Hierarchical TiO2 ellipsoids 250–500 nm in size have been synthesized on a large scale by a template-free hydrothermal route. The submicrometer-sized hierarchitectures are assembled from highly crystallized anatase nanorods about 17 nm in diameter with macroporous cavities on the outer shells. Based on the time-dependent morphological evolution under hydrothermal conditions, an oriented attachment process is proposed to explain formation of the hierarchical structures. Such hierarchical TiO2 not only adsorbs large amounts of dye molecules due to high surface area, but also shows good light scattering caused by the submicrometer size. The TiO2 hierarchitectures were deposited on top of a transparent TiO2 nanocrystalline main layer to construct a double-layered photoanode for dye-sensitized solar cell (DSC) application, exhibiting enhanced light harvesting and power-conversion efficiency compared to a commercial TiO2-based electrode.
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