Image contrast analysis of STM images of self-assembled dioctadecyl chalcogenides on graphite at the liquid-solid interface

The structures of self-assembled monolayers of dioctadecyl selenide (CH3(CH2)(17))(2)Se and dioctadecyl telluride (CH3(CH2)(17))(2)Te, as well as dioctadecyl ether (CH3(CH2)(17))(2)O and dioctadecyl sulfide (CH3(CH2)(17))(2)S, on graphite at the liquid-solid interface were systematically investigated by scanning tunneling microscopy (STM). Both dioctadecyl selenide and telluride formed monolayer structures in which the tilt angle between the molecular axis of the alkyl chain and the lamellae axis was 90 degrees, while dioctadecyl ether assembled with a tilt angle of 60 degrees. Dioctadecyl sulfide was found to make two different self-assembled structures having tilt angles of 60 and 90 degrees. When selenide was embedded in ether compounds in mixed self-assembled monolayers, the alkyl chains of the selenide become blurred, implying that the alkyl chains in the monolayers were unstable. This is in contrast with the structure of co-adsorbed monolayers of the ether and sulfide compounds, where the images of all alkyl chains hod high spatial resolution. For the co-adsorbed monolayers, the image contrast of chalcogen atoms was normalized compared with that of alkyl chains of the ether compound in the some image frame. The normalized image contrast was found to be independent of the measurement conditions involving tip shapes, having the following trend, Te > Se > S > C > O. The difference in the normalized image contrast among chalcogen atoms are discussed based on fundamental parameters like polarizability and atomic radii.