Thermodynamic investigation of the MOCVD of copper films frombis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II)

Abstract

Equilibrium concentrations of various condensed and gaseous phases have been thermodynamically calculated, using the free energy minimization criterion, for the metalorganic chemical vapour deposition (MOCVD) of copper films using bis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II) as the precursor material. From among the many chemical species that may possibly result from the CVD process, only those expected on the basis of mass spectrometric analysis and chemical reasoning to be present at equilibrium, under different CVD conditions, are used in the thermodynamic calculations. The study predicts the deposition of pure, carbon-free copper in the inert atmosphere of argon as well as in the reactive hydrogen atmosphere, over a wide range of substrate temperatures and total reactor pressures. Thin films of copper, grown on SiO 2 /Si(100) substrates from this metalorganic precursor by low pressure CVD have been characterized by XRD and AES. The experimentally determined composition of CVD-grown copper films is in reasonable agreement with that predicted by thermodynamic analysis.

Deposition of Copper by the H2-Assisted Reduction of Cu(tmod)2 in Supercritical Carbon Dioxide: Kinetics and Reaction Mechanism

“…By comparison, the activation energy for metal organic chemical vapor deposition (MOCVD) using copper(II) hexafluoroacetylacetone, Cu(hfac) 2 , has been reported to be ∼75−80 kJ/mol. , In those studies, the surface reaction was assumed to be the rate-limiting step. The activation energy calculated from data reported for MOCVD using bis(2,2,6,6-tetramethyl-3,5-heptadionato)copper(II), Cu(tmhd) 2 , was ∼60 kJ/mol . Son et al reported an activation energy of 62.8 kJ/mol for copper deposition from hexafluoroacetylacetonatecopper(I) allyltrimethylsilane, (hfac)Cu(ATMS), in a reaction rate-limited regime .…”

Photofragmentation Pathways and Photodeposition of Nanoparticles from a Gas Phase Copper-Containing Precursor

“…The heaviest masses and most prominent peaks were formed from the loss of t -butyl groups from each ligand (Figure a). As shown previously in studies of this compound using either photons or electrons as the ionization source, the loss of a t -butyl group from a TMHD ligand is an important step to reaching the formation of neutral copper. − As a t -butyl group dissociates, a hydrogen atom from the dissociated t -butyl takes its place. This mechanism has been reported using electroionization mass spectrometry .…”

“…using either photons or electrons as the ionization source, the loss of a t-butyl group from a TMHD ligand is an important step to reaching the formation of neutral copper. [41][42][43][44] As a t-butyl group dissociates, a hydrogen atom from the dissociated t-butyl takes its place. This mechanism has been reported using electroionization mass spectrometry.…”

CVD of Conducting Ultrathin Copper Films

“…The hydrogen reduction route requires the attainment of a considerable nominal thickness before coalescence occurs, and consequently, values of the electrical resistivity are mostly provided for thicknesses exceeding 100 nm, 13,16,[21][22][23][24][25][26][27][28] as presented in Fig. 4b.…”