Volatile and Thermally Stable Mid to Late Transition Metal Complexes Containing α-Imino Alkoxide Ligands, a New Strongly Reducing Coreagent, and Thermal Atomic Layer Deposition of Ni, Co, Fe, and Cr Metal Films

Kalutarage, Lakmal C.; Martin, Philip D.; Heeg, Mary Jane; Winter, Charles H.

doi:10.1021/ja407014w

Cited by 44 publications

(61 citation statements)

References 32 publications

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“…The growth rate, ca. 0.09 Å/cycle, is similar to the values observed for the separate Cu (0.12 Å/cycle) and Mn (0.08 Å/cycle) processes (30,31). The compositions of the films are close to the idealized 70% Cu and 30% Mn on Si/SiO2, Co, Ru, and thermal SiO2 surfaces, but are Mn-rich on H-terminated Si.…”

Section: Ald Growth Of Cu/mn Alloy Filmssupporting

confidence: 78%

“…Despite extensive efforts, we have been unable to prepare Cu precursors that have improved properties compared to Cu(dmap)2 (28,30). Accordingly, this Cu precursor was chosen for the present study.…”

Section: Resultsmentioning

confidence: 99%

“…These stacks were constructed by depositing 1000 cycles of Cu on Pd, Pt, or Ru substrates using Cu(dmap)2, formic acid, and BH3(NHMe2) at 150 °C according to our recent report (31), followed by 1000 cycles of Mn using 1 and BH3(NHMe2) at 225 °C (30), and then 2000 cycles of Cu using 1 and BH3(NHMe2) at 150 °C (31). All three ALD processes were run sequentially without air breaks.…”

Section: Ald Growth Of Cu/mn/cu Stacksmentioning

confidence: 99%

“…We have recently described the thermal ALD growth of Ni, Co, Fe, Mn, and Cr thin films using metal(II) precursors containing -imino alkoxide ligands and BH3(NHMe2) as the reducing co-reagent at temperatures of 180-225 °C (30). We have also reported the ALD growth of Cu films from Cu(dmap)2 (dmap = 1-dimethylamino-2-propoxy) and BH3(NHMe2) within an ALD window of 130-165 °C (31).…”

Section: Introductionmentioning

confidence: 99%

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Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

2014

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This paper describes the thermal ALD growth of Cu/Mn alloy films using the precursors Cu(OCHMeCH2NMe2)2, Mn2(tBuNCH-C(tBu)(Me)O)4, and BH3(NHMe2) at 160 °C. Deposition rates of about 0.09 Å/cycle were observed on a variety of substrates. Cu:Mn ratios of about 70:30 were obtained by controlling the number of Cu and Mn cycles. X-ray photoelectron spectroscopy confirms the presence of metallic Cu and Mn within the Cu/Mn alloys. Similar precursors and chemistry were used to deposit 35-50 nm thick Cu/Mn/Cu film stacks on Ru, Pd, and Pt substrates. Depth profiling of stacks that were overcoated with an SiO2 layer showed that the Mn atoms diffuse to the SiO2/Cu interface in samples grown on Pd and Pt, both in as-deposited films and those that were annealed at 350 °C. With Ru substrates, the Mn atoms collected slightly at the SiO2/Cu interface, but primarily remained distributed throughout the film in as-deposited and annealed samples.

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Section: Ald Growth Of Cu/mn Alloy Filmssupporting

confidence: 78%

Section: Resultsmentioning

confidence: 99%

Section: Ald Growth Of Cu/mn/cu Stacksmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

2014

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“…Indirect methods like reduction of CuO by isoproponal 10 , Cu 2 O by formic acid over ruthenium 11 and Cu 3 N by H 2 12 have also been tried. Kalutarage et al 13 have reported the use of BH 3 (NHMe 2 )…”

Section: Introductionmentioning

confidence: 99%

Quantum Chemical Study of the Effect of Precursor Stereochemistry on Dissociative Chemisorption and Surface Redox Reactions During the Atomic Layer Deposition of the Transition Metal Copper

Dey¹,

Elliott²

2015

J. Phys. Chem. C

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Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu (II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu (II) /Cu (I) / Cu (0) intermediate complexes from the respective Cu (II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu 55 cluster. Cu (I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu(II) versus Cu(I) compounds. A pair of CuEt intermediates or the dimer Cu 2 Et 2 reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu (I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface.

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Geometry and Spin Change at the Heart of a Cobalt(II) Complex: A Special Case of Solvatomorphism

Cibian

Hanan

2015

Chemistry A European J

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Structural analysis and spectroscopic methods revealed a special case of solvatomorphism: hydrogen-bonding-induced geometry and spin change within a same N,O-(bis)chelate of cobalt(II). Solid-state structures are presented for both the tetrahedral and the solvated square-planar forms of the complex. Magnetic-moment measurements and ESR spectroscopy confirmed the high-spin state of the tetrahedral form (μeff =4.7 μB ) and the low-spin state of the square-planar solvatomorph. Specific hydrogen-bonding interactions between the solvent molecules and the complex chelate ring (O1⋅⋅⋅H-CHCl2 (d=2.26 Å, D=3.24 Å, θ=173°); O2⋅⋅⋅H-CHCl2 (d=2.22 Å, D=3.19 Å, θ=165°)) play a pivotal role in biasing the system toward the low-spin ground state.

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Volatile and Thermally Stable Mid to Late Transition Metal Complexes Containing α-Imino Alkoxide Ligands, a New Strongly Reducing Coreagent, and Thermal Atomic Layer Deposition of Ni, Co, Fe, and Cr Metal Films

Cited by 44 publications

References 32 publications

Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

Manganese Precursor Selection and the Thermal Atomic Layer Deposition of Copper/Manganese Alloy Films

Quantum Chemical Study of the Effect of Precursor Stereochemistry on Dissociative Chemisorption and Surface Redox Reactions During the Atomic Layer Deposition of the Transition Metal Copper

Geometry and Spin Change at the Heart of a Cobalt(II) Complex: A Special Case of Solvatomorphism

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