Studies of Intra-Chain and Inter-Chain Charge Carrier Conduction in Acid Doped Poly(3,4-ethylenedioxythiophene) Polystyrene Sulfonate Thin Films

Poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) is a conductive water-processable polymer with many important applications in organic electronics. The electrical conductivity of PEDOT:PSS layers is very diverse and can be changed by changing the processing and post-deposition conditions, e.g., by using different solvent additives, doping or modifying the physical conditions of the layer deposition. Despite many years of intensive research on the relationship between the microstructure and properties of these layers, there are still gaps in our knowledge, especially with respect to the detailed understanding of the charge carrier transport mechanism in organic semiconductor thin films. In this work, we investigate the effect of acid doping of PEDOT:PSS thin films on the intra-chain and inter-chain conductivity by developing a model that treats PEDOT:PSS as a nanocomposite material. This model is based on the effective medium theory and uses the percolation theory equation for the electrical conductivity of a mixture of two materials. Here its implementation assumes that the role of the highly conductive material is attributed to the intra-chain conductivity of PEDOT and its quantitative contribution is determined based on the optical Drude–Lorentz model. While the weaker inter-chain conductivity is assumed to originate from the weakly conductive material and is determined based on electrical measurements using the van der Pauw method and coherent nanostructure-dependent analysis. Our studies show that doping with methanesulfonic acid significantly affects both types of conductivity. The intra-chain conductivity of PEDOT increases from 260 to almost 400 Scm⁻¹. Meanwhile, the inter-chain conductivity increases by almost three orders of magnitude, reaching a critical state, i.e., exceeding the percolation threshold. The observed changes in electrical conductivity due to acid doping are attributed to the flattening of the PEDOT/PSS gel nanoparticles. In the model developed here, this flattening is accounted for by the inclusion shape factor.