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.

Dye-sensitized solar cells (DSC) have attracted considerable scientific and industrial interest during the past decade as an economically feasible alternative to conventional photovoltaic devices. DSCs have the potential to be as efficient as silicon solar cells, but at a fraction of the cost of silicon solar cells. The unique advantage of DSC compared to conventional solar cells is that the light absorption, electron transport and hole transport are handled by different components which reduces the chance of recombination. In the present work, to facilitate DSC with good energy conversion efficiency, its performance have been evaluated as a function of titania layer morphology, redox couple concentration and the catalytic layer on the counter electrode. The results that are obtained in the present investigations have been organized as follows Chapter 1 gives a brief exposure to DSC technology. Special emphasize has been on the structure and individual components of the DSC. Chapter 2 describes various experimental techniques that are employed to fabricate and characterize DSCs under study. Chapter 3 presents a systematic study of the characteristics of DSC made of three different types of electrodes namely: TiO2 nanotubes (TNT) which have excellent electron transport properties, TiO2 microspheres (TMS) which possess high surface area and light scattering ability and TiO2 nano particles (TNP) possessing high surface area. The electronic, morphological, optical and surface properties of individual electrodes are studied. The highest efficiency of 8.03% is obtained for DSCs prepared with TMS electrodes. A higher value of effective diffusion coefficient (Deff) and diffusion length (Ln) of electrons as obtained by electrochemical impedance spectroscopy (EIS) analysis confirms a high charge collection efficiency in microsphere based cell. Chapter 4 gives a detailed study of DSCs fabricated with a tri-layer photo anode with TNTs as light scattering layer. The tri-layer structure has given an enhanced efficiency of 7.15% which is 16% higher than TNP based cell and 40% higher than TNT based cells. Chapter 5 deals with the investigations on the effect of concentration of redox couple on the photovoltaic properties of DSC for different ratios of [I2] to [LiI] (1:2, 1:5 and 1:10) with five viii concentrations of I2 namely 0.01 M, 0.03 M, 0.05 M, 0.08 M and 0.1M in acetonitrile. It is found that the open circuit potential (Voc) decreases with increase in the ratio of redox couple whereas short circuit current density (Jsc) and fill factor (FF) increase. The reason for the decline in Voc is the higher recombination between electrons in the conduction band of TiO2 and the I3- ions present in the electrolyte, induced by the absorptive Li+ ions. In addition using EIS it is found that the τ improves with the increase in [LiI] at a particular [I2], whereas at a fixed [I2]/ [LiI] ratio the increase in [I2] is found to reduce the τ and Deff due to the enhanced recombination. Chapter 6 describes the application of carbon based counter electrode (CE) materials for DSCs. Two counter electrode materials have been investigated namely (1) Multiwalled carbon nanotubes (MWCNT) synthesized by pyrolysis method and (2) Platinum decorated multiwalled carbon nanotubes (Pt/MWCNT) prepared by chemical reduction of platinum precursors. Using Pt/MWCNT composite electrode the DSC achieved an energy conversion efficiency of 6.5 %. From the analysis on symmetric cells, it is found that electro catalytic activity of Pt/MWCNT CE is similar to that of platinum CE, though the platinum loading is very less for the former. This is attributed to the effective utilization of catalyst owing to high surface area arising from the increased surface roughness. Chapter 7 discusses the application of titanium foil in place of glass substrate for the photo anode. The titanium foil offers fabrication of flexible DSC. The performance of DSC with TMS layers and aligned titania nanotube arrays (TNA) prepared by anodization method is studied. Compared to TMS based cell, TNA has given a better efficiency at a lower thickness. Chapter 8 presents the scheme used to seal DSCs and its stability analysis. We have employed the usual hot melt sealing for edge whereas hole sealing is carried out with tooth pick and a UV curable adhesive. The degradation in efficiency is found to be 20% for low efficiency cells whereas, for high efficiency cells it is found to be 45% after 45 days. The leakage of highly volatile acetonitrile through the edge and hole is found to be responsible for the reduction in the performance of the device. Hence a high temperature sealing method is proposed to fabricate stable cells. Chapter 9 gives summary and conclusions of the present work