Microwave Processing Controls the Morphology of Block Copolymer-Templated Mesoporous Cobalt Oxide Films

Microwave heating provides an efficient method to rapidly heat materials through interaction of microwaves with the media. Here, we demonstrate the rapid synthesis of mesoporous cobalt oxide films through the heating of the silicon substrate by microwaves. A non-sol-gel approach based on cobalt nitrate-citric acid complex cooperative assembly with a poly[methoxy poly(ethylene glycol)methacrylate]-block-poly(butyl acrylate) (PMPEGMA-b-PBA) block copolymer was used to fabricate the cobalt oxide through a cobalt carbonate intermediate. The time required to convert cobalt carbonate to cobalt oxide with the full removal of the PMPEGMA-b-PBA template can be decreased by two orders of magnitude with microwaves in comparison to standard heating in a furnace at 350 °C. At the highest microwave power examined (1500 W), this can be accomplished within 2 s, while >5 min is required at 350 °C in a furnace. At a microwave power of <400 W, there is insufficient energy to induce the transition from carbonate to oxide, but even at only 420 W, the oxide can be formed within 26 s. The rapid heating by the microwaves tends to increase the crystallinity and mean crystal size of the cobalt oxide within the mesoporous films. Despite the growth of larger average crystals, the pore size and porosity tend to be larger when the film is processed using microwaves. Higher microwave power leads to larger average crystals and average pore size. These results suggest that rapid processing to crystallize frameworks in mesoporous materials may allow for highly crystalline frameworks without loss of the templated mesostructure.