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Optoelectronic characterisation techniques are assessed in their application to three solar cell systems. Charge injection barriers are found in PbS/ZnO colloidal quantum dot solar cells through the use of temperature dependent current-voltage and capacitance-voltage measurements. The injection barriers are shown to complicate the Mott-Schottky capacitance analysis which determines built-in bias and doping density. A model that incorporates depletion capacitance and a constant capacitance arising from the injection barriers is given to explain the Mott-Schottky plots. The junction mechanism at the PbS/ZnO interface is found to transition from excitonic to p-n behaviour based on the amount of UV photodoping the cell has received. External quantum efficiency analysis at different photodoping times reveals a growing charge collection region within the material, demonstrating the shift to p-n behaviour. This is further supported by the observance of depletion capacitance behaviour after, but not before, UV photodoping. Defects within GaAs cells containing InAs quantum dots are found to enhance the sub-bandgap performance of the cell using external quantum efficiency analysis. This is verified by illuminated current-voltage analysis using a 1000 nm high pass optical filter to block photons of larger energy than the bandgap. Using capacitance-voltage analysis, high temperature rapid thermal annealing is shown to induce defects in dilute nitride cells, which explains the drop in open circuit voltage compared to lower temperature annealed cells. The doping level of polymer solar cells exposed to air is found to increase with continued exposure using Mott-Schottky capacitance analysis. Current-voltage measurements show the formation of an Al2O3 barrier layer at the polymer/aluminium interface. The usefulness of capacitance-voltage measurements to probe the polymer/fullerene interface is investigated in thermally evaporated thiophene/C60 cells.