Who's on first? Tracking in real time the growth of multiple crystalline phases of an organic semiconductor: Tetracene on SiO2.

We have examined the effect of growth rate on the evolution of two polymorphs of thin films of tetracene on SiO2 using synchrotron X-ray radiation and molecular beam techniques. Ex situ X-ray reflectivity shows that tetracene forms two phases on SiO2: a thin-film phase and a bulk phase. We have used in situ, real-time grazing incidence diffraction during growth to reveal the nature of growth concerning these two phases. We observe that there is initially growth of only the thin-film phase, up to a thickness of several monolayers. This is followed by the nucleation of the bulk phase, growth of both phases, and finally growth of only the bulk phase. We find that the deposited thickness when the bulk phase nucleates increases with increasing growth rate. Similarly, we find that the deposited thickness at which the thin-film phase saturates also increases with increasing growth rate. These apparent dependencies on growth rate are actually a consequence of the local coverage, which depends on growth rate, particularly for the former effect. At low growth rates, there is 3D growth resulting from the upward transport of tetracene at island edges, resulting in tall features where molecules escape the influence of the substrate and form into the bulk phase. Increasing the growth rate leads to growth that is more 2D and uniform in coverage, delaying the formation of the bulk phase.