Charge Trapping versus Exciton Delocalization in CdSe Quantum Dots

The spectroscopic and photophysical similarities and differences between charge trapping by surface ligands on CdSe quantum dots and charge delocalization into the shell in excited CdSe core/shell nanocrystals are discussed. Optical absorption and resonance Raman spectroscopies are used to study small CdSe quantum dots coated with organic ligands that accept electrons (methyl viologen) or holes (phenothiazine, 4-methylbenzenethiol), as well as with semiconductor shells that delocalize electrons (CdS) or holes (CdTe). The organic ligands have only a small effect on the optical absorption spectrum and contribute negligibly to the resonance Raman spectra, indicating little participation of ligand orbitals in the initial excitation. The semiconductor shells more strongly red-shift the absorption spectrum by delocalizing the electron and/or hole into the shell, and vibrations of the shell appear in the resonance Raman spectrum, showing that the shell is involved in the vertical excitation. The qualitative differences between ligand and semiconductor shells are discussed in terms of the energetics and coupling strengths.