Nanopatterning organic monolayers on Si(100) by selective chemisorption of norbornadiene

Abeln, G. C.; Lee, S. Y.; Lyding, Joseph W.; Thompson, Donald B.; Moore, J.S.

doi:10.1063/1.119010

Cited by 48 publications

(37 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…21,22 To understand this result, we have considered the energy change for a hypothetical process in which NBE approaches a fully passivated surface, displacing two gas-phase H 2 molecules as it binds to the surface. PW91 predicts that it costs 12 kcal mol Ϫ1 to complete this substitution, indicating that the reaction is thermodynamically unfavored.…”

Section: E Binding To An Incompletely Passivated Surfacementioning

confidence: 96%

“…Some STM studies 9 have found there to be little translational or rotational order in NBE monolayers, while others 21,22 find monolayers with small regions of local order only. These studies have shown that the C-C double bonds can react with the surface in a number of ways and the binding is clearly more complex than was initially envisaged.…”

Section: Introductionmentioning

confidence: 99%

“…9,[21][22][23] Norbornadiene ͑NBE͒ has two parallel carbon-carbon double bonds separated by 2.43 Å, a distance close enough to that between two neighboring silicon dimers to suggest that it could react twice with the surface to bridge the adjacent Si dimers along a dimer row. Such a binding should guarantee the azimuthal orientation of the apex atom of norbornadiene to the surface, and by appropriate control of the chemistry of this atom, norbornadiene could be used as a glue that ensures that a molecule attached to it is oriented vertically from the surface.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Modeling the adsorption of norbornadiene on the Si(001) surface: The predominance of non-[2+2]-cycloaddition products

Bilić

Reimers

Hush

2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

Norbornadiene (NBE) chemisorbs to a Si(001) surface in a flagpolelike structure that has potential as an anchor point for nanoscale molecular devices to the surface. Its bindings to the reconstructed Si(001)-(2×1) surface and a partially depassivated Si(001)-(2×1)-H surfaces are modeled by slab-based density functional theory using the PW91 density functional. This method is shown to quantitatively and qualitatively reproduce many known properties of bulk silicon, the silicon surface reconstruction, and the gas-phase NBE molecule. Four strongly bound adsorbate configurations are found, with the C–C bonds located either above a Si–Si dimer row or trough, oriented either parallel or perpendicular to each other. The calculated binding energies are 96, 85, 81, and 72 kcal mol−1 for the perpendicular row, perpendicular trough, parallel row, and parallel trough configurations, respectively, evaluated at quarter-monolayer coverage on the bare surface, with hydrogen passivation of the surrounding sites having little influence. These results indicate that the observed structural disorder for NBE adsorption on the bare surface at very high coverage results from kinetic rather than thermodynamic control of the reaction products. Such kinetic control is shown to be associated with large barriers in excess of 40 kcal mol−1 for possible adsorbate annealing processes, with desorption into a (partially or fully) physisorbed precursor state being required. Enhanced disorder is also predicted arising from the strong partial binding of NBE through one alkene linkage only, with the analogous four structural motifs being calculated to be very similar in energy. The lowest-energy single-alkene-bonded structure is predicted to be of the parallel–above-row type, consistent with the observed structures for most monoalkene adducts. Preference for the uncommon perpendicular binding of NBE is predicted to arise from unfavorable interactions within the silicon lattice when parallel binding occurs on adjacent rows, a binding motif that is observed for only the simplest monoalkene, ethylene, and only at high coverage. The primary reaction products of NBE are not those predicted by a [2+2] cycloaddition reaction between C=C and Si=Si double bonds, suggesting that, in general, this is not the mechanism for chemisorption of alkenes on Si(001). Rather, the reaction products are those expected on the basis that the silicon dimer bond is biradical in nature. Careful structural, polarization, and band-structure analyses of the reconstructed surface are also shown to provide no evidence for the existence for a doubly bonded silicon dimer.

show abstract

Section: E Binding To An Incompletely Passivated Surfacementioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Modeling the adsorption of norbornadiene on the Si(001) surface: The predominance of non-[2+2]-cycloaddition products

Bilić

Reimers

Hush

2003

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…[206]. Copyright 2007 Elsevier B.V. [210]. It should be noted, however, that the investigation by Hovis et al published later the same year used high-coverage limit to demonstrate the lack of order in this addition process and infrared investigation to show that at least some of the norbornadiene molecules keep their double bonds intact upon adsorption on a clean Si(100)-2×1, as a pronounced ν =C-H absorption peak, characteristic of an unsaturated molecule was observed at 3057 cm −1 [209].…”

Section: Simple Derivatives Of Ethylenementioning

confidence: 97%

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Leftwich

Teplyakov

2007

Surface Science Reports

123

View full text Add to dashboard Cite

“…S canning tunnelling microscopy (STM) facilitates atomic-scale lithography by hydrogen resist patterning; the technique is especially useful for fundamental processes such as patterned oxidation 1 , metallization 2,3 , dopant incorporation 4 , templating of organic molecules 5,6 and fabrication of quantum cellular automata devices 7 , all at the atomic-scale. Sharpening of probes further extends to fi eld emitters 8 in displays and electron microscopes as well as razor blade manufacturing 9 .…”

mentioning

confidence: 99%

Field-directed sputter sharpening for tailored probe materials and atomic-scale lithography

et al. 2012

View full text Add to dashboard Cite

Fabrication of ultrasharp probes is of interest for many applications, including scanning probe microscopy and electron-stimulated patterning of surfaces. These techniques require reproducible ultrasharp metallic tips, yet the effi cient and reproducible fabrication of these consumable items has remained an elusive goal. Here we describe a novel biased-probe fi elddirected sputter sharpening technique applicable to conductive materials, which produces nanometer and sub-nanometer sharp W, Pt-Ir and W-HfB 2 tips able to perform atomic-scale lithography on Si. Compared with traditional probes fabricated by etching or conventional sputter erosion, fi eld-directed sputter sharpened probes have smaller radii and produce lithographic patterns 18 -26 % sharper with atomic-scale lithographic fi delity.

show abstract

Nanopatterning organic monolayers on Si(100) by selective chemisorption of norbornadiene

Cited by 48 publications

References 9 publications

Modeling the adsorption of norbornadiene on the Si(001) surface: The predominance of non-[2+2]-cycloaddition products

Modeling the adsorption of norbornadiene on the Si(001) surface: The predominance of non-[2+2]-cycloaddition products

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

Field-directed sputter sharpening for tailored probe materials and atomic-scale lithography

Contact Info

Product

Resources

About