Morphology of Poly (3,4-Ethylene Dioxythiophene) (PEDOT) Thin Films, Crystals, Cubic Phases, Fibers and Tubes.

Abstract

Poly(3,4-ethylene dioxythiophene) (PEDOT) is a chemically stable, conjugated polymer that is of considerable interest for a variety of organic electronic devices including microfabricated neural electrodes that interface with living cortical tissue. The properties of conducting polymers are strongly dependent on the morphology and structure of the material in the solid-state. The rigid π-π conjugated conformation of PEDOT facilitates charge transport and favors crystallization that reduces solubility and processability, making detailed studies of PEDOT morphology difficult. This has also made it hard to control the microstructure at a variety of length scales. In this dissertation the morphology of PEDOT has been studied and controlled at several different length scales from nanometers to micrometers. On the nanoscale, the primary intermolecular (100) d-spacing in PEDOT crystals has been controlled from 1.15 nm to 1.52 nm by using different counter-ions as dopants. The surface morphology and crystallinity of electrochemically deposited PEDOT films have been controlled by changing deposition conditions. A highly ordered, crystalline PEDOT-Br phase was formed during electrochemical deposition in the presence of bromine counterions. On the tens of nanometers scale, isotropic PEDOT bicontinuous cubic structures with extremely large surface areas were developed using ternary non-ionic surfactant, water and oil systems. On the micrometer scale, aligned PEDOT fibers and tubes were prepared by electrospinning blends of poly(lactide-co-glycolide) (PLGA) or poly(caprolactone) (PCL) and EDOT monomer onto a rotating wheel or a dielectric gap in a metal substrate. These aligned fibers and tubes were shown to precisely direct neural regeneration in specific directions in vitro. These developments help understand the structure and properties of conjugated polymers for use in organic electronic devices.