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In this study, various alkyl 3,4-ethylenedioxythiophene derivatives (methyl to dodecyl) were used as monomers for the electrodeposition of conducting polymer films from hydrophilic to superhydrophobic. For a deposition charge of 100 mC/cm2, the study of their surface wettability reveals that superhydrophobic properties with relatively low sliding angles and hysteresis are produced from hexyl chains. The influence of the intrinsic hydrophobicity and the surface structuration is determined by producing smooth surfaces for each polymer by reducing the deposition charge to 0·5 mC/cm2. This study reveals that the superhydrophobic films are produced from intrinsically hydrophobic polymers, while it is also possible to produce hydrophobic films from hydrophilic polymers. In this article, the influence of the alkyl chain length on the surface structuration (nanoporosity and microstructures) is also discussed. Furthermore, supplementary information is available at http://www.icevirtuallibrary.com/upload/10.1680si.12.00009_SupplementaryInformation.pdf

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