The understanding of the optical characteristics and the influence of thermally induced crystallization is vital to evaluate newly synthesized organic semiconductors for their potential applications. Variable‐angle spectroscopic ellipsometry (VASE) is employed to determine the complex dielectric function of two recently developed discrete oligomers based on naphthalene diimide (NDI) and bithiophene (T2), applying an anisotropic optical model. It is shown that the as‐cast films are optically near‐isotropic, while the annealed films exhibit pronounced anisotropies with respect to the orientation of the π−π* transition. Differences between the two distinct molecules are observed and discussed. The degree of optical anisotropy is quantified using the average molecular orientation angle φ, associated with the orientation of the π−π* transition dipole, and the related orientation order parameter S. The molecules are shown to form crystallites of several microns in size upon annealing. Imaging ellipsometry is thus additionally employed to study their optical anisotropy on a microscopic scale, and the agreement with results from macroscopic measurements is evaluated.
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