Enhancement of electron-hole exchange interaction in CdSe nanocrystals: A quantum confinement effect

Photoluminescence of CdSe nanocrystals in a glass matrix was investigated at low temperature with size-selective excitation. The emission spectrum consists of a line a few meV below the excitation laser energy (denoted the F line) and a two-phonon replica superimposed on a broadband. The energy difference between the excitation energy and the F-line position increases with decreasing nanocrystal size. From the analysis of the time behavior of the luminescence and the degree of linear polarization, we attribute the F line to the recombination of the optically forbidden A exciton. Radiation recombination is made possible through a phonon-assisted virtual transition to the confined B-exciton state. The experimental degree of linear polarization is in good agreement with the theoretical calculations. The value of the electron-hole exchange energy obtained from the energy separation between the excitation energy and the F line is much larger than the bulk value and reaches 24 meV in 30-Angstrom-diam. nanocrystals. The size dependence of the exchange energy is in good agreement with the theoretical prediction in the limit of small nanocrystals.