Process for the generation of thin inorganic films

Abstract

The present invention is in the field of processes for the generation of thin inorganic films on substrates, in particular atomic layer deposition processes. The present invention relates to a process comprising bringing a compound of general formula (I) into the gaseous or aerosol state and depositing the compound of general formula (I) from the gaseous or aerosol state onto a solid substrate, wherein M is Mn, Ni or Co, X is a ligand which coordinates M, n is 0, 1, or 2, R.sup.1, R.sup.2 are an alkyl group, an alkenyl group, an aryl group or a silyl group, m is 1, 2, or 3, R.sup.3, R.sup.4, and R.sup.5 are an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and p is 1, 2 or 3. ##STR00001##

Claims

1. A process, comprising: bringing a compound of formula (I): ##STR00008## into a gaseous or aerosol state, and depositing the compound from the gaseous or aerosol state onto a solid substrate, thereby forming a deposited compound, wherein M is Mn, Ni or Co, X is a ligand which coordinates M, n is 0, 1, or 2, R.sup.1, R.sup.2 are an alkyl group, an alkenyl group, an aryl group or a silyl group, m is 1, 2, or 3, R.sup.3, R.sup.4, and R.sup.5 are an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and p is 1, 2 or 3.

2. The process according to claim 1, wherein only two of R.sup.3, R.sup.4 and R.sup.5 are the same or all R.sup.3, R.sup.4 and R.sup.5 are different to each other.

3. The process according to claim 1, wherein n is 0, m is 2 and p is 1.

4. The process according to claim 1, wherein R.sup.1 and R.sup.2 are a silyl group.

5. The process according to claim 1, wherein R.sup.3, R.sup.4 and R.sup.5 are methyl, ethyl, iso-propyl or tert-butyl.

6. The process according to claim 1, wherein M is Co.

7. The process according to claim 1, further comprising: chemisorbing the compound on a surface of the solid substrate.

8. The process according to claim 1, further comprising: decomposing the deposited compound by removing all ligands.

9. The process according to claim 8, further comprising: exposing the deposited compound to a reducing agent.

10. The process according to claim 8, wherein a sequence of the depositing the compound onto the solid substrate and the decomposing the deposited compound is performed at least twice.

11. A process for forming a film on a solid substrate, comprising: applying, to the solid substrate, a compound of formula (I), ##STR00009## wherein M is Mn, Ni or Co, X is a ligand which coordinates M, n is 0, 1, or 2, R.sup.1, R.sup.2 are an alkyl group, an alkenyl group, an aryl group or a silyl group, m is 1, 2, or 3, R.sup.3, R.sup.4, and R.sup.5 are an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group, and p is 1, 2 or 3.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIGS. 1 to 4 depict the thermal gravimetric data of the compounds in the examples.

EXAMPLES

Example 1 (Comparative Example)

(2) ##STR00003##

(3) A cooled solution of NaN(SiMe.sub.3).sub.2 (7.34 g, 40.0 mmol) in THF (40 mL, 36 C.) was added dropwise to a cooled slurry of CoCl.sub.2 (2.60 g, 20.0 mmol) in THF (20 mL, 36 C.). A color-change from blue to green was observed. After stirring for 1 h at room temperature all volatiles were removed under vacuum. The dark green solid was extracted with pentanes (330 mL) and filtered through a P3 glass frit. Removal of the solvent yielded C-0 as green crystals (7.01 g, 77.5%). Dual Sublimation (40 C./1 mtorr) for 20 h respectively afforded an analytically pure sample. Crystals for X-ray crystallography were obtained by slow evaporation of a solution in pentane at 36 C.

(4) .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): (ppm)=162.6 (br, 4H, CH.sub.2CH.sub.2O or CH.sub.2CH.sub.2O), 97.0 (br, 4H, CH.sub.2CH.sub.2O or CH.sub.2CH.sub.2O), 16.4 (br, 36H, SiMe.sub.3).

(5) Elemental analysis: Calculated for C.sub.16H.sub.44CoN.sub.2OSi.sub.4: C, 42.53; H, 9.82; N, 6.20. Found: C, 42.05; H, 10.58; N, 6.20.

(6) C-0 has a vapor pressure of 1 mbar at 102 C. Upon sublimation, a metallic residue is observed at the place of vaporization. The thermogravimetric (TG) analysis including the differential thermogravimetry (DTA) is shown in FIG. 1. The residual mass at 300 C. is 5.1%, the maximum DTA is at 159 C.

Example 2

(7) ##STR00004##

(8) PMe.sub.3 (0.25 mL, 2.42 mmol) solved in cold Et.sub.2O (2 mL, 36 C.) was added dropwise to cooled solution of C-0 (1.0 g, 2.21 mmol) in Et.sub.2O (3 mL, 36 C.). No color change was observed. Stirring at room temperature for 16 h resulted in a turquoise solution. Removing of the solvent under vacuum afforded C-1 as crude product (966 mg). Sublimation (75 C./1 mtorr) for 14 h gave an analytically pure sample as a turquoise solid (608 mg, 60%). Crystals for X-ray crystallography were obtained by slow evaporation of a pentanes-solution at 36 C.

(9) .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): (ppm)=168.8 (br, 9H, PMe.sub.3), 24.2 (br, 36H, SiMe.sub.3).

(10) Elemental analysis: Calculated for C.sub.15H.sub.45CoN.sub.2PSi.sub.4: C, 39.53; H, 9.95; N, 6.15. Found: C, 39.04; H, 10.43; N, 5.97.

(11) C-1 has a vapor pressure of 1 mbar at 138 C. Upon sublimation, no residue is observed at the place of vaporization. TG and DTA are shown in FIG. 2. The residual mass at 300 C. is 14.1%, the maximum DTA is at 193 C.

Example 3

(12) ##STR00005##

(13) P(i-Pr).sub.3 (0.35 mL, 1.77 mmol) solved in cold Et.sub.2O (2 mL, 36 C.) was added dropwise to cooled solution) of C-0 (800 mg, 1.77 mmol) in Et.sub.2O (3 mL, (36 C.). Stirring at room temperature for three days resulted in a green solution. Removing of the solvent under vacuum afforded 3 as crude product. Sublimation (80 C./1 mtorr) for 17 h gave an analytically pure sample of bright green solid (714 mg, 75%). Crystals for X-ray crystallography were obtained by slow evaporation of a pentanes-solution at 36 C.

(14) .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): (ppm)=175.5 (br, P(CH(CH.sub.3).sub.2).sub.3), 31.7 (br, 18H, P(CH(CH.sub.3).sub.2).sub.3), 19.6 (br, 36H, SiMe.sub.3).

(15) Elemental analysis: Calculated for C.sub.21H.sub.57CoN.sub.2PSi.sub.4: C, 46.71; H, 10.64; N, 5.19. Found: C, 46.01; H, 11.72; N, 5.08.

(16) C-2 has a vapor pressure of 1 mbar at 133 C. Upon sublimation, no residue is observed at the place of vaporization. TG and DTA are shown in FIG. 3. The residual mass at 300 C. is 14.3%, the maximum DTA is at 191 C.

Example 4

(17) ##STR00006##

(18) PMe.sub.2t-Bu (0.25 mL, 1.80 mmol) solved in cold Et.sub.2O (2 mL, 36 C.) was added dropwise to cooled solution of C-0 (813 mg, 1.80 mmol) in Et.sub.2O (3 mL, 36 C.). Stirring at room temperature for 17 h resulted in a green solution. Removing of the solvent afforded C-3 as crude product. Sublimation (60 C./1 mtorr) for 22 h gave an analytically pure sample of green solid (545 mg, 51%). Crystals for X-ray crystallography were obtained by slow evaporation of a pentanes-solution at 36 C.

(19) .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): (ppm)=152.1 (br, 6H, PMe.sub.2t-Bu), 54.6 (br, 9H, PMe.sub.2t-Bu), 21.8 (br, 36H, SiMe.sub.3).

(20) Elemental analysis: Calculated for C.sub.18H.sub.51CoN.sub.2PSi.sub.4: C, 43.42; H, 10.33; N, 5.63. Found: C, 41.00; H, 9.94; N, 5.85.

Example 5

(21) ##STR00007##

(22) Pi-Pr.sub.2t-Bu (0.28 mL, 1.30 mmol) solved in cold Et.sub.2O (5 mL, 36 C.) was added dropwise to cooled solution of C-0 (587 mg, 1.30 mmol) in Et.sub.2O (2 mL, 36 C.). Stirring at room temperature for 23 h resulted in a green solution. Removing of the solvent under vacuum afforded C-4 as green oil. Drying in vacuum for 9 h gave a green solid as crude product. Sublimation (60 C./1 mtorr) for 22 h gave an analytically pure sample of green solid (320 mg, 44%). Crystals for X-ray crystallography were obtained by slow evaporation of a pentanes-solution at room temperature.

(23) .sup.1H-NMR (300 MHz, C.sub.6D.sub.6): (ppm)=120.8 (br, P(CH(CH.sub.3).sub.2)t-Bu), 31.0 (br, 6H, P(CHCH.sub.3CH.sub.3)t-Bu or P(CHCH.sub.3CH.sub.3)t-Bu), 27.5 (br, 9H P(CH(CH.sub.3).sub.2)t-Bu), 22.4 (br, 6H, P(CHCH.sub.3CH.sub.3)t-Bu or P(CHCH.sub.3CH.sub.3)t-Bu), 16.5 (br, 36H, SiMe.sub.3).

(24) Elemental analysis: Calculated for C.sub.22H.sub.66CoN.sub.2PSi.sub.4: C, 46.70; H, 10.96; N, 4.80. Found: C, 47.70; H, 10.74; N, 5.06.

(25) C-4 has a vapor pressure of 1 mbar at 100 C. Upon sublimation, no residue is observed at the place of vaporization. TG and DTA are shown in FIG. 4. The residual mass at 300 C. is 3.3%, the maximum DTA is at 159 C.