CN102399648A - 一种含氟清洗液 - Google Patents
一种含氟清洗液 Download PDFInfo
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- CN102399648A CN102399648A CN2010102777030A CN201010277703A CN102399648A CN 102399648 A CN102399648 A CN 102399648A CN 2010102777030 A CN2010102777030 A CN 2010102777030A CN 201010277703 A CN201010277703 A CN 201010277703A CN 102399648 A CN102399648 A CN 102399648A
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- Prior art keywords
- fluorine
- scavenging solution
- acid
- alcohol
- weight percent
- Prior art date
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 27
- 239000011737 fluorine Substances 0.000 title claims abstract description 27
- 238000004140 cleaning Methods 0.000 title abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000002000 scavenging effect Effects 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 230000007797 corrosion Effects 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003352 sequestering agent Substances 0.000 claims description 6
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 4
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 4
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 claims description 4
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 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
- 239000008103 glucose Substances 0.000 claims description 4
- ICJBPZBRDLONIF-UHFFFAOYSA-N hexane-1,1,1,2,2,3-hexol Chemical compound CCCC(O)C(O)(O)C(O)(O)O ICJBPZBRDLONIF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical group CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical group CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 claims description 2
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 claims description 2
- -1 trihydroxyethyl Neutral ammonium fluoride Chemical compound 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- 239000004065 semiconductor Substances 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005530 etching Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001020 plasma etching Methods 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 abstract 1
- 238000004377 microelectronic Methods 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 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
- 238000005406 washing Methods 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- 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
- C11D3/43—Solvents
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- 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
- C11D7/261—Alcohols; Phenols
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
本发明公开了一种具有低氮氧化硅刻蚀速率的半导体工业用含氟清洗液,该清洗液组合物含有:a)氟化物 0.1%~20%,b)多元醇0.01%~20%,c)水5%~75%,d)溶剂1%~75%,e)其他添加剂 0~20%。本发明的清洗液组合物可有效地清洗半导体制造过程中等离子刻蚀残留物,同时对于基材如低介质材料(SiO2、PETEOS)和一些金属物质(如Ti,Al,Cu)等具有较低的蚀刻速率;特别是氮氧化硅刻蚀速率较低,从而进一步扩大含氟清洗液的清洗操作窗口,并进一步提高含氟清洗液的使用寿命,降低半导体厂的运营成本,在半导体晶片清洗等微电子领域具有良好的应用前景。
Description
技术领域
本发明涉及一种半导体工业用含氟清洗液。
背景技术
在半导体元器件制造过程中,光阻层的涂敷、曝光和成像对元器件的图案制造来说是必要的工艺步骤。在图案化的最后(即在光阻层的涂敷、成像、离子植入和蚀刻之后)进行下一工艺步骤之前,光阻层材料的残留物需彻底除去。在掺杂步骤中离子轰击会硬化光阻层聚合物,因此使得光阻层变得不易溶解从而更难于除去。至今在半导体制造工业中一般使用两步法(干法灰化和湿蚀刻)除去这层光阻层膜。第一步利用干法灰化除去光阻层(PR)的大部分;第二步利用缓蚀剂组合物湿蚀刻/清洗工艺除去且清洗掉剩余的光阻层,其步骤一般为清洗液清洗/漂洗/去离子水漂洗。在这个过程中只能除去残留的聚合物光阻层和无机物,而不能攻击损害金属层(如铝层)和非金属层(如氮氧化硅层)。
现有技术中典型的清洗液有以下几种:胺类清洗液(羟胺类),半水性胺基(非羟胺类)清洗液以及氟化物类清洗液。其中前两类清洗液需要在高温下清洗,一般在60℃到80℃之间,存在对金属的腐蚀速率较大的问题;而现存的氟化物类清洗液虽然能在较低的温度(室温到50℃)下进行清洗,但仍然存在着各种各样的缺点,例如不能同时控制金属和非金属基材的腐蚀,清洗后容易造成通道特征尺寸的改变,从而改变半导体结构;另一方面由于其较大蚀刻速率,清洗操作窗口比较小等。US5320709公开了一种清洗组合物包括:多元醇、氟化铵用于去除半导体基板上的有机金属残留物、有机硅的残留物和氧化硅,但特别指明其水含量不超过4%,而且其对有机聚合物的去除能力较弱。US 6,828,289公开的清洗液组合物包括:酸性缓冲液、有机极性溶剂、含氟物质和水,且pH值在3~7之间,其中的酸性缓冲液由有机羧酸或多元酸与所对应的铵盐组成,组成比例为10∶1至1∶10之间,并特别指出其不含有多元醇。如US 5,698,503公开了含氟清洗液,但大量使用多元醇,其含量为55-85%;因此造成清洗液的粘度与表面张力都很大,从而影响清洗效果。如US 5,972,862公开了含氟物质的清洗组合物,其包括含氟物质、无机或有机酸、季铵盐和有机极性溶剂,pH为7~11,由于其清洗效果不是很稳定,存在多样的问题。
因此尽管已经揭示了一些清洗液组合物,但还是需要而且近来更加需要制备一类更合适的清洗组合物或体系,适应新的清洗要求,比如环境更为友善、低缺陷水平、低刻蚀率以及较大操作窗口和较长的使用寿命。
发明内容
本发明的目的是为了解决如何安全、健康和有效的清洗半导体工业中等离子刻蚀残留物,并提供了一种安全有效的使用寿命长的清洗液组合物。
本发明是一种用于半导体工业中等离子刻蚀残留物的清洗液组合物,其包括氟化物、多元醇、水、溶剂、其他本领域的常规添加剂。其中所述的其他本领域的常规添加剂包括但不限于腐蚀抑制剂及螯合剂等中的一种和多种。
所述的清洗液组合物重量百分比含量为:
a)氟化物 0.1%~20%
b)多元醇 0.01%~20%
c)水 5%~75%
d)溶剂 1%~75%
e)其他本领域的常规添加剂0~20%
本发明所述的氟化物较佳地为氟化氢、或氟化氢与碱形成的盐。该碱可以是氨水、季胺氢氧化物和醇胺。氟化物较佳地为氟化氢(HF)、氟化铵(NH4F)、氟化氢铵(NH4HF2)、四甲基氟化铵(N(CH3)4F)或三羟乙基氟化铵(N(CH2OH)3HF)中的一种或多种。
本发明所述的多元醇是指二元醇、三元醇、四元醇、五元醇和六元醇。较佳地为乙二醇、1,2-丙二醇、丙三醇、丁四醇、戊五醇、核糖、核酮糖、葡萄糖、葡萄糖醇、己六醇、甘露醇和山梨醇;更较佳地为四元醇、五元醇和六元醇,优选丁四醇、戊五醇、核糖、核酮糖、葡萄糖、葡萄糖醇、己六醇、甘露醇和山梨醇。
本发明还可进一步含有水。
本发明中,所述的溶剂可选自亚砜、砜、咪唑烷酮、吡咯烷酮、咪唑啉酮、醚、酰胺中的一种或多种。其中,所述的亚砜较佳的为二甲基亚砜;所述的砜较佳的为环丁砜;所述的咪唑烷酮较佳的为1,3-二甲基-2-咪唑烷酮;所述的吡咯烷酮较佳的为N-甲基吡咯烷酮、羟乙基吡咯烷酮;所述的咪唑啉酮较佳的为1,3-二甲基-2-咪唑啉酮(DMI);所述的醚较佳的为丙二醇单甲醚、二丙二醇单甲醚;所述的酰胺较佳的为二甲基甲酰胺、二甲基乙酰胺。
本发明的清洗液还可含有其他本领域的常规添加剂,如腐蚀抑制剂及螯合剂等。其含量一般不超过20%。在本发明中,所述的腐蚀抑制剂可以为本领域常用的腐蚀抑制剂,优选来自苯并三氮唑类、羧酸(酯)类、聚羧酸(酯)类和膦酸(酯)类缓蚀剂等。如苯并三氮唑、苯甲酸、聚丙烯酸、1,3-(羟乙基)-2,4,6-三膦酸等。在本发明中,所述的螯合剂是指含有多个官能团的有机化合物。优选乙醇酸、丙二酸、柠檬酸、亚氨基二乙酸、氨三乙酸、三乙醇胺、乙二胺四乙酸、邻苯二酚、没食子酸、水杨酸、五甲基二乙烯三胺、氨基磺酸和磺基水杨酸等。
本发明的积极进步效果在于:本发明清洗液组合物能在一个温度比较大的范围内发挥作用,一般在室温到55℃范围内,并且能用于很广的领域中,比如批量浸泡式/批量旋转式/单片旋转式。同时,清洗液组合物有较小的金属和电介物质刻蚀率。
本发明的清洗液组合物还可有效地清洗金属和半导体制造过程中等离子刻蚀残留物,而且不会侵蚀SiO2、离子增强四乙氧基硅烷二氧化硅(PETEOS)、硅、氮氧化硅和一些金属物质(如Ti,Al,Cu)。对于半导体制造工业来说,本发明的清洗液组合物能在批量浸泡、批量旋转和单片旋转处理器中使用。
具体实施方式
表1等离子刻蚀残留物清洗液实施例1~20
我们选用了上表中部分实施例进行了性能测试,以说明本发明的效果,其结果见下表2。
表2部分实施例性能测试结果一览
溶液的金属腐蚀速率测试方法:
1)利用Napson四点探针仪测试4*4cm铝空白硅片的电阻初值(Rs1);
2)将该4*4cm铝空白硅片浸泡在预先已经恒温到40℃的溶液中60分钟;
3)取出该4*4cm铝空白硅片,用去离子水清洗,高纯氮气吹干,再利用Napson四点探针仪测试4*4cm铝空白硅片的电阻值(Rs2);
4)把上述电阻值和浸泡时间输入到合适的程序可计算出其腐蚀速率。溶液的非金属腐蚀速率测试方法:
1)利用Nanospec6100测厚仪测试4*4cm氮氧化硅硅片的厚度(T1);
2)将该4*4cmPETEOS硅片浸泡在预先已经恒温到40℃的溶液中60分钟;
3)取出该4*4cm氮氧化硅硅片,用去离子水清洗,高纯氮气吹干,再利用Nanospec6100测厚仪测试4*4cm氮氧化硅硅片的厚度(T2);
4)把上述厚度值和浸泡时间输入到合适的程序可计算出其腐蚀速率。
晶圆清洗的方法:
1)将待清洗的晶圆放入预先已经恒温到40℃的溶液中;
2)按照金属线浸泡20分钟、通道和金属垫浸泡30分钟的原则浸泡晶圆;
3)浸泡时间到后,取出该晶圆,用去离子水清洗,高纯氮气吹干后;送SEM测试。
从表2中可以看出:本发明的清洗液组合物对半导体制成中所用的金属(如金属铝)和非金属(如氮氧化硅)基本不会侵蚀,其腐蚀速率均接近或小于半导体业界通常所要求的2埃每分钟。用该溶液对等离子刻蚀残留物进行清洗发现,其等离子刻蚀残留物均被去除,而且没有腐蚀金属和非金属。
综上,本发明的清洗液清洗能力强,能同时对金属线(Metal)/通道(Via)/金属垫(Pad)晶圆清洗,能同时控制金属和非金属的腐蚀速率,特别是氮氧化硅刻蚀速率较低,从而有利于扩大含氟清洗液的清洗操作窗口,延长清洗液的使用寿命,降低半导体厂的运营成本。具有较大的操作窗口,能同时适用于批量浸泡式(wet Batch)/批量旋转喷雾式(Batch-spray)/单片旋转式(single wafer tool)。
Claims (14)
1.一种含氟清洗液,其包括:氟化物、多元醇、水、溶剂;其中:所述多元醇的重量百分比含量为0.01%~20%,所述水的重量百分比含量为5%~75%。
2.如权利要求1所述含氟清洗液,其特征在于,所述氟化物的重量百分比含量为0.1%~20%,所述溶剂的重量百分比含量为1%~75%。
3.如权利要求1所述含氟清洗液,其特征在于,所述氟化物为氟化氢、或氟化氢与碱形成的盐,该碱是氨水、季胺氢氧化物或醇胺。
4.如权利要求3所述含氟清洗液,其特征在于,所述氟化物为氟化氢(HF)、氟化铵、氟化氢铵、四甲基氟化铵和/或三羟乙基氟化铵。
5.如权利要求1所述含氟清洗液,其特征在于,所述多元醇为二元醇、三元醇、四元醇、五元醇和/或六元醇。
6.如权利要求5所述含氟清洗液,其特征在于,所述多元醇为乙二醇、1,2-丙二醇、丙三醇、丁四醇、戊五醇、核糖、核酮糖、葡萄糖、葡萄糖醇、己六醇、甘露醇和/或山梨醇。
7.如权利要求6所述含氟清洗液,其特征在于,所述多元醇为丁四醇、戊五醇、核糖、核酮糖、葡萄糖、葡萄糖醇、己六醇、甘露醇和/或山梨醇。
8.如权利要求1所述含氟清洗液,其特征在于,所述溶剂选自亚砜、砜、咪唑烷酮、吡咯烷酮、咪唑啉酮、醚和酰胺中的一种或多种。
9.如权利要求1所述含氟清洗液,其特征在于,所述亚砜为二甲基亚砜;所述砜为环丁砜;所述咪唑烷酮为1,3-二甲基-2-咪唑烷酮;所述吡咯烷酮为N-甲基吡咯烷酮和/或羟乙基吡咯烷酮;所述咪唑啉酮为1,3-二甲基-2-咪唑啉酮;所述醚为丙二醇单甲醚和/或二丙二醇单甲醚;所述酰胺为二甲基甲酰胺和/或二甲基乙酰胺。
10.如权利要求1所述含氟清洗液,其特征在于,所述含氟清洗液还含有其他添加剂。
11.如权利要求10所述含氟清洗液,其特征在于,所述其他添加剂的重量百分比含量为不超过20%。
12.如权利要求10所述含氟清洗液,其特征在于,所述其他添加剂为腐蚀抑制剂和/或螯合剂
13.如权利要求12所述含氟清洗液,其特征在于,所述腐蚀抑制剂选自苯并三氮唑、苯甲酸、聚丙烯酸和1,3-(羟乙基)-2,4,6-三膦酸中的一种或多种;所述的螯合剂是含有多个官能团的有机化合物。
14.如权利要求12所述含氟清洗液,其特征在于,所述螯合剂选自乙醇酸、丙二酸、柠檬酸、亚氨基二乙酸、氨三乙酸、三乙醇胺、乙二胺四乙酸、邻苯二酚、没食子酸、水杨酸、五甲基二乙烯三胺、氨基磺酸和磺基水杨酸中的一种或多种。
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