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. In particular, the present invention relates to a process comprising bringing a compound of general formula (I) into the gaseous or aerosol state L.sub.n . . . M . . . X.sub.m (I) and depositing the compound of general formula (I) from the gaseous or aerosol state onto a solid substrate, wherein M is a metal, L is a ligand which coordinates to M and contains at least one phosphorus-carbon multiple bond, wherein L contains a phosphorus-containing heterocyclic ring or a phosphorus-carbon triple bond, X is a ligand which coordinates to M, n is 1 to 5, and m is 0 to 5.

Claims

1. A process comprising bringing a compound of formula (I) into the gaseous or aerosol state
L.sub.n - - - M - - - X.sub.m (I) and depositing the compound of general formula (I) from the gaseous or aerosol state onto a solid substrate, wherein: M is a metal, L is a ligand which coordinates to M and comprises at least one phosphorus-carbon multiple bond, wherein L comprises a phosphorus-containing heterocyclic ring or a phosphorus-carbon triple bond, X is a ligand which coordinates to M, n is 1 to 5, and m is 0 to 5.

2. The process according to claim 1, wherein the compound of formula (I) is a compound of formula (Ia) ##STR00010## wherein R.sup.1 and R.sup.2 are each independently nothing, hydrogen, an alkyl group, an aryl group or a silyl group, and wherein R.sup.3 and R.sup.4 are each independently an alkyl group, an aryl group or a silyl group.

3. The process according to claim 1, wherein the compound of formula (I) is a compound of formula (Ib) ##STR00011## wherein R.sup.5 is nothing, hydrogen, an alkyl group, an aryl group or a silyl group, and wherein R.sup.6 to R.sup.9 are each independently hydrogen, an alkyl group, an aryl group or a silyl group.

4. The process according to claim 1, wherein the compound of formula (I) is a dimer of formula (Ic) ##STR00012## wherein R.sup.5 is an alkyl group, an aryl group or a silyl group.

5. The process according to claim 1, wherein M is Ni, Co, Mn, Ti, Ta or W.

6. The process according to claim 1, wherein at least one X is a cycopentadienyl derivative.

7. The process according to claim 1, wherein at least one X is CO.

8. The process according to claim 1, wherein the compound of formula (I) is chemisorbed on a surface of the solid substrate.

9. The process according to claim 1, wherein the deposited compound of formula (I) is decomposed by removal of all ligands L and X.

10. The process according to claim 1, wherein the deposited compound of formula (I) is exposed to a reducing agent.

11. The process according to claim 1, wherein a 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.

12. (canceled)

Description

EXAMPLES

Example 1

[0069] ##STR00004##

[0070] Compound Ia-1 was synthesized according to the procedure by Wolf et al. in Angewandte Chemie International Edition volume 47 (2008), page 4584. It sublimes at 90 to 100 C. at 10.sup.2 mbar, its melting point is 193 C.

[0071] FIG. 1 shows the thermogravimetric analysis data of Ia-1. The residual mass at 500 C. is 27%.

Example 2

[0072] ##STR00005##

[0073] Compound Ia-2 was synthesized according to the procedure by Wolf et al. in Angewandte Chemie International Edition volume 47 (2008), page 4584. It sublimes at 90 to 100 C. at 10.sup.2 mbar, its melting point is 185 C.

[0074] FIG. 2 shows the thermogravimetric analysis data of Ia-1. The residual mass at 500 C. is 37%.

Example 3

[0075] ##STR00006##

[0076] Compound Ia-3 was synthesized according to the procedure by Wolf et al. in Chemistry, A European Journal, volume 16 (2010), page 14322. It sublimes at 100 C. at 10.sup.2 mbar, its melting point is 196 C.

[0077] FIG. 3 shows the thermogravimetric analysis data of Ia-3. The residual mass at 500 C. is 38%.

Example 4

[0078] ##STR00007##

[0079] A solution of Me3SiCl in toluene (0.15 M, 0.87 mmol, 5.7 mL) was added to a solution of [K(thf).sub.2{Co(P.sub.2C.sub.2tBu.sub.2).sub.2}] (0.43 g, 0.79 mmol) in toluene (30 mL) at room temperature. The reaction mixture was stirred overnight whereupon a dark red solution was formed. The solvent was then removed in vacuo and the deep red residue was extracted with n-pentane (20 mL). Concentrating the red extract to ca. 10 mL and storage at 30 C. for two days gave red crystals of Ia-4. Yield: 0.24 g (58%). It was found that compound Ia-4 contains a variable amount of [Co(P.sub.2C.sub.2tBu.sub.2).sub.2H] (Ia-3).The contamination was determined to be ca. 4% according to the .sup.1H NMR spectrum.

[0080] .sup.1H NMR (400.13 MHz, C.sub.6D.sub.6): =0.28 (d, J(H,P)=7.0 Hz, 9H, SiMe.sub.3), 1.24 (s, 18H, tBu), 1.30 (s, 18H, tBu);

[0081] .sup.31P{.sup.1H} NMR (161.98 MHz, C.sub.6D.sub.6): =1.9 (s, 1P), 19.3 (s, 1P), 21.8 (s, 2P). The NMR shifts are similar to the known complex [Co(P.sub.2C.sub.2tPent.sub.2SiMe.sub.3)(P.sub.2C.sub.2tPent.sub.2)] with tPent instead of tBu substituents.

[0082] Compound Ia-4 sublimes at 80 to 90 C. at 10.sup.2 mbar, its melting point is 193 C.

[0083] FIG. 4 shows the thermogravimetric analysis data of Ia-4. The residual mass at 500 C. is 30%.

Example 5

[0084] ##STR00008##

[0085] Compound Ic-1 was synthesized according to Burckett-St. Laurent et al. in the Journal of the Chemical Society, Chemical Communications 1981, page 1141-1143. It is purely sublimable due to its waxy, oily nature.

[0086] FIG. 5 shows the thermogravimetric analysis data of Ic-1. The residual mass at 500 C. is 39%.

Example 6

[0087] ##STR00009##

[0088] Compound Ib-4 was synthesized according to Organometallics volume 16 (1997), page 2049. The obtained compound is an orange-brown oil.

[0089] FIG. 6 shows the thermogravimetric analysis data of Ib-4. The residual mass at 500 C. is 11.58%.