A novel CVD copper process is described using two new copper CVD precursors, KI3 and KI5, for the fabrication of IC or TSV (Through Silicon Via) copper interconnects. The highly conformal CVD copper can provide seed layers for subsequent copper electroplating or can be used to directly fabricate the interconnect in one step. These new precursors are thermally stable yet chemically reactive under CVD conditions, growing copper films of exceptionally high purity at high growth rates. Their thermal stability can allow for elevated evaporation temperatures to generate the high precursor vapor pressures needed for deep penetration into high aspect ratio TSV vias. Using formic acid vapor as a reducing gas with KI5, copper films of > 99.99 atomic % purity were grown at 250°C on titanium nitride at a growth rate of > 1500 Å/min. Using tantalum nitride coated TSV type wafers, ~ 1700 Å of highly conformal copper was grown at 225°C into 32 µm × 5 µm trenches with good adhesion. With ruthenium barriers we were able to grow copper at 125°C at a rate of 20 Å/min to give a continuous ~ 300 Å copper film. In this respect, rapid low temperature CVD copper growth offers an alternative to the long cycle times associated with copper ALD which can contribute to copper agglomeration occurring.
We report the synthesis, characterization, and experimental density function theory-derived properties of new volatile strontium and barium imidazolate complexes, which under atomic layer deposition conditions using ozone as a reagent can deposit crystalline strontium oxide at 375 °C.
A series of new non-fluorinated volatile copper precursors are described which have been designed for ALD of copper. These new molecules are low melting solids which show outstanding thermal stability and high chemical reactivity with molecular hydrogen to give pure copper films on ruthenium substrates in the temperature range of 130-200°C. Using ruthenium (001) substrates results in strongly adherent ALD copper films which are preferentially oriented (111) for optimal electrical performance.
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