The crucial role played by the solution–vapor interface in determining the growth and morphology of an organic semiconductor thin film formed by solvent evaporation has been examined in atomic detail. Specifically, how the loss of individual solvent molecules from the surface of the solution induces solute assembly has been studied using molecular dynamics simulations. The system consisted of bis(2-phenylpyridine) (acetylacetonate)­iridium­(III) [Ir­(ppy)2(acac)] and 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) in chloroform at 310 K. The simulations clearly indicate that (a) the system does not undergo uniform phase separation (spinodal decomposition), (b) solute aggregation initiates at the solution–vapor interface, (c) the distribution of solvent in the film is nonhomogeneous, (d) this nonhomogeneous distribution can induce preferential alignment of host molecules, and (e) a portion of the solvent likely remains trapped within the film. The work not only demonstrates the ability to directly model evaporation in atomic detail on the relevant length scales but also shows that atomistic simulations have the potential to shed new light on morphological properties of a wide range of organic semiconductor devices manufactured using solution-processing methods.

Atomistic nonequilibrium molecular dynamics simulations have been used to model the morphology of small-molecule bulk heterojunction films formed by vapor deposition as used in organic photovoltaics. Films comprising C and 1, 5, 10, and 50 wt % of 1,1-bis[4-bis(4-methylphenyl)aminophenyl]cyclohexane (TAPC) were compared to films of neat C. The simulations suggest that if holes can hop between donor molecules separated by as little as 1.2-1.5 nm, then a TAPC concentration of 5 wt % is sufficient to form a percolating donor network and facilitate charge extraction. The results provide an explanation for why low donor content organic photovoltaics can still have high efficiencies. In addition, the roughness, porosity, and crystallinity of the films were found to decrease with increasing TAPC content.

The performance of organic optoelectronic devices, such as organic light-emitting diodes (OLEDs) and organic solar cells (OSCs), is intrinsically related to the molecular-scale morphology of the thin films from which they are composed. However, the experimental characterization of morphology at the molecular level is challenging due to the often amorphous or at best semicrystalline nature of these films. Classical molecular modeling techniques, such as molecular dynamics (MD) simulation, are increasingly used to understand the relationship between morphology and the properties of thin-film devices. PyThinFilm () is an open-source Python package which allows fully automated MD simulations of thin film growth to be performed using vacuum and/or solution deposition processes. PyThinFilm utilizes the GROMACS simulation package in combination with interaction parameters from the Automated Topology Builder (). Here, PyThinFilm is described along with an overview of applications in which PyThinFilm has been used to study the thin films of organic semiconductor materials typically used in OLEDs and OSCs.