In this paper, we have elucidated the fundamental principle of employing CV to investigate the band structures of semiconductor nanocrystals (SNCs), and have also built up an optimal protocol for performing such investigation. By utilizing this protocol, we are able to obtain well-defined and characteristic electrochemical redox signals of SNCs, which allows us to intensively explore the influences of the particle size, the surface ligand and particle composition on the band structures of CdSe, CdTe and their alloy nanocrystals. The size-, ligand- and composition-dependent band structures of CdSe and CdTe nanocrystals (NCs) have therefore been mapped out, respectively, which are generally consistent with the previous theoretical and experimental reports. We believe that the optimal protocol and the original results regarding electrochemical characterization of SNCs demonstrated in this paper will definitely benefit the better understanding, modulation and application of the unique electronic and optical properties of SNCs.
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