Controlled Stepwise Growth of Siloxane Chains Using Bivalent Building Units With Different Functionalities

Organic/inorganic hybrids of silicon and their subsequent chemical modification are of interest for tailoring and structuring surfaces on the nanoscale. The formation of monolayers on hydroxylated silicon surfaces was employed to synthesize molecular dimethylsiloxane chains by wet-chemical condensation reactions, using dimethylmonochlorosilane as the precursor. The SiH group of the resulting dimethylsilyl termination could be selectively oxidized to the SiOH group, which opened the possibility of bonding another species. By repeating the condensation and oxidation cycle the stepwise growth of one-dimensional dimethylsiloxane chains was achieved. The ongoing chain growth was characterized by attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy, x-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry (SE), and determination of the surface energy by contact-angle experiments.

Molecular Orbital Modeling of Water Adsorption on a Tetrasiloxane Ring

ABSTRACTA water molecule hydrogen bonded to a surface SiOH group produces an IR vibrational transmission peak (ν3) at 2.82 μm. Water was adsorbed into the pores of a metal alkoxide derived silica gel monolith, and the increase in the wavelength of the first vibrational overtone (2ν3) of this peak was measured as a function of the adsorbed water content W (g H2O/g SiO2). The peak shifted from 1.390 to 1.420 μm as W increased by 0.14 g/g. Intermediate Neglect of Differential Overlap (INDO) Molecular Orbital (MO) theory was used to model this process. The effect of a H2O molecule, hydrogen bonded to a hydroxylated tetrasiloxane ring, on the structure of the ring and the water molecule was investigated. The bond length of the O-H group H-bonded to the water molecule increased, as expected from the increase in wavelength of the 2ν3 IR peak.

Bonded Hydrogen in Silicon Oxide Thin Films Deposited By Remote Plasma Enhanced Chemical Vapor Deposition

ABSTRACTWe have deposited a range of silicon oxides by the Remote Plasma Enhanced CVD method. By varying gas mixtures and/or substrate temperature, it is possible to deposit films that are essentially stoichiometric SiO_, Si-deficient oxides which have OH groups but no SiH and Si-rich oxides which have SiH groups and no OH. This paper addresses three issues : (1) the nature of the infrared vibrations associated with the SiH and SiOH groups; (2) the use of D for H substitutions to study the vibrations in (1); and (3) the chemical origin of the SiOH group in the Si-deficient films.

Vibrational Assignments of Organosilanetriols. II. Crystalline Phenylsilanetriol and Phenylsilanetriol-D3

Fourier transform infrared spectra (3800 to 450 cm−1) and laser Raman spectra (4000 to 0 cm−1) of crystalline phenylsilanetriol and phenylsilanetriol-d3, and liquid state phenylsilanetriol and phenylsilanetriol-d3 are first reported. Complete band assignments are attempted. All vibrational modes of the SiOH group except for the SiC torsional mode, including the SiOH in-plane and out-of-plane bending modes, are observed. In addition to the phenylsilanetriols, infrared and laser Raman spectra of crystalline diphenylsilanediol and triphenylsilanol are also studied to aid the band assignments.