PTCDA molecules on a KBr/InSb system: a low temperature STM study

We have used scanning tunnelling microscopy (STM) at 77 K to investigate 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) molecules adsorbed on an ultrathin (1-2 monolayer (ML)) film of KBr grown on a c(8 × 2)InSb(001) substrate. The molecules are stabilized both at the KBr steps and on the terraces. On the 1 ML film the PTCDA molecules appear predominantly as single entities, whereas on the 2 ML film formation of molecular clusters is preferred. Differences in the adsorption configurations indicate that the interaction between the molecules and the surface differs significantly for the cases of 1 and 2 ML films. We present images of the molecules obtained with sub-molecular resolution for both filled and empty state sampling modes. We argue that the highest occupied molecular orbital (the lowest unoccupied molecular orbital) is responsible for intramolecular contrast in filled (empty) state images of the molecules, even though they are deformed due to strong interaction with the substrate.