Synthesis and characterization of aniline copolymers containing carboxylic groups and their application as sensitizer and hole conductor in solar cells

Copolymers of m-aminobenzoic acid and o-anisidine doped with p-toluenesulphonic acid in different proportions were successfully synthesized by oxidative polymerization. The copolymers were characterized by FT-IR, UV-vis, H-1 NMR and EPR spectroscopies, cyclic voltammetry, conductivity and SEM. The copolymer with equivalent amounts of the monomers o-anisidine and m-aminobenzoic acid presented the highest conductivity, The EPR analyses and SEM images show that this copolymer provides more homogeneous films with particle size distribution of approximately 1-2 mu m. The copolymer with a high fraction of o-anisidine gives rises to films with larger particle sizes and a more defined electrochemical process. The m-aminobenzoic acid monomer was intentionally chosen in order to promote a better electronic coupling between the conducting copolymer and the TiO2 surface. The copolymers were tested as both sensitizers and hole conducting materials in dye-sensitized solar cells. The device assembled using the copolymer with the highest proportion of m-aminobenzoic acid units as sensitizer produced the highest photocurrent (I-sc = 0.254 mA cm(-2)) and photovoltage (V-oc = 0.252 V) at 100 mW cm(-2). The energy diagram shows that although the electronic injection from the conducting polymer excited state is an allowed process the regeneration of the positive charges created after the electron transfer process is forbidden, thus explaining the low efficiency of solar energy conversion. When this copolymer was applied as a hole conducting material, an improvement in the V-oc to 0.4 V, was observed, indicating that this material is more suitable for charge transport when applied in this type of solar cells. (C) 2009 Elsevier B.V. All rights reserved.