An Improved Optical Method for Determining the Order Parameter in Thin Oriented Molecular Films and Demonstration of a Highly Axial Dipole Moment for the Lowest Energy π–π* Optical Transition in Poly(9,9‐ dioctylfluorene‐co‐bithiophene)

Understanding the complex interplay between the 3D structural hierarchy within thin films of conjugated polymers and the properties of devices based thereon is starting to be recognized as an important challenge in the continued development of these materials for a range of applications. As a result, for example, accurate measurements of molecular orientation and elucidation of its influence on optical characteristics are of significant interest. Here we report an improved optical method to determine both the order parameter and the angle between the polymer backbone director and the optical transition dipole moment for the lowest energy π–π* absorption peak in uniaxially aligned thin films of conjugated polymers. The method uses a combination of polarized Raman spectroscopy and UV‐vis spectroscopy and is based on a general theoretical treatment to describe the expected Raman and optical absorption anisotropies of such films. It is applied to study the orientation within thermotropically aligned films of the electroluminescent fluorene‐based copolymer poly(9,9‐dioctylfluorene‐co‐bithiophene) (F8T2). A more highly axial transition dipole moment is found for the dominant long wavelength absorption peak of F8T2 compared to that of other fluorene‐based (co)polymers. The angle between the polymer backbone director and the transition dipole is estimated to be β ≤ 3°, a deduction that helps to explain the relatively large optical dichroism for aligned films of F8T2 and that offers the prospect of highly polarized electroluminescence from F8T2‐based light‐emitting diodes.