Enabling enelike reactions on Si(111)-7x7 through tuning organic molecular structures.

We previously demonstrated that acetonitrile (N[triple bond]C-CH(3)) binds to the adjacent adatom-rest atom pair of Si(111)-7x7 through a [2+2]-like cycloaddition reaction, forming a (Si)N=C(Si)-CH(3)-like surface species [Tao et al., J. Phys. Chem. B 106, 3890 (2002)]. Current investigation clearly showed that chloroacetonitrile (N[triple bond]C-CH(2)Cl), propargyl chloride (HC[triple bond]C-CH(2)Cl), and 3-chloropropionitrile (N[triple bond]C-CH(2)-CH(2)Cl) react with the surface via enelike reactions, concurrently involving N[triple bond]C/C[triple bond]C as well as the breakage of the C-Cl/C-H bond. Further separation of the unsaturated bond (C[triple bond]C) from the C-Cl bond using CH(2) spacers in 5-chloro-1-pentyne (CH[triple bond]C-CH(2)CH(2)CH(2)Cl) would direct the reaction to a [2+2]-like cycloaddition. These experimental results clearly suggest the possibility of controlling the surface reaction pathways by tuning the organic molecular structures. This strategy can be useful in designing and fabricating functional molecular templates on Si(111)-7x7.

Binding of glycine and L-cysteine on Si(111)-7 x 7.

The adsorption of glycine and l-cysteine on Si(111)-7 x 7 was investigated using high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS). The observation of the characteristic vibrational modes and electronic structures of NH3+ and COO- groups for physisorbed glycine (l-cysteine) demonstrates the formation of zwitterionic species in multilayers. For chemisorbed molecules, the appearance of nu(Si-H), nu(Si-O), and nu(C=Omicron) and the absence of nu(O-H) clearly indicate that glycine and l-cysteine dissociate to produce monodentate carboxylate adducts on Si(111)-7 x 7. XPS results further verified the coexistence of two chemisorption states for each amino acid, corresponding to a Si-NH-CH2-COO-Si [Si-NHCH(CH2SH)COO-Si] species with new sigma-linkages of Si-N and Si-O, and a NH2-CH2-COO-Si [NH2CH(CH2SH)COO-Si] product through the cleavage of the O-H bond, respectively. Glycine/Si(111)-7 x 7 and l-cysteine/Si(111)-7 x 7 can be viewed as model systems for further modification of Si surfaces with biological molecules.

A [4+2]-like cycloaddition of methyl methacrylate on Si(100)-2 x 1.

The attachment of methyl methacrylate (MMA) on Si(100)-2x1 was investigated using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) calculations. The HREELS spectra of chemisorbed MMA show the disappearance of characteristic vibrations of C=O (1725 cm(-1)) and C(sp(2))-H (3110, 1400, and 962 cm(-1)) coupled with the blue shift of the C=C stretching mode by 34 cm(-1) compared to those of physisorbed molecules. These results clearly demonstrate that both C=C and C=O in MMA directly participate in the interaction with the surface to form a SiCH(2)C(CH(3))=C(OCH(3))OSi species via a [4+2]-like cycloaddition. This binding configuration was further supported by XPS, UPS, and DFT studies.

Dry synthesis of triple cumulative double bonds (C=C=C=N) on Si(111)-7 x 7 surfaces.

The interactions of cyanoacetylene and diacetylene with a Si(111)-7 x 7 surface have been studied as model systems to mechanistically understand the chemical binding of unsaturated organic molecules to diradical-like silicon dangling bonds. Vibrational studies show that cyanoacetylene mainly binds to the surface through a diradical reaction involving both cyano and C[triple bond]C groups with an adjacent adatom-rest atom pair at 110 K, resulting in an intermediate containing triple cumulative double bonds (C=C=C=N). On the other hand, diacetylene was shown to the covalently attached to Si(111)-7 x 7 only through one of its C[triple bond]C groups, forming an enynic-like structure with a C=C-C[triple bond]C skeleton. These chemisorbed species containing triple cumulative double bonds (C=C=C=N) and C=C-C[triple bond]C may be employed as precursors (or templates) for further construction of bilayer organic films on the semiconductor surfaces.

Binding mechanisms of methacrylic acid and methyl methacrylate on si(111)-7 x 7 -- effect of substitution groups.

The interaction of methacrylic acid and methyl methacrylate with Si(111)-7 x 7 has been investigated using high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS). While methacrylic acid chemisorbs dissociatively through O-H bond cleavage, methyl methacrylate is covalently attached to the silicon surface via a [4+2] cycloaddition. The different reaction pathways of these two compounds on Si(111)-7 x 7 demonstrate that the substitution groups play an important role in determining the reaction channels for multifunctional molecules, leading to the desired flexibility in the organic modification of silicon surfaces.

Formation of molecular templates containing cumulative double bonds (C=C=C) at organic/silicon hybrid interfaces.

The cumulative double bond (C=C=C), an important intermediate in synthetic organic chemistry, was successfully prepared via the selective attachment of acetylethyne to Si(111)-7 x 7. The experimental observation of the characteristic vibrational modes and electronic structures of the C=C=C group in the surface species demonstrates the [4 + 2]-like cycloaddition occurring between the terminal O and C atoms of acetylethyne and the neighboring Si adatom-rest atom pair, consistent with the prediction of density functional theory calculations. Scanning tunneling microscopy images further reveal that the molecules selectively bind to the adjacent adatom-rest atom pairs on Si(111)-7 x 7.

Selective bonding of pyrazine to silicon(100)-2x1 surfaces: the role of nitrogen atoms.

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.