The spectral breadth of conjugated polymers gives these materials a clear advantage over other molecular compounds for organic photovoltaic applications and is a key factor in recent efficiencies topping 10%. But why do excitonic transitions, which are inherently narrow, lead to absorption over such a broad range of wavelengths in the first place? Using single-molecule spectroscopy, we address this fundamental question in a model material, poly(3-hexylthiophene). Narrow zero-phonon lines from single chromophores are found to scatter over 200nm, an unprecedented inhomogeneous broadening which maps the ensemble. The giant red-shift between solution and bulk films arises from energy transfer to the lowest-energy chromophores in collapsed polymer chains which adopt a highly-ordered morphology. We propose that the extreme energetic disorder of chromophores is structural in origin. This structural disorder on the single-chromophore level may actually enable the high degree of polymer chain ordering found in bulk films: both structural order and disorder are crucial to materials physics in devices.
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