The Pyrolytic Decomposition of Owens-Illinois Resin Gr650, an Organosilicon Compound

Abstract

The pyrolytic conversion of an organosilsesquioxane (Owens-Illinois resin GR650) to SiO2 is characterized by ir spectroscopy, thermogravimetry and evolved gas analysis (line-of-sight mass spectroscopy). Scanning calorimetry, ramping at 10°C/min, on the as-received (room temperature annealed) resin indicates a glass transition temperature of 67°C which decreases to 58°C for an unrelaxed sample. The ir spectra have bands which can be assigned to Si-CH3 and Si-O-Si modes. For 30 minute isothermal anneals at temperatures above 420°C there is a continuous decrease in the bands associated with the Si-CH3 groups such that after 30 minutes at 650°C the ir spectrum has evolved to that for SiO2. Evolved gas analysis indicates that there are four major components evolving. Over the temperature range (ramping at 10°C/min) ∼180 to ∼500°C we observe C2H5OH and H2O, both of which are condensation reaction products from the curing reaction. Methane is a major evolving species over the temperature range ∼500 to ∼800°C and the thermal spectrum is double peaked which we attribute to CH3+ bound to the inside and outside of the polymer cage structures. The final major component detected was H2, over the temperature range ∼600 to ∼1100°C, which was attributed to pyrolysis of the organic components, both trapped and evolving. The features of the weight loss curve can be accounted for by the measured evolving species spectra.

Synchrotron X-ray Reflectivity Study on the Structure of Templated Polyorganosilicate Thin Films and Their Derived Nanoporous Analogues

“…This may be explained mainly with the presence of pendant, nonbinding methyl groups and of branched, ladder, as well as polyhedral, cagelike structures − in PMSSQ, which lead to a reduced mass density. Bagley et al have shown by infrared spectroscopic measurements, that the methyl groups are not removed upon curing at 420 °C or below . The undesired pyrolitic transformation of PMSSQ into SiO 2 occurs at temperatures higher than 600 °C.…”

“…Bagley et al have shown by infrared spectroscopic measurements, that the methyl groups are not removed upon curing at 420 °C or below. 7 The undesired pyrolitic transformation of PMSSQ into SiO 2 occurs at temperatures higher than 600 °C. The larger decrease of the film electron density in the case of the samples which initially contained some porogen (cf.…”

“…[4][5][6] One promising class of candidates for a low-k material is spinon glasses, as, e.g., polyorganosilicate poly(methylsilses-quioxane) (PMSSQ), having an empirical formula of (CH 3 -SiO 1.5 ) n . 7,8 It is characterized by an inherently low dielectric constant ranging from 2.7 to 2.9, a low moisture uptake, and an excellent thermal stability up to 500 °C. 6,9 Its dielectric constant may be further decreased when incorporating an organic supramolecular template as a pore generator (porogen) into the PMSSQ matrix and subsequently heating to elevated temperatures.…”

“…Star-shaped macromolecules such as poly( -caprolactone) as well as hyperbranched polyesters have proven to be suitable porogens. 7,11 Particularly in the case of high porosity, however, PMSSQ films have a potential lack of mechanical stability in various semiconductor fabrication steps such as chemical mechanical planarization and multilevel stacking. Reliable insulating thin films for chip integration are required to have a high surface hardness as well as mechanical toughness in order to withstand such severe mechanical stress conditions.…”

“…It is well conceived that by 2003 low- k material will be used in combination with copper interconnects in the back-end-of-the-line processes for the fabrication of integrated circuits with a feature dimension of 0.13 μm , Continuous reduction of the dielectric constant to less than 2.2 seems to be inevitable for future generation devices and is believed to be only possible by incorporating nanometer-sized, air-filled pores in insulating matrixes. − One promising class of candidates for a low- k material is spin-on glasses, as, e.g., polyorganosilicate poly(methylsilsesquioxane) (PMSSQ), having an empirical formula of (CH 3 −SiO 1.5 ) n . , It is characterized by an inherently low dielectric constant ranging from 2.7 to 2.9, a low moisture uptake, and an excellent thermal stability up to 500 °C. , Its dielectric constant may be further decreased when incorporating an organic supramolecular template as a pore generator (porogen) into the PMSSQ matrix and subsequently heating to elevated temperatures. ,, This results in the thermal decomposition and volatization of the porogen, leaving behind air-filled pores in the PMSSQ film. Star-shaped macromolecules such as poly(ε-caprolactone) as well as hyperbranched polyesters have proven to be suitable porogens. , Particularly in the case of high porosity, however, PMSSQ films have a potential lack of mechanical stability in various semiconductor fabrication steps such as chemical mechanical planarization and multilevel stacking.…”