Photoelectrochemical properties of ZnO nanocrystals/MEH-PPV composite: The effects of nanocrystals synthetic route, film deposition and electrolyte composition

• The photoelectrochemical processes at ZnO nanocrystals/MEH-PPV hetero-junction were studied.
• Fluorescence quenching of the polymer at the MEH-PPV/ZnO interface was observed.
• Non-hydrolytic ZnO junction showed higher photocurrents than hydrolytic equivalent.
• The blends showed higher photocurrents than those obtained with double layers film.
• Film thickness and different counterions in solution influenced the charge transfer.

This paper reports a study on the photoelectrochemical processes occurring at the interface of ZnO nanocrystals/MEH-PPV composites. Colloidal chemical routes were used to obtain size controlled non-hydrolytic ZnO nanocrystals (NCs) dispersible in organic solvents, while a low molecular weight poly[2-methoxy-5-(2′-ethyl-hexyloxy)phenylene vinylene] (MEH-PPV), characterized by high degree of structural order, was synthesized via an organometallic method. The optical properties of the nanocomposite material were comprehensively investigated on solution and on films deposited by spin coating. Remarkably, a significant fluorescence quenching of the polymer at the MEH-PPV/ZnO junction was observed. Photoelectrochemical measurements demonstrated that the photoactivity of the composite material was significantly improved in the case of non-hydrolytic NCs with respect to hydrolytic route prepared ZnO. Moreover, the effective role of the organic/inorganic blend to improve the charge transfer with respect to the double layer hetero-junction was confirmed, thanks to the extended interfaces which enable an effective electron transfer between the hetero-junction components. The system was also studied at different film thicknesses and electrolyte compositions. The results indicated that film photoactivity increased with film thickness up to 300 nm due to the presence of a large number of interfaces, while the change of cation size influenced the ionic conductivity through the nanocomposite film. It was shown that efficient photoconductivity requires not only efficient charge separation, but also efficient transport of the carriers to the electrodes without recombination.