Charge Carrier Induced Structural Ordering And Disordering in Organic Mixed Ionic Electronic Conductors

Abstract Operational stability underpins the successful application of organic mixed ionic‐electronic conductors (OMIECs) in a wide range of fields, including biosensing, neuromorphic computing, and wearable electronics. In this work, both the operation and stability of a p‐type OMIEC material of various molecular weights are investigated. Electrochemical transistor measurements reveal that device operation is very stable for at least 300 charging/discharging cycles independent of molecular weight, provided the charge density is kept below the threshold where strong charge–charge interactions become likely. When electrochemically charged to higher charge densities, an increase in device hysteresis and a decrease in conductivity due to a drop in the hole mobility arising from long‐range microstructural disruptions are observed. By employing operando X‐ray scattering techniques, two regimes of polaron‐induced structural changes are found: 1) polaron‐induced structural ordering at low carrier densities, and 2) irreversible structural disordering that disrupts charge transport at high carrier densities, where charge–charge interactions are significant. These operando measurements also reveal that the transfer curve hysteresis at high carrier densities is accompanied by an analogous structural hysteresis, providing a microstructural basis for such instabilities. This work provides a mechanistic understanding of the structural dynamics and material instabilities of OMIEC materials during device operation.