Novel Effects of Compressed CO₂ Molecules on Structural Ordering and Charge Transport in Conjugated...

We report the effects of compressed CO₂ molecules as a novel plasticization agent for poly(3-hexylthiophene) (P3HT)-conjugated polymer thin films. In situ neutron reflectivity experiments demonstrated the excess sorption of CO₂ molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results proved that these CO₂ molecules accelerated the crystallization process of the polymer on the basis of ex situ grazing incidence X-ray diffraction measurements after drying the films via rapid depressurization to atmospheric pressure: both the out-of-plane lamellar ordering of the backbone chains and the intraplane π-π stacking of the side chains were significantly improved, when compared with those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO₂-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared with those in the thermally annealed counterpart. This is attributed to the CO₂-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO₂ regardless of the type of polymers, the present findings suggest that CO₂ annealing near the critical point can be useful as a robust processing strategy for improving the structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer:fullerene bulk heterojunction films.