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

A promising conducting polymer poly(3,4-ethylenedioxythiophene):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^-.