Linker-assisted attachment of cdse quantum dots to TiO₂: Time- and concentration-dependent adsorption, agglomeration, and sensitized photocurrent

We have characterized the concentration and time dependences of the attachment of colloidal CdSe quantum dots (QDs) to 16-mercaptohexadanoic acid (MHDA)-functionalized nanocrystalline TiO₂ thin films. The amount of QDs and the extent of their agglomeration on MHDA-functionalized TiO₂ films were characterized by transmission- and reflectance-mode UV/vis absorption spectroscopy and scanning electron microscopy. Optically transparent films with spatially homogeneous coloration and minimal agglomeration of QDs were prepared from 2.2 and 5.0 μM toluene dispersions of QDs at short reaction times (<5 h). In contrast, prolonged exposure of MHDA-functionalized TiO₂ films to 22 μM dispersions of QDs yielded relatively opaque QD-functionalized films with spatially inhomogeneous coloration and substantial agglomeration of QDs. Agglomeration of QDs decreased the absorbed photon-to-current efficiencies of QD-sensitized solar cells (QDSSCs) by almost 3-fold. These results highlight the profound influence of agglomeration on the optical properties and interfacial electron-transfer reactivity of QD-functionalized TiO₂ films prepared by in situ linker-assisted assembly as well as the photoelectrochemical performance of QDSSCs incorporating such films.