Author ORCID Identifier

https://orcid.org/0000-0002-9789-4383

Date Available

11-5-2025

Year of Publication

2025

Document Type

Doctoral Dissertation

Degree Name

Doctor of Philosophy (PhD)

College

Arts and Sciences

Department/School/Program

Chemistry

Faculty

Dr. John E. Anthony

Abstract

Organic semiconductor materials (OSCs) are rapidly becoming a vital part of the technological landscape. They possess unique properties that make them attractive for the electronics industry. Relatively low-temperature and low-cost processing are a large part of the promise of OSCs. Perhaps more importantly, organic materials can be modified in a relatively straightforward manner, presenting an opportunity for them to be tuned and adapted to a variety of purposes and applications. Polycyclic aromatic hydrocarbons (PAHs) form a large group within the field of OSC research. Some of the most promising high-performance materials in this category to-date are acenes and heteroacenes. This manuscript focuses on the development of new acene- and heteroacene-based OSCs and strengthening the field's understanding of how modification of OSC molecular structures can affect the crystallographic structure and properties of the resulting material.

Chapter 2 explores the systematic variation of trialkylsilylethynyl solubilizing groups on pentacene and anthradithiophene OSC chromophores, with a focus on linking molecular modification to resultant changes in the crystal packing of the material. A new design principle for pentacene-based OSCs is presented, namely a focus on isotropicity in electronic coupling through geometric alignment. Additionally, several novel high-performance pentacene and anthradithiophene OSCs and their development are discussed.

Chapter 3 covers the design and crystal engineering of trimeric benzodithiophene OSCs. The effects of changing heteroatoms in the chromophore are explored, including the detailed analysis of intermolecular interactions in the crystal structures of a series of benzodifuran, benzodithiophene, benzodiselenophene, and naphthothiophene materials. A new method of harnessing CH-pi interactions in solubilizing groups to guide the formation of desired crystal structures is detailed. The role of selective fluorination in this class of OSCs is also evaluated.

Chapter 4 expands upon chapter 3 by introducing a related class of trimeric OSCs based on trimeric heteroacene chromophores with a novel method of attaching solubilizing groups, namely silylphenyl and silylthiophenyl connectors rather than silylethynyl. This chapter also describes the design and synthesis of several isoindigo derivatives, along with evaluation of their suitability for n-type semiconductor devices.

Digital Object Identifier (DOI)

https://doi.org/10.13023/etd.2025.485

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