ZnO–ionic liquid hybrid films: electrochemical synthesis and application in dye-sensitized solar cells

Abstract

An innovative ionic liquid (IL)-based synthesis route was developed to obtain ZnO-based hybrid nanostructured films with a modified surface. In particular, ZnO–IL hybrid films, with thickness from 1.5 to 4.5 μm and an appealing sponge-like morphology, were obtained from the electrochemical reduction of NO₃⁻ in ionic liquid-based electrolytes containing Zn²⁺. The presence of the ionic liquid moieties and/or derivatives in the as-deposited films was demonstrated by Fourier transform infra-red spectroscopy and energy dispersive X-ray spectroscopy. However, a relatively soft thermal annealing (i.e. 1 hour in air at 350 °C) was proved to be an effective way to remove the ionic liquid content from the samples, leading to porous ZnO films with high specific surface area. In comparison to ionic liquid-free samples, a blue shift of ∼40 meV in the absorption onset is detected for the ZnO-PYR14TFSI hybrid films, which suggests a modification of the bandgap. Both kind of films (i.e. ZnO–IL and ZnO) were sensitized with an indoline dye, coded D358, and evaluated as photoanodes in Dye-sensitized Solar Cells (DSCs). Although less D358 was adsorbed onto ZnO–IL samples (suggesting co-adsorption of the IL and D358), a clear enhancement (by a factor of ca. 2) of the power conversion efficiency was detected in DSC based on ZnO–IL hybrid films. This improvement was mainly due to a huge increase (∼180 mV) in the photovoltage, which reaches values of up to 780 mV. The DSC characterization, by electrochemical impedance spectroscopy and open circuit voltage decay techniques, indicates that the photovoltage improvement is likely due to a negative displacement of the conduction band in hybrid films. Therefore, the use of metal oxide–IL hybrid anodes appears to be a promising strategy to increase the open circuit voltage of the DSCs.