Pressure-Tuned Core/Shell Configuration Transition of Shell Thickness-Dependent CdSe/CdS Nanocrystals

Pressure is adopted as a "clean" tool to achieve a core/shell configuration transition of CdSe/CdS nanocrystals (NCs) from quasi-type II to type I. The pressure-dependent photoluminescence (PL) spectra demonstrate a sudden decrease in PL intensity, because of the enhanced rate of exciton-exciton annihilation of type I structured CdSe/CdS NCs. Likewise, the large decrease in the PL lifetime with pressure confirms that the electron wave function mainly localizes into the CdSe core, indicating the decreased separation of electrons and holes in type I band alignment. We propose that pressure increases the conduction band energy of the CdS shell but hardly changes that of the CdSe core with almost both unchanged valence band energies, thus ultimately increasing the conduction band offsets between the CdSe core and CdS shell to form the type I core/shell configuration. Our studies elucidate the significance of external pressure in determining the electronic and optical properties of core/shell nanomaterials.