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One-dimensional nanostructures for opto-electronic and sensing devices

Posted on:2010-09-22Degree:Ph.DType:Thesis
University:University of California, Santa BarbaraCandidate:Schierhorn, MartinFull Text:PDF
GTID:2448390002989624Subject:Chemistry
Abstract/Summary:
This thesis focuses on the synthesis and characterization of oriented, one-dimensional nanostructures for photovoltaic and sensing application. Porous aluminum oxide (PAO) was used as a hard template for nanostructure design. The fabrication of PAO and its use for nanomaterials synthesis are discussed in detail.;The majority of the work presented in this thesis focuses on CdSe nanorod electrode arrays with the nanorods aligned normal to the substrate for photovoltaic applications. Photovoltaic characteristics were determined electrochemically in an aqueous solution using polysulfide (Sn2-) as the redox mediator. Isolating the back electrode from the electrolyte with TiO2 electron blocking layer increased the open circuit voltage from -0.23 V to -0.34 V and the fill factor from 0.42 to 0.57. Depending on the electrolyte concentration, IPCE values between 2.5 and 8% were observed for devices made with freestanding PAO templates at an incident wavelength of 500 nm. Internal quantum efficiencies were estimated to approach 50%. More detailed structure-function relationships could be established when nanorod arrays were fabricated using PAO on solid, transparent substrates. Nanorod lengths were varied between 50 and 500 nm, while keeping the diameter at 65 nm. The electrochemical photovoltaic performance was found to depend critically on nanorod length and crystallinity. Arrays of rods annealed at 500°C showed an order of magnitude improvement in white light power conversion efficiency over unannealed samples. The largest power conversion efficiency of 0.52% was observed for nanorods 445 +/- 82 nm in length annealed at 500°C. Internal quantum efficiencies were measured to be ∼ 45%. The technique described is generally applicable to fabricating highly aligned nanorods of a broad range of materials on a robust transparent conductor.;To test their application for photovoltaic devices, the fabrication of CdSe:P3HT inorganic-organic hybrid solar cells was explored. Initial experiments suggest improved use of the solar spectrum in the blue region when using the hybrid system. A linear dependence of short circuit currents on nanorod length was found. Largest efficiencies of 1.00 +/- 0.14% were determined for devices with rod lengths of 721 +/- 15 nm.;Finally, a technique is described for synthesizing ordered, 2-dimensional arrays of anisotropic metal-silica hybrids. Silver nanoparticles 35 +/- 6 nm in diameter were grown electrochemically into highly-ordered porous aluminum oxide templates (PAO) and covered with silica on all but a small portion of their surfaces. The resulting structure was functionalized with 4-aminobenzenthiol and used as a SERS-active substrate. SERS signal intensities enhanced, on average, by factors ∼10 to 20 (and at times considerably more) resulted from the formation of small aggregates of these encapsulated nanoparticles over an equivalent number of widely spaced arrays of "single" particles. A special feature of this system is the minimization of the silver surface area that is available for analyte binding---significantly reducing the loss of analyte to non-enhancing regions of the substrate as well as decreasing the contribution of impurities and other undesired species to the SERS signals.
Keywords/Search Tags:Photovoltaic, PAO, Devices
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