Engineering Materials Properties and Process Technologies for Electronic and Energy Applications

Abstract

In this thesis, we pushed the boundaries of knowledge toward exciting new alternatives in the fields of electronic materials and energy. In Part 1, we focused on organic semiconductors, assessing how disorder on different length scales impacts the electrical properties in organic thin-film transistors (OTFTs). We first explored the effect of disorder at the molecular scale due to the coexistence of isomers in thin films. By blending fractional quantities of syn and anti isomers of triethylsilylethynyl anthradithiophene (TES ADT), we found that the electrical properties of devices comprising the anti isomer plummet to that of syn after the addition of only 10% syn. Through single-crystal computational analysis, we determined that the addition of syn disorders the two-dimensional electronic coupling between anti molecules, thereby increasing charge trapping and decreasing mobilities in OTFTs with increasing syn concentrations in the active layers.

We also elucidated the impact of disorder stemming from boundaries between crystalline superstructures in polycrystalline thin films. By measuring the electrical characteristics of OTFTs across interspherulite boundaries (ISBs) in TES ADT and rubrene thin films, we found the energy barriers for charge transport across ISBs to be more akin to those found across the boundaries between polymer crystallites than between conventional molecular-semiconductor grains. In contrast to sharp, creviced grain boundaries, ISBs presumably comprise trapped molecules that electrically connect neighboring spherulites, as polymer chains connect crystallites in polymer-semiconductor thin films.

In Part 2, we turned our focus to the production of alternative liquid fuels, evaluating process designs to produce “drop-in” replacement diesel and gasoline from non-food biomass and domestic natural gas. By considering the storage of captured byproduct CO2 in nearby depleted shale-gas wells, these processes produce liquid fuels with low-to-negative lifecycle greenhouse-gas emissions. We assessed the economics of these processes under a range of effective emissions prices, finding that fuels from first-of-a-kind facilities will compete with petroleum-derived fuels when the prices of crude oil and emissions are at least $100/bbl and $250/tCO2,eq, respectively. Since “learning by doing” facilitates economic competitiveness, we estimate that fuels from future plants will compete at oil prices as low as $85/bbl without any emissions price.