Precursor chemistry for TiO2: titanium complexes with a mixed nitrogen/oxygen ligand sphere

Abstract

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 Bronstedt acid/base reactions, using the malonate-ligands di-isopropylmalonate (Hdpml) and di-tert-butylmalonate (Hdbm]). Four representative complexes were synthesized and fully characterised by H-1 NMR, C-13 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