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.

Tin disulfide (SnS2) is a two-dimensional semiconducting van der Waals material with an indirect band gap. We measured the mobility and recombination dynamics of charge carriers as a function of temperature and charge density. Excess electrons and holes were generated by pulsed irradiation with 3 MeV electrons. The charge carriers were probed by time-resolved microwave conductivity measurements. The mobility and decay pathways of the charge carriers were determined by a global kinetic rate equation model including decay of charges by recombination and trapping. We found high mobilities for electrons and holes near 100 cm2 V−1 s−1. The mobility decreases at higher temperature, which is typical for bandlike transport. The second-order recombination rate constant is found to be thermally activated with an activation energy close to the energy difference of the direct and indirect band gap of SnS2. We demonstrate that the radiative recombination is reaction-limited and takes place via the Γ-point after thermal excitation of electrons from the M-point to the Γ-point, while a phonon emission-related recombination between the indirect band gap (M-point electrons and Γ-point holes) has no relevant contribution to the population decay. The observed effects result in an unusual increase of radiative electron−hole recombination constant with temperature.