Publications

Vacuum-arc deposition is used to deposit multilayer C films by modulating the sample bias during deposition. Effect of varying the sublayer thickness in multilayer films consisting of alternating layers of ``hard`` (68.4 GPa, -100 V bias) and ``soft`` (27.5 GPa, - 200 V bias) was investigated. Films consisting of equal thickness layers of hard and soft material and an individual layer thickness varying from 10 to 35 nm were deposited. Mechanical property measurements were obtained by finite element modeling of nanoindentation load-displacement curves. The film hardness values were about 20% below the average of the component layers and relatively independent of the layer thickness. TEM revealed deterioration of the multilayer structure when the sublayer thickness was below 15 nm due to implantation damage of the hard layers caused by the energetic C{sup +} ions of the soft layers (-2000 V bias) deposited over them. Pin-on-disk wear tests show that the wear rate drops when sublayer thickness is decreased below 20 nm and remains constant with further decreases in the layer thickness.

We have initiated studies using both solution and solid state magic angle spinning {sup 17}O NMR for a series of oxidatively aged polymers. This short note reports the solution {sup 17}O NMR for oxidatively degraded polypropylene, ethylene-propylene-diene, polyisoprene, and nitrile rubber. Enriched O{sub 2} is used during the accelerated aging. 3 figs, 7 refs.

Results appear to confirm the concept of surfactant-templating of thin film mesostructures. Final film pore structure depends on starting surfactant and water concentrations and process time scale (governed by evaporation rate). Surfactant ordering at substrate-film and film-vapor interfaces orients the porosity of adjoining films, leading to graded structures. SAW experiments show that depending on processing conditions, the porosity may be open or closed (restricted). Open porosity is monosized. Upon pyrolysis, lamellar structures collapse, while the hexagonal structures persist; when both hexagonal and lamellar structures are present, the hexagonal may serve to pillar the lamellar, avoiding its complete collapse. Thick lamellar films can be prepared because the surfactant mechanically decouples stress development in adjoining layers. Upon drying and heating, each individual layer can shrink due to continuing condensation reactions without accumulating stress. During surfactant pyrolysis, the layers coalesce to form a thick crack-free layer. Formation of closed porosity films is discussed.

GaAs Junction Field Effect Transistors (JFETs) are reported with gate lengths down to 0.3 micrometers. The structure is fully self-aligned and employs all ion implantation doping. p[sup +]-gate regions are formed with either Zn or Cd implants along with a P coimplantation to reduce diffusion. The source and rain implants are engineered with Si or SiF implants to minimize short channel effects. JFETs with 0.3 micrometer gate length are demonstrated with a sub-threshold slope of 110 mV/decade along with an intrinsic unity current gain cutoff frequency as high as 52 GHz.

As problems of violence and crime become more prevalent in our schools (or at least the perception of their prevalence), more and more school districts will elect to use security technologies to control these problems. While the desired change in student and community attitudes will require significant systemic change through intense U.S. social programs, security technologies can greatly augment school staff today by providing services similar to having extra adults present. Technologies such as cameras, sensors, drug detection, biometric and personnel identification, lighting, barriers, weapon and explosives detection, anti-graffiti methods, and duress alarms can all be effective, given they are used in appropriate applications, with realistic expectations and an understanding of limitations. Similar to a high-risk government facility, schools must consider a systems (`big picture`) approach to security, which includes the use of personnel and procedures as well as security technologies, such that the synergy created by all these elements together contributes more to the general `order maintenance` of the facility than could be achieved by separate measures not integrated or related.

Site-characterization studies at the Waste Isolation Pilot Plant (WIPP) site in southeastern New Mexico, US identified ground-water flow in the Culebra Dolomite Member of the Rustler Formation as the most likely geologic pathway for radionuclide transport to the accessible environment in the event of a breach of the WIPP repository through inadvertent human intrusion. The results of recent tracer tests, as well as hydraulic tests, laboratory measurements, and re-examination of Culebra geology and stratigraphy, have led to a significant refinement of the conceptual model for transport in the Culebra. Tracer test results and geologic observations suggest that flow occurs within fractures, and to some extent within interparticle porosity and vugs connected by microfractures. Diffusion occurs within all connected porosity. Numerical simulations suggest that the data from the tracer tests cannot be simulated with heterogeneous single-porosity models; significant matrix diffusion appears to be required. The low permeability and lack of significant tracer recovery from tracers injected into the upper Culebra suggest that transport primarily occurs in the lower Culebra.

The solubility of Np(V) and Np(VI) has been measured in three synthetic Na-K-Mg-Cl brines in the presence of CO{sub 2}(g). Experiments were prepared from oversaturation by adding an excess of NpO{sub 2}{sup +} or NpO{sub 2}{sup 2+} to the brines and allowing the neptunium solids to precipitate. Vessels were maintained in contact with fixed CO{sub 2}(g) partial pressures at constant pH and 24 {+-} 1 C. Dissolved Np(V) concentrations decreased several orders of magnitude within the first 100 days of the experiment, while dissolved Np(VI) concentrations decreased initially but then remained relatively constant for more than 400 days. The solid phases formed in all experiments were identified by X-ray powder diffraction as KNpO{sub 2}CO{sub 3}{center_dot}xH{sub 2}O(s). Steady state concentrations for Np(V) are similar to those observed for Pu(V) in the same brines under the same conditions, where Pu occurs predominantly as Pu(V). Similarly, steady state concentrations for Np(VI), which was not reduced over a two year period, compare well with measured Pu(VI) concentrations in the same brines before the Pu(VI) was reduced to Pu(V).

The Atmospheric Radiation Measurement Program is a multi-laboratory, interagency program as part of DOE`s principal entry into the US Global Change Research Program. Two issues addressed are the radiation budget and its spectral dependence, and radiative and other properties of clouds. Measures of solar flux divergence and energy exchanges between clouds, the earth, its oceans, and the atmosphere through various altitudes are sought. Additionally, the program seeks to provide measurements to calibrate satellite radiance products and validate their associated flux retrieval algorithms. Unmanned Aerospace Vehicles fly long, extended missions. MPIR is one of the primary instruments on the ARM-UAV campaigns. A shutter mechanism has been developed and flown as part of an airborne imaging radiometer having application to spacecraft or other applications requiring low vibration, high reliability, and long life. The device could be employed in other cases where a reciprocating platform is needed. Typical shutters and choppers utilize a spinning disc, or in very small instruments, a vibrating vane to continually interrupt incident light or radiation that enters the system. A spinning disk requires some sort of bearings that usually have limited life, and at a minimum introduce issues of reliability. Friction, lubrication and contamination always remain critical areas of concern, as well as the need for power to operate. Dual vibrating vanes may be dynamically well balanced as a set and are frictionless. However, these are limited by size in a practical sense. In addition, multiples of these devices are difficult to synchronize.

A mathematical framework is developed for the study of materials containing axisymmetric inclusions or flaws such as ellipsoidal voids, penny-shaped cracks, or fibers of circular cross-section. The general case of nonuniform statistical distributions of such heterogeneities is attacked by first considering a spatially uniform distribution of flaws that are all oriented in the same direction. Assuming an isotropic substrate, the macroscopic material properties of this simpler microstructure naturally should be transversely isotropic. An orthogonal basis for the linear subspace consisting of all double-symmetric transversely-isotropic fourth-order tensors associated with a given material vector is applied to deduce the explicit functional dependence of the material properties of these aligned materials on the shared symmetry axis. The aligned and uniform microstructure seems geometrically simple enough that the macroscopic transversely isotropic properties could be derived in closed form. Since the resulting properties are transversely isotropic, the analyst must therefore be able to identify the appropriate coefficients of the transverse basis. Once these functions are identified, a principle of superposition of strain rates ay be applied to define an expectation integral for the composite properties of a material containing arbitrary anisotropic distributions of axisymmetric inhomogeneities. A proposal for coupling plastic anisotropy to the elastic anisotropy is presented in which the composite yield surface is interpreted as a distortion of the isotropic substrate yield surface; the distortion directions are coupled to the elastic anisotropy directions. Finally, some commonly assumed properties (such as major symmetry) of the Cauchy tangent stiffness tensor are shown to be inappropriate for large distortions of anisotropic materials.

This paper presents a performance assessment model of dissolved actinide concentrations for the Waste Isolation Pilot Plant (WIPP). The model assesses the concentration of each actinide oxidation state and combines these concentrations with an oxidation state distribution. The chemical behavior of actinides in the same oxidation state is presumed to be very similar for almost all situations, but exceptions arising from experimental evidence are accommodated. The code BRAGFLO calculates the gas pressure, brine mass, gas volume, and mass of remaining Fe and cellulosics for each time step and computational cell. The total CO{sub 2} in the repository and dissolved Ca(OH){sub 2} is estimated. Lookup tables are constructed for pmH and f(CO{sub 2}) as a function of brine type and volume, moles of CO{sub 2}, and Ca(OH){sub 2}. Amounts of five soluble complexants are considered. A model based on the formulation of Harvie et al. produces tables of solubilities for each actinide oxidation state as a function of pmH, f(CO{sub 2}), brine composition, and complexant. Experimental data yield lookup tables of fractions of Th, U, Np, Pu, and Am in each oxidation state as a function of f(CO{sub 2}) and complexant. The tables are then used to provide a concentration of a particular actinide at particular values of pmH and f(CO{sub 2}). Under steady-state conditions, the oxidation state of each actinide that is most stable in the particular chemical environment controls the concentration of that actinide in solution. In the absence of steady-state conditions, the oxidation state distribution of interest is that of the dissolved actinide, and the oxidation states may be treated as if they were separate compounds.

A model is developed to predict the thermal response of real electronic devices during pulsed Nd:YAG laser welding. Modeling laser-part interaction requires incorporation of weld pool hydrodynamics, and laser-metal vapor and laser-surface interactions. Although important information can be obtained from these models, they are not appropriate for use in design of actual components due to computational limitations. In lieu of solving for these detailed physics, a simple model is constructed. In this model, laser-part interactions are accounted for through an empirically determined energy transfer efficiency which is developed through the use of modeling and experiments. This engineering model is appropriate since part thermal response near the weld pool and weld pool shape is not of interest here. Reasonable agreement between predictions and experimental measurements for welding of real components are indicated.

Artificially enhancing the solder ability of a surface can at times prove to be advantageous. As chip packaging geometries become increasingly complex, the issue of solder wettability becomes significantly more important. Here, the authors examine the effect of varying substrate surface roughness on solder wettability (area of spread) and the time required to reach terminal area of spread. Results are given for solder wetting experiments that were performed on copper (Cu) substrates having chemically etched surfaces, as well as, Alumina (Al{sub 2}O{sub 3}) substrates electroplated with various thicknesses of palladium (Pd). The effect of etching on the Al{sub 2}O{sub 3}/Pd specimens was also examined as related to surface roughness and solder spread. These surface treatments were found to significantly alter wettability. Substantial improvements were observed in both solder wettability and time to wet with the uniformly etched Cu surfaces used in this study. For the Cu substrates, the average terminal area of spread is shown to be directly related to the substrates root mean square (RMS) surface roughness. The rate of wetting of the Cu surfaces is also shown to increase when chemical surface treatment is used. Maximum wetting on the Al{sub 2}O{sub 3}/Pd specimens was found to be directly related to surface smoothness. The average terminal area of spread of Al{sub 2}O{sub 3}/Pd specimens is inversely related to the vertical distance from the highest surface peak to the deepest surface valley (i.e., peak-to-peak variation).

Glasses are used extensively by the electronics industry for packaging and in components. Because glasses have such low fracture toughness, glass components must maintain low tensile stresses to avoid cracking and ensure product stability. Modeling is a key tool for developing designs with low tensile stresses. Thermoelastic analyses are ideal for modeling slow, oven controlled processes where the temperature varies uniformly. Many processing environments, however, involve rapid heating and cooling cycles that produce nonhomogeneous temperature fields causing the volume and stresses in the glass to relax at different rates. This structural relaxation is an important nonlinear material behavior that gives rise to a point-to-point variability in effective properties of the material. To accurately model such stresses, a thermal analysis must be coupled to a structural analysis that employs a viscoelastic model of glass. Laser sealing of glasses is an example of a process where thermal history is an important factor in determining the residual stress state. Recent needs to consider laser sealing methods for fiber optic connectors and flat panel displays have spurred the development of coupled, three-dimensional thermal and structural finite element codes. Analyses of the temperatures and stresses generated in a flat panel display during a laser sealing operation are presented, an the idiosyncrasies and importance of modeling coupled thermal/structural phenomena are discussed.

A study was undertaken to examine the use of a number of solution additives in 1M LiPF{sub 6}/ethylene carbonate (EC)-dimethyl carbonate (DMC) solutions to improve the performance of carbon anodes derived from polymethylacrylonitrile (PMAN)-divinylbenzene (DVB) copolymers. The study goals were to improve the cycle life and reduce the formation of the passivation layer during the first reduction, thereby minimizing the irreversible-capacity losses. Additives studied were 12-crown-4 (12-Cr-4) ether, decalin, and dilithium phthalocyanine (Li{sub 2}Pc). The carbon performance was characterized by galvanostatic cycling, cyclic voltammetry, and complex-impedance spectroscopy. Limited success was obtained with 12-Cr-4 ether at 0.25 M and decalin at 1 v/o. Poor results were noted with Li{sub 2}Pc at 0.025 M and 0.5 M.

A study was undertaken to examine the effects of partial oxidation on the electrochemical performance of carbons derived from poly(methylacrylonitrile) (PMAN)-divinylbenzene (DVB) co-polymers. Mild oxidation was examined as a possible technique to increase the reversible capacity, improve cycleability, and reduce the amount of irreversible capacity associated with the formation of the passivation layer during the first reduction. Oxidizing conditions involved treatment of the PMAN carbon prepared at 700 C with dry CO{sub 2} or with steam at 600 C for one hour. The effects on the performance in 1M LiPF{sub 6}/ethylene carbonate (EC)-dimethyl carbonate (DMC) solutions were evaluated by galvanostatic cycling tests, complex-impedance spectroscopy, and, to a more limited extent, cyclic voltammetry. Partial oxidation of PMAN carbon showed little or no overall beneficial effects in performance relative to the control.

This paper presents ion beam induced charge collection (IBICC) contrast images showing regions of differing charge collection efficiency within optoelectronic modulator devices. The experiments were carried out at the Sandia nuclear microprobe using 18 MeV carbon and 2 MeV helium ions. Lines of varying densities are observed to run along the different (110) directions which correlate with misfit dislocations within the 392nm thick strained-layer superlattice quantum well of the modulator structure. Independent cross-sectional TEM studies and the electrical properties of the devices under investigation suggest the presence of threading dislocations in the active device region at a density of {approximately}10{sup 6} cm{sup {minus}2}. However, no clear evidence of threading dislocations was observed in the IBICC images as they are possibly masked by the strong contrast of the misfit dislocations. Charge carrier transport within the modulator is used to explain the observed contrast. The different signal to noise levels and rates of damage of the incident ions are assessed.

The authors have demonstrated the utility of microbeam - Rutherford Back Scattering ({mu} RBS) in spatially resolved studies of operational plasma effects on the interior surfaces of plasma flat panel displays manufactured by Photonics Imaging. The experiments were performed at the Sandia Nuclear microprobe using a 2.8 MeV He beam with an average beam spot size of less than 8{mu}m. The interior surface of the top panes of the flat panels is composed of approximately 800 nm of MgO on top of a 2000nm thick PbO layer. {mu}-RBS of sample panels operated under varying conditions measured changes in the surface MgO film thickness due to plasma erosion and redeposition as accurately as {+-}1.5 nm. The high accuracy in the MgO thickness measurement was achieved by inferring the MgO thickness from the shift of the Pb front edge in the RBS spectrum. An estimate for the thickness accuracy as a function of the acquired statistics is presented. The surface of the flat panels` bottom panes is also comprised of MgO on top of PbO. However, troughs {approximately}100 {mu}m wide by 10{mu}m deep were partially filled with phosphor and cover the entire width of the surface. This leaves only 100pm long sections of MgO within the trough exposed. Using {mu}-RBS, the authors were able to analyze the surface composition of these regions.

Ceramic-metal composites can be made by reactive penetration of molten metals into dense ceramic performs. The metal penetration is driven by a large negative Gibbs energy for reaction, which is different from the more common physical infiltration of porous media. Reactions involving Al can be written generally as (x+2)Al + (3/y)MO{sub y} {yields} Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO{sub y} is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperature above about 900{degrees}c, molten Al reduces mullite to produce Al{sub 2}O{sub 3} + M{sub 3/y}Al{sub x}, where MO is an oxide that is wet by molten Al. In low Po{sub 2} atmospheres and at temperatures above about 900{degrees}C, molten al reduces mullite to produce Al{sub 2}O{sub 3} and Si. The Al/mullite reaction has a {Delta}G{sub r}{degrees} (1200K) of -1014 kJ/mol and, if the mullite is fully dense, the theoretical volume change on reaction is less than 1%. A microstructure of mutually-interpenetrating metal and ceramic phases generally is obtained. Penetration rate increases with increasing reaction temperature from 900 to 1150{degrees}C, and the reaction layer thickness increases linearly with time. Reaction rate is a maximum at 1150{degrees}C; above that temperature the reaction slows and stops after a relatively short period of linear growth. At 1300{degrees}C and above, no reaction layer is detected by optical microscopy. Observations of the reaction front by TEM show only al and Al{sub 2}O{sub 3} after reaction at 900{degrees}C, but Si is present in increasing amounts as the reaction temperature increases to 1100{degrees}C and above. The kinetic and microstructural data suggest that the deviation from linear growth kinetics at higher reaction temperatures and longer times is due to Si build-up and saturation at the reaction front. The activation energy for short reaction times at 900 to 1150{degrees}C varies from {approximately}90 to {approximately}200 kJ/mole.

The partially stabilized zirconia powders used to plasma spray thermal barrier coatings typically exhibit broad particle-size distributions. There are conflicting reports in the literature about the extent of injection-induced particle-sizing effects in air plasma-sprayed materials. If significant spatial separation of finer and coarser particles in the jet occurs, then one would expect it to play an important role in determining the microstructure and properties of deposits made from powders containing a wide range of particle sizes. This paper presents the results of a study in which a commercially available zirconia powder was fractionated into fine, medium, and coarse cuts and sprayed at the same torch conditions used for the ensemble powder. Diagnostic measurements of particle surface temperature, velocity, and number-density distributions in the plume for each size-cut and for the ensemble powder are reported. Deposits produced by traversing the torch back and forth to produce a raised bead were examined metallographically to study their shape and location with respect to the torch centerline and to look at their internal microstructure. The results show that, for the torch conditions used in this study, the fine, medium, and coarse size-cuts all followed the same mean trajectory. No measureable particle segregation effects were observed. Considerable differences in coatings microstructure were observed. These differences can be explained by the different particle properties measured in the plume.

Consider mapping a regular i x j quadrilateral mesh of a rectangle onto a surface. The quality of the mapped mesh of the surface depends heavily on which vertices of the surface correspond to corners of the rectangle. The authors problem is, given an n-sided surface, chose as corners four vertices such that the surface resembles a rectangle with corners at those vertices. Note that n could be quite large, and the length and width of the rectangle, i and j, are not prespecified. In general, there is either a goal number or a prescribed number of mesh edges for each bounding curve of the surface. The goals affect the quality of the mesh, and the prescribed edges may make finding a feasible set of corners difficult. The algorithm need only work for surfaces that are roughly rectangular, particular those without large reflex angles, as otherwise an unstructured meshing algorithm is used instead. The authors report on the theory and implementation of algorithms for this problem. They also given an overview of a solution to a related problem called interval assignment: given a complex of surfaces sharing curves, globally assign the number of mesh edges or intervals for each curve such that it is possible to mesh each surface according to its prescribed quadrilateral meshing algorithm, and assigned and user-prescribed boundary mesh edges and corners. They also note a practical, constructive technique that relies on interval assignment that can generate a quadrilateral mesh of a complex of surfaces such that a compatible hexahedral mesh of the enclosed volume exists.

Convergent lines of evidence are reviewed which show that near-interfacial oxide traps (border traps) that exchange charge with the Si can strongly affect the performance, radiation response, and long-term reliability of MOS devices. Observable effects of border traps include capacitance-voltage (C-V) hysteresis, enhanced 1/f noise, compensation of trapped holes, and increased thermally stimulated current in MOS capacitors. Effects of faster (switching times between ∼10-6 s and ∼1 s) and slower (switching times greater than ∼1 s) border traps have been resolved via a dual-transistor technique. In conjunction with studies of MOS electrical response, electron paramagnetic resonance and spin dependent recombination studies suggest that E' defects (trivalent Si centers in SiO2 associated with O vacancies) can function as border traps in MOS devices exposed to ionizing radiation or high-field stress. Hydrogen-related centers may also be border traps. © 1996 IEEE.

Structurally disordered refractory ternary films such as titanium silicon nitride (Ti-Si-N) have potential as advanced diffusion barriers in future ULSI metallization schemes. Here we present results on purely thermal metallorganic chemical vapor deposition (CVD) of Ti-Si-N. At temperatures between 300 and 450 °C, tetrakis(diethylamido)titanium (TDEAT), silane, and ammonia react to grow Ti-Si-N films with Si contents of 0-20 at.%. Typical impurity contents are 5-10 at.%H and 0.5 to 1.5 at.% C, with no O or other impurities detected in the bulk of the film. Although the film resistivity increases with increasing Si content, it remains below 1000 μΩ-cm for films with less than 5 at.% Si. These films are promising candidates for advanced diffusion barriers.

Ion implantation has been an enabling technology for the realization of many high performance electronic devices in III-V semiconductor materials. We report on advances in ion implantation processing technology for application to GaAs JFETs, AlGaAs/GaAs HFETs, and InGaP or InAlP-barrier HFETs. In particular, the GaAs JFET has required the development of shallow p-type implants using Zn or Cd with junction depths down to 35 nm after the activation anneal. Implant activation and ionization issues for AlGaAs will be reported along with those for InGaP and InAlP. A comprehensive treatment of Si-implant doping of AlGaAs is given based on the donor ionization energies and conduction band density-of-states dependence on Al-composition. Si and Si+P implants in InGaP are shown to achieve higher electron concentrations than for similar implants in AlGaAs due to the absence of the deep donor (DX) level. An optimized P co-implantation scheme in InGaP is shown to increase the implanted donor saturation level by 65%.

III-N photonic devices have made great advances in recent years following the demonstration of doping of GaN p-type with Mg and n-type with Si. However, the deep ionization energy level of Mg in GaN (approximately 160 meV) limits the ionized of acceptors at room temperature to less than 1.0% of the substitutional Mg. With this in mind, we used ion implantation to characterize the ionization level of Ca in GaN since Ca had been suggested by Strite to be a shallow acceptor in GaN. Ca-implanted GaN converted from n-to-p type after a 1100 °C activation anneal. Variable temperature Hall measurements give an ionization level at 169 meV. Although this level is equivalent to that of Mg, Ca-implantation may have advantages (shallower projected range and less straggle for a given energy) than Mg for electronic devices. In particular, we report the first GaN device using ion implantation doping. This is a GaN junction field effect transistor (JFET) which employed Ca-implantation. A 1.7 μm JFET had a transconductance of 7 mS/mm, a saturation current at 0 V gate bias of 33 mA/mm, a ft of 2.7 GHz, and a fmax of 9.4 GHz. O-implantation was also studied and shown to create a shallow donor level (approximately 25 meV) that is similar to Si. SIMS profiles of as-implanted and annealed samples showed no measurable redistribution of either Ca or O in GaN at 1125 °C.

The spectral editing properties of the 29Si NMP, INEPT heteronuclear transfer experiment have been utilized for the identification and characterization of hydrolysis and initial condensation products in methyltrimethoxysilane (MTMS) sol-gel materials. 29Si NMR assignments in MTMS are complicated by a small spectral dispersion (approximately 0.5 ppm) and two different 29Si-1H J couplings. By using analytical expressions for the INEPT signal response with multiple heteronuclear J couplings, unambiguous spectral assignments can be made. For this organomethoxysilane the rate of hydrolysis was found to be very rapid and significantly faster than either the water- or alcohol-producing condensation reactions. The hydrolysis species of both the MTMS monomer and its initial T1 condensation products follow statistical distributions that can be directly related to the extent of the hydrolysis reactions. The role of the statistical distribution of hydrolysis products on the production and synthetic control of organically modified sol-gels is discussed.