CdSe nanoplatelets can be synthesized with different lateral sizes; very small nanoplatelets have almost quantum dot like features (almost discrete exciton states), while very large ones are expected to have properties of colloidal quantum wells (exciton continuum). However, nanoplatelets can be in an intermediate confinement regime with a rich substructure of excitons, which is neither quantum dot like nor an ideal 2D exciton. In this manuscript, we discuss the experimental transition energies and relaxation dynamics of exciton states in CdSe platelets with varying lateral dimensions and compare them with a microscopic theoretical model including exciton-phonon scattering. The model takes special care of the interplay of confinement and Coulomb coupling in the intermediate regime showing strong changes with respect to simple weak or strong confinement models by solving the full four dimensional lateral factorization free exciton wavefunction. Depending on the platelet size broad resonances previously attributed to just ground and excited states are actually composed of a rich substructure of several exciton states in their temporal dynamics. We show that these factorization free exciton states can explain the spectral features observed in photoluminescence experiments. Furthermore we demonstrate that the interplay of exciton bright and dark states provides principle insights into the overall temporal relaxation dynamics, and allows tuning of the exciton cooling via lateral platelet size. Our results and theoretical approach are directly relevant for understanding e.g. the size tuneability of lasing, excitonic cooling dynamics or light harvesting applications in these and similar 2D systems of finite lateral size.

A spectroscopic study of the optical non-linearities of PbSe colloidal solutions was performed with the Z-scan technique, at wavelengths between 1200 and 1750 nm. No non-linear absorption is observed, while the third-order non-linear refractive index n₂ shows clear resonances, somewhat blueshifted relative to the exciton transitions in the absorbance spectrum. The occurrence of thermal effects is ruled out by time-resolved measurements. At resonance, measured n₂ values exceed typical bulk semiconductor values by two orders of magnitude. At high optical intensity, the refractive index change saturates, indicating that state filling lies at the origin of the observed effect.

A spectroscopic study of the optical nonlinearity of PbSe colloidal solutions was performed with the Z -scan technique at wavelength intervals of 1200-1350 and 1540-1750 nm. While nonlinear absorption remains below the detection threshold, the third order nonlinear refractive index n2 shows clear resonances, somewhat blueshifted relative to the exciton transitions in the absorbance spectrum. The occurrence of thermal effects is ruled out by time-resolved measurements. At 1.55 μm, measured (resonant) n2 values exceed typical bulk semiconductor values by two orders of magnitude. At high optical intensity, the refractive index change saturates, indicating that statefilling lies at the origin of the observed effect.