Pb clustering and PbI<sub>2</sub> nanofragmentation during methylammonium lead iodide perovskite degradation.

Alberti, Alessandra; Bongiorno, Corrado; Smecca, Emanuele; Deretzis, Ioannis; La Magna, Antonino; Spinella, Corrado · Nat Commun · 2019

basic_science · Level V

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Abstract

Studying defect formation and evolution in MethylAmmonium lead Iodide (MAPbI<sub>3</sub>) perovskite layers has a bottleneck in the softness of the matter and in its consequent sensitivity to external solicitations. Here we report that, in a polycrystalline MAPbI<sub>3</sub> layer, Pb-related defects aggregate into nanoclusters preferentially at the triple grain boundaries as unveiled by Transmission Electron Microscopy (TEM) analyses at low total electron dose. Pb-clusters are killer against MAPbI<sub>3</sub> integrity since they progressively feed up the hosting matrix. This progression is limited by the concomitant but slower transformation of the MAPbI<sub>3</sub> core to fragmented and interconnected nano-grains of 6H-PbI<sub>2</sub> that are structurally linked to the mother grain as in strain-relaxed heteroepitaxial coupling. The phenomenon occurs more frequently under TEM degradation whilst air degradation is more prone to leave uncorrelated [001]-oriented 2H-PbI<sub>2</sub> grains as statistically found by X-Ray Diffraction. This path is kinetically costlier but thermodynamically favoured and is easily activated by catalytic species.