Cu-TBPP and PTCDA molecules on insulating surfaces studied by ultra-high-vacuum non-contact AFM

Nony, Laurent; Bennewitz, Roland; Pfeiffer, Olivier; Gnecco, Enrico; Baratoff, A.; Meyer, Ernst; Eguchi, Toyoaki; Gourdon, André; Joachim, Christian

doi:10.1088/0957-4484/15/2/019

Cited by 83 publications

(78 citation statements)

References 19 publications

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“…[16][17][18][19][20][21][22][23][24] Adsorption geometries in particular can be investigated using scanning probe methods such as non-contact atomic force microscopy (NC-AFM). [25][26][27] However, achieving high resolution in NC-AFM images at room temperature is still a challenge 28 and often the interpretation of images down to an atomistic level requires a detailed understanding of the tip-sample interactions.…”

Section: -15mentioning

confidence: 99%

Calculating the Entropy Loss on Adsorption of Organic Molecules at Insulating Surfaces

et al. 2016

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Although it is recognized that dynamic behavior of adsorbing molecules strongly affects the entropic contribution to adsorption free energy, detailed studies of the adsorption entropy of large organic molecules at insulating surfaces are still rare. We compared adsorption of two different functionalized organic molecules, 1,3,5-tri-(4-cyano-4,4 biphenyl)-benzene (TCB) and 1,4-bis(cyanophenyl)-2,5-bis(decyloxy)benzene (CDB), on the KCl (001) surface using density functional theory (DFT) and molecular dynamics (MD) simulations. The accuracy of the van der Waals corrected DFT-D3 was benchmarked using Møller-Plesset perturbation theory calculations. Classical force fields were then parameterized for both the TCB and CDB molecules on the KCl (001) surface. These force fields were used to perform potential of mean force (PMF) calculations of adsorption of individual molecules and extract information on the entropic contributions to adsorption energy. The results demonstrate that entropy losses upon adsorption are significant for flexible molecules, such as considered here, and even at relatively low temperatures (e.g. 400 K) can match the enthalpy contribution to adsorption energy.

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Section: -15mentioning

confidence: 99%

Calculating the Entropy Loss on Adsorption of Organic Molecules at Insulating Surfaces

et al. 2016

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“…6 Moreover, atomic depth rectangular pits can be used as a means of trapping the molecules, resulting in islands which have the dimensions of the templating pits. 7,8,13 To date, there is little known about the pit trapping mechanism, nor the nature of the bonding between organic molecules such as PTCDA and insulating surfaces in general-a topic that has proved controversial for PTCDA on metal surfaces. [14][15][16][17][18][19][20][21] In order to investigate the nucleation and the trapping of PTCDA molecules, we used irradiation to controllably produce monolayer ͑ML͒ depth pits to act as trapping sites and used NC-AFM to study PTCDA in the submonolayer regime.…”

Section: Introductionmentioning

confidence: 99%

Role of van der Waals forces in the adsorption and diffusion of organic molecules on an insulating surface

et al. 2009

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All material supplied via Aaltodoc is protected by copyright and other intellectual property rights, and duplication or sale of all or part of any of the repository collections is not permitted, except that material may be duplicated by you for your research use or educational purposes in electronic or print form. You must obtain permission for any other use. Electronic or print copies may not be offered, whether for sale or otherwise to anyone who is not an authorised user. The adsorption and diffusion of 3,4,9,10-perylene-tetracarboxylic-dianhydride ͑PTCDA͒ molecules on a nanostructured KBr ͑001͒ surface were investigated by combining noncontact atomic force microscopy ͑NC-AFM͒ and first-principles calculations. Atomically resolved measurements demonstrate trapping of PTCDA molecules in intentionally created rectangular monolayer-deep substrate pits and a preferential adsorption at kink sites. In order to understand the experimental results, we found that it was essential to include a firstprinciples treatment of the van der Waals interactions. We show that at some sites on the surface, 85% of the molecular binding is provided by van der Waals interactions, and in general it is always the dominant contribution to the adsorption energy. It also qualitatively changes molecular diffusion on the surface. Based on the specificity of the molecular interaction at kink sites, the species of the imaged ionic sublattice in the NC-AFM measurements could be identified.

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“…These systems are typically characterized by weak molecule-surface interactions as insulating materials are in general chemically poorly reactive. [15][16][17] As a result, molecules are often observed to interact stronger with each other rather than with the substrate 18,19 , forming less stable assemblies or bulk-like crystallites instead of monolayers 18,19 , which constitutes a strong limitation for exploring self-assembly principles. For this reason, the study of molecular self-assembly has only recently been extended to insulators and versatile strategies to realize functionalized surfaces still need to be explored.…”

Section: Introductionmentioning

confidence: 99%

Increasing the Templating Effect on a Bulk Insulator Surface: From a Kinetically Trapped to a Thermodynamically More Stable Structure

et al. 2016

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Molecular self-assembly, governed by the subtle balance between intermolecular and moleculesurface interactions, is generally associated with the thermodynamic ground state, while the competition between kinetics and thermodynamics during its formation is often neglected. Here, we present a simple model system of a benzoic acid derivative on a bulk insulator surface.Combining high-resolution non-contact atomic force microscopy experiments and density functional theory, we characterize the structure and the thermodynamic stability of a set of temperature-dependent molecular phases formed by 2,5-dihydroxybenzoic acid molecules, selfassembled on the insulating calcite (10.4) surface. We demonstrate that a striped phase forms before the thermodynamically favored dense phase, indicating a kinetically trapped state. Our theoretical analysis elucidates that this striped-to-dense phase transition is associated with a distinct change in the chemical interactions involved in the two phases. The striped phase is characterized by a balance between the molecule-molecule and the molecule-substrate interactions, reminiscent of the molecular bulk. In contrast, the dense phase is formed by up-right standing molecules that strongly anchor to the surface with a comparatively little influence of the intermolecular interactions, i.e., in the latter case the substrate acts as a template for the molecular structure. The kinetic trapping stems from a relatively strong intermolecular interaction between molecules in the striped phase that need to be broken before the substrate-templated dense phase can be formed. Thus, our results provide molecular level insights into two qualitatively different bonding motifs of a simple organic molecule on a bulk insulator surface. This understanding is mandatory for obtaining predictive power in the rational design of molecular structures on insulating surfaces.

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Cu-TBPP and PTCDA molecules on insulating surfaces studied by ultra-high-vacuum non-contact AFM

Cited by 83 publications

References 19 publications

Calculating the Entropy Loss on Adsorption of Organic Molecules at Insulating Surfaces

Calculating the Entropy Loss on Adsorption of Organic Molecules at Insulating Surfaces

Role of van der Waals forces in the adsorption and diffusion of organic molecules on an insulating surface

Increasing the Templating Effect on a Bulk Insulator Surface: From a Kinetically Trapped to a Thermodynamically More Stable Structure

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