A novel selective and bottom-up deposition process from supercritical CO2 is proposed and demonstrated. Supercritical CO2 fluids are dense media, and a deposition precursor dissolving wherein can easily condences in hollow/concave features. By combining this capillary condensation phenomenon with proper reaction chemistry, it was realized to deposit Ru an Cu in holes and trenches structures preferentially. The capillary condensation occurs better in the narrower features, we call this method “gtopography-sensitive” selective deposition technique.

The kinetics of the deposition of ruthenium thin films from the hydrogen assisted reduction of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclooctadiene)ruthenium(II), [Ru(tmhd)2cod], in supercritical carbon dioxide was studied in order to develop a rate expression for the growth rate as well as to determine a mechanism for the process. The deposition temperature was varied from 240°C to 280°C and the apparent activation energy was 45.3 kJ/mol. Deposition rates up to 30 nm/min were attained. The deposition rate dependence on precursor concentrations between 0 and 0.2 wt. % was studied at 260°C with excess hydrogen and revealed first order deposition kinetics with respect to precursor at concentrations lower then 0.06 wt. % and zero order dependence at concentrations above 0.06 wt. %. The effect of reaction pressure on the growth rate was studied at a constant reaction temperature of 260°C and pressures between 159 bar to 200 bar and found to have no measurable effect on the growth rate.

Initial nucleation and succeeding coalescence in supercritical fluid deposition (SCFD) of Cu was studied in situ by using our devised monitoring technique, i.e. surface reflectivity measurement of visible white light. Fabrication of 10nm-thick smooth and continuous Cu film required by ULSI metallization, was succeeded. Complete filling without any seems and voids into various via patterns of 50 - 200 nm in diameter and 1 μm in depth was also achieved, which was revealed through angled polishing of patterned substrate.

Ultra-thin conformal polytetrafluoroethylene (PTFE) films were prepared by a novel physical vapor technique i.e., pulsed electron deposition (PED) technique. Prepared PTFE or Teflon thin films show high degree of conformity on patterned substrates. Under optimized deposition conditions the films exhibit superhydrophobicity. The PED processed films were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM) micrographs and the surface morphology and the conformal nature of the films were studied. The chemical nature and hydrophobicity were studied by FTIR and contact angle measurements, respectively.