A novel method achieving ultra-high geometrical resolution in scanning tunnelling microscopy

Temirov, Ruslan; Soubatch, Serguei; Neucheva, Olga; Lassise, Adam; Tautz, F. Stefan

doi:10.1088/1367-2630/10/5/053012

Cited by 176 publications

(192 citation statements)

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“…Reported values include 2.4 Å for NC-Ph 3 -CN 5-fold coordinated to Ce adatoms on Ag(111), 12 2.15 Å for TCNQ 4-fold coordinated to Mn atoms on Cu(100), 33 1.9 Å for NC-Ph n -CN 3-fold coordinated to Co atoms on Ag(111), 34 and the same value for NC-Ph 5 -CN 3-fold coordinated to Cu atoms on Cu(111). 7 A model for the irregular honeycomb pattern together with a high-resolution STM image measured with a D 2 -terminated tip 35,36 is shown in Figure 3d, with those molecules aligned along direction 1 represented in bold. The Journal of Physical Chemistry C Article Upon closer inspection, the STM images reveal that NC-Ph 3 -CN molecules have a slightly curved appearance.…”

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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“…[1][2][3][4][5][6][7][8][9][10] Perylene derivatives sublimated under vacuum have the ability to self-assemble on at metal surfaces and to form two-dimensional hydrogen-bonded nanoarchitectures. [11][12][13][14][15][16][17] These molecules can also form multicomponent organic structures when mixed with complementary building blocks. [18][19][20][21][22] Perylene derivatives are thus very attractive to fabricate new devices as new organic at-heterojunction solar cells for example.…”

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confidence: 99%

Localized intermolecular electronic coupling in two-dimensional self-assembled 3,4,9,10-perylenetetracarboxylic diimide nanoarchitectures

Hieulle

Silly

2013

J. Mater. Chem. C

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International audienceTailoring the structural and electronic properties of perylene diimide derivative films is essential for developing next generation organic photovoltaic devices. Here we show that 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) molecules self-assemble into a new two-dimensional structure after annealing. Scanning tunneling microscopy (STM) reveals strong localized inter-molecular electronic coupling at room temperature when molecules are arranged in a side-by-side packing

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“…2f. They reveal strong non-linearities in I(V) that are a generic feature of nanoscale junctions in the presence of H 2 or D 2 ; their specific shape is a fingerprint of the junction state [12][13][14][15] . The dI/dV(x,y,V) data cube allows us to reconstruct dI/dV images at any chosen value of the bias voltage ( Fig.…”

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confidence: 99%

“…The energy of the excitation is defined by the local potential which in turn is related to the microscopic shape of the tip, the local structure of the surface, the tipsurface distance and the hydrogen coverage. Due to this complex dependence the dI/dV(V) spectra measured in the presence of H 2 (D 2 ) become intrinsically irreproducible, although their generic features such as spikes are always present [12][13][14][15] . In contrast to the spectra the STHM imaging is much more robust.…”

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confidence: 99%

“…Our experiments show that increasing the coverage stabilizes the geometric STHM contrast, either via an increased frequency of trapping events and/or by the additional confining potentials of H 2 (D 2 ) molecules in the neighbourhood of the junction. Incidentally, the influence of those neighbouring molecules on the junction can be directly monitored by the evolution of the dI/dV spikes as a function of exposure time, even after the STHM mode has established itself 12 .…”

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Chemical contrast in STM imaging of transition metal aluminides

Duguet

Thiel

2012

Progress in Surface Science

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The force imaging mode is achieved by condensing molecular hydrogen (H 2 ) or deuterium (D 2 ) in the cold (T <10 K) junction of an ultra-high vacuum STM and is therefore called scanning tunnelling hydrogen microscopy (STHM) 12 . H 2 (D 2 ) adsorption abruptly changes the STM image contrast (cf. Fig. 2a). At low coverages the imaging tends to change back spontaneously to the conventional mode after a short time. However, as the H 2 (D 2 ) coverage increases, the STHM mode becomes stable for arbitrarily long times. Operating the STM in the new regime, we have imaged prototypical organic molecules adsorbed on noble metal surfaces, in particular Ag and Au (Fig. 1a-c), at constant tip height. The obtained contrast closely corresponds to the chemical

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A novel method achieving ultra-high geometrical resolution in scanning tunnelling microscopy

Cited by 176 publications

References 28 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)

Localized intermolecular electronic coupling in two-dimensional self-assembled 3,4,9,10-perylenetetracarboxylic diimide nanoarchitectures

Chemical contrast in STM imaging of transition metal aluminides

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A novel method achieving ultra-high geometrical resolution in scanning tunnelling microscopy

Cited by 176 publications

References 28 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)

Localized intermolecular electronic coupling in two-dimensional self-assembled 3,4,9,10-perylenetetracarboxylic diimide nanoarchitectures

Chemical contrast in STM imaging of transition metal aluminides

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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)