When a temperature differential is applied across a semiconductor, a thermal voltage develops across it in response. The ratio of this thermal voltage to the applied temperature differential is the Seebeck coefficient, a transport coefficient that complements measurements of electrical and thermal conductivity. The physical interpretation of the Seebeck coefficient is the entropy per charge carrier divided by its charge and is hence a direct measurement of the carrier entropy in the solid state.

This PhD thesis has three major outcomes. The first major outcome is a demonstration of how the Seebeck coefficient can be used as a tool to quantify the role of energetic disorder in organic semiconductors. To this end, a microfabricated chip was designed to perform accurate measurements of the Seebeck coefficient within the channel of the active layer in a field-effect transistor (FET). When measured within an FET, the Seebeck coefficient can be modulated using the gate electrode. The extent to which the Seebeck coefficient is modulated gives a clear idea of charge carrier trapping and the distribution of the density of states within the organic semiconductor.

The second major outcome of this work is the observation that organic semiconducting polymers show Seebeck coefficients that are temperature independent and strongly gate voltage modulated. The extent to which the Seebeck coefficient is modulated in the polymer PBTTT is found to be larger than that in the polymer IDTBT. Taken together with conventional charge transport measurements on IDTBT, the voltage modulated Seebeck coefficient confirms the existence of a vanishingly small energetic disorder in this material.

In the third and final outcome of this thesis, the magnitude of the Seebeck coefficient is shown to be larger for organic small molecules as compared to organic polymers. The basis for this is not yet clear. There are reports that such an observation is substantiated through a larger contribution from vibrational entropy that adds to the so called entropy-of-mixing contribution so as to boost the magnitude of the Seebeck coefficient in organic small molecules. As of now, this remains an open question and is a potential starting point for future work.

The practical implications of this PhD thesis lie in building cost-effective and environmentally friendly waste-heat to useful energy converters based on organic polymers. The efficiency of heat to energy conversion by organic polymers tends to be higher than that for conventional semiconductors owing to the presence of narrow bands in organic polymer semiconductors.