Understanding and Designing Carbon-based Thermoelectric Materials with Atomic-Scale Simulations

Thermoelectric (TE) materials, which can convert unused waste heat into useful electricity or vice versa, could play an important role in solving the current global energy challenge of providing sustainable and clean energy. Nevertheless, thermoelectrics have long been too inefficient to be utilized due to the relatively low energy conversion efficiency of present thermoelectrics. One way to obtain improved efficiency is to optimize the so-called TE figure of merit, ZT = SM/bc, which is determined by the transport properties of the active layer material. To this end, higher-efficiency thermoelectrics will be enabled by a deep understanding of the key TE properties, such as thermal and charge transport and the impact of structural and chemical changes on these properties, in turn providing new design strategies for improved performance. To discover new classes of thermoelectric materials, computational materials design is applied to the field of thermoelectrics. This thesis presents a theoretical investigation of the influence of chemical modifications on thermal and charge transport in carbon-based materials (e.g., graphene and crystalline C60 ), with the goal of providing insight into design rules for efficient carbon-based thermoelectric materials. We carried out a detailed atomistic study of thermal and charge transport in carbon-based materials using several theoretical and computational approaches equilibrium molecular dynamics (EMD), lattice dynamics (LD), density functional theory (DFT), and the semi-classical Boltzmann theory. We first investigated thermal transport in graphene with atomic-scale classical simulations, which has been shown that the use of two-dimensional (2D) periodic patterns on graphene substantially reduces the room-temperature thermal conductivity compared to that of the pristine monolayer. This reduction is shown to be due to a combination of boundary effects induced from the sharp interface between sp 2 and sp 3 carbon as well as clamping effects induced from the