Temperature-resolved Fourier transform infrared study of condensation reactions and porogen decomposition in hybrid organosilicon-porogen films

Abstract

Composite organosilicon/porogen thin films were deposited via pulsed-plasma chemical vapor deposition. The organosilicon monomer was polymerized using water as the oxidant, allowing incorporation of silanol (Si–OH) moieties for subsequent condensation reactions and crosslinking for enhanced mechanical properties. The porogen monomer [methylmethacrylate (MMA)] was codeposited in the same step, and the degree of MMA incorporation was shown to scale with both the peak plasma power and porogen flow rate. Fourier transform infrared (FTIR) spectroscopy spectra of the composite material show features from both the organosilicon precursor and the porogen species, indicating that both materials are successfully incorporated into the thin film. The kinetics of both the condensation reaction and porogen removal were determined by a temperature/time-resolved FTIR method. The condensation reaction and crosslinking events occur between 100 and 425 °C. Porogen decomposition occurs simultaneously between approximately 325 and 400 °C, which is consistent with the decomposition of poly(methylmethacrylate). Using these data, the activation energy for the primary decomposition mode was found to be approximately 53.6 kJ/mol (12.8 kcal/mol). Both the index of refraction and the dielectric constant scale with the degree of porogen removal, suggesting the formation of free volume in the films. The lowest index of refraction and dielectric constant obtained was 1.404 and 2.3, respectively, for a 1 h anneal at 425 °C. Worst-case thickness loss for the films was approximately 36% of the as-deposit thickness.