Influence of Simultaneous Tuning of Molecular Weights and Alkyl Substituents of Poly(thienoisoindigo-alt-naphthalene)s on Morphology and Change Transport Properties

To simultaneously assess the impact of molecular weight (Mn) and alkyl substituent variations of polymers on the structural and optoelectronic properties, herein, we conduct a systematic study of a series of poly­(thienoisoindigo-alt-naphthalene) (PTIIG-Np)-based polymers containing different alkyl substituents (2-hexyldecyl (HD), 2-octyldodecyl (OD), and 2-decyltetradecyl (DT) chains) and Mn’s (low (L) and high (H)). All of the polymers produce almost identical energy levels, whereas their optical spectra show a clear dependence on Mn’s and the alkyl substituents. Interestingly, increasing the alkyl substituent sizes of the polymers steadily increases the lamellar d-spacings (d100), ultimately leading to a densely packed lamellar structure for PTIIGHD-Np. In addition, both H-PTIIGOD-Np and H-PTIIGDT-Np exhibit larger π-stacking crystallites than the corresponding low-Mn polymers, while for PTIIGHD-Np, their size increases in the low-Mn batch. Ultimately, L-PTIIGHD-Np shows the best hole mobility of 1.87 cm2 V–1 s–1 in top-gate and bottom-contact organic field-effect transistors (OFETs) with a poly­(methyl methacrylate), which is nearly 1 order of magnitude higher than other polymers tested in this study. Our results demonstrate that the simultaneous Mn and alkyl substituent engineering of the polymers can optimize their film morphology to produce high-performance OFETs.