The effects of process conditions and substrate on copper MOCVD using liquid injection of (hfac)Cu(vtmos)

Copper MOCVD (metalorganic chemical vapor deposition) using liquid injection for effective delivery of the (hfac)Cu(vtmos) [1,1,1,5,5,5-hexafluoro-2,4-pentadionato(vinyltrimethoxysilane) copper(I)] precursor has been performed to clarify growth behavior of copper films onto TiN, <100> Si, and Si₃N₄ substrates. Especially, we have studied the influences of process conditions and the substrate on growth rates, impurities, microstructures, and electrical characteristics of copper films. As the reactor pressure was increased, the growth rate was governed by a pick-up rate of (hfac)Cu(vtmos) in the vaporizer. The apparent activation energy for copper growth over the surface-reaction controlled regime from 155°C to 225°C was in the range 12.7–32.5 kcal/mol depending upon the substrate type. It revealed that H₂ addition at 225°C substrate temperature brought about a maximum increase of about 25% in the growth rate compared to pure Ar as the carrier gas. At moderate deposition temperatures, the degree of a <111> preferred orientation for the deposit was higher on the sequence of 3N₄. The relative impurity content within the deposit was in the range 1.1 to 1.8 at.%. The electrical resistivity for the Cu films on TiN illustrated three regions of the variation according to the substrate temperature, so the deposit at 165°C had the optimum resistivity value. However, the coarsened microstructures of Cu on TiN prepared above 275°C gave rise to higher electrical resistivities compared to those on Si and Si₃N₄ substrates.