Non-corrosive cleaning compositions for removing etch residues

• US 7,935,665 B2
• Filed: 04/24/2003
• Issued: 05/03/2011
• Est. Priority Date: 04/25/2002
• Status: Expired due to Fees

• Current Assignee: Fujifilm Electronic Materials USA Incorporated (Fujifilm Holdings Corporation)
• Original Assignee: Fujifilm Electronic Materials USA Incorporated (Fujifilm Holdings Corporation)
• Inventors: Ferreira, Lawrence, Leon, Vincent G., Elderkin, Michelle
• Primary Examiner(s): DELCOTTO, GREGORY R
• Application Number:
  US10/421,506
• Publication Number:
  US 20030235996A1
• Time in Patent Office: 2,931 Days
• Field of Search: 510/175, 510/176, 510/245, 510/255, 510/258, 510/477, 510/488, 510/505, 510/506
• US Class Current: 510/176
• CPC Class Codes: C11D 2111/20 Industrial or commercial equipment, e.g. reactors, tubes or engines
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 2111/46 applying energy, e.g. irradiation
• CPC Class Codes: C11D 7/265 Carboxylic acids or salts thereof
• CPC Class Codes: C11D 7/28 containing halogen
• CPC Class Codes: C11D 7/32 containing nitrogen
• CPC Class Codes: C11D 7/3245 Aminoacids
• CPC Class Codes: C11D 7/34 containing sulfur
• CPC Class Codes: G03F 7/42 Stripping or agents therefor
• CPC Class Codes: G03F 7/422 using liquids only G03F7/421 takes precedence
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/02071 the processing being a delineation, e.g. RIE, of conductive layers

Abstract

A non-corrosive cleaning composition that is aqueous-based, non-hazardous and will not harm the environment and is useful primarily for removing both fresh and aged plasma etch residues from a substrate. The composition comprises (a) water; and (b) a synergistic combination of at least one tricarboxylic acid and at least one carboxylic acid. Preferably, the at least one carboxylic acid has a pKa value ranging from 3 to 6. Also, a method for removing etch residues from a substrate. The method includes the steps of (a) providing a substrate with etch residue; and (b) contacting the substrate with a cleaning composition comprising water; and a synergistic combination of at least one tricarboxylic acid and at least one carboxylic acid.

Claims

1. A non-corrosive cleaning composition consisting of:

(a) water;

(b) a combination of at least one tricarboxylic acid and at least one carboxylic acid, wherein said at least one carboxylic acid is selected from the group consisting of;

acetic, propionic, butyric, valeric, trimethylacetic, isovaleric, succinic, methylsuccinic, glutaric, suberic, glycolic, 2-hydroxyisobutyric, 3-hydroxybutyric, malic, citramalic, tartaric, ethoxyacetic, tetrahydro-3-furoic, diglycolic, mercaptosuccinic, thiolactic, cyclohexylacetic, dicyclohexylacetic, and 1,1-cyclohexanediacetic, and said at least one tricarboxylic acid and said at least one carboxylic acid is present in a weight ratio of about 1;

5 to about 5;

1; and

(c) at least one solvent selected from the group consisting of polyol compounds, glycol ethers, and any combinations thereof; and

(d) optionally, at least one surfactant.

2. The composition of claim 1, wherein said composition removes an etch residue from a substrate.

3. The composition of claim 2, wherein said etch residue is a plasma etch residue.

4. The composition of claim 1, wherein said combination of said at least one tricarboxylic acid and at least one carboxylic acid provides an enhanced cleaning composition compared to a cleaning composition having only tricarboxylic acid or carboxylic acid alone.

5. The composition of claim 1, wherein said at least one tricarboxylic acid has the formula:

6. The composition of claim 5, wherein said at least one tricarboxylic acid having said formula is selected from the group consisting of:

tricarballylic acid, beta-methyltricarballylic acid, citric acid, nitromethanetrispropionic acid, and 2-(carboxylmethylthio) succinic acid.

7. The composition of claim 1, wherein said at least one tricarboxylic acid is present in said composition in an amount about 0.01 wt. % to about 10 wt. %.

8. The composition of claim 1, wherein said at least one tricarboxylic acid is present in said composition in an amount about 0.05 wt. % to about 3 wt. %.

9. The composition of claim 1, wherein said at least one tricarboxylic acid is present in said composition in an amount about 0.1 wt. % to about 2 wt. %.

10. The composition of claim 1, wherein said at least one carboxylic acid is present in said composition in an amount about 0.01 wt. % to about 10 wt. %.

11. The composition of claim 1, wherein said at least one carboxylic acid is present in said composition in an amount about 0.05 wt. % to about 3 wt. %.

12. The composition of claim 1, wherein said at least one carboxylic acid is present in said composition in an amount about 0.1 wt. % to about 2 wt. %.

13. The composition of claim 1, wherein said at least one tricarboxylic acid and said at least one carboxylic acid is present in said composition in a weight ratio of about 1:

3 to about 3;

1.

14. The composition of claim 1, wherein said at least one tricarboxylic acid and said at least one carboxylic acid is present in said composition in a weight ratio of about 1:

1.

15. A non-corrosive cleaning composition consisting of:

(a) water;

(b) a combination of at least one tricarboxylic acid and at least one carboxylic acid which is different from the at least one tricarboxylic acid, said at least one tricarboxylic acid and said at least one carboxylic acid being present in a weight ratio of about 1;

5 to about 5;

1, said at least one tricarboxylic acid is at least citric acid and being present in said composition in an amount about 0.05 wt. % to about 3 wt. %, said at least one carboxylic acid being present in said composition in an amount about 0.05 wt. % to about 3 wt. %, and all of the pKa values of said at least one carboxylic acid ranging from about 3 to about 6;

(c) at least one hydroxylammonium compound having the formula;

r(NR¹⁰R¹¹R¹²OH)⁺(x<sup>−

r</sup>)

R¹⁰, R¹¹, and R¹² are individually selected from hydrogen, lower alkyl groups having 1 to 4 carbon atoms, lower alkoxy groups having 1 to 4 carbon atoms, hydroxyl and hydroxyl-substituted lower alkyl groups having 1 to 4 carbon atoms, with the proviso that at least two of R¹⁰, R¹¹, and R¹² are either hydrogen, lower alkyl group or lower alkoxy group, X is an anionic moiety that forms a water-soluble salt with the hydroxylammonium cations or quaternary ammonium cations, and r is the valence of X and is from 1 to 3; and

optionally, (d) at least one component selected from the group consisting of;

a surfactant, and a solvent and combinations thereof, the solvent being selected from the group consisting of polyol compounds, glycol ethers, and any combinations thereof, and the polyol compounds are selected from the group consisting of (C₂-C₂₀) alkanediols and (C₂-C₂₀) alkanetriols.

16. The composition of claim 15, wherein said at least one hydroxylammonium compound is at least one selected from the group consisting of hydroxylammonium salts, hydroxylammonium nitrate, hydroxylammonium sulfate, hydroxylammonium phosphate, hydroxylammonium chloride, hydroxylammonium oxalate, hydroxylammonium citrate, hydroxylammonium fluoride, N,N-diethylhydroxylammonium sulfate, and N,N-diethylhydroxylammonium nitrate.

17. The composition of claim 15, wherein said at least one hydroxylammonium compound is present in an amount about 0.001 wt. % to about 10 wt. %.

18. A non-corrosive cleaning composition consisting of:

(a) water;

(b) a combination of at least one tricarboxylic acid and at least one carboxylic acid, and

(c) at least one solvent,

wherein the at least one carboxylic acid is selected from the group consisting of;

acetic, propionic, butyric, valeric, trimethylacetic, isovaleric, succinic, methylsuccinic, glutaric, suberic, glycolic, lactic, 2-hydroxyisobutyric, 3-hydroxybutyric, malic, citramalic, tartaric, ethoxyacetic, tetrahydro-3-furoic, diglycolic, mercaptosuccinic, thiolactic, cyclohexylacetic, dicyclohexylacetic, and 1,1-cyclohexanediacetic, the at least one solvent is selected from the group consisting of polyol compounds, glycol ethers, and any combinations thereof, and said at least one tricarboxylic acid and said at least one carboxylic acid is present in a weight ratio of about 1;

5 to about 5;

1.

19. The composition of claim 18, wherein said solvent is present in said composition in an amount about 0.1 wt. % to about 30 wt. %.

20. A non-corrosive cleaning composition for removing plasma etch residue on a substrate consisting of

water,

a combination of lactic acid and citric acid, the lactic acid being present in the composition in an amount about 0.05 wt. % to about 3 wt. % and the citric acid being present in the composition in an amount about 0.05 wt. % to about 3 wt. %,

at least one hydroxylammonium compound present in said composition in an amount about 0.001 wt. % to about 10 wt. %, and

optionally, at least one component selected from a group consisting of:

a surfactant, a solvent, and combinations thereof, the solvent being selected from the group consisting of polyol compounds, glycol ethers, and any combinations thereof, and the polyol compounds are selected from the group consisting of (C₂-C₂₀) alkanediols and (C₂-C₂₀) alkanetriols.

21. The composition of claim 20, wherein said at least one hydroxylammonium compound is hydroxylammonium sulfate.

22. A non-corrosive cleaning composition consisting of:

(a) water;

(b) a combination of at least one tricarboxylic acid and at least one carboxylic acid, wherein said at least one carboxylic acid is selected from the group consisting of;

propionic, butyric, valeric, trimethylacetic, isovaleric, succinic, methylsuccinic, glutaric, suberic, glycolic, 2-hydroxyisobutyric, 3-hydroxybutyric, citramalic, tartaric, ethoxyacetic, tetrahydro-3-furoic, diglycolic, mercaptosuccinic, thiolactic, cyclohexylacetic, dicyclohexylacetic, and 1,1-cyclohexanediacetic, said at least one tricarboxylic acid is at least citric acid and is present in said composition in an amount about 0.05 wt. % to about 3 wt. %, said at least one carboxylic acid is present in said composition in an amount about 0.05 wt. % to about 3 wt. %, and said at least one tricarboxylic acid and said at least one carboxylic acid is present in a weight ratio of about 1;

5 to about 5;

1; and

(c) at least one non-ionic surfactant.

23. The composition of claim 22, wherein the surfactant has a polyoxyethylene group.

24. A non-corrosive cleaning composition consisting of:

(a) water;

(b) a combination of at least one tricarboxylic acid and at least one carboxylic acid, said at least one tricarboxylic acid and said at least one carboxylic acid being present in a weight ratio of about 1;

5 to about 5;

1, wherein said at least one carboxylic acid is selected from the group consisting of;

acetic, propionic, butyric, valeric, trimethylacetic, isovaleric, succinic, methylsuccinic, glutaric, suberic, glycolic, 2-hydroxyisobutyric, 3-hydroxybutyric, malic, citramalic, tartaric, ethoxyacetic, tetrahydro-3-furoic, diglycolic, mercaptosuccinic, thiolactic, cyclohexylacetic, dicyclohexylacetic, and 1,1-cyclohexanediacetic, said at least one tricarboxylic acid is at least citric acid and is present in said composition in an amount about 0.05 wt. % to about 3 wt. %, said at least one carboxylic acid is present in said composition in an amount about 0.05 wt. % to about 3 wt. %;

(c) at least one hydroxylammonium compound having the formula;

r(NR¹⁰R¹¹R¹²OH)⁺(x<sup>−

r</sup>)

wherein R¹⁰, R¹¹, and R¹² are individually selected from hydrogen, lower alkyl groups having 1 to 4 carbon atoms, lower alkoxy groups having 1 to 4 carbon atoms, hydroxyl and hydroxyl-substituted lower alkyl groups having 1 to 4 carbon atoms, with the proviso that at least two of R¹⁰, R¹¹, and R¹² are either hydrogen, lower alkyl group or lower alkoxy group, X is an anionic moiety that forms a water-soluble salt with the hydroxylammonium cations or quaternary ammonium cations, and r is the valence of X and is from 1 to 3; and

optionally, at least one component selected from the group consisting of;

a surfactant, and a solvent and combinations thereof, the solvent being selected from the group consisting of polyol compounds, glycol ethers, and any combinations thereof, wherein the polyol compounds are selected from the group consisting of (C₂-C₂₀) alkanediols and (C₂-C₂₀) alkanetriols.

25. The composition of claim 24, wherein said at least one hydroxylammonium compound is at least one selected from the group consisting of:

hydroxylammonium salts, hydroxylammonium nitrate, hydroxylammonium sulfate, hydroxylammonium phosphate, hydroxylammonium chloride, hydroxylammonium oxalate, hydroxylammonium citrate, hydroxylammonium fluoride, N,N-diethylhydroxylammonium sulfate, and N,N-diethylhydroxylammonium nitrate.

26. The composition of claim 24, wherein said at least one hydroxylammonium compound is present in an amount about 0.001 wt. % to about 10 wt. %.