Publications

We have investigated the thermochromic transition of an ultrathin poly(diacetylene) film. The Langmuir film is composed of three layers of polymerized 10,12-pentacosadiynoic acid [CH{sub 3}(CH{sub 2}){sub 11}C{triple_bond}CC{triple_bond}C(CH{sub 2}){sub 8}COOH] (poly-PCDA) organized into crystalline domains on a silicon substrate. Spectroscopic ellipsometry and fluorescence intensity measurements are obtained with in-situ temperature control. Poly-PCDA films exhibit a reversible thermal transition between the initial blue form and an intermediate ''purple'' form that exists only at elevated temperature (between 303-333 K), followed by an irreversible transition to the red form after annealing above 320 K. We propose that the purple form is thermally distorted blue poly-PCDA, and may represent a transitional configuration in the irreversible conversion to red. This hypothesis is supported by the appearance of unique features in the absorption spectra for each form as derived from the ellipsometry measurements. Significant fluorescence emission occurs only with the red form, and is reduced at elevated temperatures while the absorption remains unchanged. Reduced emission is likely related to thermal fluctuations of the hydrocarbon side chains. Time-resolved fluorescence measurements of the irreversible transition have been performed. Using a first-order kinetic analysis of these measurements we deduce an energy barrier of 17.6 {+-} 1.1 kcal mol{sup -1} between the blue and red forms.

This study examines adhesion between silane-coated micromachined surfaces that are exposed to humid conditions. Our quantitative values for interfacial adhesion energies are determined from an in-situ optical measurement of deformations in partly-adhered cantilever beams. We coated micromachined cantilevers with either ODTS (C{sub 18}H{sub 37}SiCl{sub 3}) or FDTS (C{sub 8}F{sub 17}C{sub 2}H{sub 4}SiCl{sub 3}) with the objective of creating hydrophobic surfaces whose adhesion would be independent of humidity. In both cases, the adhesion energy is significantly lower than for uncoated, hydrophilic surfaces. For relative humidities (RH) less than 95% (ODTS) and 80% (FDTS) the adhesion energy was extremely low and constant. In fact, ODTS-coated beams exposed to saturated humidity conditions and long (48 hour) exposures showed only a factor of two increase in adhesion energy. Surprisingly, FDTS coated beams, which initially have a higher contact angle (115{degree}) with water than do ODTS coated beams (112{degree}), proved to be much more sensitive to humidity. The FDTS coated surfaces showed a factor of one hundred increase in adhesion energy after a seven hour exposure to 90% RH. Atomic force microscopy revealed agglomerated coating material after exposed to high RH, suggesting a redistribution of the monolayer film. This agglomeration was more prominent for FDTS than ODTS. These findings suggest a new mechanism for uptake of moisture under high humidity conditions. At high humidities, the silane coatings can reconfigure from a surface to a bulk phase leaving behind locally hydrophilic sites which increase the average measured adhesion energy. In order for the adhesion increase to be observed, a significant fraction of the monolayer must be converted from the surface to the bulk phase.

This is the final report of an LDRD program entitled 'Scanning Probe-Based Processes for Nanometer-Scale Device Fabrication'. This program intends to expand Sandia's expertise in scanning-probe based fabrication and characterization of nanostructures. Our object is to achieve an order of magnitude decrease in feature size compared to conventional fabrication technology. We are exploring approaches to nanostructure fabrication and characterization using scanning probe-based (STM, AFM). We also are developing numerical simulations of localized electric field and emission current to explore mechanisms and characterize limits to processing techniques. We emphasize novel fabrication processes and characterization of physical, chemical and electronic effects in nanostructures.

We study the evolution of layer morphology during the early stages of metal chemical vapor deposition (CVD) onto Si(100) via pyrolysis of Fe(CO){sub 5} below 250{degrees}C. Scanning tunneling microscopy (STM) shows that nuclei formation is limited by precursor dissociation which occurs on terraces, not at step sites. Also, the average size of clusters formed during CVD is larger than for Fe growth by evaporation (a random deposition process). Based on STM data and Monte Carlo simulations, we conclude that the CVD-growth morphology is affected by preferential dissociation of Fe(CO){sub 5} molecules at existing Fe clusters -- an autocatalytic effect. We demonstrate that nucleation kinetics can be used to control formation of metal nanostructures on chemically tailored surfaces. Reactive sites on Si (001) are first passivated by hydrogen. H atoms are locally removed by electron stimulated desorption using electrons emitted from the STM tip. Subsequent pyrolysis of Fe(CO){sub 5} leads to selective nucleation and growth of Fe films in the areas where H has been removed.