Solvent vapor annealing for controlled pore expansion of block copolymer-assembled inorganic mesoporous films

Mesoporous inorganic thin films are promising materials architectures for a variety of high-value applications, ranging from optical coatings and purification membranes to sensing and energy storage devices. Having precise control over the structural parameters of the porous network is crucial for expanding their applicability. To this end, the use of block copolymers (BCP) as sacrificial structure-directing agents via micelle co-assembly is a particularly attractive route, since the resultant pore size is directly related to scaling laws for the radius of gyration of the pore-forming macromolecule. However, tailoring the molecular weight of the BCP via bespoke synthesis is an elaborate process that requires precise control over highly sensitive reactions conditions. Alternative methods have emerged, based on supramolecular assembly or the addition of different swelling agents, but, to-date, these present a negative impact on the structural order and pore size dispersity of the final inorganic mesoporous films. In this work, we propose a novel and effective method for control over pore size, porosity and structural order, which relies on a synergistic combination of BCP selective swelling via solvent vapor annealing (SVA) and locking of the structure by condensation of the inorganic sol-gel precursors. The results obtained in this work for TiO2 establish SVA as a new, straightforward, simple, and powerful route efor the fabrication of mesoporous thin-film materials with controllable structural characteristics.