Cobalt(I) Olefin Complexes: Precursors for Metal-Organic Chemical Vapor Deposition of High Purity Cobalt Metal Thin Films.

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.

Cobalt(III) diazabutadiene precursors for metal deposition: nanoparticle and thin film growth.

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.

Exclusive formation of SnO by low temperature single-source AACVD.

An easily synthesised Sn(II) bis(ureide) derivative is shown to be a single-source precursor for the aerosol-assisted CVD of SnO, providing unprecedented levels of oxidation state control at temperatures as low as 250 °C.

CVD of pure copper films from novel iso-ureate complexes.

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.

Multinuclear copper(I) guanidinate complexes.

A series of multinuclear Copper(I) guanidinate complexes have been synthesized in a succession of reactions between CuCl and the lithium guanidinate systems Li{L} (L = Me(2)NC((i)PrN)(2) (1a), Me(2)NC(CyN)(2) (1b), Me(2)NC((t)BuN)(2)(1c), and Me(2)NC(DipN)(2) (2d) ((i)Pr = iso-propyl, Cy = cyclohexyl, (t)Bu = tert-butyl, and Dip = 2,6-disopropylphenyl) made in situ, and structurally characterized. The di-copper guanidinates systems with the general formula [Cu(2){L}(2)] (L = {Me(2)NC((i)PrN)(2)} (2a), {Me(2)NC(CyN)(2)} (2b), and {Me(2)NC(DipN)(2)} (2d) differed significantly from related amidinate complexes because of a large torsion of the dimer ring, which in turn is a result of transannular repulsion between adjacent guanidinate substituents. Attempts to synthesis the tert-butyl derivative [Cu(2){Me(2)NC((t)BuN)(2)}(2)] result in the separate formation and isolation of the tri-copper complexes [Cu(3){Me(2)NC((t)BuN)(2)}(2)(µ-NMe(2))] (3c) and [Cu(3){Me(2)NC((t)BuN)(2)}(2)(µ-Cl)] (4c), both of which have been unambiguously characterized by single crystal X-ray diffraction. Closer inspection of the solution state behavior of the lithium salt 1c reveals a previously unobserved equilibrium between 1c and its starting materials, LiNMe(2) and N,N'-di-tert-butyl-carbodiimide, for which activation enthalpy and entropy values of ΔH(‡) = 48.2 ± 18 kJ mol(-1) and ΔS(‡) = 70.6 ± 6 J/K mol have been calculated using 1D-EXSY NMR spectroscopy to establish temperature dependent rates of exchange between the species in solution. The molecular structures of the lithium complexes 1c and 1d have also been determined and shown to form tetrameric and dimeric complexes respectively held together by Li-N and agostic Li···H-C interactions. The thermal chemistry of the copper complexes have also been assessed by thermogravimetric analysis.

Synthesis, characterization, and materials chemistry of Group 4 silylimides.

This paper focuses on the development of potential single source precursors for M-N-Si (M = Ti, Zr or Hf) thin films. The titanium, zirconium, and hafnium silylimides (Me(2)N)(2)MNSiR(1)R(2)R(3) [R(1) = R(2) = R(3) = Ph, M = Ti(1), Zr (2), Hf (3); R(1) = R(2) = R(3) = Et, M = Ti (4), Zr (5), Hf (6); R(1) = R(2) = Me, R(3) = (t)Bu, M = Ti (7), Zr (8), Hf (9); R(1) = R(2) = R(3) = NMe(2), M = Ti (10), Zr (11), Hf (12)] have been synthesized by the reaction of M(NMe(2))(4) and R(3)R(2)R(1)SiNH(2). All compounds are notably sensitive to air and moisture. Compounds 1, 2, 4, and 7-10 have been structurally characterized, and all are dimeric, with the general formula [M(NMe(2))(2)(µ-NSiR(3))](2), in which the µ(2)-NSiR(3) groups bridges two four-coordinate metal centers. The hafnium compound 3 possesses the same basic dimeric structure but shows additional incorporation of liberated HNMe(2) bonded to one metal. Compounds 11 and 12 are also both dimeric but also incorporate additional µ(2)-NMe(2) groups, which bridge Si and either Zr or Hf metal centers in the solid state. The Zr and Hf metal centers are both five-coordinated in these species. Aerosol-assisted CVD (AA-CVD) using 4-7 and 9-12 as precursors generates amorphous films containing M, N, Si, C, and O; the films are dominated by MO(2) with smaller contributions from MN, MC and MSiON based on XPS binding energies.

Synthesis and structure of 6-aminofulvene-2-aldiminate complexes.

We report here a synthetic route to bis(N,N'-aryl)-6-aminofulvene-2-aldimine (AFA) ligand systems, specifically Ph(2)-AFAH and Dip(2)-AFAH. The synthesis and structural characterization of a series of Cu(I) complexes [(Ph(2)-AFA)Cu(CNPh)(2)] (2), [(Ph(2)-AFA)Cu(CN(i)Pr)] (3), and [(Dip(2)-AFA)Cu(CN(i)Pr)] (4), from the reaction of the corresponding lithiated AFA systems with Cu-Cl derivatives are reported; notably in the case of [(Ph(2)-AFA)Cu(CNPh)(2)] studies have revealed the existence of two structural isomers (2a and 2b), both of which can be isolated and structurally characterized. Density functional theory (DFT) calculations suggest that the two crystal forms are comparatively close in energy, and geometry optimization reveals a convergence of these two forms to a geometry that more closely resembles the solid-state structure of isomer 2b, having a CH···π interaction. The reactions of the AFA compounds Ph(2)-AFAH and Dip(2)-AFAH with ZnMe(2) and AlMe(3) have also been investigated, and the results of these reactions are described here.

Unprecedented double migratory insertion of phenyl isocyanide into cyclopentadienyl C-H bonds.

The reaction of [(eta(5)-C(5)H(5))Cu(CNPh)] with phenyl-isocyanide results in an unprecedented double migratory insertion into two sp(2) C-H bonds of a eta(5)-coordinated cyclopentadienyl group, and formation of the 6-aminofulvene-2-aldimine complexes [(CNPh)Cu{kappa(2)-N,N-C(5)H(3)-1,2-(CHNPh)(2)}] and [(CNPh)(2)Cu{kappa(2)-N,N-C(5)H(3)-1,2-(CHNPh)(2)}], respectively, both of which have been structurally characterised.

Complexes of Triamidoamines with the Early Actinides. Synthetic Routes to Monomeric Compounds of Tetravalent Uranium and Thorium Containing Halide and Amide Ligands.

The reaction of the lithiated triamidoamine [Li(3)(NN'(3))(THF)(3)] [NN'(3) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)] with AnCl(4) (An = U, Th) followed by sublimation gives monomeric [An(NN'(3))Cl]. Reaction of these complexes with SiMe(3)X (X = Br, I) gives [An(NN'(3))X]. The amido derivatives [An(NN'(3))(NEt(2))] are prepared from H(3)(NN'(3)) and [U(NEt(2))(4)] and from [Th(NN'(3))Cl] and [Li(NEt(2))]. In each case, the complexes [U(NN'(3))X] (X = Cl, Br, I, NEt(2)) are shown by X-ray crystallography to contain a triamidoamine ligand disposed with 3-fold symmetry about the metal center. The structures are distorted from trigonal bipyramidal by displacement of the uranium atoms out of the equatorial plane of the three amido nitrogen atoms by ca. 0.8 Å. The ligand backbone is distorted in such a manner as to cause the tert-butyldimethylsilyl groups to encircle the equatorial plane of the metal atom rather than surround the apical coordination site as is observed in the transition metal complexes of this type. Variation of the auxiliary ligand has little effect on the orientation, bond lengths, and angles within the (triamidoamine)uranium fragment. The tert-butydimethysilyl-substituted triamidoamine ligand is thus ideally suited for coordination to large metals since it stabilizes the formation of 3-fold symmetric structures while also allowing reactivity at the fifth coordination site.