Two-Dimensional Infrared Vibrational Echo Spectroscopy Measurements of the Structural Dynamics Occurring in Conducting Polymer Thin Films.

Abstract

The research presented in this thesis is concerned with the elucidation of the origin of structural dynamics and their relationship to charge mobility in conducting polymer systems. In the past thirty years, research in the field of electrically conducting polymers has grown immensely. Interest in such polymers is due mainly to their unique semiconducting properties and thus their potential application in plastic electronics. While it is known that the charge transport of such polymers is linked to their molecular structure, very little is known about the relationship between charge transport and structural dynamics. In particular, this work has focused on the conducting polymers poly(3-hexylthiophene) (P3HT) and polyaniline (PANI). Samples of each polymer were studied using two-dimensional infrared vibrational echo spectroscopy (2D-IR VES), as well as one-dimensional infrared, UV-visible, and fluorescence spectroscopies. Additional characterizations of the polymers were performed, and included transmission electron microscopy (TEM), hole-mobility and resistance measurements. The vibrational echo technique was especially well suited for this study because it removed inhomogeneous broadening and allowed for the monitoring of the time evolution of molecular structure on the picosecond time scale. Viewed together, the studies presented in this work have begun to correlate specific structural dynamics with changes in the film conductivities.