From Lead Iodide to a Radical Form Lead‐Iodide Superlattice: High Conductance Gain and Broader Band for Photoconductive Response

Superlattice materials offer new opportunities to modify optical and electrical properties of recently emerging 2D materials. The insertion of tetraethylbenzidine (EtDAB) into interlamination of the established 2D PbI 2 semiconductor through a mild solution method yielded the first lead iodide superlattice, EtDAB⋅4PbI 2 (EtDAB=tetraethylbenzidine), with radical and non‐radical forms. The non‐radical form has a non‐ionic structure that differs from the common ionic structures for inorganic–organic hybrid lead halides. The radical form shows five orders of magnitude greater conductance and broader photoconductive response range (UV/Vis → UV/Vis‐IR), than pure PbI 2 and the non‐radical form of the superlattice.