Enhanced deposition of noble metals

• US 9,587,307 B2
• Filed: 07/24/2013
• Issued: 03/07/2017
• 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
• Application Number:
  US13/950,049
• Publication Number:
  US 20140087076A1
• Time in Patent Office: 1,322 Days
• Field of Search: None
• US Class Current: 1/1
• 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 nitride, carbide or alloy thin film comprising one or more noble metals on a substrate, the method comprising a deposition cycle comprising, in order:

contacting the substrate with a first vapor phase metal reactant comprising a first metal, wherein the vapor phase metal reactant does not comprise a noble metal, such that first reactant species adsorb on the substrate surface;

removing excess first vapor phase metal reactant;

contacting the substrate with a second vapor phase noble-metal reactant comprising a second metal that is a noble metal, such that the second reactant reacts with adsorbed first reactant species on the substrate; and

removing excess second noble-metal reactant,

wherein the deposition cycle forms a monolayer of a nitride, carbide or alloy compound comprising the first metal and second metal and is repeated to form the thin film.

2. The method of claim 1, additionally comprising contacting the substrate with a third vapor phase reactant and removing excess third vapor phase reactant.

3. The method of claim 2, wherein the third vapor phase reactant is a scavenging agent that can remove halide or organic ligands.

4. The method of claim 1, wherein the compound thin film is a noble metal nitride thin film.

5. The method of claim 4, additionally comprising contacting the substrate with a third vapor phase reactant, wherein the third vapor phase reactant contributes nitrogen to the growing film.

6. The method of claim 4, additionally comprising contacting the substrate with a third vapor phase reactant, wherein the third vapor phase reactant does not contribute nitrogen to the growing film.

7. The method of claim 1, wherein the compound thin film is a noble metal carbide thin film.

8. The method of claim 7, additionally comprising contacting the substrate with a third vapor phase reactant, wherein the third vapor phase reactant contributes carbon to the growing film.

9. The method of claim 7, additionally comprising contacting the substrate with a third vapor phase reactant, wherein the third vapor phase reactant does not contribute carbon to the growing film.

10. The method of claim 1, wherein the first vapor phase metal 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 1, wherein the first vapor phase metal reactant is a metal halide reactant.

12. The method of claim 1, wherein the first vapor phase metal reactant is a metalorganic compound.

13. The method of claim 1, wherein the first vapor phase metal reactant adsorbs on the substrate surface in a self-limiting manner.

14. The method of claim 1, wherein the substrate temperature during depositing the compound thin film is less than about 300°

C.

15. An atomic layer deposition process for depositing a film comprising a noble metal compound on a substrate in a reaction chamber comprising multiple deposition cycles, at least one deposition cycle comprising alternately and sequentially contacting the substrate with vapor phase pulses of three reactants:

a first reactant comprising a first metal that is not a noble metal, a second reactant comprising a second metal that is a noble metal and a third reactant comprising nitrogen or carbon,

wherein the at least one deposition cycle forms a monolayer of a compound comprising the first metal and the second metal.

16. The method of claim 15, wherein the third reactant removes halide or organic ligands from the growing film.

17. The method of claim 15, wherein the second reactant is not provided in at least one of the multiple deposition cycles in the atomic layer deposition process.

18. The method of claim 15, wherein the third reactant is not provided in at least one of the multiple deposition cycles in the atomic layer deposition process.