Well-Organized Mesoporous TiO₂ Photoanode by Using Amphiphilic Graft Copolymer for Efficient Perovskite Solar Cells

The control of the thickness and porosity of a mesoporous TiO₂ layer is important to improve the photovoltaic performance of perovskite solar cells. We produced organized mesoporous TiO₂ (om-TiO₂) layers using a low-cost amphiphilic graft copolymer, poly­(vinyl chloride)-graft-poly­(oxyethylene methacrylate) (PVC-g-POEM), as a sacrificial template. This simple but effective synthetic approach generates highly mesoporous and well-organized TiO₂ nanostructures with interconnected and size-tunable features. Specifically, the average pore size increased with the amount of hydrophobic PVC main chain in the graft copolymer, which acted as the pore forming agent. Perovskite layers were prepared on top of an om-TiO₂ layer according to a two-step sequential deposition: after coating the PbI₂ solution in dimethylformamide (DMF) on an om-TiO₂ substrate, the substrate was prewetted in isopropyl alcohol (IPA) solvent before immersing into a CH₃NH₃I/IPA solution. This prewetting treatment not only improves the yields of conversion from PbI₂ to CH₃NH₃PbI₃, but also increases the size of perovskite crystals with cuboid morphology. On varying the pore size and the film thickness of the om-TiO₂ layer, the device performance attained 11.9% of power conversion efficiency (PCE) at pore size 70 nm and film thickness 300 nm. We measured extracted charge densities and decays of transient photovoltage to understand the kinetics of charge recombination in relation to the corresponding device performance.