Models for electron transport and back reaction in dye-sensitized nanocrystalline solar cells were investigated by developing novel measurement techniques and the results were used to test two complementary models; diffusive electron transport within the TiO2 medium and the quasi-static approximation to deal with non steady-state conditions where trapping plays a role. These will be shown to be partly correct and the shortfalls highlighted and discussed. In the end it was found that more knowledge of the parameters governing the behaviour of electrons is required to further test and develop the models. The incorporation of a secondary sensing electrode allowed the internal quasi-Fermi level (QFL) within the TiO2 to be probed. The behaviour of the voltage measured by the secondary sensing electrode was in accordance with diffusive electron transport in the TiO2. This was confirmed by measuring the QFL along the current-voltage curve of the cell, and by the temperature dependence of the measured QFL. Discrepancies concerning the behaviour of the ideality of the open-circuit voltage (and hence the electron lifetime) between experiment and modelling are highlighted and discussed throughout. Assuming an Arrhenius relationship simple expressions for the temperature dependence of the open-circuit voltage were derived and experimentally tested. The trapped electron density was measured along the current-voltage curve. With the inclusion of the secondary sensing electrode and measuring the trap distribution, the way the trapped charge varied could be modelled and compared to experiment. This provided an important link between the free and trapped electron density profiles but again highlighted shortcomings of the applied models. The quasi-static approximation was tested against a full numerical solution (continuum model) to determine the phase space in which it is applicable. Knowing this, an almost ideally behaving cell was used to test the quasi-static approximation. Having shown that it was valid for the given cell, the quasi-static approximation was used to determine how the conduction band electron lifetime varied with temperature, resulting in an Arrhenius dependence of the back reaction rate of electrons. A strong temperature dependence of the electron lifetime, and hence a strong temperature dependence of the electron diffusion length was demonstrated.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:442040 |
| Date | January 2007 |
| Creators | Lobato, Killian Paulo Kiernan |
| Contributors | Peter, Laurence |
| Publisher | University of Bath |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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