In this work the optical response, spectroscopic behaviour, and optoelectronic properties of solution and solid state composite systems based on α,ω-dihexylsexithiophene/tris(8-hydroxyquinolinate) gallium (DH6T/Gaq3) are studied upon the incorporation of different molar percentages of Gaq3. UV-vis, PL, FTIR spectrophotometers and SEM technique were utilized to perform the investigations. The results showed a reduced energy band (Eg) (from 2.33eV to 1.83eV) and a broadened absorption spectrum for the blend system when 29.8% molar of Gaq3 was incorporated. These were attributed to the enhanced intermolecular interactions that are brought about by the increased strength of π-π overlap between the molecular moieties. A mathematical formula was developed to interpret the non-monotonic change occurred in Eg, while numerical calculations have been made to assign the type and nature of the electronic transitions governing the spectroscopic behaviour of the system. The results were elaborated and comprehensively discussed in terms of the exciton generation, energy band theory, molecular interactions, and spatial geometry.
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