Dynamic interactions between poly(3-hexylthiophene) and single-walled carbon nanotubes in marginal solvent

Interfacial interactions between conjugated polymers and carbon nanotubes are pivotal in determining the device performance of nanotube-based polymer electronic devices. Here, we report on interfacial structures and crystallization kinetics of poly(3-hexylthiophene) (P3HT) in the presence of single-walled carbon nanotubes (SWNTs) in anisole by means of transmission electron microscope (TEM) and ultraviolet-visible (UV-vis) absorption spectroscopy. Confined on SWNT surfaces, the P3HT forms nanofibril crystals perpendicular to the long axis of SWNTs. The equilibrium dissolution temperature of the P3HT crystals in anisole is determined to be 381 ± 10 K according to the Hoffman-Weeks extrapolation approach. Upon cooling, the polymer solution spontaneously undergoes a time-dependent chromism. Various kinetics factors such as crystallization temperature, concentration, and SWNT loading have been investigated. It is found that the growth rate (G) of the crystals scales with concentration (C) as G ∝ C(1.70±0.16). The Avrami model is utilized to analyze the nucleation mechanism and the Avrami exponents vary between 1.0 and 1.3. The Lauritzen-Hoffman theory is applied to study the chain-folding process. The fold surface free energy is calculated to be (5.28-11.9) × 10(-2) J m(-2). It is evident that the addition of 0.30 wt % SWNTs reduces the fold surface free energy by 55.6%.