Ultralow Dielectric Constant Tetravinyltetramethylcyclotetrasiloxane Films Deposited by Initiated Chemical Vapor Deposition (iCVD)

Simultaneous improvement of mechanical properties and lowering of the dielectric constant occur when films grown from the cyclic monomer tetravinyltetramethylcyclotetrasiloxane (V4D4) via initiated chemical vapor deposition (iCVD) are thermally cured in air. Clear signature from silsesquioxane cage structures in the annealed films appear in the Fourier transform IR (1140 cm(-1)) and Raman (1117 cm(-1)) spectra. The iCVD method consumes an order of magnitude lower power density than the traditional plasma-enhanced CVD, thus preserving the precursor's delicate ring structure and organic substituents in the as-deposited films. The high degree of structural retention in the as-deposited film allows for the beneficial formation of intrinsically porous silsesquioxane cages upon annealing in air. Complete oxidation of the silicon creates 'Q' groups, which impart greater hardness and modulus to the films by increasing the average connectivity number of the film matrix beyond the percolation of rigidity. The removal of labile hydrocarbon moieties allows for the oxidation of the as-deposited film while simultaneously inducing porosity. This combination of events avoids the typical trade-off between improved mechanical properties and higher dielectric constants. Films annealed at 410 degrees C have a dielectric constant of 2.15, and a hardness and modulus of 0.78 and 5.4 GPa, respectively. The solvent-less and low-energy nature of iCVD make it attractive from an environmental safety and health perspective.