Electroconductive polymers (ECP) are critical for the design of soft electronic and bioelectronic devices. Polyaniline:
camphorsulfonic acid (PANI:CSA) is an example of a biocompatible and affordable ECP, whose electroconductivity
is highly dependent on chain organization/conformation. PANI:CSA aggregation ordering is
overlooked in most works, but it can greatly impact the performance of PANI:CSA-based devices and limit their
applicability. A simple and cheap method to avoid random coil aggregation of PANI:CSA is to select solvents with
pseudo-doping properties. This work presents a novel alternative solvent system, based on trifluoroethanol (TFE)
and hexafluoropropanol (HFP) mixtures, capable of being removed without hampering the structural and
electrical properties of PANI:CSA. For the first time, we present a systematic study that compares the performance
of solvent systems containing different amounts of TFE and HFP, which, unlike m-cresol, the goldenstandard
of pseudo-doping, are easy to remove without compromising the ECP’s electroconductivity and
biocompatibility. We also evaluate the influence of the processing method, drop-casting vs spin-coating, on the
structural and electrical properties of the obtained samples. Samples obtained by spin-coating show a more
consistent improvement in electroconductivity (σ(TFE) = 61 S cm􀀀 1, σ(TFE:HFP (50:50 vol)) = 70 S cm􀀀 1) and
more intense near-infrared (NIR) absorption bands. Atomic force microscopy (AFM), Raman spectroscopy and Xray
photoelectron spectroscopy (XPS) indicate that samples processed with HFP and m-cresol have higher
benzenoid content, lower random coil aggregation and more efficient CSA doping. The solvent system comprised
of equal parts of TFE and HFP was found to simultaneously enhance the electrical properties and structural
ordering of PANI:CSA. We believe our results are critical for the fabrication of PANI-based next generation
bioelectronic devices.