Study of free volume and crystallinity in polybithiophene and poly(3-methylthiophene)

Compressed pellets of partly crystalline, chemically synthesized, doped (Cl^? and FeCl) polybithiophene (PBTd), poly(3-methylthiophene) (P3MTd), and their neutral (dedoped) forms (PBTn and P3MTn) were studied by wide-angle x-ray diffraction and positron annihilation lifetime spectroscopy. As synthesized, PBTd and P3MTd polymers have a helical syn conformation they crystallize in the hexagonal system. On dedoping, PBT macromolecules change their helical syn conformation in a rodlike anti conformation and crystallize in the orthorhombic or monoclinic system, whereas P3MT macromolecules retain their helical syn conformation. Chemical doping–dedoping cycles lead to amorphous PBT and P3MT in either doped or dedoped states. The P3MT helical macromolecule behaves like a spiral spring; by doping, it becomes axially compressed. The unit-cell volume of P3MTd is smaller than that of P3MTn. The positron lifetime spectra for all polymers were resolved, without constraint, into three components. The τ₁ lifetime is attributed to free-positron annihilation events, the τ₂ lifetime to positrons annihilating trapped in voids, and the τ₃ lifetime to positrons annihilating as o-Ps trapped in cavities located inside the polymer grains for P3MTn and at the surface of the grains for PBTd, PBTn, and P3MTd. Most positrons annihilate when trapped in voids, both in doped and dedoped PBT and P3MT. The doping apparently increases the concentration of the voids and their mean diameter in P3MT, and probably also in PBT. Cavities anchored in the bulk are produced by dedoping. © 1993 John Wiley & Sons, Inc.