article · Journal of Polymer Science
Treating films of the conducting copolymer PEDOT:PSS with solvents such as DMSO or DMF significantly increases their electrical conductivity. Spectroscopic techniques, including in situ ATR, PM-IRRAS, and XPS, reveal the structural mechanisms behind this improvement. The solvent treatment triggers a conformational reorganisation in the polymer layer by releasing excess PSS chains that contain specific sodium and sulfonic acid groups. Hydrogen bonding between sulfonic acid functions drives the rearrangement of the poly(styrene sulfonic/sulfonate) chains. Furthermore, residual water molecules are shown to play a critical role in this process. They facilitate the removal of excess sulfonate and sulfonic groups, assist in separating the polymer chains so they can be extracted, and help establish a PEDOT molecular conformation that allows for improved electrical conduction.
Conducting polymers are valuable materials across modern electronics and energy technologies. Understanding the exact chemical mechanisms by which solvent treatments boost the electrical conductivity of PEDOT:PSS films provides fundamental insights into polymer behaviour, helping researchers systematically optimise processing methods rather than relying on empirical trial and error.
The abstract does not indicate an application pathway, focusing strictly on the molecular mechanisms of conductivity enhancement in early-stage laboratory research.
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Abstract The treatment of water‐soluble PEDOT:PSS copolymer film by DMSO or DMF considerably enhances its electrical conductivity. The mechanism leading to a new molecular conformation in the PEDOT:PSS layer was investigated by in situ ATR, PM‐IRRAS and XPS spectroscopies. The release of PSS chains containing excess [Na + , (−Φ‐SO 3 − )‐] and (−Φ‐SO 3 H)‐] moieties by the solvent treatment and the implications of this process are discussed. By comparison with a NaPSS/HPSS adduct, the essential role of the conformational reorganization of the poly(styrene sulfonic/sulfonate) chains via hydrogen bonds between SO 3 H functions is demonstrated. Residual water molecules play a fundamental role both in the removal of excess sulfonates or sulfonic groups, the separation of the (Na, H, PSS) chains, which can then be extracted, and the establishment of the suitable PEDOT conformation.
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DOI: 10.1002/pol.20220605
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