We report the synthesis and characterization of a family of organometallic cobalt(I) metal precursors based around cyclopentadienyl and diene ligands. The molecular structures of the complexes cyclopentadienyl-cobalt(I) diolefin complexes are described, as determined by single-crystal X-ray diffraction analysis. Thermogravimetric analysis and thermal stability studies of the complexes highlighted the isoprene, dimethyl butadiene, and cyclohexadiene derivatives [(C5H5)Co(η(4)-CH2CHC(Me)CH2)] (1), [(C5H5)Co(η(4)-CH2C(Me)C(Me)CH2)] (2), and [(C5H5)Co(η(4)-C6H8)] (4) as possible cobalt metal organic chemical vapor deposition (MOCVD) precursors. Atmospheric pressure MOCVD was employed using precursor 1, to synthesize thin films of metallic cobalt on silicon substrates under an atmosphere (760 torr) of hydrogen (H2). Analysis of the thin films deposited at substrate temperatures of 325, 350, 375, and 400 °C, respectively, by scanning electron microscopy and atomic force microscopy reveal temperature-dependent growth features. Films grown at these temperatures are continuous, pinhole-free, and can be seen to be composed of hexagonal particles clearly visible in the electron micrograph. Powder X-ray diffraction and X-ray photoelectron spectroscopy all show the films to be highly crystalline, high-purity metallic cobalt. Raman spectroscopy was unable to detect the presence of cobalt silicides at the substrate/thin film interface.

A family of group 13 metal dimethyl complexes of the general formula [Me2M{MeC(O)CHC(NCH2CH2OMe)CF3}] [M = Al (2), Ga (3) or In (4)] was synthesised by reaction of the isolated free ligand 1 with the corresponding trimethyl metal reagents. The isolated complexes 2-4 were characterised by elemental analysis and NMR spectroscopy, and the molecular structures of the complexes were determined by single-crystal X-ray diffraction, which revealed them to be monomeric fivecoordinate complexes with coordination of the pendent etherbearing lariat in the solid state. Thermogravimetric analysis showed complexes 2-4 all to have residual masses at 200 degrees C of 2.4 % or less, well below the value for the respective metal oxides, and vapour pressure measurements showed the indium complex 4 to be an order of magnitude less volatile (0.09 Torr at 80 degrees C) than the Al (2) and Ga (3) analogues, despite their being isoleptic systems. Complexes 2-4 were investigated for their utility in the low-pressure metal organic chemical vapour deposition of the respective metal oxides in the absence of additional oxidant at 400 degrees C on silicon substrates.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A novel family of zinc bis(-ketoiminate) complexes 2b-2h have been synthesized by reaction of the isolated free ligands 1a-h with dimethylzinc. The isolated zinc complexes were characterized by elemental analysis, NMR spectroscopy, and in the case of 2b-d and 2f-h, the molecular structures of the complexes were determined by single-crystal X-ray diffraction which reveals the compounds to be pseudo-octahedral six-coordinate, monomeric homoleptic complexes in the solid state. TG analysis showed complexes 2b-f all to have residual masses at 400 degrees C of 10% or less, well below the value for ZnO and thus indicative of volatility. Of these systems 2b [Zn{MeC(O)CHC(NCH2CH2OMe)CF3}(2)] has been investigated for its utility in the AP-MOCVD growth of F-doped ZnO (ZnO:F) in the absence of additional oxidant at 400 degrees C on glass and silicon substrates.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We report the synthesis and characterisation of a new family of copper(i) metal precursors based around alkoxy-N,N'-di-alkyl-ureate ligands, and their subsequent application in the production of pure copper thin films. The molecular structure of the complexes bis-copper(i)(methoxy-N,N'-di-isopropylureate) (1) and bis-copper(i)(methoxy-N,N'-di-cyclohexylureate)(5) are described, as determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted complex 1 as a possible copper CVD precursor. Low pressure chemical vapour deposition (LP-CVD) was employed using precursor 1, to synthesise thin films of metallic copper on ruthenium substrates under an atmosphere of hydrogen (H2). Analysis of the thin films deposited at substrate temperatures of 225 °C, 250 °C and 300 °C, respectively, by SEM and AFM reveal the films to be continuous and pin hole free, and show the presence of temperature dependent growth features on the surface of the thin films. Energy dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic copper.

We report the synthesis and characterization of a family of cobalt(III) metal precursors, based around cyclopentadienyl and diazabutadiene ligands. The molecular structure of the complexes cyclopentadienyl-Cobalt(III)(N,N'-dicyclohexyl-diazabutadiene) (2c) and cyclopentadienyl-Cobalt(III)(N,N'-dimesityl-diazabutadiene) (2d) are described, as determined by single crystal X-ray diffraction analysis. Thermogravimetric analysis of the complexes highlighted the isopropyl derivative CpCo((i)Pr2-dab) (2a) as a possible cobalt metal chemical vapor deposition (CVD) precursor. Atmospheric pressure CVD (AP-CVD) was employed using precursor 2a to synthesize thin films of metallic cobalt on silicon substrates under an atmosphere of hydrogen (H2). Analysis of the thin films deposited at substrate temperatures of 250 °C, 275 °C, 300 °C, 325 °C, and 350 °C, respectively, by scanning electron microscopy (SEM) and atomic force microscopy (AFM) reveal temperature dependent growth features: films grown at 325 and 350 °C are continuous and pinhole free, whereas those films grown at substrate temperatures of 250 °C, 275 °C, and 300 °C consist of crystalline nanoparticles. Powder X-ray diffraction (PXRD) and X-ray photoelectron spectroscopy (XPS) all show the films to be high purity metallic cobalt. Raman spectroscopy has also been used to prove the absence of cobalt silicides at the substrate/thin film interface.