Correlation of viscoelastic properties with solvation of regioregular poly(3-decylthiophene) films

Viscoelastic properties of regioregular poly(3-decylthiophene) films cast on gold electrodes and exposed to acetonitrile/LiClO4 solution were studied using high-frequency acoustic impedance. Values of shear moduli, G = G' + jG'', were determined under conditions of potentiodynamic and potentiostatic electrochemical control, as functions of potential (0.0 < E/V < 0.8), temperature (5 < T/ degrees C < 70), and angular frequency (omega = 2pi f; 10 < f/MHz < 110). The effect of potential was small, of temperature was significant, and of frequency was dominant. The principle of time-temperature equivalence was used to construct master relaxation curves. Application of activation, Williams-Landel-Ferry, and Rouse-Zimm models shows the material to be quite different from other thiophene-based conducting polymers, namely, poly(3,4-ethylenedioxythiophene) and regioregular poly(3-hexylthiophene). Detailed exploration of the data reveals novel insights into the compositional origins--notably with regard to solvation--of the shear modulus behavior.