Manipulating Band Structure through Reconstruction of Binary Metal Sulfide for High‐Performance Thermoelectrics in Solution‐Synthesized Nanostructured Bi₁₃S₁₈I₂

Reconstructing canonical binary compounds by inserting a third agent can significantly modify their electronic and phonon structures. Therefore, it has inspired the semiconductor communities in various fields. Introducing this paradigm will potentially revolutionize thermoelectrics as well. Using a solution synthesis, Bi 2 S 3 was rebuilt by adding disordered Bi and weakly bonded I. These new structural motifs and the altered crystal symmetry induce prominent changes in electrical and thermal transport, resulting in a great enhancement of the figure of merit. The as‐obtained nanostructured Bi 13 S 18 I 2 is the first non‐toxic, cost‐efficient, and solution‐processable n‐type material with z T =1.0.