Publications

Abstract not provided.

Abstract not provided.

Abstract not provided.

Ultradoping introduces unprecedented dopant levels into Si, which transforms its electronic behavior and enables its use as a next-generation electronic material. Commercialization of ultradoping is currently limited by gas-phase ultra-high vacuum requirements. Solvothermal chemistry is amenable to scale-up. However, an integral part of ultradoping is a direct chemical bond between dopants and Si, and solvothermal dopant-Si surface reactions are not well-developed. This work provides the first quantified demonstration of achieving ultradoping concentrations of boron (∼1e14 cm2) by using a solvothermal process. Surface characterizations indicate the catalyst cross-reacted, which led to multiple surface products and caused ambiguity in experimental confirmation of direct surface attachment. Density functional theory computations elucidate that the reaction results in direct B−Si surface bonds. This proof-of-principle work lays groundwork for emerging solvothermal ultradoping processes.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Recent news reports coming from Asia and the UK have highlighted the emerging threats of Non-Traditional Agents (NTAs) to national security. The UK incident underscores how NTAs may linger in the environment and at trace. Building on Sandia's extensive analytical chemistry work in this field, a polysilphenylene analog of Sandia's proprietary DKAP polymer coatings was synthesized and evaluated for high temperature operation. Initial test results are inconclusive as to the improved thermal stability of the new polymer with TGA/DSC results indicating a lower glass transition go temperature for the new "Hot DKAP" material and a similar to slightly lower start to mass loss for "Hot DKAP", but slower degradation rate in clean dry air. Additional testing with a TGA-MS system to identify what the fragments lost as a function of temperature is still needed to fully characterize the materials thermal properties. In addition, the material still needs to be evaluated for thermodynamic properties for analytes of interest using either GC or SPC coated devices.

We report a novel approach whereby cross-linked polybutadiene (PB) networks can be depolymerized in situ based on thermally activated alkene metathesis. A commercially available latent Ru catalyst, HeatMet, was compared to the common second-generation Hoveyda-Grubbs catalyst, HG2, in the metathetic depolymerization of PB. HeatMet was found to possess exceptional stability and negligible activity toward PB under ambient conditions, in solution and in bulk. This enabled cross-linked networks to be prepared containing homogeneously distributed Ru catalyst. The dynamic mechanical properties of networks containing HeatMet and cross-linked using alcohol-isocyanate or thiol-ene chemistry were evaluated during cross-linking and post-cross-linking under isothermal and nonisothermal heating. In both cases, above minimum catalyst loadings ranging from 0.004 to 0.024 mol %, the networks exhibited rapid degelation into a soluble oil upon heating to 100 °C. At these temperatures, extensive depolymerization of the PB segments through ring-closing metathesis of 1,4/1,2 diads by the activated HeatMet introduced network defects in significantly greater proportion than the original number of cross-links. The in situ depolymerization of cross-linked PB networks through latent catalysis, as described here, may enable facile disposal and recycling of PB encapsulants and adhesives, among other applications.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

A small, consumable-free, low-power, ultra-high-speed comprehensive GC×GC system consisting of microfabricated columns, nanoelectromechanical system (NEMS) cantilever resonators for detection, and a valve-based stop-flow modulator is demonstrated. The separation of a highly polar 29-component mixture covering a boiling point range of 46 to 253 °C on a pair of microfabricated columns using a Staiger valve manifold in less than 7 seconds, and just over 4 seconds after the ensemble holdup time is demonstrated with a downstream FID. The analysis time of the second dimension was 160 ms, and peak widths in the second dimension range from 10-60 ms. A peak capacity of just over 300 was calculated for a separation of just over 6 s. Data from a continuous operation testing over 40 days and 20000 runs of the GC×GC columns with the NEMS resonators using a 4-component test set is presented. The GC×GC-NEMS resonator system generated second-dimension peak widths as narrow as 8 ms with no discernable peak distortion due to under-sampling from the detector.

We describe for the first time hydrogen bonded acid (HBA) polymer, poly[methyl[3-(2-hydroxyl, 4,6-bistrifluoromethyl)- phenyl]propylsiloxane], (DKAP), as stationary phase for gas chromatography (μGC) of organophosphate (OP), chemical warfare agent (CWA) surrogates, dimethylmethylphosphonate (DMMP), diisopropylmethylphosphonate (DIMP), diethylmethylphosphonate (DEMP), and trimethylphosphate (TMP), with high selectivity. Absorption of OPs to DKAP was one-to-several orders of magnitude higher relative to commercial polar, mid-polar, and nonpolar stationary phases. We also present for the first-time thermodynamic studies on the absorption of OP vapors and quantitative binding energy data for interactions with various stationary phases. These data help to identify the best pair of hetero-polar columns for a two-dimensional GC system, employing a nonpolar stationary phase as GC1 and DKAP as the GC2 stationary phase, for selective and rapid field detection of CWAs.

Abstract not provided.

Abstract not provided.

This report catalogues the results of a project exploring the incorporation of organometallic compounds into thermosetting polymers as a means to reduce their residual stress. Various syntheses of polymerizable ferro cene derivatives were attempted with mixed success. Ultimately, a diamine derivative of ferrocene was used as a curing agen t for a commercial epoxy resin, where it was found to give similar cure kinetics and mechanical properties in comparison to conventional curing agents. T he ferrocen e - based material is uniquely able to relax stress above the glass transition, leading to reduced cure stress. We propose that this behavior arises from the fluxional capacity of ferrocene. In support of this notion, nuclear magnetic resonance spectroscopy indicates a substantial increase in chain flexibility in the ferrocene - containing network. Although t he utilization of fluxionality is a novel approach to stress management in epoxy thermosets, it is anticipated to have greater impact in radical - cured ther mosets and linear polymers.

Physical stress relaxation in rubbery, thermoset polymers is limited by cross-links, which impede segmental motion and restrict relaxation to network defects, such as chain ends. In parallel, the cure shrinkage associated with thermoset polymerizations leads to the development of internal residual stress that cannot be effectively relaxed. Recent strategies have reduced or eliminated such cure stress in thermoset polymers largely by exploiting chemical relaxation processes, wherein temporary cross-links or otherwise transient bonds are incorporated into the polymer network. Here, we explore an alternative approach, wherein physical relaxation is enhanced by the incorporation of organometallic sandwich moieties into the backbone of the polymer network. A standard epoxy resin is cured with a diamine derivative of ferrocene and compared to conventional diamine curing agents. The ferrocene-based thermoset is clearly distinguished from the conventional materials by reduced cure stress with increasing cure temperature as well as unique stress relaxation behavior above its glass transition in the fully cured state. The relaxation experiments exhibit features characteristic of a physical relaxation process. Furthermore, the cure stress is observed to vanish precipitously upon deliberate introduction of network defects through an increasing imbalance of epoxy and amine functional groups. We postulate that these beneficial properties arise from fluxional motion of the cyclopentadienyl ligands on the polymer backbone.

Abstract not provided.

We demonstrate matter-wave interference in a warm vapor of rubidium atoms. Established approaches to light-pulse atom interferometry rely on laser cooling to concentrate a large ensemble of atoms into a velocity class resonant with the atom optical light pulse. In our experiment, we show that clear interference signals may be obtained without laser cooling. This effect relies on the Doppler selectivity of the atom interferometer resonance. This interferometer may be configured to measure accelerations, and we demonstrate that multiple interferometers may be operated simultaneously by addressing multiple velocity classes.

Abstract not provided.

Abstract not provided.

The in-situ hydrolysis and subsequent condensation reaction of the chemical agent simulant diethyl chlorophosphate (DECP) was characterized by high-resolution 31P NMR spectroscopy following the addition of water in sub-equimolar concentrations. The identification and quantification of the multiple pyrophosphate and larger polyphosphate chemical species formed through a series of self-condensation reactions are reported. The DECP hydrolysis kinetics and distribution of breakdown species was strongly influenced by the water concentration and reaction temperature.

Abstract not provided.

Abstract not provided.

Preparation of sodium zirconium silicate phosphate (NaSICon), Na1+ xZr2SixP3− xO12(0.25 ≤ x ≤ 1.0), thin films has been investigated via a chemical solution approach on platinized silicon substrates. Increasing the silicon content resulted in a reduction in the crystallite size and a reduction in the measured ionic conductivity. Processing temperature was also found to affect microstructure and ionic conductivity with higher processing temperatures resulting in larger crystallite sizes and higher ionic conductivities. The highest room temperature sodium ion conductivity was measured for an x = 0.25 composition at 2.3 × 10−5 S/cm. The decreasing ionic conductivity trends with increasing silicon content and decreasing processing temperature are consistent with grain boundary and defect scattering of conducting ions.

This report describes a new, bio-inspired approach to electrical energy storage, based on the generation, maintenance, and discharge of ion concentration gradients. This approach was investigated as part of a Laboratory Directed Research and Development program at Sandia National Laboratories in Albuquerque, NM between October 2012 and September 2015. In particular, this report describes the development of ion-selective nanoporous membranes, controlled through pore morphology and Sandia-developed electrochemical functionalization. In addition, it describes a potential avenue to functionalize synthetic polymer membranes in a way that facilitates oriented ion pump binding to polymer surfaces. Finally, it highlights a number of new computational findings central to the understanding and ultimate design of synthetic ion channels and ion gates needed for biomimetic ion-based electrochemical energy storage.

Abstract not provided.

Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

Evaluating the stability of coupling reagents, quality control (QC), and surface functionalization metrology are all critical to the production of high quality peptide microarrays. We describe a broadly applicable screening technique for evaluating the fidelity of solid phase peptide synthesis (SPPS), the stability of activation/coupling reagents, and a microarray surface metrology tool. This technique was used to assess the stability of the activation reagent 1-{[1-(Cyano-2-ethoxy-2-oxo-ethylidenaminooxy)dimethylamino-morpholinomethylene]}methaneaminiumHexafluorophosphate (COMU) (Sigma-Aldrich, St. Louis, MO, USA) by SPPS of Leu-Enkephalin (YGGFL) or the coupling of commercially synthesized YGGFL peptides to (3-aminopropyl)triethyoxysilane-modified glass surfaces. Coupling efficiency was quantitated by fluorescence signaling based on immunoreactivity of the YGGFL motif. It was concluded that COMU solutions should be prepared fresh and used within 5 h when stored at ∼23 °C and not beyond 24 h if stored refrigerated, both in closed containers. Caveats to gauging COMU stability by absorption spectroscopy are discussed. Commercial YGGFL peptides needed independent QC, due to immunoreactivity variations for the same sequence synthesized by different vendors. This technique is useful in evaluating the stability of other activation/coupling reagents besides COMU and as a metrology tool for SPPS and peptide microarrays.

Optical fluorescence-based DNA assays are commonly used for pathogen detection and consist of an optical substrate containing DNA capture molecules, binding of target RNA or DNA sequences, followed by detection of the hybridization event with a fluorescent probe. Though fluorescence detection can offer exquisite signal-to-background ratios, with high specificity, vast opportunities exist to improve current optical-based genomic sensing approaches. For these reasons, there is a clear need to explore alternative optical sensing paradigms to alleviate these restrictions. Bio-templated nanomaterial synthesis has become a powerful concept for developing new platforms for bio-sensing, as the biomolecule of interest can act as part of the sensing transducer mechanism. We explored the use of DNA origami structures to immobilize gold nanoparticles in very precise localized arrangements producing unique optical absorption properties with implications in novel DNA sensing schemes. We also explored the use of in-situ TEM as a novel characterization method for DNA-nanoparticle assemblies.

Modification of the dipeptide of phenylalanine, FF, with a boronic acid (BA) functionality imparts unique aqueous self-assembly behavior that responds to multiple stimuli. Changes in pH and ionic strength are used to trigger hydrogelation via the formation of nanoribbon networks. Furthermore, we show for the first time that the binding of polyols to the BA functionality can modulate a peptide between its assembled and disassembled states.

Abstract not provided.

Polycarbonate is a desirable material for many applications due to its favorable mechanical and optical properties. Here, we report a simple, safe, environmentally friendly aqueous method that uses diamines to functionalize a polycarbonate surface with amino groups. The use of water as the solvent for the functionalization ensures that solvent induced swelling does not affect the optical or mechanical properties of the polycarbonate. We characterize the efficacy of the surface amination using X-ray photo spectroscopy, Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and contact angle measurements. Furthermore, we demonstrate the ability of this facile method to serve as a foundation upon which other functionalities may be attached, including antifouling coatings and oriented membrane proteins. (Chemical Presented).

Abstract not provided.

Abstract not provided.

The ability of three aryldiazonium salts to spontaneously assemble onto the surface of type 440C stainless steel is investigated in acetonitrile (ACN) and the model hydraulic fluids tributyl phosphate (TBP) and hexamethyldisiloxane (HMDS). Competition between native oxide formation and organic film growth at different diazonium salt concentrations is monitored by electrochemical impedance spectroscopy. At 1 mM diazonium salt, 70% of total assembly is complete within 10 min, though total surface coverage by organics is limited to ≈0.15 monolayers. Adding HCl to the electrolyte renders native oxide formation unfavorable, yet the diazonium molecules are still unable to the increase surface coverage over 1 M-10 μM HCl in solution. X-ray photoelectron spectroscopy confirms preferential bonding of organic molecules to iron over chromium, while secondary ion mass spectroscopy reveals the ability of these films to self-heal when mechanically removed or damaged. Aging the diazonium salts in these nonaqueous environments demonstrates that up to 90% of the original diazonium salt concentration remains after 21 days at room temperature, while increasing the temperature beyond 50 °C results in complete decomposition within 24 h, regardless of solvent-salt combination. It is concluded that the investigated diazonium molecules will not spontaneously form a continuous monolayer on 440C stainless steel immersed in ACN, TBP, or HMDS.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Electro-optical organic materials hold great promise for the development of high-efficiency devices based on exciton formation and dissociation, such as organic photovoltaics (OPV) and organic light-emitting devices (OLEDs). However, the external quantum efficiency (EQE) of both OPV and OLEDs must be improved to make these technologies economical. Efficiency rolloff in OLEDs and inability to control morphology at key OPV interfaces both reduce EQE. Only by creating materials that allow manipulation and control of the intimate assembly and communication between various nanoscale excitonic components can we hope to first understand and then engineer the system to allow these materials to reach their potential. The aims of this proposal are to: 1) develop a paradigm-changing platform for probing excitonic processes composed of Crystalline Nanoporous Frameworks (CNFs) infiltrated with secondary materials (such as a complimentary semiconductor); 2) use them to probe fundamental aspects of excitonic processes; and 3) create prototype OPVs and OLEDs using infiltrated CNF as active device components. These functional platforms will allow detailed control of key interactions at the nanoscale, overcoming the disorder and limited synthetic control inherent in conventional organic materials. CNFs are revolutionary inorganic-organic hybrid materials boasting unmatched synthetic flexibility that allow tuning of chemical, geometric, electrical, and light absorption/generation properties. For example, bandgap engineering is feasible and polyaromatic linkers provide tunable photon antennae; rigid 1-5 nm pores provide an oriented, intimate host for triplet emitters (to improve light emission in OLEDs) or secondary semiconducting polymers (creating a charge-separation interface in OPV). These atomically engineered, ordered structures will enable critical fundamental questions to be answered concerning charge transport, nanoscale interfaces, and exciton behavior that are inaccessible in disordered systems. Implementing this concept also creates entirely new dimensions for device fabrication that could both improve performance, increase durability, and reduce costs with unprecedented control of over properties. This report summarizes the key results of this project and is divided into sections based on publications that resulted from the work. We begin in Section 2 with an investigation of light harvesting and energy transfer in a MOF infiltrated with donor and acceptor molecules of the type typically used in OPV devices (thiophenes and fullerenes, respectively). The results show that MOFs can provide multiple functions: as a light harvester, as a stabilizer and organizer or the infiltrated molecules, and as a facilitator of energy transfer. Section 3 describes computational design of MOF linker groups to accomplish light harvesting in the visible and facilitate charge separation and transport. The predictions were validated by UV-visible absorption spectroscopy, demonstrating that rational design of MOFs for light-harvesting purposes is feasible. Section 4 extends the infiltration concept discussed in Section to, which we now designate as "Molecule@MOF" to create an electrically conducting framework. The tailorability and high conductivity of this material are unprecedented, meriting publication in the journal Science and spawning several Technical Advances. Section 5 discusses processes we developed for depositing MOFs as thin films on substrates, a critical enabling technology for fabricating MOF-based electronic devices. Finally, in Section 6 we summarize results showing that a MOF thin film can be used as a sensitizer in a DSSC, demonstrating that MOFs can serve as active layers in excitonic devices. Overall, this project provides several crucial proofs-of- concept that the potential of MOFs for use in optoelectronic devices that we predicted several years ago [ 3 ] can be realized in practice.

Gd2O3 films were prepared on (0001)-oriented AlxGa1-xN (0≤x≤0.67) thin film substrates via reactive molecular-beam epitaxy. X-ray diffraction revealed that these films possessed the cubic bixbyite structure regardless of substrate composition and were all 111-oriented with in-plane rotations to account for the symmetry difference between the oxide film and nitride epilayer. Valence band offsets were characterized by X-ray photoelectron spectroscopy and were determined to be 0.41±0.02eV, 0.17±0.02eV, and 0.06±0.03eV at the Gd2O3/AlxGa1-xN interfaces for x=0, 0.28, and 0.67, respectively.

Abstract not provided.

Abstract not provided.

Controlling the size and shape of nanopores in polymer membranes can significantly impact transport of molecular or ionic species through these membranes. Here we describe a facile method to controllably form conical nanopores in ion-tracked polycarbonate membranes. Commercial polycarbonate ion-tracked membranes were placed between a concentrated alkaline solution and an acidic solution. By varying the height of the acidic solution, the hydrostatic pressure was controlled, regulating the acid flux through the nanopores. The resulting asymmetric etching of the membrane produced conical pores with controllable aspect ratios. Scanning electron microscopy of both the pores and nickel nanostructures electrolessly templated in the pores confirms their conical shape. This safe, straightforward approach obviates the need to use large voltages, currents, and/or plasma etching equipment traditionally employed to create conical nanopores. © 2014 The Royal Society of Chemistry.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Bioweapons and emerging infectious diseases pose growing threats to our national security. Both natural disease outbreak and outbreaks due to a bioterrorist attack are a challenge to detect, taking days after the outbreak to identify since most outbreaks are only recognized through reportable diseases by health departments and reports of unusual diseases by clinicians. In recent decades, arthropod-borne viruses (arboviruses) have emerged as some of the most significant threats to human health. They emerge, often unexpectedly, from cryptic transmission foci causing localized outbreaks that can rapidly spread to multiple continents due to increased human travel and trade. Currently, diagnosis of acute infections requires amplification of viral nucleic acids, which can be costly, highly specific, technically challenging and time consuming. No diagnostic devices suitable for use at the bedside or in an outbreak setting currently exist. The original goals of this project were to 1) develop two highly sensitive and specific diagnostic assays for detecting RNA from a wide range of arboviruses; one based on an electrochemical approach and the other a fluorescent based assay and 2) develop prototype microfluidic diagnostic platforms for preclinical and field testing that utilize the assays developed in goal 1. We generated and characterized suitable primers for West Nile Virus RNA detection. Both optical and electrochemical transduction technologies were developed for DNA-RNA hybridization detection and were implemented in microfluidic diagnostic sensing platforms that were developed in this project.

Chemical functionalization is required to adapt graphenes properties to many applications. However, most covalent functionalization schemes are spontaneous or defect driven and are not suitable for applications requiring directed assembly of molecules on graphene substrates. In this work, we demonstrated electrochemically driven covalent bonding of phenyl iodoniums onto epitaxial graphene. The amount of chemisorption was demonstrated by varying the duration of the electrochemical driving potential. Chemical, electronic, and defect states of phenyl-modified graphene were studied by photoemission spectroscopy, spatially resolved Raman spectroscopy, and water contact angle measurement. Covalent attachment rehybridized some of the delocalized graphene sp2 orbitals to localized sp3 states. Control over the relative spontaneity (reaction rate) of covalent graphene functionalization is an important first step to the practical realization of directed molecular assembly on graphene. More than 10 publications, conference presentations, and program highlights were produced (some invited), and follow-on funding was obtained to continue this work.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Field-structured chemiresistors (FSCRs) are polymer based sensors that exhibit a resistance change when exposed to an analyte of interest. The amount of resistance change depends on the polymer-analyte affinity. The affinity can be manipulated by modifying the polymer within the FSCRs. In this paper, we investigate the ability of chemically modified FSCRs to sense hydrogen peroxide vapor. Five chemical species were chosen based on their hydrophobicity or reactivity with hydrogen peroxide. Of the five investigated, FSCRs modified with allyl methyl sulfide exhibited a significant response to hydrogen peroxide vapor. Additionally, these same FSCRs were evaluated against a common interferrant in hydrogen peroxide detection, water vapor. For the conditions investigated, the FSCRs modified with allyl methyl sulfide were able to successfully distinguish between water vapor and hydrogen peroxide vapor. A portion of the results presented here will be submitted to the Sensors and Actuators journal.

Abstract not provided.

Abstract not provided.

Abstract not provided.

The advancement of materials technology towards the development of novel 3D nanostructures for energy applications has been a long-standing challenge. The purpose of this project was to explore photolithographically defineable pyrolyzed photoresist carbon films for possible energy applications. The key attributes that we explored were as follows: (1) Photo-interferometric fabrication methods to produce highly porous (meso, micro, and nano) 3-D electrode structures, and (2) conducting polymer and nanoparticle-modification strategies on these structures to provide enhanced catalytic capabilities and increase conductivity. The resulting electrodes were then explored for specific applications towards possible use in battery and energy platforms.

Abstract not provided.

Abstract not provided.

There is national interest in the development of sophisticated materials that can automatically detect and respond to chemical and biological threats without the need for human intervention. In living systems, cell membranes perform such functions on a routine basis, detecting threats, communicating with the cell, and triggering automatic responses such as the opening and closing of ion channels. The purpose of this project was to learn how to replicate simple threat detection and response functions within artificial membrane systems. The original goals toward developing 'smart skin' assemblies included: (1) synthesizing functionalized nanoparticles to produce electrochemically responsive systems within a lipid bilayer host matrices, (2) calculating the energetics of nanoparticle-lipid interactions and pore formation, and (3) determining the mechanism of insertion of nanoparticles in lipid bilayers via imaging and electrochemistry. There are a few reports of the use of programmable materials to open and close pores in rigid hosts such as mesoporous materials using either heat or light activation. However, none of these materials can regulate themselves in response to the detection of threats. The strategies we investigated in this project involve learning how to use programmable nanomaterials to automatically eliminate open channels within a lipid bilayer host when 'threats' are detected. We generated and characterized functionalized nanoparticles that can be used to create synthetic pores through the membrane and investigated methods of eliminating the pores either through electrochemistry, change in pH, etc. We also focused on characterizing the behavior of functionalized gold NPs in different lipid membranes and lipid vesicles and coupled these results to modeling efforts designed to gain an understanding of the interaction of nanoparticles within lipid assemblies.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Formation of complex nanomaterials would ideally involve single-pot reaction conditions with one reactive site per nanoparticle, resulting in a high yield of incrementally modified or oriented structures. Many studies in nanoparticle functionalization have sought to generate highly uniform nanoparticles with tailorable surface chemistry necessary to produce such conjugates, with limited success. In order to overcome these limitations, we have modified commercially available nanoparticles with multiple potential reaction sites for conjugation with single ssDNAs, proteins, and small unilamellar vesicles. These approaches combined heterobifunctional and biochemical template chemistries with single molecule optical methods for improved control of nanomaterial functionalization. Several interesting analytical results have been achieved by leveraging techniques unique to SNL, and provide multiple paths for future improvements for multiplex nanoparticle synthesis and characterization. Hyperspectral imaging has proven especially useful for assaying substrate immobilized fluorescent particles. In dynamic environments, temporal correlation spectroscopies have been employed for tracking changes in diffusion/hydrodynamic radii, particle size distributions, and identifying mobile versus immobile sample fractions at unbounded dilution. Finally, Raman fingerprinting of biological conjugates has been enabled by resonant signal enhancement provided by intimate interactions with nanoparticles and composite nanoshells.

Abstract not provided.

Abstract not provided.

Conductive polymers have become an extremely useful class of materials for many optical applications. We have developed an electrochemical growth method for depositing highly conductive ({approx}100 S/cm) polypyrrole. Additionally, we have adapted advanced fabrication methods for use with the polypyrrole resulting in gratings with submicron features. This conductive polymer micro-wire grid provides an optical polarizer with unique properties. When the polymer is exposed to ionizing radiation, its conductivity is affected and the polarization properties of the device, specifically the extinction ratio, change in a corresponding manner. This change in polarization properties can be determined by optically interrogating the device, possibly from a remote location. The result is a passive radiation-sensitive sensor with very low optical visibility. The ability to interrogate the device from a safe standoff distance provides a device useful in potentially dangerous environments. Also, the passive nature of the device make it applicable in applications where external power is not available. We will review the polymer deposition, fabrication methods and device design and modeling. The characterization of the polymer's sensitivity to ionizing radiation and optical testing of infrared polarizers before and after irradiation will also be presented. These experimental results will highlight the usefulness of the conductive infrared polarizer to many security and monitoring applications.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Polymer electronic devices and materials have vast potential for future microsystems and could have many advantages over conventional inorganic semiconductor based systems, including ease of manufacturing, cost, weight, flexibility, and the ability to integrate a wide variety of functions on a single platform. Starting materials and substrates are relatively inexpensive and amenable to mass manufacturing methods. This project attempted to plant the seeds for a new core competency in polymer electronics at Sandia National Laboratories. As part of this effort a wide variety of polymer components and devices, ranging from simple resistors to infrared sensitive devices, were fabricated and characterized. Ink jet printing capabilities were established. In addition to promising results on prototype devices the project highlighted the directions where future investments must be made to establish a viable polymer electronics competency.

Abstract not provided.

The gas-phase {mu}ChemLab{trademark} developed by Sandia can detect volatile organics and semi-volatiles organics via gas phase sampling . The goal of this three year Laboratory Directed Research and Development (LDRD) project was to adapt the components and concepts used by the {mu}ChemLab{trademark} system towards the analysis of water-borne chemicals of current concern. In essence, interfacing the gas-phase {mu}ChemLab{trademark} with water to bring the significant prior investment of Sandia and the advantages of microfabrication and portable analysis to a whole new world of important analytes. These include both chemical weapons agents and their hydrolysis products and disinfection by-products such as Trihalomethanes (THMs) and haloacetic acids (HAAs). THMs and HAAs are currently regulated by EPA due to health issues, yet water utilities do not have rapid on-site methods of detection that would allow them to adjust their processes quickly; protecting consumers, meeting water quality standards, and obeying regulations more easily and with greater confidence. This report documents the results, unique hardware and devices, and methods designed during the project toward the goal stated above. It also presents and discusses the portable field system to measure THMs developed in the course of this project.

Abstract not provided.

Molecular electronic based chemical vapor sensors were assembled using noble metal nanoparticles and short conjugated phenylene ethynylene (PE) based molecules. Sacrificial capping ligands on the nanoparticles were replaced by tighter binding PE ligands. The films were assembled between pairs of electrodes by iteratively exposing the substrates to solutions of the nanoparticles and PE crosslinking bridging ligands. Some of the conjugated bridging molecules contained an electron deficient phenol to provide a simple platform for developing sensor applications. The phenol is calculated to have a significant change in its HOMO/LUMO gap in the presence of specific analytes. Judicious combination of nanoparticle size and ligand structure provides a film in which the organic bridging ligands dramatically affect film conductance. Specifically, π-conjugated ligands lower resistance more in films with smaller nanoparticles. Thus the sensing mechanism of these films is not based on the typical swelling mechanism but rather on the modulation of the molecular electronic structure of the conducting PE bridging ligands.

Abstract not provided.

Nanoparticles have received much attention and have been the subject of many reviews. Nanoparticles have also been used to form super molecular structures for molecular electronic, and sensor applications. However, many limitations exist when using nanoparticles, including the ability to manipulate the particles post synthesis. Current methods to prepare nanoparticles employ functionalities like thiols, amines, phosphines, isocyanides, or a citrate as the metal capping agent. While these capping agents prevent agglomeration or precipitation of the particles, most are difficult to displace or impede packing in nanoparticle films due to coulombic repulsion. It is in this vein that we undertook the synthesis of nanoparticles that have a weakly bound capping agent that is strong enough to prevent agglomeration and in the case of the platinum particles allow for purification, but yet, easily displaced by other strongly binding ligands. The nanoparticles where synthesized according to the Brust method except stearonitrile was used instead of an aliphatic thiol. Both platinum and gold were examined in this manner. A representative procedure for the synthesis of platinum nanoparticles involved the phase transfer of chloroplatinic acid (0.37 g, 0.90 mmol) dissolved in water (30 mL) to a solution of tetraoctylammonium bromide (2.2 g, 4.0 mmol) in toluene (80 mL). After the chloroplatinic acid was transferred into the organic phase the aqueous phase was removed. Stearonitrile (0.23 g, 0.87 mmol) was added and sodium borohydride (0.38 g, 49 mmol) in water (25 mL) was added. The solution turned black almost immediately and after 15 min the organic phase was separated and passed through a 0.45 {micro}m Teflon filter. The resulting solution was concentrated and twice precipitated into ethanol ({approx}200 mL) to yield 0.11 g of black platinum nanoparticles. TGA experiments showed that the Pt particles contained 35% by mass stearonitrile. TEM images showed an average particle size of 1.3 {+-} 0.3 nm. A representative procedure for the synthesis of gold nanoparticles involved the transfer of hydrogen tetrachloroaurate (0.18 g, 0.53 mmol) dissolved in water (15 mL) to a solution of tetraoctylammonium bromide (1.1 g, 2.0 mmol) in toluene (40 mL). After the gold salt transferred into the organic phase the aqueous phase was removed. Stearonitrile (0.23 g, 0.87 mmol) was added and sodium borohydride (0.19 g, 5.0 mmol) in water (13 mL) was added. The solution turned dark red almost immediately, and after 15 min the organic phase was separated and passed through a 0.45 {micro}m Teflon filter. The resulting solution was used without purification via precipitation because attempts at precipitation with ethanol resulted in agglomeration. TEM images showed an average particle size of 5.3 {+-} 1.3 nm. The nanoparticles synthesized were also characterized using atomic force microscopy in tapping mode. The AFM images agree with the TEM images and show a relatively monodispersed collection of nanoparticles. Platinum nanoparticles were synthesized without stearonitrile to show that the particles were in fact capped with the stearonitrile and not the tetraoctylammonium bromide. In the absence of stearonitrile the nanoparticles would not redissolve in hexane or toluene after precipitation. While it is possible the tetraoctylammonium bromide helps prevent agglomeration by solvation into the capping stearonitrile ligand layer on the particles recovery of a quantitative amount of the starting tetraoctylammonium bromide was difficult and we cannot rule out that some small amount of tetraoctylammonium bromide serves in a synergistic capacity to help solubilize the isolated platinum particles. Several exchange reactions were carried out using the isolated Pt nanoparticles. The stearonitrile cap was exchanged for hexadecylmercaptan, octanethiol, and benzeneethylthiol. In a typical exchange reaction, Pt nanoparticles (10 mg) were suspended in hexane (10 mL) and the exchange ligand was added (50 {micro}L). The solutions were allowed to stir overnight and precipitated twice using ethanol. TGA experiments confirmed ligand exchange. We have also shown that these particles may be assembled in a layer by layer (LBL) fashion to build up three dimensional assemblies. As an example of this LBL assembly a substrate consisting of gold electrodes separated by 8 {micro}m on a quartz wafer was first functionalized by immersing in a solution of 1,8-octanedithiol (50 {micro}L) in hexane (10 mL) for 15 min, rinsed with hexane (10 mL), ethanol (10 mL), and dried under a stream of nitrogen. The scaffold was then placed in a toluene solution containing Au nanoparticles capped with stearonitrile (10 mg/mL) for 15 minutes. The scaffold was then rinsed with hexane (10 mL), ethanol (10 mL), and dried under a stream of nitrogen. The substrate was then immersed iteratively between the 1,8-octanedithiol and the Au nanoparticle solution 4 more times.

The synthesis and characterization of soluble and processable high molecular weight polysilsesquioxanes with carboxylate functionalities was discussed. It was found that the tert-butyl functionality in these polymers was eliminated to give carboxylic acids functionalized polysilsesquioxane or methyltin carboxylatosilsesquioxane gels. The analysis showed that the polysilsesquioxane binds and removes tin through gelation.

Abstract not provided.

Abstract not provided.

A variety of organic and hybrid organic-inorganic polymer systems were prepared and evaluated for their bulk response to optical, thermal and chemical environmental changes. These included modeling studies of polyene-bridged metal porphyrin systems, metal-mediated oligomerization of phosphaalkynes as heteroatomic analogues to polyacetylene monomers, investigations of chemically amplified degradation of acid- and base-sensitive polymers and thermally responsive thermoplastic thermosets based on Diels-Alder cycloaddition chemistry. The latter class of materials was utilized to initiate work to develop a new technique for rapidly building a library of systems with varying depolymerization temperatures.

Four of the better developed resist schemes that are outgrowths of DUV (248 and 193 nm) resist development are considered as candidates for EUV. They are as follows: trilayer, a thin imaging layer on top of a refractor masking/pattern transfer layer on top of a planarizing and processing layer (PPL); solution developed, organometallic bilayer where the imaging and masking layer have been combined into one material on top of a PPL; and finally silylated resists. They are examined in a very general form without regard to the specifics of chemistry of the variations within each group, but rather to what is common to each group and how that affects their effectiveness as candidates for a near term EUV resist. In particular they are examined with respect to sensitivity, potential resolution, optical density, etching selectivity during pattern transfer, and any issues associated with pattern fidelity such as swelling.

We recently described a near-surface imaging scheme that employs disilanes and a bilayer resist scheme which together dramatically improve silicon contrast. A relatively thin 0.25 to 0.1 {mu}m imaging layer of a chemically amplified photo-crosslinking resist (Shipley XP-8844 or XP-9472) is spin coated on top of a thicker (0.25-0.5 {mu}m) layer of hard-baked resist (such as Shipley MP-1807). This bilayer scheme improves silicon contrast and provides additional advantages such as providing a planarizing layer and a processing layer.

Recent results in the use of disilanes as silylating reagents for near-surface imaging with deep-UV (248 nm) and EUV (13.5 nm) lithography are reported. A relatively thin imaging layer of a photo-cross-linking resist is spun over a thicker layer of hard-baked resist that functions as a planarizing layer and antireflective coating. Photoinduced acid generation and subsequent heating crosslinks and renders exposed areas impermeable to an aminodisilane that reacts with the unexposed regions. Subsequent silylation and reactive ion etching afford a positive-tone image. The use of disilanes introduces a higher concentration of silicon into the polymer than is possible with silicon reagents that incorporate only one silicon atom per reactive site. The higher silicon content in the silylated polymer increases etching selectivity between exposed and unexposed regions and thereby increases the contrast. Additional improvements that help to minimize flow during silylation are also discussed, including the addition of bifunctional disilanes. We have resolved high aspect ratio, very high quality 0.20 {mu}m line and space patterns at 248 nm with a stepper having a numerical aperture (NA)= 0.53, and have resolved {<=} 0.15 {mu}m line and spaces at 13.5 nm.