IP Library Granted Patent US 10,072,237
Granted Patent B2
US 10,072,237 · App. 15/227,450 · Granted Sep 11, 2018

Photoresist cleaning composition used in photolithography and a method for treating substrate therewith

View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 10,072,237
App. No.
15/227,450
Granted
Sep 11, 2018
Kind
B2
Abstract

It is disclosed a photoresist cleaning composition for stripping a photoresist pattern having a film thickness of 3-150 μm, which contains (a) quaternary ammonium hydroxide (b) a mixture of water-soluble organic solvents (c) at least one corrosion inhibitor and (d) water, and a method for treating a substrate therewith.

Claims (20)

1. A photoresist cleaning composition for stripping a photoresist pattern having a film thickness of 3-150 μm, which comprises (a) 0.5-5 mass % of at least one quaternary ammonium hydroxide or mixtures of two or more quaternary ammonium hydroxides; (b) 60-97.5 mass % of a mixture of water-soluble organic solvent comprising dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof, and at least one additional organic solvent or two or more additional organic solvents; (c) 0.5-15 mass % of two or more corrosion inhibitors comprising PEI and at least one corrosion inhibitor or a mixture of two or more corrosion inhibitors selected from the group consisting of catechol, tert-butyl catechol, ammonium benzoate, benzoic acid, salicylic acid, citric acid, gallic acid, mono or dihydroxybenzoic acid, diethylhydroxylamine (DEHA), hydroxylamine or dipropylhydroxylamine or salts thereof or mixtures thereof; and (d) 0.5-25 mass % of water.

2. The photoresist cleaning composition of claim 1 , wherein said (b) comprises 80-96 mass % of said dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof, and 1-4 mass % of said at least one additional organic solvent or two or more additional organic solvents; and said (c) compises 1-5 mass %; and said (d) comprises 1-10 mass %.

3. The photoresist cleaning composition of claim 1 , wherein said (b) comprises 80-96 mass % dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof, and 1-4 mass % of at least one additional organic solvent or two or more additional organic solvents; wherein said (c) is 1-10 mass %; and said (d) is 1-10 mass %.

4. The photoresist cleaning composition of claim 1 , wherein said (b) comprises 35-50 mass % dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof and 45-58 mass % of additional organic solvent or two or more additional organic solvents; said (c) is 1-10 mass %; and said (d) is 1-10 mass %.

5. The photoresist cleaning composition of claim 1 , wherein said (a) is 1-5 mass %; said (b) is 78-85 mass %; said (c) is 10.5-15 mass %; and said (d) is 1-10 mass %.

6. The photoresist cleaning composition of claim 1 , wherein said (a) is 1-5 mass %; said (b) is 59-84 mass % dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof and 1-20 mass % of at least one additional organic solvent or two or more additional organic solvents; said (c) 10.5-15 mass %; and said (d) is 1-10 mass %.

7. The photoresist cleaning composition of claim 1 , wherein said at least one corrosion inhibitor is selected from the group consisting of catechol, tert-butyl catechol, ammonium benzoate, benzoic acid, salicylic acid, citric acid, gallic acid, mono or dihydroxybenzoic acid, polyethyleneimine (PEI), diethylhydroxylamine (DEHA), hydroxylamine or dipropylhydroxylamine or salts thereof or mixtures thereof or mixtures of any of the corrosion inhibitors.

8. The photoresist cleaning composition of claim 1 , which comprises (b) 82-97.5 mass % of said mixture of water-soluble organic solvent; (c) 1-5 mass % of said corrosion inhibitors; and (d) 1-10 mass % of said water.

9. The photoresist cleaning composition of claim 8 , wherein said at least one additional organic solvent is selected from the group consisting of propylene glycol, tetrahydrofurfuryl alcohol, a glycol ether, gamma-butyrolactone, gamma-valerolactone, dimethylacetamide, monoethanolamine and aminopropylmorpholine and mixtures thereof.

10. A photoresist cleaning composition for stripping a photoresist pattern having a film thickness of 3-150 μm, which comprises (a) 1-5 mass % of at least one quaternary ammonium hydroxide or mixtures of two or more quaternary ammonium hydroxides; (b) 78-85 mass % of a mixture of water-soluble organic solvent comprising dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof and at least one additional organic solvent or two or more additional organic solvents; (c) 10-20 mass % of diethylhydroxylamine (DEHA), hydroxylamine or dipropylhydroxylamine or salts thereof or mixtures thereof and 0.5-5 mass % of at least one additional corrosion inhibitor or mixtures of two or more additional corrosion inhibitors; and (d) 1-10 mass % of water.

11. A photoresist cleaning composition for stripping a photoresist pattern having a film thickness of 3-150 μm, which comprises (a) 1-5 mass % of at least one quaternary ammonium hydroxide or mixtures of two or more quaternary ammonium hydroxides; (b) 59-84 mass % dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof and 1-20 mass % of at least one additional organic solvent or two or more additional organic solvents; (c) 10-20 mass % of diethylhydroxylamine (DEHA), hydroxylamine or dipropylhydroxylamine or salts thereof or mixtures thereof and 0.5-5 mass % of at least one additional corrosion inhibitor or mixtures of two or more additional corrosion inhibitors; and (d) is 1-10 mass % water.

12. The photoresist cleaning composition of claim 11 , wherein said (b) is 64-69 mass % of a mixture of organic solvents comprising dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof, and at least one additional organic solvent or two or more additional organic solvents comprising alkanolamine.

13. The photoresist cleaning composition of claim 11 , wherein said (b) comprises dimethylsulfoxide and said at least one additional organic solvent is selected from the group consisting of propylene glycol, tetrahydrofurfuryl alcohol, a glycol ether, gamma-butyrolactone, gamma-valerolactone, dimethylacetamide, monoethanolamine and aminopropylmorpholine and mixtures thereof.

14. The photoresist cleaning composition of claim 11 , wherein said (a) comprises 1-3 mass % of a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide or tetraethylammonium hydroxide, and mixtures thereof; said (b) is dimethylsulfoxide and said at least one additional organic solvent is selected from the group consisting of propylene glycol, tetrahydrofurfuryl alcohol, glycol ether, gamma-butyrolactone, gamma-valerolactone, dimethylacetamide, monoethanolamine and aminopropylmorpholine and mixtures thereof; and said (c) comprises at least one corrosion inhibitor selected from the group consisting of catechol, tert-butyl catechol, ammonium benzoate, benzoic acid, salicylic acid, citric acid, gallic acid, mono or dihydroxybenzoic acid, polyethyleneimine (PEI) or mixtures thereof; and said (d) is 2-5 mass %.

15. The photoresist cleaning composition of claim 14 , wherein said (b) comprises dimethylsulfoxide and 1-6 mass % of said at least one additional organic solvent selected from the group consisting of propylene glycol, tetrahydrofurfuryl alcohol, dipropyleneglycol methylether, gamma-butyrolactone, gamma-valerolactone, dimethylacetamide, monoethanolamine and aminopropylmorpholine or mixtures thereof; and said (c) is 0.5-3 mass %.

16. A method for treating a substrate, comprising forming a photoresist pattern having a film thickness of 3-150 μm on a substrate having a metallic thin film thereon, providing a conductive layer on a metallic thin film-exposed area or a photoresist pattern uncovered area, and bringing the photoresist pattern into contact with the photoresist cleaning composition comprising (a) 0.5-5 mass % of at least one quaternary ammonium hydroxide or mixtures of two or more quaternary ammonium hydroxides; (b) 60-97.5 mass % of a mixture of water-soluble organic solvent comprising dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof, and at least one additional organic solvent or two or more additional organic solvents; (c) 0.5-15 mass % of at least one corrosion inhibitor or a mixture of two or more corrosion inhibitors selected from the group consisting of catechol, tert-butyl catechol, ammonium benzoate, benzoic acid, salicylic acid, citric acid, gallic acid, mono or dihydroxybenzoic acid, polyethyleneimine (PEI), diethylhydroxylamine (DEHA), hydroxylamine or dipropylhydroxylamine or salts thereof or mixtures thereof; and (d) 0.5-25 mass % of water to strip and dissolve the photoresist pattern.

17. The method for treating a substrate according to claim 16 , wherein the said (b) is 82-97.5 mass %; said (c) is 1-5 mass %; and said (d) is 1-10 mass %.

18. The method for treating a substrate according to claim 17 , wherein said (c) comprises a mixture of two or more corrosion inhibitors comprising PEI.

19. The method for treating a substrate according to claim 16 , wherein said (b) comprises 35-50 mass % dimethylsulfoxide (DMSO), sulfolane or dimethylsulfone or mixtures thereof and 45-58 mass % of additional organic solvent or two or more additional organic solvents; said (c) is 1-10 mass %; and said (d) is 1-10 mass %.

20. The method for treating a substrate according to claim 19 , wherein (c) further comprises 10-20 mass % of diethylhydroxylamine (DEHA), hydroxylamine or dipropylhydroxylamine or salts thereof or mixtures thereof.

Assignments (4)
RELEASE OF SECURITY INTEREST Recorded Oct 7, 2019
From: CITIBANK, N.A., AS AGENT
To: VERSUM MATERIALS US, LLC
Reel/Frame 050647/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 20, 2017
From: AIR PRODUCTS AND CHEMICALS, INC.
To: VERSUM MATERIALS US, LLC
Reel/Frame 041772/0733 →
PATENT SECURITY AGREEMENT Recorded Oct 27, 2016
From: VERSUM MATERIALS US, LLC
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 040503/0442 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 10, 2016
From: CHANG, RANDY LI-KAI; PARRIS, GENE EVERAD; CHEN, HSIU MEI; LEE, YI-CHIA; LIU, WEN DAR; CHEN, TIANNIU; MATZ, LAURA M; LO, RYBACK LI CHANG; MENG, LING-JEN
To: AIR PRODUCTS AND CHEMICALS, INC.
Reel/Frame 039976/0833 →
Cited By (1)
US 12,655,367