Electrochemical Characterization of Rapid Discharge Sintering (RDS) NiO Cathodes for Dye-Sensitized Solar Cells of <i>p</i>-Type

Abstract

Nickel oxide (NiO) thin films with thickness ranging in the interval 0.2 - 3.5 μm have been deposited onto conductive transparent substrate via the method of plasma-assisted rapid discharge sintering (RDS) with microwave heating starting from NiO nanoparticles with diameter 50 nm. The optical and electrochemical properties of the RDS NiO films in the pristine state were characterized in non aqueous electrolyte with the solvent 3-methoxy-propionitrile (3-MPN). Upon electrochemical cycling of NiO in 3-MPN we observed two characteristic oxidation peaks referring to the two nickel centred processes Ni(II)→Ni(III) and Ni(III)→Ni(IV), which are both localized prevalently on the surface of the metallic oxide. The oxide films prepared with the RDS method were also sensitized with different types of commercial dyes, either organometallic (N719, black dye) or organic (squaraine 2, erythrosine B), to compare the corresponding p -type dye-sensitized solar cells ( p -DSCs). All dyes here employed matched the energies of their frontier orbitals with the upper edge of NiO valence band and the redox level of the triiodide/iodide couple. The comparison of the performances of the p -DSCs based on RDS NiO which differed exclusively for the nature of the sensitizer showed that the extent of electronic conjugation in the structure of the dye is crucial for the control of the photovoltaic performance of the corresponding p -DSC.