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the lines indicates that the growth rate has a negative 1⁄2 order dependence for each of the byproducts separately. There are two possibilities to account for this result. Byproduct competition for hydrogen, in order to hydrogenate ligand decomposition products, may have consumed the available hydrogen in the system. However, given that the amount of hydrogen in the reactor is in excess of 1000 times the necessary amount for complete reduction of all loaded precursor, it is not likely the reason. It is proposed that the ligands are occupying the surface active sites thereby reducing the probability for a successful surface reaction. 35 30 25 20 15 10 5 0 0 0.2 0.4 0.6 0.8 1 TMHD Concentration (wt.%) 3.5 3 2.5 2 -2.5 -2 -1.5 -1 -0.5 ln(C) Figure 2.18: Growth rate dependence upon tmhd concentration. Reaction conditions: 260 °C, 0.09 wt. % Ru(tmhd)2cod, 0.3 wt. % hydrogen, 3 minutes heating. Using differential kinetics (inset), negative first order kinetics is observed with addition of tmhd from concentrations between 0 wt. % - 0.9 wt. %. 41 Growth Rate (nm/min) ln(R)PDF Image | Supercritical Fluid Deposition Of Thin Metal Films
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