Intercalative Poly(carbazole) Precursor Electropolymerization within Hybrid Nanostructured Titanium Oxide Ultrathin Films

A protocol for nanostructuring and electropolymerization of a hybrid semiconductor polycarbazole-titanium oxide ultrathin film is described. Ultrathin (<100 nm) films based on polycarbazole precursor polyelectrolytes and titanium oxide (TiOx) have been fabricated by combining the layer-by-layer (LbL) and surface sol-gel layering techniques. Film growth was followed and confirmed through UV-vis spectroscopy, ellipsometry and quartz crystal microbalance with dissipation (QCM-D). Subsequent anodic electrochemical oxidation of the carbazole pendant units afforded a conjugated polymer network (CPN) film within intercalating TiOx layers of cross-linked and π-conjugated carbazole units. Cyclic voltammetry (CV), UV-vis, and fluorescence spectroscopy measurements confirmed this process. The LbL-driven polyelectrolyte deposition process resulted in a quantified electrochemical response, proportional to the number of layers, while the TiOx acted as a dielectric spacer limiting electron transfer kinetics and attenuating energy transfer in fluorescence. Electro-optical properties were compared with other polycarbazole thin film materials with respect to bandgap energy (Eg). The straightforward protocol in film nanostructuring and barrier/dielectric properties of the inorganic oxide slab (denoted here as, TiOx) should enable applications in organic light-emitting diodes (OLEDs), dielectric mirrors, planar waveguides, and photovoltaic devices for these hybrid ultrathin films.