Deposition of ruthenium and/or ruthenium oxide films

• US 20060013955A1
• Filed: 07/11/2005
• Published: 01/19/2006
• Est. Priority Date: 07/09/2004
• Status: Abandoned Application

• Current Assignee: Avid Technology Incorporated
• Original Assignee: Avid Technology Incorporated
• Inventors: Senzaki, Yoshihide
• Application Number:
  US11/179,078
• Publication Number:
  US 20060013955A1
• Time in Patent Office: Days
• US Class Current: 427/248.100
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/406 of iron group metals
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD

Abstract

The present invention relates generally to methods for depositing ruthenium and/or ruthenium oxide films in the formation of semiconductor devices. More specifically, the present invention provides methods for deposition of ruthenium containing metal and metal-oxygen based films on the surface of a substrate.

Claims

1. A method of forming a ruthenium-containing film on the surface of a substrate, characterized in that:

a first precursor containing at least one ruthenium atom is converted from a liquid state to a gaseous state;

said gaseous state of said first precursor is conveyed to a process chamber and forms a monolayer on the surface of the substrate;

excess amounts of the first precursor are removed from the process chamber;

at least one oxygen-containing reactant is conveyed to the process chamber and reacts with the monolayer of the first precursor to form a ruthenium metal-containing material; and

excess amounts of the activated oxygen-containing reactant are removed from the process chamber.

2. The method of claim 1 wherein, the substrate surface is selected from semiconductor materials, compound semiconductor materials, silicon, plastics, polymers, metals, alloys, organics, inorganics, and mixtures thereof.

3. The method of claim 1 wherein the first precursor is selected from any one or more of:

Ru₃(CO)₁₂

Ru(CO)₄L, where L is (CF₃)CC(CF₃)

Ru(CO)₃(COD), where COD is cyclooctadiene

Ru(β

-diketonate)₃, Ru(thd)₃, (where thd is tetramethylheptadionate)

Ru(OR)₃, where R is C1-C6 carbons

RuX₃, where X is a halogen atom such as Cl, F, Br, and I

Ru(RCp)(R′

Cp), where R and R′

are H or C1-C6 carbons

Ru(RCp)R″

, where R is H, or C1-C6 carbons, and R″

is C3 to C10 carbons, and mixtures thereof.

4. The method of claim 1, wherein said oxygen-containing reactant is selected from any one or more of:

oxygen, water, peroxides, air, nitrous oxide, nitric oxide, H₂O₂, and mixtures thereof.

5. The method of claim 1, wherein the oxygen-containing reactant activated, and is selected from any one or more of:

ozone, singlet oxygen, triplet oxygen, atomic oxygen, excited species of O, OH, NO, and mixtures thereof.

6. The method of claim 1, wherein the partial pressure of the oxygen-containing reactant is selected to result in the deposition of a ruthenium film on the surface of the substrate.

7. The method of claim 1, wherein the partial pressure of the oxygen-containing reactant is selected to result in the deposition of a conductive ruthenium oxide film on the surface of the substrate.

8. The method of claim 1, wherein said film forming method is carried out at a temperature in the range of approximately 20 to 800°

C.

9. The method of claim 1, wherein said film forming method is carried out at a temperature in the range of approximately 20 to 270°

C.

10. The method of claim 1, wherein said process chamber is at a pressure in the range of approximately 0.001 mTorr to 600 Torr.

11. The method of claim 1, wherein said process chamber is at a pressure in the range of approximately 10 mTorr to 5 Torr.

12. The method of claim 1, wherein the total gas flow rate to the process chamber comprising the conveying of the first precursor, the oxygen-containing reactant, and additional purge gases during any single step is in the range of approximately 0 to 20,000 sccm.

13. The method of claim 1, wherein said process chamber is configured to house a single substrate.

14. The method of claim 1, wherein said process chamber is configured to house a plurality of substrates.

15. The method of claim 14, wherein the plurality of substrates numbers between 1 and 200.

16. The method of claim 14, wherein the plurality of substrates numbers between 1 and 150.

17. The method of claim 14, wherein the plurality of substrates numbers between 1 and 100.

18. The method of claim 14, wherein the plurality of substrates numbers between 1 and 50.

19. The method of claim 14, wherein the plurality of substrates numbers between 1 and 25.

20. The method of claim 1 wherein the first precursors is of the formula Ru(CpR)₂, where R is an alkyl group and Cp is cyclopentadiene.

21. A method of forming a ruthenium-containing film on the surface of a substrate, characterized in that one or more ruthenium-containing precursors selected from any one or more of:

Ru(CpR)₂, where R is an alkyl group and Cp is cyclopentadiene Ru₃(CO)₁₂;

Ru(CO)₄L, where L is (CF₃)CC(CF₃);

Ru(CO)₃(COD), where COD is cyclooctadiene;

Ru(β

-diketonate)₃;

Ru(thd)₃, (where thd is tetramethylheptadionate);

Ru(OR)₃, where R is C1-C6 carbons;

RuX₃, where X is a halogen atom such as Cl, F, Br, and I;

Ru(RCp)(R′

Cp), where R and R′

are H or C1-C6 carbons;

Ru(RCp)R″

, where R is H, or C1-C6 carbons, and R″

is C3 to C10 carbons, and mixtures thereof,

are conveyed to a process chamber in a vaporous state to form a monolayer of the ruthenium-containing precursor on the surface of one or more substrates, and subsequently one or more oxygen-containing precursors are conveyed to the process chamber and interact with the monolayer to form a ruthenium metal or ruthenium metal oxide layer on the substrate.