Process for the generation of thin silicon-containing films

Abstract

The present invention is in the field of processes for the generation of thin inorganic films on substrates. In particular, the present invention relates to a process comprising depositing the compound of general formula (I) onto a solid substrate, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 is hydrogen, an alkyl group, an alkenyl group, an aryl group or a silyl group, wherein not more than three of R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 are hydrogen, X is a group which binds to silicon, m is 1 or 2, n is 0, 1, or 2, and Si is in the oxidation state +2. ##STR00001##

Claims

1. A process, comprising depositing a compound of formula (I): ##STR00010## onto a solid substrate, wherein: R1, R2, R3, R4, and R5 independently represent hydrogen, an alkyl group, an alkenyl group, an aryl group or a silyl group, wherein not more than three of R1, R2, R3, R4, and R5 are hydrogen, X is an amine, an aryl group, an imine ligand, or an amidine ligand, m is 1, n is 1, and Si is in the oxidation state +2.

2. The process according to claim 1, wherein three of R1, R2, R3, R4, and R5 are hydrogen and the remaining two are groups with branching at the atom which is attached to the cyclopentadienyl ring, or not more than two of R1, R2, R3, R4, and R5 are hydrogen.

3. The process according to claim 1, wherein R1, R2, R3, R4, R5 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, trimethylsilyl or triethylsilyl.

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

5. The process according to claim 1, wherein the compound of formula (I) is deposited from gaseous or aerosol phase onto the solid substrate.

6. The process according to claim 1, wherein the compound of formula (I) is deposited from solution onto the solid substrate.

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

8. 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.

9. A process, comprising forming a film of the compound of general formula (I), wherein: ##STR00011## R1, R2, R3, R4, and R5 is hydrogen, an alkyl group, an alkenyl group, an aryl group or a silyl group, wherein not more than three of R1, R2, R3, R4, and R5 are hydrogen, X is an amine, an aryl group, an imine ligand, or an amidine ligand, m is 1, n is 1, and Si is in the oxidation state +2.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the thermogravimetric analysis of compound C-1.

(2) FIG. 2 shows the thermogravimetric analysis of compound C-93.

(3) FIG. 3 shows the crystal structure of compound C-a-1.

EXAMPLES

(4) Thermogravimetric analysis was performed with about 20 mg sample. It was heated by a rate of 5° C./min in an argon stream.

Example 1

(5) ##STR00006##

(6) Compound C-1 was synthesized according to the procedure by Jutzi et al. in Angewandte Chemie International Edition, volume 25 (1986), page 164. The thermogravimetric analysis is depicted in FIG. 1. The mass loss at 250° C. is 97.27%.

Example 2

(7) ##STR00007##

(8) Compound C-93 was synthesized according to the procedure by Jutzi et al. in Chemical Communications 2006, page 3519. The thermogravimetric analysis under vacuum is depicted in FIG. 2. The mass loss at 150° C. is 89.89%.

Example 3

(9) ##STR00008##

(10) Compound 1 was prepared according to Kessler et al. Chemistry a European Journal, volume 19 (2013) page 6350-6357. A solution of potassium hexamethyldisilazane (KHMDS) 3.74 g (18.7 mmol) in Et.sub.2O (˜80 ml) was added at room temperature to a stirred suspension of compound 1 (3.30 g, 9.20 mmol) in Et.sub.2O (˜100 ml). The reaction mixture was stirred overnight to give a yellowish suspension. All volatiles were removed in vacuo. The remaining solid was washed twice with hexane (2×80 ml) and kept in vacuo for 1 h to afford 3.90 g (8.97 mmol) of compound 1 as a creamy solid.

(11) ##STR00009##

(12) Compound 3 was prepared according to Ghadwal et al. Angewandte Chemie International Edition volume 48 (2009) page 5683-5686. THF (˜15 ml) was added at room temperature to a stirred mixture of compound 3 (0.680 g, 1.39 mmol) and compound 2 (0.851 g, 1.96 mmol) placed in a 50-ml Schlenk flask. Stirring was continued overnight to afford a yellow suspension. All volatiles were removed in vacuo. The residue was extracted with hexane (˜10 ml) and filtered. The solvent from the filtrate was removed in vacuo. Extraction with a cold pentane (˜−60° C.) followed by filtration, concentration (to ˜1 ml) and crystallization at −30° C. afforded C-a-1 co-crystallized with compound 1 and pentane (ratio 2:1:1) as colorless crystals (0.081 g, corresponding to 0.14 mmol of ansa-silicocene).

(13) Crystals suitable for X-ray analysis were grown from pentane after storing overnight at −30° C. The crystal structure of C-a-1 is shown in FIG. 3.

(14) .sup.1H NMR (400.13 MHz, 300 K, benzene-d.sub.6): δ=0.51 (s, 12H, SiMe.sub.2), 1.88 (s, 12H, Cp.sup.R-Me), 2.22 (s, 12H, Cp.sup.R-Me);

(15) .sup.13C{.sup.1H}NMR (100.61 MHz, 300 K, benzene-d.sub.6): δ=0.2 (s, Si—CH.sub.3), 11.6 (s, Cp.sup.R—CH.sub.3), 15.2 (s, Cp.sup.R—CH.sub.3), 102.0, 124.2, 135.4 (Cp.sup.R—C);

(16) .sup.29Si{.sup.1H}NMR (79.49 MHz, 300 K, benzene-d.sub.6): δ=−22.0 (SiMe.sub.2), −268.2 (SiCp.sup.R).