IP Library Granted Patent US 7,521,405
Granted Patent B2
US 7,521,405 · App. 10/804,513 · Granted Apr 21, 2009

Process solutions containing surfactants

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Quick Facts
Patent No.
US 7,521,405
App. No.
10/804,513
Granted
Apr 21, 2009
Kind
B2
Abstract

Process solutions comprising one or more surfactants are used to reduce the number of defects in the manufacture of semiconductor devices. In certain embodiments, the process solution may reduce post-development defects such as pattern collapse or line width roughness when employed as a rinse solution either during or after the development of the patterned photoresist layer. Also disclosed is a method for reducing the number of defects such as pattern collapse and/or line width roughness on a plurality of photoresist coated substrates employing the process solution of the present invention.

Claims (54)

1. A process rinse solution to reduce at least one defect selected from pattern collapse and line width roughness on the surface of a substrate that has been patterned and developed, the solution comprising an aqueous solvent, a non-aqueous solvent, and at least one surfactant selected from the group of surfactants having the formula (IVa), (IVb), (V), (VII), (IXc), (Xa), or (Xd):

wherein R, R 1 , R 4 , and R 12 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; R 5 is a straight, a branched, or a cyclic alkyl group having from 1 to 10 carbon atoms; R 10 is a hydrogen atom or a group represented by the formula

R 11 is a straight, a branched, or a cyclic alkyl group having from 4 to 22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y are each independently a hydrogen atom or a hydroxyl group; i, m, and n, are each independently a number that ranges from 0 to 20; r and s are each independently 2 or 3; t is a number that ranges from 0 to 2; j is a number that ranges from 1 to 5; and x is a number that ranges from 1 to 6.

2. The process solution of claim 1 wherein the non-aqueous solvent is miscible in the aqueous solvent.

3. The process solution of claim 1 wherein the at least one surfactant is a surfactant having the following formula (IVa):

wherein R 1 and R 4 are each independently a straight or a branched alkyl group having from 3 to 25 carbon atoms and r and s are each independently 2 or 3.

4. The process solution of claim 1 wherein the at least one surfactant is a surfactant having the following formula (IVb):

wherein R 1 and R 4 are each independently a straight or a branched alkyl group having from 3 to 25 carbon atoms and r is 2 or 3.

5. The process solution of claim 1 wherein the at least one surfactant is a surfactant having the following formula (V):

wherein R 1 and R 4 are each independently a straight or branched alkyl group having from 3 to 25 carbon atoms and X and Y are each independently a hydrogen atom or a hydroxyl group.

6. The process solution of claim 1 wherein the at least one surfactant is a surfactant having the following formula (VIII):

wherein R 10 is a hydrogen atom or a group represented by the formula

R 11 is independently a straight, branched, or cyclic alkyl group having from 4 to 22 carbon atoms; r and s are each independently 2 or 3; and x is a number that ranges from 1 to 6.

7. The process solution of claim 1 wherein the at the at least one surfactant is a surfactant having the following formula (IXc):

wherein R 1 , R 4 , and R 12 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms.

8. The process solution of claim 1 wherein the at the at least one surfactant is a surfactant having the following formula (Xa):

R 1 —NH(CH 2 CH 2 O) m H  Xa

wherein R 1 is a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; and m is a number that ranges from 0 to 20.

9. The process solution of claim 1 wherein the at the at least one surfactant is a surfactant having the following formula (Xd):

wherein R is independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; and i, m, and n are each independently a number ranging from 0 to 20.

10. The process solution of claim 1 wherein the non-aqueous solvent is at least one seleced from the group consisting of: ethylether, ethylene glycol monomethyl ether, 2-methoxyethyl ether, a nitrile, lactates, pyruvates, diols, tetrahydrofuran, acetone, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, cyclohexanone, acetone, 1-methyl-2-pyrodidianone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, N-methyl pyrrolidone, ethylene carbonate, propylene carbonate, glycerol and derivatives, acetic acid anyhydride, propionic acid and propionic acid anhydride, dimethyl sulfone, benzophenone, diphenyl sulfone, phenol, m-cresol, dimethyl sulfoxide, diphenyl ether, propylene glycol propyl ether, methanol, ethanol, 3-heptanol, 2-methyl-1-pentanol, 5-methyl-2-hexanol, 3-hexanol, 2-heptanol, 2-hexanol, 2,3-dimethyl-3-pentanol, propylene glycol methyl ether acetate, ethylene glycol, isopropyl alcohol, n-butyl ether, propylene glycol n-butyl ether, 1-butoxy-2-propanol, 2-methyl-3-pentanol, 2-methoxyethyl acetate, 2-butoxyethanol, 2-ethoxyethyl acetoacetate, 1-pentanol, and propylene glycol methyl ether.

11. The process solution of claim 1 further comprising at least one surfactant selected from the group consisting of formula (I) and (II):

wherein p and q are each independently a number from 0 to 20.

12. A process rinse solution to reduce at least one defect selected from pattern collapse and line width roughness on the surface of a substrate that has been patterned and developed, the solution consisting of an aqueous solvent, a non-aqueous solvent, and at least one surfactant selected from the group of surfactants having the formula (IVa), (lVb), (V), (VIII), (IXa), (IXb), (IXc), (Xa), (Xb), (Xc), or (Xd):

wherein R, R 1 , R 4 , and R 12 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; R 2 is a hydrogen atom or a straight, a branched, or a cyclic alkyl group having from 1 to 5 carbon atoms; R 5 is a straight, a branched, or a cyclic alkyl group having from 1 to 10 carbon atoms; R 10 is a hydrogen atom or a group represented by the formula

R 11 is a straight, a branched, or a cyclic alkyl group having from 4 to 22 carbon atoms; W is a hydrogen atom or an alkynyl group; X and Y are each independently a hydrogen atom or a hydroxyl group; i, m, and n are each independently a number that ranges from 0 to 20; r and s are each independently 2 or 3; t is a number that ranges from 0 to 2; j is a number that ranges from 1 to 5; and x is a number that ranges from 1 to 6.

13. The process solution of claim 12 wherein the non-aqueous solvent is miscible in the aqueous solvent.

14. The process solution of claim 12 wherein the at least one surfactant is a surfactant having the following formula (IVa):

wherein R 1 and R 4 are each independently a straight or a branched alkyl group having from 3 to 25 carbon atoms and r and s are each independently 2 or 3.

15. The process solution of claim 12 wherein the at least one surfactant is a surfactant having the following formula (IVb):

wherein R 1 and R 4 are each independently a straight or a branched alkyl group having from 3 to 25 carbon atoms and r is 2 or 3.

16. The process solution of claim 12 wherein the at least one surfactant is a surfactant having the following formula (V):

wherein R 1 and R 4 are each independently a straight or branched alkyl group having from 3 to 25 carbon atoms and X and Y are each independently a hydrogen atom or a hydroxyl group.

17. The process solution of claim 12 wherein the at least one surfactant is a surfactant having the following formula (VIII):

wherein R 10 is a hydrogen atom or a group represented by the formula

R 11 is independently a straight, branched, or cyclic alkyl group having from 4 to 22 carbon atoms; r and s are each independently 2 or 3; and x is a number that ranges from 1 to 6.

18. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (IXa):

R 1 —NH 2   IXa

wherein R, is a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms.

19. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (IXb):

R 1 —N—R 4   IXb

wherein R 1 and R 4 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms.

20. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (IXc):

wherein R 1 , R 4 , and R 12 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms.

21. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (Xa):

R 1 —NH(CH 2 CH 2 O) m H  Xa

wherein R 1 is a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; and m is a number that ranges from 0 to 20.

22. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (Xb):

wherein R 1 and R 2 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; and m and n are each independently a number that ranges from 0 to 20.

23. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (Xc):

wherein R 1 and R 2 are each independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; and m is a number that ranges from 0 to 20.

24. The process solution of claim 12 wherein the at the at least one surfactant is a surfactant having the following formula (Xd):

wherein R is independently a straight, a branched, or a cyclic alkyl group having from 3 to 25 carbon atoms; and i, m, and n are each independently a number ranging from 0 to 20.

25. The process solution of claim 12 wherein the non-aqueous solvent is at least one seleced from the group consisting of: ethylether, ethylene glycol monomethyl ether, 2-methoxyethyl ether, a nitrile, lactates, pyruvates, diols, tetrahydrofuran, acetone, 1,4-dioxane, 1,3-dioxolane, ethyl acetate, cyclohexanone, acetone, 1-methyl-2-pyrodidianone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, N-methyl pyrrolidone, ethylene carbonate, propylene carbonate, glycerol and derivatives, acetic acid anyhydride, propionic acid and propionic acid anhydride, dimethyl sulfone, benzophenone, diphenyl sulfone, phenol, m-cresol, dimethyl sulfoxide, diphenyl ether, propylene glycol propyl ether, methanol, ethanol, 3-heptanol, 2-methyl-1-pentanol, 5-methyl-2-hexanol, 3-hexanol, 2-heptanol, 2-hexanol, 2,3-dimethyl-3-pentanol, propylene glycol methyl ether acetate, ethylene glycol, isopropyl alcohol, n-butyl ether, propylene glycol n-butyl ether, 1-butoxy-2-propanol, 2-methyl-3-pentanol, 2-methoxyethyl acetate, 2-butoxyethanol, 2-ethoxyethyl acetoacetate, 1-pentanol, and propylene glycol methyl ether.

Assignments (8)
CHANGE OF LEGAL ENTITY Recorded Jul 27, 2020
From: AZ ELECTRONIC MATERIALS S.À R.L.
To: AZ ELECTRONIC MATERIALS GMBH
Reel/Frame 053323/0760 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 27, 2020
From: AZ ELECTRONIC MATERIALS GMBH
To: MERCK PATENT GMBH
Reel/Frame 053323/0770 →
MERGER Recorded Jul 27, 2020
From: AZ ELECTRONIC MATERIALS (LUXEMBOURG) S.À R.L.
To: RIDGEFIELD ACQUISITION
Reel/Frame 053324/0198 →
MERGER Recorded Jul 27, 2020
From: RIDGEFIELD ACQUISITION
To: AZ ELECTRONIC MATERIALS S.À R.L.
Reel/Frame 053323/0591 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 20, 2017
From: AIR PRODUCTS AND CHEMICALS, INC.
To: VERSUM MATERIALS US, LLC
Reel/Frame 041772/0733 →
CHANGE OF ADDRESS Recorded Jan 12, 2017
From: AZ ELECTRONIC MATERIALS (LUXEMBOURG) S.À R.L.
To: AZ ELECTRONIC MATERIALS (LUXEMBOURG) S.À R.L.
Reel/Frame 041345/0585 →
CHANGE OF ADDRESS Recorded Jul 15, 2014
From: AZ ELECTRONIC MATERIALS (LUXEMBOURG) S.A.R.L.
To: AZ ELECTRONIC MATERIALS (LUXEMBOURG) S.A.R.L.
Reel/Frame 033329/0264 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 10, 2012
From: AIR PRODUCTS AND CHEMICALS, INC.
To: AZ ELECTRONIC MATERIALS (LUXEMBOURG) S.A.R.L.
Reel/Frame 028191/0393 →