A dithiocarbamate anchoring group as a flexible platform for interface engineering

Abstract

The molecular organization and electrostatic properties of dithiocarbamate-anchored self-assembled monolayers on Au(111) are studied by spectroscopic experiments and theoretical simulations.

X-Ray Photoelectron Spectroscopy for Determining Interface Dipoles of Self-Assembled Monolayers

“…[63,68,[101][102][103][104][105][106] We have also found it to provide a very good description of core-level shifts in SAMs. [21,22,48,49,64,65] In fact, when modelling the XP spectra of (partially) aromatic hydrocarbon SAMs bonded to Au substrates, we typically find that shifting the calculated spectra to higher binding energies by between 18.9 to 19.0 eV [22,49,107,108] yields an excellent correlation with experimental data. Therefore, throughout the manuscript work-function shifts relative to the peak position of the vacuum-level aligned system VIa are reported.…”

“…Indeed, for the atoms in a SAM that are in the immediate vicinity of the interface, this typically modify the core-level binding energies, [67][68][69]110,125,126] an effect that has also been observed for simulations on SAMs. [108] In experiments on extended, upright standing molecules it will, however, be inconsequential for the measured spectra, as the atoms in the immediate vicinity of the interface affected by these "chemical" shifts hardly contribute to the measured spectra. This is a consequence of the finite escape depth of the photoelectrons.…”

Molecular Self‐Assembly of Phenylselenyl Chloride on a Au(111) Surface

“…Self‐assembled monolayers (SAMs) prepared by adsorption of organic molecules onto metals have been the subject of enormous scientific interest because they provide a convenient route for tailoring the surface and physical properties of metals 1–3 . Such properties are controlled simply through appropriate selection of absorbate chemical structure, such as the headgroup and/or terminal functional group 1–18 . This advantageous trait enables SAMs to be utilized in a wide array of applications, such as surface wetting, biosensors, nanolithography, and electronic devices 1–4 .…”

“…[1][2][3] Such properties are controlled simply through appropriate selection of absorbate chemical structure, such as the headgroup and/or terminal functional group. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] This advantageous trait enables SAMs to be utilized in a wide array of applications, such as surface wetting, biosensors, nanolithography, and electronic devices. [1][2][3][4] SAMs derived from organic thiols or disulfides on Au(111) have been extensively studied due to their high structural order and chemical stability resulting from strong chemical interactions between the sulfur headgroup and the gold surface.…”

“…New SAM precursors may provide novel opportunities for practical application of SAMs. To this end, numerous studies have been performed to probe the formation, structure, and physical properties of SAMs on gold that are prepared by other sulfur (S)-containing precursors, such as protected thiols, 5,9 thiosulfates, 10 thiocyanates, [11][12][13][14] dithiocabamates, 15,16 and sulfenyl chloride. 17,18 Recently, SAMs on Au(111) prepared by organic selenols, protected selenols, and diselenides that have a selenium (Se) headgroup have drawn much attention because of their unique structural features and physical properties.…”