Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 109, Issue 10, Pages 4554-4560Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp045562+
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In this work, we use first principles simulations to provide features of the dynamic scanning force microscopy imaging of adsorbed organic layers on insulating surfaces. We consider monolayers of formic (HCOOH) and acetic (CH3COOH) acid and a mixed layer of acetic and trifluoroacetic acids (CF3COOH) on the TiO2(110) surface and study their interaction with a silicon dangling bond tip. The results demonstrate that the silicon tip interacts more strongly with the substrate and the COO- group than the adsorbed acid headgroups, and, therefore, molecules would appear dark in images. The pattern of contrast and apparent height of molecules is determined by the repulsion between the tip and the molecular headgroups and by significant deformation of the monolayer and individual molecules. The height of the molecule on the surface and the size of the headgroup play a large role in determining access of the tip to the substrate and, hence, the contrast in images. Direct imaging of the molecules themselves could be obtained by providing a functionalized tip with attraction to the molecular headgroups, for example, a positive potential tip.
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