METAL COMPLEXES FOR GAS-PHASE THIN-FILM DEPOSITION

Abstract

Metal complexes of formula (I) are described:

[M(L.sup.1).sub.x(L.sup.2).sub.y(hydra).sub.z].sub.n  formula (I) wherein: M=metal atom having an atomic number selected from the ranges a) through c): a) 12, 21 to 34, with the exception of 30, b) 39 to 52, with the exception of 48, c) 71 to 83, with the exception of 80, L.sup.1=neutral or anionic ligand, with x=0 or 1, L.sup.2=neutral or anionic ligand, with y=0 or 1, (hydra)=acetone dimethylhydrazone monoanion, with z=1, 2, or 3, n=1 or 2, and the total charge of the complex is 0.

Claims

1.-15. (canceled)

16. A metal complex of formula (I):
[M(L.sup.1).sub.x(L.sup.2).sub.y(hydra).sub.z].sub.n  formula (I) wherein: M=metal atom having an atomic number selected from the ranges a) through c): a) 12, 21 to 34, with the exception of 30, b) 39 to 52, with the exception of 48, c) 71 to 83, with the exception of 80, L.sup.1=neutral or anionic ligand, with x=0 or 1, L.sup.2=neutral or anionic ligand, with y=0 or 1, (hydra)=acetone dimethylhydrazone monoanion, with z=1, 2, or 3, n=1 or 2, and the total charge of the complex is 0.

17. The metal complex according to claim 16, wherein M is selected from the group consisting of Ti, Co, Ga, Ge, As, Se, Ru, Pd, In, Sb, Te, Ir, Au, and Bi, and preferably selected from Co, Ga, Ge, Ru, In, and Ir.

18. The metal complex according to claim 16, wherein L.sup.1 and L.sup.2 are independently selected from the group consisting of Cl, H, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclopentadienyl, methylcyclopentadienyl, isopropylcyclopentadienyl, arene, phosphine, isonitrile, and carbonyl.

19. The metal complex according to claim 16, wherein x=y=1, wherein, optionally, z=1.

20. The metal complex according to claim 16, wherein M=Ru, L.sup.1=arene, with x=1, L.sup.2=Cl, H, methyl, ethyl, propyl, isopropyl, or tert-butyl, with y=1, z=1, and n=1.

21. The metal complex according to claim 20, wherein the arene is an arene substituted with 1 to 6 identical or different C.sub.1-C.sub.8 hydrocarbon radicals or is an unsubstituted arene.

22. The metal complex according to claim 21, wherein the arene is selected from 4-isopropyltoluene and benzene.

23. The metal complex according to claim 16, wherein M=In, L.sup.1=Cl, H, methyl, ethyl, propyl, isopropyl, or tert-butyl, with x=1, L.sup.2=Cl, H, methyl, ethyl, propyl, isopropyl, or tert-butyl, with y=1, z=1, and n=2.

24. The metal complex according to claim 16, wherein L.sup.2 is selected from methyl and ethyl.

25. The metal complex according to claim 16, the metal complex is selected from the group consisting of [RuCl(p-cymene)(hydra)], [RuMe(p-cymene)(hydra)], and [InMe.sub.2(hydra)].sub.2.

26. A method for producing the metal complex according to claim 16, comprising the steps of: (i) reacting acetone dimethylhydrazone with a Li-organic compound to produce Li(hydra), (ii) reacting Li(hydra) with a compound having the formula [ML.sup.1.sub.x1L.sup.2.sub.y1].sub.n1, with x.sub.1=0, 1, or 2, y.sub.1=0, 1, or 2, n.sub.1=1 or 2, to produce a compound of the formula [M(L.sup.1).sub.x(L.sup.2).sub.y(hydra).sub.z].sub.n.

27. The method according to claim 26, wherein L.sup.2 is either H, methyl, ethyl, propyl, isopropyl, or tert-butyl or, following step (ii), is converted to H, methyl, ethyl, propyl, isopropyl, or tert-butyl in a step (iii).

28. A method for depositing the metal in a CVD process or an ALD process which comprises utilizing the metal complex according to claim 16.

29. A method in which the metal complex according to claim 16 is used as a precursor for producing a layer from the metal.

30. A metallized surface obtainable by depositing a metal on a surface from a gas phase comprising the metal complex according to claim 16.

Description

EXEMPLARY EMBODIMENTS

[0118] In the following examples: [0119] H-hydra means: acetone dimethylhydrazone [0120] hydra means: acetone dimethylhydrazone anion [0121] p-cymene means: 4-isopropyltoluene

Example 1—Preparation of H-Hydra

[0122] ##STR00008##

[0123] MgSO.sub.4 (15.0 g) was first put into acetone (50 mL, exc.), and N,N-dimethylhydrazine (16.4 g/20.6 mL, 272 mmol, 1.0 eq) was added to the suspension while stirring. The mixture was heated for 7 hours under reflux conditions and then filtered by means of a folded filter. After extraction of the solid with acetone (15 mL), the filtrate was freed from the solvent in vacuo, and acetone dimethylhydrazone was obtained as a colorless liquid (14.8 g, 147 mmol, 54%).

TABLE-US-00001 .sup.1H-NMR CDCl.sub.3, 300.2 MHz: δ/ppm = 2.39 (s, 6 H, NMe.sub.2), 1.93 (s, 3 H, Me), 1.88 (s, 3 H, Me). .sup.1H-NMR C.sub.6D.sub.6, 300.2 MHz: δ/ppm = 2.39 (s, 6 H, NMe.sub.2), 1.70 (s, 3 H, Me), 1.70 (s, 3 H, Me). .sup.13C-NMR C.sub.6D.sub.6, 75.5 MHz: δ/ppm = 163.5 (C.sub.q), 47.2 (NMe.sub.2), 24.9 (Me), 17.6 (Me). HR-EI(+)-MS Calculated for [M + H].sup.+ = 101.1073 m/z, found: 101.1071 m/z.

Example 2—Preparation of Li(Hydra)

[0124] ##STR00009##

[0125] n-hexane (100 mL) was added to acetone dimethylhydrazone (14.8 g, 147 mmol, 1.0 eq), and the mixture was cooled to 0° C. An nBuLi solution (2.43 M in n-hexane, 60.5 mL, 147 mmol, 1.0 eq) was added via a dropping funnel over a period of two hours, wherein precipitation of a colorless solid was observed. The mixture was stirred overnight, wherein it could warm to room temperature. The resulting solid was separated by filtration, washed with n-hexane (30 mL), and finally dried in vacuo. Li(hydra) could be obtained as a colorless solid.

TABLE-US-00002 .sup.1H-NMR (THF-d.sub.8, 300.2 MHz): δ/ppm = 1.98 (s, 6 H, NMe.sub.2), 1.56 (s, 2.5 H, CH.sub.2.5), 1.48 (s, 2.5 H, CH.sub.2.5). .sup.1H-NMR (toluene-d.sub.8, 300.2 MHz): δ/ppm = 2.37 (s, 6 H, NMe.sub.2), 1.70 (s, 5 H, CH.sub.2 + CH.sub.3). .sup.13C-NMR (THF-d.sub.8, 75.5 MHz): δ/ppm = 163.6 (C.sub.q), 47.2 (NMe.sub.2), 17.5 (Me). .sup.7Li-NMR (THF-d.sub.8, 116.7 MHz): δ/ppm = 1.37 (s), 0.53 (s). Ultimate analysis C.sub.5H.sub.11N.sub.2Li (106.10 g/mol) calculated: C: 56.60%, H: 10.45%, N: 26.40% found: C: 54.29%, H: 9.41%, N: 24.21%.

Example 3—Preparation of [RuCl(P-Cymene)(Hydra)]

[0126] ##STR00010##

[0127] Li(hydra) (200 mg, 0.94 mmol, 2.0 eq) was first put into toluene (25 mL) at 0° C.; then, [RuCl.sub.2(p-cymene)].sub.2 (289 mg, 0.47 mmol, 1.0 eq) was added. The mixture was stirred for 16 hours, allowing it to reach room temperature and to take on a deep red color. The reaction solution was then filtered through Celite®, the filter cake was extracted with further amounts of toluene (10 mL), and the filtrate obtained was freed from all volatile constituents in a fine vacuum. Finally, it was possible to isolate [RuCl(p-cymene)(hydra)] from the residue as a dark red solid (20.1 mg, 56.4 μmol, 12%) by means of sublimation (FV/120° C.).

TABLE-US-00003 .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): 4.74 (d, .sup.3J.sub.HH = 5.6 Hz, 1 H, H-5), 4.45 (d, .sup.3J.sub.HH = 5.8 Hz, 1 H, H-6), 4.18 (d, .sup.3J.sub.HH = 5.6 Hz, 1 H, H-9), 3.91 (d, .sup.3J.sub.HH = 5.8 Hz, 1 H, H-8), 3.46 (d, .sup.2J.sub.HH = 15.6 Hz, 2 H, H-3), 3.28 (s, 3 H, H-13), 3.20 (d, .sup.2J.sub.HH = 15.6 Hz, 1 H, H-3), 2.73 (sept, 1 H, H-10), 2.24 (s, 3 H, NMe.sub.2), 2.01 (s, 3 H, H-1), 1.71 (s, 3 H, NMe.sub.2), 1.16 (d, .sup.3J.sub.HH = 6.9 Hz, 3 H, H- 11/12), 1.07 (d, .sup.3J.sub.HH = 7.1 Hz, 3 H, H-11/12). .sup.13C-NMR (C.sub.6D.sub.6, 75.5 MHz): δ/ppm = 181.5 (C-2), 108.5 (C-4), 93.0 (C-7), 82.5 (C- 6/8), 81.3 (C-5/9), 80.8 (C-6/8), 79.7 (C-5/9), 59.3 (NMe.sub.2), 56.1 (NMe.sub.2), 37.8 (C-3), 31.2 (C-10), 23.3 (C-11/12), 22.0 (C-11/12), 21.4 (C-1), 17.9 (C-13). HR-EI(+)-MS calculated for: [M].sup.+ = 370.0750 m/z, found: 370.0881 m/z. Ultimate analysis C.sub.15H.sub.25N.sub.2ClRu (369.90 g/mol) calculated: C: 48.71%, H: 6.81%, N: 7.57% found: C: 49.50%, H: 6.80%, N: 8.67%. TGA (T.sub.S = 25° C., T.sub.E = 800° C., 10° C./min, m = 5.05 mg) stages: 2, T = 156.1° C. (3% reduction), T.sub.MA = 184.0° C. (1st process), T.sub.MA = 262.0 (2nd process), total mass reduction: 3.73 mg (73.8%). SDTA (T.sub.S = 25° C., T.sub.E = 800° C., 10° C./min, m = 5.05 mg) T.sub.M(onset) = 88.4° C., T.sub.M(max) = 98.4° C. (endothermic), T.sub.D1(onset) = 163.2° C., T.sub.D1(max) = 180.3° C. (exothermic), T.sub.D2(onset) = 252.3° C., T.sub.D2(max) = 263.0° C. (exothermic).

Example 4—Preparation of [RuMe(P-Cymene)(Hydra)]

[0128] ##STR00011##

[0129] Li(hydra) (200 mg, 0.94 mmol, 2.0 eq) was first put into toluene (25 mL) at 0° C.; then, [RuCl.sub.2(p-cymene)].sub.2 (289 mg, 0.47 mmol, 1.0 eq) was added. The mixture was stirred for 16 hours, allowing it to reach room temperature and to take on a deep red color. MeLi (0.94 mmol, 2.0 eq) was added in situ at 0° C. After a reaction time of 16 hours, during which time the mixture was allowed to reach room temperature, all volatile constituents were removed in a fine vacuum. The residue obtained was taken up in n-hexane (10 mL), filtered through Celite®, and the filter cake extracted with further amounts of n-hexane (10 mL). After the filtrate had been dried in a fine vacuum, it was possible to precipitate [RuMe(p-cymene)(hydra)] in a fine vacuum at 110° C. from the residue as a yellow oil.

TABLE-US-00004 .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): 4.27-4.21 (m, 3 H, H-5, H-9, H-8), 4.05 (d, .sup.3J.sub.HH = 5.5 Hz, H-6), 3.34 (d, .sup.2J.sub.HH = 16.5 Hz, H-3), 2.66 (s, 3 H, NMe.sub.2), 2.49 (sept, 1 H, H- 10), 2.48 (s, 3 H, NMe.sub.2), 2.11 (d, .sup.2J.sub.HH = 16.7 Hz, H-3), 2.06 (s, 3 H, H-1), 1.89 (s, 3 H, H-13), 1.12 (d, .sup.3J.sub.HH = 6.8 Hz, H-11, H-12), 0.46 (s, 3 H, RuMe). HR-EI(+)-MS calculated for: [M].sup.+ = 370.0750 m/z, found: 370.0881 m/z. TGA (T.sub.S = 25° C., T.sub.E = 600° C., 10° C./min, m = 9.70 mg) stages: 1, T = 146.1° C. (3% reduction), T.sub.MA = 179.8° C., total mass reduction: 6.12 mg (63.0%). SDTA (T.sub.S = 25° C., T.sub.E = 600° C., 10° C./min, m = 9.70 mg) T.sub.D(onset) = 161.9° C., T.sub.D(max) = 178.2° C. (exothermic).

Example 5—Preparation of [InMe.SUB.2.(Hydra)].SUB.2

[0130] ##STR00012##

[0131] Li(hydra) (300 mg, 2.83 mmol, 1.0 eq) and InMe.sub.2Cl (510 mg, 2.83 mmol, 1.0 eq) were provided together, cooled to 0° C., and then cold Et.sub.2O (0° C., 15 mL) was added. The mixture was stirred for 5 hours at 0° C. and was then allowed to warm to room temperature over 16 hours. The suspension was filtered through Celite®, and the filter cake was extracted with further amounts of Et.sub.2O (10 mL). The filtrate was freed from the solvent in a fine vacuum, and the remaining yellow oil was freeze-dried several times. The viscous oil was then re-condensed in a fine vacuum at 120° C. In this case, it was also possible to isolate a viscous oil, from which colorless crystals of the dinuclear target compound crystallized out.

TABLE-US-00005 .sup.1H-NMR (C.sub.6D.sub.6, 300.2 MHz): 2.13 (s, 6 H, NMe.sub.2), 1.92 (s, 3 H, CH.sub.3), 1.28 (s, 2 H, CH.sub.2), −0.11 (s, 6 H, InMe.sub.2). HR-EI(+)-MS calculated for [InMe.sub.2].sup.+: m/z = 144.9508, found: m/z = 144.9536. calculated for [C.sub.6H.sub.14N.sub.2≡hydra].sup.+: m/z = 114.1157, found: m/z = 114.9082. calculated for [C.sub.2H.sub.6N≡NMe.sub.2].sup.+: m/z = 44.0500, found: m/z = 43.9963.

[0132] Single crystal X-ray structure analysis was able to determine that it is a homodinuclear indium complex with a bridging C,N coordination mode. According to its structure, the complex of this example can also be expressed with the following formula: [Me.sub.2In(η-hydra).sub.2InMe.sub.2].

LITERATURE

[0133] [1] T. Fujisawa, M. Takeuchi, T. Sato, Chemistry Letters, 1982, 1521-1524 [0134] [2] D. J. Cárdenas, A. M. Echavarren, A. Vegas, Organometallics 1994, 13, 882-889 [0135] [3] S. Javed, D. M. Hoffman, Inorganic Chemistry 2008, 47, 11984-11992 [0136] [4] S. Javed, D. M. Hoffman, Eur. J. Inorg. Chem. 2008, 47, 5251-5256 [0137] [5] R. H. Wiley, S. C. Slaymaker, H. Kraus, J. Org. Chem. 1957, 22, 204-207 [0138] [6] C. Qi, F. Hasenmaile, V. Gandon, D. Laboef, ACS Catalysis 2018, 8, 1734-1739 [0139] [7] E. J. Corey, D. Enders, Chem. Ber. 1978, 111, 1362-1383. [0140] [8] P. Y. Géant, E. Grenet, J. Martinez, X. J. Salom-Roig, Tetrahedron Asymmetry 2016, 27, 22-30, [0141] [9] D. Enders, W. Dahmen, E. Dederichs, W. Gatzweiler, P. Weuster, Synthesis (Stuttg). 1990, 11, 1013-1019.