Formulations including a 1,3-dicarbonyl compound chelating agent and copper corrosion inhibiting agents for stripping residues from semiconductor substrates containing copper structures

{
  "publication_number": "US6660700B2",
  "country": "US",
  "kind": "B2",
  "title": "Formulations including a 1,3-dicarbonyl compound chelating agent and copper corrosion inhibiting agents for stripping residues from semiconductor substrates containing copper structures",
  "abstract": "A semiconductor wafer cleaning formulation, including 2-98% wt. organic amine, 0-50% wt. water, 0.1-60% wt. 1,3-dicarbonyl compound chelating agent, 0-25% wt. of additional different chelating agent(s), 0.5-40% wt. nitrogen-containing carboxylic acid or an imine, and 2-98% wt polar organic solvent. The formulations are useful to remove residue from wafers following a resist plasma ashing step, such as inorganic residue from semiconductor wafers containing delicate copper interconnecting structures.",
  "claims": [
    "1. A method for fabricating a semiconductor wafer including the steps comprising: plasma etching a metalized layer from a surface of the wafer; plasma ashing a resist from the surface of the wafer; cleaning the wafer with a semiconductor wafer cleaning formulation comprising the following components in the percentage by weight (based on the total weight of the formulation) ranges shown: organic amine(s) 2-98% water 0-50% 1,3-dicarbonyl compound chelating agent 0.1-60% additional different chelating agent(s) 0-25% nitrogen-containing carboxylic acid or imine 0.5-40% polar organic solvent 2-98% TOTAL 100%.",
    "2. The method of claim 1 wherein said organic amine(s) comprises a compound selected from the group consisting of: Pentamethyldiethylenetriamine (PMDETA) 5-95% Triethanolamine (TEA) 5-95%.",
    "3. The method of claim 1 wherein said 1,3-dicarbonyl compound chelating agent comprises a compound selected from the group consisting of: 2,4-pentanedione 2-90% N,N-Dimethylacetoacetamide 2-90% methyl acetoacetate 15-70% dimethylmalonate 10-48.3%.",
    "4. The method of claim 1 wherein said nitrogen-containing carboxylic acid or imine comprises a compound selected from the group consisting of: iminodiacetic acid (IDA) 0.5-2.5% glycine 0.5-2.5% nitrilotriacetic acid (NTA) 0.5-2.5% 1,1,3,3-tetramethylguanidine (TMG) 0.5-2.5%.",
    "5. The method of claim 1 wherein said polar organic solvent comprises a solvent species selected from the group consisting of: ethylene glycol 0-74% N-methylpyrrolodone (NMP) 0-49% sulfolane 0-10%.",
    "6. The method of claim 1 wherein said additional different chelating agent(s) comprises a compound selected from the group consisting of: ammonium pyrrolidinedithiocarbamate 0-25% ammonium carbamate 0-15% ammonium oxalate 0-15% ammonium thiocyanate 0-15% ammonium thiosulfate 0-15% trifluoroacetic acid 0-12%.",
    "7. The method of claim 1 wherein said organic amine(s) comprises a compound selected from the group consisting of: pentamethyldiethylenetriamine (PMDETA) monoethanolamine diglycolamine triethanolamine (TEA) diazabicyclo (2.2.2) octane diethylenetriamine 3,3′-iminobis (N,N-dimethylpropylamine) N-methylimidazole tetraethylenepentamine triethylenetetramine trimethoxyethoxyethylamine diethanolamine methyldiethanolamine tetramethylhexanediamine N,N-diethylethanolamine.",
    "8. The method of claim 1 wherein said 1,3-dicarbonyl compound chelating agent comprises a compound selected from the group consisting of: 2,4-pentanedione N,N-Dimethylacetoacetamide methyl acetoacetate dimethylmalonate N-methylacetoacetamide acetoacetamide malonamide.",
    "9. The method of claim 1, wherein said nitrogen-containing carboxyl acid or imine comprises a compound selected from the group consisting of: iminodiacetic acid (IDA) glycine nitrilotriacetic acid (NTA) 1,1,3,-tetramethylguanidine (TMG) CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3)2 CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3) 2 CH 3 C(═NH)CH 2 C(O)CH 3 (CH 3 CH 2) 2 NC(═NH)N(CH 3 CH 2) 2 HOOCCH 2 N(CH 3) 2 HOOCCH 2 N(CH 3)CH 2 COOH.",
    "10. The method of claim 1 wherein said organic amine(s) comprises a compound selected from the group consisting of: pentamethyldiethylenetriamine (PMDETA) 5-95% triethanolamine (TEA) 5-95%. said 1,3-dicarbonyl compound chelating comprises a compound selected from the group consisting of: 2,4-pentanedione 2-90% N,N-Dimethylacetoacetamide 2-90% methyl acetoacetate 15-70% dimethylmalonate 10-48.3% said nitrogen-containing carboxylic acid or imine comprises a compound selected from the group consisting of: iminodiacetic acid (IDA) 0.5-2.5% glycine 0.5-2.5% nitrilotriacetic acid (NTA) 0.5-2.5% 1,1,3,3-tetramethylguanidine (TMG) 0.5-2.5% and said polar organic solvent comprises a compound selected from the group consisting of: ethylene glycol 0-74% N-methylpyrrolodone (NMP) 0-49% sulfolane 0-10%.",
    "11. The method of claim 1 wherein the formulation comprises a chelating agent having the formula: X - CHR - Y in which R is either hydrogen or an aliphatic group and X and Y are functional groups containing multiply bonded moieties having electron-withdrawing properties.",
    "12. The method of claim 11 wherein each of X and Y is independently selected from CONH 2, CONHR′, CONR′R″, CN, NO 2, SOR′, and SO 2 Z in which R′ and R″ are alkyl and Z is hydrogen, halo, or alkyl.",
    "13. The method of claim 1 comprising a nitrogen-containing carboxylic acid having the formula: COOH - CH 2 - NRR′ wherein each of R and R′ is independently selected from the group consisting of hydrogen, alkyl, aryl, and carboxylic acids.",
    "14. A method of removing residue from a wafer following a resist plasma ashing step on said wafer, comprising contacting the wafer with a cleaning formulation, including (i) organic amine(s), (ii) water, (iii) 1,3-dicarbonyl compound chelating agent, (iv) nitrogen-containing carboxylic acid or imine, (v) polar organic solvent, and optionally (vi) additional different chelating agent(s)."
  ],
  "description_excerpt": "This is a divisional Of U.S. Ser. No. 09/732,370, Filed On Dec. 8, 2000, now U.S. Pat. No. 6,344,432.\n\n1. Field of the Invention\n\nThe present invention relates generally to chemical formulations that are useful in semiconductor wafer fabrication and particularly to chemical formulations that are utilized to remove residue from wafers following a resist plasma ashing step. More specifically, the present invention relates to cleaning formulations for removal of inorganic residue from semiconductor wafers containing delicate copper interconnecting structures.\n\n2. Description of the Prior Art\n\nVarious chemical formulations are conventionally employed to remove residue and clean wafers following a resist ashing step. Some of these chemical formulations include akaline compositions containing amines and/or tetraalkyl ammonium hydroxides, water and/or other solvents, and chelating agents. Such formulations have associated drawbacks which include unwanted removal of metal or insulator layers and the promotion of corrosion of desirable metal layers, particularly copper or copper alloys features.\n\nSome of such formulations employ corrosion-inhibiting additives to prevent undesirable copper metal corrosion during the cleaning process. However, conventional corrosion-inhibiting additives typically have detrimental effects on the cleaning process because such additives interact with the residue and inhibit dissolution of such residue in the cleaning fluid.",
  "cpc": [
    "H10P 70/273",
    "C11D 1/00",
    "C11D 2111/22",
    "C11D 3/2072",
    "C11D 7/02",
    "C11D 7/261",
    "C11D 7/264",
    "C11D 7/265",
    "C11D 7/266",
    "C11D 7/32",
    "C11D 7/3209",
    "C11D 7/3218",
    "C11D 7/3245",
    "C11D 7/3263",
    "C11D 7/3272",
    "C11D 7/3281",
    "C11D 7/34",
    "C11D 7/5009",
    "C11D 7/5013",
    "C23G 5/02",
    "G03F 7/425",
    "H10P 50/287",
    "H10P 70/15",
    "H10P 70/234"
  ],
  "ipc": [
    "C11D 11/00",
    "C11D 3/20",
    "C11D 7/02",
    "C11D 7/26",
    "C11D 7/28",
    "C11D 7/32",
    "C11D 7/34",
    "C11D 7/50",
    "C11D 7/60",
    "C23G 5/02",
    "G03F 7/42",
    "H01L 21/02",
    "H01L 21/304",
    "H01L 21/311",
    "H01L 21/3213"
  ],
  "assignees": [
    "Advanced Technology Materials Inc"
  ],
  "inventors": [
    "William A. Wojtczak",
    "Ma. Fatima Seijo",
    "David Bernhard",
    "Long Nguyen"
  ],
  "filing_date": "2001-11-15",
  "publication_date": "2003-12-09",
  "grant_date": "2003-12-09",
  "priority_date": "1999-08-20",
  "application_number": "US-337301-A",
  "family_id": "24943259",
  "cited_by_count": 10,
  "citations": [
    "US5290361A",
    "US5840127A",
    "US5630904A",
    "JPH0870127A",
    "US5885362A",
    "WO1998022568A1",
    "WO1998028395A1",
    "US6030491A",
    "US6211126B1",
    "US6248704B1",
    "US6344432B1",
    "US6566315B2"
  ]
}