Energy dissipation via radiative recombination and vibronic relaxation in σ-delocalized silicon backbone network polymers

The nature of ultrafast energy dissipation in poly(n-hexylsilyne), a prototypical σ-delocalized alkysilicon network polymer, is explored. This disordered silicon backbone material exhibits strong near-UV to visible band-edge absorption and a high quantum yield of visible emission. The time evolution of the emission band is studied over four decades of time using time-resolved luminescence as a probe. The data indicate that while there is an ‘intrinsic’ Stokes shift after photoexcitation due to kinetic energy relaxation (<10ps), thermalization within a dense band of vibronic states via intramolecular phonon-assisted hopping on a nanosecond timescale is the dominant mechanism for excited-state decay. The data can be understood in terms of theoretical predictions for energy relaxation in disordered materials.