## 3 Results and Discussions
### Characterization of Materials
In addition to the influence of the roughness on the conductive properties, W substrates composite materials family showed a strong dependence with the intrinsic conductivity of the deposited polymers, highlighting the good performance and properties of materials prepared in-situ with PEDOT:Triflate. PTfWSp and PTfWCt showed very similar performances, Sa (7-9 \(\upmu\)m) and improved \(\sigma_{\text{s}}\) values (0.5-0.8 \(\text{S}\,\text{cm}^{-1}\)) comparing with PEDOT:Tosyllate derived composite materials regardless the in-situ process. The substrates used to prepare the last family of composite materials (C) were performed _ad-hoc_ in our laboratories using cellulose microfibers as detailed above. After preparing the composite materials by means of the different in-situ approaches, easily reproducible materials were obtained presenting similar \(\sigma_{\text{s}}\) values regardless the CPs used and taking into account the significant difference in roughness covering a wide range of Sa values obtained from the profilometry (Figure S9 and Table S2). C derived composite materials Sa values showed in general higher variations than commercial substrates, which can be useful, depending of the applications, where surface parameters of these composite materials can be tuned depending of the applications (printed circuits, diodes, capacitors, supercapacitors, etc.) [14]. Composite materials derived from PEDOT:PSS are induced to a surface morphological modification by the solvent, water in case, which swell cellulose fibers preventing the polymer to homogenously coat the cellulose fibers resulting in heterogeneous materials with lower \(\sigma\) values than expected. As observed previously for composite materials prepared with W substrates, the use of water-based solutions does not help for a suitable processing of untreated raw cellulose substrates. In the case of PDBProDOT, the use of solutions aiding the processability of CPs allowing a slow coating formation \begin{table}
\begin{tabular}{c c c c c} \hline \hline
**Samples** & \(\sigma_{\text{s}}\) **(S-cm\({}^{-1}\))** & **PEDOT Content** & **PEDOT Mass Loading** & **Sa (\(\upmu\)m)** \\  & & **(wt.\%)** & **(mg-cm\({}^{-2}\))** & **Sa (\(\upmu\)m)** \\ \hline _PTsWCt_ & 0.05 & 43 & 7.4 & \(15.9\pm 9.5\) \\ _PTSCCt_ & 0.07 & 34 & 5.6 & \(13.6\pm 3.9\) \\ _PTscSp_ & 0.31 & 45 & 8.8 & \(11.6\pm 3.1\) \\ _PTfWCt_ & 0.60 & 80 & 36.4 & \(9.2\pm 1.7\) \\ _PTfWSp_ & 0.46 & 24 & 2.7 & \(7.0\pm 1.5\) \\ _PTfCSp_ & 0.77 & 38 & 6.7 & \(6.2\pm 0.5\) \\ \hline \hline \end{tabular}
\end{table} 
Table 4: Surface conductivities, polymer content, mass loading and roughness values for in-situ prepared composite materials. Figure 7: (a) \(\sigma_{\text{s}}\) dependence on PEDOT mass loading; and (b) \(\sigma_{\text{s}}\) dependence on Sa roughness for composite materials prepared on different substrates: Whatman® paper (black); acetate cellulose (red) and cellulose microfibers (blue). with longer crystallization times, as is well known the linear relationship between CPs crystallinity (percentage and quality) and conductive properties [41], is not a favorable strategy in the development of composite materials derived of PDBProDOT with improved conductivities and processability. Then, despite interaction of cellulose fibers with solvents is fundamental, processing by casting achieved a more homogeneous coatings in case of soluble polymers as PEDOT:PSS and PDBProDOT, contrary to the case of non-soluble studied polymers PEDOT:Tosylate and PEDOT:Triflate where processing by spray-coating resulted in composite materials with better performance. Then, roughness properties are more dependent mostly of the chemical and structural nature of the substrate and interactions with solvents in contrast with \(\sigma\)s, which are mainly influenced by the CPs used. Hence, from Figure 7a, we can observe the non-existence of a direct correlation between PEDOT mass loading presented in each composite material with \(\sigma\)s values.