Roughness evolution in strongly interacting donor:acceptor mixtures of molecular semiconductors. An in situ, real-time growth study using x-ray reflectivity.

The evolution of surface roughness in binary mixtures of the two molecular organic semiconductors (OSCs) diindenoperylene (DIP) as electron-donor and 1, 3, 4, 5, 7, 8-hexafluoro-tetracyano naphthoquinodimethane (F6TCNNQ) as electron-acceptor is studied. We co-deposit DIP and F6TCNNQ in vacuum with varying relative molar content while keeping a molar excess of DIP in order to produce phase-heterogeneous mixtures. The excess DIP phase segregates in pristine crystallites, whereas the remaining mixed phase is constituted by DIP:F6TCNNQ co-crystallites. We calculate the surface roughness as function of film thickness by modelling x-ray reflectivity data acquired in situ and in real-time during film growth. To model the experimental data, two distinct approaches, namely the kinematic approximation and the Parratt formalism, are applied. A comparative study of surface roughness evolution as function of DIP:F6TCNNQ mixing ratio is carried out implementing the Trofimov growth model within the kinematic approximation. Depending on the thickness regime, mixing ratio-specific trends are identified and discussed. To explain them, a growth mechanism for binary heterogeneous mixtures of strongly interacting OSCs is proposed.