Entropy-Gated Thermally Activated Delayed Emission Lifetime in Phenanthrene-Functionalized CsPbBr₃ Perovskite...

Charge and electronic energy transfer form the basis of many natural and artificial energy transduction systems. The energy landscapes that drive these transfer processes are often constructed from enthalpy changes. In contrast, the entropic effect, although occasionally invoked to explain some excited-state dynamics, has rarely been used to actively control charge/energy flow. Here we derive a generic formula describing how entropy can quantitatively gate the thermally activated delayed emission lifetime in semiconductor nanocrystal-molecular triplet acceptor complexes and experimentally verify the model using highly emissive, quantum-confined CsPbBr₃ nanocrystals surface-functionalized with multiple phenanthrene triplet acceptors. Triplet energy transfer from photoexcited CsPbBr₃ nanocrystals to phenanthrene is followed by thermally activated repopulation of nanocrystal excitons, leading to delayed nanocrystal emission. The lifetime of delayed emission increases with the phenanthrene/nanocrystal ratio, due to lowering of the free energy of the acceptor state by entropic gain. This study points toward a direction of using entropy to artificially design donor-acceptor light-emitting materials with predetermined excited-state lifetimes.