Molecular beam epitaxy of organic films investigated by high resolution low energy electron diffraction (SPA-LEED): 3,4,9,10-perylenetetracarboxylicacid-dianhydride (PTCDA) on Ag(1 1 1)

A detailed investigation of the multilayer growth of PTCDA on Ag(1 1 1) by high resolution LEED (SPA-LEED) is reported. The first two monolayers are closed and exhibit a structure, which is commensurate with respect to the underlying Ag(1 1 1) surface. The lattice parameters are close to those of the (1 0 2) plane of the β bulk phase of PTCDA, with deviations ⩽2%. The vertical stacking of the second layer with respect to the first monolayer (observed at 300 K) corresponds to that in the β bulk phase of PTCDA. At high growth temperatures (400 K), Stranski–Krastanov growth occurs from the third monolayer onward, and PTCDA clusters, preferentially with few well defined facets, grow. The structure of the clusters is that of the thermodynamically more stable α bulk phase of PTCDA. Contrary, at low growth temperatures (200 K), the growth proceeds in the Frank van der Merve mode, with several open layers. From slope selection there is evidence for an Ehrlich–Schwoebel barrier. The lateral packing of the PTCDA grown at low temperatures corresponds within error to that of the β bulk phase. The low temperature structure and morphology is meta-stable. Short annealing at 300 K flattens the PTCDA film, and prolonged annealing at 400 K causes the film to adapt the structure and morphology obtained directly at 400 K growth temperature. Presumably, the formation of layers with a β-phase-like lattice at low temperature is due to the better fit of the β phase, compared to the α phase lattice, to the underlying commensurate monolayer. However, at high growth temperatures, the thermodynamically more stable α phase grows, reducing the area of lattice misfit to the underlying commensurate first two layers by formation of clusters.