Cleaning formulation for removing residues on surfaces

Patent metadata

Field	Value
Publication number	US-10696933-B2
Application number	US-201916660170-A
Country	US
Kind code	B2
Filing date	Oct 22, 2019
Priority date	Dec 6, 2013
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

This disclosure relates to a cleaning composition that contains 1) at least one redox agent; 2) at least one first chelating agent, the first chelating agent being a polyaminopolycarboxylic acid; 3) at least one metal corrosion inhibitor, the metal corrosion inhibitor being a substituted or unsubstituted benzotriazole; 4) at least one organic solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers; 5) at least one quaternary ammonium hydroxide; and 6) water. This disclosure also relates to a method of using the above composition for cleaning a semiconductor substrate.

First claim

What is claimed is:

1. A cleaning composition, comprising:
1) at least one redox agent;
2) at least one first chelating agent, the first chelating agent being a polyaminopolycarboxylic acid;
3) at least one metal corrosion inhibitor, the metal corrosion inhibitor being a substituted or unsubstituted benzotriazole;
4) at least one organic solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers;
5) at least one quaternary ammonium hydroxide; and
6) water;
wherein the composition is free of a metal halide.

2. The composition of claim 1 , wherein the pH of the composition is between about 6 and about 11.

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

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

5. The composition of claim 1 , wherein the polyaminopolycarboxylic acid is selected from the group consisting of mono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkylether polyamine polycarboxylic acids.

6. The composition of claim 1 , wherein the polyaminopolycarboxylic acid is selected from the group consisting of butylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, trans-1,2-diaminocyclohexane tetraacetic acid, ethylendiamine diacetic acid, ethylendiamine dipropionic acid, 1,6-hexamethylene-diamine-N,N,N′,N′-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropane tetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanol tetraacetic acid, and (hydroxyethyl)ethylenediaminetriacetic acid.

7. The composition of claim 1 , wherein the at least one first chelating agent comprises diethylenetriaminepentaacetic acid.

8. The composition of claim 1 , wherein the at least one first chelating agent is from about 0.01% to about 1% by weight of the composition.

9. The composition of claim 1 , wherein the at least one metal corrosion inhibitor comprises benzotriazole optionally substituted by at least one substituent selected from the group consisting of alkyl groups, aryl groups, halogen groups, amino groups, nitro groups, alkoxy groups, and hydroxyl groups.

10. The composition of claim 1 , wherein the at least one metal corrosion inhibitor is selected from the group consisting of benzotriazole, 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthotriazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4-triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-t-butyl benzotriazole, 5-(1′,1′-diimethylpropyl)-benzotriazole, 5-(1′,1′,3′-trimethylbutyl)benzotriazole, 5-n-octyl benzotriazole, and 5-(1′,1′,3′,3′-tetramethylbutyl)benzotriazole.

11. The composition of claim 1 , wherein the at least one metal corrosion inhibitor comprises 5-methyl-1H-benzotriazole.

12. The composition of claim 1 , wherein the at least one metal corrosion inhibitor is from about 0.05% to about 1% by weight of the composition.

13. The composition of claim 1 , wherein the at least one quaternary ammonium hydroxide comprises tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, dimethyldiethylammonium hydroxide, choline, tetraethanolammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, or benzyltributylammonium hydroxide.

14. The composition of claim 1 , wherein the at least one quaternary ammonium hydroxide comprises tetraethyl ammonium hydroxide or tetrabutyl ammonium hydroxide.

15. The composition of claim 1 , wherein the at least one quaternary ammonium hydroxide is from about 0.1% to about 3% by weight of the composition.

16. The composition of claim 1 , wherein the at least one organic solvent is from about 1% to about 30% by weight of the composition.

17. The composition of claim 1 , wherein the water is from about 78% to about 98% of the composition.

18. A method, comprising:
contacting a semiconductor substrate containing post etch residues and/or post ash residues with a cleaning composition of claim 1 .

19. A composition, comprising hydroxylamine, diethylenetriaminepentaacetic acid, a chlorhexidine salt, 5-methyl-1H-benzotriazole, tetrabutyl ammonium hydroxide, ethylene glycol butyl ether, and water.

20. The composition of claim 19 , wherein the composition comprises:
from about 0.5% to about 20% by weight of hydroxylamine;
from about 0.01% to about 1% by weight of diethylenetriamine pentaacetic acid;
from about 0.01% to about 1.8% by weight of a chlorhexidine salt;
from about 0.05% to about 1% by weight of 5-methyl-1H-benzotriazole;
from about 0.1% to about 3% by weight of tetrabutyl ammonium hydroxide;
from about 1% to about 30% by weight of ethylene glycol butyl ether; and
from about 78% to about 98% of the water.

21. A composition, further comprising:
1) at least one redox agent;
2) at least one first chelating agent, the first chelating agent being a polyaminopolycarboxylic acid;
3) at least one second chelating agent different from the first chelating agent, the second chelating agent comprising at least two nitrogen-containing groups;
4) at least one metal corrosion inhibitor, the metal corrosion inhibitor being a substituted or unsubstituted benzotriazole;
5) at least one organic solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers;
6) at least one quaternary ammonium hydroxide; and
7) water.

22. The composition of claim 21 , wherein the at least one second chelating agent comprises a compound of Structure (III) or a salt thereof:

in which
R 20 , R 21 , R 22 , and R 23 are independently selected from the group consisting of hydrogen substituted or unsubstituted aryl, substituted or unsubstituted C 3 -C 10 cyclic alkyl, and substituted or unsubstituted C 1 -C 10 linear or branched alkyl;
each R 24 is independently selected from the group consisting of hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted phenylethyl, or substituted or unsubstituted benzyl alkyl; and
m is an integer from 1 to 10;
provided that at least one of R 20 , R 21 , R 22 , R 23 and R 24 is an aryl group or contains an aryl substituent and that at least

Assignees

• Fujifilm Electronic Mat Usa Inc

Inventors

• Takahashi Tomonori
• Du Bing
• Wojtczak William A
• Dory Thomas
• Kneer Emil A

Classifications

• H10P76/204

  of organic photoresist masks · CPC title

• H10P70/273

  the processing being a delineation of conductive layers, e.g. by RIE · CPC title

• H10P70/234

  the processing being the formation of vias or contact holes · CPC title

• H10P70/27

  during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers · CPC title

• H10P50/287

  by chemical means · CPC title