Single Molecule and Single Atom Sensors for Atomic Resolution Imaging of Chemically Complex Surfaces

Kichin, Georgy; Weiss, Christian; Wagner, Christian; Tautz, F. Stefan; Temirov, Ruslan

doi:10.1021/ja204624g

Cited by 114 publications

(116 citation statements)

References 16 publications

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“…The first is very regular and is shown in Figure 2, while the second involves more Figure 2b. These images were obtained with a CO-functionalized tip 32 and clearly reveal the three phenyl rings of each molecule and the coordination adatoms. Each of the rotational domains involves molecules in directions 2 and 2̅ , rotated by + or −11°from the ⟨112̅ ⟩ directions, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)

2015

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We report on low-temperature scanning tunneling microscopy and spectroscopy measurements on NC-Ph 3 -CN molecules adsorbed at 300 K on a Cu(111) surface. Upon cooling, the molecules form chain and honeycomb structures, incorporating Cu adatoms supplied by the substrate as metal linkers. In these assemblies, the molecules align along two main directions, with a relative abundance that depends on the coordination number and on the bond length. We show spectroscopic data about the unoccupied molecular orbitals and investigate the patterns obtained by depositing different amounts of molecules. Comparison of these results with the ones obtained for NC-Ph 5 -CN molecules on the same substrate enables us to establish a hierarchy of the different interaction forces at work in the system. ■ INTRODUCTIONSupramolecular chemistry at surfaces is a topic of widespread interest because low-dimensional architectures with specific functionalities can be created. 1−4 A detailed understanding of the mechanism underlying the self-assembly of the various organic and metal−organic networks is important to realize the desired morphology, chemical composition, and eventually functionality. In this respect, regular porous networks are especially promising: They act as templates for the positioning of molecules or metal atoms and clusters onto well-defined sites within the cavities 5−8 as well as on the ligand molecules. 9 Moreover, depending on the metal atoms used for the coordination nodes, regular arrays of transition-metal 10,11 or rare earth atoms 12 can be created.Molecular adsorption and assembly are controlled by several competing interactions. 13−16 For the case of metal−organic porous networks, there are the van der Waals forces between the organic molecules and the surface and the corrugation of this potential energy surface upon translation and rotation of the molecules. A second ingredient is the potential energy surface felt by the metal coordination atoms, that is, their preferred adsorption sites and their diffusion barriers. Finally, there are the bond angle, distance, and coordination number of the metal−organic coordination bond.To shed light on the hierarchy of these energies, we report here on the self-assembly of NC-Ph 3 -CN molecules on Cu(111). When deposited on the substrate kept at room temperature, upon cooling NC-Ph 3 -CN molecules form chain and honeycomb structures and the molecules align with orientations that deviate from the crystallographic high symmetry directions of the surface. The comparison with the motifs formed by NC-Ph 5 -CN molecules on the same substrate 17 enables us to estimate which interaction dominates in each case, depending on the number of phenyl rings in the system. To complement the characterization of the observed metal−organic structures, we report spectroscopic data for the molecular orbitals. Moreover, the dependence of the obtained structures on the molecular coverage is discussed.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)

2015

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“…High resolution measurements were carried out by functionalizing the STM tip with a CO molecule. [35][36][37] The molecular coverage (monolayer (ML)) is defined in terms of the densest structure we have observed, i.e., the compact structure formed at room temperature reported in Sec. III E. The evaporation flux and the deposition time, and therefore the molecular exposure, are identical for each preparation.…”

Section: Methodsmentioning

confidence: 99%

Temperature-dependent self-assembly of NC–Ph5–CN molecules on Cu(111)

Pivetta

Pacchioni

Fernandes

et al. 2015

The Journal of Chemical Physics

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We present the results of temperature-dependent self-assembly of dicarbonitrile-pentaphenyl molecules (NC-Ph 5 -CN) on Cu(111). Our low-temperature scanning tunneling microscopy study reveals the formation of metal-organic and purely organic structures, depending on the substrate temperature during deposition (160-300 K), which determines the availability of Cu adatoms at the surface. We use tip functionalization with CO to obtain submolecular resolution and image the coordination atoms, enabling unequivocal identification of metal-coordinated nodes and purely organic ones. Moreover, we discuss the somewhat surprising structure obtained for deposition and measurement at 300 K. C 2015 AIP Publishing LLC. [http://dx

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“…We'll discuss just how Pauli exclusion is exploited in state-of-the-art scanning probe microscopy, what pitfalls there might be in interpreting features in DFM images as arising directly from chemical bonds, and to what extent scanning probe measurements of tip-sample interactions provide deeper experimental insights into the exclusion principle itself. We should also stress right from the outset that although we concentrate on dynamic force microscopy throughout this chapter, prior to Gross et al's 2009 paper, Temirov, Tautz and co-workers had achieved unprecedented spatial resolution using a technique for which they coined the term scanning tunnelling hydrogen microscopy (STHM) [9,10,11,12]. Both STHM and the type of DFM imaging introduced by Gross et al [1] exploit Pauli exclusion as a means to acquire exceptionally high resolution.…”

Section: Intramolecular Resolution Via Pauli Exclusionmentioning

confidence: 99%

Pauli’s Principle in Probe Microscopy

Jarvis

Sweetman

Kantorovich

et al. 2015

Advances in Atom and Single Molecule Machines

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It appears to be one of the few places in physics where there is a rule which can be stated very simply, but for which no one has found a simple and easy explanation. The explanation is deep down in relativistic quantum mechanics. This probably means that we do not have a complete understanding of the fundamental principle involved.RP Feynman, The Feynman Lectures on Physics, Vol III, Chapter 4 (1964) AbstractExceptionally clear images of intramolecular structure can be attained in dynamic force microscopy through the combination of a passivated tip apex and operation in what has become known as the "Pauli exclusion regime" of the tip-sample interaction. We discuss, from an experimentalist's perspective, a number of aspects of the exclusion principle which underpin this ability to achieve submolecular resolution. Our particular focus is on the origins, history, and interpretation of Pauli's principle in the context of interatomic and intermolecular interactions.

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Single Molecule and Single Atom Sensors for Atomic Resolution Imaging of Chemically Complex Surfaces

Cited by 114 publications

References 16 publications

Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)

Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)

Temperature-dependent self-assembly of NC–Ph5–CN molecules on Cu(111)

Pauli’s Principle in Probe Microscopy

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Single Molecule and Single Atom Sensors for Atomic Resolution Imaging of Chemically Complex Surfaces

Cited by 114 publications

References 16 publications

Competing Interactions in the Self-Assembly of NC-Ph3-CN Molecules on Cu(111)

Competing Interactions in the Self-Assembly of NC-Ph3-CN Molecules on Cu(111)

Temperature-dependent self-assembly of NC–Ph5–CN molecules on Cu(111)

Pauli’s Principle in Probe Microscopy

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Product

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Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)

Competing Interactions in the Self-Assembly of NC-Ph₃-CN Molecules on Cu(111)