We systematically investigated the effect of the molecular weight of additives on the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) by using different concentrations and molecular weights of polyethylene glycol (PEG) and ethylene glycol (EG). The conductivity enhancement depends on both the molecular weight and concentration of PEG used. The conductivity of PEDOT:PSS was enhanced from 0.3 S cmā1 to 805 S cmā1 with 2% PEG but to only 640 S cmā1 with 6% EG. PEGs with molecular weight higher than 400 have too low mobility to impart the required screening effect, and hence, the conductivity enhancement is less. Through FTIR, XPS and AFM investigations, the mechanism for the conductivity enhancement is found to be charge screening between PEDOT and PSS followed by phase separation and reorientation of PEDOT chains leading to bigger and better connected particles. The molecular weight and concentration of PEG also affect solar cell performances even though the conductivities are the same. Due to their high conductivity and high transmittance, ITO-free organic solar cell devices fabricated using PEDOT:PSS treated with 2% PEG anodes exhibited performance almost equal to that of the ITO counterparts.
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