Resonant Soft X-ray Scattering Reveals the Distribution of Dopants in Semicrystalline Conjugated Polymers

The distribution of counterions and dopants within electrically doped semicrystalline conductive polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT), plays a pivotal role in charge transport. The distribution of counterions in doped films of P3HT with controlled crystallinity was examined using polarized resonant soft X-ray scattering (P-RSoXS). The changes in scattering of doped P3HT films containing trifluoromethanesulfonimide (TFSI−) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ•−) as counterions to the charge carriers revealed distinct differences in their nanostructure. The scattering anisotropy of P-RSoXS from doped blends of P3HT was examined as a function of the soft X-ray absorption edge and found to vary systematically with the composition of crystalline and amorphous domains and by the identity of the counterion. A computational methodology was developed and used to simulate the soft X-ray scattering as a function of morphology and molecular orientatio..., Materials and Processing Conditions. Low number-average molecular mass regioregular (RRe) P3HT [4.5 kg/mol, dispersity (Đ) = 1.6], high molecular mass RRe P3HT (23 kg/mol, Đ = 1.8), and regiorandom (RRa) P3HT (16.3 kg/mol, Đ = 2.5) (Figure 2), were dissolved in an equal-volume mixture of chlorobenzene and dichlorobenzene. P3HT solutions of varying blend composition were drop cast onto substrates to form (700 to 1000) nm thick films. P3HT films were doped in an inert nitrogen glovebox atmosphere, enclosing the film and ≈3 mg of F4TCNQ crystals within a jar in the orientation depicted in Figure 3.36 The jar was heated to 200 °C for 45 min, allowing for sublimation of F4TCNQ to oxidize the P3HT film. TFSI−-containing samples were formed by anion exchange from immersion in a concentrated LiTFSI solution (0.03 mass fraction in acetonitrile) for 120 min at 60 °C. Table S1 in the corresponding article summarizes the varying P3HT blend compositions utilized in this study, resultant levels of ag..., , # Resonant Soft X-ray Scattering Reveals the Distribution of Dopants in Semicrystalline Conjugated Polymers

[https://doi.org/10.5061/dryad.6t1g1jx65](https://doi.org/10.5061/dryad.6t1g1jx65)

## Description of the data and file structure

This work focuses on the analysis of Polarized Resonant Soft X-Ray Scattering (P-RSoXS) from a conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT), doped with two distinct small molecules: trifluoromethanesulfonimide (TFSI⁻) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ•⁻). A digital twin of the material system was developed to simulate the P-RSoXS experiments. To support the model's development, various physical characterization methods were employed, including Atomic Force Microscopy (AFM) to assess sample surface morphology, Grazing Incidence Wide Angle X-Ray Scattering (GIWAXS) to determine crystal orientation distribution, UV-vis spectroscopy to evaluate sample crystallinity, and X-Ray Photoelectron Spectroscopy (XPS) to...