Biexcitonic fine structure of CdSe nanocrystals probed by polarization-dependent two-dimensional photon echo spectroscopy

The spectroscopy of colloidal CdSe nanocrystals is investigated using two-dimensional photon echo (2DPE) spectroscopy with copolarized and cross-polarized pulse sequences. Clearly resolved excited state absorption features are observed to beat at the frequency of the longitudinal-optical phonon, and the phase of this beating is found to be polarization-dependent. A simulation is performed using the excitonic and biexcitionic fine structure states predicted by theory, and the polarization-dependent beating allows each feature to be assigned to a particular excited state absorption pathway. Owing to their circularly polarized selection rules, the polarization-dependent 2DPE technique provides valuable insights into the spectroscopy of quantum dots. In particular, transient absorption features observed in pump-probe studies of CdSe quantum dots can now be assigned to specific fine structure transitions to the ground state biexciton.