Influence of Functional Groups in Substituted Aromatic Molecules on the Selection of Reaction Channel in Semiconductor Surface Functionalization

Teplyakov, Andrew V.

doi:10.1002/9781118199770.ch6

Cited by 3 publications

(4 citation statements)

References 270 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An example of a low-coverage STM study that compares the reaction of an aromatic ring in pyridine to the formation of a Si–N dative bond on Si(100) is given in Figure . However, in principle, the retention of aromaticity in a reaction of aromatic compounds with the silicon surface and the formation of aromatic surface species upon this reaction have been found to be the main driving forces determining the distribution of surface products. ,,,, Elaborate chemical schemes that may involve partial blocking of the surface reactive sites with hydrogen (as in studies of aromatic amines on H-covered Si(100)) or, on the contrary, may promote multiple surface reactions of substituted heteroaromatics with clean silicon ,, that can in principle lead to stable Si–N linkages as well; however, these schemes generally produce low-coverage Si–N linkages and complex product distributions and are outside the main focus of this article.…”

Section: Preparation Of Si–n Linkages On Oxide-free Silicon Single Cr...mentioning

confidence: 99%

Silicon Surface Functionalization Targeting Si–N Linkages

Tian

Teplyakov

2012

Langmuir

Self Cite

View full text Add to dashboard Cite

Silicon substrates have been a fascinating topic of fundamental and applied research for well over 50 years. They have attracted even more attention over the last couple of decades with advances in chemical functionalization that made oxide-free silicon surfaces a reality. Fundamentally new electronic properties and chemical reactivity became available, and the focus of chemical research turned more toward targeting specific chemical bonds and functionalities on silicon. Although thermodynamics clearly drives most processes under ambient conditions toward the formation of an oxide layer, kinetic control of the oxidation processes and thermodynamic tricks based on gaining stability of surface monolayers with high-density assembly have allowed for the formation of stable Si-C bonds and Si-O-C linkages on oxide-free silicon crystals. This feature article targets recent advances in making Si-N linkages on the same oxide-free single crystals. It covers the range of chemical approaches to achieving this goal and offers possible chemistry that can take advantage of the systems produced. The present status of the field and the future directions of its development will be considered.

show abstract

Section: Preparation Of Si–n Linkages On Oxide-free Silicon Single Cr...mentioning

confidence: 99%

Silicon Surface Functionalization Targeting Si–N Linkages

Tian

Teplyakov

2012

Langmuir

Self Cite

View full text Add to dashboard Cite

show abstract

“…Interest in the organic functionalization of semiconductor surfaces has seen tremendous growth over the last several decades due to existing and potential applications in such diverse fields as microelectronics, catalysis, and biosensing. − The silicon and germanium surfaces in particular have attracted much attention due to their electronic properties and well-defined reactivity. The clean (100) surfaces of silicon and germanium are characterized by rows of asymmetrically tilted dimers, which can be used as a template to modify the surface using controlled reactions with organic molecules.…”

Section: Introductionmentioning

confidence: 99%

Adsorption and Dissociation of a Bicyclic Tertiary Diamine, Triethylenediamine, on a Si(100)-2 × 1 Surface

et al. 2016

View full text Add to dashboard Cite

This study investigates the adsorption and thermal transformations of a bicyclic tertiary amine, triethylenediamine, on the clean Si(100)-2 × 1 surface. Below room temperature, triethylenediamine adsorption leads to the formation of a strong dative bond between one of the nitrogen atoms of this compound and the silicon surface. In contrast to previously studied amines, the datively adsorbed triethylenediamine features a second tertiary amine entity that is not bonded to the surface, with a lone pair orbital that is directed away from the surface and is available for further reactions. The thermal chemistry and electronic properties of triethylenediamine on silicon are studied using thermal desorption spectroscopy, infrared spectroscopy, and Xray photoelectron spectroscopy. Near-edge X-ray absorption fine structure measurements are utilized to clarify the geometry of the adsorbates at room temperature. Density functional theory calculations are used to describe the binding geometry and electronic properties of the resulting surface species and the likely reaction paths at elevated temperatures.

show abstract

Section: Resultsmentioning

confidence: 97%

“…In summary, the temperature-dependent studies show that increased selectivity of the reaction toward the nitrogen datively bonded product over the carbon cycloaddition product can be achieved by decreasing the temperature, a phenomenon known in the literature as kinetic trapping, where products with the lowest activation barrier are maximized. 110 Coverage-Dependence Results. Figure 6 shows the compositional fractions of the individual components of the C (1s) and N (1s) XP spectra as a function of coverage for chemisorbed pyrazine on Ge(100)-2×1 at 300 K. From the saturation results discussed in the first section (see Figure 3), we found that upon adsorption of pyrazine on germanium, there are two main products: 2N and 2C.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Effect of Heteroaromaticity on Adsorption of Pyrazine on the Ge(100)-2×1 Surface

et al. 2020

View full text Add to dashboard Cite

The reaction of pyrazine with the Ge(100)-2×1 surface has been investigated by X-ray photoelectron spectroscopy (XPS) and density functional theory calculations. Results show that pyrazine reacts with the surface through both the nitrogen and carbon atoms of the ring to form N-dative bonds and cycloaddition products, respectively. These products are assigned based on calculated electron core level binding and adsorption energies, as well as experimental XPS results. We find that the product distribution changes as a function of coverage and temperature, and in all cases, both dative bonded and cycloaddition products are present. A temperature dependence analysis shows evidence of molecular desorption as well as changes in the product distribution. We found that the number of nitrogen dative bonds is maximized at low temperature through kinetic trapping, while carbon cycloaddition products are promoted with increasing thermal energy. Coverage dependence analysis shows that as the surface becomes crowded, most of the reactions occur through the nitrogen moiety. The nature of surface-adsorbate bonding is revealed by natural population analysis and energy decomposition analysis. We find strong evidence for the dative bond character from molecule to surface donation of the nitrogen lone pairs and surface to molecule back-donation from Ge–Gesubsurface bonds. A loss of aromaticity is found for the structure with two dative bonds. The reaction to the cycloaddition product shows signatures of an inverse electron-demand Diels–Alder reaction.

show abstract

Influence of Functional Groups in Substituted Aromatic Molecules on the Selection of Reaction Channel in Semiconductor Surface Functionalization

Cited by 3 publications

References 270 publications

Silicon Surface Functionalization Targeting Si–N Linkages

Silicon Surface Functionalization Targeting Si–N Linkages

Adsorption and Dissociation of a Bicyclic Tertiary Diamine, Triethylenediamine, on a Si(100)-2 × 1 Surface

Effect of Heteroaromaticity on Adsorption of Pyrazine on the Ge(100)-2×1 Surface

Contact Info

Product

Resources

About