LAUSR

Chemical doping can be used to tune the optoelectronic properties of conjugated polymers (CPs), extending their applications as conducting materials. Unfortunately, chemically doped CP films containing excess dopants exhibit an increase in energetic disorder upon structural alteration, and Coulomb interactions between charge carriers and dopants also affect such disorder. The increase in energetic disorder leads to a broadening of the density of states, which consequently impedes efficient charge transport in chemically doped CPs. However, the molecular origins that are inherently resistant to such incidental increase of energetic disorder in chemically doped CPs have not been sufficiently explored. Here, it is discovered that energetic disorder in chemically doped CPs can be suppressed to a level close to the theoretical limit. Indacenodithiophene‐co‐benzothiadiazole (IDTBT) doped with triethyloxonium hexachloroantimonate (OA) exhibits disorder‐free charge‐transport characteristics and band‐like transport behavior with astonishing carrier mobility as a result of reinforced 1D intramolecular transport. Molecular structure of IDTBT provides a capability to lower the energetic disorder that generally arises from the inclusion of heterogeneous dopants. The results suggest the possibilities of implementing disorder‐free CPs that exhibit excellent charge transport characteristics in the chemically doped state and satisfy a prerequisite for their availability in the industry.