Selective bonding of pyrazine to silicon(100)-2×1 surfaces: The role of nitrogen atoms

Abstract

The covalent binding of pyrazine on Si(100) have been investigated using high-resolution electron energy loss spectroscopy (HREELS) and x-ray photoelectron spectroscopy. Experimental results clearly suggest that the attachment occurs exclusively through the bonding of the two para-nitrogen atoms with the surface without the involvement of the carbon atoms, as evidenced from the retention of the (sp2) C-H stretching mode in HREELS and a significant down shift of 1.6 eV in the binding energy of N 1s. The binding mechanism for pyrazine on Si(100) demonstrates that reaction channels for heteroatomic aromatic molecules are strongly dependent on the electronic properties of the constituent atoms.

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

“…As was stated above, Huang et al determined that pyrazine binds with its two para-nitrogen atoms to the Si(100)-2×1 substrate [249]. The specific configuration for this adduct was suggested by Shimomura et al, who used a combination of STM, photoelectron diffraction, and DFT calculations [248,349] to determine that pyrazine binds to the neighboring dimers of the parallel rows on Si(100)-2×1 via the formation of two Si-N linkages causing the loss of aromaticity, as is depicted in Fig.…”

“…A summary by Lu and Lin [242] has considered pyridine, pyrazine, and s-triazine on Si (100) Although theoretical predictions suggested that the former case is favorable [61,242], later experimental investigations utilizing HREELS and XPS showed that pyrazine actually binds via its two para-nitrogen atoms to the Si(100)-2×1 surface [249]. s-triazine was also shown theoretically to be able to react via the [4 + 2] pathway.…”

“…These structures form one-dimensional molecular chains that have a potential to be utilized for further surface modification. However, according to Huang et al [249], a combination of HREELS and XPS studies of isotopicallysubstituted pyridines suggest that these products are formed even at 110 K, where a single binding energy for N 1s is observed at 399.0 eV and the HREELS spectra show the loss of aromaticity. Thus, it is unlikely that kinetic regime will be able to provide a chemical handle for alternative surface modification.…”

Geometric and electronic structures of pyrazine molecule chemisorbed on Si(100) surface by XPS and NEXAFS spectroscopy

“…Subsequently, by the analysis of the high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS), the researchers presented another different adsorption model (Mode I in FIG. 1) where two para-nitrogen atoms directly bonded to the silicon dangling bonds to form a kind of 1,4-N,N -dihydropyrazinelike adduct at 300 K [13]. Recently, by using scanning tunneling microscopy (STM), photoelectron diffraction (PED) and density functional theory (DFT), one definite 1D molecular chain arranged along the direction of the dimer bond was proposed (Mode VI from FIG.…”

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

“…From the many molecules studied for adsorption on group 14 semiconductors, heteroaromatic molecules have gained much interest, covering a wide range of functional groups. − The interest in these molecules comes from a desire to understand the role of aromaticity on surface reactions, which can serve as the guiding principle for surface modification. ,, …”