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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 2.19: Growth rate dependence upon cod 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 cod from concentrations between 0 wt. % - 0.9 wt. % .....................42 2.20: Growth rate dependence upon cot concentration. Reaction conditions: 260 °C, 0.09 wt. % Ru(tmhd)2cod, 0.3 wt. % hydrogen, 3 minutes heating. Cot has a weak negative effect on growth rates between 0 wt. % - 0.9 wt. % .............................43 2.21: Schematic of the proposed mechanism for the deposition of ruthenium via the hydrogen assisted reduction of bis(2,2,6,6-tetramethyl-heptane-3,5-dionato)(1,5- cyclooctadiene)ruthenium(II) in supercritical carbon dioxide via the supercritical fluid deposition process.......................................................................................47 3.1: Custom built 316 stainless steel cold wall reactor with resistive heated aluminum sample stage.........................................................................................................59 3.2: Chemical structure of bis (2,2,7 - trimethyloctane- 3, 5-dionato) copper, Cu(tmod)2 ............................................................................................................61 3.3: Experimental sample stack for mechanical adhesion testing of copper deposited film on unmodified TaN capped substrates. Si, SiO2, Epoxy, TaN thicknesses are approximately 700-750 μm, 500 nm, 5 μm and 30 nm, respectively. Cu thickness varies according to Table 3.1...............................................................64 3.4: Experimental sample stack for mechanical adhesion testing of copper deposited film on poly(acrylic acid) modified TaN capped substrates. PAA thickness approximately 15 nm...........................................................................................64 3.5: Schematic and force diagram for four point bend technique.................................65 3.6: Load versus displacement plot for sample A-5, unmodified surface.....................67 3.7: Load versus displacement plot for sample B-3, poly(acrylic acid) modified surface ..................................................................................................................68 3.8: Statistical data for adhesion energy versus thickness of the deposited copper film for both treated and untreated substrates .............................................................68 3.9: Representation of the post mechanical tested sample stack with directionality indication of XPS for sputter depth profiling ......................................................69 xviiiPDF Image | Supercritical Fluid Deposition Of Thin Metal Films
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