Enhanced deposition of noble metals

• US 8,501,275 B2
• Filed: 09/21/2011
• Issued: 08/06/2013
• Est. Priority Date: 03/15/2005
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Haukka, Suvi P., Tuominen, Marko J., Rahtu, Antti
• Primary Examiner(s): MILLER, JR, JOSEPH ALBERT
• Application Number:
  US13/239,090
• Publication Number:
  US 20120189774A1
• Time in Patent Office: 685 Days
• Field of Search: None
• US Class Current: 427/248.1
• CPC Class Codes: C23C 16/0218 in a reactive atmosphere C23C16/0227 takes precedence
• CPC Class Codes: C23C 16/08 from metal halides
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: H01L 21/28562 Selective deposition

Abstract

The invention relates generally to processes for enhancing the deposition of noble metal thin films on a substrate by atomic layer deposition. Treatment with gaseous halides or metalorganic compounds reduces the incubation time for deposition of noble metals on particular surfaces. The methods may be utilized to facilitate selective deposition. For example, selective deposition of noble metals on high-k materials relative to insulators can be enhanced by pretreatment with halide reactants. In addition, halide treatment can be used to avoid deposition on the quartz walls of the reaction chamber.

Claims

1. A method for depositing a noble metal, the method comprising:

contacting a substrate in a reaction chamber comprising quartz walls with a vapor phase reactant comprising a metal halide or metal organic reactant thereby forming a surface termination comprising the metal halide or metal organic on the substrate, wherein the vapor phase reactant does not comprise a noble metal, wherein the substrate and the chamber walls are at the same temperature and wherein the temperature is selected such that the halide or metal organic reacts with the substrate surface but not with the reaction chamber walls;

removing excess vapor phase reactant; and

depositing noble metal on the surface termination comprising the metal halide or metal organic in the quartz reaction chamber by an atomic layer deposition (ALD) process by providing a noble metal reactant and an oxygen reactant.

2. The method of claim 1, wherein the noble metal is preferentially deposited on the substrate relative to the quartz walls of the reaction chamber.

3. The method of claim 1, wherein contacting the substrate with the vapor phase reactant is self limiting.

4. The method of claim 1, wherein the substrate temperature during providing the vapor phase reactant is less than about 300°

C.

5. The method of claim 1, wherein the substrate temperature during depositing noble metal is less than about 300°

C.

6. The method of claim 1, wherein the substrate comprises one or more of HfO₂, Al₂O₃ and silicon.

7. The method of claim 1, wherein the noble metal reactant is a cyclopentadienyl reactant.

8. The method of claim 1, wherein the noble metal is ruthenium.

9. The method of claim 1, wherein the substrate comprises a metal oxide surface.

10. The method of claim 1, wherein the metal organic reactant comprises one or more of:

Sc, Ti, V, Fe, Cr, Mn, Zn, B, C, Al, Si, P, Zr, Nb, Mo, In, Ga, Ge, Sn, Hf, Ta and W.

11. The method of claim 10, wherein the metal organic reactant comprises one or more ligands selected from the group consisting of:

substitued or non-substitued alkyl-, alkylamide-, alkoxide-, amidinate-, aryl-, betadiketonate-, imido-amido- and cyclopentadienyl-compounds.

12. The method of claim 1, wherein the metal organic reactant is one of trimethylaluminum, tetrakis(ethylmethyl)aminohafnium, tetrakis(dimethyl)aminohafnium, tetrakis(diethyl)aminohafnium, tetrakis(ethylmethyl)aminozirconium, tetrakis(dimethyl)aminozirconium and tetrakis(diethyl)aminozirconium.

13. The method of claim 1, wherein the surface termination comprising the metal halide or metal organic is formed on one surface of the substrate and not formed on other surfaces of the substrate.

14. The method of claim 13, wherein the surface termination comprising the metal halide or metal organic is formed on a high-k material on the substrate.

15. The method of claim 1, wherein the substrate temperature is from about 150°

C. to about 300°

C. during providing the vapor phase reactant and depositing the noble metal.

16. The method of claim 1, further comprising contacting the substrate with a scavenging agent after depositing the noble metal on the substrate.

17. The method of claim 16, wherein the scavenging agent comprises hydrogen, hydrogen plasma or radicals, nitrogen and hydrogen plasma or radicals, or ammonia.

18. The method of claim 1, wherein the ALD process comprises alternately and sequentially providing the noble metal reactant and the oxygen reactant until the noble metal is formed to a desired thickness.

19. A method for depositing a film comprising a noble metal on a substrate in a reaction chamber comprising quartz walls the method comprising:

contacting the substrate in the reaction chamber with a vapor phase reactant comprising a metal halide or metal organic compound, wherein the vapor phase reactant does not comprise a noble metal, wherein the substrate and the chamber walls are at the same temperature and wherein the temperature is selected such that the metal halide or metal organic compound reacts with the substrate but does not appreciably react with the walls of the reaction chamber;

removing excess vapor phase reactant; and

depositing the film comprising the noble metal on the substrate surface having the halide or metal organic terminated surface by an atomic layer deposition (ALD) process comprising alternate and sequential pulses of a reactant comprising a noble metal and a reactant comprising oxygen.

20. The method of claim 19, wherein the substrate temperature during depositing the film comprising noble metal is less than about 300°

C.

21. The method of claim 19, wherein the noble metal is preferentially deposited on the substrate relative to the quartz walls of the reaction chamber.

22. The method of claim 19, wherein the substrate temperature during contacting the substrate with the vapor phase reactant is less than about 300°

C.