Date of Award

Spring 5-2012

Degree Type

Dissertation

Degree Name

Ph.D.

Degree Program

Chemistry

Department

Chemistry

Major Professor

Tarr Mathew A

Second Advisor

Wiley John B

Third Advisor

Caruntu Gabriel

Fourth Advisor

Zhou Weilie

Fifth Advisor

Mobley David L

Abstract

Dye-sensitized solar cells (DSSCs) have attained considerable attention during the last decade because of the potential of becoming a low cost alternative to silicon based solar cells. Electron transport is one of the prominent processes in the cell and it is further a complex process because the transport medium is a mesoporous film. The gaps in the pores are completely filled by an electrolyte with high ionic strength, resulting in electron-ion interactions. Therefore, the electron transport in these so called state-of-the-art systems has a practical limit because of the low electron diffusion coefficient (Dn) in this mesoporous film photoanode. This work focuses on the influence of the advanced core-shell nanoarchitecture geometry on electron transport and also on the influence of electron-ion interactions. In order to achieve the proposed goals, DSSCs based on ordered, highly aligned, 3D radial core-shell Au-TiO2 hybrid nanowire arrays were fabricated, using three different approaches. J-V, IPCE, and EIS characteristics were studied. The efficiency, light scattering and charge transport properties of the core-shell nanowire based devices were compared to TiO2 nanotube as well as TiO2 mesoporous film based DSSCs. The Au nanowires inside the crystalline TiO2 anatase nanoshell provided a direct conduction path from the TiO2 shell to the TCO substrate and improved transport of electrons between the TiO2 and the TCO. The optical effects were studied by IPCE measurement which demonstrated that Au-TiO2 nanowires showed an improved light harvesting efficiency, including at longer wavelengths where the sensitizer has weak absorption. The metal nanostructures could enhance the absorption in DSSCs by either scattering light enabling a longer optical path-length, localized surface plasmon resonance (LSPR) or by near-field coupling between the surface plasmon polariton (SPP) and the dye excited state. Rapid, radial electron collection is of practical significance because it should allow alternate redox shuttles that show relatively fast electron-interception dynamics to be utilized without significant sacrifice of photocurrent. A combination of improved electron transport and enhanced light harvesting capability make Au-TiO2 core-shell nanowire arrays a promising photoanode nanoarchitecture for improving photovoltaic efficiency while minimizing costs by allowing thinner devices that use less material in their construction.

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The University of New Orleans and its agents retain the non-exclusive license to archive and make accessible this dissertation or thesis in whole or in part in all forms of media, now or hereafter known. The author retains all other ownership rights to the copyright of the thesis or dissertation.

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