Complexes of metal(II) halides of the first transition series with N,N,N′,N′-tetramethylmethane-diamine, -ethane-1,2-diamine and -propane-1,3-diamine

Handley, Darren A; Hitchcock, Peter B.; Lee, Ting Huei; Leigh, G.J.

doi:10.1016/s0020-1693(00)00384-4

Cited by 34 publications

(20 citation statements)

References 8 publications

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“…The properties of the sublimate are identical with those of [Ni 3 Cl 5 (TMEDA) 3 ]Cl. In contrast, NiCl 2 (TMPDA) is a monomeric compound that shows almost quantitative sublimation at 150–175 °C/0.4 mbar. The synthesis and characterization of NiCl 2 (TMPDA) and NiCl 2 (TMEDA) 2 are given in Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Väyrynen

Hatanpää

Mattinen

et al. 2018

Adv Materials Inter

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crystal structures of the participating metal components. An intermetallic compound is formed when the bonds between the dissimilar atoms are stronger than the bonds between the atoms of the same element.Because of their specific structure, intermetallic compounds usually exhibit unique physical and chemical properties that are potentially superior to their disordered alloy analogues and the pure metals. Such properties include, for example, magnetoresistance, [3,4] superconductivity, [5][6][7] enhanced catalytic activity, [8,9] and hydrogen storage capability. [10] Intermetallics and alloys containing Co or Ni and Sn with varying stoichiometry have mostly been studied as anode materials for Li-and Na-ion batteries. [11][12][13][14][15][16][17][18][19] As ferromagnetic materials, they also show potential for magnetic devices. [20][21][22] Furthermore, intermetallic Co-Sn and Ni-Sn compounds have also been studied for catalytic purposes. [23][24][25][26] For future applications like nanoelectronic devices, it is pivotal to be able to control the thickness and composition of thin films with sub-nanometer accuracy. Atomic layer deposition (ALD) is a thin film preparation method based on repeated, saturative, and irreversible surface reactions between alternately supplied gaseous precursors ensuring self-limiting growth of the desired material. [27,28] Owing to the self-limiting growth mechanism, ALD can be used to deposit uniform thin films over complex structures in a controlled and reproducible manner. No previous reports on the ALD of intermetallic Co 3 Sn 2 or Ni 3 Sn 2 thin films are found in the literature, and the ALD of other intermetallic compounds has also been scarce if existent at all. Intermetallic phases in Pt-In, [29] Pt-Sn, [30] and Ni-Fe [31] systems have been obtained by the postdeposition reduction of the corresponding ALD oxides. There are also some ALD studies on metal alloys, such as Pt-Ir, [32] Pd-Pt, [33][34][35] Ru-Pt, [36] Ru-Co, [37] Co-W, [38,39] Co-Pt, [40] Ru-Mn, [41] and Cu-Mn, [42] but no reports exist on materials exhibiting a specific intermetallic structure. Co-Sn and Ni-Sn with varying stoichiometry, including the intermetallic Co 3 Sn 2 and Ni 3 Sn 2 phases, have generally been prepared by, for example, ball Intermetallics form a versatile group of materials that possess unique properties ranging from superconductivity to giant magnetoresistance. The intermetallic Co-Sn and Ni-Sn compounds are promising materials for magnetic applications as well as for anodes in lithium-and sodium-ion batteries. Herein, a method is presented for the preparation of Co 3 Sn 2 and Ni 3 Sn 2 thin films using diamine adducts of cobalt(II) and nickel(II) chlorides, CoCl 2 (TMEDA) and NiCl 2 (TMPDA) (TMEDA = N,N,N′,N′tetramethylethylenediamine, TMPDA = N,N,N′,N′-tetramethyl-1,3propanediamine) combined with tributyltin hydride. The films are grown by atomic layer deposition (ALD), a technique that enables conformal film deposition with sub-nanometer thickness control. The Co 3 Sn 2 process fulfills the ...

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Section: Resultsmentioning

confidence: 99%

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Väyrynen

Hatanpää

Mattinen

et al. 2018

Adv Materials Inter

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“…[33][34][35] In solution, at room temperature, the observation of one singlet in the 1 H NMR spectrum for the Nbonded methyl groups leads us to presume fast averaging of the four tertiary amine donors, of which three are coordinated at any one time, resulting in a tetrahedral or trigonalpyramidal coordination geometry around copper(I). Combining the colourless reactants immediately produced a yellow-orange solution, with only very little precipitate after 3 h. Removal of the solvent in vacuo left a green-brownish solid.…”

Section: [Cu I (2)](pf 6 ) (8)mentioning

confidence: 99%

Copper Complexes of “Superpodal” Amine Ligands and Reactivity Studies towards Dioxygen

et al. 2012

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The results of studies focussed on copper complexes of a variety of ligands with an NN4 donor set are reported. The permethylated tetrapodal ligand 2 forms a complex with copper(I) which, upon reaction with dioxygen at –90 °C, yields a product having a bis(μ‐oxido)dicopper(III) core (“O‐type” product, 10), as inferred from UV/Vis and resonance‐Raman spectroscopic data. The UV/Vis spectrum of 10 has two bands at 300 and 404 nm, with extinction coefficients of 9400 and 10400 L mol–1 cm–1, respectively. Resonance‐Raman spectra display two 16O/18O‐sensitive bands which, based on the isotopic shifts and the absolute frequencies, are attributed to the Cu–O stretching modes of the O‐type product. Complex 10 shows tyrosinase‐like activity, as its reaction with sodium p‐tert‐butylphenolate at –90 °C in THF yields p‐tert‐butylcatechol, in an ortho‐hydroxylation reaction (yield: 30 %). Two new rigid tetrapodal pentadentate ligands (the “superpods” 3 and 4) can be synthesized by condensation of the primary polyamine 1 with paraformaldehyde. Their copper(II) complexes (5 and 6) have been spectroscopically characterized. As ascertained by X‐ray crystallography, 5 has the CuII ion in a tetragonal‐pyramidal environment, with almost uniform Cu–N bond lengths (basal bonds: 2.052 Å and 2.070 Å; apical bond: 2.077 Å). No significant Jahn–Teller distortion is observed here. In 6, the ligand acts as a multinucleating donor, which leads to the formation of a ladder‐like cluster of [Cu(μ3‐OH)] units containing a total of two ligands, six copper(II) ions, four hydroxido ligands and eight trifluoroacetate ions. Two of the trifluoroacetate ions are non‐coordinating. Variable‐temperature magnetic susceptibility data are reported for this hexanuclear copper(II) cluster. Copper(I) complexes of 1 and 3 have been characterized and allowed to react with molecular oxygen, which caused the decomposition of the complexes. The IR spectra of the oxygenation products have bands at 1652 and 1632 cm–1, respectively, which are absent in the spectra of 1 and 3, suggesting that amine functions have been oxidized to imines.

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“…NiCl 2 (TMPDA) is a strictly monomeric compound that can be sublimed quantitatively under reduced pressure (160–180 °C/0.5 mbar). The volatility is exemplified by the vacuum TGA shown in Figure b.…”

Section: Resultsmentioning

confidence: 99%

Atomic Layer Deposition of Nickel Nitride Thin Films using NiCl₂(TMPDA) and Tert‐Butylhydrazine as Precursors

Väyrynen

Hatanpää

Mattinen

et al. 2019

Physica Status Solidi (a)

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This article describes the atomic layer deposition (ALD) of nickel nitride and nickel thin films using a diamine adduct of Ni(II) chloride, NiCl 2 (TMPDA) (TMPDA ¼ N,N,N 0 ,N 0 ,-tetramethyl-1,3-propanediamine), as the metal precursor. Owing to the high reducing power of tert-butylhydrazine (TBH), the films are grown at low temperatures of 190-250 C. This is one of the few lowtemperature ALD processes that can be used to grow Ni 3 N and Ni metal on both insulating and conductive substrates. The films are characterized in terms of crystallinity, morphology, composition, resistivity, and coercivity. Xray diffraction shows reflections compatible with either hexagonal Ni or Ni 3 N. Composition analyses suggest that the films are close to stoichiometric Ni 3 N. Despite the nitride component, the films exhibit low resistivity values and at the lowest, a resistivity of 37 μΩ cm is achieved. The result is lower than what is typically observed for Ni x N films and not much higher than the best results concerning ALD Ni metal. The nitrogen content of the films is lowered down to 1.2 at% by postdeposition reduction at 150 C in 10% forming gas. After the reduction, the nonmagnetic nitride films are converted to ferromagnetic Ni metal.

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Complexes of metal(II) halides of the first transition series with N,N,N′,N′-tetramethylmethane-diamine, -ethane-1,2-diamine and -propane-1,3-diamine

Cited by 34 publications

References 8 publications

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Copper Complexes of “Superpodal” Amine Ligands and Reactivity Studies towards Dioxygen

Atomic Layer Deposition of Nickel Nitride Thin Films using NiCl₂(TMPDA) and Tert‐Butylhydrazine as Precursors

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Complexes of metal(II) halides of the first transition series with N,N,N′,N′-tetramethylmethane-diamine, -ethane-1,2-diamine and -propane-1,3-diamine

Cited by 34 publications

References 8 publications

Atomic Layer Deposition of Intermetallic Co3Sn2 and Ni3Sn2 Thin Films

Atomic Layer Deposition of Intermetallic Co3Sn2 and Ni3Sn2 Thin Films

Copper Complexes of “Superpodal” Amine Ligands and Reactivity Studies towards Dioxygen

Atomic Layer Deposition of Nickel Nitride Thin Films using NiCl2(TMPDA) and Tert‐Butylhydrazine as Precursors

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Product

Resources

About

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Atomic Layer Deposition of Intermetallic Co₃Sn₂ and Ni₃Sn₂ Thin Films

Atomic Layer Deposition of Nickel Nitride Thin Films using NiCl₂(TMPDA) and Tert‐Butylhydrazine as Precursors