We report on structural investigations of a series of regioregular poly(3-hexylthiophene) with well-defined molecular weight (5-19 kg/mol) using DSC, small angle and wide-angle X-ray scattering, and AFM. With increasing temperature, we identify three ordered phases, namely 3D crystalline, 2D crystalline with disordered side chains, and a layered phase of smectic symmetry, followed by complete melting. Although all samples crystallize in extended chain conformation, the lower molecular weight material exhibits a lower crystallinity, most likely caused by noncrystallizable end groups. The crystallinity increases strongly with increasing molecular weight, which could be a possible explanation for the known dependence of charge transport properties on molecular weight.

Highly oriented films of an electron accepting polymer semiconductor, poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (PNDI2OD-T2), are obtained by two different methods, namely directional epitaxial crystallization (DEC) on 1,3,5-trichlorobenzene (TCB) and epitaxy on friction transferred poly(tetrafluoroethylene) (PTFE) substrates. Two distinct polymorphs with unprecedented intrachain resolution are identified by high-resolution transmission electron microscopy (HR-TEM). Form I is obtained by DEC on TCB, whereas highly oriented films of form II are obtained on PTFE substrates after melting at T = 300 °C and cooling at 0.5 K/min. In form I, both electron diffraction and HR-TEM indicate a segregated stacking of bithiophene (T2) and naphthalene diimide (NDI) units forming separate columns. In form II, a ∼c/2 shift between successive π-stacked chains leads to mixed π-overlaps of T2 and NDI. Form I can be transformed into form II by annealing at T > 250 °C. The different π-stacking of NDI and T2 in the two polymorphs have characteristic signatures in the UV-vis spectra, especially in the charge transfer band around 750 nm which is also observed in spin-coated films.

A highly efficient, simple, and environmentally friendly protocol for the synthesis of an alternating naphthalene diimide bithiophene copolymer (PNDIT2) via direct arylation polycondensation (DAP) is presented. High molecular weight (MW) PNDIT2 can be obtained in quantitative yield using aromatic solvents. Most critical is the suppression of two major termination reactions of NDIBr end groups: nucleophilic substitution and solvent end-capping by aromatic solvents via C-H activation. In situ solvent end-capping can be used to control MW by varying monomer concentration, whereby end-capping is efficient and MW is low for low concentration and vice versa. Reducing C-H reactivity of the solvent at optimized conditions further increases MW. Chain perfection of PNDIT2 is demonstrated in detail by NMR spectroscopy, which reveals PNDIT2 chains to be fully linear and alternating. This is further confirmed by investigating the optical and thermal properties as a function of MW, which saturate at Mn ≈ 20 kDa, in agreement with controls made by Stille coupling. Field-effect transistor (FET) electron mobilities μsat up to 3 cm(2)/(V·s) are measured using off-center spin-coating, with FET devices made from DAP PNDIT2 exhibiting better reproducibility compared to Stille controls.

Molecular doping of organic semiconductors is critical for optimizing a range of optoelectronic devices such as field‐effect transistors, solar cells, and thermoelectric generators. However, many dopant:polymer pairs suffer from poor solubility in common organic solvents, which leads to a suboptimal solid‐state nanostructure and hence low electrical conductivity. A further drawback is the poor thermal stability through sublimation of the dopant. The use of oligo ethylene glycol side chains is demonstrated to significantly improve the processability of the conjugated polymer p(g42T‐T)—a polythiophene—in polar aprotic solvents, which facilitates coprocessing of dopant:polymer pairs from the same solution at room temperature. The use of common molecular dopants such as 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) and 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) is explored. Doping of p(g42T‐T) with F4TCNQ results in an electrical conductivity of up to 100 S cm−1. Moreover, the increased compatibility of the polar dopant F4TCNQ with the oligo ethylene glycol functionalized polythiophene results in a high degree of thermal stability at up to 150 °C.

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