Evidence in Support of Exciton to Ligand Vibrational Coupling in Colloidal Quantum Dots

The Perspective focuses on the investigation of an unresolved conflict in semiconductor colloidal quantum dots (CQDs) research, concerning the influence of the immediate surrounding on the optical properties of the materials. Today's advanced synthetic colloidal procedures offer formation of a high-quality inorganic crystallite, capped with various organic/inorganic molecular ligands. The Perspective aims to clarify whether exciton recombination processes in CQDs are influenced by the type of crystallite-ligand bonding and, moreover, whether these excitonic processes experience direct coupling to the ligands' vibrational modes. Most ligands used have redox characteristics whose functional groups are added on to the CQDs' surface via coordination, covalent or ionic bonding. The surface-ligand bonding introduces electronic states either above or below the intraband/interband energy gap, resulting in electronic passivation or in creation of trapping states that affect intraband and interband relaxation processes. Furthermore, crystalline electronic states may have a direct coupling to molecular vibrational states via direct overlap of electronic wave functions or through a long-range energy-transfer process. Also, photoejected carriers resulting from an Auger process or ionization processes may diffuse temporarily onto a ligand site. These scenarios are discussed in the current publication with supporting theoretical and experimental observations.