Spectroscopy of Resonant Intermediate States for Triplet-Triplet Annihilation Upconversion in Crystalline Rubrene: Radical Ions as Sensitizers.

Abstract

Photoluminescence upconversion in crystalline rubrene can proceed without an added sensitizer, but the mechanism for this process has not been well-understood. In particular, the species responsible for photon absorption has not been identified to date. To gain insight into the identity of the intermediate state, we measured the near-infrared (NIR) upconversion photoluminescence (UCPL) excitation spectrum of rubrene crystals and found three distinct spectral features. The UCPL yield has a quartic dependence on the laser intensity, implying a four-photon process. On the basis of electronic spectra of radical cations and anions of rubrene, we propose a mechanism in which photoexcited radical anions and cations undergo recombination, forming an excited neutral triplet while conserving spin. The triplets formed this way ultimately undergo triplet-triplet annihilation, resulting in the observed photoluminescence. This mechanism explains the origin of the NIR absorption as well as the four-photon nature of the UCPL process.