Fundamental studies of nanoarchitectured dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) are a promising candidate for next-generation photovoltaic panels due to their low cost, easy fabrication processes and relatively high efficiency. Despite the considerable effort on the advancement of DSSCs, the efficiency of DSSCs has been stalled for nearly two decades due to the complex interplay among various DSSC parameters. Particularly, in a conventional DSSC, a thicker semiconductor photovoltaic (PV) layer, i.e., a dye-sensitized TiO2 nanoparticle layer, is required to accommodate more light-induced charge separation centers to enhance light harvesting efficiency. However, a thicker PV layer concurrently increases the charge transport distance in the PV layer; so the system suffers from more charge recombination, leading to significant deterioration in charge collection efficiency. The conflicting demands on the thickness of PV layer by these two critical elementary photoelectrochemical processes becomes a fundamental limitation for further advancement in DSSCs and limits the choice of redox mediators and electrode materials in DSSCs. Hence, the focus of this dissertation research work is to systematically explore a transformative way to fundamentally resolve the conflicting interplay between light harvesting and charge transport. First, our strategy is to allocate part of the roughness factor to the collecting anode instead of imparting all the roughness factors onto the semiconductor PV layer attached to the anode. As a proof of concept, we first synthesized and characterized a microscopically rough Zn collecting anode, on which ZnO nanotips are grown. For the same surface roughness factor, the length of the ZnO nanotips supported on such a rough Zn anode can be much shorter than that of the ZnO nanowires supported on a planar anode. Our Zn-microtip|ZnO-nanotip DSSCs exhibit enhanced fill factor, Voc and Jsc. The investigation of kinetics indicates that the electron collection time is much faster than the electron lifetime due to the short electron transport distance. Apparently, in contrast to the surface roughness factor of a TiO 2 nanoparticulate film, typically well above 1000, the surface roughness factor of our Zn-microtip|ZnO-nanotip electrode is still very low. Thus, we integrated the above idea in the conventional TiO2-based DSSCs such that the advantage of high surface roughness in conventional NP-based DSSC can be retained. We designed and fabricated an array of metal micropillars by a lithographic method as additional electron collection pathways on a planar TCO anode. The surface roughness is distributed between the collecting electrode and the semiconductor layer. The electron transport kinetics was insightfully studied by electrochemical impedance technique, which suggests that the charge collection efficiency can be enhanced without sacrificing the thickness of TiO2 nanoparticle layer. Furthermore, novel TCO nanoarchitectures were explored by converting the 2-D planar TCO to 3-D structure with intentional incorporation of functional optical structures, e.g., photonic crystals in the cell, to synergistically enhance light harvesting efficiency by light trapping effect, while still keep the short charge transport path length at the TCO/semiconductor interface. A novel 3-D nanophotonic crystal TCO electrode was synthesized using a 3-D template-assisted and solution-chemistry-based method. The optical and electrical properties of the 3-D photonic crystal FTO electrodes are studied by UV-Vis transmittance spectroscopy, Hall effect and sheet resistance measurement. In addition, an ultrathin TiO2 layer is coated on all surfaces of the IO-FTO electrodes using the atomic layer deposition technique. Cyclic voltammetry study indicates that the resulting TiO2-coated 3-D FTO shows excellent potentials as electrodes for electrolyte-based DSSCs