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We use time-, wavelength-, temperature-, polarization-resolved luminescence to elucidate the nature of the absorbing and ‘‘band edge’’ luminescing states in 32 Å diameter wurtzite CdSe quantum crystallites. Time-resolved emission following picosecond size-selective resonant excitation of the lowest excited state shows two components—a temperature insensitive 100 ps component and a microsecond, temperature sensitive component. The emission spectrum, showing optic phonon vibrational structure, develops a ∼70 wave number red shift as the fast component decays. Photoselection shows the slow component to be reverse polarized at 10 K, indicating this component to be the result of a hole radiationless transition. The 100 ps emitting state is repopulated thermally as temperature increases from 10 to 50 K. All available data are interpreted by postulating strong resonant mixing between a standing wave molecular orbital delocalized inside the crystallite and intrinsic surface Se lone pair states. The apparent exciton transition is assigned to a ∼130 wave number wide band of eigenstates with the hole localized principally on the surface. The band contains strongly emitting ‘‘doorway’’ states and weakly emitting ‘‘background’’ states. The hole becomes mobile among these states as T increases to 50 K. It is suggested that such resonant mixing may be general in II–VI and III–V crystallites.
Bawendi et al. (Wed,) studied this question.