An Insulating Al₂O₃ Overlayer Prevents Lateral Hole Hopping Across Dye-Sensitized TiO₂ Surfaces

Three chromophores of the general form [Ru(bpy')₂(4,4'-(PO₃H₂)₂-2,2'-bipyridine)]²⁺, where bpy' is 4,4'-(C(CH₃)₃)₂-2,2'-bipyridine (Ru(dtb)₂P); 4,4'-(CH₃O)₂-2,2'-bipyridine (Ru(OMe)₂P), and 2,2'-bipyridine (RuP) were anchored to mesoporous thin films of TiO₂ nanocrystallites at saturation surface coverages to investigate lateral self-exchange Ru^III/II intermolecular hole hopping in 0.1 M LiClO₄/CH₃CN electrolytes. Hole hopping was initiated by a potential step 500 mV positive of the E_1/2 (Ru^III/II) potential or by pulsed laser (532 nm, 8 ns fwhm) excitation and monitored by visible absorption chronoabsorptometry and time-resolved absorption anisotropy measurements, respectively. The hole hopping rate constant k_R extracted from the potential step data revealed self-exchange rate constants that followed the trend: TiO₂|Ru(OMe)₂P (k_et = 1.4 × 10⁶ s^-1) > TiO₂|RuP (7.1 × 10⁵ s^-1) > TiO₂|Ru(dtb)₂P (6.5 × 10⁴ s^-1). Analysis of the anisotropy data with Monte Carlo simulations provided hole hopping rate constants for TiO₂|RuP and TiO₂|Ru(dtb)₂P that were within experimental error the same as that measured with the potential step. The hole hopping rate constants were found to trend with the TiO₂(e^-)|Ru^III → TiO₂|Ru^II charge recombination rate constants. The atomic layer deposition of an ∼10 Å layer of Al₂O₃ on top of the dye-sensitized films was found to prevent hole hopping by both initiation methods even though the chromophore surface coverage exceeded the percolation threshold and excited-state injection was efficient. The dramatic hole hopping turnoff was attributed to a larger outer-sphere reorganization energy for self-exchange due to the restricted access of electrolyte to the redox active chromophores. The implications of these findings for solar energy conversion applications are discussed.