Growth of ordered molecular layers of PTCDA on Pb/Si(111) surfaces: a scanning tunneling microscopy study

The growth of well-ordered layers of PTCDA (3,4,9,10-perylene-tetracarboxylic-dianhydride) molecules on Pb/Si(111) surfaces has been investigated by scanning tunneling microscopy (STM) under ultra-high vacuum conditions. These Pb/Si(111) substrates, which present several distinct phases with different reconstructions, have allowed the exploration of new passivation schemes for the growth of ordered organic layers on Si(111) surfaces. According to our STM measurements, the higher Pb coverage phases (namely the so-called hexagonal incommensurate and reconstructions) present rather inert surfaces that allow easy diffusion of PTCDA molecules at room temperature and the formation of a well ordered first molecular layer which displays a herringbone reconstruction. For multilayer PTCDA coverage on these Pb/Si(111) phases, the formation of three-dimensional crystallites, with structure similar to that of the bulk PTCDA crystal, has been observed, indicating that a Stranski-Krastanov growth mode is dominant. On lower Pb coverage substrates (presenting the defective and mosaic reconstructions) no long range PTCDA order has been obtained. The systematic variation of the substrate reconstruction has allowed in the present work the relation of the surface reactivity of each reconstruction to the formation of ordered layers of PTCDA on Pb/Si(111) substrates.