Potential-Modulated Attenuated Total Reflectance Characterization of Charge Injection Processes in Monolayer-Tethered CdSe Nanocrystals

Reversible electron injection into pyridine-capped CdSe nanocrystals (pyr-CdSe NCs), tethered to indium−tin oxide (ITO) substrates using mercaptoalkylcarboxylic acids, is characterized using attenuated total reflectance (ATR) spectroelectrochemistry on a planar waveguide. The sensitivity of this technique provides for characterization of redox processes in submonolayer films of pyr-CdSe NCs. Optically determined onset potentials for electron injection, measured as bleaching/recovery of the exciton absorption band, provide estimates for the conduction band edge ( E CB ). Potential-modulated attenuated total reflectance (PM-ATR), in which the in-phase and out-of-phase reflectance response is measured as a function of modulation frequency, provides estimates for rates of electron injection. These apparent rate constants are found to be nearly independent of tether chain length, suggesting that communication between tethered NCs and electrochemically less active (i.e., less conductive) regions on the ITO surface is rate-limiting.