Dynamics and reversibility of oxygen doping and de-doping for conjugated polymer.

We perform comprehensive long-time monitoring of the p-doping and de-doping of poly(3-hexyl thiophene) under changing external conditions of oxygen, light, and temperature. They are shown to be controlled by the complex adsorption and desorption process with time scales ranging from seconds to weeks. The oxygen doping at atmospheric pressure takes several hours in the dark. The doping is dramatically accelerated to be within seconds with light of wavelength of 500–700 nm. Even at low oxygen pressure of 10^-4 torr doping occurs within minutes with light. The de-doping by oxygen desorption takes as long as weeks at room temperature and vacuum of 10^-4 torr, but when the temperature is raised to near the polymer glass temperature of 370 K, the de-doping is accelerated to minutes as the enhanced chain motion releases the trapped oxygen. Even though visible and near infrared light causes very efficient doping within seconds or minutes depending on vacuum level, such light-induced doping is not a chemical reaction and is fully reversible by thermal annealing at the end without sacrificing the mobility. For the polymer field-effect transistors, only the carrier density is changed while the mobility remains roughly a constant for all the conditions. [ABSTRACT FROM AUTHOR]