CdSe Quantum Dot-Sensitized TiO2 Electrodes: Effect of Quantum Dot Coverage and Mode of Attachment

We have investigated the sensitization of nanoporous titanium dioxide by previously synthesized CdSe quantum dots (QDs) protected with trioctylphosphine. Covering the nanoporous TiO2 films with QDs has been achieved using two strategies: (i) direct adsorption from dichoromethane dispersions and (ii) anchoring the QDs through a molecular linker, concretely, mercaptopropionic acid (MPA). In contrast with MPA-mediated adsorption, direct adsorption leads to a high degree of QD aggregation, as revealed by atomic force microscopy (AFM) images obtained with both TiO2 nanoporous films and monocrystalline surfaces. Importantly, at saturation, only 14% of the real surface area of a 5-mu m thick P25 TiO2 layer is covered for both attachment modes. For MPA attachment, the incident photon-to-current efficiency (IPCE) increases with the loading, whereas a maximum (close to 40% at the QD excitonic peak) is defined for intermediate coverages in the case of QD direct adsorption. In addition, for equivalent QD loading, IPCE values are larger in the case of direct adsorption.