Portland State University. Departmentof Chemistry
Date of Award
Doctor of Philosophy (Ph.D.) in Chemistry
1 online resource (xiv, 130 p.) : ill.
Dye-sensitized solar cells, Solar cells -- Research, Photovoltaic power generation
In order to become a viable alternative to silicon photovoltaics, dye-sensitized solar cells must overcome several issues primarily resulting from their use of a liquid electrolyte. Much research has gone into correcting these shortcomings by replacing the liquid electrolyte with solid-state hole-transport media. Using these solid-state materials brings new difficulties, such as completely filling the pores in the TiO₂nanostructure, and achieving good adhesion with the dye-coated TiO₂. A novel approach to addressing these difficulties is the inverse dye-sensitized solar cell design. In this method the devices are constructed in reverse order, with the solid-state hole-transport medium providing the nanostructure instead of the TiO₂. This allows new materials and methods to be used which may better address these issues. In this project, inverse dye-sensitized solar cells using polyaniline nanofibers as the hole transport medium were prepared and characterized. The devices were prepared on fluorine-doped tin oxide (FTO) coated glass electrodes. The first component was a dense spin-coated polyaniline blocking layer, to help prevent short circuiting of the devices. The second layer was a thin film of drop cast polyaniline nanofibers which acted as the hole transport medium and provided high surface area for the dye attachment. The dye used was 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP), which was covalently attached to the nanofibers using a Friedel-Crafts acylation. Titania gel was then deposited into the pores of the nanofiber film by controlled hydrolysis of a titanium complex (Tyzor LA). A back electrode of TiO₂nanoparticles sintered on FTO was pressed on top to complete the devices. A typical device generated an open circuit voltage of 0.17 V and a closed circuit current of 5.7 nA/cm² while the highest open circuit voltage recorded for any variation on a device was 0.31 V and the highest short circuit current was 52 nA/cm² under AM 1.5 simulated olar spectrum at 100 mW/cm². Initially prepared devices did not generate a measureable photocurrent due to two materials flaws. The first was traced to the poorly developed conduction band of the titania gel, as deposited from Tyzor LA hydrolysis, resulting in poor electron conduction. This prevented the titania gel from efficiently functioning as the electron transport medium. A remedy was found in adding a layer of sintered anatase TiO₂nanoparticles on the back electrode to serve as the electron transport medium. However, this remedy does not address the issue of the inability of titania gel to efficiently transport electrons photogenerated deep in the nanofiber film to the back electrode. The second flaw was found to originate from fast recombination kinetics between electrons in TiO₂and holes in polyaniline. However, a positive feature was that the titania gel intended to be used as the electron transport medium was found to sufficiently insulate the interface such that the recombination rate slowed enough to allow generation of a measureable photocurrent. Electronic insulation was further enhanced by co-attaching decanoic acid onto the polyaniline nanofibers to fill in pinholes between the dye molecules. While these solutions were not ideal, they were intended to be diagnostic in nature and supplied critical information about the weak links in the device design, thus pointing the way toward improving device performance. Significant enhancements can be expected by addressing these issues in further detail.
Hesselsweet, Ian Brock, "Polyaniline Nanofibers as the Hole Transport Medium in an Inverse Dye-Sensitized Solar Cell" (2010). Dissertations and Theses. Paper 710.