TWI425323B - 用以移除後蝕刻及灰化之光阻劑殘餘物及總體光阻劑之組合物 - Google Patents
用以移除後蝕刻及灰化之光阻劑殘餘物及總體光阻劑之組合物 Download PDFInfo
- Publication number
- TWI425323B TWI425323B TW095115752A TW95115752A TWI425323B TW I425323 B TWI425323 B TW I425323B TW 095115752 A TW095115752 A TW 095115752A TW 95115752 A TW95115752 A TW 95115752A TW I425323 B TWI425323 B TW I425323B
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- Prior art keywords
- composition
- water
- phosphorus
- acid
- containing inorganic
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 72
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 18
- 238000004140 cleaning Methods 0.000 claims description 57
- 239000000758 substrate Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 25
- 238000004377 microelectronic Methods 0.000 claims description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 230000003628 erosive effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 150000002443 hydroxylamines Chemical class 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims 2
- 150000004696 coordination complex Chemical class 0.000 claims 2
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 claims 1
- 229960000485 methotrexate Drugs 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000004380 ashing Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- -1 glycol ethers Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 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 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical class CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 1
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical class CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 235000010388 propyl gallate Nutrition 0.000 description 1
- 229940075579 propyl gallate Drugs 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic 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
-
- 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)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本發明係關於用於清潔微電子基板、特別地含鋁或鈦之微電子組分之方法及後蝕刻及/或光阻劑灰化殘餘物清潔組合物。本發明之組合物提供對金屬之增進保護，意即在該等微電子基板接受清洗及後續水性沖洗時抑制侵蝕作用。
人們提出了許多光阻劑剝除劑及殘餘物移除劑用於微電子領域作為製造線之下游或背端清潔劑。在製造過程中，將一光阻材料薄膜沉積於一基板材料上，接著將電路設計成像於該薄膜上。在烘焙之後，用一光阻顯影劑移除經曝光之電阻。再將所得成像利用電漿蝕刻氣體或化學蝕刻劑溶液轉移至一般為介電質或金屬之下層材料。該等蝕刻劑氣體或化學蝕刻劑溶液有選擇地腐蝕未經光阻劑保護之基板區域。作為電漿蝕刻製程之結果，光阻劑及受蝕刻材料副產物作為殘餘物沉積於基板及光阻劑上之蝕刻開口(通孔)的側壁周圍或其上。
此外，在終止蝕刻步驟之後，必須自該基板之經保護區域移除抗蝕刻遮罩以便可進行下一處理操作。此操作可利用適當電漿灰化氣體或濕式化學剝除劑在一電漿灰化步驟中完成。亦證明難以尋找用於移除此抗蝕遮罩材料而無例如侵蝕、蝕刻或鈍化金屬電路之不利影響的適合清潔組合物。
由於微電子製造整合水平有所提高且圖案化微電子裝置尺寸變小，提供在不產生其他有害影響之條件下具有適當剝除及清潔特性之適當光阻劑剝除及清潔組合物變得日益困難。在半導體及平板顯示器(FPD)領域中，在光阻劑剝除、殘餘物移除及水沖洗過程中之金屬侵蝕問題係一嚴重缺點，特別是在使用諸如鋁、鈦及鎢及合金之備選金屬時。
微電子應用之典型殘餘物移除劑可為含鹼組合物，該組合物包括與有機胺或羥胺或通常溶於極性溶劑及其他溶劑化劑中試圖減少金屬及介電質腐蝕或侵蝕之其他強鹼摻合之極性有機溶劑。胺、羥胺或其他強鹼顯示提高了溶劑摻合物中移除光阻劑及殘餘物之有效性。然而，該等鹼性灰化殘餘物移除調配物自空氣中吸收二氧化碳，其在大多數情況下縮短清潔劑溶液之有效浴槽壽命。此外，此等鹼性清潔劑組合物起作用較慢且需要基板在高溫下長時間保持在清潔劑溶液中。此外，在此類型移除劑之後進行水沖洗會產生強鹼性水溶液且其可導致圖案化線路損失大量金屬，特別是在鹼性水溶液中對侵蝕非常敏感之鋁。此使得在清潔/剝除步驟與水性沖洗之間必需進行中間沖洗。該中間沖洗通常使用異丙醇，增添非吾人所樂見之時間、安全問題、環境影響及加工處理成本。
因此需要能夠自微電子基板完全移除蝕刻及/或灰化殘餘物、及總體光阻劑之光阻劑及殘餘物剝除及清潔組合物，尤其需要該等不生產任何顯著金屬侵蝕之清潔劑及殘餘物移除組合物。
本發明提供用於清潔微電子基板之清潔組合物，其能夠本質上完全清潔該等基板且抑制金屬侵蝕或本質上不對該等基板之金屬元件產生侵蝕，且相較於先前技術之含鹼清潔組合物所需之清潔時間而言用較短之清潔時間及在較低之溫度下完成此清潔作用。本發明亦提供使用該等清潔組合物清潔微電子基板而不對微電子基板之金屬元件不產生任何顯著侵蝕的方法。本發明之清潔組合物包含(a)至少一水溶性或可與水混溶之有機溶劑，(b)至少一未經中和之含磷無機酸，及(c)水。本發明之清潔組合物可視情況在該等組合物中具有其他組分，諸如界面活性劑、金屬錯合劑或螯合劑、侵蝕抑制劑，及其類似物。本發明之清潔組合物特徵為沒有會中和含磷無機酸組分之有機胺、羥胺或諸如銨鹼及其類似物之其他強鹼。本發明之清潔及殘餘物移除組合物特別適於清潔含有鋁、鈦及鎢之微電子基板。
本發明提供用於清潔微電子基板之清潔組合物，其能夠本質上完全清潔該等基板且抑制金屬侵蝕或本質上不對該等基板之金屬元件產生侵蝕。本發明亦提供使用該等清潔組合物清潔微電子基板而不對微電子基板之金屬元件產生任何顯著侵蝕之方法。本發明之清潔組合物包含(a)至少一有機溶劑，(b)至少一未經中和之含磷無機酸，及(c)水。
本發明之清潔組合物含有一或多種水溶性或與水混溶之適當有機溶劑。在該等多種有機溶劑中適合者為醇類；多羥基醇類，諸如甘油；二醇類，諸如丙二醇及二乙二醇；二醇醚，諸如2－(2－乙氧基乙氧基)乙醇(卡必醇)；烷基－吡咯啶酮，諸如N－甲基吡咯啶酮(NMP)；1－羥烷基－2－吡咯啶酮，諸如1－(2－羥乙基)－2－吡咯啶酮(HEP)；二甲基甲醯胺(DMF)；二甲基乙醯胺(DMAC)；碸，諸如環丁碸；及亞碸，諸如二甲亞碸(DMSO)；該等有機溶劑較佳為極性有機溶劑。較佳之水溶性有機溶劑為二乙二醇、丙二醇、N－甲基吡咯啶酮、環丁碸、DMSO及二甲基乙醯胺。本發明之清潔組合物含有一或多種有機溶劑，其量一般為組合物重量之約35%至約95%、較佳約60%至約90%、更佳約75%至約85%。
本發明之清潔組合物含有一或多種未經中和之含磷無機酸。在本發明之清潔組合物中可使用任何適合之未經中和含磷無機酸。該等未經中和之含磷無機酸實例包括但不限於亞磷酸(H3
PO3
)、次磷酸(H3
PO2
)及磷酸(H3
PO4
)。清潔組合物之未經中和之含磷無機酸組分於該清潔組合物中存在之量應使得有機溶劑組分與該未經中和之含磷無機酸組分的重量比為約3：1至約40：1、較佳約3：1至約20：1且更佳為約4：1至約10：1。
本發明清潔組合物之水組分可佔該組合物重量之約3%至約60%、較佳約5%至約50%、且更佳約5%至約10%。一般而言，由於該等酸通常以含水溶液形式提供，因此水組分將作為未經中和含磷無機酸組分之部分添加至清潔組合物。然而水可作為除了酸組分或除酸組分另外之單獨組分添加。
本發明之組合物亦可含有任何適當之水溶性兩性、非離子、陽離子或陰離子界面活性劑。添加界面活性劑將減小調配物之表面張力且改良待清潔表面之濕潤度且因此改良組合物之清潔作用。若希望進一步抑制鋁侵蝕，則亦可添加該界面活性劑以降低鋁侵蝕速率。此外，界面活性劑性質可有助於分散微粒，促進更徹底清潔。本發明之組合物中可使用任何適當之兩性、陽離子或非離子之界面活性劑。特別適合之界面活性劑實例包括但不限於：3,5－二甲基－1－己炔－3－醇(Surfynol－61)、乙氧基化2,4,7,9－四甲基－5－癸炔－4,7－二醇(Surfynol－465)、聚四氟乙烯乙醯氧基丙基甜菜鹼(Zonyl FSK)、Zonyl FSH、Triton X－100、即辛基苯氧基聚乙氧基乙醇，及其類似物。界面活性劑一般將佔組合物重量之0至約5重量%、較佳0.001至約3重量%。
本發明之清潔組合物亦可視情況含有其他組分，包括但不限於微電子清潔組合物中所採用之侵蝕抑制劑及類似抗蝕組分。該等化合物可包括：兒茶酚、間苯二酚、五倍子酸、沒食子酸丙酯、連苯三酚、對苯二酚、苯幷三唑之衍生物，及諸如檸檬酸、酒石酸、葡糖酸、醣二酸、甘油酸、草酸、鄰苯二甲酸、順丁烯二酸、扁桃酸、丙二酸、乳酸及水楊酸之多官能羧酸。
不需要有機或無機螯合劑或金屬錯合劑，但當併入本發明之清潔組合物中時可提供諸如改良產品穩定性、清潔及預防侵蝕之實質性利益。適當之螯合劑或錯合劑實例包括但不限於：反－1,2－環己烷二胺四乙酸(CyDTA)、乙二胺四乙酸(EDTA)、焦磷酸鹽、亞烷基二磷酸衍生物(例如1－羥基乙烷－1,1－二膦酸鹽(HEDPA))。該螯合劑於組合物中之量將佔該組合物重量之0至約5重量%、較佳約0.1至約2重量%。
在本發明之一較佳實施例中該清潔組合物包含次磷酸及水連同N－甲基吡咯啶酮、環丁碸、二乙二醇及DMSO之一或多種。在另一較佳實施例中該清潔組合物包含亞磷酸及水連同N－甲基吡咯啶酮、環丁碸、二乙二醇及DMSO之一或多種。
在本發明之另一態樣中本發明包含一種清潔微電子基板之方法，該基板含有光阻劑聚合材料、諸如灰化或蝕刻殘餘物之殘餘物及含有金屬之層，該方法包含使該基板與一清潔組合物接觸充以清潔該基板之時間，其中該清潔組合物包含下列組分：a.至少一水溶性或可與水混溶之有機溶劑，b.至少一未經中和之含磷無機酸，及c.水，其中該組合物不含會中和含磷無機酸組分之有機胺、羥胺及強鹼。該方法特別適於清潔含有多個金屬層之微電子基板且尤其是特徵為存在鋁、鈦及鎢金屬之基板。
由下列實例來說明本發明之組合物、其清潔微電子基板之用途及其非金屬侵蝕特性但並不限於該等實例。
在下列實例及表中使用下列縮寫。
NMP＝N－甲基吡咯啶酮DEG＝二乙二醇DMSO－二甲亞碸PG＝丙二醇DMAC＝二甲基乙醯胺HPA＝次磷酸PA＝亞磷酸HEDPA＝1－羥基乙烷－1,1－二膦酸
藉由將具有Al/TiN(鋁/氮化鈦)層之基板浸漬於本發明之組合物中來測試本發明之組合物清潔微電子裝置之能力，該等基板已塗佈有光阻劑、經曝光、顯影、硬蝕刻及灰化以產生一般在低溫下很難清潔之富鈦通孔。將該等樣本基板在45℃下浸漬於清潔組合物中10分鐘，隨後由DI水沖洗1分鐘。表1中之結果證明本發明組合物之清潔作用及相對非侵蝕性質。
藉由將具有Al/TiN層之基板浸漬於本發明之組合物中來測試本發明之組合物清潔微電子裝置之能力，該等基板已塗佈有光阻劑、經曝光、顯影、硬蝕刻及灰化以產生一般比實例1－7之通孔更易清潔之金屬線。將該等樣本基板在65℃下浸漬於組合物中20分鐘，隨後以DI水沖洗1分鐘。表2中之結果證明本發明組合物之清潔作用及相對非侵蝕性質，尤其在備選添加物存在時。
雖然本文已參考其特定實施例描述本發明，但應瞭解可在不背離本文所揭示之本發明概念之精神及範圍的條件下進行改變、修改及變化。因此，意欲包含所有屬於所附申請專利範圍之精神及範圍內之改變、修改及變化。
Claims (12)
- 一種用於清潔微電子基板之組合物，其實質上由下列組分組成：(a)至少一水溶性或可與水混溶之有機溶劑，(b)至少一未經中和之含磷無機酸，及(c)水，及視情況加入的(d)至少一界面活性劑；(e)至少一侵蝕抑制劑；及(f)至少一金屬錯合劑或螯合劑，其中該組合物不含會中和該含磷無機酸組分之有機胺、羥胺及強鹼，且其中該可與水混溶之有機溶劑實質上組成該組合物重量之約35%至約95%，且該有機溶劑組分與該未經中和含磷無機酸組分之重量比係在約3：1至約40：1之範圍內，該水在該組合物中之量係佔以該組合物之重量計約5%至約10%。
- 如請求項1之組合物，其中該未經中和之含磷無機酸包含選自由亞磷酸(H3 PO3 )、次磷酸(H3 PO2 )及磷酸(H3 PO4 )所組成之群之酸。
- 如請求項2之組合物，其中該水溶性或可與水混溶之有機溶劑組分係選自由N-甲基吡咯啶酮、環丁碸、二甲基碸、二乙二醇、丙二醇及二甲基乙醯胺所組成之群。
- 如請求項2之組合物，其中該未經中和之含磷無機酸包含亞磷酸(H3 PO3 )。
- 如請求項3之組合物，其中該未經中和之含磷無機酸包含次磷酸(H3 PO2 )。
- 如請求項1之組合物，其中存在1-羥基乙烷-1,1-二膦酸作為侵蝕抑制劑。
- 一種清潔微電子基板之方法，該基板含有光阻劑聚合材料、殘餘物及金屬，該方法包含使該基板與清潔組合物接觸足以清潔該基板之時間，其中該清潔組合物實質上由下列組分組成：(a)至少一水溶性或可與水混溶之有機溶劑，(b)至少一未經中和含磷無機酸，及(c)水，及視情況加入的(d)至少一界面活性劑；(e)至少一侵蝕抑制劑；及(f)至少一金屬錯合劑或螯合劑，其中該組合物不含會中和該含磷無機酸組分之有機胺、羥胺及強鹼，其中該可與水混溶之有機溶劑實質上組成該組合物重量之約35%至約95%，且該有機溶劑組分與該未經中和含磷無機酸組分之重量比在約3：1至約40：1之範圍內，該水在該組合物中之量係佔以該組合物之重量計約5%至約10%。
- 如請求項7之方法，其中該未經中和之含磷無機酸包含選自由亞磷酸(H3 PO3 )、次磷酸(H3 PO2 )及磷酸(H3 PO4 )所組成之群之酸。
- 如請求項8之方法，其中該水溶性或可與水混溶之有機溶劑組分係選自由N-甲基吡咯啶酮、環丁碸、二甲亞碸、二乙二醇、丙二醇及二甲基乙醯胺所組成之群。
- 如請求項8之方法，其中該未經中和之含磷無機酸包含亞磷酸(H3 PO3 )。
- 如請求項9之方法，其中該未經中和之含磷無機酸包含次磷酸(H3 PO2 )。
- 如請求項7之方法，其中存在1-羥基乙烷-1,1-二膦酸作為侵蝕抑制劑。
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| CN101373342B (zh) * | 2008-10-23 | 2011-03-02 | 江阴江化微电子材料股份有限公司 | 一种酸性剥离液及其制备方法 |
| US20110253171A1 (en) * | 2010-04-15 | 2011-10-20 | John Moore | Chemical Composition and Methods for Removing Epoxy-Based Photoimageable Coatings Utilized In Microelectronic Fabrication |
| US8921295B2 (en) | 2010-07-23 | 2014-12-30 | American Sterilizer Company | Biodegradable concentrated neutral detergent composition |
| EP3480288A1 (en) * | 2017-11-07 | 2019-05-08 | Henkel AG & Co. KGaA | Fluoride based cleaning composition |
| WO2020257103A1 (en) * | 2019-06-19 | 2020-12-24 | Versum Materials Us, Llc | Cleaning composition for semiconductor substrates |
| JP2023046519A (ja) | 2021-09-24 | 2023-04-05 | 富士フイルム株式会社 | 薬液、処理方法 |
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- 2006-04-18 BR BRPI0611377-0A patent/BRPI0611377A2/pt not_active IP Right Cessation
- 2006-04-18 WO PCT/US2006/014466 patent/WO2006121580A2/en active Application Filing
- 2006-04-18 KR KR1020077025627A patent/KR20080005408A/ko not_active Application Discontinuation
- 2006-04-18 CA CA002606849A patent/CA2606849A1/en not_active Abandoned
- 2006-04-18 CN CN2006800155059A patent/CN101171551B/zh active Active
- 2006-04-18 EP EP06750494.4A patent/EP1883863B1/en not_active Not-in-force
- 2006-05-03 MY MYPI20062030A patent/MY144723A/en unknown
- 2006-05-03 TW TW095115752A patent/TWI425323B/zh active
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2007
- 2007-08-16 ZA ZA200706853A patent/ZA200706853B/xx unknown
- 2007-11-01 IL IL187121A patent/IL187121A/en not_active IP Right Cessation
- 2007-11-06 NO NO20075670A patent/NO20075670L/no not_active Application Discontinuation
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| US20030152874A1 (en) * | 2001-12-12 | 2003-08-14 | Hijiri Nakahara | Photoresist stripping composition and process for stripping resist |
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Also Published As
| Publication number | Publication date |
|---|---|
| ZA200706853B (en) | 2008-09-25 |
| CN101171551B (zh) | 2012-12-26 |
| WO2006121580A3 (en) | 2007-02-15 |
| JP2008541426A (ja) | 2008-11-20 |
| IL187121A (en) | 2013-06-27 |
| BRPI0611377A2 (pt) | 2010-08-31 |
| MY144723A (en) | 2011-10-31 |
| EP1883863B1 (en) | 2014-01-22 |
| EP1883863A2 (en) | 2008-02-06 |
| KR20080005408A (ko) | 2008-01-11 |
| NO20075670L (no) | 2007-11-06 |
| CA2606849A1 (en) | 2006-11-16 |
| WO2006121580A2 (en) | 2006-11-16 |
| US7754668B2 (en) | 2010-07-13 |
| TW200702942A (en) | 2007-01-16 |
| IL187121A0 (en) | 2008-02-09 |
| US20080261846A1 (en) | 2008-10-23 |
| CN101171551A (zh) | 2008-04-30 |
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