Copper(I) amidinate was investigated to produce copper films in conventional low pressure chemical vapor deposition (CVD) using hydrogen as reducing gas-reagent. Copper films were deposited on steel, silicon, and substrates in the temperature range at a total pressure of . The growth rate on steel follows the surface reaction between atomic hydrogen and the entire precursor molecule up to . A significant increase of the growth rate at temperatures higher than was attributed to thermal decomposition of the precursor molecule. It is shown that meets the specifications for the metal organic chemical vapor deposition of Cu-based alloy coatings containing oxophilic elements such as aluminum.
Thermal properties of oxygen-, phosphorus-, and halogen-free dimethylgold(III) diethyldithiocarbamate complex (CH3)2AuS2CN(C2H5)2 (gold, dimethyl(diethylcarbamodithioato -S,S′)-) having excellent storage stability and the mechanism of its decomposition to elemental gold were studied. Saturated vapor pressure was found to be ~10−3–10−1 Torr at 50–90°C. Decomposition of the vapor on the surface starts at T = 210°C. The temperature dependence of gas phase composition was studied using the original mass spectrometric technique, it was established that the decomposition of the compound on the surface in vacuum follows three main pathways. Two of them result in the formation of elemental gold, saturated C2–C4 alkanes and (1) protonated ligand or (2) methylated ligand. The third one results in elemental gold and gaseous products: C2–C3 alkylmercaptanes and CH3SCN(C2H5)2. The formation of gold as a sole solid product within the temperature range 210–240°C was confirmed by X-ray photoelectron spectroscopy analysis. It was shown that the compound exhibits the best combination of volatility, thermal, and storage stability among volatile organogold complexes and thus it may be a promising precursor for obtaining gold films by chemical vapor deposition.
Preparation of volatile heterometallic precursors is a significant step on the way to advanced multicomponent materials. Study of molecular transformations in solution upon precursor synthesis is of importance to optimize the preparation of the stable solid product of desired composition. Two new volatile heterobimetallic complexes, cis-PdL2*Pb(hfa)2 and cis-CuL2*Pb(hfa)2, were obtained (L = 2-methoxy-2,6,6-trimethylheptane-3,5-dionate, hfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate) under cocrystallization of trans-bis-beta-diketonates of Pd(II) and Cu(II) with Pb(hfa)2 from organic solvents. Crystals of these compounds are built of discrete bimetallic molecules where transition metal complex isomerized from trans-to-cis form. Complexation followed by isomerization was studied by solution NMR. The bimetallic molecular species were formed early in solution. Enthalpy and activation energy of isomerization were estimated to be 49 and 93 kJ mol−1, respectively. A new synthesis technique of Pd(II) beta-diketonates which is distinguished by simplicity and selectivity as well as the crystal structure of trans-PdL2 is described. Volatility of all obtained compounds was confirmed by thermogravimetric analysis and fractional sublimation in vacuum; Pd-containing heterobimetallic complex appeared to be more volatile than both the initial monometallic complexes and Cu-containing complex.
A series of new heterometallic compounds have been obtained by the co-crystallization of Cu(II) methoxy-substituted β-diketonates and Pb(II) hexafluoroacetylacetonate (hfac) from organic solvents. Their crystal structures were established by X-ray analysis. It is shown that the formation of heterometallic compounds proceeds with geometrical isomerization of the initial copper complexes, which can be controlled by varying terminal substituents in the ligand. Due to the ability of copper complexes to isomerize, the structure of the resulting heterocomplexes can be flexibly and purposefully changed from polymeric to discrete molecular forms. The study of the thermal properties shows that all the reported compounds are volatile and can be re-sublimed in a vacuum, with their composition and structure being retained.
Volatile heterobimetallics based on Pb(hfac)2 as a host material and a range of Pd(ii) β-diketonates have been studied to trace the influence of the nature of initial monometallic complexes on the structure, composition and thermal properties.