Electronic states of organic semiconductors vis-à-vis interactions between molecules in a submonolayer through time-restricted electrostatic assembly

Abstract

We have made in-depth studies to revisit time-restricted layer-by-layer (LbL) electrostatic assembly process of a couple of organic molecules. The studies have been made in relation to electronic states of metal phthalocyanines. We show that by shortening dipping time for adsorption of the active molecules, mass adsorbed in each monolayer can be decreased and hence intermolecular spacing between the molecules can be increased. We have characterized the (sub)monolayers deposited on an electrode with scanning tunneling microscope tip to record tunneling current through the molecules. Results show that the highest occupied molecular orbitals and lowest unoccupied molecular orbitals, and also the difference between the orbitals, that is, the transport gap of the molecules in a (sub)monolayer depends on the dipping time of LbL assembly or molecule-to-molecule separation. We show that interactions between molecules in a monolayer decrease the transport gap of the metal phthalocyanines.