Novel mixed amido-malonato complexes of titanium are reported. The complexes were synthesized by partially replacing the amido groups from the complexes [Ti(NMe2)4] and [Ti(NEt2)4] via Brønstedt acid/base reactions, using the malonate-ligands di-isopropylmalonate (Hdpml) and di-tert-butylmalonate (Hdbml). Four representative complexes were synthesized and fully characterised by 1H NMR, 13C NMR, CHN analysis and mass spectrometry. The crystal structures of the six-coordinated complexes [Ti(NMe2)2(dbml)2] (3) and [Ti(NEt2)2(dbml)2] (4) are presented and discussed. The complexes are solids and the chemical and thermal characteristics of the complexes strongly depend on the substitution at the malonate ligand. While dpml containing complexes show a promising behaviour for classical MOCVD, dbml containing complexes seem to be more suitable for liquid injection-metal-organic chemical vapour deposition (LI-MOCVD). Based on its thermal characteristics, the most promising complex for thermal CVD, [Ti(NEt2)2(dpml)2] (2) was selected for preliminary MOCVD experiments, which indicate a good suitability for the deposition of TiO2 thin films.
Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. "CVD phase stability diagrams" have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as functions of CVD parameters. For the process conduced in argon ambient, the analysis predicts the simultaneous deposition of MnO and elemental carbon in 1:3 molar proportion, over a range of temperatures. The analysis predicts also that, if CVD is carried out in oxygen ambient, even a very low flow of oxygen leads to the complete absence of carbon in the film deposited oxygen, with greater oxygen flow resulting in the simultaneous deposition of two different manganese oxides under certain conditions. The results of thermodynamic modeling have been verified quantitatively for lowpressure CVD conducted in argon ambient. Indeed, the large excess of carbon in the deposit is found to constitute a MnO/C nanocomposite, the associated cauliflower-like morphology making it a promising candidate for electrode material in supercapacitors. CVD carried out in oxygen flow, under specific conditions, leads to the deposition of more than one manganese oxide, as expected from thermodynamic analysis (and forming an oxide-oxide nanocomposite). These results together demonstrate that thermodynamic analysis of the MOCVD process can be employed to synthesize thin films in a predictive manner, thus avoiding the inefficient trial-and-error method usually associated with MOCVD process development. The prospect of developing thin films of novel compositions and characteristics in a predictive manner, through the appropriate choice of CVD precursors and process conditions, emerges from the present work.
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