Publications

In-situ filling through hydrolysis and condensation of silicon alkoxides dissolved into polymers has been utilized to generate nanocomposites in which the filler phase can be intimately associated with the polymer on relatively small length scales. One problem of the method has been achieving useful fill volumes without bulk phase separation of the growing inorganic component from the polymer. In this paper, we describe the preparation of a new class of nanocomposite materials in which the inorganic filler phase is pre-assembled before copolymerization with an organic monomer. Maleimide monomers, prepared from alkoxysilylpropyl amines and maleic anhydride, were protected against side reactions by forming the oxonorbornene Diels-Alder adduct with furan. The monomers were then reacted under sol-gel conditions to form oligomers or polymers making up the filler phase. The material was activated by thermal deprotection of the maleimide and reacted with organic monomers or polymers to form the filled nanocomposite.

Progress towards the development of such algorithms as been reported for waveguide analysis'-3and vertical-cavity laser simulation. In all these cases, the higher accuracy order was obtained for a single spatial dimension. More recently, this concept was extended to differencing of the Helmholtz Equation on a 2-D grid, with uniform regions treated to 4th order and dielectric interfaces to 3'd order5. No attempt was made to treat corners properly. In this talk I will describe the extension of this concept to allow differencing of the Helmholtz Equation on a 2-D grid to 6* order in uniform regions and 5* order at dielectric interfaces. In addition, the first known derivation of a finite difference equation for a dielectric comer that allows correct satisfaction of all boundary conditions will be presented. This equation is only accurate to first order, but as will be shown, results in simulations that are third-order-accurate. In contrast to a previous approach3 that utilized a generalized Douglas scheme to increase the accuracy order of the difference second derivative, the present method invokes the Helmholtz Equation itself to convert derivatives of high order in a single direction into mixed

The computing power available to scientists and engineers has increased dramatically in the past decade, due in part to progress in making massively parallel computing practical and available. The expectation for these machines has been great. The reality is that progress has been slower than expected. Nevertheless, massively parallel computing is beginning to realize its potential for enabling significant breakthroughs in science and engineering. This paper provides a perspective on the state of the field, colored by the authors' experiences using large-scale parallel machines at Sandia National Laboratories. We address trends in hardware, system software and algorithms, and we also offer our view of the forces shaping the parallel computing industry.

To physically investigate permeability upscaling, over 13,000 permeability values were measured with four different sample supports (i.e., sample volumes) on a block of Berea Sandstone. At each sample support, spatially exhaustive permeability datasets were measured, subject to consistent flow geometry and boundary conditions, with a specially adapted minipermeameter test system. Here, we present and analyze a subset of the data consisting of 2304 permeability values collected from a single block face oriented normal to stratification. Results reveal a number of distinct and consistent trends (i.e., upscaling) relating changes in key summary statistics to an increasing sample support. Examples include the sample mean and semivariogram range that increase with increasing sample support and the sample variance that decreases. To help interpret the measured mean upscaling, we compared it to theoretical models that are only available for somewhat different flow geometries. The comparison suggests that the nonuniform flow imposed by the minipermeameter coupled with permeability anisotropy at the scale of the local support (i.e., smallest sample support for which data is available) are the primary controls on the measured upscaling. This work demonstrates, experimentally, that it is not always appropriate to treat the local-support permeability as an intrinsic feature of the porous medium, that is, independent of its conditions of measurement.

Isotopic labeling experiments have revealed correlations between hydrogen reactions, Ga desorption, and ammonia decomposition in GaN CVD. Low energy electron diffraction (LEED) and temperature programmed desorption (TPD) were used to demonstrate that hydrogen atoms are available on the surface for reaction after exposing GaN(001) to deuterium at elevated temperatures. Hydrogen reactions also lowered the temperature for Ga desorption significantly. Ammonia did not decompose on the surface before hydrogen exposure. However, after hydrogen reactions altered the surface, N15H3 did undergo both reversible and irreversible decomposition. This also resulted in the desorption of N2 of mixed isotopes below the onset of GaN sublimation. This suggests that the driving force of the high nitrogen-nitrogen bond strength (226 kcal/mol) can lead to the removal of nitrogen from the substrate when the surface is nitrogen rich. Overall, these findings indicate that hydrogen can influence GaN CVD significantly, being a common factor in the reactivity of the surface, the desorption of Ga, and the decomposition of ammonia.

Advanced rechargeable lithium-ion batteries are presently being developed and commercialized worldwide for use in consumer electronics, military and space applications. The motivation behind these efforts involves, among other things, a favorable combination of energy and power density. For some of the applications the power sources may need to perform at a reasonable rate at subambient temperatures. Given the nature of the lithium-ion cell chemistry the low temperature performance of the cells may not be very good. At Sandia National Laboratories, we have used different electrochemical techniques such as impedance and charge/discharge at ambient and subambient temperatures to probe the various electrochemical processes that are occurring in Li-ion cells. The purpose of this study is to identify the component that reduces the cell performance at subambient temperatures. We carried out 3-electrode impedance measurements on the cells which allowed us to measure the anode and cathode impedances separately. Our impedance data suggests that while the variation in the electrolyte resistance between room temperature and -20°C is negligible, the cathode electrolyte interfacial resistance increases substantially in the same temperature span. We believe that the slow interfacial charge transfer kinetics at the cathode electrolyte may be responsible for the increase in cell impedance and poor cell performance. © Copyright 1999 Society of Automotive Engineers, Inc.

This paper addresses key issues for the cost-effective use of COTS (Commercially available Off The Shelf) microelectronics in radiation environments that enable circuit or system designers to manage risks and ensure mission success. We review several factors and tradeoffs affecting the successful application of COTS parts including (1) hardness assurance and qualification issues, (2) system hardening techniques, and (3) life-cycle costs. The paper also describes several experimental studies that address trends in total-dose, transient, and single-event radiation hardness as COTS technology scales to smaller feature sizes. As an example, the level at which dose-rate upset occurs in Samsung SRAMs increases from 1.4x10s rad(Si)/s for a 256K SRAM to 7.7xl09rad(Si)/s for a 4M SRAM, indicating unintentional hardening improvements in the design or process of a commercial technology. Additional experiments were performed to quantify variations in radiation hardness for COTS parts. In one study, only small (10-15%) variations were found in the dose-rate upset and latchup thresholds for Samsung 4M SRAMs from three different date codes. In another study, irradiations of 4M SRAMs from Samsung, Hitachi, and Toshiba indicate large differences in total-dose radiation hardness. The paper attempts to carefully define terms and clear up misunderstandings about the definitions of "COTS'1 and "radiation-hardened (RH)" technology. © 1999 IEEE.

The rutile TiO2(110) (1 × 1) surface is considered the prototypical 'well-defined' system in the surface science of metal oxides. Its popularity results partly from two experimental advantages: (i) bulk-reduced single crystals do not exhibit charging, and (ii) stoichiometric surfaces, as judged by electron spectroscopies, can be prepared reproducibly by sputtering and annealing in oxygen. We present results that show that this commonly applied preparation procedure may result in a surface structure that is by far more complex than generally anticipated. Flat, (1 × 1)-terminated surfaces are obtained by sputtering and annealing in ultrahigh vacuum. When re-annealed in oxygen at moderate temperatures (470-660 K), irregular networks of partially connected, pseudohexagonal rosettes (6.5 × 6 Å wide), one-unit cell wide strands, and small (≈tens of Å) (1 × 1) islands appear. This new surface phase is formed through reaction of oxygen gas with interstitial Ti from the reduced bulk. Because it consists of an incomplete, kinetically limited (1 × 1) layer, this phenomenon has been termed 'restructuring'. We report a combined experimental and theoretical study that systematically explores this restructuring process. The influence of several parameters (annealing time, temperature, pressure, sample history, gas) on the surface morphology is investigated using STM. The surface coverage of the added phase as well as the kinetics of the restructuring process are quantified by LEIS and SSIMS measurements in combination with annealing in 18O-enriched gas. Atomic models of the essential structural elements are presented and are shown to be stable with first-principles density functional calculations. The effect of oxygen-induced restructuring on surface chemistry and its importance for TiO2 and other bulk-reduced oxide materials is briefly discussed.

We describe the microfabrication of an extremely compact optical system as a key element in an integrated capillary channel electrochromatograph with fluorescence detection. The optical system consists of a vertical cavity surface-emitting laser (VCSEL), two high performance microlenses, and a commercial photodetector. The microlenses are multilevel diffractive optics patterned by electron beam lithography and etched by reactive ion etching in fused silica. The design uses substrate-mode propagation within the fused silica substrate. Two generations of optical subsystems are described. The first generation design has a 6 mm optical length and is integrated directly onto the capillary channel-containing substrate. The second generation design separates the optical system onto its own substrate module and the optical path length is further compressed to 3.5 mm. The first generation design has been tested using direct fluorescence detection with a 750 nm VCSEL pumping a 10-4 M solution of CY-7 dye. The observed signal-to-noise ratio of better than 100:1 demonstrates that the background signal from scattered pump light is low despite the compact size of the optical system and is adequate for system sensitivity requirements. © 1999 American Vacuum Society.

A computational procedure for extracting substructure-by-substructure flexibility properties from global modal parameters is presented. The present procedure consists of two key features: an element-based direct flexibility method, which uniquely determines the global flexibility without resorting to case-dependent redundancy selections, and the projection of kinematically inadmissible modes that are contained in the iterated substructural matrices. The direct flexibility method is used as the basis of an inverse problem, whose goal is to determine substructural flexibilities given the global flexibility, geometrically determined substructural rigid-body modes, and the local-to-global assembly operators. The resulting procedure, given accurate global flexibility, extracts the exact element-by-element substructural flexibilities for determinate structures. For indeterminate structures, the accuracy depends on the iteration tolerance limits. The procedure is illustrated using both simple and complex numerical examples and appears to be effective for structural applications such as damage localization and finite element model reconciliation.

Evidence for capillary waves at a liquid-vapor interface are presented from extensive molecular dynamics simulations of a system containing up to 1.24 million Lennard-Jones particles. Careful measurements show that the total interfacial width depends logarithmically on L∥, the length of the simulation cell parallel to the interface, as predicted theoretically. The strength of the divergence of the interfacial width on L∥ depends inversely on the surface tension γ. This allows us to measure γ two ways since γ can also be obtained from the difference in the pressure parallel and perpendicular to the interface. These two independent measures of γ agree provided that the interfacial order parameter profile is fit to an error function and not a hyperbolic tangent, as often assumed. We explore why these two common fitting functions give different results for γ.

Previous photopumping studies of coupled vertical cavity laser structures have demonstrated three mode coupling (two photonic and one excitonic), dual wavelength emission, and short pulse generation. This paper reports on electrically injected coupled resonator vertical-cavity laser diodes, including two novel modulation approaches.

Consider the 2-matching problem defined on the complete graph, with edge costs which satisfy the triangle inequality. We prove that the value of a minimum cost 2-matching is bounded above by 4/3 times the value of its linear programming relaxation, the fractional 2-matching problem. This lends credibility to a long-standing conjecture that the optimal value for the traveling salesman problem is bounded above by 4/3 times the value of its linear programming relaxation, the subtour elimination problem. © Springer-Verlag 1999.

Diamond films were grown by chemical deposition of hydrocarbon species in a vapor composed predominantly of hydrogen. The rate constants of the surface reactions and the concentrations of the gas-phase species were used as input to a variable time step Monte Carlo algorithm, which simulates the evolution of the diamond growth surface by tracking the occupancies of surface sites. The results of the combined tight binding and density functional theory quantum mechanical calculations are presented, suggesting that the etching of isolated, monomolecular moieties occurred at an appreciable rate, while etching from larger carbon islands was nor favorable.

We study the low-temperature in-plane magnetoresistance of tunnel-coupled quasi-one-dimensional quantum wires. The wires are defined by two pairs of mutually aligned split gates on opposite sides of a ⩽1-μm-thick (Formula presented) double-quantum-well heterostructure, allowing independent control of the width of each quantum well. In the ballistic regime, when both wires are defined and the field is perpendicular to the current, a large resistance peak at ∼6 T is observed with a strong gate voltage dependence. The data are consistent with a counting model whereby the number of subbands crossing the Fermi level changes with field due to the formation of an anticrossing in each pair of one-dimensional subbands. © 1999 The American Physical Society.

We describe a very-low power consumption circuit for processing the pulses from a semiconductor radiation detector. The circuit was designed for use with a cadmium zinc telluride (CZT) detector for unattended monitoring of stored nuclear materials. The device is intended to be battery powered and operate at low duty-cycles over a long period of time. This system will provide adequate performance for medium resolution gamma-ray pulse-height spectroscopy applications. The circuit incorporates the functions of a charge sensitive preamplifier, shaping amplifier, and peak sample and hold circuit. An application specific integrated circuit (ASIC) version of the design has been designed, built and tested. With the exception of the input field effect transistor (FET), the circuit is constructed using bipolar components. In this paper the design philosophy and measured performance characteristics of the circuit are described.

We report the stability of TlBa2CaCu2O7 and Tl2Ba2CaCu2O8 on LaAlO3(100) epitaxial thin films, under a variety of conditions. All films are stable in acetone and methanol and with repeated thermal cycling to cryogenic temperatures. Moisture, especially vapor, degrades film quality rapidly. These materials are stable to high temperatures in either N2 or O2 ambients. While total degradation, resulting from Tl depletion, occurs at the same temperatures for both phases, 600 °C in N2 and 700 °C in O2, the onset of degradation occurs at somewhat lower temperatures for TlBa2CaCu2O7 than for Tl2Ba2CaCu2O8.

Tailoring of porous materials involves not only chemical synthetic techniques for tailoring microscopic properties such as pore size, pore shape, pore connectivity, and pore surface reactivity, but also materials processing techniques for tailoring the meso- and the macroscopic properties of bulk materials in the form of fibers, thin films and monoliths. These issues are addressed in the context of five specific classes of porous materials: oxide molecular sieves, porous coordination solids, porous carbons, sol-gel derived oxides, and porous heteropolyanion salts. Reviews of these specific areas are preceded by a presentation of background material and review of current theoretical approaches to adsorption phenomena. A concluding section outlines current research needs and opportunities.

A new multidimensional high lateral resolution ion beam analysis technique, ion-electron emission microscopy (IEEM) is described. Using MeV energy ions, IEEM is shown to be capable of ion beam induced charge collection (IBICC) measurements in semiconductors. IEEM should also be capable of microscopically and multidimensionally mapping the surface and bulk composition of solids. As such, IEEM has nearly identical capabilities as traditional nuclear microprobe analysis, with the advantage that the ion beam does not have to be focused. The technique is based on determining the position where an individual ion enters the surface of the sample by projection secondary electron emission microscopy. The x-y origination point of a secondary electron, and hence the impact coordinates of the corresponding incident ion, is recorded with a position sensitive detector connected to a standard photoemission electron microscope (PEEM). These signals are then used to establish coincidence with IBICC, atomic, or nuclear reaction induced ion beam analysis signals simultaneously caused by the incident ion. © 1999 Elsevier Science B.V. All rights reserved.

A series of controlled impact experiments has been performed to determine the shock loading and release behavior of two types of concrete, differentiated by aggregate size, but with average densities varying by less than 2 percent. Hugoniot stress and subsequent release data was collected over a range of approximately 3 to 25 GPa using a plate reverberation technique in combination with velocity interferometry. The results of the current data are compared to those obtained in previous studies on concrete with a different aggregate size but similar density. Results indicate that the average loading and release behavior are comparable for the three types of concrete discussed in this paper. Residual strain is also indicated from these measurements. © 1999 Elsevier Science Ltd. All rights reserved.

Project 'Rolling Thunder' is a dish/Stirling demonstration project at Ft. Huachuca in southeastern Arizona. As part of the project, Sandia decided to retrofit a SOLO 161 Stirling engine on the CPG-460 at Ft. Huachuca. Although the SOLO 161 PCU has operated nearly flawlessly and the CPG-460 has been, for the most part, a solid and reliable component, integration of the SOLO PCU with the CPG-460 into a functional system required significant attention.

Resistive bolometry is an accurate, robust, spectrally broadband technique for measuring absolute x-ray fluence and flux. Bolometry is an independent technique for x-ray measurements that is based on a different set of physical properties than other diagnostics such as x-ray diodes, photoconducting detectors, and P-I-N diodes. Bolometers use the temperature-driven change in element resistivity to determine the total deposited energy. The calibration of such a device is based on fundamental material properties and its physical dimensions. We describe the use of nickel and gold bolometers to measure x rays generated by high-power z pinches on Sandia's Saturn and Z accelerators. The Sandia bolometer design described herein has a pulse response of ∼1 ns. We describe in detail the fabrication, fielding, and data analysis issues leading to highly accurate x-ray measurements. The fundamental accuracy of resistive bolometry will be discussed. © 1999 American Institute of Physics.

We have developed a comprehensive diagnostic package for observing z-pinch radiation along the pinch axis on the Z accelerator. The instrumentation, fielded on the axial package, are x-ray diagnostics requiring direct lines of sight to the target. The diagnostics require vacuum access to the center of the accelerator. The environment is a hostile one, where we must deal with an intense, energetic photon flux (>100 keV) debris (e.g., bullets or shrapnel), and mechanical shock in order for the diagnostics to survive. In addition, practical constraints require the package be refurbished and utilized on a once a day shot schedule. In spite of this harsh environment, we have successfully fielded the diagnostic package with a high survivability of the data and the instruments. In this article, we describe the environment and issues related to the reentrant diagnostic package's implementation and maintenance. © 1999 American Institute of Physics.

Lattice defects are introduced into the structure to suppress the motion of magnetic vortices and enhance the critical current density in high temperature superconductors. Point defects are not very effective pinning sites for the cuprate superconductors; however, extended defects, such as linear tracks, have been shown to be strong pinning sites. We study the superconducting cuprate Tl-2212 (the numbers designate Tl-Ba-Ca-Cu stoichiometry). Large enhancements of vortex pinning potential were observed in Tl-2212 after high-intermediate energy heavy-ion irradiations where non-continuous extended defects were induced at dE/dx of 9 to 15.2 keV/nm (60 MeV Au, 60 MeV Cu, and 30 MeV Au) and continuous linear defects were induced at 19.5 keV/nm (88 MeV Au). Our research addresses the question of pinning in highly anisotropic materials like Tl-2212 where the vortices are `pancakes' rather than `rods' and suitable defect structures may be discontinuous extended damage domains. The defect microstructure and the effectiveness of the pinning potential in Tl-2212 after irradiation by intermediate energy Au at lower dE/dx of 5-15 keV/nm, where recoils are more significant, is studied using high resolution transmission electron microscopy digital imaging and a SQUID magnetometer. The nature of the ion irradiation damage at these intermediate dE/dx will be correlated to the average vortex pinning potential and the TRIMRC calculations for recoils.

Sol-gel processing of materials is plagued by shrinkage during polymerization of the alkoxide monomers and processing (aging and drying) of the resulting gels. We have developed a new class of hybrid organic-inorganic materials based on the solventless ring-opening polymerization (ROP) of monomers bearing the 2,2,5,5-tetramethyl-2,5-disilaoxacyclopentyl group, which permits us to drastically reduce shrinkage in sol-gel processed materials. Because the monomers are polymerized through a chain growth mechanism catalyzed by base rather than the step growth mechanism normally used in sol-gel systems, hydrolysis and condensation products are entirely eliminated. Furthermore, since water is not required for hydrolysis, an alcohol solvent is not necessary. Monomers with two disilaoxacyclopentyl groups, separated by a rigid phenylene group or a more flexible alkylene group, were prepared through disilylation of the corresponding diacetylenes, followed by ring closure and hydrogenation. Anionic polymerization of these materials, either neat or with 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane as a copolymer, affords thermally stable transparent gels with no visible shrinkage. These materials provide an easy route to the introduction of sol-gel type materials in encapsulation of microelectronics, which we have successfully demonstrated.