Self-assembled ordered carbon-nanotube arrays and membranes.

Imagine free-standing flexible membranes with highly-aligned arrays of carbon nanotubes (CNTs) running through their thickness. Perhaps with both ends of the CNTs open for highly controlled nanofiltration? Or CNTs at heights uniformly above a polymer membrane for a flexible array of nanoelectrodes or field-emitters? How about CNT films with incredible amounts of accessible surface area for analyte adsorption? These self-assembled crystalline nanotubes consist of multiple layers of graphene sheets rolled into concentric cylinders. Tube diameters (3-300 nm), inner-bore diameters (2-15 nm), and lengths (nanometers - microns) are controlled to tailor physical, mechanical, and chemical properties. We proposed to explore growth and characterize nanotube arrays to help determine their exciting functionality for Sandia applications. Thermal chemical vapor deposition growth in a furnace nucleates from a metal catalyst. Ordered arrays grow using templates from self-assembled hexagonal arrays of nanopores in anodized-aluminum oxide. Polymeric-binders can mechanically hold the CNTs in place for polishing, lift-off, and membrane formation. The stiffness, electrical and thermal conductivities of CNTs make them ideally suited for a wide-variety of possible applications. Large-area, highly-accessible gas-adsorbing carbon surfaces, superb cold-cathode field-emission, and unique nanoscale geometries can lead to advanced microsensors using analyte adsorption, arrays of functionalized nanoelectrodes for enhanced electrochemical detection of biological/explosive compounds, or mass-ionizers for gas-phase detection. Materials studies involving membrane formation may lead to exciting breakthroughs in nanofiltration/nanochromatography for the separation of chemical and biological agents. With controlled nanofilter sizes, ultrafiltration will be viable to separate and preconcentrate viruses and many strains of bacteria for 'down-stream' analysis

Electroforming of Bi(1-x)Sb(x) nanowires for high-efficiency micro-thermoelectric cooling devices on a chip.

Active cooling of electronic systems for space-based and terrestrial National Security missions has demanded use of Stirling, reverse-Brayton, closed Joule-Thompson, pulse tube and more elaborate refrigeration cycles. Such cryocoolers are large systems that are expensive, demand large powers, often contain moving parts and are difficult to integrate with electronic systems. On-chip, solid-state, active cooling would greatly enhance the capabilities of future systems by reducing the size, cost and inefficiencies compared to existing solutions. We proposed to develop the technology for a thermoelectric cooler capable of reaching 77K by replacing bulk thermoelectric materials with arrays of Bi{sub 1-x}Sb{sub x} nanowires. Furthermore, the Sandia-developed technique we will use to produce the oriented nanowires occurs at room temperature and can be applied directly to a silicon substrate. Key obstacles include (1) optimizing the Bi{sub 1-x}Sb{sub x} alloy composition for thermoelectric properties; (2) increasing wire aspect ratios to 3000:1; and (3) increasing the array density to {ge} 10{sup 9} wires/cm{sup 2}. The primary objective of this LDRD was to fabricate and test the thermoelectric properties of arrays of Bi{sub 1-x}Sb{sub x} nanowires. With this proof-of-concept data under our belts we are positioned to engage National Security systems customers to invest in the integration of on-chip thermoelectric coolers for future missions

Nanoporous-carbon adsorbers for chemical microsensors.

Chemical microsensors rely on partitioning of airborne chemicals into films to collect and measure trace quantities of hazardous vapors. Polymer sensor coatings used today are typically slow to respond and difficult to apply reproducibly. The objective of this project was to produce a durable sensor coating material based on graphitic nanoporous-carbon (NPC), a new material first studied at Sandia, for collection and detection of volatile organic compounds (VOC), toxic industrial chemicals (TIC), chemical warfare agents (CWA) and nuclear processing precursors (NPP). Preliminary studies using NPC films on exploratory surface-acoustic-wave (SAW) devices and as a {micro}ChemLab membrane preconcentrator suggested that NPC may outperform existing, irreproducible coatings for SAW sensor and {micro}ChemLab preconcentrator applications. Success of this project will provide a strategic advantage to the development of a robust, manufacturable, highly-sensitive chemical microsensor for public health, industrial, and national security needs. We use pulsed-laser deposition to grow NPC films at room-temperature with negligible residual stress, and hence, can be deposited onto nearly any substrate material to any thickness. Controlled deposition yields reproducible NPC density, morphology, and porosity, without any discernable variation in surface chemistry. NPC coatings > 20 {micro}m thick with density < 5% that of graphite have been demonstrated. NPC can be 'doped' with nearly any metal during growth to provide further enhancements in analyte detection and selectivity. Optimized NPC-coated SAW devices were compared directly to commonly-used polymer coated SAWs for sensitivity to a variety of VOC, TIC, CWA and NPP. In every analyte, NPC outperforms each polymer coating by multiple orders-of-magnitude in detection sensitivity, with improvements ranging from 103 to 108 times greater detection sensitivity! NPC-coated SAW sensors appear capable of detecting most analytes tested to concentrations below parts-per-billion. In addition, the graphitic nature of NPC enables thermal stability > 600 C, several hundred degrees higher than the polymers. This superior thermal stability will enable higher-Temperature preconcentrator operation, as well as greatly prolonged device reliability, since polymers tend to degrade with time and repeated thermal cycling

A tunable electrochromic fabry-perot filter for adaptive optics applications.

The potential for electrochromic (EC) materials to be incorporated into a Fabry-Perot (FP) filter to allow modest amounts of tuning was evaluated by both experimental methods and modeling. A combination of chemical vapor deposition (CVD), physical vapor deposition (PVD), and electrochemical methods was used to produce an ECFP film stack consisting of an EC WO{sub 3}/Ta{sub 2}O{sub 5}/NiO{sub x}H{sub y} film stack (with indium-tin-oxide electrodes) sandwiched between two Si{sub 3}N{sub 4}/SiO{sub 2} dielectric reflector stacks. A process to produce a NiO{sub x}H{sub y} charge storage layer that freed the EC stack from dependence on atmospheric humidity and allowed construction of this complex EC-FP stack was developed. The refractive index (n) and extinction coefficient (k) for each layer in the EC-FP film stack was measured between 300 and 1700 nm. A prototype EC-FP filter was produced that had a transmission at 500 nm of 36%, and a FWHM of 10 nm. A general modeling approach that takes into account the desired pass band location, pass band width, required transmission and EC optical constants in order to estimate the maximum tuning from an EC-FP filter was developed. Modeling shows that minor thickness changes in the prototype stack developed in this project should yield a filter with a transmission at 600 nm of 33% and a FWHM of 9.6 nm, which could be tuned to 598 nm with a FWHM of 12.1 nm and a transmission of 16%. Additional modeling shows that if the EC WO{sub 3} absorption centers were optimized, then a shift from 600 nm to 598 nm could be made with a FWHM of 11.3 nm and a transmission of 20%. If (at 600 nm) the FWHM is decreased to 1 nm and transmission maintained at a reasonable level (e.g. 30%), only fractions of a nm of tuning would be possible with the film stack considered in this study. These tradeoffs may improve at other wavelengths or with EC materials different than those considered here. Finally, based on our limited investigation and material set, the severe absorption associated with the refractive index change suggests that incorporating EC materials into phase correcting spatial light modulators (SLMS) would allow for only negligible phase correction before transmission losses became too severe. However, we would like to emphasize that other EC materials may allow sufficient phase correction with limited absorption, which could make this approach attractive

Understanding and predicting metallic whisker growth and its effects on reliability : LDRD final report.

Tin (Sn) whiskers are conductive Sn filaments that grow from Sn-plated surfaces, such as surface finishes on electronic packages. The phenomenon of Sn whiskering has become a concern in recent years due to requirements for lead (Pb)-free soldering and surface finishes in commercial electronics. Pure Sn finishes are more prone to whisker growth than their Sn-Pb counterparts and high profile failures due to whisker formation (causing short circuits) in space applications have been documented. At Sandia, Sn whiskers are of interest due to increased use of Pb-free commercial off-the-shelf (COTS) parts and possible future requirements for Pb-free solders and surface finishes in high-reliability microelectronics. Lead-free solders and surface finishes are currently being used or considered for several Sandia applications. Despite the long history of Sn whisker research and the recently renewed interest in this topic, a comprehensive understanding of whisker growth remains elusive. This report describes recent research on characterization of Sn whiskers with the aim of understanding the underlying whisker growth mechanism(s). The report is divided into four sections and an Appendix. In Section 1, the Sn plating process is summarized. Specifically, the Sn plating parameters that were successful in producing samples with whiskers will be reviewed. In Section 2, the scanning electron microscopy (SEM) of Sn whiskers and time-lapse SEM studies of whisker growth will be discussed. This discussion includes the characterization of straight as well as kinked whiskers. In Section 3, a detailed discussion is given of SEM/EBSD (electron backscatter diffraction) techniques developed to determine the crystallography of Sn whiskers. In Section 4, these SEM/EBSD methods are employed to determine the crystallography of Sn whiskers, with a statistically significant number of whiskers analyzed. This is the largest study of Sn whisker crystallography ever reported. This section includes a review of previous literature on Sn whisker crystallography. The overall texture of the Sn films was also analyzed by EBSD. Finally, a short Appendix is included at the end of this report, in which the X-Ray diffraction (XRD) results are discussed and compared to the EBSD analyses of the overall textures of the Sn films. Sections 2, 3, and 4 have been or will be submitted as stand-alone papers in peer-reviewed technical journals. A bibliography of recent Sandia Sn whisker publications and presentations is included at the end of the report

Nano electrode arrays for in-situ identification and quantification of chemicals in water.

The nano electrode arrays for in-situ identification and quantification of chemicals in water progress in four major directions. (1) We developed and engineering three nanoelectrode array designs which operate in a portable field mode or as distributed sensor network for water systems. (2) To replace the fragile glass electrochemical cells using in the lab, we design and engineered field-ready sampling heads that combine the nanoelectrode arrays with a high-speed potentiostat. (3) To utilize these arrays in a portable system we design and engineered a light weight high-speed potentiostat with pulse widths from 2 psec. to 100 msec. or greater. (4) Finally, we developed the parameters for an analytical method in low-conductivity solutions for Pb(II) detection, with initial studies for the analysis of As(III) and As(V) analysis in natural water sources

CMS physics technical design report : Addendum on high density QCD with heavy ions

Peer reviewe

Sensor for cell signaling proteins.

Thiolated cyclodextrins have been shown to be useful as modifiers of electrode surfaces for application in electrochemical sensing. The adsorption of three different thiolated {beta}-cyclodextrin ({beta}-CD) derivatives onto gold (Au) electrodes was studied by monitoring ferricyanide reduction and ferrocene carboxylic acid (FCA) oxidation at the electrode surface using cyclic voltammetry. Electrodes modified with the {beta}-CD MJF-69 derivative bound FCA within the CD cavity. The monolayer acted as a conducting layer with an increase in the oxidation current. On the other hand, the {beta}-CD layer inhibited the reduction of ferricyanide at the electrode surface since ferricyanide is larger than the cavity of the {beta}-CD derivative and thus unable to form an inclusion complex

Understanding and predicting metallic whisker growth and its effects on reliability : LDRD final report.

Tin (Sn) whiskers are conductive Sn filaments that grow from Sn-plated surfaces, such as surface finishes on electronic packages. The phenomenon of Sn whiskering has become a concern in recent years due to requirements for lead (Pb)-free soldering and surface finishes in commercial electronics. Pure Sn finishes are more prone to whisker growth than their Sn-Pb counterparts and high profile failures due to whisker formation (causing short circuits) in space applications have been documented. At Sandia, Sn whiskers are of interest due to increased use of Pb-free commercial off-the-shelf (COTS) parts and possible future requirements for Pb-free solders and surface finishes in high-reliability microelectronics. Lead-free solders and surface finishes are currently being used or considered for several Sandia applications. Despite the long history of Sn whisker research and the recently renewed interest in this topic, a comprehensive understanding of whisker growth remains elusive. This report describes recent research on characterization of Sn whiskers with the aim of understanding the underlying whisker growth mechanism(s). The report is divided into four sections and an Appendix. In Section 1, the Sn plating process is summarized. Specifically, the Sn plating parameters that were successful in producing samples with whiskers will be reviewed. In Section 2, the scanning electron microscopy (SEM) of Sn whiskers and time-lapse SEM studies of whisker growth will be discussed. This discussion includes the characterization of straight as well as kinked whiskers. In Section 3, a detailed discussion is given of SEM/EBSD (electron backscatter diffraction) techniques developed to determine the crystallography of Sn whiskers. In Section 4, these SEM/EBSD methods are employed to determine the crystallography of Sn whiskers, with a statistically significant number of whiskers analyzed. This is the largest study of Sn whisker crystallography ever reported. This section includes a review of previous literature on Sn whisker crystallography. The overall texture of the Sn films was also analyzed by EBSD. Finally, a short Appendix is included at the end of this report, in which the X-Ray diffraction (XRD) results are discussed and compared to the EBSD analyses of the overall textures of the Sn films. Sections 2, 3, and 4 have been or will be submitted as stand-alone papers in peer-reviewed technical journals. A bibliography of recent Sandia Sn whisker publications and presentations is included at the end of the report