Ultrafast
charge delocalization dynamics in excited states of internal
donor–acceptor copolymer poly[2,7-(9,9-bis(2-ethylhexyl)-dibenzosilole)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole] (PSiF-DBT)
was studied by resonant Auger spectroscopy (RAS) measured around silicon
and sulfur K edges using the core-hole clock approach. The effect
of the thermal annealing treatment at 100 and 200 °C on the charge
transfer delocalization times and molecular orientation were probed.
Exponential dependence of charge transfer times (τ CT) with photon energy was found at both absorption edges with a decreasing
curve slope with the thermal treatment. Features characteristics of
the Auger Resonant Raman effect were observed at sulfur KL2,3L2,3 Auger decay spectra. Edge-on and plane-on molecular
orientations with respect to the substrate surface were measured for
the thiophene and benzothiadiazole units, respectively, using angular-dependent
NEXAFS spectra at the S K edge. Molecular orientation of silafluorene
was also probed by NEXAFS at the Si K edge. The improvement of the
polymer ordering with annealing was evaluated by NEXAFS. Differences
in charge transfer times at Si and S K edges may be related to the
localized–delocalized character of the molecular orbitals (MOs)
involved in those excitation processes, which was corroborated by
theoretical calculations at the Hartree–Fock (HF) level, with
explicit relaxation of molecular orbitals due to the core-hole. The
molecular orientation effect in the charge transfer process was also
investigated through the nonadiabatic coupling matrix elements involving
the first low-lying excited states in both K edge excitations.