PROCESS FOR THE GENERATION OF METAL- OR SEMIMETAL-CONTAINING FILMS

Abstract

The present invention is in the field of processes for preparing inorganic metal- or semimetal-containing films. The process comprising (a) depositing a metal- or semimetal-containing compound from the gaseous state onto a solid substrate and (b) bringing the solid substrate in contact with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) in the gaseous state (I) (II) (III) (IV) . . . (V) (VI) (VII) wherein A is NR or O, E is CR″, CNR″.sub.2, N, PR″.sub.2, or SOR″, G is CR′ or N, R is an alkyl group, an alkenyl group, an aryl group, or a silyl group and R′ and R″ are hydrogen, an alkyl group, an alkenyl group, an aryl group, or a silyl group.

Claims

1.-15. (canceled)

16. Process for preparing inorganic metal- or semimetal-containing films comprising (a) depositing a metal- or semimetal-containing compound from the gaseous state onto a solid substrate and (b) bringing the solid substrate in contact with a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) in the gaseous state ##STR00027## wherein A is NR or O, E is CR″, CNR″.sub.2, N, PR″.sub.2, or SOR″ G is CR′ or N, R is an alkyl group, an alkenyl group, an aryl group, or a silyl group and R′ and R″ are hydrogen, an alkyl group, an alkenyl group, an aryl group, or a silyl group.

17. The process according to claim 16, wherein R is methyl, ethyl, iso-propyl, sec-butyl, tert-butyl, trimethylsilyl.

18. The process according to claim 16, wherein R bears no hydrogen atom in the 1-position.

19. The process according to claim 16, wherein R′ in the 3 position of the ligand in the compound of general formula (I) or (II) is H.

20. The process according to claim 16, wherein the metal- or semimetal-containing compound contains Ti, Ta, Mn, Mo, W, Ge, Ga, As, In, Sb, Te, Al or Si.

21. The process according to claim 16, wherein the metal- or semimetal-containing compound is a metal or semimetal halide.

22. The process according to claim 16, wherein the sequence containing (a) and (b) is performed at least twice.

23. The process according to claim 16, wherein the process is an atomic layer deposition process.

24. The process according to claim 16, wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a molecular weight of not more than 600 g/mol.

25. The process according to claim 16, wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a vapor pressure at least 1 mbar at a temperature of 200° C.

26. The process according to claim 16, wherein the compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) has a melting point of −80 to 125° C.

27. The process according to claim 16, wherein the inorganic metal- or semimetal-containing films contains a metal, a metal nitride, a metal carbide, a metal carbonitride, a metal alloy, an intermetallic compound or mixtures thereof

28. The process according to claim 16, wherein the inorganic metal- or semimetal-containing films contains less than 5 weight-% nitrogen.

29. Use of a compound of general formula (I), (II), (III), (IV), (V), (VI), or (VII) as reducing agent in a vapor deposition process.

30. Use according to claim 29, wherein the vapor deposition process is an atomic layer deposition process.

Description

EXAMPLES cl Example 1a: Synthesis of 4-(Isopropylamino) Pent-3-en-2-one (i.SUB.PrNacacH.)

[0070] A solution of 2,4-pentanedione (10.4 mL, 0.1 mol) in 100 mL of ethanol was added dropwise into a solution of isopropylamine (8.7 mL, 0.1 mol) in 100 mL of ethanol. The resultant pale yellow solution was refluxed at 100° C. for 18 h in a 250 mL round bottomed flask. The intense yellow colored solution was reduced in volume under reduced pressure. Fractional distillation of the residue at 78° C. under reduced pressure (0.8 Torr) afforded i.sub.PrNacacH (11.859 g, 84% yield) as a pale-yellow liquid.

[0071] 1.sub.H NMR (400 MHz, C.sub.6D.sub.6) δ=0.82 (d, 6H), 1.51 (s, 3H), 1.96 (s, 3H), 3.19 (m, 1H), 4.83 (s, 1H), 11.10 (s, 1H). 13.sub.C{1.sub.H} NMR (100 MHz, C.sub.6D.sub.6) δ=18.59, 24.07, 29.23, 44.69, 95.47, 161.17, 194.26.

Example 1b: Synthesis of N, N′-Diisopropyl-2,4-pentanediketimine (i.SUB.PrNacNacH.)

[0072] A solution of i.sub.PrNacacH (5.376 g, 0.038 mol) in dimethyl sulfate (6 mL, 0.063 mol) was stirred for 5 minutes at ambient temperature and was then allowed to stand for 24 h, affording a viscous, orange colored solution. Subsequent addition of excess isopropylamine (7 mL, 0.081 mol) and stirring for 1 h at ambient temperature increased the color intensity of the solution. A mixture of excess sodium methoxide in methanol (11 mL, 0.048 mol) was added and the mixture was stirred for 1 h at ambient temperature. The volatile components were evaporated under reduced pressure, and then water (40 mL) was added to the resultant product. The flask contents were transferred to a separatory funnel. The crude product was extracted with pentane (10×40 mL) and the combined organic fractions were dried over anhydrous Na.sub.2SO.sub.4. The solution was filtered through fluted filter paper to afford a clear solution. The volatile components were removed under reduced pressure to afford i.sub.PrNacNacH (2.195 g) as an orange oil.

[0073] 1.sub.H NMR (400 MHz, C.sub.6D.sub.6) δ=1.13 (d, 12H), 1.73 (s, 6H), 3.48 (m, 2H), 4.48 (s, 1H), 11.66 (s, 1H).

[0074] 13.sub.C{1.sup.H} NMR (100 MHz, C.sub.6D.sub.6) δ=19.16, 25.44, 47.35, 94.98,158.33.

[0075] The crude product was used to synthesize the aluminum complex without further purification.

Example 1c: Synthesis of Compound Ia-1

[0076] A solution of AlCl.sub.3(0.372 g, 2.8 mmol) in 30 mL of diethyl ether was cannulated into a stirred solution of LiAlH.sub.4 (0.334 g, 8.4 mmol) in 30 mL of diethyl ether at 0° C. in an ice bath. The resultant cloudy solution was warmed to room temperature, stirred for 40 minutes, and then recooled to −30° C. Then, a solution of i.sub.PrNacNacH (2.035 g, 11.16 mmol) in 40 mL of diethyl ether was added dropwise. The resultant mixture was stirred at ambient temperature for 18 h and was then filtered through a 2-cm plug of Celite on a coarse glass frit. The diethyl ether was evaporated from the filtrate under reduced pressure to collect the intense yellow colored, creamy product. The crude product was purified by sublimation at 50° C. under reduced pressure to afford compound Ia-1 as pale-yellow crystals (1.251 g, 53% yield). mp=62-63° C.

[0077] 1.sub.H NMR (400 MHz, C.sub.6D.sub.6) δ=1.31 (d, 12H), 1.56 (s, 6H), 3.48 (m, 2H), 4.41 (s, 1H).

[0078] 13.sub.C{1.sub.H} NMR (100 MHz, C.sub.6D.sub.6) δ=21.88, 23.12, 50.59, 97.73, 166.96.

[0079] The thermogravimetric analysis result is shown in FIG. 1.

Example 2a: Synthesis of 4-(sec-butylamino) pent-3-en-2-one (S.SUB.BuNacacH.)

[0080] A solution of 2,4-pentanedione (10.4 mL, 0.1 mol) in 100 mL ethanol was added dropwise into a solution of sec-butylamine (10 mL, 0.1 mol) in 100 mL ethanol. The resultant pale yellow solution was refluxed at 100° C. for 18 h in a 250 mL round bottomed flask. The intense yellow colored solution was reduced in volume under reduced pressure. Fractional distillation of the residue at 97° C. at 0.8 Torr afforded 5.sub.BuNacacH as a pale yellow liquid (14.332 g, 92.3% yield).

[0081] 1.sub.H NMR (400 MHz, C.sub.6D.sub.6) δ=0.68 (t, 3H), 0.80 (d, 3H), 1.16 (m, 2H), 1.51 (s, 3H), 1.98 (s, 3H), 3.00 (m, 1H, 4.84 (s,1H), 11.13 (s,1H).

[0082] 13.sub.C{1.sub.H} NMR (100 MHz, C.sub.6D.sub.6) δ=10.69, 18.86, 21.95, 29.23, 31.12, 50.35, 95.51, 161.63, 194.30.

Example 2b: Synthesis of N, N′-Di(sec-butyl)-2,4-pentanediketimine (S.SUB.BuNacNacH.)

[0083] A solution of S.sub.BuNacacH (4.005 g, 0.026 mol) in dimethyl sulfate (4 mL,0.043 mol) was stirred for 5 min at ambient temperature and was then allowed to stand for 24 h, affording a viscous, orange colored solution. Subsequently, excess sec-butylamine (6 mL, 0.059 mol) was added and the solution was stirred for an additional two hours at ambient temperature. A mixture of excess sodium methoxide in methanol (7.5 mL, 0.033 mol) was added and the mixture was stirred for one hour. The volatile components were evaporated under reduced pressure and water (20 mL) was added to the resultant product. The flask contents were transferred to a separatory funnel. The crude product was extracted with pentane (10×35 mL) and the combined organic fractions were dried over anhydrous Na.sub.2SO.sub.4. The solution was filtered through a fluted paper filter. The residual solvents were evaporated under reduced pressure to afford crude S.sub.BuNacNacH (5.810 g). The crude product was distilled at 85-87° C. at 0.8 Torr to afford S.sub.BuNacNacH as a pale-yellow liquid (2.405 g, 45% yield).

[0084] 1.sub.H NMR (400 MHz, C.sub.6D.sub.6) δ=0.90 (t, 6H), 1.07 (d, 6H), 1.46 (m, 4H), 1.73 (s, 6H), 3.27 (m, 2H), 4.45 (s,1H), 11.52 (s,1H).

[0085] 13.sub.C{1.sub.H} NMR (100 MHz, C.sub.6D.sub.6) δ=11.15, 19.43, 23.04, 32.54, 52.98, 95.16, 158.67.

Example 2c: Synthesis of Compound Ia-2

[0086] A solution of AlCl.sub.3(0.381 g, 2.85 mmol) in 30 mL of diethyl ether was cannulated into a stirred solution of LiAlH.sub.4 (0.343 g, 8.57 mmol) in 30 mL of diethyl ether at 0° C. in an ice bath. The resultant cloudy solution was warmed to room temperature, stirred for 40 minutes, and then recooled to −30° C. Then, a solution of S.sub.BuNacNacH (2.405 g, 11.43 mmol) in 40 mL of diethyl ether was added dropwise. The resultant mixture was stirred at ambient temperature for 18 h and was then filtered through a 2-cm plug of Celite on a coarse glass frit. The diethyl ether was evaporated from the filtrate under reduced pressure to collect the yellow colored, creamy product. The crude product was purified by sublimation at 45° C. at 0.8 Torr to afford compound la-2 as pale-yellow crystals (0.967 g, 35.5% yield). mp=40° C.

[0087] 1.sub.H NMR (400 MHz, C.sub.6D.sub.6) δ=0.83 (6H, 2 CH(CH.sub.3) CH.sub.2CH.sub.3), 1.32 (6H, 2 CH(CH.sub.3) CH.sub.2CH.sub.3), 1.59 (8H, 2 β-C (CH.sub.3)+2 CH(CH.sub.3)CHH′CH.sub.3), 2.00 (2H, 2 CH(CH.sub.3)CHH′CH.sub.3), 3.23 (2H, CH (CH.sub.3)CH.sub.2CH.sub.3), 4.50 (1H, a-CH).

[0088] 13.sub.C{1.sub.H} NMR (100 MHz, C.sub.6D.sub.6) δ=12.10, 21.54, 22.46, 30.43, 56.80, 97.91, 167.23.

[0089] The thermogravimetric analysis result is shown in FIG. 1.