Multiphonon emission model of spin-dependent exciton formation in organic semiconductors

The maximum efficiency in organic light-emitting diodes (OLEDs) depends on the ratio, $r=k_S/k_T$, where $k_S$ ($k_T$) is the singlet (triplet) exciton formation rate. Several recent experiments found that r increases with increasing oligomer length from a value $r \approx 1$ in monomers and short oligomers. Here, we model exciton formation as a multi-phonon emission process. Our model is based on two assertions: (i) More phonons are emitted in triplet formation than in singlet formation. (ii) The Huang-Rhys parameter for this phonon emission is smaller in long oligomers than in short ones. We justify these assertions based on recent experimental and theoretical data.