CN1982426B - Slow-releasing agent system for cleaning semiconductor chip - Google Patents
Slow-releasing agent system for cleaning semiconductor chip Download PDFInfo
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- CN1982426B CN1982426B CN2005101116025A CN200510111602A CN1982426B CN 1982426 B CN1982426 B CN 1982426B CN 2005101116025 A CN2005101116025 A CN 2005101116025A CN 200510111602 A CN200510111602 A CN 200510111602A CN 1982426 B CN1982426 B CN 1982426B
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- acid
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- releasing agent
- agent system
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 18
- 238000004140 cleaning Methods 0.000 title abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 27
- 150000003384 small molecules Chemical class 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 15
- 239000003112 inhibitor Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 11
- 238000005530 etching Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000452 restraining effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- -1 metal oxide compound Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000003923 scrap metal Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/267—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
A corrosion-inhibitor system for cleaning semiconductor wafer consists of water and/or solvent and polymer containing carboxy. It can be used between room-temperature to 85degree. It is safe, non-toxic, and healthy and has gentle condition and could inhibit metal or non-metal corrosion.
Description
Technical field
The present invention relates to be used in a kind of semiconductor fabrication the slow-releasing agent system that semiconductor wafer cleans.
Background technology
In the semiconductor components and devices manufacturing processed, the coating of photoresist layer, exposure and imaging are necessary process steps to the pattern manufacturing of components and parts.Before last (promptly after coating, imaging, ion implantation and the etching at photoresist layer) of patterning carried out next processing step, the residue of photoresist layer material need thoroughly be removed.Can sclerosis photoresist layer polymkeric substance in doping step intermediate ion bombardment (ion bombardment), thus therefore make photoresist layer become to be difficult for molten more being difficult to be removed.So far the general two-step approach (dry ashing and wet etching) of using is removed this layer photoresistance tunic in semi-conductor industry.The first step utilizes dry ashing to remove the major part of photoresist layer; Second step utilized composite corrosion inhibitor wet etching/cleaning to remove and wash remaining photoresist layer.In the cleaning process in second step, composite corrosion inhibitor can only be removed polymkeric substance photoresist layer (PR) and inorganic residue, and can not attack infringement metal level such as aluminium lamination, and this step needs for a long time usually; And, often need at high temperature carry out in order to help removing of photoresist layer.
As the 5334332 (Lee of US in the prior art, EKC), US 5417877 (Ward, Ashland) US6030932 (Leon, Olin) and US 6635186 (Small, EKC) etc. patent all discloses some and has been used for the composite corrosion inhibitor that wet etching is removed photoresist layer, and these composite corrosion inhibitors comprise toxicants such as pyrocatechol or oxine.Although these composite corrosion inhibitor corrosion mitigating effects that contain pyrocatechol or derivatives thereof, oxine or other inhibiter are good, but common concentration height of this composite corrosion inhibitor and strong toxicity, and need at high temperature to use, the harm unfriendly to environment, that generation is very big, unfavorable to HUMAN HEALTH.Therefore press for the novel inhibiting solution system of developing.
Summary of the invention
The object of the present invention is to provide a kind of slow-releasing agent system that semiconductor wafer cleans that is used for, this slow-releasing agent system comprises water and/or solvent, it is characterized in that also comprising a kind of carboxylic polymkeric substance, and wherein, at least a monomer of synthetic this polymkeric substance contains carboxyl.
The slow-releasing agent system that is used for the semiconductor wafer cleaning of the present invention comprises carboxylic polymkeric substance, and it can be to metal such as Al etc. or nonmetal Si or nonmetal oxide SiO
2Deng corrosion produce restraining effect; Carboxylic polymkeric substance in this slow-releasing agent system can play the effect of corrosion inhibitor, tensio-active agent and sequestrant etc.; The slow-releasing agent system that is used for the semiconductor wafer cleaning of the present invention not only has environment friendliness, safety non-toxic, helps healthy characteristics; And the good restraining effect arranged all in fluorine-containing and not fluorine-containing system; Use slow-releasing agent system of the present invention can reduce the etch-rate of aluminium, and attack SiO hardly
2And Si.Of the present inventionly be used for slow-releasing agent system that semiconductor wafer cleans and can between room temperature to 85 ℃, use, can be used for recirculation system, spraying plating instrument and single-wafer processing.
In the present invention, described carboxylic polymkeric substance is carboxylic homopolymer and/or carboxylic multipolymer and/or carboxylic homopolymer salt and/or carboxylic copolymer salt.
In a preferred embodiment of the present invention, described carboxylic homopolymer is polymaleic anhydride (HPMA), polyacrylic acid (PAA) and/or polymethyl acrylic acid, preferred polymaleic anhydride and/or polyacrylic acid; In another preferred embodiment of the present invention, described carboxylic multipolymer is multipolymer (as: vinylformic acid and the maleic acid between the carboxylic monomer, methacrylic acid and maleic acid), or multipolymer (as: vinylbenzene and acrylic copolymer between vinyl monomer and the carboxylic monomer, vinylbenzene and maleic acid, vinyl cyanide and maleic acid, ethene and acrylic copolymer, vinyl cyanide and acrylic copolymer, vinylbenzene and Sipacril 2739OF, ethene and Sipacril 2739OF and/or vinyl cyanide and Sipacril 2739OF or the like), preferred vinylformic acid and maleic acid; In a preferred embodiment more of the present invention, described salt is ammonium salt, sylvite and/or sodium salt, and preferred ammonium salt is as ammonium polyacrylate (SD).
In the present invention, so long as existing carboxylic polymkeric substance all can be used in the slow-releasing agent system of the present invention in the prior art, carboxylic polymericular weight size does not influence and realizes purpose of the present invention.If the polymkeric substance that has certain mass concentration in the slow-releasing agent system of the present invention also correspondingly has certain density carboxyl in this slow-releasing agent system.This is because for the polymkeric substance of certain mass concentration, if the molecular weight of polymkeric substance is big, the mole number of polymkeric substance is just correspondingly few in the slow-releasing agent system; If the molecular weight of polymkeric substance is little, the mole number of polymkeric substance is also just correspondingly many in the slow-releasing agent system, that is to say, forms certain polymkeric substance, also just correspondingly contains certain density carboxyl on the polymkeric substance of its certain mass concentration.No matter the molecular weight size of this polymkeric substance, as long as the carboxyl on this polymkeric substance reaches certain concentration in slow-releasing agent system, promptly the slow-releasing agent system of carbonyl bearing polymer is used to clean semiconductor wafer and all can suppresses metal such as Al, nonmetal as Si and scrap metal oxide compound such as SiO
2Deng corrosion.In slow-releasing agent system of the present invention, the concentration of the carboxyl on the polymkeric substance preferably is 25ppm～50,000ppm.
In further preferred embodiment of the present invention, this slow-releasing agent system can also comprise small molecules acid and/or small molecules alkali.
This small molecules acid can be various small molecules acid, and preferred organic acid more preferably contains the small molecules acid of single or many carboxyls; This organic acid is preferably 2-phosphonic acids butane-1,2, and 4-tricarboxylic acid (PBTCA), oxalic acid (OA), citric acid and/or gallic acid more preferably are 2-phosphonic acids butane-1,2,4-tricarboxylic acid (PBTCA) and/or oxalic acid.
This small molecules alkali can be various small molecules alkali, preferably contains single or polyhydric small molecules alkali, more preferably ammoniacal liquor and/or Tetramethylammonium hydroxide (TMAH).
In slow-releasing agent system of the present invention, the concentration of this carboxylic polymkeric substance can be various concentration, and is preferred 0.00001～10%, more preferably 0.01～3%; The concentration of this small molecules acid and/or small molecules alkali is preferred 0～10%, and more preferably 0～5%; The concentration of this water and/or solvent can be various concentration of the prior art, and is preferred 80～99.99999%, more preferably 92～99.99%, and above concentration all refers to account for the mass concentration of whole slow-releasing agent system.
In the present invention, described solvent is meant organic solvent, can be various organic solvents or its mixture, as: N-Methyl pyrrolidone (NMP), gamma-butyrolactone (GBL), N, N-N,N-DIMETHYLACETAMIDE (DMAC), diethylene glycol monobutyl ether (DGMBE) and/or thanomin (EA) more preferably are NMP, DGMBE and/or EA.
The slow-releasing agent system that is used for the semiconductor wafer cleaning of the present invention can also comprise other corrosion inhibitor, tensio-active agent and/or sequestrant.
Positive progressive effect of the present invention is: the slow-releasing agent system that is used for the semiconductor wafer cleaning of the present invention has environment friendliness, safety non-toxic, helps healthy characteristics, can between room temperature to 85 ℃, use, and in fluorine-containing and not fluorine-containing system to metal or nonmetal the good restraining effect arranged all.
Embodiment
Comparative example 1 '～4 ' and embodiment 1～22
Table 1 slow-releasing agent system of the present invention and contrast system (not fluorine-containing system)
DI: deionized water; NA does not add this composition.
Table 2 slow-releasing agent system of the present invention and contrast system (fluorine-containing system)
| Embodiment | DI ％ | NMP ％ | SD ％ | NH 3H 2O ％ | PBTCA ％ | HPMA ％ | NH 4F ％ |
| 4’ | 29 | 70 | NA | NA | NA | NA | 1.0 |
| 15 | 29.4 | 70 | NA | NA | 0.1 | 0.1 | 0.4 |
| 16 | 29.8 | 70 | NA | NA | 0.1 | 0.1 | NA |
| 17 | 28.3 | 70 | NA | 0.5 | 0.1 | 0.1 | 1.0 |
| 18 | 28.4 | 70 | NA | 0.5 | NA | 0.1 | 1.0 |
| 19 | 28.2 | 70 | 0.1 | 0.5 | 0.2 | NA | 1.0 |
| 20 | 28.8 | 70 | 0.1 | NA | 0.1 | NA | 1.0 |
| 21 | 28.9 | 70 | 0.1 | NA | NA | NA | 1.0 |
| 22 | 28.4 | 70 | 0.1 | 0.5 | NA | NA | 1.0 |
DI: deionized water; NA does not add this composition.
Each composition in above-mentioned table 1 and the table 2 is proportionally mixed, make slow-releasing agent system of the present invention and correlated system.
Effect embodiment 1
System of comparative example 1 '～3 ' and the slow-releasing agent system of embodiment 1～9 are used to clean the blank Al wafer of etching in not fluorine-containing system.Testing method and condition: 25 ℃, shaking table is 60 rpms, and the time is 30 minutes.Etch-rate is to test to calculate after its etching front and rear surfaces resistance change by four utmost point probe machines to get, and the result is as shown in table 3.
Table 3 slow-releasing agent system in not fluorine-containing system to the etch-rate of blank Al wafer
| Slow-releasing agent system | 1’ | 2’ | 3’ | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Rate， A/min | 2.94 | 3.89 | 5.89 | 0.80 | -0.19 | 2.5 | 1.96 | -0.57 | -0.76 | 1.95 | 1.55 | 1.3 |
Annotate: Rate represents etch-rate; Etch-rate is a negative value, and the expression etch-rate is almost nil.
In the semi-conductor cleaning,, illustrate that then slow-releasing agent system has the goodish effect of corrosion inhibition if metal etch speed is less than or equal to 2.0A/min.As can be seen from Table 3, the slow-releasing agent system that does not contain carbonyl bearing polymer to the etch-rate of blank Al wafer greater than 2.0A/min; The slow-releasing agent system of carboxylic polymkeric substance of the present invention is used to clean blank Al wafer, and the Al etch-rate can obviously reduce the etch-rate of Al, even reach 0A/min all less than 2.0A/min, has suppressed the Al corrosive nature fully.Thereby the slow-releasing agent system that carboxylic polymkeric substance of the present invention is described can suppress the Al corrosion significantly, thereby the photoresist layer organic residue and/or the inorganic residue that help the Al wafer are effectively removed.
Effect embodiment 2
The foregoing description 4 slow-releasing agent systems are used to clean the blank SiO of etching
2Wafer, testing method and condition: 25 ℃, shaking table is 60 rpms, and the time is 30 minutes, with NANOSPEC THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS (purchasing the company in NANO metrics) test SiO
2Chip etching front and rear surfaces Thickness Variation calculates etch-rate.
The result shows: in the present invention, and SiO
2Etch-rate be 0.78A/min, its etch-rate illustrates that less than 2A/min slow-releasing agent system of the present invention also can suppress SiO
2Corrosion.
Effect embodiment 3
Comparative example 4 ' system and the slow-releasing agent system of embodiment 15～22 are used to clean the blank Al wafer of etching.Testing method and condition: 25 ℃, shaking table is 60 rpms, and the time is 30 minutes.Etch-rate is to test to calculate after its etching front and rear surfaces resistance change by four utmost point probe machines to get, and the result is as shown in table 4.
Table 4 slow-releasing agent system of the present invention is used for the etch-rate of fluorine-containing system to blank Al wafer
| Slow-releasing agent system | 4’ | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 |
| Rate，A/min | 3.09 | 1.70 | 0.80 | -0.01 | -0.36 | 1.16 | 1.60 | 1.88 | 0.79 |
Annotate: Rate represents etch-rate; Etch-rate is a negative value, and the expression etch-rate is almost nil.
In the semi-conductor cleaning, fluorochemical commonly used is assisted the residue of removing on the wafer, but fluorochemical often also increases simultaneously the etch-rate of metal.Show as table 4 data, in containing the system of fluorochemical, slow-releasing agent system of the present invention is used to clean blank Al wafer, the Al etch-rate is also very little, also the etch-rate of Al can be reduced to below the 2.0A/min, the slow-releasing agent system (as embodiment 21) that does not contain small molecules acid and small molecules alkali even only contain carbonyl bearing polymer also can be reduced to the Al etch-rate 1.88A/min, and the corrosion of Al has obtained complete inhibition.
Conclusion: the slow-releasing agent system that is used for the carbonyl bearing polymer of semiconductor wafer cleaning of the present invention has environment friendliness, safety non-toxic, helps healthy characteristics, can between room temperature to 85 ℃, use, and in fluorine-containing and not fluorine-containing system to metal or nonmetal the good restraining effect arranged all.
Claims (2)
1. one kind is used for the slow-releasing agent system that semiconductor wafer cleans, and this slow-releasing agent system is by water, organic solvent, carboxylic polymkeric substance, and small molecules acid and/or small molecules alkali composition, it is characterized in that,
At least a monomer of synthetic this polymkeric substance contains carboxyl, and described organic solvent is N-Methyl pyrrolidone, gamma-butyrolactone, N,N-dimethylacetamide and/or thanomin;
Described small molecules acid is 2-phosphonic acids butane-1,2,4-tricarboxylic acid, oxalic acid, citric acid and/or gallic acid, and described small molecules alkali is ammoniacal liquor and/or Tetramethylammonium hydroxide; Wherein:
Described carboxylic polymkeric substance is polyacrylic acid, polymethyl acrylic acid, vinylformic acid and maleic acid, vinylbenzene and acrylic copolymer, vinylbenzene and maleic acid and/or vinyl cyanide and maleic acid;
The concentration of this small molecules acid and/or small molecules alkali is for being no more than 10%, and the concentration of this water and organic solvent is 80～99.99999%, and the concentration of this carboxylic polymkeric substance is 0.00001～10%, and above concentration all refers to account for the mass concentration of whole slow-releasing agent system.
2. slow-releasing agent system according to claim 1, it is characterized in that: the concentration of this small molecules acid and/or small molecules alkali is for being no more than 5%, the concentration of this water and organic solvent is 92～99.99%, the concentration of this carboxylic polymkeric substance is 0.01～3%, and above concentration all refers to account for the mass concentration of whole slow-releasing agent system.
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| CN2005101116025A CN1982426B (en) | 2005-12-16 | 2005-12-16 | Slow-releasing agent system for cleaning semiconductor chip |
| PCT/CN2006/002622 WO2007068176A1 (en) | 2005-12-16 | 2006-10-08 | A system of corrosion inhibitor for cleaning semiconductor wafets |
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| CN2005101116025A CN1982426B (en) | 2005-12-16 | 2005-12-16 | Slow-releasing agent system for cleaning semiconductor chip |
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