KR102347596B1 - Composition of aqueous cleaner for removing residue - Google Patents
Composition of aqueous cleaner for removing residue Download PDFInfo
- Publication number
- KR102347596B1 KR102347596B1 KR1020150091250A KR20150091250A KR102347596B1 KR 102347596 B1 KR102347596 B1 KR 102347596B1 KR 1020150091250 A KR1020150091250 A KR 1020150091250A KR 20150091250 A KR20150091250 A KR 20150091250A KR 102347596 B1 KR102347596 B1 KR 102347596B1
- Authority
- KR
- South Korea
- Prior art keywords
- fluoride
- composition
- aqueous
- group
- compound
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- -1 aminosilane compound Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004065 semiconductor Substances 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 22
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 20
- 239000003599 detergent Substances 0.000 claims abstract description 17
- 238000004380 ashing Methods 0.000 claims abstract description 15
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000005468 ion implantation Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 150000008624 imidazolidinones Chemical class 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 4
- 150000003457 sulfones Chemical class 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 150000001298 alcohols Chemical group 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 2
- 229910004129 HfSiO Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910008599 TiW Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical class C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000052 poly(p-xylylene) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001470 polyketone Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001709 polysilazane Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims 3
- 239000011775 sodium fluoride Substances 0.000 claims 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims 2
- 229910019311 (Ba,Sr)TiO Inorganic materials 0.000 claims 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims 1
- 229910016569 AlF 3 Inorganic materials 0.000 claims 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims 1
- 239000004965 Silica aerogel Substances 0.000 claims 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 56
- 229920002120 photoresistant polymer Polymers 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000003989 dielectric material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- APURLPHDHPNUFL-UHFFFAOYSA-M fluoroaluminum Chemical compound [Al]F APURLPHDHPNUFL-UHFFFAOYSA-M 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 2
- QNHNSPNFZFBEQR-UHFFFAOYSA-N n'-(3-trihydroxysilylpropyl)ethane-1,2-diamine Chemical compound NCCNCCC[Si](O)(O)O QNHNSPNFZFBEQR-UHFFFAOYSA-N 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- AZLXQBNSOMJQEJ-UHFFFAOYSA-N 1,3-di(propan-2-yl)imidazolidin-2-one Chemical compound CC(C)N1CCN(C(C)C)C1=O AZLXQBNSOMJQEJ-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-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
- PJEXUIKBGBSHBS-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrolidin-2-one Chemical compound OCN1CCCC1=O PJEXUIKBGBSHBS-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DCALJVULAGICIX-UHFFFAOYSA-N 1-propylpyrrolidin-2-one Chemical compound CCCN1CCCC1=O DCALJVULAGICIX-UHFFFAOYSA-N 0.000 description 1
- ZENKESXKWBIZCV-UHFFFAOYSA-N 2,2,4,4-tetrafluoro-1,3-benzodioxin-6-amine Chemical group O1C(F)(F)OC(F)(F)C2=CC(N)=CC=C21 ZENKESXKWBIZCV-UHFFFAOYSA-N 0.000 description 1
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HRWADRITRNUCIY-UHFFFAOYSA-N 2-(2-propan-2-yloxyethoxy)ethanol Chemical compound CC(C)OCCOCCO HRWADRITRNUCIY-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- FETMDPWILVCFLL-UHFFFAOYSA-N 2-[2-(2-propan-2-yloxyethoxy)ethoxy]ethanol Chemical compound CC(C)OCCOCCOCCO FETMDPWILVCFLL-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- NUPIRAOAZXINLS-UHFFFAOYSA-N NCCNCCC[Si](O)(O)O.NCCNCCC[Si](O)(O)O Chemical compound NCCNCCC[Si](O)(O)O.NCCNCCC[Si](O)(O)O NUPIRAOAZXINLS-UHFFFAOYSA-N 0.000 description 1
- MJRSPVBOOTUYTK-UHFFFAOYSA-N NCCNCCNCCC[Si](OC)(OC)OC.NCCNCCNCCC[Si](OC)(OC)OC Chemical compound NCCNCCNCCC[Si](OC)(OC)OC.NCCNCCNCCC[Si](OC)(OC)OC MJRSPVBOOTUYTK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PDDBPPDHEVWBRW-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN.CO[Si](OC)(OC)CCCNCCN PDDBPPDHEVWBRW-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- 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
- C11D7/50—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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
Landscapes
- 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)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
본 발명은 수성 세정제 조성물에 관한 것으로, 더욱 상세하게는 무기계 불소 화합물, 아미노실란계 화합물, 극성 유기용매 및 물을 포함하는 수성 세정제 조성물에 관한 것이다.
상기 수성 세정제 조성물은 이온주입, 에칭 및/또는 애싱 공정 이후 기판에 생성된 잔류물을 효과적으로 제거할 뿐만 아니라 기판 상의 절연막, 금속막에 대한 부식성도 매우 낮아 반도체 제조 공정의 생산성 및 신뢰성을 크게 향상시킬 수 있다.The present invention relates to an aqueous detergent composition, and more particularly, to an aqueous detergent composition comprising an inorganic fluorine compound, an aminosilane compound, a polar organic solvent, and water.
The aqueous cleaner composition not only effectively removes residues generated on the substrate after ion implantation, etching and/or ashing process, but also has very low corrosiveness to the insulating film and metal film on the substrate, thereby greatly improving the productivity and reliability of the semiconductor manufacturing process. can
Description
본 발명은 우수한 잔류물 제거 성능 및 반도체를 구성하는 다른 막질에 대한 부식 방지 효과를 확보할 수 있는 수성 세정제 조성물에 관한 것이다.The present invention relates to an aqueous cleaning composition capable of securing excellent residue removal performance and corrosion-preventing effect on other film qualities constituting a semiconductor.
IT(information technology) 분야의 발전과 함께 현대 사회에서 반도체 직접 회로(IC;integrated circuit), 반도체 소자, 반도체 장치 등의 역할은 갈수록 중요해지고 있으며, 다양한 산업 분야의 전자기기에서 광범위하게 사용되고 있다. 최근 전자기기들이 소형화, 박형화, 경량화, 고성능화가 진행됨에 따라 여기에 사용되는 반도체 소자 역시 기판의 단위 면적당 전기 부품 밀도를 증가시키고 반도체의 동작 속도를 향상시키기 위해서 수십 나노미터(㎚) 이하의 미세한 전자회로의 형성이 필요하게 되었다.BACKGROUND With the development of information technology (IT), roles of semiconductor integrated circuits (ICs), semiconductor devices, and semiconductor devices are becoming increasingly important in modern society, and are widely used in electronic devices in various industrial fields. Recently, as electronic devices are miniaturized, thinner, lighter, and higher in performance, the semiconductor devices used here also increase the density of electrical components per unit area of the substrate and improve the operating speed of semiconductors. It became necessary to form a circuit.
반도체 소자 또는 액정 표시 소자는 포토리소그래피(photolithography) 기술을 사용하여 기판 위에 미세한 전자회로 패턴을 형성한다. 구체적으로는, 산화 규소 등의 절연막이나 Al, Cu, Si, Ti 등의 금속층 또는 Spin-on-glass(SOG), 불소함유 수지, 하프늄 산화물 등의 층간 절연막이 형성된 기판상에, 포토레지스트를 도포한 다음, 이것을 선택적으로 노광, 현상 처리하여 포토레지스트 패턴을 형성한다. 그 다음에, 패턴화된 포토레지스트를 마스크로 하여 절연막 및 배선층, 또는 저유전 층간 절연막에 대해서 에칭 처리한 뒤, 불필요해진 포토레지스트를 제거한다. A semiconductor device or a liquid crystal display device uses a photolithography technique to form a fine electronic circuit pattern on a substrate. Specifically, a photoresist is applied on a substrate on which an insulating film such as silicon oxide, a metal layer such as Al, Cu, Si, or Ti, or an interlayer insulating film such as spin-on-glass (SOG), fluorine-containing resin, or hafnium oxide is formed. Then, it is selectively exposed and developed to form a photoresist pattern. Then, using the patterned photoresist as a mask, the insulating film and the wiring layer or the low dielectric interlayer insulating film are etched, and then the unnecessary photoresist is removed.
이와 같은 전자회로 패턴의 형성 과정에서, 불필요한 포토레지스트의 제거는 통상적으로 다양한 유기용제로 구성되는 포토레지스트 박리액을 사용하여 행해져 왔다. 최근 회로 패턴의 미세화에 따라 포토레지스트 역시 정밀도가 우수하게 제거할 수 있는 방법으로 에싱(ashing) 처리가 많이 이용되고 있다. In the process of forming such an electronic circuit pattern, unnecessary photoresist removal has been generally performed using a photoresist stripper composed of various organic solvents. Recently, according to the miniaturization of circuit patterns, ashing process is widely used as a method for removing photoresist with excellent precision.
에싱 처리는 플라즈마 등의 에너지를 이용하여 포토레지스트를 회(ash)화하여 제거하는 것이다. 이러한 에싱 처리 후에 포토레지스트를 제거한 표면에는 포토레지스트 에싱 잔류물로 불리는 불완전 회화물(ashed product)을 비롯하여 앞선 에칭 시에 패턴의 측벽 부근에 생기는 측벽 퇴적막이 충분히 제거되지 않고 남아있다. 이때 측벽 퇴적막이라 함은, 에칭 공정에서 포토레지스트 마스크의 측벽이나 패턴 측벽에, 에칭 가스, 포토레지스트, 하지 절연막, 배선층, 저유전 층간 절연막 및 기판이 복잡하게 반응하여 형성되는 난용성 생성물이다. The ashing process removes the photoresist by ashing it using energy such as plasma. After the ashing process, the sidewall deposition film generated near the sidewall of the pattern during the previous etching, including an ashed product called a photoresist ashing residue, is not sufficiently removed from the surface from which the photoresist is removed after the ashing process. In this case, the sidewall deposition film is a poorly soluble product formed by a complex reaction between an etching gas, a photoresist, an underlying insulating film, a wiring layer, a low dielectric interlayer insulating film, and a substrate on the sidewall or pattern sidewall of the photoresist mask in the etching process.
이러한 측벽 퇴적막이나 포토레지스트의 불완전회화물은 에칭으로서 반응성 이온 에칭(RIE)을 수행한 경우에는 특히 용해성의 낮다. 이때 반응성 이온 에칭은기판에 부전압을 걸어 불화 탄소, 불화 수소, 염화수소 등의 할로겐 가스를 포함한 반응성 가스에 플라스마를 조사해, 피처리층의 식각을 수행하는 기법이며, 이방성이 우수한 드라이 에칭으로서 많이 행해지고 있는 방법이다. Such a sidewall deposition film or incompletely etched photoresist has low solubility, particularly when reactive ion etching (RIE) is performed as etching. At this time, reactive ion etching is a technique for etching the target layer by applying a negative voltage to the substrate and irradiating plasma to a reactive gas containing halogen gas such as carbon fluoride, hydrogen fluoride, or hydrogen chloride. there is a way
또한, 포토레지스트가 이온 주입 처리에 노출된 경우 에싱 처리 후에 포토레지스트의 불완전 회화물이 현저하게 생성된다. 이때 이온 주입 처리는 절연의 기판에서 원하는 위치에 회로 패턴을 형성하기 위해서, 포토레지스트에 인, 붕소, 안티몬 및 비소 등의 이온을 주입(implantation)하는 조작이다. In addition, when the photoresist is exposed to an ion implantation treatment, an incomplete char of the photoresist is significantly produced after the ashing treatment. In this case, the ion implantation process is an operation of implanting ions such as phosphorus, boron, antimony, and arsenic into the photoresist in order to form a circuit pattern at a desired position on the insulating substrate.
현상 후의 포토레지스트를 포함하여, 에싱 처리 후의 제거면에 남아있는 포토레지스트의 불완전 회화물이나 측벽 퇴적막은 배선 패턴의 접촉 불량을 일으키므로 세정이 필요하다. Incompletely painted photoresist or sidewall deposition film remaining on the removed surface after the ashing process, including the photoresist after development, causes poor contact in the wiring pattern, so cleaning is required.
각종 유기용매로 되는 용액이 잔류물 제거용으로 사용되어, 포토레지스트를 포함하는 잔류물 제거가 시도되고 있다. 그러나 이온 주입 처리한 포토레지스트는 변질되고, 에싱 후의 포토레지스트 잔류물은 고도의 중합물이거나, 혹은 일부 무기화되어 있어 제거가 쉽지 않고 주변의 금속막, 절연막에 부식이 생기는 문제점이 있다. 이에 보다 효과적으로 잔류물을 제거할 수 있는 세정제의 개발을 위해 많은 연구가 진행되었다.Solutions made of various organic solvents are used for removing residues, and attempts have been made to remove residues including photoresists. However, the photoresist treated by ion implantation is deteriorated, and the photoresist residue after ashing is either a highly polymerized material or partially inorganic, so it is not easy to remove, and there is a problem in that the surrounding metal film and insulating film are corroded. Accordingly, many studies have been conducted to develop a cleaner capable of more effectively removing residues.
일례로, 일본 공개특허공보 제2000-194144호(TOKUYAMA CORP, 2000.07.14)는 불화 암모늄 화합물, 양쪽성 계면활성제 및 물로 이루어진 포토레지스트 에싱 잔재 세정액을 기재하고 있다. As an example, Japanese Laid-Open Patent Publication No. 2000-194144 (TOKUYAMA CORP, July 14, 2000) describes a photoresist ashing residue cleaning solution consisting of an ammonium fluoride compound, an amphoteric surfactant, and water.
또한, 대한민국 공개특허 제2005-0025316호(에어 프로덕츠 앤드 케미칼스, 인코오포레이티드, 2005.03.14)에서는 유기용매, 물, 디카르복실유기산, 염기, 플루오르화 이온 재료로 이루어진 에칭 잔류물 제거용 조성물을 기재하고 있다. In addition, in Korean Patent Laid-Open No. 2005-0025316 (Air Products & Chemicals, Inc., March 14, 2005), an organic solvent, water, dicarboxylic acid, base, and fluoride ion material for removing etching residues The composition is described.
이들 특허들은 전술한 조성을 사용하여 잔류물의 효율적인 제거를 꾀하고 있으나, 그 효과가 충분치 않으며 조성 내 포함된 계면활성제로 인해 세정시 거품이 발생하거나 주변의 다른 막질에 대한 보호 효과가 부족한 문제점이 있다. Although these patents try to efficiently remove residues using the above-described composition, the effect is not sufficient, and there is a problem in that bubbles are generated during cleaning due to the surfactant included in the composition or the protective effect on other surrounding film quality is insufficient.
이에 미세 회로 형성 공정을 거친 이후 발생하는 잔류물을 효과적으로 제거함과 동시에 기판상에 존재하는 금속막, 절연막에 대한 보호 효과를 확보하기 위해 다각적으로 연구한 결과, 본 출원인은 무기계 불소 화합물, 아미노실란계 화합물, 극성 유기용매 및 물을 사용할 경우, 반도체 제조 공정의 세정 단계에서 상기 문제점을 해결할 수 있음을 확인하여 본 발명을 완성하였다.Accordingly, as a result of various studies to effectively remove residues generated after the microcircuit formation process and at the same time secure the protective effect on the metal film and insulating film existing on the substrate, the present applicant has found that inorganic fluorine compounds, aminosilane-based compounds When a compound, a polar organic solvent, and water are used, the present invention was completed by confirming that the above problems can be solved in the cleaning step of the semiconductor manufacturing process.
따라서, 본 발명의 목적은 세정시 잔류물에 대한 높은 선별성을 가져 다른 막질에 대한 부식 방지 효과를 갖는 수성 세정제 조성물을 제공하는 것이다.Accordingly, it is an object of the present invention to provide an aqueous cleaning composition having a high selectivity for residues during cleaning and thus having a corrosion-preventing effect on other film qualities.
상기 목적을 달성하기 위해, 본 발명은 무기계 불소 화합물, 아미노실란계 화합물, 극성 유기용매 및 물을 포함하는 수성 세정제 조성물을 제공한다.In order to achieve the above object, the present invention provides an aqueous detergent composition comprising an inorganic fluorine compound, an aminosilane compound, a polar organic solvent, and water.
상기 무기계 불소 화합물은 불화암모늄(ammonium fluoride, NH4F), 중불화암모늄(ammonium bifluoride, NH4HF2), 불화나트륨(sodium fluoride, NaF), 중불화나트륨(sodium bifluoride, NaHF2), 불화 칼륨(potassium fluoride, KF), 중불화 칼륨(potassium bifluoride, KHF2), 불화붕소산(fluoroboric acid, HBF4), 불화붕산암모늄(Ammonium fluoborate, NH4BF4), 불화알루미늄(aluminium fluoride, AlF3), 불화수소(hydrogen fluoride, HF) 및 이들의 조합으로 이루어진 군으로부터 선택된 1종일 수 있다.The inorganic fluorine compound is ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), sodium fluoride (NaF), sodium bifluoride (NaHF 2 ), fluoride Potassium fluoride (KF), potassium bifluoride (KHF 2 ), fluoroboric acid (HBF 4 ), ammonium fluoride (NH 4 BF 4 ), aluminum fluoride (AlF) 3 ), may be one selected from the group consisting of hydrogen fluoride (HF) and combinations thereof.
상기 아미노실란계 화합물은 하기 화학식 1로 표시되는 화합물일 수 있다.The aminosilane-based compound may be a compound represented by Formula 1 below.
[화학식 1][Formula 1]
(상기 화학식 1에서, R1 내지 R3 및 n은 명세서 내 설명한 바와 같다)(In Formula 1, R 1 to R 3 and n are the same as described in the specification)
상기 극성 유기용매는 알코올류, 글리콜류, 락톤류, 락탐류, 설폭사이드류, 설폰류, 아미드류, 우레아류, 이미다졸리디논류, 니트릴류 및 이들의 조합으로 이루어진 군으로부터 선택된 1종일 수 있다. The polar organic solvent may be one selected from the group consisting of alcohols, glycols, lactones, lactams, sulfoxides, sulfones, amides, ureas, imidazolidinones, nitriles, and combinations thereof. have.
상기 수성 세정제 조성물은 전체 조성물 100 중량%를 만족하도록, 무기계 불소 화합물 0.5 내지 5 중량%, 아미노실란계 화합물 0.1 내지 3 중량%, 극성 유기용매 50 내지 90 중량%, 및 잔부로 물을 포함할 수 있다.The aqueous detergent composition may include 0.5 to 5% by weight of an inorganic fluorine compound, 0.1 to 3% by weight of an aminosilane compound, 50 to 90% by weight of a polar organic solvent, and water as the balance to satisfy 100% by weight of the total composition have.
또한, 상기 수성 세정제 조성물은 반도체 제조 공정에서 세정 단계에 사용하여 금속막 및 절연막의 손상없이 잔류물을 제거할 수 있다.In addition, the aqueous cleaning composition can be used in a cleaning step in a semiconductor manufacturing process to remove residues without damaging the metal film and the insulating film.
본 발명에 따른 수성 세정제 조성물은 잔류물 제거력 및 제거 속도가 우수하며 기판상에 함께 적층되는 금속, 유전체 물질에 대한 부식성이 적어 반도체 소자의 미세 회로 형성에 있어 개선된 세정 성능으로 생산성 및 신뢰성을 크게 향상시킬 수 있다.The aqueous cleaner composition according to the present invention has excellent residue removal power and removal speed, and has low corrosiveness to metal and dielectric materials laminated together on a substrate, thereby greatly improving productivity and reliability with improved cleaning performance in forming microcircuits of semiconductor devices. can be improved
본 발명은 반도체 제조 공정 중 세정 단계에 있어 금속, 유전체 물질로 이루어진 다른 막질에 대한 손상없이 기판 표면에 잔존하는 각종 잔류물을 효과적으로 제거하는 수성 세정제 조성물을 제시한다.The present invention provides an aqueous cleaner composition that effectively removes various residues remaining on the surface of a substrate without damage to other films made of metals and dielectric materials in the cleaning step of a semiconductor manufacturing process.
반도체 소자는 증착, 사진 식각, 에칭, 이온주입, 에싱 등의 수많은 단계를 거치며 일련의 과정을 거쳐 제조되는데 각 과정 후에는 많은 잔사물, 이물이 기판 표면에 남게된다. 이때 발생한 오염물은 반도체 소자의 구조적 형상과 전기적 특성에 문제를 야기한다. 따라서 기판 상에 회로 패턴을 형성함에 따라 노출된 금속, 유전체 물질을 공격하지 않으면서 잔류물만을 선택적으로 제거할 수 있는 세정제 조성물이 필요하다.Semiconductor devices are manufactured through a series of steps, such as deposition, photolithography, etching, ion implantation, and ashing. After each process, many residues and foreign substances are left on the surface of the substrate. Contaminants generated at this time cause problems in the structural shape and electrical characteristics of the semiconductor device. Therefore, there is a need for a cleaning composition capable of selectively removing only residues without attacking metal and dielectric materials exposed as a circuit pattern is formed on a substrate.
이에 본 발명에서는 무기계 불소 화합물, 아미노실란계 화합물, 극성 유기용매와 함께 물을 포함하는 수성 세정제 조성물 사용하여 보다 안정적이고 효과적으로 잔류물이 제거됨과 동시에 금속막, 절연막을 보호할 수 있도록 하였다.Accordingly, in the present invention, an aqueous cleaning composition containing water together with an inorganic fluorine compound, an aminosilane compound, and a polar organic solvent is used to more stably and effectively remove residues and protect the metal film and the insulating film.
자세히 설명하면, 무기계 불소 화합물은 분자 구조 내 불소 이온을 해리하여 다양한 유·무기 성분으로 이루어진 잔류물을 용해시킨다. 또한, 아미노실란계 화합물은 잔류물과 함께 세정제에 접촉할 수 있는 금속, 유전체 물질로 이루어진 막에 대한 손상을 방지하여 잔류물만을 선별적으로 제거될 수 있도록 한다.More specifically, inorganic fluorine compounds dissociate fluorine ions in the molecular structure to dissolve residues composed of various organic and inorganic components. In addition, the aminosilane-based compound prevents damage to a film made of a metal or dielectric material that may come into contact with the cleaning agent together with the residue, so that only the residue can be selectively removed.
이하 각 조성을 설명한다.Hereinafter, each composition will be described.
본 발명에서의 무기계 불소 화합물은 물에 녹아 불소 이온 또는 다원자 불소 이온을 생성한다. 이러한 불소 이온은 반도체 제조 공정 중에 생성된 각종 잔류물을 분해하여 용해시키는 역할을 한다. 특히, 본 발명에서는 세정제 조성물에서는 통상적으로 많이 사용되는 불화알킬암모늄 화합물 대신 무기계 불소 화합물을 사용함으써 개선된 안정성, 제거 성능을 얻을 수 있다. 구체적으로, 불화알킬암모늄 화합물은 극성 양성자성 용매에 잘 용해되기 때문에 세정제 조성물에 사용가능한 용매의 종류가 극성 양성자성 용매로 제한되며, 본 발명의 무기계 불소 화합물에 비해 잔류물 제거력이 부족하다.The inorganic fluorine compound in the present invention dissolves in water to generate fluorine ions or polyatomic fluorine ions. These fluorine ions serve to decompose and dissolve various residues generated during the semiconductor manufacturing process. In particular, in the present invention, improved stability and removal performance can be obtained by using an inorganic fluorine compound instead of the commonly used alkylammonium fluoride compound in the cleaning composition. Specifically, since the alkylammonium fluoride compound is well soluble in the polar protic solvent, the type of solvent that can be used in the cleaning composition is limited to the polar protic solvent, and the residue removal power is insufficient compared to the inorganic fluorine compound of the present invention.
상기 무기계 불소 화합물은 불화암모늄(ammonium fluoride, NH4F), 중불화암모늄(ammonium bifluoride, NH4HF2), 불화나트륨(sodium fluoride, NaF), 중불화나트륨(sodium bifluoride, NaHF2), 불화 칼륨(potassium fluoride, KF), 중불화 칼륨(potassium bifluoride, KHF2), 불화붕소산(fluoroboric acid, HBF4), 불화붕산암모늄(Ammonium fluoborate, NH4BF4), 불화알루미늄(aluminium fluoride, AlF3), 불화수소(hydrogen fluoride, HF) 및 이들의 조합으로 이루어진 군으로부터 선택된 1종이상의 화합물일 수 있다. 본 발명에 있어서, 상기 무기계 불소 화합물은 불화암모늄 또는 중불화암모늄을 사용하는 것이 바람직하다. The inorganic fluorine compound is ammonium fluoride (NH 4 F), ammonium bifluoride (NH 4 HF 2 ), sodium fluoride (NaF), sodium bifluoride (NaHF 2 ), fluoride Potassium fluoride (KF), potassium bifluoride (KHF 2 ), fluoroboric acid (HBF 4 ), ammonium fluoride (NH 4 BF 4 ), aluminum fluoride (AlF) 3 ), hydrogen fluoride (HF), and a combination thereof may be at least one compound selected from the group consisting of. In the present invention, it is preferable to use ammonium fluoride or ammonium bifluoride as the inorganic fluorine compound.
이러한 무기계 불소 화합물은 전체 조성물 100 중량% 내에서 0.5 내지 5 중량%로 사용되는 것이 바람직하며, 1 내지 5 중량%인 것이 더욱 바람직하다. 상기 무기계 불소 화합물이 0.5 중량% 미만으로 사용하는 경우, 세정 속도 및 세정력이 감소하게 되며, 반대로 5 중량%를 초과하는 경우, 금속, 유전체 물질로 이루어진 다른 막질에 대한 공격이 발생할 수 있다.The inorganic fluorine compound is preferably used in an amount of 0.5 to 5% by weight in 100% by weight of the total composition, more preferably 1 to 5% by weight. When the inorganic fluorine compound is used in an amount of less than 0.5% by weight, the cleaning rate and cleaning power are reduced, and, conversely, when it exceeds 5% by weight, attack on other film qualities made of metals and dielectric materials may occur.
본 발명에서의 아미노실란계 화합물은 세정제 조성물에 함께 노출되는 금속, 실리콘 산화물, 유전체 물질을 보호하는 역할을 한다. 바람직하기로, 상기 아미노실란계 화합물은 하기 화학식 1로 표시된다. 이러한 아미노실란계 화합물은 기존에 다른 막질에 대한 부식 방지를 위해 사용되는 유기산 화합물에 비해 비공유 전자쌍을 다량 포함하기 때문에 금속막, 절연막과 향상된 결합력을 가지며 이로 인해 보호 효과를 개선할 수 있다.The aminosilane-based compound in the present invention serves to protect the metal, silicon oxide, and dielectric material exposed together with the cleaning composition. Preferably, the aminosilane-based compound is represented by the following formula (1). Since these aminosilane-based compounds contain a large amount of lone electron pairs compared to organic acid compounds used for corrosion prevention of other film materials, they have improved bonding strength with metal films and insulating films, thereby improving the protective effect.
(상기 화학식 1에서, (In Formula 1,
R1 및 R2는 서로 같거나 다르며 각각 독립적으로 탄소수 1 내지 20의 알킬렌기이고, R 1 and R 2 are the same as or different from each other and are each independently an alkylene group having 1 to 20 carbon atoms,
R3은 수소 또는 탄소수 1 내지 20의 알킬기이며,R 3 is hydrogen or an alkyl group having 1 to 20 carbon atoms,
n은 1 내지 10의 정수이다)n is an integer from 1 to 10)
본 발명에 언급하는 알킬기는 오로지 탄소 및 수소 원자로만 이루어지며, 불포화도가 없고, 단일 결합에 의해 분자의 나머지에 결합되는 직쇄형 또는 측쇄형의 탄화수소 라디칼을 의미한다. 이러한 알킬기의 예로는 메틸기, 에틸기, n-프로필기, 이소프로필기, n-부틸기, 이소부틸기, sec-부틸기, t-부틸기, 펜틸기, 이소아밀기, 헥실기 등을 들 수 있으나 이에 한정되지 않는다.The alkyl group referred to in the present invention means a straight-chain or branched hydrocarbon radical, which consists only of carbon and hydrogen atoms, has no degree of unsaturation, and is bonded to the rest of the molecule by a single bond. Examples of such an alkyl group include a methyl group, ethyl group, n -propyl group, isopropyl group, n -butyl group, isobutyl group, sec -butyl group, t -butyl group, pentyl group, isoamyl group, hexyl group, etc. However, the present invention is not limited thereto.
본 발명에서 언급하는 알킬렌기는 알킬기를 구성하는 같거나 다른 두개의 탄소 원자들로부터 두 개의 수소 원자를 제거함으로써 유도되는 알킬기의 2가 형태로 직쇄형, 측쇄형 또는 시클릭 탄화수소 라디칼을 의미한다. 이러한 알킬렌기의 예로는 메틸렌 (-CH2-), 1,1-에틸 (-CH(CH3)-), 1,2-에틸 (-CH2CH2-), 1,1-프로필 (-CH(CH2CH3)-), 1,2-프로필 (-CH2CH(CH3)-), 1,3-프로필 (-CH2CH2CH2-), 1,4-부틸 (-CH2CH2CH2CH2-) 등을 들 수 있으나 이에 한정되지 않는다.The alkylene group referred to in the present invention refers to a straight-chain, branched-chain or cyclic hydrocarbon radical in the divalent form of an alkyl group derived by removing two hydrogen atoms from the same or different two carbon atoms constituting the alkyl group. Examples of such alkylene groups include methylene (-CH 2 -), 1,1-ethyl (-CH(CH 3 )-), 1,2-ethyl (-CH 2 CH 2 -), 1,1-propyl (-) CH(CH 2 CH 3 )-), 1,2-propyl (-CH 2 CH(CH 3 )-), 1,3-propyl (-CH 2 CH 2 CH 2 -), 1,4-butyl (-) CH 2 CH 2 CH 2 CH 2 -) and the like, but is not limited thereto.
바람직하기로, 상기 R1 및 R2는 탄소수 1 내지 10의 알킬렌기이며, 상기 R3는 수소 또는 탄소수 1 내지 10의 알킬기이고, 상기 n은 1 내지 5의 정수일 수 있다.Preferably, R 1 and R 2 are an alkylene group having 1 to 10 carbon atoms, R 3 is hydrogen or an alkyl group having 1 to 10 carbon atoms, and n may be an integer of 1 to 5.
구체적으로, 상기 화학식 1로 표시되는 화합물은 N-(2-아미노에틸)-(3-아미노프로필)트리메톡시실란(N-(2-Aminoethyl)-(3-aminopropyl)trimethoxysilane), N-(2-아미노에틸)-(3-아미노프로필)실란트리올(N-(2-Aminoethyl)-(3- aminopropyl)silanetriol), (3-트리메톡시실리프로필)디에틸렌트리아민((3-Trimethoxysilylpropyl)diethylenetriamine) 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 본 발명에 있어 사용가능한 화학식 1로 표시되는 화합물은 앞서 언급한 예로 한정되지 않으며 상기 조건에 맞는 것으로서 이 분야에서 공지된 것은 모두 사용가능하다. 또한, 상기 화합물은 직접 제조하거나 시판되는 것을 사용할 수 있다.Specifically, the compound represented by Formula 1 is N-(2-aminoethyl)-(3-aminopropyl)trimethoxysilane (N-(2-Aminoethyl)-(3-aminopropyl)trimethoxysilane), N-( 2-Aminoethyl)-(3-aminopropyl)silanetriol (N-(2-Aminoethyl)-(3-aminopropyl)silanetriol), (3-trimethoxysilylpropyl)diethylenetriamine ((3-Trimethoxysilylpropyl) diethylenetriamine) and the like, and these may be used alone or in combination of two or more. The compound represented by Formula 1 that can be used in the present invention is not limited to the above-mentioned examples, and any compound known in the art may be used as it satisfies the above conditions. In addition, the compound may be prepared directly or commercially available ones may be used.
상기 화학식 1로 표시되는 아미노실란계 화합물은 전체 조성물 100 중량% 내에서 0.1 내지 3 중량%로 사용되는 것이 바람직하며, 0.5 내지 2 중량%인 것이 더욱 바람직하다. 만약 상기 화학식 1로 표시되는 화합물을 0.1 중량% 미만으로 사용하는 경우, 다른 막질에 대한 보호 효과가 저하되며, 반대로 3 중량%를 초과하는 경우, 잔류물 제거력이 저하되거나 잔류, 오염 등의 부작용이 발생할 수 있다. The aminosilane-based compound represented by Formula 1 is preferably used in an amount of 0.1 to 3% by weight in 100% by weight of the total composition, more preferably 0.5 to 2% by weight. If the compound represented by Formula 1 is used in less than 0.1% by weight, the protective effect on other film quality is reduced, and on the contrary, when it exceeds 3% by weight, the removal of residues is reduced or side effects such as residues and contamination are reduced. can occur
본 발명에서의 극성 유기용매는 분해된 잔류물의 용해력을 향상시켜 세정 효과를 증진시키는 역할을 한다. 이러한 극성 유기용매는 후술하는 물과 혼합가능한 것이면 어느 것이든 사용 가능하며 본 발명에서는 특별히 한정하지 않는다. 대표적으로 알코올류, 글리콜류, 락톤류, 락탐류, 설폭사이드류, 설폰류, 아미드류, 우레아류, 이미다졸리디논류, 니트릴류 등을 들 수 있으며, 이들은 단독으로 또는 2종 이상 혼합하여 사용 될 수 있다.The polar organic solvent in the present invention serves to enhance the cleaning effect by improving the dissolving power of the decomposed residue. Any such polar organic solvent may be used as long as it is miscible with water, which will be described later, and the present invention is not particularly limited. Representatively, alcohols, glycols, lactones, lactams, sulfoxides, sulfones, amides, ureas, imidazolidinones, nitriles, etc. can be used
구체적으로, 상기 알코올류의 예로는 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, 이소부탄올, t-부탄올, 펜탄올, 헥산올, 헵탄올, 옥탄올 등을 들 수 있다.Specifically, examples of the alcohol may include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, and octanol.
상기 글리콜류의 예로는 에틸렌 글리콜, 프로필렌 글리콜, 부틸렌 글리콜 등의 알킬렌 글리콜; 에틸렌글리콜 모노메틸 에테르, 에틸렌글리콜 모노에틸에테르, 에틸렌글리콜 모노이소프로필 에테르, 에틸렌글리콜 모노부틸 에테르, 디에틸렌글리콜 모노메틸 에테르, 디에틸렌글리콜 모노에틸 에테르, 디에틸렌글리콜모노이소프로필 에테르, 디에틸렌글리콜 모노부틸 에테르, 트리에틸렌글리콜 모노메틸 에테르, 트리에틸렌글리콜 모노에틸 에테르, 트리에틸렌글리콜 모노이소프로필 에테르, 트리에틸렌글리콜 모노부틸 에테르, 폴리에틸렌글리콜 모노메틸에테르, 폴리에틸렌글리콜 모노부틸 에테르, 프로필렌글리콜 모노메틸 에테르, 디프로필렌글리콜 모노메틸 에테르, 트리프로필렌글리콜 모노메틸 에테르, 프로필렌글리콜 모노메틸 에테르 아세테이트, 테트라하이드로퍼푸릴 알코올 등을 들 수 있다. Examples of the glycols include alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol Monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether , dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, and the like.
상기 락톤류의 예로는 β―프로피오락톤, γ―부틸올락톤, γ―발레롤락톤, δ―발레롤락톤, γ―카프로락톤, ε―카프로락톤 등을 들 수 있다. Examples of the lactones include β-propiolactone, γ-butylolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone and ε-caprolactone.
상기 락탐류의 예로는 N-메틸-2-피롤리돈, N-에틸-2-피롤리돈, N-프로필-2-피롤리돈, N-히드록시메틸-2-피롤리돈, N-히드록시에틸-2-피롤리돈 등을 들 수 있다. Examples of the lactam include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N- Hydroxyethyl-2-pyrrolidone etc. are mentioned.
상기 설폭사이드류의 예로는 디메틸설폭사이드, 디에틸설폭사이드, 메틸설폭사이드 등을 들 수 있다. Examples of the sulfoxides include dimethyl sulfoxide, diethyl sulfoxide, and methyl sulfoxide.
상기 설폰류의 예로는 디메틸설폰, 디에틸설폰, 비스(2-히드록시에틸)설폰, 테트라메틸렌설폰 등을 들 수 있다. Examples of the sulfones include dimethylsulfone, diethylsulfone, bis(2-hydroxyethyl)sulfone, and tetramethylenesulfone.
상기 아미드류의 예로는 N,N-디메틸포름아미드, N-메틸포름아미드, N,N-디메틸아세트아미드, N-메틸아세토아미드, N,N-디에틸아세토아미드, 헥사메틸포스포아미드 등을 들 수 있다.Examples of the amides include N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetoamide, N,N-diethylacetoamide, hexamethylphosphoamide, and the like. can be heard
상기 우레아류의 예로는 N,N,N′,N′-테트라메틸우레아 등을 들 수 있다.Examples of the urea include N,N,N',N'-tetramethylurea.
상기 이미다졸리디논류의 예로는 1,3-디메틸-2-이미다졸리디논, 1,3-디에틸-2-이미다졸리디논, 1,3-디이소프로필-2-이미다졸리디논 등을 들 수 있다. Examples of the imidazolidinones include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone. and the like.
상기 니트릴류의 예로는 아세토니트릴 등을 들 수 있다. Examples of the nitriles include acetonitrile.
본 발명에서 상기 극성 유기용매는 메탄올, 에틸렌 글리콜, γ―부티로락톤, 디메틸설폭사이드 및 이들의 조합으로 이루어진 군으로부터 선택된 1종을 사용하는 것이 제거력과 안정성 면에서 바람직하다.In the present invention, it is preferable in terms of removal power and stability to use one selected from the group consisting of methanol, ethylene glycol, γ-butyrolactone, dimethyl sulfoxide, and combinations thereof as the polar organic solvent.
이러한 극성 유기용매는 전체 조성물 100 중량% 내에서 50 내지 90 중량%로 사용되는 것이 바람직하며, 60 내지 80 중량%인 것이 더욱 바람직하다. 만약 상기 극성 유기용매가 50 중량% 미만으로 사용되는 경우, 전체 세정제 조성물의 무기성이 향상되어 금속막, 절연막에 대한 부식이 야기될 수 있으며, 반대로 90 중량%를 초과하는 경우 세정 효과가 저하되는 문제가 발생할 수 있다.The polar organic solvent is preferably used in an amount of 50 to 90% by weight in 100% by weight of the total composition, more preferably 60 to 80% by weight. If the polar organic solvent is used in an amount of less than 50% by weight, the inorganic properties of the entire cleaning composition may be improved and corrosion to the metal film and insulating film may be caused. Conversely, if it exceeds 90% by weight, the cleaning effect is reduced Problems can arise.
본 발명의 세정제 조성물은 물을 함유하며 이는 전술한 조성을 용해시키며 특히 무기계 불소 화합물로부터 불소 이온이 효과적으로 해리될 수 있도록 하여 제거 성능을 향상시킨다. The cleaning composition of the present invention contains water, which dissolves the above-mentioned composition, and in particular, allows the fluorine ions to be effectively dissociated from the inorganic fluorine compound, thereby improving the removal performance.
상기 물은 본 발명에 있어 특히 적합한 용도인 반도체 제조 공정에 적용을 위해 기본적으로 깨끗한 물이 반드시 요구된다. 구체적으로 반도체에 영향을 미칠 수 있는 금속 및 기타 불순물은 가능한 적은 것으로 탈이온수, 초순수 등이 바람직하다, 이러한 물을 얻기 위한 방법으로서는 이온 교환법 등을 들 수 있다.For the water to be applied to a semiconductor manufacturing process, which is a particularly suitable use in the present invention, clean water is basically required. Specifically, deionized water, ultrapure water, etc. are preferable as metals and other impurities that may affect the semiconductor are as small as possible. Examples of a method for obtaining such water include an ion exchange method.
이러한 물의 함량은 특별히 한정되지 않으나 전체 조성물 100 중량%를 만족할 수 있도록 하는 잔부로 포함될 수 있다. 일례로, 상기 물은 20 내지 40 중량%인 것이 바람직하며 25 내지 35 중량%인 것이 더욱 바람직하다. 만약 상기 함량 범위 미만인 경우, 무기계 불소 화합물의 용해도가 저하될 수 있고 반대로 상기 함량 범위를 초과하는 경우, 다른 막질의 부식이 발생할 수 있다. The content of such water is not particularly limited, but may be included in the balance to satisfy 100% by weight of the total composition. For example, the water content is preferably 20 to 40 wt%, and more preferably 25 to 35 wt%. If it is less than the content range, the solubility of the inorganic fluorine compound may be reduced, and if it exceeds the content range, corrosion of other film quality may occur.
전술한 바의 수성 세정제 조성물의 제조는 본 발명에서 특별히 한정하지 않는다. 일례로 앞서 언급한 조성 및 함량을 교반기나 순환 장치에서 충분히 혼합하여 제조한다.Preparation of the aqueous detergent composition as described above is not particularly limited in the present invention. For example, it is prepared by sufficiently mixing the above-mentioned composition and content in a stirrer or a circulation device.
본 발명의 수성 세정제 조성물은 반도체 제조 공정 중 세정 단계에서 기판 표면에 존재하는 각종 오염물을 제거하기 위한 세정 단계에 사용된다.The aqueous cleaning composition of the present invention is used in a cleaning step for removing various contaminants present on the surface of a substrate during a cleaning step in a semiconductor manufacturing process.
반도체 소자는 기판 상에 금속막, 절연막, 포토레지스트막 등을 포함하며 세정 단계 이전에 현상, 에칭, 이온주입, 에싱 처리를 거치면서 기판 표면에는 다양한 막질을 구성하는 금속, 유전체 물질, 포토레지스트로부터 다양한 재료를 포함하는 유·무기 잔류물이 생성된다. A semiconductor device includes a metal film, an insulating film, a photoresist film, etc. on a substrate, and before the cleaning step, through development, etching, ion implantation, and ashing treatment, the surface of the substrate is formed from metal, dielectric material, and photoresist constituting various film qualities. Organic and inorganic residues containing various materials are produced.
상기 금속막은 반도체 제조 공정에 사용되는 것으로 예를 들면, Ge, Cu, Al, Ni, Ti, TiN, Ta, TaN, W, TiW, GaAs, SiGe 및 이들의 합금으로 이루어진 군에서 선택된 1종이 가능하다.The metal film is used in a semiconductor manufacturing process. For example, Ge, Cu, Al, Ni, Ti, TiN, Ta, TaN, W, TiW, GaAs, SiGe. And one selected from the group consisting of alloys thereof is possible.
상기 절연막은 반도체 소자에서 절연 기능을 수행하는 것으로 사용가능한 재질로는 무기물, 유기물, 금속 산화물 및 이들의 조합으로 이루어진 선택된 1종이 가능하다. The insulating film performs an insulating function in a semiconductor device, and as a usable material, one selected from an inorganic material, an organic material, a metal oxide, and a combination thereof is possible.
구체적으로 상기 무기물은 실리콘 옥사이드, 실리콘 나이트라이드, 실리콘 옥시나이트라이드, SOG(Spin on glass), SOD(Spin on dielectric) 등이 사용될 수 있다. 이때 SOG는 실록산(siloxane), 실라젠(silazene), 실리케이트(silicate) 등을, SOD는 폴리실라잔(polysilazane)을 포함할 수 있다. 이 밖에도, 포스포실리케이트(phosphosilicates), 보로실리케이트(borosilicates), 보로포스포실리케이트(borophosphosilicates)와 같은 치환된 실리케이트류(altered silicates); HSQ(hydrogen silsesquioxane), MSQ(methyl-silsesquioxane)와 같은 실세스퀴옥산류(silsesquioxanes); 실리카 에어로겔류(silica aerogels) 등이 포함되며, 이에 한정되는 것은 아니다.Specifically, as the inorganic material, silicon oxide, silicon nitride, silicon oxynitride, spin on glass (SOG), or spin on dielectric (SOD) may be used. In this case, SOG may include siloxane, silazene, silicate, and the like, and SOD may include polysilazane. In addition, substituted silicates such as phosphosilicates, borosilicates, and borophosphosilicates; silsesquioxanes such as hydrogen silsesquioxane (HSQ) and methyl-silsesquioxane (MSQ); Silica airgels and the like are included, but are not limited thereto.
상기 유기물은 알키드 수지류, 알릴 에스테르류, 벤조사이클로부텐류, 부타디엔-스티렌, 셀룰로오스, 셀룰로오스 아세테이트, 에폭시드, 에폭시 고분자류, 에틸렌-클로로트리플루오로 에틸렌, 에틸렌-테트라-플루오로에틸렌, 유리섬유강화 플라스틱(fiber glass reinforced plastic), 불화탄소 고분자류, 헥사플루오로프로필렌비닐리덴플루오라이드 공중합체, 파릴렌, 폴리아미드, 폴리이미드, 폴리아라미드, 폴리디메틸실록산, 폴리에테르설폰, 폴리에틸렌, 폴리에틸렌나프탈레이트, 폴리에틸렌테레프탈레이트, 폴리케톤, 폴리메틸메타크릴레이트, 폴리프로필렌, 폴리스티렌, 폴리설폰, 폴리테트라플루오로에틸렌, 폴리우레탄류, 폴리비닐클로라이드 등이 포함되며, 이에 한정되는 것은 아니다.The organic material is alkyd resins, allyl esters, benzocyclobutenes, butadiene-styrene, cellulose, cellulose acetate, epoxide, epoxy polymers, ethylene-chlorotrifluoroethylene, ethylene-tetra-fluoroethylene, glass fiber Fiber glass reinforced plastic, fluorocarbon polymers, hexafluoropropylene vinylidene fluoride copolymer, parylene, polyamide, polyimide, polyaramid, polydimethylsiloxane, polyethersulfone, polyethylene, polyethylene naphthalate , polyethylene terephthalate, polyketone, polymethyl methacrylate, polypropylene, polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyvinyl chloride, and the like, but is not limited thereto.
상기 금속 산화물은 Al, Ti, Zr, Hf, La, Ta, Mg, Sr, Ba 및 이들의 합금으로 이루어진 군에서 선택된 1종을 포함하며, 예를 들어, HfSiO4, HfO2, TiO2, TaO5, Al2O3, ZrO2 등이며 이에 한정되는 것은 아니다. The metal oxide includes one selected from the group consisting of Al, Ti, Zr, Hf, La, Ta, Mg, Sr, Ba, and alloys thereof, for example, HfSiO 4 , HfO 2 , TiO 2 , TaO 5 , Al 2 O 3 , ZrO 2 , and the like, but is not limited thereto.
상기 포토레지스트막으로는 포지티브형 포토레지스트, 네가티브형 포토레지스트, 포지티브형/네가티브형 듀얼톤 포토레지스트(dual tone photoresist) 등이 있으며 본 발명에서는 공지의 것이면 제한없이 적용될 수 있다.As the photoresist film, a positive type photoresist, a negative type photoresist, a positive type/negative type dual tone photoresist, etc. are used. And in the present invention, if it is known, it can be applied without limitation.
본 발명의 수성 세정제 조성물을 이용하여 미세 회로가 형성된 기판으로부터 잔류물을 제거하는 방법은 많은 양의 세정제 조성물에 박리하고자 하는 기판을 동시에 여러 장을 침지(dipping)하는 딥 방식과 한 장씩 박리액을 기판에 스프레이(분무)시켜 포토레지스트를 제거하는 매엽식 방식 모두 사용할 수 있다. 이 경우, 침지, 스프레이(분무) 또는 침지 및 스프레이의 적용 시간 및 온도는 당업자에 의해 용이하거나 적합한 조건으로 선택될 수 있다. The method of removing residues from a substrate on which a microcircuit is formed using the aqueous cleaner composition of the present invention includes a dip method of dipping several sheets of the substrate to be peeled in a large amount of cleaning composition at the same time, and a peeling solution one by one. Both the single-wafer method of removing the photoresist by spraying (spraying) on the substrate can be used. In this case, immersion, spray (spray) or application time and temperature of immersion and spray can be easily or selected by those skilled in the art under suitable conditions.
본 발명에 따른 수성 세정제 조성물은 세정 공정을 통해 변성된 여러 잔류물을 짧은 시간 내에 효과적으로 제거 가능하며 기판상의 금속막, 절연막에 대한 부식 방지력이 우수하고 잔류로 인한 문제가 발생하지 않는다. 이는 제거 대상인 잔류물만을 선택적으로 제거함과 동시에 함께 노출되는 다른 막질에 대한 영향이 없기 때문에 최종 제조된 반도체 소자 및 이를 포함하는 전자기기의 생산성 및 구동 안정성을 향상시킬 수 있다. The aqueous cleaning composition according to the present invention can effectively remove various residues modified through the cleaning process within a short time, and has excellent corrosion protection for the metal film and insulating film on the substrate and does not cause any residual problems. This selectively removes only the residue to be removed and at the same time does not affect the quality of other films exposed together, so that the productivity and driving stability of the finally manufactured semiconductor device and electronic device including the same can be improved.
또한, 본 발명의 수성 세정제 조성물은 반도체 소자 뿐 아니라 이를 포함하는 표시장치, MEMS 장치, 배선 기판 등의 제조 공정에서도 사용 가능하다.In addition, the aqueous cleaning composition of the present invention can be used not only in semiconductor devices, but also in manufacturing processes such as display devices, MEMS devices, and wiring boards including the same.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다. Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example 1 내지 13 및 1 to 13 and 비교예comparative example 1 내지 9: 수성 세정제 조성물의 제조 1 to 9: Preparation of aqueous detergent composition
실험용 비커에 하기 표 1 및 2에 기재된 성분 및 함량을 투입한 후 상온에서 500 rpm 속도로 5분 동안 교반하여 수성 세정제 조성물을 제조하였다.After adding the components and contents shown in Tables 1 and 2 to the experimental beaker, the mixture was stirred at room temperature at 500 rpm for 5 minutes to prepare an aqueous detergent composition.
(중량%)Furtherance
(weight%)
7 Example
7
화합물fluoride
compound
실란계 화합물amino
Silane-based compounds
유기용매polarity
organic solvent
방지제corrosion
inhibitor
2) A-2: 중불화암모늄
3) A-3: 테트라메틸암모늄플로라이드
4) A-4: 테트라부틸암모늄플로라이드
5) B-1: N-(2-아미노에틸)-(3-아미노프로필)트리메톡시실란
6) B-2: N-(2-아미노에틸)-(3-아미노프로필)실란트리올
7) B-3: (3-트리메톡시실리프로필)디에틸렌트리아민
8) C-1: 디메틸설폭사이드
9) C-2: γ-부틸올락톤
10) C-3: 에틸렌 글리콜
11) C-4: 메탄올
12) D-1: 옥살산
13) D-2: 아디픽산
14) D-3: 4-(아미노부틸)트리메톡시실란1) A-1: Ammonium Fluoride
2) A-2: Ammonium bifluoride
3) A-3: tetramethylammonium fluoride
4) A-4: tetrabutylammonium fluoride
5) B-1: N-(2-aminoethyl)-(3-aminopropyl)trimethoxysilane
6) B-2: N-(2-aminoethyl)-(3-aminopropyl)silanetriol
7) B-3: (3-trimethoxysilylpropyl)diethylenetriamine
8) C-1: dimethyl sulfoxide
9) C-2: γ-butylolactone
10) C-3: ethylene glycol
11) C-4: methanol
12) D-1: oxalic acid
13) D-2: adipic acid
14) D-3: 4-(aminobutyl)trimethoxysilane
(중량%)Furtherance
(weight%)
실란계 화합물amino
Silane-based compounds
2) A-2: 중불화암모늄
3) A-3: 테트라메틸암모늄플로라이드
4) A-4: 테트라부틸암모늄플로라이드
5) B-1: N-(2-아미노에틸)-(3-아미노프로필)트리메톡시실란
6) B-2: N-(2-아미노에틸)-(3-아미노프로필)실란트리올
7) B-3: (3-트리메톡시실리프로필)디에틸렌트리아민
8) C-1: 디메틸설폭사이드
9) C-2: 承부틸올락톤,
10) C-3: 에틸렌 글리콜
11) C-4: 메탄올
12) D-1: 옥살산
13) D-2: 아디픽산
14) D-3: 4-(아미노부틸)트리메톡시실란1) A-1: Ammonium Fluoride
2) A-2: Ammonium bifluoride
3) A-3: tetramethylammonium fluoride
4) A-4: tetrabutylammonium fluoride
5) B-1: N-(2-aminoethyl)-(3-aminopropyl)trimethoxysilane
6) B-2: N-(2-aminoethyl)-(3-aminopropyl)silanetriol
7) B-3: (3-trimethoxysilylpropyl)diethylenetriamine
8) C-1: dimethyl sulfoxide
9) C-2: 承butylolactone,
10) C-3: ethylene glycol
11) C-4: methanol
12) D-1: oxalic acid
13) D-2: adipic acid
14) D-3: 4-(aminobutyl)trimethoxysilane
실험예Experimental example 1: 평가 1: evaluation
(1) (One) 세정성detergency 평가 evaluation
실리콘 웨이퍼에 금속막(게르마늄 1000Å, 실리콘게르마늄 1000Å) 및 절연막(실리콘산화물 3000Å, 하프늄산화물 3000Å)을 형성한 뒤 1.2 ㎛ 두께로 포토레지스트(DWG-520)를 균일하게 코팅한 후 150 ℃에서 10분간 유지하여 박막을 형성하였다. After forming a metal film (germanium 1000 Å, silicon germanium 1000 Å) and an insulating film (silicon oxide 3000 Å, hafnium oxide 3000 Å) on a silicon wafer, uniformly coat a photoresist (DWG-520) with a thickness of 1.2 μm and then at 150° C. for 10 minutes was maintained to form a thin film.
이어서 상기 박막 위에 자외선을 조사하였다. 이때, 자외선광원은 우시오 덴끼㈜제의 초고압 수은 램프(상품명 USH-250D)를 이용하여 대기 분위기하에 200 mJ/㎠의 노광량(365 ㎚)으로 광조사하였으며, 특별한 광학 필터는 사용하지 않았다. 상기에서 자외선이 조사된 박막을 pH 10.5의 KOH 수용액 현상 용액에 80 초 동안 담궈 현상하였다. 이 박막이 입혀진 유리판을 증류수를 사용하여 세척한 다음, 질소 가스를 불어서 건조하고, 150 ℃의 가열 오븐에서 10 분 동안 가열하여 패턴을 형성하였다. 이어서, 이온 주입 및 에칭 및 에싱 처리한 후 2×2 ㎝ 크기로 잘라서 시편을 준비하였다. Then, ultraviolet rays were irradiated on the thin film. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 200 mJ/cm 2 in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 80 seconds. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150° C. for 10 minutes to form a pattern. Then, after ion implantation, etching, and ashing, a specimen was prepared by cutting it into a size of 2×2 cm.
상기 실시예 및 비교예의 수성 세정제 조성물을 60 ℃로 온도를 일정하게 유지시킨 후, 준비한 시편을 2분간 침적하였다.After maintaining a constant temperature of the aqueous detergent compositions of Examples and Comparative Examples at 60° C., the prepared specimens were immersed for 2 minutes.
이어서, 시편을 꺼내 잔류하는 세정제를 제거하기 위해 물로 1분간 세정을 실시하였으며, 세정 후 잔류하는 물을 제거하기 위하여 질소를 이용하여 완전히 건조시킨 후 FESEM(모델명:SU-8010, 제조사:히타치)을 이용하여 확인하였다. Then, the specimen was taken out and washed with water for 1 minute to remove the residual detergent. After washing, it was completely dried using nitrogen to remove the residual water, and then FESEM (model name: SU-8010, manufacturer: Hitachi) was applied. was used to confirm.
세정성 평가는 침지 시간 2분인 시편으로 판단하였으며, 이때 평가 기준은 하기와 같으며 그 결과를 하기 표 3에 나타내었다.In the evaluation of the cleaning property, it was determined that the specimen was immersed for 2 minutes, and the evaluation criteria were as follows, and the results are shown in Table 3 below.
<기준><Standard>
◎: 95% 이상 제거됨 ◎: more than 95% removed
○: 90 내지 95% 미만 제거됨○: 90 to less than 95% removed
△: 80 내지 90% 미만 제거됨△: 80 to less than 90% removed
×: 80% 미만으로 제거됨×: less than 80% removed
(2) 부식성 평가(2) Corrosion evaluation
실리콘 웨이퍼에 금속막(게르마늄 1000Å, 실리콘게르마늄 1000Å) 및 절연막(실리콘산화물 3000Å, 하프늄산화물 3000Åm)을 형성한 기판을 이용하여, 후 2×2 ㎝ 크기로 잘라서 시편을 준비하였다. A specimen was prepared by using a substrate on which a metal film (germanium 1000 Å, silicon germanium 1000 Å) and an insulating film (silicon oxide 3000 Å, hafnium oxide 3000 Åm) were formed on a silicon wafer, and then cut to a size of 2×2 cm.
상기 실시예 및 비교예의 수성 세정제 조성물을 60 ℃로 온도를 일정하게 유지시킨 후, 준비한 시편을 10분간 침적하였다.After maintaining a constant temperature of the aqueous detergent compositions of Examples and Comparative Examples at 60° C., the prepared specimens were immersed for 10 minutes.
이어서, 시편을 꺼내 잔류하는 세정제를 제거하기 위해 물로 1분간 세정을 실시하였으며, 세정 후 잔류하는 물을 제거하기 위하여 질소를 이용하여 완전히 건조시킨 후 FESEM(모델명:SU-8010, 제조사:히타치)을 이용하여 확인하였다. 상기 시편의 막질별 막두께를 측정한 뒤 막 두께의 변화값으로 식각 속도를 계산하였으며 얻어진 결과는 하기 표 3에 나타내었다.Then, the specimen was taken out and washed with water for 1 minute to remove the residual detergent. After washing, it was completely dried using nitrogen to remove the residual water, and then FESEM (model name: SU-8010, manufacturer: Hitachi) was applied. was used to confirm. After measuring the film thickness for each film quality of the specimen, the etch rate was calculated using the change value of the film thickness, and the results obtained are shown in Table 3 below.
(3) 용해성 평가(3) Solubility evaluation
상기 실시예 및 비교예의 세정제 조성물을 실온에서 24시간 동안 방치한 후 육안으로 상태를 관찰하였다. 이때 평가 기준은 아래와 같으며 그 결과를 표 3에 나타내었다.After the cleaning compositions of Examples and Comparative Examples were left at room temperature for 24 hours, the state was observed with the naked eye. At this time, the evaluation criteria are as follows, and the results are shown in Table 3.
<기준> <Standard>
○: 하부의 침전이 발생되지 않으며 투명함○: No precipitation at the bottom and transparent
×: 하부에 침전과 용액의 현탁이 발생함×: Precipitation and suspension of the solution occur at the bottom
식각 속도
(Å/min)Ge membrane
etch rate
(Å/min)
(Å/min)SiGe film etch rate
(Å/min)
(Å/min)SiO x film etch rate
(Å/min)
(Å/min)HfO x film etch rate
(Å/min)
상기 표 3에 나타낸 바와 같이, 상기 실시예 1 내지 13의 경우 세정성 및 다른 막질에 대한 부식 방지 효과가 우수함을 확인할 수 있었다.As shown in Table 3, in the case of Examples 1 to 13, it was confirmed that the cleaning property and the corrosion prevention effect on other film qualities were excellent.
한편, 조성 또는 함량을 달리한 비교예 1 내지 9의 경우 세정 성능이 부족하거나 금속막, 절연막에 심각한 손상이 발생함을 확인할 수 있었다. On the other hand, in the case of Comparative Examples 1 to 9 in which the composition or content was different, it was confirmed that the cleaning performance was insufficient or serious damage to the metal film and the insulating film occurred.
본 발명의 수성 세정제 조성물은 기판 표면에 생성되는 잔류물에 대한 우수한 세정 성능을 가짐과 동시에 함께 노출되는 금속막, 절연막에 대한 보호 효과를 가져 최종 얻어지는 반도체 소자의 생산성 및 신뢰성을 개선시킬 수 있다. The aqueous cleaning composition of the present invention has excellent cleaning performance for residues generated on the surface of the substrate and at the same time has a protective effect on the metal film and insulating film exposed together, thereby improving the productivity and reliability of the semiconductor device finally obtained.
Claims (9)
상기 아미노실란계 화합물은 하기 화학식 1로 표시되는 화합물인 것을 특징으로 하는, 수성 세정제 조성물.
[화학식 1]
(상기 화학식 1에서,
R1 및 R2는 서로 같거나 다르며 각각 독립적으로 탄소수 1 내지 20의 알킬렌기이고,
R3은 수소 또는 탄소수 1 내지 20의 알킬기이며,
n은 1 내지 10의 정수이다)Including inorganic fluorine compounds, aminosilane compounds, polar organic solvents and water,
The aminosilane-based compound is an aqueous detergent composition, characterized in that the compound represented by the following formula (1).
[Formula 1]
(In Formula 1,
R 1 and R 2 are the same as or different from each other and are each independently an alkylene group having 1 to 20 carbon atoms,
R 3 is hydrogen or an alkyl group having 1 to 20 carbon atoms,
n is an integer from 1 to 10)
무기계 불소 화합물 0.5 내지 5 중량%,
아미노실란계 화합물 0.1 내지 3 중량%,
극성 유기용매 50 내지 90 중량%, 및
잔부로 물을 포함하는 것을 특징으로 하는 수성 세정제 조성물.According to claim 1, wherein the aqueous detergent composition is based on the weight of the total composition,
0.5 to 5 wt% of an inorganic fluorine compound;
0.1 to 3 wt% of an aminosilane-based compound;
50 to 90% by weight of a polar organic solvent, and
An aqueous detergent composition comprising water as the balance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150091250A KR102347596B1 (en) | 2015-06-26 | 2015-06-26 | Composition of aqueous cleaner for removing residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150091250A KR102347596B1 (en) | 2015-06-26 | 2015-06-26 | Composition of aqueous cleaner for removing residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170001366A KR20170001366A (en) | 2017-01-04 |
| KR102347596B1 true KR102347596B1 (en) | 2022-01-06 |
Family
ID=57831537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150091250A KR102347596B1 (en) | 2015-06-26 | 2015-06-26 | Composition of aqueous cleaner for removing residue |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR102347596B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101878123B1 (en) * | 2018-03-27 | 2018-07-13 | 곽도혁 | Cleaning liquid for wafer chuck table and chemical cleaning method of wafer chuck table using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6203854B1 (en) * | 1997-09-17 | 2001-03-20 | Brent International Plc | Methods of and compositions for preventing corrosion of metal substrates |
| US6677286B1 (en) | 2002-07-10 | 2004-01-13 | Air Products And Chemicals, Inc. | Compositions for removing etching residue and use thereof |
| JP5237300B2 (en) * | 2006-12-21 | 2013-07-17 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Liquid cleaning agent to remove residues after etching |
-
2015
- 2015-06-26 KR KR1020150091250A patent/KR102347596B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170001366A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100958068B1 (en) | Microelectronic cleaning and arc remover compositions | |
| KR101206366B1 (en) | Composition for removing a photoresist residue and polymer residue, and residue removal process using same | |
| KR101056544B1 (en) | Peeling and Cleaning Compositions for Microelectronic Substrates | |
| KR102499429B1 (en) | cleansing formula | |
| KR102434147B1 (en) | Cleaning formulations for removing residues on semiconductor substrates | |
| US20100294306A1 (en) | Method and solution for cleaning semiconductor device substrate | |
| KR102490840B1 (en) | Cleaning compositions for removing residues on semiconductor substrates | |
| JP4988165B2 (en) | Photoresist stripping composition and method for stripping photoresist | |
| JP2002184743A (en) | Stripping composition | |
| CN113557287B (en) | Etching solution and method for selectively removing silicon nitride in semiconductor device manufacturing process | |
| CN111356759A (en) | Stripper solution and method of using stripper solution | |
| KR102347596B1 (en) | Composition of aqueous cleaner for removing residue | |
| CN114466852A (en) | Etching composition and method for selectively removing silicon nitride in semiconductor device manufacturing process | |
| KR20220058948A (en) | etching composition | |
| KR20240076803A (en) | Formulation for removing photoresist and metal-containing residues after dry etching | |
| KR20170028525A (en) | Cleaning composition | |
| TW202313946A (en) | Post-dry etching photoresist and metal containing residue removal formulation | |
| JPH1167703A (en) | Cleaning solvent for manufacturing semiconductor element and semiconductor element using the same | |
| KR20230056740A (en) | cleaning composition | |
| KR102397091B1 (en) | Resist stripper composition and a method of stripping resist using the same | |
| CN114269893A (en) | Photoresist stripping composition | |
| KR20170010532A (en) | Composition of cleaning solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |