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Control is exerted over the exciton-polariton physics in metal -Poly(9,9-dioctyl fluorene) - metal microcavities via conformational changes tothe polymer backbone. Using thin-film samples containing increasing fractionsof $\beta$-phase chain segments, a systematic study is reported for the modecharacteristics and resulting light emission properties of cavities containingtwo distinct exciton sub-populations within the same semiconductor. Ultrastrongcoupling for disordered glassy-phase excitons is observed from angle-resolvedreflectivity measurements, with Rabi splitting energies in excess of 1.05 eV(more than 30% of the exciton transition energy) for both TE- and TM-polarizedlight. A splitting of the lower polariton branch is then induced viaintroduction of $\beta$-phase excitons and increases with their growingfraction. In all cases, the photoluminescence emanates from the lowermostpolariton branch, allowing conformational control to be exerted over theemission energy and its angular variation. Dispersion-free cavities with highlysaturated blue-violet emission are thus enabled. Experimental results arediscussed in terms of the full Hopfield Hamiltonian generalized to the case oftwo exciton oscillators. The importance of taking account of the molecularcharacteristics of the semiconductor for an accurate description of its strongcoupling behaviour is directly considered, in specific relation to the role ofthe vibronic structure.

Conformational Control of Exciton-Polariton Physics in Metal - Poly(9,9-dioctylfluorene) - Metal Cavities