Evidence for Morphology Control by Polyelectrolyte Templating in PEDT:PSSH

• Published in: Advanced functional materials 2024-11, Vol.34 (45), p.n/a
• Main Authors: Koh, Qi‐Mian, Seah, Qiu‐Jing, Yang, Jin‐Cheng, Mazlan, Nur Syafiqah, Hoh, Quan‐En, Seah, Zong‐Long, Png, Rui‐Qi, Ho, Peter K.H., Chua, Lay‐Lay
• Format: Article
• Language: English
• Subjects: Conducting polymers; Electrical resistivity; interpolyelectrolyte complexes; Morphology; Optical properties; PEDT:PSSH; polyelectrolyte; Polyelectrolytes; Polymerization; Polystyrene resins; Work functions
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202407493

Despite decades of research, the fundamental question of structure and morphology of the poly(3,‐4‐ethylenedioxythiophene):poly(styrene sulfonate) complex (PEDT: PSS) electrically conducting polymer remains open. Here, through a systematic study of the polymerization of 3,4‐ethylenedioxythiophene (EDT) on two series of sulfonated polystyrenes, i.e., PS‐co‐SSH and PS‐co‐SSNa, with per cent sulfonation 24 ≲ x ≲ 100, this study shows that the substrate polyelectrolyte not only affords charge compensation and processability, but also templates the morphology of the growing PEDT chain—whether extended, coiled or collapsed. This determines the electrical, electronic and optical properties of the resultant PEDT: PSS interpolyelectrolyte complexes, including their work function. This study calls this the Polyelectrolyte Template model. The PEDT: PSS complex retains memory of its polymerization morphology even after subsequent ion‐exchange, for example, to the same acid form. Electrical conductivity decreases sharply with decreasing x, and depends on whether the polymerization is templated with the H+ or Na+ form of the polyelectrolyte. The work function is less sensitive to x, but exhibits a transition from low to high work function (5.2–5.3 eV) when x exceeds a threshold, which indicates formation of a polar surface driven by molecular‐scale segregation of the PSS counteranion. This surface segregation also affects the ability of these complexes to inject holes into very large‐ionization‐energy semiconductors. Using sulfonated polystyrenes—PS‐co‐SSH and PS‐co‐SSNa—as substrate polyelectrolytes for the polymerization of PEDT, the authors discover the effect of Polyelectrolyte Templating, where the morphology of the substrate polyelectrolyte determines that of the growing PEDT chain—whether extended, coiled or collapsed, and hence the electrical, electronic and optical properties of the resultant PEDT: PSSH interpolyelectrolyte complexes, including their work function.