Tetracarbonylnickel Ni(CO)4

Tetracarbonylnickel Ni(CO)4 is colorless liquid (melting point –19.3 °C), has 18 electrons. Ni(CO)4  is very volatile (has boiling point 42.1 °C).

Ni(CO)4 is toxic (due to elimination of CO and formation of pyrophoric nickel(0));  can form explosive mixtures with air.

Synthesis of Ni(CO)4:

1. Direct synthesis from fine dispersed Ni and carbon monoxide CO under pressure:

Ni + 4 CO → Ni(CO)4  (Mond-Langer-Quincke, 1890)

2. [Ni(NH3)6]2+ + 5CO + 2H2O → Ni(CO)4 + (NH4)2CO3 + 2NH4+ + 2NH3 (180 °C, 150 bar)

Deposition using Ni(CO)4

Tetracarbonylnickel Ni(CO)4) is a conventional precursor for the deposition of metallic nickel films. Ni(CO)4) works fine as Ni precursor, however its extreme toxicity is serious drawback.

Ni metal layer has been deposited by hydrogen reduction of nickel cyclopentadienyl NiCp2 at 200°C.[i]

  Kinetics of CVD using Ni(CO)4:  precursor decomposition starts at 35 – 80 °C, reaction is initially homogeneous, but becomes heterogeneous, when a nickel film developed. Below 175 °C deposition temperature Ni deposition is controlled by the surface reaction rate; above 175 °C growth temperature, mass transfer of Ni(CO)4 to the substrate surface is controlling/limiting the growth.

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

Ni(CO)4 for metallic Ni and permalloy films by MOCVD

      Nickel tetracarbonyl Ni(CO)4, combined with Fe(CO)5 as Fe source, was applied as Ni precursor for the atmospheric pressure MOCVD of thin films of Ni and Fe-Ni alloys in a wide composition range (including permalloy) at growth temperature 200°C. The obtained permalloy layers were studied by detailed magnetoresistance measurements; the maximum magnetoresistance was achived at composition of ~90%Ni/ 10%Fe, the maximum sensitivity at ~80%Ni/ 20%Fe, in agreement with literature. The magnetic properties were improved by both application of 80 mT magnetic field during deposition and sample annealing at > 200°C temperatures.[i]

 [i] P.A. Lane, P.J. Wright, P.E. Oliver, Ch.L. Reeves, A.D. Pitt, J.M. Keen, M.C. L. Ward, M.E. G. Tilsley, N.A. Smith, B. Cockayne , I. Rex Harris , Chem. Vapor Dep., 1997, Vol.3, Iss.2, p.97-101, «  Growth of Iron, Nickel, and Permalloy Thin Films by MOCVD for Use in Magnetoresistive Sensors », https://doi.org/10.1002/cvde.19970030208, https://onlinelibrary.wiley.com/doi/abs/10.1002/cvde.19970030208

Ni(CO)4 for metallic Ni films by laser induced CVD

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