Comparison of (hexafluoroacetylacetonate)Cu(vinyltrimethylsilane) and (hexafluoroacetylacetonate)Cu(allyltrimethylsilane) for metalorganic chemical vapor deposition of copper

Abstract

For the metalorganic chemical vapor deposition (MOCVD) of copper, (hfac)Cu(VTMS) (hfac = hexafluoroacetylacetonate, VTMS = vinyltrimethylsilane) and (hfac)Cu(ATMS) (ATMS = allyltrimethylsilane) were compared, and the effect of L ligand in (hfac)Cu–L was examined. It was found by 1H-NMR (nuclear magnetic resonance) that the thermal stability of (hfac)Cu(VTMS) was better than that of (hfac)Cu(ATMS) due to the relatively weak Cu–ATMS bond. From in situ Fourier transform infrared spectroscopy (FTIR) experiments, the formation of Cu(hfac)2, the product of disproportion reaction of Cu(hfac), was observed in the gas phase and (hfac)Cu(ATMS) was found to be more reactive to form Cu(hfac)2. The minimum temperature for the deposition of copper films from (hfac)Cu(ATMS) was as low as 60 °C, which was about 70 °C lower than from (hfac)Cu(VTMS). The grain size of the film deposited with (hfac)Cu(ATMS) was substantially larger than that with (hfac)Cu(VTMS), which showed that the chemical reactivity of the precursor had an influence on the microstructure along with the deposition temperature.

Metal–Organic Derivatives with Fluorinated Ligands as Precursors for Inorganic Nanomaterials

“…One drawback of these Cu I complexes, though, is that they are thermally unstable and need to be stored at low temperature or added excess of parent ligands during CVD to stabilize them. 412,413 …”

Preparation of thin copper films from the vapour phase of volatile copper(I) and copper(II) derivatives by the CVD method

“…A certain role in these features of CVD processes is apparently associated with the fact that (HFA)Cu(ATMS) is even less stable thermally than (HFA)Cu(VTMS) and (HFA)Cu(VTMOS), and hence it is more reactive. 323,326 At a temperature as low as 60 8C, the IR spectra of (HFA)Cu(ATMS) vapour contain bands corresponding to Cu(HFA) 2 . It is interesting that the morphology of the copper film surfaces obtained also depends on the reactivity of the starting compounds: for example, the grain size in the copper films obtained from (HFA)Cu(ATMS) vapour is much larger than that in the copper films obtained from (HFA)Cu(VTMS) vapour.…”

“…It is interesting that the morphology of the copper film surfaces obtained also depends on the reactivity of the starting compounds: for example, the grain size in the copper films obtained from (HFA)Cu(ATMS) vapour is much larger than that in the copper films obtained from (HFA)Cu(VTMS) vapour. 323 b. Complexes of copper(I) b b-diketonates with isocyanides Of copper(I) b-diketonate complexes stabilised by interactions of the copper(I) ion with the double bond, those with tert-butyl isocyanide (Bu t NC) are considered as promising starting CCC for the preparation of copper films by CVD technology. It should be noted that the corresponding complexes of copper(I) derivatives with nitriles RCN decompose even at room temperature.…”

Precursor to Gas Sensor: A Detailed Study of the Suitability of Copper Complexes as an MOCVD Precursor and their Application in Gas Sensing

“…So sublimation and deposition temperatures are high and deposition rates are very low. 21,22 According to previous reports, fluorinated βdiketonates 23,24 are volatile, but depositions are irreproducible; contaminated with fluorine; and the halide byproducts are corrosive. 25 Copper(II) keto-ester complexes are a promising alternative, but they are poorly studied.…”