Synchrotron small angle x-ray scattering study of dye-sensitized/-unsensitized TiO₂ nanoparticle colloidal solution

The wide-gap semiconductor TiO_2 nanoparticles with and without dye sensitization have been studied by small angle x-ray scattering using synchrotron radiation. Surface properties of the colloidal TiO_2 nanoparticles have been analysed in terms of the surface fractal dimensions (D_\rm s), showing that D_\rm s changes from 3.25 to 2.34 when TiO_2 nanoparticles are sensitized by ATRA (all-trans-retinoic acid), which reveals that the surface of the particles become relatively smooth after dye sensitization. The size distribution of gyration radius of TiO_2 nanoparticles in the colloids M(R_\rm g) has been successfully determined by the Shull－Roess method. The main peak of M(R_\rm g) for the unsensitized TiO_2 colloid is located at 2.1nm, corresponding to a spherical diameter of 5.4nm, and this value for the ATRA sensitized TiO_2 increases to 2.4nm, indicating a spherical diameter of 6.4nm. Such a size enlargement of TiO_2 nanoparticles suggests that there is a coating of ATRA on the TiO_2 surface, supporting the view that a monolayer of the dye has been attached to the surface of the TiO_2 nanoparticle.