PEDOT:PSS is conductive polymer coated on top of photo-resist like PMMA for discharging the dielectric substrate
You should do surface treatment on PMMA surface. By performing some surface treatment like plasma on the surface of PMMA, the surface energy of PMMA surface increase and wetting occurs.
What kind of PEDOT:PSS did you used? Possible simple way is to add some surfactant.
I think you can do some pre-treatment before your spin-coating, oxygen plasma and Silicified by APTES are good choice
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