Effect of Coordination Sphere Geometry of Copper Redox Mediators on Regeneration and Recombination Behavior in Dye-Sensitized Solar Cell Applications

Abstract

The recombination of injected electrons with oxidized redox species and regeneration behavior of copper redox mediators are investigated for four copper complexes, [Cu(dmby)2]2+/1+ (dmby = 6,6′-dimethyl-2,2′-bipyridine), [Cu(tmby)2]2+/1+ (tmby = 4,4′,6,6′- tetramethyl-2,2′-bipyridine), [Cu(eto)2]2+/1+ (eto = 4-ethoxy-6,6′-dimethyl-2,2′-bipyridine), and [Cu(dmp)2]2+/1+ (dmp = bis(2,9-dimethyl-1,10-phenantroline). These complexes were examined in conjunction with the D5, D35, and D45 sensitizers, having various degrees of blocking moieties. The experimental results were further supported by density functional theory calculations, showing that the low reorganization energies, λ, of tetra-coordinated Cu(I) species (λ = 0.31–0.34 eV) allow efficient regeneration of the oxidized dye at driving forces down to approximately 0.1 eV. The regeneration electron transfer reaction is in the Marcus normal regime. However, for Cu(II) species, the presence of 4-tert-butylpyridine (TBP) in electrolyte medium results in pen...