LIQUID COMPOSITION CONTAINING AMINOETHER FOR DEPOSITION OF METAL-CONTAINING FILMS

• US 20110212629A1
• Filed: 08/30/2010
• Published: 09/01/2011
• Est. Priority Date: 09/08/2009
• Status: Active Grant

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Spence, Daniel P., Matz, Laura M., Lei, Xinjian, Ivanov, Sergei Vladimirovich, Norman, John Anthony Thomas
• Granted Patent: US 8,507,704 B2
• Time in Patent Office: Days
• US Class Current: 438/778
• CPC Class Codes: C09D 1/00 Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/404 of alkaline earth metals
• CPC Class Codes: C23C 16/448 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials

Abstract

A formulation, comprising: a) at least one metal-ligand complex, wherein one or more ligands are selected from the group consisting of β-diketonates, β-ketoiminates, β-ketoesterates, β-diiminates, alkyls, carbonyls, alkyl carbonyls, cyclopentadienyls, pyrrolyls, alkoxides, amidinates, imidazolyls, and mixtures thereof; and the metal is selected from Group 2 to 16 elements of the Periodic Table of the Elements; and, b) at least one aminoether selected from the group consisting of R¹R²NR³OR⁴NR⁵R⁶, R¹OR⁴NR⁵R⁶, O(CH₂CH₂)₂NR¹, R¹R²NR³N(CH₂CH₂)₂O, R¹R²NR³OR⁴N(CH₂CH₂)₂O, O(CH₂CH₂)₂NR¹OR²N(CH₂CH₂)₂O, and mixtures thereof, wherein R^1-6 are independently selected from group consisting of C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic, C_1-10 alkylamine, C_1-10 alkylaminoalkyl, C_1-10 ether, C₄-C₁₀ cyclic ether, C₄-C₁₀ cyclic aminoether, and mixture thereof.

Claims

1. A formulation, comprising:

a) at least one metal-ligand complex, wherein one or more ligands are selected from the group consisting of β

-diketonates, β

-ketoiminates, β

-ketoesterates, β

-diiminates, alkyls, carbonyls, alkyl carbonyls, cyclopentadienyls, pyrrolyls, alkoxides, amidinates, imidazolyls, and mixtures thereof; and

the metal is selected from Group 2 to 16 elements of the Periodic Table of the Elements; and

, b) at least one aminoether selected from the group consisting of R¹R²NR³OR⁴NR⁵R⁶, R¹OR⁴NR⁵R⁶, O(CH₂C₂)₂NR¹, R¹R²NR³N(CH₂CH₂)₂O, R¹R²NR³OR⁴N(CH₂CH₂)₂O, O(CH₂CH₂)₂NR¹OR²N(CH₂CH₂)₂O, and mixtures thereof, wherein R^1-6 are independently selected from group consisting of C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic, C_1-10 alkylamine, C_1-10 alkylaminoalkyl, C_1-10 ether, C₄-C₁₀ cyclic ether, C₄-C₁₀ cyclic aminoether, and mixture thereof.

2. The formulation of claim 1 wherein the ligand of the metal-ligand complex is selected from the group consisting of monodentate, bidentate, multidentate and mixtures thereof.

3. The formulation of claim 1 wherein the formulation is in the liquid phase.

4. The formulation of claim 1 wherein the formulation comprises aminoethers with a general formula of:

R¹R²NR³OR⁴NR⁵R⁶, wherein R¹-R⁶ are independently selected from group consisting of C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic.

5. The formulation of claim 1 wherein the formulation comprises aminoethers with a general formula of:

R¹OR⁴NR⁵R⁶, wherein R^1-6 are selected independently from the group consisting of C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic.

6. The formulation of claim 1 wherein the formulation comprises cyclic aminoethers with a general formula:

O(CH₂CH₂)₂NR¹, wherein R¹ is C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic.

7. The formulation of claim 1 wherein the formulation comprises cyclic aminoethers with a general formula:

R¹R²NR³N(CH₂CH₂)₂O, wherein R^1-4 are individually;

C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic.

8. The formulation of claim 1 wherein the formulation comprises cyclic aminoethers with a general formula:

R¹R²NR³OR⁴N(CH₂CH₂)₂O, wherein R^1-4 are individually;

C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl, C₆-C₁₀ aromatic.

9. The formulation of claim 1 wherein the formulation comprises cyclic aminoethers with a general formula:

O(CH₂CH₂)₂NR¹OR²N(CH₂CH₂)₂O, wherein R^1-2 are individually;

C_1-10 linear alkyl, C_1-10 branched alkyl, C_1-10 cyclic alkyl.

10. The formulation of claim 1 wherein the aminoether is selected from the group consisting of:

11. The formulation of claim 4 wherein the metal-ligand complex is selected from the group consisting of:

(a) metal β

-diketonates having the formula;

12. The formulation of claim 1 wherein the aminoether is selected from the group consisting of 2,2′

-oxybis(N,N-dimethylethanamine), 4-[2-(dimethylamino)ethyl]morpholine, and mixtures thereof.

13. The formulation of claim 12 wherein the aminoether is 2,2′

-oxybis(N,N-dimethylethanamine) having less than 20 ppm of water.

14. The formulation of claim 12 wherein the aminoether is 2,2′

-oxybis(N,N-dimethylethanamine) having less than 100 ppm of additional compounds containing hydroxyl or amine functionality.

16. The formulation of claim 1 in a stainless steel vessel.

17. The formulation of claim 16 wherein the vessel'"'"'s interior is electropolished.

18. The formulation of claim 16 wherein the vessel has an inlet valve and an outlet valve.

19. The formulation of claim 18 wherein the valves are automatic actuated valves.

20. The formulation of claim 19 wherein the valves are pneumatic actuated valves.

21. The formulation of claim 19 wherein the valves are electric solenoid actuated valves.

22. The formulation of claim 16 wherein the vessel has a diptube.

23. The formulation of claim 22 wherein the diptube is the outlet.

24. The formulation of claim 22 wherein the diptube is the inlet.

25. The formulation of claim 1 including a chemical stabilizer.

26. The formulation of claim 25 wherein the stabilizer is a free radical scavenger.

27. The formulation of claim 25 wherein the stabilizer is a polymerization inhibitor.

28. The formulation of claim 25 wherein the stabilizer is an antioxidant.

29. The formulation of claim 1 having a viscosity less than 50 cP.

30. The formulation of claim 1 comprising 2,2′

-oxybis(N,N-dimethylethanamine) and lanthanum complex selected from a group consisting of LaCp₃, La(MeCp]₃, La(EtCp)₃, or La(ⁱPrCp)₃

31. The formulation of claim 1 comprising bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′

)strontium and 2,2′

-oxybis(N,N-dimethylethanamine).

32. The formulation of claim 1 comprising bis(2,2-dimethyl-5-(1-dimethylamino-2-propylimino)-3-hexanonato-N,O,N′

)strontium and 2,2′

-oxybis(N,N-dimethylethanamine).

33. The formulation of claim 1 comprising Sr(^tBu₃Cp)₂ and 2,2′

-oxybis(N,N-dimethylethanamine).

34. The formulation of claim 1 comprising Ba(^tBu₃Cp)₂ and 2,2′

-oxybis(N,N-dimethylethanamine).

35. The formulation of claim 1 comprising Sr(ⁱPr₃Cp)₂ and 2,2′

-oxybis(N,N-dimethylethanamine).

36. The formulation of claim 1 comprising Ba(ⁱPr₃Cp)₂ and 2,2′

-oxybis(N,N-dimethylethanamine).

37. A process for depositing a metal-containing film by chemical vapor deposition or atomic layer deposition comprising contacting a substrate under conditions to deposit a metal-containing film from a formulation of claim 1 and depositing such metal-containing film.

38. A process for depositing a metal-containing film by chemical vapor deposition or atomic layer deposition comprising contacting a substrate under conditions to deposit a metal-containing film from a formulation of claim 10 and depositing such metal-containing film.

39. A process for depositing a metal-containing film by chemical vapor deposition or atomic layer deposition comprising contacting a substrate under conditions to deposit a metal-containing film from a formulation of claim 11 and depositing such metal-containing film.

40. The process of claim 37 wherein the formulation is delivered by direct liquid injection through a vaporizer.

15. A liquid formulation useful for deposition of metal-containing thin films in making semiconductor devices, comprising;

a) at least one metal-ligand complex selected from the group consisting of bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′

)strontium, bis(2,2-dimethyl-5-(1-dimethylamino-2-propylimino)-3-hexanonato-N,O,N′

)strontium, bis(2,2-dimethyl-5-(dimethylaminoethyl-imino)-3-hexanonato-N,O,N′

)bis(tert-butoxy)titanium, tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium (IV), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum, Sr(^tBu₃Cp)₂, Ba(^tBu₃Cp)₂, Sr(ⁱPr)₃Cp)₂, Ba(ⁱPr₃Cp)₂, LaCp₃, La(MeCp)₃, La(EtCp)₃, La(ⁱPrCp)₃, zirconium tert-butoxide, bis(2-tert-butyl-4,5-di-tert-amylimidazolyl)strontium, bis(2-tert-butyl-4,5-di-tert-amylimidazolyl)barium, bis(2,5-di-tert-butyl-pyrrolyl)strontium, bis(2,5-di-tert-butyl-pyrrolyl)barium, Ru(EtCp)₂, Ru(EtCp)(DMPD) and mixtures thereof; and

,

b) at least one aminoether selected from the group consisting of 2,2′

-oxybis(N,N-dimethylethanamine), 4-[2-(dimethylamino)ethyl]morpholine, and mixtures thereof.