Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.
Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.
Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.
Open Access Dissertation
Doctor of Philosophy (PhD)
Polymer Science and Engineering
Year Degree Awarded
Month Degree Awarded
Prof. Alfred J. Crosby
Prof. Alejandro L. Briseno
Prof. Ashwin Ramasubramaniam
Polymer and Organic Materials | Semiconductor and Optical Materials
The study of the physical properties of organic crystalline semiconductors has allowed the advent of a new generation of high-performance organic electronic devices. Exceptional charge-transport properties and recent developments in large-area patterning techniques make organic single crystals (OSCs) excellent candidates for their utilization in the next-generation of electronic technologies, including flexible and conformable organic thin-film devices. In spite of the profound knowledge of the structural and electrical properties of OSCs, knowledge of the mechanical properties and the effects of mechanical strain is almost non-existent. This dissertation aims to bring new understanding of the intrinsic mechanical properties and the effect of mechanical strains in charge transport phenomena in organic semiconductors.
The wrinkling instability is chosen as the metrology tool for the effective in-plane elastic constants of OSCs. We demonstrate that the wrinkling instability can be used to obtain the elastic constants of single crystals of rubrene, tetracene, PDIF-CN$_2$ (N,N'-1H,1H-perfluorobutyldicyanoperylene-carboxydi-imide) and perylene. We demonstrate that wrinkling is a practical method to map the in-plane mechanical anisotropy in OSCs. In addition, we utilize wrinkling to characterize how the elastic modulus of pBTTT (poly(2,5-bis(3-alkylthiophen- 2-yl)thieno[3,2-b]thiophene)) changes with increasing molecular weight, from the monomer to the pentamer and the high molecular weight polymer.
To elucidate the effects of mechanical strain on charge transport, we first demonstrate and quantify the existence of a piezoresistive effect in rubrene crystals by the application of bending strains along its b  axis. A piezoresistive coefficient of approximately 11.26 is determined and confirmed through density functional theory (DFT) calculations. Second, we take advantage of wrinkling as a unique way to strain the conducting channel of field-effect transistors in a non-destructive, reversible, and predictable manner. We observe field-effect mobility modulation upon wrinkling and establish that it is controlled by the strain experienced by the insulator-semiconductor interface upon deformation. Finally, we propose a model based on plate bending to quantify the net strain at the insulator-semiconductor interface and predict the change in mobility. These contributions are the first to quantitatively correlate the crystal structure and the mechanical properties of OSCs, as well as the first to study electro-mechanical behavior in OSCs.
Reyes-Martinez, Marcos A., "Mechanical and Electro-Mechanical Properties of Crystalline Organic Semiconductors" (2015). Doctoral Dissertations. 395.