High-Efficiency Near-Infrared-to-Visible Photon Upconversion in Poly(vinyl alcohol) Porous Film

Triplet-triplet annihilation photon upconversion (TTA-UC) has received significant attention in energy harvesting applications such as solar cells. The realization of high UC performance in the form of films is a crucial factor for the incorporation of this technology into large-area devices. Herein, we propose a porous UC film, prepared by a simple emulsification method with a poly(vinyl alcohol) (PVA) aqueous solution and a toluene solution of chromophores (rubrene/Pd-tetraphenyl-tetraanthraporphyrin pair) that achieved considerable UC performance in the near-infrared (NIR) (810 nm) to visible (560 nm) range with a maximum quantum yield of 3.7 % (out of 50 %) under an air atmosphere. Notably, the films displayed a clear UC emission when using an NIR light-emitting diode as a low-power-density non-coherent light source, which was confirmed by the naked eye. Excitation-power-dependent time-resolved photoluminescence measurements showed almost identical triplet lifetimes of emitter species for the films and toluene solutions; however, smaller threshold intensities (Ith = 1–2 W/cm2) were observed for the films compared to those of the solutions (Ith = ~10 W/cm2). An evaluation of the remaining toluene in the film and UC emission behavior in liquid nitrogen suggested that the chromophores exist as an amorphous solid in the pores, thus enabling hybrid triplet energy transfer (chromophore-mobility-based and exciton migration) in this unique film. The presented methodology can be generalized to other wavelengths and can enable diverse applications of the TTA-UC technology.