Hard-Cation-Soft-Anion Ionic Liquids for PEDOT:PSS Treatment

A promising conducting polymer poly(3,4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) experiences significant conductivity enhancement when treated with proper ionic liquids (ILs). Based on the hard-soft-acid-base principle, we propose a combination of a hydrophilic hard cation A(+) (instead of the commonly used 1-ethyl-3-methyl imidazolium, EMIM+) and a hydrophobic soft anion X- (such as tetracyanoborate, TCB-) as the best ILs for this purpose. Such ILs would decouple hydrophilic-but-insulating PSS- from conducting-but hydrophobic PEDOT+ most efficiently by strong interactions with hydrophilic A(+) and hydrophobic X-, respectively. Such a favorable ion exchange between PEDOT+:PSS- and A(+):X- ILs would allow the growth of conducting PEDOT+ domains decorated by X-, not disturbed by PSS- or A(+). Using density functional theory calculations and molecular dynamics simulations, we demonstrate that a protic cation-(aliphatic N-alkyl pyrrolidinium, in particular) combined with the hydrophobic anion TCB- indeed outperforms EMIM+ by promptly leaving hydrophobic TCB- and strongly binding to hydrophilic PSS-.