Thermochromic transitions in poly(di-n-hexylsilane) films

The spectra of absorption (77–398 K) and luminescence (5 K) of poly(di-n-hexylsilane) films are studied in relation to the heating of the films above the phase transition temperature. Two new absorption bands in the region of the band of the gauche conformation are found. The position and intensity of these bands depend on the annealing temperature, annealing regime, and sample thickness. These bands are assumed to be associated with the appearance of a liquid crystalline phase in the polymer, which is determined by intermolecular interactions between neighboring polymer chains. The appearance of the liquid crystalline phase in the heat-treated polymer films is confirmed by the increase in their birefringence in comparison with the birefringence of the initial films and by the observation of a stable orientation of an E 7 nematic liquid crystal applied to the surface of an annealed sample. In addition, the absorption spectra of the films cooled after the annealing exhibit many new bands in comparison with the spectra of the initial samples. These bands are associated with the appearance in the polymer of defect states and longer segments as a result of orientation of polymer chains. The appearance of longer segments is consistent with the observation of a long-wavelength band in the luminescence spectra of the annealed samples.