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...电掺杂半结晶导电聚合物（如聚(3-己基噻吩-2,5-二基)，poly(3-hexylthiophene-2,5-diyl)，简称P3HT）中，反离子与掺杂剂的分布对电荷输运起着至关重要的作用。本研究采用偏振共振软X射线散射（polarized resonant soft X-ray scattering, P-RSoXS）技术，对结晶度可控的掺杂P3HT薄膜中的反离子分布进行了表征。以三氟甲磺酰亚胺（trifluoromethanesulfonimide, TFSI⁻）和2,3,5,6-四氟-7,7,8,8-四氰基对苯二醌二甲烷（2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, F4TCNQ•⁻）作为载流子反离子的掺杂P3HT薄膜，其散射信号变化揭示了二者纳米结构的显著差异。本研究还探究了掺杂P3HT共混物的P-RSoXS散射各向异性随软X射线吸收边的变化规律，发现其随晶区与非晶区的组分占比以及反离子种类呈系统性变化。本研究开发了一套计算方法，用于模拟软X射线散射信号随形貌与分子取向……以及材料与制备工艺条件的变化关系。本研究选用了三种P3HT样品：数均分子量为4.5 kg/mol、分散度（dispersity, Đ）为1.6的低分子质量区域规整（regioregular, RRe）P3HT，分子量为23 kg/mol、Đ=1.8的高分子质量RRe P3HT，以及分子量为16.3 kg/mol、Đ=2.5的区域无规（regiorandom, RRa）P3HT（如图2所示）。将其溶解于等体积混合的氯苯与二氯苯溶剂中。将不同共混组分比例的P3HT溶液滴涂于基底上，制备得到厚度为700~1000 nm的薄膜。掺杂过程在惰性氮气手套箱中完成：将P3HT薄膜与约3 mg的F4TCNQ晶体按图3所示的方式置于密封罐内，将罐体加热至200 ℃并保温45 min，使F4TCNQ升华并氧化P3HT薄膜。含TFSI⁻的样品则通过阴离子交换法制备：将薄膜浸没于质量分数为0.03的LiTFSI乙腈溶液中，在60 ℃下反应120 min。对应论文中的表S1汇总了本研究使用的各类P3HT共混组分比例以及最终的团聚…… # 共振软X射线散射揭示半结晶共轭聚合物中的掺杂剂分布 [https://doi.org/10.5061/dryad.6t1g1jx65](https://doi.org/10.5061/dryad.6t1g1jx65) ## 数据与文件结构说明 本数据集聚焦于共轭聚合物聚(3-己基噻吩-2,5-二基)（P3HT）的偏振共振软X射线散射（Polarized Resonant Soft X-Ray Scattering, P-RSoXS）分析，该P3HT分别采用两种不同的小分子进行掺杂：三氟甲磺酰亚胺（TFSI⁻）与2,3,5,6-四氟-7,7,8,8-四氰基对苯二醌二甲烷（F4TCNQ•⁻）。本研究构建了该材料体系的数字孪生模型，用于模拟P-RSoXS实验过程。为支撑模型开发，本研究采用了多种物理表征手段：包括利用原子力显微镜（Atomic Force Microscopy, AFM）表征样品表面形貌，掠入射广角X射线散射（Grazing Incidence Wide Angle X-Ray Scattering, GIWAXS）测定晶体取向分布，紫外-可见吸收光谱（UV-vis spectroscopy）评估样品结晶度，以及X射线光电子能谱（X-Ray Photoelectron Spectroscopy, XPS）用于……