Nanocasting of carbon films with interdigitated bimodal three-dimensionally ordered mesopores by template-replica...

Carbon films with interdigitated bimodal three-dimensionally ordered mesoporosity (ib3DOm) are realized by a scalable nanoreplication process that removes the common need plaguing hard-templating strategies for multistep prefabrication of porous sacrificial templates. Specifically, evaporation-induced convective codeposition of size-tunable (ca. 20-50 nm) silica nanoparticles with a surrogate molecular carbon precursor (glucose), followed by carbonization and template etching, leads to remarkably ordered, crack-free mesoporous carbon films of tunable thickness (ca. 100-1000 nm) and pore size. Association of the molecular carbon precursor with the assembling pore forming particles is found to transition the system among three distinct film morphologies (collapsed, ib3DOm C, disordered), thereby establishing a pseudophase behavior controlled by silica solids content and incipient glucose concentration. Namely, a parametric window wherein ib3DOm C films can be realized is identified, with a diffuse lower phase boundary associated with collapsing carbon films, and a more distinct order-to-disorder transition encountered at higher glucose concentrations. Mechanistic insight suggests that glucose association with the lysine-silica nanoparticle surface modulates the lattice spacing, d, of the periodically ordered mesopores in the coassembled films, with the onset of the order-to-disorder transition occurring at a critical normalized lattice spacing, dc/D ∼ 1.16. This appears to apply across the phase space associated with D = 50 nm silica particles and to translate among other phase spaces associated with smaller particles (e.g., 30 nm). We briefly demonstrate the robustness of the codeposition process for realizing ib3DOm C films on rough FTO glass substrates and show that, in this form, these materials hold potential as low-cost alternatives to costly platinum electrodes for dye-sensitized solar cells.