Illumination-induced metastable polaron-supporting state in poly(p-phenylene vinylene) films

We found an illumination-induced metastable polaron-supporting state in films of a soluble derivative of poly-$p$-phenylene vinylene (MEH-PPV). Pristine, nonilluminated MEH-PPV polymer films do not show long-lived photogenerated polarons. Prolonged UV illumination, however, is found to induce a reversible, metastable state characterized by its ability to support abundant long-lived photogenerated polarons. In the dark, the illumination-induced metastable state reverts back to the state of the original MEH-PPV within about $30\min$ at room temperature. Relying on the well-established ubiquitous reversible photoinduced cyclization of diarylethenes into dihyrophenanthrene derivatives, we propose a reversible mechanism in which UV illumination transforms cis native defects in the polymer chains into metastable deep traps that substantially increase the photogenerated polaron lifetime in the film.