UC Berkeley

This dissertation presents a study of thermal and electrical transport phenomena in heterostructures of transition metal oxides, with specific interest in understanding and tailoring thermoelectricity in these systems. Thermoelectric energy conversion is a promising method for waste heat recovery and the efficiency of such an engine is directly related to a material dependent figure of merit, Z, given as S²σ/κ, where S is thermopower and σ and κ are electrical and thermal conductivity respectively. Achieving large figure of merit has been hampered by the coupling between these three thermoelectric coefficients, and the primary aim of this study is to understand the nature of thermoelectricity in complex oxides and identify mechanisms which can allow tuning of one or more thermoelectric coefficients in a favorable manner. Unlike the heavily studied conventional thermoelectric semiconductors, transition metals based complex oxides show conduction band characteristics dominated by d-bands, with much larger effective masses and varying degrees of electron correlations. These systems provide for exotic thermoelectric effects which are typically not explained by conventional theories and hence provide an ideal platform for exploring the limits of thermoelectricity. Meanwhile, oxides are composed of earth abundant elements and have excellent high temperature stability, thus providing compelling technological possibilities for thermoelectrics based power generation. In this dissertation, we address specific aspects of thermoelectricity in model complex oxide systems such as perovskite titanates and layered cobaltates to understand thermal and thermoelectric behavior and explore the tunability of thermoelectricity in these systems.

The demonstration of band engineering as a viable method to tune physical properties of materials is explored. The model system used for this case is strontium titanate, where two dopants such as La on the Sr-site and oxygen vacancies are employed to achieve band engineering. This method was used to obtain tunable transparent conducting properties and thermoelectric properties for heavily doped strontium titanate. The second aspect investigated is the use of strongly correlated materials for thermoelectricity. The cobaltates, specifically layered cobaltates, show large thermopower even at very large carrier densities. The coupling of thermopower and electrical conductivity is shown to be weaker for a strongly correlated material such as cobaltate, which opens up possibilities of complete decoupling of all three thermoelectric coefficients. Finally, the thermal properties of complex oxides, specifically in perovskite titanates, is addressed in detail. Thermal conductivity is demonstrated to be a sensitive probe for defects in a system, where processing conditions play a significant role in modulating the crystallinity of the material. The perovskite titanate superlattice system of strontium titanate and calcium titanate is used beat alloy limit. It also shows interesting period thickness dependent thermal properties. The possible origin of this effect is briefly discussed and future directions for this research is also elaborated in detail.