Dataset DOI: 10.5061/dryad.9ghx3ffwh

Description of the data and file structure

This dataset contains the raw (or preliminarily processed) data of experimental results collected to publish manuscript: "Intrinsic Doping and Electrostatic Complexation of Sulfonated Poly(3,4-ethylenedioxythiophenes) (PEDOTs)", authored by Hyunki Yeo, Anush Singhal, Alexandra Zele, Rachel A. Segalman, and Michael L. Chabinyc. 

Experimental Methods

pH measurements and UV-vis spectroscopy of solutions upon titration. 1 mM aqueous solution of PEDOT-SS-Na was prepared. Titration among adding HCl solution was demonstrated with a Mettler Toledo InLab probe connected to a ThermoFisher pH meter, while the concentration and output pH were logged. On every integer pH, the solution was carried out for Uv-vis measurements using an Agilent Cary 60 UV-vis spectrophotometer.

Conductivity Measurements. PEDOT-nS films were prepared by drop-casting a 1 mM aqueous solution onto quartz substrates (25 mm × 25 mm × 1 mm). The films were then further annealed at 90°C for 30 minutes on a hot plate, followed with vacuum overnight. Electrical conductivity measurements were carried out on the resulting films (0.5 ~ 1 µm thickness) using the standard four-point probe meter (Ossilla, T2001A4). Film thickness was determined in dry air using a Bruker Dektak XT stylus profilometer. Complex films were blade coated on top of quartz or silicon substrates and followed the same procedure.

Cyclovoltammetry Measurements. CV measurements were carried out with potentiostat (Biologic, SP-200), in air in a solution of acetonitrile (thin films) with 5 wt % water containing 0.01 M LiTFSI, to be consistent with all other measurements conducted under ambient conditions. This choice was deliberate to reflect realistic device environments where oxygen is inevitably present and to ensure that all redox features observed are representative of performance under practical operating conditions. Both PEDOT-nS systems exhibited typical redox activity consistent with other conjugated polymers, maintaining broad features even at scan rates up to 200 mV/s. Adding 5% water to the electrolyte was essential for reproducible electrochemistry, but higher water content dissolved the polymer films. This balance optimizes dielectric properties to enable ion transport while preserving film integrity.

UV-vis-NIR spectroscopy of films. Films used for conductivity measurements were directly taken to absorption spectra collection, using an Shimadzu UV3600 UV-Nir-NIR spectrometer.

Grazing incidence wide angle X-ray scattering (GIWAXS). Identical films for UV-vis-NIR measurements were brought on beamline 11–3 at the Stanford Synchrotron Radiation Lightsource (SSRL). LaB6 was used as a calibration for the beam center and sample-to-detector distance (315 mm). 2D GIWAXS scattering images were collected using 2D Rayonix MX225 CCD area detector at an incidence angle of 0.10° with 30 s exposure times. The samples were kept under helium during X-ray exposure to minimize sample degradation and scattering from O2. The collected data was processed using Nika, a 2D data reduction macro on Igor Pro using established procedures.

Transmission Small angle X-ray scattering (SAXS) and Wide angle X-ray scattering (WAXS). Dried samples were placed in aluminum washers lined with Kapton tape, then the other side of the samples were sealed using Kapton tape. Measurements were carried out in a home built Next Generation SAXS/WAXS system.

X-ray diffraction (XRD). Polymers prepared in their powder form were loaded on an amorphous silicon disk. Measurement was carried out in a Panalytical Empyrean Powder Diffractometer. X-ray photoelectron spectroscopy (XPS). Experiments were conducted using an Escalab Xi+ Spectrometer (ThermoFisher Scientific) equipped with a monochromatic Al Kα X-ray source, operated under an ultra high vacuum of approximately 5 × 10-9 mbar. Charge compensation was achieved using a dual-mode low energy ion-electron flood gun. High-resolution spectra were collected at a pass energy of 20 eV with a step size of 0.05 eV (5 times), while survey scans were acquired at 100 eV pass energy with 0.5 eV intervals once.

Thermographic analysis (TGA). Thermogravimetric analysis (TGA) data were collected using a TA Instruments Q600 SDT Series simultaneous thermal analyzer, and the experiments were performed under a helium environment at a gas flow rate of 100 mL min-1. Samples were initially held isothermal for 10 min at 20 ℃, then heated to 800 ℃ at a rate of 10 ℃ min-1.

Files and variables

Each file names are associated with the content and description of data.

File names are formatted as: "Figure XX_Data Type and variables_Material_Sample type".

Plotted figures and type of variables, materials, and sample type are also defined in original manuscript.

Commonly used variables with abbreviations:

• q: q-factor (unit: Å^-1) in GIWAXS, WAXS and SAXS raw datafiles
• C: concentration (unit: mmol L^-1) in concentration datafiles
• V: voltage (unit: V) in CV and conductivity datafiles
• I: current (unit: A) in CV and conductivity datafiles
• E: binding energy (unit: eV) in XPS datafiles