Abstract
Metal–organic hybrid structures have been demonstrated to be a versatile platform to study primary aspects of light–matter interaction by means of emerging states comprising excitonic and plasmonic properties. Here we are studying the wave-vector-dependent photoexcitations in gold layers covered by molecular films of zinc phthalocyanine and its fluorinated derivatives (FnZnPc, with n = 0, 4, 8, 16). These layered metal–organic samples show up to four anticrossings in their dispersions correlating in energy with the respective degree of ZnPc fluorination. By means of complementary structural and theoretical data, we attribute the observed anticrossings to three main scenarios of surface plasmon coupling: (i) to aggregated α-phase regions within the FnZnPc layers at 1.75 and 1.85 eV, (ii) to a coexisting F16ZnPc β-polymorph at 1.51 eV, and (iii) to monomers, preferentially located at the metal interface, at 2.15 eV. Whereas energy and splitting of the monomer anticrossings depend on strength and average tilting of the molecular dipole moments, the aggregate-related anticrossings show a distinct variation with degree of fluorination. These observations can be consistently explained by a change in FnZnPc dipole density induced by an increased lattice spacing due to the larger molecular van der Waals radii upon fluorination. The reported results prove Au/FnZnPc bilayers a model system to demonstrate the high sensitivity of exciton–plasmon coupling on the molecular alignment at microscopic length scales.
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