Bimodal Porosity and Stability of a TiO Gig-Lox Sponge Infiltrated with Methyl-Ammonium Lead Iodide Perovskite.

We created a blend between a TiO sponge with bimodal porosity and a Methyl-Ammonium Lead Iodide (MAPbI) perovskite. The interpenetration of the two materials is effective thanks to the peculiar sponge structure. During the early stages of the growth of the TiO sponge, the formation of 5-10 nm-large TiO auto-seeds is observed which set the micro-porosity (<5 nm) of the layer, maintained during further growth. In a second stage, the auto-seeds aggregate into hundreds-of-nm-large meso-structures by their mutual shadowing of the grazing Ti flux for local oxidation. This process generates meso-pores (10-100 nm) treading across the growing layer, as accessed by tomographic synchrotron radiation coherent X-ray imaging and environmental ellipsometric porosimetry. The distributions of pore size are extracted before (>47% V) and after MAPbI loading, and after blend ageing, unfolding a starting pore filling above 80% in volume. The degradation of the perovskite in the blend follows a standard path towards PbI accompanied by the concomitant release of volatile species, with an activation energy of 0.87 eV under humid air. The use of dry nitrogen as environmental condition has a positive impact in increasing this energy by ~0.1 eV that extends the half-life of the material to 7 months under continuous operation at 60 °C.