The photoluminescence (PL) quantum yield of semiconductor nanocrystals (NCs) is hampered by in-gap trap states due to dangling orbitals on the surface of the nanocrystals. While crucial for the rational design of nanocrystals, the understanding of the exact origin of trap states remains limited. Here, we treat CdTe nanocrystal films with different metal chloride salts and we study the effect on their optical properties with in situ spectroelectrochemistry, recording both changes in absorption and photoluminescence. For untreated CdTe NC films we observe a strong increase in the PL intensity as the Fermi-level is raised electrochemically and trap states in the bandgap become occupied with electrons. Upon passivation of these in-gap states we observe an increase in the steady state PL and, for the best treatments, we observe that the PL no longer depends on the position of the Fermi level in the band gap, demonstrating the effective removal of trap states. The most effective treatment is obtained for Z-type passivation with CdCl₂, for which the steady state PL increased by a factor 40 and the PL intensity became nearly unaffected by the applied potential. X-ray Photoelectron Spectroscopy measurements show that treatment with ZnCl₂ mainly leads to X-type passivation with chloride ions, which increased the PL intensity by a factor four and made the PL less susceptible to modulation by applying a potential with respect to unpassivated nanocrystal films. We elucidate the spectroelectrochemical signatures of trap states within the bandgap and conclude that undercoordinated Te at the surface constitutes the largest contribution to in-gap trap states, but that other surface states that likely originate on Cd atoms should also be considered.

Control over the charge density is very important for implementation of colloidal semiconductor nanocrystals into various optoelectronic applications. A promising approach to dope nanocrystal assemblies is charge injection by electrochemistry, in which the charge compensating electrolyte ions can be regarded as external dopant ions. To gain insight into the doping mechanism and the role of the external dopant ions, we investigate charge injection in ZnO nanocrystal assemblies for a large series of charge compensating electrolyte ions with spectroelectrochemical and electrochemical transistor measurements. We show that charge injection is limited by the diffusion of cations in the nanocrystal films as their diffusion coefficient are found to be ∼7 orders of magnitude lower than those of electrons. We further show that the rate of charge injection depends strongly on the cation size and cation concentration. Strikingly, the onset of electron injection varies up to 0.4 V, depending on the size of the electrolyte cation. For the small ions Li⁺ and Na⁺ the onset is at significantly less negative potentials. For larger ions (K⁺, quaternary ammonium ions) the onset is always at the same, more negative potential, suggesting that intercalation may take place for Li⁺ and Na⁺. Finally, we show that the nature of the charge compensating cation does not affect the source-drain electronic conductivity and mobility, indicating that shallow donor levels from intercalating ions fully hybridize with the quantum confined energy levels and that the reorganization energy due to intercalating ions does not strongly affect electron transport in these nanocrystal assemblies.