On the Role of Collective Electrostatic Effects in Electronic Level Pinning and Work Function Changes by Molecular Adlayers: The Case of Partially Fluorinated DNTTs Adsorbed Flat‐Lying on Various Metals and Hetero‐Structures

Abstract Modifying the work function of metal electrodes by monolayers of molecules with specifically tailored electronic properties is a versatile tool, but such chemical modifications often also affect the adsorption geometry and packing density, making microscopic modeling difficult. Using scanning tunneling microscopy, it is shown that the recently synthesized partially fluorinated dinaphthothienothiophenes (DNTTs) adopt the same interface structure on different metal substrates independent of the degree of fluorination. Combining Kelvin probe measurements and density functional theory (DFT) calculations, a highest occupied molecular orbital (HOMO) pinning effect for such F_xDNTTs on Au(111) and Ag(111) induced by collective electrostatic interactions in the monolayer is observed. Since the adsorption of weakly interacting molecules such as the F_xDNTTs is not restricted to specific surfaces as is the case with SAMs, this concept is extended to metal substrates with quite different work function values. For a low work function surface such as Cs(110), a lowest unoccupied molecular orbital (LUMO) pinning effect is predicted at the theoretical level. Since such alkali metal surfaces are not experimentally accessible, a well‐defined Cs monolayer on Cu(100) as a low work function substrate is used instead. For this substrate, however, a variation is observed in the LUMO energies and the work function as a function of the degree of fluorination. This is attributed to the formation of a second interface dipole at the buried Cs/Cu interface, which is modulated with the degree of fluorination and competes with the dipole at the outer molecule/Cs interface. Such a second internal interface dipole, which can be modified by the top layer, has to be considered when going to more complex heterointerfaces.