Novel monomeric barium complexes as volatile precursors for chemical vapour deposition

A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD). A novel pathway providing an unprecedented sequence of barium carbamates is reported. New dianionic bis β-ketoesterates and their barium, strontium and calcium derivatives were synthesised. High resolution mass spectrometry showed some barium derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Calcium and strontium complexes were found to have nuclearities that varied according to their ionic radii relative to the chain length of the encapsulating ligand.     

Superbulky metallocene complexes of the heavier alkaline-earth metals strontium and barium

Superbulky sandwich complexes with the cyclopentadienyl ligand (4-nBu-C(6)H(4))(5)Cp (abbreviated here as Cp(BIG)) have been prepared by reaction of Cp(BIG)H with benzylic strontium or barium reagents. Both metallocenes have been structurally characterized by single crystal X-ray diffraction. Even for the larger metallocene (Cp(BIG))(2)Ba a highly symmetric sandwich complex with parallel Cp rings was isolated (Cp(center)-Ba = 2.667(1) A). Both structures show evidence for a C-HC(pi) network between the Cp ligands. These attractive forces induce an inward out-of-plane bending of the aryl substituents (Sr 3.4(2) degrees ; Ba 5.3(2) degrees ). A linear correlation between this bending angle and metal size has been found.     

New cationic group 4 metal alkyl complexes

Cationic group 4 metal alkyl complexes containing tetradentate Schiff base ligands, (acen) Zr(R)⁺ and (F6-acen) Zr(R)⁺, are prepared by protonolysis of suitable neutral dialkyl precursors. These complexes display electrophilic behavior and are moderately active ethylene polymerization catalysts in the presence of 1 molar equivalent of AlR₃.     

New baths for the deposition of manganese and cobalt oxides

New methods have been adopted for the anodic deposition of the different manganese and cobalt oxides. The deposition of the diferent oxides is usually carried out from their metal salt solutions in presence of a reducing agent. The oxides deposited are as follows: Mn₂O₃ from manganous sulphate in presence of boric, acid and formaldehyde at pH=5.5, Mn₃O₄ from manganous sulphate in presence of formic acid at pH=5.0 MnO from manganous sulphate-ammonium chloride solution in presence of telluric acid, Co₂O₃ from cobalt chloride in presence of telluric acid and sodium fluoride, Co₃O₄ from cobaltite in presence of formaldehyde and potassium chloride and finally CoO from cobalt chloride in presence of alcohol. The results of chemical analysis revealed that the purity of the oxides is 99.99% and their molecular formulae are MnO_1.5, MnO_1.33, MnO, CoO_1.5, CoO_1.33 and CoO respectively.     

A general route for RuO2 deposition on metal oxides from RuO4

A novel method for the deposition of RuO(2) from RuO(4)(g) on diverse metal oxides has been developed by grafting dopamine onto the otherwise un-reactive metal oxide surface. Oxygen evolution reaction on TiO(2) and the photoelectrochemical improvement of WO(3) by deposition of RuO(2) are just a few examples where this novel deposition method can be used.     

Atomic layer deposition and chemical vapor deposition precursor selection method application to strontium and barium precursors

A new selection method for atomic layer deposition (ALD) or chemical vapor deposition (CVD) precursors is proposed and tested. Density functional theory was used to simulate Sr and Ba precursors, and several precursors were selected and used to grow films via ALD as test cases for the precursor selection method. The precursors studied were M(x)2 (M = Sr, Ba; x = tetramethylheptanedionate (tmhd), acetylacetonate (acac), hexafluoroacetylacetonate (hfac), cyclopentadienyl (H(5)C(5)), pentamethylcyclopentadienyl (Me(5)C(5)), n-propyltetramethylcyclopentadienyl (PrMe(4)C(5)), tris(isopropylcyclopentadienyl) (Pr(3)(i)H(2)C(5)), tris(isopropylcyclopentadienyl)(THF) (Pr(3)(i)H(2)C(5))(OC(4)H(8)), tris(isopropylcyclopentadienyl)(THF)2 (Pr(3)(i)H(2)C(5))(OC(4)H(8))2, tris(tert-butylcyclopentadienyl) (Bu(3)(t)H(2)C(5)), tris(tert-butylcyclopentadienyl)(THF) (Bu(3)(t)H(2)C(5))(OC(4)H(8)), heptafluoro-2,2-dimethyl-3,5-octanedionate (fod)). The energy required to break bonds between the metal atom and the ligands was calculated to find which precursors react most readily. In the case of tmhd and Cp precursors, the energy required to break bonds in the precursor ligand was studied to evaluate the most likely mechanism of carbon incorporation into the film. Trends for Ba and Sr followed each other closely, reflecting the similar chemistry among alkaline earth metals. The diketonate precursors have stronger bonds to the metals than the Cp precursors, but weaker bonds within the ligand, explaining the carbon contamination found in experimentally grown films. Atomic layer deposition of SrO was tested with Sr(tmhd)2 and Sr(PrMe(4)Cp)2 and oxygen, ozone, and water as oxygen sources. No deposition was measured with tmhd precursors, and SrO films were deposited with PrMe(4)Cp with a source temperature of 200 degrees C and at substrate temperatures between 250 and 350 degrees C with growth rates increasing for oxygen sources in this order: O2 < H2O < O2 + H2O. The experimental results support the predictions based upon calculations: PrMe(4)Cp and Me(5)Cp precursors are expected to be the best precursors among those studied for Ba and Sr film growth.     

A structural study of calcium,strontium and barium crown ether complexes

Complexes involving the perchlorate, chloride, bromide or iodide salts of the heavy group 2 elements, calcium, strontium or barium, and either 15-crown-5 or 18-crown-6 have been synthesized and their X-ray crystal structures determined. A variety of coordination modes are presented between the crown ether and metal ions.     

New volatile β-diketonate complexes of barium with sterically hindered methoxy-β-diketones as precursors for CVD

The new β-diketones with a methoxy group of the type (R¹R²)C(OCH₃)COCH₂COR³ and their barium complexes have been synthesized. The barium β-diketonates obtained were identified and characterized by elemental, IR and Raman spectroscopic analyses. TG, DTG and DTA analyses carried out in vacuo and at atmospheric pressure have allowed the determination of the relative volatility and thermal stability of these barium complexes. The influence of the methoxy group, by type of substituent in the ligand, has been investigated by mass spectrometry. It has been found that the introduction of bulky end substituents into the ligand does not reduce the maximal oligomerization degree of barium β-diketonates in the gas phase.     

Monohydrates of strontium and barium hydroxide

The monohydrates of strontium and barium hydroxide have been prepared by decomposition, under vacuum, of the corresponding octahydrates. X-ray powder data for both compounds are reported, together with that for anhydrous strontium hydroxide; the latter is included in order to clarify an apparent anomaly in the literature.

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Zusammenfassung Es wurden die Monohydrate von Strontium und Bariumhydroxid im Vakuum aus den entsprechenden Octahydraten hergestellt. Röntgenographische Daten für beide Verbindungen sowie für wasserfreies Strontiumhydroxid wurden gegeben; für Letzteres, um gewisse Anom alien in der Literatur zu klären.

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Résumé Préparation des hydroxydes de strontium et de baryum monohydratés par décomposition dans le vide des octohydrates correspondants. Etude par rayons X de ces composés ainsi que de l'hydroxyde de strontium anhydre, dans le but, pour ce dernier, d'élucider certaines anomalies de la littérature.

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The authors wish to thank Mr. A. Miller for taking the X-ray powder photographs.     

Syntheses and structures of strontium, barium, and europium bis(diphosphanylamido) complexes

Bis(diphosphanylamido) complexes of strontium and europium, [{(Ph(2)P)(2)N}(2)M(THF)(3)] (M = Sr (1), Eu (2)), have been prepared by reaction of [K(THF)(n)()][N(PPh(2))(2)] (n = 1.25, 1.5) and MI(2). The single-crystal X-ray structures of compounds 1 and 2 always show a eta(2) coordination of the ligand via the nitrogen and one phosphorus atom. In solution, a dynamic behavior of the ligand is observed, which is caused by the rapid exchange of the two different phosphorus atoms. As a result of the radius of the larger ion, treatment of [K(THF)(n)()][N(PPh(2))(2)] with BaI(2) gives the coordination polymer [{(Ph(2)P)(2)N}(2)Ba(THF){(Ph(2)P)(2)N}K](n)() (3). Two of the three {(Ph(2)P)(2)N}(-) ligands of compound 3 bind to the metal in eta(2) (N, P) while the third shows a heteroallylic (P, P) coordination mode. In the solid state, the infinite chain is formally held together by pi coordination of the phenyl rings to the potassium atoms.     

Atomic layer deposition of metal oxides on pristine and functionalized graphene

We investigate atomic layer deposition (ALD) of metal oxide on pristine and functionalized graphene. On pristine graphene, ALD coating can only actively grow on edges and defect sites, where dangling bonds or surface groups react with ALD precursors. This affords a simple method to decorate and probe single defect sites in graphene planes. We used perylene tetracarboxylic acid (PTCA) to functionalize the graphene surface and selectively introduced densely packed surface groups on graphene. Uniform ultrathin ALD coating on PTCA graphene was achieved over a large area. The functionalization method could be used to integrate ultrathin high-kappa dielectrics in future graphene electronics.     

Substitution of barium for strontium in hydroxovanadate structure

A possibility of substitution of barium for strontium in Sr₁₀(VO₄)₆(OH)₂ is studied by X-ray powder diffraction and IR spectroscopy. According to X-ray powder diffraction data, single-phase solid solutions Sr_{10 ? x} Ba _x (VO₄)₆(OH)₂ are formed with x = 0–2.5 with an increase in the unit cell parameters.     

Calcium, strontium, barium, and ytterbium complexes with cyclooctatetraenyl or cyclononatetraenyl ligands

Neutral triple-decker complexes of the heavy alkaline earth metals and ytterbium with tetraisopropylcyclopentadienide anions as terminal ligands and a cyclooctatetraene dianion as a middle deck have been synthesized from tetraisopropylcyclopentadienyl metal halide precursors and disodium cyclooctatetraenide. The pentaisopropylcyclopentadienyl analogue [{(C5iPr5)Yb}2(C8H8)] was prepared from ytterbium metal, cyclooctatetraene, and the free pentaisopropylcyclopentadienyl radical. X-ray crystal structure determinations for the barium and the calcium derivative show an almost linear arrangement of ring centers and metal atoms in both cases with metal-ring center distances of 2.33 A (Ca-Cp), 1.99/1.98 A (Ca-COT) and 2.71 A (Ba-Cp), 2.40 A (Ba-COT). The geometrical features of these molecules could be modeled quite accurately with density functional calculations. With potassium cyclononatetraenide, sparingly soluble bis(cyclononatetraenyl)barium could be prepared and characterized by 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. Cyclononatetraenyl(tetraisopropylcyclopentadienyl)barium was obtained from [(C5HiPr4)BaI(THF)2]2 and KC9H9 as a 1:1 mixture with octaisopropylbarocene. Density functional calculations predict sandwich structures with parallel rings and a 2.37 A Ba-ring distance for [Ba(C9H9)2] and a 174 bending with metal-ring distances of 2.72 A (Ba-Cp) and 2.35 A (Ba-CNT) for [(C5HiPr4)Ba(C9H9)]. All alkaline earth sandwich and triple-decker complexes mentioned above have been heated to 250 degrees C without decomposition and have been sublimed in oil pump vacuum.     

The photolysis of barium and strontium azides

The effect of very high intensity UV light on powdered barium and strontium azides in vacuo in the temperature ranges −70° to 100°, and −80° to 90°, has been studied. The photolytic decompositions were characterized by a high percentage decomposition and sigmoid pressure vs time plots similar to those obtained by thermal decomposition. Kinetic analysis, the determination of activation energies, studies of the dependence of reaction rates on light intensity, and the effect of water vapour, were carried out. Mechanisms for decomposition over well defined temperature ranges are proposed.     

Platinum group metal complexes of adenosine and xanthosine

The preparation of octahedral Ru(III), Rh(III) and Ir(III) complexes of adenosine and xanthosine are reported. The complexes are characterised by their elemental analysis, conductivity and IR data. The coordinating site in nucleosides seems to be the N₇ as is the case reported in platinum(II) complexes.     

New heterobimetallic complexes containing copper(II) and a group IV metal

Summary Novel heterobimetallic chelates [Cu(en)₂Cl₂M₂Cl₄] (M = Si, Ge, Sn, Ti and Zr; en = ethylenediamine) and [Cu(en)₂Cl₂SnPh₄] prepared by reacting [Cu(en)₂]Cl₂ with group IV metal tetrachlorides and dichlorodiphenyltin(IV), respectively, were characterized by e.s.r., electronic and i.r. spectroscopy, elemental analysis and conductivity measurements. The e.s.r. spectral g-values indicate square planar geometry for [Cu(en)₂]Cl₂ and an octahedral environment for copper(II) in heterobimetallic complexes. Conductivity measurements show [Cu(en)₂]Cl₂ to be ionic and the heterobimetallic chelates to be covalent.     

Syntheses and crystal structures of hydrated complexes of strontium and barium bromides with 18-crown-6

Two complexes, namely, triaqua(18-crown-6)strontium dibromide monohydrate (I) and diaquabromo(18-crown-6)barium bromide (II), are synthesized. Their crystal structures are determined by X-ray diffraction analyses. For complex I, space group C2/c, a = 17.547 Å, b = 10.246 Å, c = 14.786 Å, β = 123.08°, Z = 4. For complex II, space group Pnma, a = 17.753 Å, b = 17.465 Å, c = 6.629 Å, Z = 4. The structures are solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.056 (I) and 0.042 (II) for 2696 (I) and 2440 (II) independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). Both complex cations—randomly disordered [Sr(18C6)(H₂O)₃]²⁺ in complex I and [BaBr(18C6)(H₂O)₂]⁺ in complex II—are of the host-guest type. The Sr²⁺ (Ba²⁺) cation resides in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In the structures complexes I and II, the coordination polyhedra of the Sr²⁺ and Ba²⁺ cations (coordination number 9) can be described as distorted hexagonal bipyramids with one apex at the O atom of the water molecule in complex I or at the Br^? ligand in complex II and the other split apex at the O atoms of two water molecules.     

New heterotrinuclear complexes containing copper(II) and a group IV metal

Summary Heterotrinuclear complexes of the type [Cu₂(TETA)₂Cl₄M] (M = Si, Ge, Sn, Ti and Zr; TETA = triethylene tetramine) have been prepared by direct reaction of [Cu[TETA)]Cl₂ with MCl₄ in a 21 ratio in MeOH. The compounds have been characterized by elemental analyses, e.s.r., electronic and i.r. spectra, magnetic susceptibility and conductivity measurements. The results indicate that [Cu(TETA)]Cl₂ is square planar and ionic, while its heterotrinuclear complexes, [Cu₂(TETA)₂Cl₄M], are covalent with an octahedral environment around the copper(II) ion.