Direct observation of oriented molecular adsorption at step edges: a cryogenic scanning tunneling microscopy study

Abstract

A cryogenic scanning tunneling microscope has been used to investigate the adsorption of thiophene, 2,5-dimethylthiophene, and 2,2′-bithiophene on the Ag(111) surface at 120 K. STM images reveal that all three molecules preferentially bond at step edges. Images of 2,2′-bithiophene and 2,5-dimethylthiophene at the step edge show them to be elongated, while thiophene molecules appear nearly circular. The observed elongation for 2,2′-bithiophene and 2,5-dimethylthiophene is attributed to geometric contrast reflecting the intrinsic shape of these molecules. All molecules of a given chemical identity appear to be oriented in the same direction with respect to the step edge, demonstrating that the interactions between the molecules and the step edge are sufficiently strong and sufficiently local to hold the molecules in specific rotational configurations at the step edge.