Carbon/molecule/copper molecular electronic junctions were fabricated by metal deposition of copper onto films of various thicknesses of fluorene (FL), biphenyl (BP), and nitrobiphenyl (NBP) covalently bonded to flat, graphitic carbon. A "crossed-wire" junction configuration provided high device yield and good junction reproducibility. Current/voltage characteristics were investigated for 69 junctions with various molecular structures and thicknesses and at several temperatures. The current/voltage curves for all cases studied were nearly symmetric, scan rate independent, repeatable at least thousands of cycles and exhibited negligible hysteresis. Junction conductance was strongly dependent on the dihedral angle between phenyl rings and on the nature of the molecule/copper "contact". Junctions made with NBP showed a decrease in conductivity of a factor of 1300 when the molecular layer thickness increased from 1.6 to 4.5 nm. The slope of ln(i) vs layer thickness for both BP and NBP was weakly dependent on applied voltage and ranged from 0.16 to 0.24 A(-1). These attenuation factors are similar to those observed for similar molecular layers on modified electrodes used to study electrochemical kinetics. All junctions studied showed weak temperature dependence in the range of approximately 325 to 214 K, implying activation barriers in the range of 0.06 to 0.15 eV. The carbon/molecule/copper junction structure provides a robust, reproducible platform for investigations of the dependence of electron transport in molecular junctions on both molecular structure and temperature. Furthermore, the results indicate that junction conductance is a strong function of molecular structure, rather than some artifact resulting from junction fabrication.

A method of producing solid-phase microextraction (SPME) fibers based on electrospinning polymers into nanofibrous mats is demonstrated. Using this method the polymer mat is attached to a stainless steel wire without the need of a binder. While applicable to any polymer that can be electrospun, a polymeric negative photoresist, SU-8 2100, is used for this initial study. SPME devices composed of carbon nanofibers are also illustrated by pyrolyzing SU-8 to produce amorphous carbon. Nonpolar compounds, benzene, toluene, ethylbenzene, and o-xylene (BTEX) and polar compounds, phenol, 4-chlorophenol and 4-nitrophenol are extracted under headspace SPME conditions. Extraction efficiencies are compared to commercial polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB), and polyacrylate (PA) fibers. For both the nonpolar and polar compounds, the carbon nanofiber based phases demonstrated enhanced or comparable (o-xylene only) extraction efficiencies. Distribution constants, K, for benzene on the electrospun fibers are of greater or similar magnitude to those of the compared commercial fibers and increase with carbonization temperature. Finally, the measured detection limits for all the organic compounds are similar to those measured with other SPME gas chromatography-flame ionization detector (GC-FID) methods with a large linear dynamic range (3 orders of magnitude) for quantification.

Techniques for microfluidic channel fabrication in soda-lime glass and fused quartz using femtosecond laser ablation and ablation in conjunction with polymer coating for surface roughness improvement were tested. Systematic experiments were done to characterize how process variables (laser fluence, scanning speed and focus spot overlap, and material properties) affect the machining feature size and quality. Laser fluence and focus spot overlap showed the strongest influence on channel depth and roughness. At high fluence, the surface roughness was measured to be between 395 nm and 731 nm RMS. At low fluence, roughness decreased to 100 nm-350 nm RMS and showed a greater dependence on overlap. The surface roughness of laser ablation was also dependent on the material properties. For the same laser ablation parameters, soda-lime glass surfaces were smoother than fused quartz. For some applications, especially those using quartz, smoother channels are desired. A hydroxyethyl methacrylate (HEMA) polymer coating was applied and the roughness of the coated channels was improved to 10-50 nm RMS.

The optimization of electrospinning SU-8 2100 negative photoresist was performed to create carbon micro/nanofibers and beads that can be patterned after electrospinning by using UV radiation. The fiber diameters had a range of 300 nm to 1 lm, based upon the selected electrospinning parameters. Low concentrations of the SU-8 2100 resulted in beads while specific higher concentrations produced well-defined fibers. Fibers and beads were converted to carbon through pyrolysis and retained their three dimensional structure. By utilizing the photosensitive properties of the SU-8 negative photoresist, the electrospun fibers were patterned by UV photolithography. The fibers and beads were characterized by SEM and Raman microscopy, respectively. V C 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: [405][406][407][408][409][410][411][412] 2010