Porous Methylsilsesquioxane for Low-k Dielectric Applications

Abstract
A commercially available spin-on glass (methylsilsesquioxane, MSQ) was modified by the introduction of porosity. The porosity reduced the effective dielectric constant of the MSQ by the incorporation of air. The pores were created by adding a sacrificial polymer (substituted norbornene polymer) to the silsesquioxane matrix. The sacrificial material was thermally decomposed to form nanosize voids within the films. The physical and electrical properties of the porous films were studied as a function of the reactivity of the sacrificial polymer with the glass, and the loading and molecular weight of the sacrificial polymer. Transmission electron microscopy was used to evaluate the porous microstructure. Cross-sectional images show pores of nearly spherical geometry with 5-20 nm diam. The dielectric constant and the index of refraction of the porous MSQ were lower after the decomposition of the sacrificial material. The dielectric constant decreased from 2.7 for a nonporous MSQ film to ∼2.2 for a film with 30 wt % loading of the sacrificial polymer. In a similar way, the index of refraction was reduced from 1.42 to 1.29 for the porous MSQ film. The mechanical properties were evaluated using nanoindentation techniques. This paper focuses on the significant improvements observed upon introduction of porosity to the films. The fracture toughness, or the resistance to crack propagation, increased dramatically with porosity, as compared with the nonporous MSQ films. As a result, thicker MSQ films can be fabricated without spontaneous cracking. The elastic modulus and the hardness of the porous films were measured and showed a reduction in both properties with increasing porosity in the film. © 2001 The Electrochemical Society. All rights reserved.