Process for removing residues from a semiconductor substrate

• US 6,033,993 A
• Filed: 09/23/1997
• Issued: 03/07/2000
• Est. Priority Date: 09/23/1997
• Status: Expired due to Term

• Current Assignee: Fujifilm Electronic Materials USA Incorporated (Fujifilm Holdings Corporation)
• Original Assignee: OLIN Microelectronic Chemicals Incorporated
• Inventors: Love, M. Lee Jr., Honda, Kenji
• Primary Examiner(s): Utech, Benjamin
• Assistant Examiner(s): Umez-Eronini, Lynette T.
• Application Number:
  US08/936,035
• Time in Patent Office: 896 Days
• Field of Search: 438/725, 438/750, 438/745, 216/96, 134/1.2, 510/175, 510/176, 510/255
• US Class Current: 438/745
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 3/0073 Anticorrosion compositions
• CPC Class Codes: C11D 7/06 Hydroxides
• CPC Class Codes: C11D 7/105 Nitrates; Nitrites
• CPC Class Codes: C11D 7/265 Carboxylic acids or salts thereof
• CPC Class Codes: C11D 7/3245 Aminoacids
• CPC Class Codes: G03F 7/422 using liquids only G03F7/421 takes precedence
• CPC Class Codes: G03F 7/425 containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• CPC Class Codes: H01L 21/0206 during, before or after processing of insulating layers
• CPC Class Codes: H01L 21/02071 the processing being a delineation, e.g. RIE, of conductive layers
• CPC Class Codes: H01L 21/31133 by chemical means
• CPC Class Codes: H01L 21/31138 by dry-etching
• CPC Class Codes: H01L 21/32135 by vapour etching only

Abstract

A process of treating a substrate having photoresist applied thereto, comprising the steps of:

(a) removing said photoresist from said substrate by a method selected from the group consisting of photoresist stripping, plasma etch residue cleaning, or a combination thereof; and

(b) rinsing said substrate with a non-corrosive rinsing composition comprising

(1) water; and

(2) one or more water-soluble corrosion inhibitors selected from the group consisting essentially of hydroxylamine, at least one hydroxylammonium salt, at least one water-soluble organic acid, at least one amino acid, and combinations thereof.

Claims

1. A process for removing residues from a substrate bearing said residues, wherein said residues comprise photoresist residues, post-etch residues, remover solution residues and combinations thereof, comprising treating the residue-bearing substrate with a rinse solution comprising about 97 to 99.9 wt. % water and about 0.1 to 3 wt. % of at least one water-soluble corrosion inhibitor selected from the group consisting of hydroxylamine, at least one hydroxylammonium salt, at least one water-soluble organic acid, at least one amino acid, and combinations thereof, wherein the weight percentages are based on the total weight of said rinse solution.

2. The process of claim 1, wherein said water-soluble corrosion inhibitor is hydroxylamine.

3. The process of claim 1, wherein said water-soluble corrosion inhibitor is an hydroxylammonium salt selected from the group consisting essentially of hydroxylammonium nitrate (HAN), hydroxylammonium sulfate (HAS), hydroxylammonium phosphate, hydroxylammonium chloride, hydroxylammonium oxalate, hydroxylammonium citrate, and combinations thereof.

4. The process of claim 1, wherein said water-soluble corrosion inhibitor is at least one water-soluble organic acid.

5. The process of claim 4, wherein said water-soluble organic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid (butanediol acid), glutaric acid, maleic acid, fumaric acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid (2-hydroxypropionoic acid), citric acid, salicylic acid, tartaric acid and gluconic acid.

6. The process of claim 4, wherein said water-soluble organic acid is selected from the group consisting of lactic acid, tartaric acid, acetic acid, gluconic acid and phthalic acid.

7. The process of claim 1, wherein said water-soluble corrosion inhibitor is at least one amino acid.

8. The process of claim 7, wherein said water-soluble corrosion inhibitor is an amino acid selected from the group consisting essentially of tricine, bicine, DL-homoserine, D-homoserine, L-homoserine, DL-threonine, D-allo-threonine, L-allo-threonine, D-threonine, L-threonine, DL-3-hydroxynorvaline, DL-methyltyrosine, D-4-hydroxyphenylglycine, DL-tyrosine, D-tyrosine, L-tyrosine, 3-(3,4-dihydroxyphenyl)-DL-alanine, 3-(3,4-dihydroxyphenyl)-L-alanine, 3-(2,4,5-trihydroxyphenyl)-DL-alanine, DL-alpha-methyltyrosine, L-alphamethyltyrosine, (-)-3-(3,4-dihydroxyphenyl)-2-methyl-L-alanine, DL-threo-3-phenylserine, DL-threo-3,4-dihydroxyphenylserine, and combinations thereof.

9. The process of claim 8, wherein said amino acid is selected from the group consisting essentially of tricine, bicine, 3-(3,4-dihydroxyphenyl)-DL-alanine, 3-(2,4,5-trihydroxyphenyl)-DL-alanine, and DL-threo-3,4-dihydroxyphenylserine.

10. A process for removing a patterned photoresist layer and residues comprising photoresist residues, post-etch residues, remover solution residues and combinations thereof, from a substrate which has a patterned photoresist layer thereon and which has been subjected to an etching operation, comprising the steps of:

(1) removing said patterned photoresist layer from said substrate;

(2) treating said substrate with a remover solution; and

(3) rinsing said substrate with a non-corrosive rinse solution comprising about 97 to 99.9 wt. % water and about 0.1 to 3 wt. % of at least one water-soluble corrosion inhibitor selected from the group consisting of hydroxylamine, at least one hydroxylammonium salt, at least one water-soluble organic acid, at least one amino acid, and combinations thereof, wherein the weight percentages are based on the total weight of said non-corrosive rinse solution.

11. The process of claim 10, wherein said water-soluble corrosion inhibitor is hydroxylamine.

12. The process of claim 10, wherein said water-soluble corrosion inhibitor is an hydroxylammonium salt selected from the group consisting essentially of hydroxylammonium nitrate, hydroxylammonium sulfate, hydroxylammonium phosphate, hydroxylammonium chloride, hydroxylammonium oxalate, hydroxylammonium citrate, and combinations thereof.

13. The process of claim 10, wherein said water-soluble corrosion inhibitor is at least one water-soluble organic acid.

14. The process of claim 13, wherein said water-soluble organic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid (butanediol acid), glutaric acid, maleic acid, fumaric acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid (2-hydroxypropionoic acid), citric acid, salicylic acid, tartaric acid and gluconic acid.

15. The process of claim 14, wherein said water-soluble organic acid is selected from the group consisting of lactic acid, tartaric acid, acetic acid, gluconic acid and phthalic acid.

16. The process of claim 10, wherein said water-soluble corrosion inhibitor is at least one amino acid.

17. The process of claim 10, wherein said water-soluble corrosion inhibitor is an amino acid selected from the group consisting essentially of tricine, bicine, DL-homoserine, D-homoserine, L-homoserine, DL-threonine, D-allo-threonine, L-allo-threonine, D-threonine, L-threonine, DL-3-hydroxynorvaline, DL-methyltyrosine, D-4-hydroxyphenylglycine, DL-tyrosine, D-tyrosine, L-tyrosine, 3-(3,4-dihydroxyphenyl)-DL-alanine, 3-(3,4-dihydroxyphenyl)-L-alanine, 3-(2,4,5-trihydroxyphenyl)-DL-alanine, DL-alpha-methyltyrosine, L-alphamethyltyrosine, (-)-3-(3,4-dihydroxyphenyl)-2-methyl-L-alanine, DL-threo-3-phenylserine, DL-threo-3,4-dihydroxyphenylserine, and combinations thereof.

18. The process of claim 17, wherein said amino acid is selected from the group consisting essentially of tricine, bicine, 3-(3,4-dihydroxyphenyl)-DL-alanine, 3-(2,4,5-trihydroxyphenyl)-DL-alanine, and DL-threo-3,4-dihydroxyphenylserine.

19. The process of claim 10, wherein said removing steps (1) and (2) each comprise a liquid photoresist stripping step.

20. The process of claim 10, wherein said removing step (1) comprises an oxygen gas plasma ashing operation.

21. The process of claim 10, wherein steps (1) and (2) are carried out simultaneously.

22. The process of claim 10, wherein step (2) is a post-etch cleaning step.