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 for the generation of inorganic films comprising depositing the compound of general formula (I) onto a solid substrate (I), wherein M is Mn, Ni or Co, X is a ligand which coordinates M, n is 0, 1, 2, 3, or 4, R.sup.1 is an alkyl group, an alkenyl group, an aryl group, a halogen, or a silyl group, R.sup.2 is an alkyl group, an alkenyl group, an aryl group, or a silyl group, p and q are 1 or 2, wherein p+q=3, and m is 1, 2, or 3.

Claims

1. A compound of formula (I) ##STR00004## wherein M is Mn, Ni or Co, X is a ligand which coordinates M, wherein at least one X coordinates M via a nitrogen atom, n is 0, 1, 2, 3, or 4, R.sup.1 is an unsubstituted alkyl group, an alkenyl group, an aryl group, a halogen, or a silyl group, R.sup.2 is an alkyl group, an alkenyl group, an aryl group, or a silyl group, p and q are 1 or 2, wherein p+q=3, and m is 1, 2, or 3.

2. The compound according to claim 1, wherein M is Co, m is 1, and n is 2.

3. The compound according to claim 1, wherein R.sup.1 and R.sup.2 are each independently methyl, ethyl, iso-propyl or tert-butyl.

4. The compound according to claim 1, wherein at least one X is bis-(trimethylsilyl)amine.

5. A process for the generation of inorganic films comprising depositing a compound of formula (I) onto a solid substrate ##STR00005## wherein M is Mn, Ni or Co, X is a ligand which coordinates M, n is 0, 1, 2, 3, or 4, R.sup.1 is an unsubstituted alkyl group, an alkenyl group, an aryl group, a halogen, or a silyl group, R.sup.2 is an alkyl group, an alkenyl group, an aryl group, or a silyl group, p and q are 1 or 2, wherein p+q=3, and m is 1, 2, or 3.

6. The process according to claim 5, wherein R.sup.1 is an unsubstituted alkyl group and R.sup.2 is an alkyl group.

7. The process according to claim 5, wherein R.sup.1 and R.sup.2 are each independently methyl, ethyl, iso-propyl or tert-butyl.

8. The process according to claim 5, wherein m is 1.

9. The process according to claim 5, wherein at least one X is an anionic ligand.

10. The process according to claim 5, wherein M is Co.

11. The process according to claim 5, wherein the compound of formula (I) is chemisorbed on the surface of the solid substrate.

12. The process according to claim 5, wherein the deposited compound of formula (I) is decomposed by removal of all ligands.

13. The process according to claim 12, wherein the deposited compound of formula (I) is exposed to a reducing agent.

14. The process according to claim 12, wherein the sequence of depositing the compound of formula (I) onto a solid substrate and decomposing the deposited compound of formula (I) is performed at least twice.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 depict the thermal gravimetric data of the compound C-1.

EXAMPLES

Example 1 (Comparative Example)

(2) ##STR00002##

(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 (3×30 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): δ (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 reveals a residual mass at 300° C. of 5.1%, the maximum DTA is at 159° C.

Example 2

(7) ##STR00003##

(8) P(OEt).sup.iPr.sub.2 (3.95 g, 24.4 mmol) solved in cold Et.sub.2O (10 mL, −36° C.) was added dropwise to a cooled solution of [Co(N(SiMe.sub.3).sub.2).sub.2(THF)](C-0) (10.0 g, 22.1 mmol) in Et.sub.2O (20 mL, −36° C.). The mixture was stirred at room temperature for 3 days. Removing of the solvent under vacuum afforded C-1 as a crude product. Sublimation (70° C./4 mtorr) for 16 h gave an analytically pure sample as a green solid (9.8 g, 82% yield). 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): δ (ppm)=55.8 (br, 6H, P(CH(CH.sub.3).sub.2), 52.5 (br, 2H, P(OCH.sub.2CH.sub.3), 29.6 (br, 6H, P(CH(CH.sub.3).sub.2), 9.5 (br, 3H, P(OCH.sub.2CH.sub.3), −20.5 (br, 36H, Si(CH.sub.3).sub.3).

(10) Elemental analysis: Calculated for C.sub.20H.sub.55CoN.sub.2OPSi.sub.4: C, 44.3; H, 10.2; N, 5.2. Found: C, 42.8; H, 10.0; N, 4.9.

(11) C-1 has a vapor pressure of 1 mbar at 112° C. Upon sublimation, no residue is observed at the place of vaporization. TG and DTA are shown in FIG. 1. The residual mass at 300° C. is 0.7%, the maximum DTA is at 142° C.