TWI749964B - 鹼性清洗組合物、清洗方法和半導體製造方法 - Google Patents
鹼性清洗組合物、清洗方法和半導體製造方法 Download PDFInfo
- Publication number
- TWI749964B TWI749964B TW109146082A TW109146082A TWI749964B TW I749964 B TWI749964 B TW I749964B TW 109146082 A TW109146082 A TW 109146082A TW 109146082 A TW109146082 A TW 109146082A TW I749964 B TWI749964 B TW I749964B
- Authority
- TW
- Taiwan
- Prior art keywords
- cleaning composition
- alkaline cleaning
- alkyl group
- alkaline
- carbons
- Prior art date
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims description 21
- 239000004065 semiconductor Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- -1 alcohol ethers Chemical class 0.000 claims abstract description 24
- 239000002798 polar solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000001241 acetals Chemical class 0.000 claims abstract description 7
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 6
- 150000004040 pyrrolidinones Chemical class 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229920002050 silicone resin Polymers 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229920002120 photoresistant polymer Polymers 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- QWRBKBNCFWPVJX-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxymethoxy)ethane Chemical compound COCCOCOCCOC QWRBKBNCFWPVJX-UHFFFAOYSA-N 0.000 claims description 5
- GHELJWBGTIKZQW-UHFFFAOYSA-N 1-propan-2-ylpyrrolidin-2-one Chemical compound CC(C)N1CCCC1=O GHELJWBGTIKZQW-UHFFFAOYSA-N 0.000 claims description 5
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 5
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 5
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 5
- 238000005530 etching Methods 0.000 claims description 5
- 238000001459 lithography Methods 0.000 claims description 5
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- RKTGAWJWCNLSFX-UHFFFAOYSA-M bis(2-hydroxyethyl)-dimethylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(C)CCO RKTGAWJWCNLSFX-UHFFFAOYSA-M 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 claims description 2
- UAHWGDYDZHBBIY-UHFFFAOYSA-N 1-[bis(2-methoxyethoxy)methoxy]-2-methoxyethane Chemical compound COCCOC(OCCOC)OCCOC UAHWGDYDZHBBIY-UHFFFAOYSA-N 0.000 claims 1
- DQWQKIYQRSRHGJ-UHFFFAOYSA-N 1-methoxy-2-(1-methoxypropan-2-yloxymethoxy)propane Chemical compound COCC(C)OCOC(C)COC DQWQKIYQRSRHGJ-UHFFFAOYSA-N 0.000 claims 1
- SQKPPECKDHASCX-UHFFFAOYSA-N butylazanium tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].CCCC[NH3+].CCCC[NH3+].CCCC[NH3+].CCCC[NH3+] SQKPPECKDHASCX-UHFFFAOYSA-N 0.000 claims 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims 1
- 239000010410 layer Substances 0.000 description 40
- 239000012855 volatile organic compound Substances 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000123 silicon containing inorganic group Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003112 inhibitor 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
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-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
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- AGGCEDYMGLPKNS-UHFFFAOYSA-N 5,5,6-trimethylundec-3-yne-2,2-diol Chemical class CCCCCC(C)C(C)(C)C#CC(C)(O)O AGGCEDYMGLPKNS-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940099690 malic acid Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- 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
-
- 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
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating 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
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Abstract
本發明提供一種鹼性清洗組合物,其包含: 鹼性化合物、5~40重量%的丙二醇單甲醚、10~30重量%的水及極性溶劑。其中,該極性溶劑包含縮醛類、醇醚類、吡咯烷酮類或其組合的溶劑,且該鹼性清洗組合物不包含苯磺酸。
Description
本發明係關於一種半導體製程的清洗組合物,特別是關於一種鹼性清洗組合物、使用該鹼性清洗組合物的清洗方法和半導體製造方法。
半導體元件通常是由矽晶圓所構成的半導體基板經由金屬配線層、介電層、絕緣層、以及抗反射層等功能層等層疊設置而形成的。上述的層疊設置係藉由黃光微影製程所形成的阻劑圖型為遮罩進行蝕刻處理,並對上述各層進行加工而成。上述微影製程中的阻劑圖型係藉由阻劑膜、或設於此等阻劑膜下層的抗反射膜、犧牲膜等膜層來形成阻劑圖型。
於蝕刻步驟中所生成的來自金屬配線層或介電層之殘渣,係使用清洗液加以去除,以避免影響後續的製程步驟,降低讓所述殘渣成為半導體元件良率的問題。一般而言,使用清洗液加以去除的塗膜對象,例如:對應g射線、i射線、KrF準分子雷射、ArF準分子雷射、EUV等各曝光波長之阻劑膜、設於此等阻劑下層之抗反射膜、由含有矽原子之矽遮罩等無機膜所構成之犧牲膜、或設於阻劑上層之保護膜等。尤其在液浸微影法中,其係於基板上依序層合阻劑下層膜、阻劑膜與保護膜等,因此發展一種可用於清洗、且有效去除各種膜層遮罩的清洗液,且不影響後續製程的良率,一直為業界持續努力的方向。
因此,本發明之目的在於提供一種鹼性清洗組合物,用以有效清洗且去除殘留在基板或半導體基板上的阻劑、含矽之無機膜或其他膜層,且所述鹼性清洗組合物不僅能減少汙染物排放達到環境保護需求的目的,且可有效避免影響後續製程的良率。
在本發明的一實施方式中, 所述鹼性清洗組合物包含鹼性化合物、5~40重量%的丙二醇單甲醚、10~30重量%的水及極性溶劑。其中,所述極性溶劑包含縮醛類、醇醚類、吡咯烷酮類或其組合的溶劑,且所述鹼性清洗組合物不包含苯磺酸。
本發明之另一目的在於提供一種清洗方法。所述清洗方法包含使用上述鹼性清洗組合物清洗並去除附著於裝置元件上的殘渣或膜的步驟;且,所述殘渣或膜係包括阻劑或含有矽原子之無機物。
本發明之另一目的更提供一種半導體製造方法。所述半導體的製造方法包含下列步驟:
提供一基板;
在所述基板上塗佈矽氧烷樹脂層;
在所述矽氧烷樹脂層上塗佈光阻層以形成一多層基板;
對所述多層基板進行微影及
乾蝕刻製程;以及
使用上述鹼性清洗組合物清洗並去除附著於所述基板上的所述矽氧烷樹脂層及所述光阻層的殘留物。
在詳細說明本發明的至少一實施例之前,應當理解的是本發明並非必要受限於其應用在以下描述中的多個示例所舉例說明的多個細節,例如,實施例的數量或採用之特定混合比例等。本發明能夠爲其他的實施例或者以各種方式被實施或實現。
[鹼性清洗組合物]
本發明提供一種可用於清洗且去除殘留在基板或半導體基板上的阻劑、含矽之無機膜或其他膜層等的鹼性清洗組合物。所述鹼性清洗組合物包含鹼性化合物、5~40重量%的丙二醇單甲醚作為第一溶劑、10~30重量%的水及極性溶劑;其中,所述極性溶劑包含縮醛類、醇醚類、吡咯烷酮類或其組合的溶劑作為第二溶劑,且所述鹼性清洗組合物不包含苯磺酸。此組合的鹼性清洗組合物不僅可有效去除殘留在基板上的阻劑、膜層等殘留物,且具有含量較低的揮發性有機化合物(VOCs),因此能達到環境保護需求的目的。以下將就各成分進行詳細說明:
[鹼性化合物]
在本發明所揭露之一種實施方式中,所述鹼性化合物可使用氫氧化四級銨、醇胺類化合物或其混合物。
其中,R
1~R
4各自獨立為碳數1~4的直鏈或具支鏈的烷基,且所述烷基為未經取代或經羥基所取代,且X為OH。
具體而言,在本發明所揭露之一種實施方式中,所述氫氧化四級銨可包含下列群組中的至少一種: 氫氧化四甲銨(TMAH)、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、乙基三甲基氫氧化銨、二乙基二甲基氫氧化銨、(2-羥乙基)三甲基氢氧化銨、雙(2-羥乙基)二甲基氢氧化銨和三(2-羥乙基)甲基氢氧化銨。在本發明所揭露之一種實施方式中,較佳為氫氧化四甲銨。
其中,R
1、R
2各自獨立為氫或碳數1~6的直鏈或具支鏈的烷基,且所述烷基為未經取代或經羥基所取代,R
3為碳數1~8的伸烷基,且所述伸烷基為未經取代或至少一個−CH
2−被−O−或−NH−取代,且−O−不與−O−或−NH−直接相連、−NH−不與−NH−直接相連;R
4、R
5各自獨立為氫或碳數1~3的烷基,且所述烷基為未經取代或經羥基所取代。
具體而言,在本發明所揭露之一種實施方式中,所述醇胺類化合物可包含下列群組中的至少一種:乙醇胺(MEA)、二乙醇胺、三乙醇胺、正丙醇胺(N-PA)、正二丙醇胺、正三丙醇胺、二異丙醇胺、三異丙醇胺、N-甲基乙醇胺、 2-氨基-2-甲基-1,3-丙二醇和2-(2-氨基乙氧基)乙醇。在本發明所揭露之一種實施方式中,較佳為正丙醇胺、乙醇胺和2-氨基-2-甲基-1,3-丙二醇。
在本發明所揭露之一種實施方式中,所述鹼性化合物亦可為上述氫氧化四級銨和上述醇胺類化合物的混合物。
具體而言,所述鹼性化合物佔所述鹼性清洗組合物總量的0.1~20重量%,且較佳為0.5~10重量%。在此等範圍內,所述鹼性化合物能有效去除阻劑、含矽之無機膜或其他膜層等殘留物。
[第一溶劑]
在本發明所揭露之一種實施方式中,所述第一溶劑包含5~40重量%的丙二醇單甲醚(PGME)。且較佳地,丙二醇單甲醚的重量百分比為15~30重量%。須注意的是,上述重量百分比為丙二醇單甲醚所佔所述鹼性清洗組合物總量的比例範圍。
具體而言,本發明的鹼性清洗組合物藉由包含該等比例範圍的丙二醇單甲醚作為第一溶劑,而能有優異的阻劑、含矽之無機膜或其他膜層等殘留物的洗淨能力。
[水]
在本發明所揭露之一種實施方式中,本發明的鹼性清洗組合物包含10~30重量%的水。且較佳地,水的重量百分比為15~25重量%。須注意的是,上述重量百分比為水所佔所述鹼性清洗組合物總量的比例範圍。
具體而言,上述作為本發明鹼性清洗組合物的水可使用純水、去離子水、離子交換水等,在此不作特別限定,只要水的重量百分比在上述比例範圍內即可。
[作為第二溶劑的極性溶劑]
在本發明所揭露之一種實施方式中,本發明的鹼性清洗組合物亦包含極性溶劑作為其第二溶劑。所述極性溶劑包含縮醛類、醇醚類、吡咯烷酮類或其組合的溶劑。
其中,R
1、R
2各自獨立為氫或碳數1~6的直鏈或具支鏈的烷基,且所述烷基為未經取代或至少一個−CH2−被−O−取代,R
3、R
4各自獨立為碳數1~4的伸烷基,R
5、R
6各自獨立為碳數1~3的烷基。
其中,R
1為氫或碳數1~4的直鏈或具支鏈的烷基,所述烷基為未經取代或經羥基所取代,R
2、R
3各自獨立為氫或碳數1~2的烷基,n為1~4的整數。
其中,R
1為碳數1~3的烷基。
具體而言,在本發明所揭露之一種實施方式中,所述極性溶劑較佳為選自下列群組中的至少一種:
4,8-二甲基-2,5,7,10-四氧雜十一烷(4,8-dimethyl-2,5,7,10-tetraoxaundecane)、2,5,7,10-四氧雜十一烷(2,5,7,10-tetraoxaundecane;TOU)、6-(2-甲氧基乙氧基)-2,5,7,10-四氧雜十一烷(6-(2-methoxyethoxy)-2,5,7,10-Tetraoxaundecane) 、丙二醇(PG)、丙二醇乙醚、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚(EDG)、二乙二醇單丁醚、二丙二醇甲醚(DPGME)、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮和N-異丙基-2-吡咯烷酮(NIP)。所述極性溶劑可包含一種或兩種以上。
所述極性溶劑更佳為選自下列群組中的至少一種:
N-異丙基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、2,5,7,10-四氧雜十一烷、二乙二醇單乙醚、二乙二醇單丁醚及丙二醇。
具體而言,所述極性溶劑佔所述鹼性清洗組合物總量的5~84.9重量%,且較佳為20~70重量%。藉由所述極性溶劑在此等比例範圍內,所述鹼性清洗組合物能有效去除阻劑、含矽之無機膜或其他膜層等殘留物。
[其他添加劑]
本發明的鹼性清洗組合物亦可包含其他添加劑,例如:界面活性劑、金屬腐蝕抑制劑等。
具體而言,所述金屬腐蝕抑制劑除了不包含苯磺酸類外,並無其他特別限定。可列舉如下: 苯並咪唑、苯並三唑、甲基苯并三唑、3-氨基-1,2,4-三唑、1,2,4-三唑、1,2,3-三唑、5-氨基四唑、2,6-吡啶二甲酸、苯基脲、對甲氧基苯酚、鄰苯二酚、間苯二酚、2-羥基吡啶、2-胺基苯酚、8-羥基喹啉、磷酸、硼酸、苯二甲酸(phthalic acid)、抗壞血酸(ascorbic acid)、己二酸(adipic acid)、蘋果酸(malic acid)、草酸(oxalic acid)、水楊酸(salicylic acid))等。
界面活性劑有陰離子型界面活性劑、陽離子型界面活性劑、非離子型界面活性劑等,在此並不特別限定;可列舉如下:聚氧乙烯烷基醚、氧化乙烯/氧化丙烯共聚物、聚氧乙烯烷基芳香醚等、炔屬醇系界面活性劑;具體而言,如:辛基酚聚氧乙烯醚、乙氧化四甲基癸炔二醇等。
[清洗方法]
本發明的清洗方法包含使用本發明的鹼性清洗組合物清洗並去除附著於任何裝置元件上的殘渣或膜,所述清洗包含各種清洗方式,例如:浸泡式清洗、噴灑式清洗,或其他清洗方式等。上述的殘渣或膜係包括阻劑或含有矽原子之無機物等。上述裝置元件並不特別限定,只要是製造過程中需要使用阻劑膜、抗反射膜、含有矽原子之矽遮罩等無機膜所構成之犧牲膜、或保護膜等膜層,而後又需要移除該等膜層者皆為本發明所述裝置元件的範圍,具體而言如半導體裝置或半導體元件等。
[半導體製造方法]
本發明亦提供一種半導體製造方法。所述半導體製造方法包含下列步驟:
提供一基板;
在所述基板上塗佈矽氧烷樹脂層;
在所述矽氧烷樹脂層上塗佈光阻層以形成一多層基板;
對所述多層基板進行微影及蝕刻製程;以及
使用本發明所述的鹼性清洗組合物清洗並去除附著於所述基板上的所述矽氧烷樹脂層及所述光阻層的殘留物。
具體而言,所述基板為半導體基板,例如:矽基板等。然後以上述矽氧烷樹脂層作為抗反射塗層,並塗布光阻層以微影製程圖案化所述矽氧烷樹脂層,並經由蝕刻製程再將圖案轉印到基板上,以完成基板的圖案化。接著,再以本發明所述的鹼性清洗組合物清洗並去除附著於所述基板上殘留的所述矽氧烷樹脂層及所述光阻層的殘留物。
[實施例]
本發明的具體實施例1~15及比較例1~14如表1所示,其去除力及揮發性有機化合物的評價結果如表2所示:
PGME: 丙二醇單甲醚
DPGME: 二丙二醇甲醚
PG: 丙二醇
EDG: 二乙二醇單乙醚
NIP: N-異丙基-2-吡咯烷酮
TOU: 2,5,7,10-四氧雜十一烷
TMAH: 氫氧化四甲銨
MEA: 乙醇胺
N-PA: 正丙醇胺
界面活性劑: 辛基酚聚氧乙烯醚,平均氧乙烯數為9
去除力評價方法:本發明以聚矽氧烷抗反射層為例,○表示可於90秒內將聚矽氧烷抗反射層清除乾淨,X表示無法於90秒內將聚矽氧烷抗反射層清除乾淨。
上述聚矽氧烷抗反射層係將聚矽氧烷樹脂旋轉塗佈在矽晶圓上,經熱處理3分鐘後形成厚度120nm的固化膜層;再將此固化膜層個別浸泡於實施例及比較例所示組成的清洗組合物作為洗劑,且洗劑溫度60℃、浸泡90秒,浸泡完成後再使用22℃純水沖洗30秒,風刀吹乾後,確認矽晶圓表面固化膜層的去除狀態。前述確認矽晶圓表面固化膜層的去除狀態可直接以肉眼目視即可判斷。
揮發性有機化合物(VOCs)評價方法:使用手持式光離子式VOC檢測器進行測定。檢測條件為於1大氣壓下,將100mL的洗劑存放於500mL瓶內,拴緊瓶口後於23℃下恆溫20分鐘。開蓋檢測時,將採樣管口放在500mL瓶口處,於30秒內讀取VOC檢測器的最大檢測值。用○表示揮發性有機化合物的含量小於50ppm,用X表示揮發性有機化合物的含量大於50ppm。
由上述實施例與比較例可知,本發明的鹼性清洗組合物由於使用比例範圍在5~40重量%的丙二醇單甲醚作為第一溶劑及10~30重量%的水,搭配其他縮醛類、醇醚類、吡咯烷酮類或其組合的極性溶劑作為第二溶劑,以及在鹼性化合物的存在下,能具有含量較低的揮發性有機化合物以及優異的殘膜去除力,進而能防止影響後續製程的良率。
反觀比較例,由於沒有使用比例範圍在5~40重量%的丙二醇單甲醚作為第一溶劑及10~30重量%的水,因此殘膜去除力不佳或是揮發性有機化合物的含量偏高,甚至兩者評價方式皆不佳。
雖然本發明已以多個較佳實施例揭露,然其並非用以限制本發明,僅用以使具有通常知識者能夠清楚瞭解本說明書的實施內容。本領域中任何熟習此項技藝之人士,在不脫離本發明之精神和範圍內,當可作各種更動、替代與修飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
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Claims (12)
- 一種鹼性清洗組合物,包含: 鹼性化合物、5~40重量%的丙二醇單甲醚、10~30重量%的水及極性溶劑; 其中,該極性溶劑包含縮醛類、醇醚類、吡咯烷酮類或其組合的溶劑,且該鹼性清洗組合物不包含苯磺酸。
- 如請求項1之鹼性清洗組合物,其中該鹼性化合物包含氫氧化四級銨、醇胺類化合物或其混合物。
- 如請求項2之鹼性清洗組合物,其中該氫氧化四級銨係選自由下列群組中的至少一種:氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、乙基三甲基氫氧化銨、二乙基二甲基氫氧化銨、(2-羥乙基)三甲基氢氧化銨、雙(2-羥乙基)二甲基氢氧化銨和三(2-羥乙基)甲基氢氧化銨; 該醇胺類化合物係選自下列群組中的至少一種: 乙醇胺、二乙醇胺、三乙醇胺、正丙醇胺、正二丙醇胺、正三丙醇胺、二異丙醇胺、三異丙醇胺、N-甲基乙醇胺、 2-氨基-2-甲基-1,3-丙二醇和2-(2-氨基乙氧基)乙醇。
- 如請求項1之鹼性清洗組合物,其中該鹼性化合物的含量為0.1~20重量%。
- 如請求項1之鹼性清洗組合物,其中該鹼性化合物為氫氧化四級銨和醇胺類化合物的混合物。
- 如請求項1之鹼性清洗組合物,其中該極性溶劑係選自下列群組中的至少一種: 4,8-二甲基-2,5,7,10-四氧雜十一烷、2,5,7,10-四氧雜十一烷、6-(2-甲氧基乙氧基)-2,5,7,10-四氧雜十一烷 、丙二醇、丙二醇乙醚、乙二醇單甲醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、二丙二醇甲醚、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮和N-異丙基-2-吡咯烷酮。
- 如請求項1之鹼性清洗組合物,其中該極性溶劑的含量為5~84.9重量%。
- 一種鹼性清洗組合物,包含: 氫氧化四級銨、5~40重量%的丙二醇單甲醚、10~30重量%的水及極性溶劑; 其中,該極性溶劑係選自N-異丙基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、2,5,7,10-四氧雜十一烷、二乙二醇單乙醚、二乙二醇單丁醚及丙二醇中的至少一種,且該鹼性清洗組合物不包含苯磺酸。
- 一種清洗方法,其係包含使用如請求項1~10中任一項的鹼性清洗組合物清洗並去除附著於裝置元件上的殘渣或膜;其中,該殘渣或膜係包括阻劑或含有矽原子之無機物。
- 一種半導體製造方法,其包含下列步驟: 提供一基板; 在該基板上塗佈矽氧烷樹脂層; 在該矽氧烷樹脂層上塗佈光阻層以形成一多層基板; 對該多層基板進行微影及蝕刻製程;以及 使用如請求項1~10中任一項的鹼性清洗組合物清洗並去除附著於該基板上的該矽氧烷樹脂層及該光阻層的殘留物。
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