Inorganic nanoclusters dispersed in organic matrices are of importance to a number of emerging technologies. However, obtaining useful properties from such organic-inorganic composites often requires high concentrations of well-dispersed nanoclusters. In order to achieve this goal the chemistry of the particle surface and the matrix must be closely matched. This is based on the premise of minimization of the interfacial free energy; an excess of free energy will cause phase separation and ultimately aggregation. Thus, the optimal system is one in which the nanoclusters are stabilized by the same molecules that make up the encapsulant. Yet, the organic matrix is typically chosen for its bulk properties, and therefore may not be amenable to chemical modification. Also, the organic-inorganic interface is often critical to establishing and maintaining the desired nanocluster (and hence composite) properties, placing further constraints on proposed chemical modification. For these reasons we have adopted the use of aminefunctionalized trimethoxysilanes (ormosils) as an optical grade encapsulant. In this work, we demonstrate that ormosils can produce beneficial optical effects that are derived from interfacial phenomena, which can be maintained throughout the encapsulation process.
Single layer transition metal sulfides (SLTMS) such as MoS{sub 2}, WS{sub 2}, and ReS{sub 2}, play an important role in catalytic processes such as the hydrofining of petroleum streams, and are involved in at least two of the slurry-catalyst hydroconversion processes that have been proposed for upgrading heavy petroleum feed and other sources of hydrocarbon fuels such as coal and shale oils. Additional promising catalytic applications of the SLTMS are on the horizon. The physical, chemical, and catalytic properties of these materials are reviewed in this report. Also discussed are areas for future research that promise to lead to advanced applications of the SLTMS.
This SAND report is the final report on Sandia's Grand Challenge LDRD Project 27328, 'A Revolution in Lighting -- Building the Science and Technology Base for Ultra-Efficient Solid-state Lighting.' This project, which for brevity we refer to as the SSL GCLDRD, is considered one of Sandia's most successful GCLDRDs. As a result, this report reviews not only technical highlights, but also the genesis of the idea for Solid-state Lighting (SSL), the initiation of the SSL GCLDRD, and the goals, scope, success metrics, and evolution of the SSL GCLDRD over the course of its life. One way in which the SSL GCLDRD was different from other GCLDRDs was that it coincided with a larger effort by the SSL community - primarily industrial companies investing in SSL, but also universities, trade organizations, and other Department of Energy (DOE) national laboratories - to support a national initiative in SSL R&D. Sandia was a major player in publicizing the tremendous energy savings potential of SSL, and in helping to develop, unify and support community consensus for such an initiative. Hence, our activities in this area, discussed in Chapter 6, were substantial: white papers; SSL technology workshops and roadmaps; support for the Optoelectronics Industry Development Association (OIDA), DOE and Senator Bingaman's office; extensive public relations and media activities; and a worldwide SSL community website. Many science and technology advances and breakthroughs were also enabled under this GCLDRD, resulting in: 55 publications; 124 presentations; 10 book chapters and reports; 5 U.S. patent applications including 1 already issued; and 14 patent disclosures not yet applied for. Twenty-six invited talks were given, at prestigious venues such as the American Physical Society Meeting, the Materials Research Society Meeting, the AVS International Symposium, and the Electrochemical Society Meeting. This report contains a summary of these science and technology advances and breakthroughs, with Chapters 1-5 devoted to the five technical task areas: 1 Fundamental Materials Physics; 2 111-Nitride Growth Chemistry and Substrate Physics; 3 111-Nitride MOCVD Reactor Design and In-Situ Monitoring; 4 Advanced Light-Emitting Devices; and 5 Phosphors and Encapsulants. Chapter 7 (Appendix A) contains a listing of publications, presentations, and patents. Finally, the SSL GCLDRD resulted in numerous actual and pending follow-on programs for Sandia, including multiple grants from DOE and the Defense Advanced Research Projects Agency (DARPA), and Cooperative Research and Development Agreements (CRADAs) with SSL companies. Many of these follow-on programs arose out of contacts developed through our External Advisory Committee (EAC). In h s and other ways, the EAC played a very important role. Chapter 8 (Appendix B) contains the full (unedited) text of the EAC reviews that were held periodically during the course of the project.
Fe nanoparticles prepared by iron carbonyl decomposition using different methods are compared structurally, chemically, and magnetically. The specific magnetization of the particles was determined from the magnetic moment, the particle size observed by transmission electron microscopy, and the total iron concentration found from calibrated X-ray fluorescence. The volume fraction of oxide is reported for particles of different sizes and for particles made by slightly different techniques.
Presented within this report are the results of a brief examination of optical tagging technologies funded by the Laboratory Directed Research and Development (LDRD) program at Sandia National Laboratories. The work was performed during the summer months of 2002 with total funding of $65k. The intent of the project was to briefly examine a broad range of approaches to optical tagging concentrating on the wavelength range between ultraviolet (UV) and the short wavelength infrared (SWIR, {lambda} < 2{micro}m). Tagging approaches considered include such things as simple combinations of reflective and absorptive materials closely spaced in wavelength to give a high contrast over a short range of wavelengths, rare-earth oxides in transparent binders to produce a narrow absorption line hyperspectral tag, and fluorescing materials such as phosphors, dies and chemically precipitated particles. One technical approach examined in slightly greater detail was the use of fluorescing nano particles of metals and semiconductor materials. The idea was to embed such nano particles in an oily film or transparent paint binder. When pumped with a SWIR laser such as that produced by laser diodes at {lambda}=1.54{micro}m, the particles would fluoresce at slightly longer wavelengths, thereby giving a unique signal. While it is believed that optical tags are important for military, intelligence and even law enforcement applications, as a business area, tags do not appear to represent a high on return investment. Other government agencies frequently shop for existing or mature tag technologies but rarely are interested enough to pay for development of an untried technical approach. It was hoped that through a relatively small investment of laboratory R&D funds, enough technologies could be identified that a potential customers requirements could be met with a minimum of additional development work. Only time will tell if this proves to be correct.
Experiments using high-resolution size exclusion chromatography (HRSEC), dynamic light scattering, and transmission electron microscopy are conducted to investigate the effects of aging of Au nanoclusters in the presence of surfactant ligands. It is observed that contrary to the expectation that aging in solution will always broaden the size dispersion and increase the average size (Ostwald ripening), a narrowing of the size dispersion and change in average size can occur with time under ambient conditions.
We report studies of the magnetic response of dilute frozen solutions of nanocrystalline Co particles grown in inverse micelles. Crystalline nanoclusters which initially exhibit only a small fraction of the bulk saturation moment restructure in solution without any change in cluster size or blocking temperature over a period of {approx}30-60 days, finally yielding a moment/atom which exceeds that of bulk Co. The saturation magnetism maintains its enhanced value for temperatures up to the melting point of the solvent matrix, but is strongly dependent on surface active additives and molecular oxygen.
We report high-pressure liquid chromatography (HPLC) and transmission electron microscopy (TEM) studies of the size distributions of nanosize gold clusters dispersed in organic solvents. These metal clusters are synthesized in inverse micelles at room temperature, and those investigated range in diameter from 1 to 10 nm. HPLC is sensitive enough to discern changes in hydrodynamic volume corresponding to only 2 carbon atoms of the passivating agent or metal core size changes of less than 4 angstrom. We have determined for the first time how the total cluster volume (metal core + passivating organic shell) changes with the size of the passivating agent.
Highly crystalline germanium (Ge) nanocrystals in the size range 2--10 nm were grown in inverse micelles and purified and size-separated by high pressure liquid chromatography with on-line optical and electrical diagnostics. The nanocrystals retain the diamond structure of bulk Ge down to at least 2.0 nm (containing about 150 Ge atoms). The background- and impurity-free extinction and photoluminescence (PL) spectra of these nanocrystals revealed rich structure which was interpreted in terms of the bandstructure of Ge shifted to higher energies by quantum confinement. The shifts ranged from {minus}0.1 eV to over 1 eV for the various transitions. PL in the range 350--700 nm was observed from nanocrystals 2--5 nm in size. The 2.0 nm nanocrystals yielded the most intense PL (at 420 nm) which is believed to be intrinsic and attributed to direct recombination at {Gamma}. Excitation at high energy (250 nm) populates most of the conduction bands resulting in competing recombination channels and the observed broad PL spectra.
Pentachlorophenol (PCP) is a toxic chlorinated aromatic molecule widely used as fungicide, a bactericide and a wood preservation, and thus ubiquitous in the environment. The authors report photo-oxidation of PCP using a variety of nanosize semiconductor metal oxides and sulfides in both aqueous and polar organic solvents and compare the photo-oxidation kinetics of these nanoclusters to widely studied bulk powders like Degussa P-25 TiO{sub 2} and CdS. They study both the light intensity dependence of PCP photooxidation for nanosize SnO{sub 2} and the size dependence of PCP photooxidation for both nanosize SnO{sub 2} and MoS{sub 2}. They find an extremely strong size dependence for the latter which they attribute to its size-dependent band gap and the associated change in redox potentials due to quantum confinement of the hole-electron pair. The authors show that nanosize MoS{sub 2} with a diameter of d=3.0 nm and an absorbance edge of {approximately}450 nm is a very effective photooxidation catalyst for complete PCP mineralization, even when using only visible light irradiation.
The authors have used a nonionic inverse micelle synthesis technique to form nanoclusters of platinum and palladium. These nanoclusters can be rendered hydrophobic or hydrophilic by the appropriate choice of capping ligand. Unlike Au nanoclusters, Pt nanoclusters show great stability with thiol ligands in aqueous media. Alkane thiols, with alkane chains ranging from C{sub 6} to C{sub 18} were used as hydrophobic ligands, and with some of these they were able to form 2-D and/or 3-D superlattices of Pt nanoclusters as small as 2.7 nm in diameter. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function of the particle centers, from which they can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the gaps between particles within superlattice domains increases, but more slowly than one might expect, possibly indicating thiol chain interdigitation.
The authors have investigated the formation of 2-D and 3-D superlattices of Au nanoclusters synthesized in nonionic inverse micelles, and capped with alkyl thiol ligands, with alkane chains ranging from C{sub 6} to C1{sub 18}. The thiols are found to play a significant role in the ripening of these nanoclusters, and in the formation of superlattices. Image processing techniques were developed to reliably extract from transmission electron micrographs (TEMs) the particle size distribution, and information about the superlattice domains and their boundaries. The latter permits one to compute the intradomain vector pair correlation function, from which one can accurately determine the lattice spacing and the coherent domain size. From these data the gap between the particles in the coherent domains can be determined as a function of the thiol chain length. It is found that as the thiol chain length increases, the nanoclusters become more polydisperse and larger, and the gaps between particles within superlattice domains increases. Annealing studies at elevated temperatures confirm nanocluster ripening. Finally, the effect of the particle gaps on physical properties is illustrated by computing the effective dielectric constant, and it is shown that the gap size now accessible in superlattices is rather large for dielectric applications.
Wellner, A.; Nellis, P.D.; Palmer, R.E.; Aindow, M.; Wilcoxon, Jess P.
The influence of the substrate on the translational and orientational ordering in sub-monolayer films of passivated multiply-twinned gold clusters has been investigated using high resolution and dark field transmission electron microscopy. Although clear differences were observed in the degree of translational ordering on amorphous carbon and etched silicon substrates, there was no corresponding variation in the crystallographic orientation of the nanocrystal cores. The results demonstrate that the orientation of passivated clusters with multiply-twinned cores is effectively random with respect to both the superlattice and the substrate.