IP Library Granted Patent US 8,889,609
Granted Patent B2
US 8,889,609 · App. 13/414,339 · Granted Nov 18, 2014

Cleaning formulations and method of using the cleaning formulations

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Quick Facts
Patent No.
US 8,889,609
App. No.
13/414,339
Granted
Nov 18, 2014
Kind
B2
Abstract

A water-rich hydroxylamine formulation for photoresist and post-etch/post-ash residue removal in applications wherein a semiconductor substrate comprises aluminum. The cleaning composition comprises from about 2 to about 15% by wt. of hydroxylamine; from about 50 to about 80% by wt. of water; from about 0.01 to about 5.0% by wt. of a corrosion inhibitor; from about 5 to about 45% by wt. of a component selected from the group consisting of: an alkanolamine having a pKa<9.0, a water-miscible solvent, and a mixture thereof. Employment of such composition exhibits efficient cleaning capability for Al substrates, minimal silicon etch while protecting aluminum for substrates comprising both materials.

Claims (51)

1. A composition useful for removing residue from a semiconductor substrate comprising:

from about 2 to about 15% by wt. of hydroxylamine;

from about 50 to about 80% by wt. of water;

from about 0.01 to about 5.0% by wt. of corrosion inhibitor;

from about 5 to about 45% by wt. of a component selected from the group consisting of: one or more alkanolamines each having a pKa<9.0, propylene glycol, and a mixture thereof,

wherein the alkanolamine is selected from the group consisting of: triethanolamine, diethanolamine, diisopropanolamine, N-methyldiethanolamine, and mixtures thereof; and

wherein the corrosion inhibitor is selected from the group consisting of: one or more linear or branched C1-C6 alkyl dihydroxybenzenes, one or more hydroxyquinolines, and mixtures thereof.

2. A composition useful for removing residue from a semiconductor substrate comprising:

from about 2 to about 10% by wt. of hydroxylamine;

from about 55 to about 80% by wt. of water;

from about 0.01 to about 5.0% by wt. of corrosion inhibitor;

from about 5 to about 42% by wt. of a component selected from the group consisting of: one or more alkanolamines each having a pKa<9.0, propylene glycol, and a mixture thereof,

wherein the alkanolamine is selected from the group consisting of: triethanolamine, diethanolamine, diisopropanolamine, N-methyldiethanolamine, and mixtures thereof; and

wherein the corrosion inhibitor is selected from the group consisting of: one or more linear or branched C1-C6 alkyl dihydroxybenzenes, one or more hydroxyquinolines, and mixtures thereof.

3. The composition of claim 1 wherein the alkanolamine is triethanolamine.

4. The composition of claim 1 wherein the corrosion inhibitor is selected from the group consisting of: tert-butyl catechol, catechol, gallic acid, 2,3-dihydroxy naphthalene, 2,3-dihydroxy tetraline, and mixtures thereof.

5. The composition of claim 4 wherein the corrosion inhibitor is tert-butyl catechol.

6. The composition of claim 4 wherein said alkanolamine is triethanolamine.

7. The composition of claim 1 wherein the composition is solvent-free.

8. The composition of claim 1 consisting of:

from about 4 to about 10% by wt. of said hydroxylamine;

from about 60 to about 80% by wt. of said water;

from about 0.1 to about 5.0% by wt. of said corrosion inhibitor;

from about 10 to about 25% by wt. of said propylene glycol; and

from about 0 to about 30% by wt. of said alkanolamine having a pKa<9.0, wherein the alkanolamine is selected from the group consisting of: triethanolamine, diethanolamine, diisopropanolamine, N-methyldiethanolamine, and mixtures thereof; and

wherein the corrosion inhibitor is selected from the group consisting of: one or more linear or branched C1-C6 alkyl dihydroxybenzenes, one or more hydroxyquinolines, and mixtures thereof.

9. The composition of claim 8 wherein the alkanolamine is triethanolamine.

10. The composition of claim 8 wherein the corrosion inhibitor is selected from the group consisting of: tert-butyl catechol, catechol, gallic acid, 2,3-dihydroxy naphthalene, 2,3-dihydroxy tetraline, and mixtures thereof.

11. The composition of claim 10 wherein the corrosion inhibitor is tert-butyl catechol.

12. A method for removing residue from a substrate comprising aluminum and silicon, the method comprising the steps of:

contacting the substrate with a cleaning composition comprising:

from about 2 to about 10% by wt. of hydroxylamine;

from about 55 to about 80% by wt. of water;

from about 0.01 to about 5.0% by wt. of a corrosion inhibitor;

from about 5 to about 42% by wt. of a component selected from the group consisting of: an alkanolamine having a pKa<9.0, propylene glycol, and a mixture thereof, wherein the alkanolamine is selected from the group consisting of: triethanolamine, diethanolamine, diisopropanolamine, N-methyldiethanolamine, and mixtures thereof; and

wherein the corrosion inhibitor is selected from the group consisting of: one or more linear or branched C1-C6 alkyl dihydroxybenzenes, one or more hydroxyquinolines, and mixtures thereof;

rinsing the substrate with water; and

drying the substrate, wherein the method excludes an intermediate IPA (isopropyl alcohol) rinse step prior to the step of rinsing the substrate with water.

13. The method of claim 12 wherein the substrate is a semiconductor substrate, said composition comprises from about 2 to about 10% by weight of said hydroxylamine; from about 55 to about 80% by weight of said water, and 5 to about 42% by wt. of said component selected from the group consisting of: an alkanolamine having a pKa<9.0, propylene glycol, and a mixture thereof; and wherein the silicon etch rate is less than 20 Å/min for said method.

14. The method of claim 13 wherein the alkanolamine is triethanolamine.

15. The method of claim 12 wherein the corrosion inhibitor is selected from the group consisting of: 2-hydroxyquinoline, 4-hydroxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, and mixtures thereof.

16. The method of claim 12 wherein the corrosion inhibitor is selected from the group consisting of: tert-butyl catechol, catechol, gallic acid, 2,3-dihydroxy naphthalene, 2,3-dihydroxy tetraline, and mixtures thereof.

17. The method of claim 16 wherein the corrosion inhibitor is tert-butyl catechol.

18. The composition of claim 5 wherein said alkanolamine is triethanolamine.

19. The composition of claim 1 , wherein said composition comprises about 5 to about 7.5% by wt. hydroxylamine;

from about 60 to about 70% by wt. of water; and

from about 0.01 to about 1% by wt. of corrosion inhibitor.

20. The composition of claim 18 , wherein said composition comprises about 5 to about 7.5% by wt. hydroxylamine;

from about 60 to about 70% by wt. of water; and

from about 0.01 to about 1% by wt. of corrosion inhibitor.

21. The composition of claim 9 wherein the corrosion inhibitor is tert-butyl catechol.

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 Apr 9, 2012
From: WU, AIPING; LEE, YI-CHIA; LIU, WEN DAR; RAO, MADHUKAR BHASKARA; BANERJEE, GAUTAM
To: AIR PRODUCTS AND CHEMICALS, INC.
Reel/Frame 028013/0075 →