Spectro-electrochemical studies of [conjugated] polymer single-molecules, nanoparticles, and thin films

Conjugated polymers are widely used and rapidly developed in practical polymer-based light-emitting electronic devices. Understanding the electrochemical reaction of conjugated polymer has become essential in the design and operation of devices such as electrochemical light-emitting diodes. In particular, we have studied the dynamics and kinetics of oxidation/reduction behavior of conjugated polymer single-molecules and nanoparticles in order to obtain the molecular level properties of deeply trapped holes in organic semiconductor devices. Theoretical calculations suggest the penetration of ions and solvent molecules effectively stabilizes the injected charges, which allows homogeneous charge distribution and further hole injection. The formation and decay of deep traps have been explored by changing the charging rate and duration. We found that the laser excitation significantly promotes the untrapping of deep holes. Electrogenerated chemiluminescence of single nanoparticles has been investigated to unravel the effects due to particle heterogeneity, which are masked in bulk electrochemical studies of nanoparticles. Bigger particles showed more intense light and longer duration time than smaller ones. Co-reactant, tripropylamine can facilitate the formation of electrogenerated chemiluminescence as well as alleviate the polymer oxidation and following irreversible electrochemical reaction. Electrochemically generated light waves from the conjugated polymer thin films have been visualized to obtain microscopic level understanding on the complex reaction mechanism. Electrochemical reaction occurs at local defects and propagates isotropically over macroscopic distances with a sharp wave front. The initially injected holes (oxidized polymers) drag counter-ions into the film, thereby induce a phase-transition-like swelling that enhances transport of ions and solvent and move forward the double layer and corresponding propagation of the wave.