The surface of nominally diamagnetic colloidal CdSe nanoplatelets can demonstrate paramagnetism owing to the uncompensated spins of dangling bonds (DBSs). We reveal that by optical spectroscopy in high magnetic fields up to 15 Tesla using the exciton spin as probe of the surface magnetism. The strongly nonlinear magnetic field dependence of the circular polarization of the exciton emission is determined by the DBS and exciton spin polarization as well as by the spin-dependent recombination of dark excitons. The sign of the exciton-DBS exchange interaction can be adjusted by the nanoplatelet growth conditions.

Coherent spin dynamics in colloidal CdSe quantum dots (QDs) typically show two spin components with different Larmor frequencies, whose origin is an open question. We exploit the photocharging approach to identify their origin and find that surface states play a key role in the appearance of the spin signals. By controlling the photocharging with electron or hole acceptors, we show that the specific spin component can be enhanced by the choice of acceptor type. In core/shell CdSe/ZnS QDs, the spin signals are significantly weaker. Our results exclude the neutral exciton as the spin origin and suggest that both Larmor frequencies are related to the coherent spin precession of electrons in photocharged QDs. The lower frequency is due to the electron confined in the middle of the QD, and the higher frequency to the electron additionally localized in the vicinity of the surface.

Colloidal semiconductor nanoplatelets exhibit strong quantum confinement for electrons and holes as well as excitons in one dimension, while their in-plane motion is free. Because of the large dielectric contrast between the semiconductor and its ligand environment, the Coulomb interaction between electrons and holes is strongly enhanced. By means of one- and two-photon photoluminescence excitation spectroscopy, we measure the energies of the 1S and 1P exciton states in CdSe nanoplatelets with thicknesses varied from 3 up to 7 monolayers. By comparison with calculations, performed in the effective mass approximation with account of the dielectric enhancement, we evaluate exciton binding energies of 195–315 meV, which is about 20 times greater than that in bulk CdSe. Our calculations of the effective Coulomb potential for very thin nanoplatelets are close to the Rytova-Keldysh model, and the exciton binding energies are comparable with the values reported for monolayer-thick transition metal dichalcogenides.

Photoinduced charging in CdSe colloidal quantum dots (QDs) is investigated by time-resolved pump–probe spectroscopy that is sensitive to electron spin polarization. This technique monitors the coherent spin dynamics of optically oriented electrons precessing around an external magnetic field. By addition of 1-octanethiol to the CdSe QD solution in toluene, an extremely long-lived negative photocharging is detected that lives up to 1 month in an N2 atmosphere and hours in an air atmosphere at room temperature. 1-Octanethiol not only acts as a hole acceptor but also results in a reduction of the oxygen-induced photo-oxidation in CdSe QDs, allowing air-stable negative photocharging. Two types of negative photocharging states with different spin precession frequencies and very different lifetimes are identified. These findings have important implications for understanding the photophysical processes in colloidal nanostructures.

Optical phonon-assisted emission of dark excitons controls the intensity and maximum position of σ− and σ+ polarized photoluminescence of CdSe nanocrystals.