A scanning tunneling microscope (STM) has been equipped with a nanoscale force sensor and signal transducer composed of a single D2 molecule that is confined in the STM junction. The uncalibrated sensor is used to obtain ultrahigh geometric image resolution of a complex organic molecule adsorbed on a noble metal surface. By means of conductance-distance spectroscopy and corresponding density functional calculations the mechanism of the sensor and transducer is identified. It probes the short-range Pauli repulsion and converts this signal into variations of the junction conductance.

Understanding the adsorption and growth mechanisms of large π -conjugated molecules on noble metal surfaces is a crucial aspect for designing and optimizing electronic devices based on organic materials. The investigation of adsorption heights for these molecules on different surfaces can be a direct measure for the strength of the adsorbate-substrate interaction, and gives insight into the fundamental bonding mechanisms. However, the adsorption strength is often also influenced by intermolecular (lateral) interactions which cause, e.g., island formation in the submonolayer regime and influence the adsorption geometry of individual molecules. The lateral structure can then dominate the vertical structure formation and influence the adsorbate-substrate interaction. In this context, the adsorption of copper-phthalocyanines on noble metal surfaces [Au(111), Ag(111), and Cu (111)] represents an ideal model system since the lateral structure formation, as well as the molecular adsorption geometries, strongly depend on coverage and temperature, and hence can be tuned easily. We demonstrate that for CuPc/Au(111), a system dominated by physisorption, the adsorption height of the molecules is independent from the lateral adsorption geometry. In contrast, a strong chemisorption of CuPc on Cu(111) shows a clear gradient in the interaction strength: Individual molecules in diluted phases are significantly stronger bonded than molecules in dense phases. This finding quantifies the increase of the exchange correlation in the binding process, which goes along with the tendency to a more site-specific adsorption geometry at small coverages.

We present a comprehensive study of structural and electronic properties of the adsorbate system H 2 -phthalocyanine (H 2 Pc) on Ag(111). A comparison with copper-phthalocyanine (CuPc) on Ag(111) allows us to elucidate the impact of the central metal atom in the molecule on the adsorbate-substrate interaction. This metal atom is one fundamental parameter which can be changed in order to modify the properties of phthalocyanine molecules, and therefore its influence on the adsorption behavior is highly relevant. From high-resolution electron diffraction, we obtained a phase diagram for submonolayer coverages which turns out to be similar to that of CuPc/Ag(111). The most striking difference is a higher stability of a commensurate phase, indicating a stronger and more adsorption site-specific bonding of the H 2 Pc molecules. Furthermore, ultraviolet photoelectron spectroscopy and x-ray standing waves prove chemisorptive interaction between molecules and substrate and a significant bending of the molecules with the nitrogen atoms approaching the surface. We conclude that the attractive interaction of metal-phthalocyanine molecules with Ag (111) is mainly mediated by the aromatic body of the molecule (the tetraazaporphyrin ring in particular) rather than by the central metallic atom which (in the case of CuPc) already shows Pauli repulsion.