Energy levels in the band gap arising from surface states can dominate the optical and electronic properties of semiconductor nanocrystal quantum dots (QDs). Recent theoretical work has predicted that such trap states in II–VI and III–V QDs arise only from two-coordinated anions on the QD surface, offering the hypothesis that Lewis acid (Z-type) ligands should be able to completely passivate these anionic trap states. In this work, we provide experimental support for this hypothesis by demonstrating that Z-type ligation is the primary cause of PL QY increase when passivating undercoordinated CdTe QDs with various metal salts. Optimized treatments with InCl3 or CdCl2 afford a near-unity (>90%) photoluminescence quantum yield (PL QY), whereas other metal halogen or carboxylate salts provide a smaller increase in PL QY as a result of weaker binding or steric repulsion. The addition of non-Lewis acidic ligands (amines, alkylammonium chlorides) systematically gives a much smaller but non-negligible increase in the PL QY. We discuss possible reasons for this result, which points toward a more complex and dynamic QD surface. Finally we show that Z-type metal halide ligand treatments also lead to a strong increase in the PL QY of CdSe, CdS, and InP QDs and can increase the efficiency of sintered CdTe solar cells. These results show that surface anions are the dominant source of trap states in II–VI and III–V QDs and that passivation with Lewis acidic Z-type ligands is a general strategy to fix those traps. Our work also provides a method to tune the PL QY of QD samples from nearly zero up to near-unity values, without the need to grow epitaxial shells.

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.