Koya NishiyamaYi-Tso HsiaoWei-Ni WuJhih-Min LinSHIH-HUANG TUNGCHENG-LIANG LIUTomoya Higashihara2025-01-212025-01-21202420507488https://www.scopus.com/record/display.uri?eid=2-s2.0-85213028570&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/724979Semiconducting polymers are lightweight, low cost, and easy to manufacture, making them promising candidates for application in electronic devices. In this study, poly(thienylene vinylene) (PTV) with alkylthio side chains, poly[3,4-bis(2-ethylhexylthio)thienylene vinylene] (P3,4EHTTV), was successfully synthesized using an environmentally friendly polymerization system that employs neither transition-metal catalysts nor halogens. The polymerization proceeded via a chain-growth mechanism, exhibiting a “quasi-living” nature. P3,4EHTTV was then combined with single-walled carbon nanotubes (SWCNTs) to fabricate nanocomposite thin films with thermoelectric (TE) properties. The strong S-π and π-π interactions between P3,4EHTTV and SWCNTs promoted the close wrapping of P3,4EHTTV around the SWCNTs, leading to effective dispersion of SWCNT bundles. The electrical conductivity of P3,4EHTTV/SWCNT nanocomposites demonstrated a pronounced p-doping effect and increased carrier mobility. Additionally, the P3,4EHTTV/SWCNT system showed favorable charge distribution and improved alignment of energy levels, contributing to considerably improved TE properties, with a record-breaking power factor of 363.7 μW m−1 K−2. These findings highlight the importance of structural design in PTV and alkylthio side-chain engineering for optimizing TE performance.falsejournal article10.1039/d4ta07611g2-s2.0-85213028570