Coalescence-Driven Verticality in Mesoporous TiO2 Thin Films with Long-Range Ordering.

Abstract

Mesoporous semiconducting films with continuous interconnectivity and minimal tortuosity, such as densely ordered arrays of vertical channels, are ideal for ensuring a maximal surface area at the heterojunction to increase the density of charges or photons. While the design of these films with nanostructures below 50 nm using modern lithography is not feasible, continuously perpendicular pores can be obtained throughout a TiO2 film using a traditional soft-templating approach and lyotropic crystal engineering. We demonstrate here that a polystyrene-b-poly(ethylene oxide) block copolymer in a three-solvent system can self-assemble into a body-centered cubic Im3̅m template. The long-range three-dimensional periodicity of the template combined with a high degree of vertical contraction results in coalescence of the pores into orthogonal channels that are strongly interconnected with their nearest neighbors in the (011̅) plane. This work presents evidence of lateral long-range ordering with continuously transverse vertical porosity in a TiO2 material, which will enable functional applications, such as filtration, sensing, catalysis, and optoelectronics. To this end, we demonstrate the ability of the films to template and host methylammonium lead iodide perovskite nanocrystals.