Deposition Order Controls the First Stages of a Metal–Organic Coordination Network on an Insulator Surface

Schüller, Lukas; Haapasilta, Ville; Kühn, Stefan; Pinto, Henry P.; Bechstein, Ralf; Foster, Adam S.; Kühnle, Angelika

doi:10.1021/acs.jpcc.6b04672

Cited by 13 publications

(18 citation statements)

References 40 publications

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“…Consequently, depending on the concentration of metal atoms on the surface, clustering will take place. In the case of iron such on-surface clustering has been observed experimentally on calcite (10.4) surface, also supported by DFT calculations [21].…”

Section: Resultssupporting

confidence: 69%

Adsorption and migration of single metal atoms on the calcite (10.4) surface

Pinto¹,

Haapasilta²,

Lokhandwala³

et al. 2017

J. Phys.: Condens. Matter

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Transition metal atoms are one of the key ingredients in the formation of functional 2D metal organic coordination networks. Additionally, the co-deposition of metal atoms can play an important role in anchoring the molecular structures to the surface at room temperature. To gain control of such processes requires the understanding of adsorption and diffusion properties of the different transition metals on the target surface. Here, we used density functional theory to investigate the adsorption of 3d (Ti, Cr, Fe, Ni, Cu), 4d (Zr, Nb, Mo, Pd, Ag) and 5d (Hf, W, Ir, Pt, Au) transition metal adatoms on the insulating calcite (10.4) surface. We identified the most stable adsorption sites and calculated binding energies and corresponding ground state structures. We find that the preferential adsorption sites are the Ca-Ca bridge sites. Apart from the Cr, Mo, Cu, Ag and Au all the studied metals bind strongly to the calcite surface. The calculated migration barriers for the representative Ag and Fe atoms indicates that the metal adatoms are mobile on the calcite surface at room temperature. Bader analysis suggests that there is no significant charge transfer between the metal adatoms and the calcite surface.

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Section: Resultssupporting

confidence: 69%

Adsorption and migration of single metal atoms on the calcite (10.4) surface

Pinto¹,

Haapasilta²,

Lokhandwala³

et al. 2017

J. Phys.: Condens. Matter

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“…According to the calculations, the adsorption energy is 2.4 eV, in line with room temperature adsorption and earlier calculations with similar molecules on calcite. 34 In a recent investigation, the biphenyl-4,4 0 -dicarboxylic acid molecule, which also anchors to the surface via two COOH groups, was calculated to have several adsorption positions on calcite, all with similar energies. 34 Most probably, 3BBA will also have several stable adsorption geometries with adsorption energies of the order of 2.4 eV.…”

Section: Self-assembled Structuresmentioning

confidence: 99%

Diacetylene polymerization on a bulk insulator surface

Richter

Haapasilta

Venturini

et al. 2017

Phys. Chem. Chem. Phys.

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Molecular electronics has great potential to surpass known limitations in conventional silicon-based technologies. The development of molecular electronics devices requires reliable strategies for connecting functional molecules by wire-like structures. To this end, diacetylene polymerization has been discussed as a very promising approach for contacting single molecules with a conductive polymer chain. A major challenge for future device fabrication is transferring this method to bulk insulator surfaces, which are mandatory to decouple the electronic structure of the functional molecules from the support surface.Here, we provide experimental evidence for diacetylene polymerization of 3,3 0 -(1,3-butadiyne-1,4-diyl)bisbenzoic acid precursors on the (10.4) surface of calcite, a bulk insulator with a band gap of around 6 eV. When deposited on the surface held at room temperature, ordered islands with a (1 Â 3) superstructure are observed using dynamic atomic force microscopy. A distinct change is revealed upon heating the substrate to 485 K. After heating, molecular stripes with a characteristic inner structure are formed that excellently match the expected diacetylene polymer chains in appearance and repeat distance. The corresponding density functional theory computations reveal molecular-level bonding patterns of both the (1 Â 3) superstructure and the formed striped structure, confirming the assignment of on-surface diacetylene polymerization. Transferring the concept of using diacetylene polymerization for creating conductive connections to bulk insulator surfaces paves the way towards application-relevant systems for future molecular electronic devices.

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“…More crucially, existing work only demonstrates order on a local scale with very small domain sizes of the MOF. [ 1,26–30 ] The characterization of single layer MOFs in a gated device environment has not been realized yet, since it is even more challenging to fabricate 2D MOFs on a three‐terminal device. However, this could be alternatively achieved by gating the 2D MOFs using local electric fields induced by the tip of a scanning probe microscope.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Local Probe Gating of a Monolayer Metal‐Organic Framework

Yan

Silveira

Alldritt

et al. 2021

Adv Funct Materials

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Achieving large-area uniform 2D metal-organic frameworks (MOFs) and controlling their electronic properties on inert surfaces is a big step toward future applications in electronic devices. Here a 2D monolayer Cu-dicyanoanthracene MOF with long-range order is successfully fabricated on an epitaxial graphene surface. Its structural and electronic properties are studied by low-temperature scanning tunneling microscopy and spectroscopy complemented by density-functional theory calculations. Access to multiple molecular charge states in the 2D MOF is demonstrated using tip-induced local electric fields. It is expected that a similar strategy could be applied to fabricate and characterize 2D MOFs with exotic, engineered electronic states.

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Deposition Order Controls the First Stages of a Metal–Organic Coordination Network on an Insulator Surface

Cited by 13 publications

References 40 publications

Adsorption and migration of single metal atoms on the calcite (10.4) surface

Adsorption and migration of single metal atoms on the calcite (10.4) surface

Diacetylene polymerization on a bulk insulator surface

Synthesis and Local Probe Gating of a Monolayer Metal‐Organic Framework

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