Band Engineering in Thermoelectric Materials Using Optical, Electronic, and Ab-Initio Computed Properties

Thermoelectric materials have demanded a significant amount of attention for their ability to convert waste heat directly to electricity with no moving parts. A resurgence in thermoelectrics research has led to significant enhancements in the thermoelectric figure of merit, zT, even for materials that were already well studied. This thesis approaches thermoelectric zT optimization by developing a detailed understanding of the electronic structure using a combination of electronic/thermoelectric properties, optical properties, and ab-initio computed electronic band structures. This is accomplished by applying these techniques to three important classes of thermoelectric materials: IV-VI materials (the lead chalcogenides), Half-Heusler’s (XNiSn where X=Zr, Ti, Hf), and CoSb₃ skutterudites.

In the IV-VI materials (PbTe, PbSe, PbS) I present a shifting temperature-dependent optical absorption edge which correlates well to the computed ab-initio molecular dynamics result. Contrary to prior literature that suggests convergence of the primary and secondary bands at 400 K, I suggest a higher convergence temperature of 700, 900, and 1000 K for PbTe, PbSe, and PbS, respectively. This finding can help guide electronic properties modelling by providing a concrete value for the band gap and valence band offset as a function of temperature.

Another important thermoelectric material, ZrNiSn (half-Heusler), is analyzed for both its optical and electronic properties; transport properties indicate a largely different band gap depending on whether the material is doped n-type or p-type. By measuring and reporting the optical band gap value of 0.13 eV, I resolve the discrepancy in the gap calculated from electronic properties (maximum Seebeck and resistivity) by correlating these estimates to the electron-to-hole weighted mobility ratio, A, in narrow gap materials (A is found to be approximately 5.0 in ZrNiSn).

I also show that CoSb₃ contains multiple conduction bands that contribute to the thermoelectric properties. These bands are also observed to shift towards each other with temperature, eventually reaching effective convergence for T>500 K. This implies that the electronic structure in CoSb₃ is critically important (and possibly engineerable) with regards to its high thermoelectric figure of merit.

A negatividade enquanto estrutura ontológica da existência segundo Heidegger

A presente dissertação tem por objeto o tema da negatividade ontológica constitutiva da existência humana na obra Ser e Tempo de Martin Heidegger. Na primeira parte é analisada as descrições efetuadas por Heidegger na primeira seção de Ser e Tempo sobre a dinâmica existencial do homem compreendido como ser-aí (Dasein). Nesse primeiro momento é evidenciado o caráter negativo da existência. Para tanto, partiremos da reconstrução dos conceitos de existência e deu seu caráter intencional e poder-ser (Seinkonnen) em Ser e Tempo. Na segunda parte, a análise da tonalidade afetiva da angústia é o ponto de partida para se chegar ao modo de ser do homem, descrito por Heidegger como cuidado (Sorge). Argumentaremos também, que o cuidado é o único modo de ser compatível com um ente que em seu modo de ser mais próprio é marcado por uma negatividade (incompletude) radical. Por último, em nosso terceiro capítulo, apresentaremos, em seus traços gerais, a possibilidade compatível com o caráter de poder-ser do ser-aí: a possibilidade da morte, compreendida ontologicamente como ser-para-a-morte. Na conclusão, apontaremos o interesse maior de Heidegger em investigar a dinâmica existencial do ser-aí. Esse interesse consiste, em visualizar, por meio do que Heidegger chama de crise existencial do ser-aí (proporcionada pela angústia) o ponto de gênese das ontologias.

Three essays on economics and information shocks

A person living in an industrialized society has almost no choice but to receive information daily with negative implications for himself or others. His attention will often be drawn to the ups and downs of economic indicators or the alleged misdeeds of leaders and organizations. Reacting to new information is central to economics, but economics typically ignores the affective aspect of the response, for example, of stress or anger. These essays present the results of considering how the affective aspect of the response can influence economic outcomes.

The first chapter presents an experiment in which individuals were presented with information about various non-profit organizations and allowed to take actions that rewarded or punished those organizations. When social interaction was introduced into this environment an asymmetry between rewarding and punishing appeared. The net effects of punishment became greater and more variable, whereas the effects of reward were unchanged. The individuals were more strongly influenced by negative social information and used that information to target unpopular organizations. These behaviors contributed to an increase in inequality among the outcomes of the organizations.

The second and third chapters present empirical studies of reactions to negative information about local economic conditions. Economic factors are among the most prevalent stressors, and stress is known to have numerous negative effects on health. These chapters document localized, transient effects of the announcement of information about large-scale job losses. News of mass layoffs and shut downs of large military bases are found to decrease birth weights and gestational ages among babies born in the affected regions. The effect magnitudes are close to those estimated in similar studies of disasters.