Process for the generation of metal- or semimetal-containing 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. It relates to a process for preparing 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 with the deposited metal- or semimetal-containing compound in contact with compound of general formula (II), (III), or (IV), wherein E is Ge or Sn, R is an alkyl group, an alkenyl group, an aryl group, or a silyl group, R′ are an alkyl group, an alkenyl group, an aryl group, or a silyl group, X is nothing, hydrogen, a halide, an alkyl group, an alkylene group, an aryl group, an alkoxy group, an aryl oxy group, an amino group, or a amidinate group, or an guanidinate group, L is an alkyl group, an alkenyl group, an aryl group, or a silyl group. ##STR00001##

Claims

1. Process for preparing 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 with the deposited metal- or semimetal-containing compound in contact with a compound of general formula (II), (III), or (IV) ##STR00008## wherein E is Ge or Sn, R is an alkyl group, an alkenyl group, an aryl group, or a silyl group, R′ are an alkyl group, an alkenyl group, an aryl group, or a silyl group, X is nothing, hydrogen, a halide, an alkyl group, an alkylene group, an aryl group, an alkoxy group, an aryl oxy group, an amino group, or an amidinate group, or a guanidinate group, L is an alkyl group, an alkenyl group, an aryl group, or a silyl group, wherein compound of the compound of general formula (II) is a compound of general formula (IIa), (IIc), (IIf) or (IIg) ##STR00009## wherein R′ is an alkyl group, an alkenyl group, an aryl group, or a silyl group.

2. The process according to claim 1, wherein the compound of general formula (II), (III), or (IV) is a compound of general formula (IIa), (IIc), (IIf) or (IIg).

3. The process according to claim 1, wherein the compound of general formula (III) is a compound of general formula (IIIa) or (IIIb) ##STR00010##

4. The process according to claim 1, wherein the compound of general formula (IV) a compound of general formula (IVa) or (IVb) ##STR00011##

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

6. The process according to claim 1, wherein the compound of general formula (II), (III), or (IV) has a molecular weight of not more than 600 g/mol.

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

8. The process according to claim 1, wherein (a) and (b) are successively performed at least twice.

9. The process according to claim 1, wherein the metal- or semimetal-containing compound contains Ti, Ta, Mn, Mo, W, Ge, Ga, As or Al.

10. The process according to claim 1, wherein the metal- or semimetal-containing compound is a metal or semimetal halide.

11. The process according to claim 1, wherein the metal- or semimetal-containing compound and the compound of general formula (II), (III), or (IV) are brought into the gaseous state by heating them to a temperature of 20° C. to 200° C.

12. The process according to claim 1, wherein the metal- or semimetal-containing film is a metal or semimetal film, a metal or semimetal nitride film, a metal or semimetal carbide film, a metal or semimetal carbonitride film, a metal or semimetal alloy films, or an intermetallic compound film.

13. The process according to claim 1, wherein the metal- or semimetal-containing film has an electrical conductivity of at least 10.sup.4 S/m.

14. The process according to claim 1, wherein metal- or semimetal-containing film contains in sum less than 5 weight-% nitrogen.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows the thermogravimetry (TG) and the differential thermogravimetry (DTG) curves of compound IIc-1.

(2) FIG. 2 shows the thermogravimetry (TG) and the differential thermogravimetry (DTG) curves of compound IIc-3.

(3) FIG. 3 shows the thermogravimetry (TG) and the differential thermogravimetry (DTG) curves of compound IIg-3.

EXAMPLES

(4) All manipulations were carried out under a protective atmosphere of argon (purity >99.999%), using Schlenk techniques or in a glovebox. Dioxane was refluxed over Na/benzophenone and distilled before use. Deuterated solvent (C.sub.6D.sub.6) was dried over potassium then distilled under argon. NMR spectra were recorded on a Bruker Avance III 300 MHz spectrometer. High resolution mass spectrum (MS-Cl) was recorded on Finnigan 950S mass spectrometer (methane, 4.7 kV). Germanium dichloride adduct with dioxane was purchased from ABCR and was used without further purification. Starting materials diamine MeN(CH.sub.2CH.sub.2CH.sub.2N(H)SIMe).sub.2 and its di-lithium salt were prepared according to literature procedure: Thomas A. Lowes, Benjamin D. Ward, Robert A. Whannel, Stuart R. Dubberley, Philip Mountford, Chemical Communications, 2005, 113-115.

(5) Synthesis of IIg-3

(6) ##STR00007##

(7) A solution of germanium dichloride adduct with dioxane GeCl.sub.2*dioxane (1.27 g, 5.48 mmol) in dioxane (˜30 mL) was added dropwise to a precooled solution (15° C.) of lithium 2,2,7,12,12-pentamethyl-3,7,11-triaza-2,12-disilatridecane-3,11-diide (1.66 g, 5.50 mmol) in dioxane ˜40 mL. The reaction mixture was stirred overnight at room temperature to give a yellowish solution. All volatiles were removed in vacuo. The remaining residue was extracted with hexane (˜70 mL) and filtered. Solvent was removed in vacuo. A remaining oil was kept in vacuo (4*10.sup.−2 mbar/bath temp. from 60-95° C. for 20 minutes) to afford as a residue compound IIg-3 (1.77 g, 4.91 mmol) as a yellowish oil.

(8) .sup.1H NMR (300.13 MHz, 300 K, CD.sub.6): δ=3.38 (m, 2H, CH.sub.2) 3.08 (m, 2H, CH.sub.2), 2.72 (br, 2H, CH.sub.2), 1.87 (s, 3H, NCH.sub.3), 1.86 (br, 2H, CH.sub.2), 1.25 (m, 4H, CH.sub.2), 0.31 (s, 18H, Si(CH.sub.3).sub.3). .sup.13C{.sup.1H} NMR (75.47 MHz, 300 K, CD.sub.6): δ=57.50, 43.59, 43.54 (NCH.sub.2, NCH.sub.3), 27.80 (NCH.sub.2CH.sub.2), 1.46 (Si(CH.sub.3).sub.3).

(9) HR MS (Cl, m/z): [M+H].sup.+ found 362.1500, calculated for C.sub.13H.sub.34N.sub.3GeSi.sub.2 362.1503.