Triplet Energy Transfer from CsPbBr₃ Nanocrystals Enabled by Quantum Confinement

Abstract

The spectral properties of lead halide perovskite nanocrystals (NCs) can be engineered by tuning either their sizes via the quantum confinement effect or their compositions using anion and/or cation exchange. To date, the latter is more frequently adopted, primarily because of the ease of ion exchange for lead halide perovskites, making the quantum confinement effect seemingly redundant for perovskite NCs. Here we report that quantum confinement is required for triplet energy transfer (TET) from perovskite NCs to polycyclic aromatic hydrocarbons (PAHs). Static and transient spectroscopy measurements on CsPbBr3 NC–pyrene hybrids showed that efficient TET occurred only for small-sized, quantum-confined CsPbBr3 NCs. The influences of the size-dependent driving force and spectral overlap on the TET rate were found to be negligible. Instead, the TET rate scaled linearly with carrier probability density at the NC surface, consistent with a Dexter-type TET mechanism requiring wave function exchange between the NC donors and pyrene acceptors. Efficient TET funnels the excitation energy generated in strongly light-absorbing perovskite NCs into long-lived triplets in PAHs, which may find broad applications such as photon upconversion and photoredox catalysis.