IP Library Granted Patent US 10,702,893
Granted Patent B2
US 10,702,893 · App. 15/923,116 · Granted Jul 7, 2020

Cleaning compositions for removing residues on semiconductor substrates

Inventors: Joseph Gregory McAlpin (Tempe, AZ); Thomas Dory (Gilbert, AZ)
Assignee: Fujifilm Electronic Materials U.S.A., Inc.
B08B3/08C11D3/0042C11D3/04C11D3/044C11D3/046C11D3/1213C11D3/2006C11D3/2041C11D3/2068C11D3/28C11D3/30C11D3/33C11D3/349C11D3/3409C11D3/43C11D7/06C11D7/10C11D7/20C11D7/261C11D7/263C11D7/3281C11D11/0047H01L21/0206H01L21/02068H01L21/02071C11D3/2048C11D3/3427
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Quick Facts
Patent No.
US 10,702,893
App. No.
15/923,116
Granted
Jul 7, 2020
Kind
B2
Abstract

This disclosure relates to a cleaning composition that contains 1) at least one redox agent; 2) at least one water soluble organic solvent; 3) at least one metal-containing additive; 4) at least one cyclic amine, and 5) water.

Claims (59)

1. A cleaning composition, comprising:

1) at least one redox agent;

2) at least one water soluble organic solvent;

3) at least one metal-containing additive in an amount from about 0.001% by weight to about 0.5% by weight of the composition;

4) at least one cyclic amine; and

5) water.

2. The composition of claim 1 , wherein the composition has a pH from about 7 to about 12.

3. The composition of claim 1 , wherein the at least one cyclic amine comprises a cyclic amine of formula (I):

in which

n is 1, 2, or 3;

m is 1, 2, or 3;

each of R 1 -R 10 , independently, is H, C 1 -C 6 alkyl, or aryl; and

L is —O—, —S—, —N(R a )—, or —C(R a R b )—, in which each of R a and R b , independently, is H, C 1 -C 6 alkyl, or aryl; and

R 11 is H or together with R a forms a second bond between L and the C atom to which R 11 is attached.

4. The composition of claim 3 , wherein the cyclic amine of formula (I) is

5. The composition of claim 1 , wherein the at least one cyclic amine is from about 0.1% by weight to about 2% by weight of the composition.

6. The composition of claim 1 , wherein the at least one redox agent comprises hydroxylamine.

7. The composition of claim 1 , wherein the at least one redox agent is from about 0.5% by weight to about 20% by weight of the composition.

8. The composition of claim 1 , wherein the at least one water soluble organic solvent comprises two organic solvents.

9. The composition of claim 8 , wherein the two organic solvents are each independently selected from the group consisting of alkylene glycols and alkylene glycol ethers.

10. The composition of claim 1 , wherein the at least one water soluble organic solvent is from about 60% by weight to about 95% by weight of the composition.

11. The composition of claim 1 , wherein the at least one metal-containing additive comprises a metal halide, a metal hydroxide, a metal boride, a metal alkoxide, a metal oxide, or a metal-containing ammonium salt.

12. The composition of claim 1 , wherein the at least one metal-containing additive comprises a Group 2A metal, a Group 3B metal, a Group 4B metal, a Group 5B metal, or a lanthanide metal.

13. The composition of claim 12 , wherein the at least one metal-containing additive comprises Ca, Ba, Ti, Hf, Sr, La, Ce, W, V, Nb, or Ta.

14. The composition of claim 1 , wherein the at least one metal-containing additive comprises a tungsten boride, Ca(OH) 2 , BaCl 2 , SrCl 2 , LaCl 3 , CeCl 3 , (NH 4 ) 2 TiF 6 , BaTiO 3 , Ti(OEt) 4 , Ti(OCH(CH 3 ) 2 ) 4 , HfO 2 , V 2 O 5 , Nb 2 O 5 , or TaF 3 .

15. The composition of claim 1 , wherein the at least one metal-containing additive is from about 0.001% by weight to about 0.4% by weight of the composition.

16. The composition of claim 1 , wherein the water is from about 5% by weight to about 28% by weight of the composition.

17. The composition of claim 1 , further comprising a pH adjusting agent, the pH adjusting agent being different from the at least one cyclic amine.

18. The composition of claim 1 , further comprising at least one cleaning additive.

19. The composition of claim 18 , wherein the at least one cleaning additive comprises a sulfur-containing additive.

20. The composition of claim 19 , wherein the sulfur-containing additive comprises a thiol or a thioether.

21. A cleaning composition, comprising:

1) at least one redox agent

2) at least one water soluble organic solvent

3) at least one metal-containing additive;

4) at least one cyclic amine;

5) at least one sulfur-containing additive; and

6) water;

wherein the sulfur-containing additive comprises 3-amino-5-mercapto-1H-1,2,4-triazole, β-mercaptoethanol, 3-amino-5-methylthio-1H-1,2,4-triazole, 1-phenyl-1H-tetrazole-5-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-pyridinethiol, or 3-mercapto-propionic acid.

22. The composition of claim 19 , wherein the sulfur-containing additive is from about 0.01% by weight to about 0.15% by weight of the composition.

23. The composition of claim 18 , wherein the at least one cleaning additive comprises an organic acid.

24. The composition of claim 23 , wherein the organic acid comprises a carboxylic acid or a sulfonic acid.

25. The composition of claim 23 , wherein the at least one organic acid is from about 0.1% by weight to about 0.5% by weight of the composition.

26. The composition of claim 18 , wherein the at least one cleaning additive comprises an amino acid.

27. The composition of claim 26 , A cleaning composition, comprising:

1) at least one redox agent

2) at least one water soluble organic solvent

3) at least one metal-containing additive;

4) at least one cyclic amine;

5) at least one amino acid; and

6) water;

wherein the amino acid is glycine.

28. The composition of claim 26 , wherein the amino acid is from about 0.01% by weight to about 0.15% by weight of the composition.

29. A method, comprising:

contacting a semiconductor substrate containing post etch residues or post ashing residues with a cleaning composition of claim 1 .

30. The method of claim 29 , wherein the semiconductor substrate further comprises a layer comprising a material selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx, ZrOx, HfOx, and TaOx.

31. The method of claim 29 , further comprising rinsing the semiconductor substrate with a rinse solvent after the contacting step.

32. The method of claim 31 , further comprising drying the semiconductor substrate after the rinsing step.

33. The method of claim 29 , further comprising forming a semiconductor device from the semiconductor substrate.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 26, 2020
From: MCALPIN, JOSEPH GREGORY; DORY, THOMAS
To: FUJIFILM ELECTRONIC MATERIALS U.S.A., INC.
Reel/Frame 052749/0017 →
Continuity (2)
Provisional Application 62475947 · Mar 24, 2017
Related Publication 20180272386A1 · Sep 27, 2018