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Journal Article

Origin of spectral broadening in pi-conjugated amorphous semiconductors


Lupton,  J. M.
MPI for Polymer Research, Max Planck Society;

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Lupton, J. M., Samuel, I. D. W., & Burn, P. L. (2002). Origin of spectral broadening in pi-conjugated amorphous semiconductors. Physical Review B, 66(15): 155206. doi:10.1103/PhysRevB.66.155206.

Cite as: http://hdl.handle.net/11858/00-001M-0000-000F-64D4-A
We present a study of the picosecond fluorescence dynamics of pi-conjugated semiconducting organic dendrimers in the solid state. By varying the degree of branching within the dendrons, referred to as the dendrimer generation, a control of intermolecular spacing of the emissive core and therefore of the lattice parameter for Forster-type energy transfer is achieved. This allows a distinction between spectral diffusion and excimer formation as the two main sources of spectral broadening in organic semiconductors. Whereas Forster-type dispersive spectral relaxation is independent of temperature but strongly dependent on the interchromophore distance, excimer formation is also strongly thermally activated due to temperature-dependent conformational changes and the influence of thermally activated dynamic disorder. The rapid spectral diffusion allows a determination of the excimer rise in the emission, which is shown to have a profound impact on the steady state luminescence properties of dendrimer films. We show that the dendrimer generation not only allows a microscopic control of intermolecular interactions but also a direct control of the rate of spectral diffusion. Implications for the design of novel materials for optoelectronic devices are discussed.