METHOD OF FORMING RUTHENIUM FILM FOR METAL WIRING STRUCTURE

• US 20080054472A1
• Filed: 09/01/2006
• Published: 03/06/2008
• Est. Priority Date: 09/01/2006
• Status: Active Grant

• Current Assignee: ASM Japan K.K. (ASM International NV)
• Original Assignee: ASM Japan K.K. (ASM International NV)
• Inventors: INOUE, Hiroaki, SHINRIKI, Hiroshi
• Granted Patent: US 7,435,484 B2
• Time in Patent Office: Days
• US Class Current: 257/762
• CPC Class Codes: C23C 16/02 Pretreatment of the material to be coated C23C16/04 takes precedence
• CPC Class Codes: C23C 16/0245 by etching with a plasma
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/76814 post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76873 for electroplating
• CPC Class Codes: H01L 2221/1089 Stacks of seed layers
• CPC Class Codes: H01L 23/53238 Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 23/53295 Stacked insulating layers
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: Y10T 428/12875 Platinum group metal-base component
• CPC Class Codes: Y10T 428/12903 Cu-base component
• CPC Class Codes: Y10T 428/265 1 mil or less

Abstract

A method of depositing a ruthenium(Ru) thin film on a substrate in a reaction chamber, includes: (i) supplying a gas of a ruthenium precursor into the reaction chamber so that the gas of the ruthenium precursor is adsorbed onto the substrate, wherein the ruthenium precursor a ruthenium complex contains a non-cyclic dienyl; (ii) supplying an excited reducing gas into the reaction chamber to activate the ruthenium precursor adsorbed onto the substrate; and (iii) repeating steps (i) and (ii), thereby forming a ruthenium thin film on the substrate.

Claims

1. A method of depositing a ruthenium(Ru) thin film on a substrate in a reaction chamber, comprising:

(i) supplying a gas of a ruthenium precursor into the reaction chamber so that the gas of the ruthenium precursor is adsorbed onto the substrate, said ruthenium precursor a ruthenium complex containing a non-cyclic dienyl;

(ii) supplying an excited reducing gas into the reaction chamber to activate the ruthenium precursor adsorbed onto the substrate; and

(iii) repeating steps (i) and (ii), thereby forming a ruthenium thin film on the substrate.

2. The method according to claim 1, wherein the ruthenium complex has a structure of Xa-Ru-Xb, wherein at least one of Xa or Xb is a non-cyclic dienyl.

3. The method according to claim 2, wherein the non-cyclic dienyl is a non-cyclic pentadienyl.

4. The method according to claim 3, wherein the non-cyclic pentadienyl has at least one side chain of C1-2 alkyl.

5. The method according to claim 4, wherein the non-cyclic pentadienyl has two side chains of methyl.

6. The method according to claim 2, wherein Xa is a non-cyclic dienyl, and Xb is a cyclic dienyl.

7. The method according to claim 6, wherein Xa is a non-cyclic pentadienyl and Xb is a cyclopentadienyl.

8. The method according to claim 2, wherein Xa and Xb are both non-cyclic pentadienyls.

9. The method according to claim 1, wherein the excited reducing gas is generated by applying radio-frequency power to a reducing gas.

10. The method according to claim 9, wherein the reducing gas is ammonia, hydrogen, or a mixture of nitrogen and hydrogen.

11. The method according to claim 9, wherein the excited reducing gas is an ammonia or hydrogen plasma.

12. The method according to claim 1, further comprising purging the ruthenium precursor gas from the reaction chamber after step (i) and purging the excited reducing gas from the reaction chamber after step (ii).

13. The method according to claim 1, wherein steps (i) and (ii) are repeated to form the ruthenium thin film having a thickness of no less than 0.5 nm but no more than 2.0 nm.

14. The method according to claim 1, wherein steps (i) and (ii) are repeated to form the ruthenium thin film having a thickness of no less than 0.5 nm but no more than 2.0 nm.

15. The method according to claim 1, wherein steps (i) and (ii) are repeated 50 times to 150 times.

16. The method according to claim 1, further comprising providing a metal film before steps (i)-(iii) begin wherein the ruthenium thin film is formed on the metal film.

17. The method according to claim 16, wherein the metal film is selected from the group consisting of WNC, WN, TaN, Ta, TaNC, TiN, Ti, Cu, Al, Co, and Ni.

18. The method according to claim 1, wherein in step (i), the gas of the ruthenium precursor is a first gas, and step (i) further comprises supplying a second gas of another ruthenium precursor into the reaction chamber simultaneously with the first gas.

19. The method according to claim 1, further comprising after repeating steps (i) and (ii) a give number of times:

(iv) supplying a second gas of another ruthenium precursor into the reaction chamber so that the second gas of the other ruthenium precursor is adsorbed onto the substrate;

(v) supplying an excited reducing gas into the reaction chamber to activate the other ruthenium precursor adsorbed onto the substrate; and

(vi) repeating steps (iv) and (v), thereby forming a ruthenium thin film on the substrate.

20. The method according to claim 1, further comprising after step (iii) forming a ruthenium thin film or ruthenium oxide thin film on the ruthenium thin film by CVD.

21. The method according to claim 1, further comprising after step (iii) forming a copper film on the ruthenium thin film.

22. The method according to claim 21, wherein the copper film is formed by supplying a gas of a copper precursor on the substrate, which is produced by CVD or ALD.

23. A ruthenium thin film-formed structure comprising:

a substrate;

a ruthenium thin film formed on the substrate, which is continuous without pinholes and has a thickness of no less than 0.5 nm but no more than 2.0 nm.

24. The ruthenium thin film-formed structure according to claim 23, wherein the ruthenium thin film is formed with a ruthenium complex containing a non-cyclic dienyl.

25. The ruthenium thin film-formed structure according to claim 23, wherein the substrate has a metal film, and the ruthenium thin film is formed on the metal film.

26. The ruthenium thin film-formed structure according to claim 25, wherein the metal film is selected from the group consisting of WNC, WN, TaN, Ta, TaNC, TiN, Ti, Cu, Al, Co, and Ni.

27. The ruthenium thin film-formed structure according to claim 23, further comprising a copper film on the ruthenium thin film.

28. The ruthenium thin film-formed structure according to claim 27, wherein the copper film is formed by CVD or plating.