Growth of a sea urchin-like rutile TiO ₂ hierarchical microsphere film on Ti foil for a quasi-solid-state dye-sensitized solar cell

A sea urchin-like rutile TiO₂ microsphere (RMS) film was fabricated on Ti foil via a hydrothermal process. The resulting rutile TiO₂ hierarchical microspheres with a diameter of 5-6 μm are composed of nanorods with a diameter of ∼200 nm and a length of 1-2 μm. The sea urchin-like hierarchical structure leads to the Ti foil-based RMS film possessing much better light-scattering capability in the visible region than the bare Ti foil. By using it as an underlayer of a nanosized anatase TiO₂ film (bTPP3) derived from a commercially available paste (TPP3), the corresponding bilayer Ti foil-based quasi-solid-state dye-sensitized solar cell (DSSC) only gives a conversion efficiency of 4.05%, much lower than the single bTPP3 film-based one on Ti foil (5.97%). By spin-coating a diluted TPP3 paste (sTPP3) on the RMS film prior to scraping the bTPP3 film, the resulting RMS/sTPP3/bTPP3 film-based DSSC achieves a significantly enhanced efficiency (7.27%). The electrochemical impedance spectra (EIS) show that the RMS/sTPP3/bTPP3 film possesses better electron transport capability and longer electron lifetime than the bTPP3 film. This work not only provides the first example of directly growing rutile TiO₂ hierarchically structured microsphere film on Ti foil suitable for replacing the rigid, heavy and expensive transparent conductive oxide (TCO) glass substrate to serve as a light-scattering underlayer of Ti foil-based quasi-solid-state DSSCs, but also paves a new route to develop Ti foil-based flexible DSSCs with high efficiency, low cost and a wide application field through optimizing the composition and structure of the photoanode.