Interchain Spacing and Screening Length Modification of PSS Backbone Chains in Zwitterion-Doped Poly(3,4-Ethylenedioxythiophene):Polystyrene Sulfonate

The interchain spacing and screening length modification of deuterated PSS (d-PSS) backbone chains in zwitterion-doped PEDOT:d-PSS were studied as a function of the doping concentration using small angle neutron scattering. Results suggest that the dopant, 3-(N,N-Dimethylmyristylammonio)propanesulfonate (DYMAP), forms worm-like micelle structures in the PEDOT:d-PSS dispersion that grow in size as the doping concentration increases. The interchain spacing between negatively charged d-PSS remains unaffected by DYMAP up to 15 mM doping concentration. However, from 15 to 25 mM doping concentration, the interchain spacing increases due to steric interactions of grown DYMAP worm-like micelles with the d-PSS chains. At 30 mM doping concentration, the interchain distance between negatively charged d-PSS chains is reduced due to the gelation of the PEDOT:d-PSS dispersion caused by the crosslinking between long DYMAP worm-like micelles and d-PSS chains. Meanwhile, the screening length of the neutralized d-PSS segments attached to the PEDOT oligomers increases as the DYMAP concentration increases form 5 to 30 mM due to the neutralization of the negatively charged d-PSS segments by their Coulomb interaction with the cation in DYMAP.