Nanoassemblies Based on Semiconductor Quantum Dots and Porphyrin Molecules: Structure, Exciton–Phonon Interactions, and Relaxation Processes

Experimental temperature dependences (77–293 K) of absorption and photoluminescence spectra of CdSe/ZnS semiconductor quantum dots (QDs) were analyzed based on modern models of exciton–phonon coupling. It was proven that the first excitonic transition absorption band formed with participation primarily of optical phonons of the CdSe core while the photoluminescence properties reflected the interaction of the ZnS layer with optical phonons. Photoluminescence quenching for CdSe/ZnS QDs of various diameters upon formation of nanoassemblies with porphyrin molecules was analyzed in the framework of a quantum-mechanical model. It was shown that the quenching rate constant decreased with increasing QD diameter and that the quenching process under quantum confinement conditions was due to the electron of an excited electron–hole pair tunneling onto the QD surface with subsequent localization on surface traps.