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Herein reported is the impact of the functionalization of four different semiconducting polymer structures by a linear siloxane‐terminated side‐chains. The latter is tetrasiloxane (Si4) or trisiloxane (Si3) chains, substituted at their extremity to a pentylene linker. The polymer structure is based on 5,6‐difluorobenzothiadiazole comonomer (PF2), a diketopyrrolopyrrole unit (PDPP‐TT), a naphtalediimide unit (PNDI‐T2), and a poly[bis(thiophen‐2‐yl)thieno[3,2,b]thiophene (PBTTT). The properties of these siloxane‐functionalized polymers are scrutinized and compared with the ones of their alkyl‐substituted polymer analogues. The impact of the alkyl‐to‐siloxane chain substitution clearly depends on the molecular section of the side chains. When a branched 2‐octyldodecyl chain (C20) is replaced by a Si4 chain of same molecular section, the greatest impact is the strong increase of the π‐stacking overlap of the polymer backbones. This effect leads to a significative enhancement of the charge mobility values of the polymers. As in‐plane and out‐of‐plane mobility are increased simultaneously, this π‐overlap enhancement effect happens to be preponderant over the polymer orientation variations. When a linear tetradecyl chain (C14) is replaced by a linear Si3 chain of twice larger molecular section, the polymer structure is profoundly affected. While PBTTT‐C14 is crystalline and purely edge‐on, PBTTT‐Si3 is mesomorphic and shows a mixed face‐on/edge‐on orientation. [ABSTRACT FROM AUTHOR]

In this contribution, doping of oriented thin films is investigated for three PBTTT polymers bearing different side chains including linear alkyl ─(CH 2 ) 12 ─H, single ether ─(CH 2 ) 7 ─O─(CH 2 ) 4 ─H and alkyl-siloxane ─(CH 2 ) 5 ─(Si(CH 3 ) 2 O) 2 ─Si(CH 3 ) 3 A combination of transmission electron microscopy, polarized UV-vis-NIR spectroscopy and transport measurements helps uncover the essential role of the chemical nature of side chains on the efficacy of the doping and on the resulting thermoelectric performances in oriented PBTTT films. Siloxane side chains help to reach record alignment level of PBTTT with dichroic ratio beyond 50 for an optimized rubbing temperature but they impede effective doping of PBTTT crystals with F 6 TCNNQ, resulting in very poor TE properties. By contrast, doping the amorphous phase of all three PBTTTs with magic blue (MB) results in excellent TE performances. Both, chemical nature of side chains and semi-crystalline structure of the polymer determine the efficacy of doping. The use of siloxane side chains further impacts the scaling laws S ∝ σ -1/s between the Seebeck coefficient S and the charge conductivity σ. An unexpected s  =  2 exponent is observed and tentatively attributed to the dimensionality of charge transport in the highly oriented mesophase of PBTTT., (© 2024 Wiley‐VCH GmbH.)