Poly(ethylene-co-acrylic acid)-g-poly(ethylene glycol) graft copolymer templated synthesis of mesoporous TiO2 thin films for quasi-solid-state dye sensitized solar cells

Abstract

An amphiphilic graft copolymer, poly(ethylene-co-acrylic acid)-graft-poly(ethylene glycol) (PEAA-g-PEG), consisting of a PEAA backbone and PEG side chains was synthesized via an esterification reaction. 1H nuclear magnetic resonance and Fourier-transformed infrared analysis demonstrated esterification between carboxylic acid of PEAA and hydroxyl group of PEG. Small angle X-ray scattering results revealed that the crystalline domain spacing of PEAA increased from 11.3 to 12.8nm upon using a more polar solvent with a higher affinity for poly(acrylic acid), while the crystalline domain spacing of PEAA disappeared with PEG grafting, indicating structural change to an amorphous state. Mesoporous TiO2 thin films were synthesized via a sol–gel reaction using PEAA-g-PEG graft copolymer as a structure-directing agent. The hydrophilically-preformed TiO2 nanoparticles were selectively confined in the hydrophilic PEG domains of the graft copolymer, and mesoporous TiO2 thin films were formed, as confirmed by scanning electron microscopy. The morphology of TiO2 films was tunable by varying the concentrations of polymer solutions and the amount of preformed TiO2. A quasi-solid-state dye-sensitized solar cell fabricated with PEAA-g-PEG templated TiO2 film exhibited an energy conversion efficiency of 3.8% at 100mW/cm2, which was greater than that of commercially-available paste (2.6%) at a similar film thickness (3μm). The improved performance was due to the larger surface area for high dye loading and organized structure with good interconnectivity.