed into Au foil for quantitative analysis (including light elements) using a JEOL 8530F field emission electron probe microanalyzer (EPMA). After the EPMA measurements, high precision oxygen isotopic analyses are obtained using Cameca IMS1270/1290 instruments at UCLA. The hydrated IDPs in this study are dominated by saponitic clays, with minor magnetite, carbonate and abundant organic matter. The remarkable oxygen isotopic compositions, high carbon contents, and the abundance of isotopically anomalous organic matter, together suggest that the high carbon, hydrated IDPs are derived from primitive sources not yet represented in meteorite collections such as outer main belt P- and D-type asteroids or comets.

Keller, Lindsay P.

TPSAS-NF1676L-31770-DND

HREBSD (high resolution electron backscatter diffraction) is a scanning electron microscope based diffraction technique that measures stress, elastic strain and dislocation density in crystalline materials with a spatial resolution on the order of tens of nanometers. This information represents a glut of quantitative data that may be directly incorporated in microscale crystal plasticity models. However, concerns over the accuracy of HREBSD make integration of microscopy data with material models problematic. This presentation addresses a number of issue concerning the accuracy of HREBSD, including pattern center error, cross-correlation error and random noise. Additionally, a computational framework is presented that allows for rapid, non-deterministic calibration of material models. Finally, several tests cases are presented where HREBSD is cross-validated with other diffraction techniques: X-ray diffraction, electron channeling contrast imaging and transmission electron microscopy. The accuracy of HREBSD, when incorporating these new techniques, is sufficient to measure local stress to below 10 MPa and to detect individual dislocations.

Timothy J Ruggles

New Techniques in Characterization of Ferroelectric Materials

Two new techniques have been developed to characterize Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) based ferroelectric single crystals: (i) electro-thermal imaging, and (ii) single crystal x-ray diffraction in the transmission mode. (i) Electro-thermal imaging is a remote sensing technique that can detect the polarization direction and poling state of a whole crystal slice. This imaging technique utilizes an IR camera to determine the field induced temperature change and does not require any special or destructive sample preparation. In the resulting images it is possible to distinguish regions of 180 deg domains. This powerful technique can be used remotely during poling to determine the poling state of the crystal to avoid over-poling that can result in inferior properties and/or cracking of the crystals. Electro-thermal imaging produced the first direct observations of polarization rotation. Under bipolar field, the domains near the corners were the first to switch direction. As the field increased above the coercive field, domains at the center part of the crystals switched direction. (ii) X-ray diffraction in the transmission mode has long been used in structure determination of organic crystals and proteins; however, it is not used much to characterize inorganic systems. 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 single crystals were examined by this XRD technique for the first time, and a never-before-seen super-lattice was revealed with a doubling of the unit cell in all three directions, giving a cell volume eight times that of a traditional perovskite unit cell. The significance of the super-lattice peaks increased with poling, indicating a structural contribution to ordering. Lack of such observations by electron diffraction in the transmission electron microscope examinations suggests the presence of a bulk effect.

Sehirlioglu, Alp

Unoccupied electronic resonances of Sc adsorbed on W(001) by k-resolved inverse photoemission

Scandium adsorbed on the (001) face of tungsten has been studied using Auger-electron spectroscopy, low-energy electron diffraction, k-resolved inverse photoelectron spectroscopy, work-function measurements, and relativistic-electronic-structure calculations. We find that the work function of W(001) does not decrease monotonically as a function of scandium adsorption but reaches a minimum value of Phi = 3.25 eV at 50% coverage. For a complete monolayer, an order 1 X 1 Sc overlayer is formed. Inverse photoemission in the isochromat mode was used to map the unoccupied energy levels of this overlayer along the bar-Gamma(bar-Mu) symmetry direction of the surface Brillouin zone. Local-density-functional calculations using the muffin-tin orbital method were performed for a 1 X 1 Sc overlayer on W and are compared with the experimental two-dimensional band structure.

Lamouri, A.