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Confinement Highlights the Different Electrical Transport Mechanisms Prevailing in Conducting Polymers

We study the differences in electrical charge transport dynamics of the conductivity enhancement of poly(3,4-ethylenedioxythiophene) (PEDOT) derivatives under geometrical confinement. The results of polymer blend poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) and a polymer-monomer blend, poly(3,4- ethylenedioxythiophene):tosylate, highlight the role of dopants and processing conditions of these systems under confinement. The prevailing transport length scales in confined geometry of characteristic dimensions originate from varying disorder in these polymer systems. These observable differences in two different PEDOTs introduced by molecular level reorganization can be utilized to tune conducting polymer systems for efficient electrical and thermoelectric properties. The electrical conductivity σ of the polymer system, which is a function of the electronic structure at molecular level and a connectivity parameter, has been probed in cylindrical-alumina nanoscaffolds of various channel diameters, at different frequencies ω and temperatures T. The observations also emphasize the role of disorder in these conducting polymer systems.