NICKEL β-DIKETONATES | mocvd-precursor-encyclopedia.de

NICKEL (II) β-DIKETONATES

Nickel acetylacetonate Ni(acac)2

Fig. Ni(acac)2 formula

Nickel (II) acetylacetonate (nickel bis(2,4-pentanedionate)) Ni(acac)2 (M = 256.91) is solid melting at 230°C with decomposition (by other data at 238°C).

Ni(acac)2 is volatile and was proposed as potential precursor for the growth of Ni-contaning thin films by MOCVD.

Ni(acac)2 for Ni films by pulsed spray evaporation CVD

Ni(acac)2 (dissolved in alcohols ROH as solvent and reducing agents) was tested as precursor for the deposition of metal Ni films by pulsed spray evaporation CVD at deposition temperature ≥ 220°C on glass and SiC substrates. Good resistivity smooth (<30nm roughness) Ni layers were obtained (R = 150μΩ·cm, improved upon annealing), they were hexagonal polycrystalline according to XRD. []

Ni(acac)2 for Ni films by pulsed spray evaporation CVD

Ni(acac)2 for NiO by MOCVD

Nickel acetylacetonate Ni(acac)2 (combined in the mixed toluene solution with Al(acac)3 , total metal concentrations 0.002 - 0.004 M) was applied as Ni precursor for deposition of nickel spinel NiAl2O4 thin films by combustion CVD (at 1 atm growth pressure), using flame temperature 1100°C at the silica substrate surface. Dense, nodular 1µ thick NiAl2O4 layers having face centered cubic spinel crystal lattice (according to XRD and electron diffraction combined with TEM) were grown at growth rates of 1.2-2.0 μm/h; the grain sizes were 8-88 nm by TEM. Layer composition (close to the stoichiometric values) was demonstrated by quantitative EDS. []

Nickel bis(hexafluoracetylacetonate) Ni(hfac)2

Nickel (II) bis(hexafluoracetylacetonate) Ni(hfac)2 (M = 479.79 (anhyd. basis)) is solid with melting point 213°C (with decomposition). It was characterised by FT-IR and other characterisation techniques.

Nickel hexafluoracetylacetonate Ni(hfac)2 was reported to be applicable as precursor for the growth of Ni metal layers at 250°C by MOCVD (using hydrogen H2 as reducing agent).[i]

[i] Van Hemert, R. L., J. Electrochem. Soc., 112(11):1123–1126 (1965)

Nickel bis(hexafluoracetylacetonate)(1,3-diaminopropane) Ni(hfac)2(pda)

Nickel bis(hexafluoracetylacetonate) 1,3-diaminopropane adduct Ni(hfac)2(pda) (and for comparison Ni(thd)2(pda)) was synthesized, characterized and investigated as potential nickel MOCVD precursors.

Ni(hfac)2(pda) according to single-crystal XRD is triclinic, space group P1¯, crystal parameters a = 8.5379(4), b = 10.4994(4), c = 11.4186(4) Å, α = 112.091(1), β = 98.385(1), γ = 92.937(1).

Thermal properties of Ni(hfac)2(pda) were studied by TGA/DTA: the chelate sublimes practically without decomposition. Differential scanning calorimetry (DSC) was used to determine thermodynamic parameters (ΔmpH, ΔmpS) and Tmp of the complex.

Ni(hfac)2(pda) for Ni metal films by MOCVD

Ni(hfac)2(pda) (and for comparison Ni(thd)2(pda)) was tested as precursor for deposition of Ni metal thin films on Ta/Si substrates by low pressure MOCVD at growth temperature 573 K (300°C). (Ni(hfac)2(pda) precursor was evaporated at 383 K (110°C)). The grown Ni films were one-phase cubic, according to XRD and SEM.[i]

[i] S.I. Dorovskikh, E.A. Bykova, N.V. Kuratieva, L.N. Zelenina, Yu.V. Shubin, N.B. Morozova, I.K. Igumenov, J. Organomet. Chem., 2012, Vol.698, p.22-27, « Synthesis, crystal structures and thermal behavior of Ni(pda)(hfac)2 and Ni(pda)(thd)2 as potential MOCVD precursors (pda-1,3-diaminopropane, hfac-1,1,1,5,5,5-hexafluoro-2,4-pentanedionato(-), thd-2,2,6,6-tetrametyl-3,5-heptanedionato(-)) », doi.org/10.1016/j.jorganchem.2011.10.020, www.sciencedirect.com/science/article/pii/S0022328X11006590

Nickel bis(2-thenoyltrifluoroacetonate) N,N,N’,N’-tetramethylethylendiamine adduct Ni(tta)2(tmeda)

Nickel bis(2-thenoyltrifluoroacetonate) N,N,N’,N’-tetramethylethylendiamine adduct Ni(tta)2·tmeda was synthesized from Ni(tta)2 and N,N,N’,N’-tetramethylethylendiamine as the Lewis base. Ni(tta)2·tmeda was characterized by elemental analyses, IR, 1H NMR, 13C NMR spectroscopy and single-crystal XRD; physical and thermal properties of Ni(tta)2·tmeda were investigated.

Ni(tta)2·tmeda was tested as a metal–organic chemical vapour deposition (MOCVD) precursor for deposition of NiO thin films on quartz substrates. The deposited NiO layers were characterized by XRD, SEM and UV spectroscopy[i]

[i] G. Malandrino, L.M.S. Perdicaro, G. Condorelli, I.L. Fragalà, P. Rossi, P.Dapporto, Dalton Trans., 2006, Iss.8, p.1101-1106, « Synthesis, characterization and application of Ni(tta)2·tmeda to MOCVD of nickel oxide thin films », DOI: 10.1039/B511317B

Ni(tta)2(tmeda) for NiO nanotubes by MOCVD

Nickel bis(2-thenoyltrifluoroacetonate) N,N,N’,N’-tetramethylethylendiamine adduct Ni(tta)2(tmeda) was applied as Ni source for the deposition of ordered homogeneous arrays of nickel (II) oxide NiO nanotubes by MOCVD template route. The X-ray diffraction pattern shows the formation of the NiO cubic phase. The formation of well ordered NiO nanotube arrays was found by SEM (after removing the template); the nanotubes were opened on both sides (by TEM). Optical anisotropy related to the vertical alignment of nanotubes was indicated by strong dependence the optical properties of NiO nanotubes on the polarization direction of the light electric field (determined by spectroscopic ellipsometry).[i]

[i] G. Malandrino, L.M.S. Perdicaro, I.L. Fragalà, R.Lo Nigro, M. Losurdo, G. Bruno, J. Phys. Chem. C, 2007, 111 (8), p.3211–3215, « MOCVD Template Approach to the Fabrication of Free-Standing Nickel(II) Oxide Nanotube Arrays: Structural, Morphological, and Optical Properties Characterization », DOI: 10.1021/jp067696o, http://pubs.acs.org/doi/abs/10.1021/jp067696o

Nickel (bis(2,2,6,6-tetramethylheptane-3,5-dionate) Ni(thd)2

Nickel (bis(2,2,6,6-tetramethylheptane-3,5-dionate) Ni(thd)2 (M = 425.23) is solid melting at 219-223°C, and subliming at 90°C/ 0.1 Torr.

Due to its volatility, Ni(thd)2 was reported to be useful as precursor for the deposition of Ni-containing layers by MOCVD.

Ni(thd)2 for Ni3N by CVD, ALD

Nickel (bis(2,2,6,6-tetramethylheptane-3,5-dionate) Ni(thd)2, in combination with NH3 as nitrogen source, was applied as precursor for the deposition of Ni3N (as well as multilayer combnation of Ni3N/ NiO/ Ni layers) at 250 °C temperature by ALD and CVD techniques. The Ni layers have been formed by decomposition of metastable Ni3N layers, i.e., the Ni3N layers act as precursor for Ni film growth (thus, Ni/NiO layer structures were produced by chemical means). Low temperature annealing conditions (180°C/ 1 Torr H2), good control of the interfaces was obtained. Ordered Ni (111)/ NiO (111) structures on α-Al2O3(00l) were prepared. Another reaction route was preparation of thin NiO(111) epitaxial seed layers with subsequent deposition of Ni3N at a high growth rate. The decomposition of the Ni3N films at 350 °C produced single phase Ni (111) layers.[i]

[i] E Lindahl, M Ottosson, JO Carlsson, Surf. Coat. Tech., 2010, Vol.205, Iss.3, p.710-716, « Growth and stability of CVD Ni3N and ALD NiO dual layers », doi.org/10.1016/j.surfcoat.2010.07.059, www.sciencedirect.com/science/article/abs/pii/S0257897210005815

Ni(thd)2 for NiO films by ALD

Nickel (II) bis(2,2,6,6‐tetramethylheptane‐3,5‐dionate) (Ni(thd)2), combined with H2O as oxygen source, was applied as precursor for the growth of polycrystalline NiO films on SiO2 substrates by ALD, using alternating pulses of the precursors, at deposition temperatures up to 275 °C. The ALD characteristics deposition process with respect to the saturation behavior of the precursors was investigated. It was found that the growth of NiO using Ni(thd)2 is strongly dependent on the surface hydroxide groups; therefore large excess of H2O is required to achieve saturation. The amount of carbon contamination in the films originating from the metal precursor thd ligand was in the range 1–2%. ALD growth behavior was lost at deposition temperature >275 °C, the thermal decomposition of the metal precursor (MOCVD process) was favoured instead. Nucleation of well-separated grains coalescing to a continuous film after ~250 ALD cycles was observed by AFM, when studying the initial nucleation process.[i]

[i] E. Lindahl, M. Ottosson, J.‐O. Carlsson, Chem. Vapor Dep., 2009, Vol.15, Iss.7‐9, p.186-191, « Atomic Layer Deposition of NiO by the Ni(thd)2/H2O Precursor Combination », doi.org/10.1002/cvde.200906762, onlinelibrary.wiley.com/doi/abs/10.1002/cvde.200906762

Ni(thd)2 for LaNiO3 by liquid injection MOCVD

Ni(thd)2 (in combination with La(thd)3), was dissolved in THF/ or heptane; the resulting solution was applied as Ni precursor for the by liquid delivery MOCVD growth of lanthanum nickelate LaNiO3 layers on 100 mm Si/SiO2 and (0001) sapphire substrates at growth temperatute 630 °C in an oxidizing atmosphere. The as-grown LaNiO3 layers were highly crystalline and highly (110) oriented (on Si/SiO2 substrates). Layer electrical resistivity was dependent on the La/Ni ratio, substrate nature, post‐deposition annealing conditions. LaNiO3 layers grown on (0001) sapphire, rapidly annealed at 750 °C, showed a minimum electrical resistivity (300 μΩ cm), whereas LNO layers grown on Si/SiO2 substrates had higher resistivity (minimum value of 1 mΩcm); their rapid annealing at 750 °C resulted in layer cracking. However, nickel-rich LaNiOx layers were more stable under annealing and showed nearly no cracking.[i]

In another report Ni(thd)2 (in combination with La(thd)3), was used as Ni source for the preparation of lanthanum nickelate LaNiO3 layers on MgO (1 0 0), LaAlO3 (0 1 2) and SrTiO3 (1 0 0) substrates. The layer crystallinity was studied by XRD; epitaxial growth with the (110) plane of the tetragonal cell of La2NiO4 parallel to the surface of the substrates was obtained; but two other minority orientations with a- and c- axis perpendicular to the surface were also present. Single in-plane orientation of the epitaxial crystallites was obtained for the layers grown on LaAlO3 (012), whereas for MgO(100) and SrTiO3(100) other in-plane orientation with crystallites tilted from 45° in the plane of the substrate were present as well.[ii]

[i] P.A. Lane, M.J. Crosbie, P.J. Wright, P.P. Donohue, P.J. Hirst, C.L. Reeves, C.J. Anthony, J.C. Jones, M.A. Todd, D.J. Williams, Chem Vapor Dep., 2003, Vol.9, Iss.2, p.87-92, « The Metal–Organic Chemical Vapor Deposition of Lanthanum Nickelate Electrodes for Use in Ferroelectric Devices », doi.org/10.1002/cvde.200390007, https://onlinelibrary.wiley.com/doi/abs/10.1002/cvde.200390007

[ii]V. Faucheux, S. Pignard, M. Audier, J. Cryst. Growth, 2005, Vol. 275, Iss.1–2, p. e947-e951, « Growth of La2NiO4 thin films by chemical vapor deposition », doi.org/10.1016/j.jcrysgro.2004.11.099 www.sciencedirect.com/science/article/pii/S002202480401591X

Nickel (bis(2,2,6,6-tetramethylheptane-3,5-dionate)(1,3-diaminopropane) Ni(thd)2(pda)

Nickel bis(hexafluoracetylacetonate) 1,3-diaminopropane adduct Ni(thd)2(pda) (and for comparison Ni(hfac)2(pda)) was synthesized, characterized and investigated as potential nickel MOCVD precursor.

The crystal structure of Ni(thd)2(pda) was determined by single-crystal XRD: the complex is triclinic, space group P1¯, crystal parameters a = 9.4622(3), b = 11.8986(5), c = 14.1575(6) Å, α = 71.600(1), β = 71.279(1), γ = 88.505(1).

Ni(thd)2(pda) was shown by TGA/DTA to sublime practically without decomposition. Thermodynamic parameters (ΔmpH, ΔmpS) and Tmp of the complex were determined by differential scanning calorimetry.

Ni(thd)2(pda) for metal Ni by MOCVD

Ni(thd)2(pda) (and for comparison Ni(hfac)2(pda)) were tested as precursors for the growth of Ni metal thin films by low pressure MOCVD on Ta/Si substrate (precursor was evaporated at 383 K (110°C), growth temperature was Ts = 573 K (300°C).

The deposited Ni films were characterized by XRD and SEM; it was demonstrated that one-phase cubic Ni films were obtained. [i]

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