Valence-Band Mixing Effects in the Upper-Excited-State Magneto-Optical Responses of Colloidal Mn²⁺-Doped CdSe Quantum Dots

We present an experimental study of the magneto-optical activity of multiple excited excitonic states of manganese-doped CdSe quantum dots chemically prepared by the diffusion doping method. Giant excitonic Zeeman splittings of each of these excited states can be extracted for a series of quantum dot sizes and are found to depend on the radial quantum number of the hole envelope function involved in each transition. As seven out of eight transitions involve the same electron energy state, 1Se, the dominant hole character of each excitonic transition can be identified, making use of the fact that the g-factor of the pure heavy-hole component has a different sign compared to pure light hole or split-off components. Because the magnetic exchange interactions are sensitive to hole state mixing, the giant Zeeman splittings reported here provide clear experimental evidence of quantum-size-induced mixing among valence-band states in nanocrystals.