The Effect of Network Geometry on Electron Transport in a Titanium Dioxide Photoanode of a Dye-sensitized Solar Cell
Item
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Title
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The Effect of Network Geometry on Electron Transport in a Titanium Dioxide Photoanode of a Dye-sensitized Solar Cell
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Identifier
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d_2009_2013:6bddeeee6001:11808
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identifier
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12420
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Creator
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Mathew, Sonia Susan,
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Contributor
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Ilona Kretzschmar
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Date
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2013
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemical engineering | Energy | Materials science | Dye-sensitized Solar Cell | Electrochemistry | Inverse Opals | Photoelectrochemical Cells | Synthesis | Titanium dioxide
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Abstract
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The dye sensitized solar cell (DSSC) is a photoelectrochemical cell that has garnered considerable attention because of its high efficiencies and potentially low production costs. The technology is based on a layer of mesoscopic TiO 2 particles, which significantly increases the optical path of the incident light that is harvested by the surface-anchored sensitizer molecules, whilst keeping an efficient contact with the electrolytic solution. The solar cell configuration that first achieved a high efficiency (∼7.5%) had a randomly connected network of titania nanoparticles, ruthenium polypyridyl complexes as the sensitizer, and an iodide/triiodide redox couple dissolved in an organic electrolyte.;While the disordered nanoparticle network has a high surface area which maximizes the photogenerated electron density, the nanostructure also has a large number of surface states. These surface states act as traps and are known to limit the transport of electrons within such electrodes thereby hindering progress in achieving higher efficiencies. The structural disorder at the contact between two crystalline nanoparticles leads to enhanced scattering of free electrons, thus reducing electron mobility. An interconnected photoanode architecture offers the potential for improved electron transport by reducing the degree of disorder.;This Thesis investigates the effect of the TiO2 network geometry on electron movement within the DSSC. In this regard, inverse opal structures with hexagonally close-packed pores and macroscopic (∼microm) order are synthesized and evaluated qualitatively and quantitatively (via FFT) with respect to their degree of interconnectedness. An inverse opal TiO2 electrode possesses advantages that supplement those of current disordered electrodes: (a) high surface area for dye adhesion, (b) large area contact between the sensitizer and the electrolyte, which aids electron transfer reactions, and (c) scattering of incident radiation due to the inherent diffraction properties of the structures, which increases the path length.;The TiO2 inverse opals are fabricated via self-assembly of colloidal particles and subsequent infiltration of the colloidal assembly with a TiO2 precursor. Heat treatment at elevated temperatures (450 °C) leads to crystalline TiO2 formation and removal of the templating colloids. Several methods of fabrication are evaluated to determine the best methods of fabrication for inverse opals of different pore sizes (0.5 microm to 10 microm). Optimum fabrication methods are determined for each particle size in the range studied.;The TiO2 inverse opals (0.1 microm to 1 microm) are exposed to an aqueous electrolyte to evaluate their electrochemical behavior. The number of surface traps is found to scale with the surface area per unit volume of the inverse opal electrodes. Compared to the standard disordered nanoporous electrode, the inverse opals show better conductivity and are less prone to recombination. The TiO2 inverse opals (0.1 microm to 1 microm) are also tested within a DSSC configuration, and illuminated with light from a compact fluorescent bulb to mimic lighting conditions ranging from indoor to outdoor conditions. The power output of the inverse opal electrodes is almost three times higher than the nanoparticle analog at low-light intensities, indicating the advantage of the interconnected nanostructure of the inverse opal electrodes under indoor light conditions. In contrast, the disordered nanoporous electrode wins out in outdoor light conditions, providing evidence that inverse opal structured electrodes have their market in indoor applications.
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Type
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dissertation
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Source
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2009_2013.csv
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degree
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Ph.D.
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Program
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Engineering
