3,4,9,10-perylene tetracarboxylic diimide molecules were evaporated onto a Ag/Si(111)-√3 × √3 surface and studied by scanning tunneling microscopy/spectroscopy and low energy electron diffraction (LEED). The growth mode was characterized as layer-by-layer growth with a single molecular unit cell in a short range order. The growth of the first two monolayers involves a molecule/substrate superstructure and a molecule/molecule superstructure. At higher coverages, the molecules in each layer were found to align so that unit cells are on top of each other. The experimentally obtained LEED pattern is described as a combination of patterns from the molecular unit cell and the molecule/substrate superstructure. The electronic structure was found to be strongly dependent on the film thickness for the first few layers: Several extra states are found at low coverages compared to higher coverages resulting in a very small pseudo gap of 0.9 eV for the first layer, which widens up to 4.0 eV for thicker films.

3,4,9,10-perylene tetracarboxylic diimide molecules were evaporated onto a Ag/Si(111)-3×3 surface and studied using photoelectron spectroscopy and near edge X-ray absorption fine structure (NEXAFS). All core levels related to the imide group of the molecules showed a partial shift to lower binding energies at low coverages. In NEXAFS spectra, the first transitions to the unoccupied states were weaker at low coverages compared to thicker films. Also, extra states in the valence band between the regular highest occupied molecular orbital and the Fermi level were found at low coverages. These changes were explained by two types of molecules. Due to charge transfer from the surface, these two types have different interactions between the imide group and the substrate. As a result, one type has a partially filled lowest unoccupied molecular orbital while the other type does not.

Perylene tetracarboxylic diimide molecules were evaporated onto a Sn/Si(111)-2 √ 3 × 2 √ 3 surface and studied using scanning tunneling microscopy (STM) and low energy electron diffraction. At low coverages, single molecules are locked into specific adsorption geometries, which are investigated in detail using high resolution STM. The electronic structure of these individual molecules was studied using bias dependent STM images. The molecules form 1D rows that become more common with increasing coverages. Possible intermolecular O• • • H interactions within the rows have been identified. At around half of a monolayer (ML), the rows of molecules interact with each other and form a commensurate 4 √ 3 × 2 √ 3 reconstruction. In a complete monolayer, several structures emerge as molecules fill in the space between the 4 √ 3 × 2 √ 3 stripes. Possible intermolecular interactions within the 1 ML structures have been discussed. At coverages above 1 ML, the growth is characterized by island growth, where the molecules are arranged according to the canted structure within the layers.

PTCDI molecules were evaporated onto a Ag/Si(111) √ 3× √ 3 surface and studied using scanning tunneling microscopy (STM) and angular resolved ultraviolet photoelectron spectroscopy (ARUPS). High resolution STM images are used to identify the delicate molecule/molecule and molecule/substrate interactions and the shapes of the molecular orbitals. The results show that the substrate/molecule interaction strongly modifies the electronic configuration of the molecules as their orbital shapes are quite different at 1 and 2 monolayer (ML) coverage. Simple models of molecular HOMO/LUMO levels and intermolecular hydrogen-bondings have been made for 1 and 2 ML PTCDI coverages to explain the STM images. Changes due to the interaction with the substrate are also found in ARUPS as extra states above the regular HOMO level at 1 ML PTCDI coverage. The ARUPS data also show that the electronic structure of the substrate remains unchanged after the deposition of molecules as the dispersion of the substrate related bands is unchanged. The changes in electronic structure of the molecules are discussed based on a HOMO/LUMO split.

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