Metal complexes with chelating C-, N-donor ligands for forming metal-containing films

• US 6,214,729 B1
• Filed: 09/01/1998
• Issued: 04/10/2001
• Est. Priority Date: 09/01/1998
• Status: Expired due to Term

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Vaartstra, Brian A., Uhlenbrock, Stefan
• Primary Examiner(s): MEEKS, TIMOTHY HOWARD
• Application Number:
  US09/144,912
• Time in Patent Office: 952 Days
• Field of Search: 427/248.1, 427/250, 427/252, 427/253, 427/249.17, 427/255.29, 427/255.38, 427/255.393, 438/681, 438/683, 438/685, 438/686
• US Class Current: 438/681
• CPC Class Codes: C23C 16/18 from metallo-organic compounds

Abstract

A method of forming a film on a substrate using transition metal or lanthanide complexes. The complexes and methods are particularly suitable for the preparation of semiconductor structures using chemical vapor deposition techniques and systems.

Claims

1. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a precursor composition comprising one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group, with the proviso that R³ and R⁴ are both methyl and optionally the R groups are replaced by multiple bonds between backbone atoms in the structure;

each L group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a silylated hydrocarbyl group, or a halide;

x=1 to 3;

n=0 to 4;

y=0 to 4; and

forming a metal-containing film from the precursor composition on a surface of the semiconductor substrate or substrate assembly.

2. The method of claim 1 wherein the step of forming a metal-containing film comprises vaporizing the precursor composition and directing it toward the semiconductor substrate or substrate assembly using a vaporization technique.

3. The method of claim 2 wherein the vaporization technique comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.

4. The method of claim 1 wherein the semiconductor substrate is a silicon wafer.

5. The method of claim 1 wherein M is selected from the group consisting of Co, Rh, Ir, Fe, Ru, Os, Ni, Pd, and Pt.

6. The method of claim 1 wherein each R¹, R², R⁵, and R⁶ is hydrogen and each R⁷ and R⁸ is a methyl group.

7. The method of claim 1 wherein each R¹ and R² is SiMe₃, each R⁵ and R⁶ is hydrogen, and each R⁷ and R⁸ is a methyl group.

8. The method of claim 1 wherein the precursor composition is a liquid.

9. The method of claim 1 wherein the precursor composition is vaporized in the presence of a reaction gas, an inert carrier gas, or a combination thereof.

10. The method of claim 9 wherein the reaction gas is SiH₄, Si₂H₆, NH₃, N₂H₄, PH₃, AsH₃, GeH₄, t-BuSbMe₂, H₂S, H₂SE, CO, CH₄, or Te(allyl)₂.

11. The method of claim 1 wherein the metal containing film is a single transition metal or a transition metal alloy film.

12. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a precursor composition comprising one or more organic solvents and one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group, with the proviso that R³ and R⁴ are both methyl and optionally the R groups are replaced by multiple bonds between backbone atoms in the structure;

each L group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a silylated hydrocarbyl group, or a halide;

x=1 to 3;

n=0 to 4;

y=0 to 4; and

vaporizing the precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the semiconductor substrate or substrate assembly to form a metal-containing film on a surface of the semiconductor substrate or substrate assembly.

13. The method of claim 12 wherein each R¹, R², R⁵, and R⁶ is hydrogen and each R⁷ and R⁸ is a methyl group.

14. The method of claim 12 wherein each R¹ and R² is SiMe₃, each R⁵ and R⁶ is hydrogen, and each R⁷ and R⁸ is a methyl group.

15. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a precursor composition comprising one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group, with the proviso that R³ and R⁴ are both methyl and optionally the R groups are replaced by multiple bonds between backbone atoms in the structure;

each L group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a silylated hydrocarbyl group, or a halide;

x=1 to 3;

n=0 to 4;

y=0 to 4; and

forming a metal-containing film from the precursor composition on a surface of the substrate.

16. The method of claim 15 wherein the step of forming a metal-containing film comprises vaporizing the precursor composition and directing it toward the substrate using a chemical vapor deposition technique.

17. The method of claim 16 wherein the precursor composition is a liquid.

18. The method of claim 15 wherein each R¹, R², R⁵, and R⁶ is hydrogen and each R⁷ and R⁸ is a methyl group.

19. The method of claim 15 wherein each R¹ and R² is SiMe₃, each R⁵ and R⁶ is hydrogen, and each R⁷ and R⁸ is a methyl group.

20. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a precursor composition comprising one or more organic solvents and one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group, with the proviso that R³ and R⁴ are both methyl and optionally the R groups are replaced by multiple bonds between backbone atoms in the structure;

each L group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a silylated hydrocarbyl group, or a halide;

x=1 to 3;

n=0 to 4;

y=0 to 4; and

vaporizing the precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the substrate to form a metal-containing film on a surface of the substrate.

21. The method of claim 20 wherein each R¹, R², R⁵, and R⁶ is hydrogen and each R⁷ and R⁸ is a methyl group.

22. The method of claim 20 wherein each R¹ and R² is SiMe₃, each R⁵ and R⁶ is hydrogen, and each R⁷ and R⁸ is a methyl group.

23. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a precursor composition comprising one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R¹ and R² group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group; and

forming a metal-containing film from the precursor composition on a surface of the semiconductor substrate or substrate assembly.

24. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a precursor composition comprising one or more organic solvents and one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R¹ and R² group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group; and

vaporizing the precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the semiconductor substrate or substrate assembly to form a metal-containing film on a surface of the semiconductor substrate or substrate assembly.

25. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a precursor composition comprising one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R¹ and R² group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group; and

forming a metal-containing film from the precursor composition on a surface of the substrate.

26. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a precursor composition comprising one or more organic solvents and one or more complexes having a structure of the formula;

 

wherein;

M is a transition metal selected from the group consisting of IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIIIB metals;

each R¹ and R² group is independently H, a hydrocarbyl group, a halogenated hydrocarbyl group, a halide, or a silylated hydrocarbyl group; and

vaporizing the precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the substrate to form a metal-containing film on a surface of the substrate.