Triplet and singlet exciton diffusion in disordered rubrene films: implications for photon upconversion

Triplet and singlet exciton diffusion plays a decisive role in triplet-triplet annihilation (TTA) and singlet fission (SF) processes of rubrene (Rub) films at low excitation power, and therefore has an important implication for TTA-mediated photon upconversion (UC). Although triplet diffusion in crystalline Rub was studied before, there is no quantitative data on diffusion in disordered Rub films most widely employed for NIR-to-Vis UC. The lack of these data hinders the progress of TTA-UC applications relying on a Rub annihilator (emitter). Herein, a time-resolved PL bulk-quenching technique was employed to estimate the exciton diffusion coefficient (D) and diffusion length (L_D) in the neat Rub films as well as Rub-doped PS films at 80 wt% doping concentration, previously reported to be optimal in terms of UC efficiency. The impact of commonly utilized singlet energy collector (sink) DBP on exciton diffusion was also assessed, highlighting its importance exclusively on the dynamics of singlets in Rub films. Our study revealed that triplet diffusion lengths (LTD) of 25-30 nm estimated for the disordered Rub films are sufficient for encountering triplets from the neighboring sensitizer molecules at a low sensitizer PdPc concentration (0.1 wt%), thereby enabling the desired TTA domination regime to be reached. Essentially, the performance of Rub-based UC systems was found to be limited by the modest maximal LTD (up to ∼55 nm) in disordered films resulting from a short maximum triplet lifetime τ_T (∼100 μs) inherent to this emitter. Thus, to enhance the NIR-to-Vis TTA-UC performance, new emitters with a longer triplet lifetime in the solid state are required.