Deciphering the Energy Transfer Mechanism Across Metal Halide Perovskite-Phthalocyanine Interfaces

Abstract

Energy transfer processes in nanohybrids are at the focal point of conceptualizing, designing, and realizing novel energy-harvesting systems featuring nanocrystals that absorb photons and transfer their energy unidirectionally to surface-immobilized functional dyes. Importantly, the functionality of these dyes defines the ultimate application. Herein, CsPbBr₃ perovskite nanocrystals (NCs) are interfaced with zinc phthalocyanine (ZnPc) dyes featuring carboxylic acid. The functionality is the photosensitization of singlet oxygen. The CsPbBr₃@ZnPc nanohybrid is to the best of our knowledge the first example, in which an unusual Dexter-type singlet energy transfer between metal halide perovskite nanocrystals and phthalocyanine dyes enables singlet oxygen generation as a proof-of-concept application. A detailed temporal picture of the singlet energy transfer mechanism is made possible by combining key time-resolved spectroscopic techniques, that are, femtosecond, nanosecond, and microsecond transient absorption spectroscopy as well as time-correlated single photon counting, and target analyses. In fact, three excitonic components in the NCs govern a concerted Dexter-type energy transfer. The work illustrates the potential of CsPbBr₃@ZnPc as a singlet photosensitizer of ZnPc to produce singlet oxygen (¹O₂) almost quantitatively while photoexciting CsPbBr₃.