CN111793531A - 用于去除蚀刻残余物的清洗液 - Google Patents
用于去除蚀刻残余物的清洗液 Download PDFInfo
- Publication number
- CN111793531A CN111793531A CN202010254166.1A CN202010254166A CN111793531A CN 111793531 A CN111793531 A CN 111793531A CN 202010254166 A CN202010254166 A CN 202010254166A CN 111793531 A CN111793531 A CN 111793531A
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- China
- Prior art keywords
- cleaning solution
- group
- acid
- alkyl
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004140 cleaning Methods 0.000 title claims abstract description 177
- 238000005530 etching Methods 0.000 title claims abstract description 77
- -1 hexafluorosilicic acid Chemical compound 0.000 claims abstract description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 239000011737 fluorine Substances 0.000 claims abstract description 21
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 7
- 150000004761 hexafluorosilicates Chemical class 0.000 claims abstract description 7
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 abstract description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 12
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 11
- 235000021317 phosphate Nutrition 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 150000003973 alkyl amines Chemical class 0.000 claims description 9
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 8
- 150000003335 secondary amines Chemical class 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 8
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical class OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims 1
- 125000005619 boric acid group Chemical class 0.000 claims 1
- 150000004653 carbonic acids Chemical class 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052710 silicon Inorganic materials 0.000 abstract description 28
- 239000010703 silicon Substances 0.000 abstract description 28
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 20
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 105
- 239000010410 layer Substances 0.000 description 47
- 235000012431 wafers Nutrition 0.000 description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 19
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 16
- 150000002367 halogens Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910004205 SiNX Inorganic materials 0.000 description 8
- 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 description 7
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- 239000012634 fragment Substances 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 229910004039 HBF4 Inorganic materials 0.000 description 4
- 229910004713 HPF6 Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 4
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910004074 SiF6 Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- YAGIMDKCMBZIIJ-UHFFFAOYSA-N CCCCCCCCN.CCCCCCCCN Chemical compound CCCCCCCCN.CCCCCCCCN YAGIMDKCMBZIIJ-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 229910006068 SO3F Inorganic materials 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 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
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- BSJIICUVGMPYSD-UHFFFAOYSA-L calcium;hexanoate Chemical compound [Ca+2].CCCCCC([O-])=O.CCCCCC([O-])=O BSJIICUVGMPYSD-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- HRXDYOKVWGTDPD-UHFFFAOYSA-N ctk4b9193 Chemical compound [NH4+].[O-]S(F)(=O)=O HRXDYOKVWGTDPD-UHFFFAOYSA-N 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-M dodecanesulfonate ion Chemical compound CCCCCCCCCCCCS([O-])(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- VXJAYNWISQFORV-UHFFFAOYSA-M potassium fluorosulfate Chemical compound [K+].[O-]S(F)(=O)=O VXJAYNWISQFORV-UHFFFAOYSA-M 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- XCXLEIPEAAEYTF-UHFFFAOYSA-M sodium fluorosulfate Chemical compound [Na+].[O-]S(F)(=O)=O XCXLEIPEAAEYTF-UHFFFAOYSA-M 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- REFMEZARFCPESH-UHFFFAOYSA-M sodium;heptane-1-sulfonate Chemical compound [Na+].CCCCCCCS([O-])(=O)=O REFMEZARFCPESH-UHFFFAOYSA-M 0.000 description 1
- NMTDPTPUELYEPL-UHFFFAOYSA-M sodium;heptanoate Chemical compound [Na+].CCCCCCC([O-])=O NMTDPTPUELYEPL-UHFFFAOYSA-M 0.000 description 1
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 1
- 125000002827 triflate group Chemical class FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- C11D7/28—Organic compounds containing halogen
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
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Abstract
本发明提供一种用于去除蚀刻残余物的清洗液,其包括含氟化合物;其中,该含氟化合物选自:氟化盐、氟代烷、六氟硅酸、六氟硅酸盐、六氟磷酸、六氟磷酸盐、氟硼酸、氟硼酸盐、三氟甲磺酸、三氟甲磺酸盐、氟磺酸、氟磺酸盐、和以上任一组合。该清洗液可提高对由蚀刻氮化硅等含硅材料产生的含硅副产物的去除能力。
Description
技术领域
本发明涉及一种用于去除蚀刻残余物的清洗液,尤指一种用于去除由蚀刻氮化硅所产生的残余物的清洗液。
背景技术
在半导体制程中,诸如氮化硅(silicon nitride)等的含硅材料常被用来制作氧化硅层(silicon oxide)的保护层。举例而言,如图1中的SiNx/SiO2/Si晶片,其中,该氧化硅层10和氮化硅层20(SiNx层)以交错(staggered)排列的方式沉积在硅晶片30上,且形成有一贯穿该氧化硅层10和该氮化硅层20的孔口40。为了形成特定的图案或结构,所述SiNx/SiO2/Si晶片浸入一蚀刻剂中,并且该蚀刻剂通常经由该孔口40开始蚀刻氮化硅层20。
一般而言,如美国专利第7,976,718号中公开的内容,磷酸(H3PO4)常被当作适合蚀刻氮化硅层的蚀刻剂。该氮化硅层在蚀刻后则产生作为残余物的含硅副产物(Si(OH)4),且沉积于该氧化硅层上。由于所述残余物会干扰后续制程,因此需要一清洗组合物以去除所述残余物。例如,美国专利10,381,226号公开使用氢氟酸(hydrofluoric acid,HF)水溶液作为所述清洗组合物。然而,所述清洗组合物在清洗过程中同样会对该氧化硅层造成侵蚀,且其对于氧化硅层的蚀刻速率过高,导致底层的氧化硅层常遭到损坏,进而导致所得的半导体设备的可靠性也降低。
随着对半导体集成密度提高、结构微型化和层体结构薄型化的要求日益高涨,所述氧化硅层和所述氮化硅层的膜厚将日益减缩,且图案精度也将日益提高。考虑到上述情况,开发一可在清洗过程中对蚀刻残余物和氧化硅之间具有高选择性的清洗液的需求也日益增长。
发明内容
有鉴于现有的清洗液无法具有足够区隔性地去除蚀刻残余物和氧化硅,本发明的目的在于提供一种在蚀刻残余物和氧化硅之间具有高去除选择率的清洗液,所述蚀刻残余物是指由蚀刻氮化硅、碳化硅(silicon carbide)、或硅锗(silicon-germanium)等含硅材料所产生的残余物。
为达成前述目的,本发明提供一种用于去除蚀刻残余物的清洗液,其包括含氟化合物;其中,该含氟化合物选自:氟化盐(fluoride salt)、氟代烷(fluoroalkane)、六氟硅酸(hexafluorosilicic acid,简称为HFSA,H2SiF6)、六氟硅酸盐(hexafluorosilicatesalt)、六氟磷酸(hexafluorophosphoric acid,HPF6)、六氟磷酸盐(hexafluorophosphatesalt)、氟硼酸(tetrafluoroboric acid,HBF4)、氟硼酸盐(tetrafluoroborate salt)、三氟甲磺酸(trifluoromethanesulfonic acid,CF3SO3H)、三氟甲磺酸盐(trifluoromethanesulfonate salt)、氟磺酸(fluorosulfonic acid,HSO3F,又可称氟代硫酸)、氟磺酸盐(fluorosulfate salt)、和以上任一组合。
本发明的清洗液通过包含特定的含氟化合物,使得该清洗液可提高对由蚀刻含硅材料而产生的含硅副产物(即残余物)的去除能力。
依据本发明,所述残余物可以是原硅酸(Si(OH)4)或其任一衍生物,该衍生物例如一由前述Si(OH)4形成的寡聚物,以及在有氟离子(F-)存在下形成的Si(OH)3F。
依据本发明,该氟化盐可包含四甲基氟化铵(tetramethylammonium fluoride,简称为TMAF,(CH3)4NF)、氟化铵(ammonium fluoride,(NH4)F)、氟化氢铵(ammonium hydrogendifluoride(NH4)HF2)、氟化钠(sodium fluoride,NaF)、氟化钙(calcium fluoride,CaF2)、氟化镁(magnesium fluoride,MgF2)或任一组合。
依据本发明,该氟代烷可包含四氟化碳(tetrafluoromethane,CF4)、二氟甲烷(difluoromethane,CH2F2)、1,1,1-三氟乙烷(1,1,1-trifluoroethane,C2H3F3)或任一组合。
依据本发明,该六氟硅酸盐可包含氟硅酸钠(Na2(SiF6))、氟硅酸钾(K2(SiF6))、氟硅酸钙(Ca(SiF6))或任一组合。
依据本发明,该六氟磷酸盐可包含六氟磷酸钠(NaPF6)、六氟磷酸钾(KPF6)、六氟磷酸镁(Mg(PF6)2)或任一组合。
依据本发明,该氟硼酸盐可包含四氟硼酸钠(NaBF4)、四氟硼酸钾(KBF4)、四氟硼酸银(AgBF4)或任一组合。
依据本发明,该三氟甲磺酸盐可包含三氟甲磺酸钠(CF3NaO3S)、三氟甲磺酸钾(CF3KO3S)或其组合。
依据本发明,该氟磺酸盐可包含氟磺酸钠(NaSO3F)、氟磺酸钾(KSO3F)、氟磺酸铵(NH4SO3F)或任一组合。
优选地,该清洗液以溶液形式存在。因此,该清洗液还包含溶剂,例如该溶剂为水,故该清洗液为一水溶液形式,但不限于此。
优选地,以该清洗液的总重为基准,该含氟化合物的浓度为0.1重量百分比(wt%)至40wt%。更优选地,该含氟化合物的浓度为0.3wt%至38wt%。在一些实施例中,该含氟化合物的浓度可为0.15wt%、0.2wt%、0.4wt%、0.5wt%、0.7wt%、0.9wt%、1.1wt%、1.3wt%、1.5wt%、1.7wt%、1.8wt%、1.9wt%、2.0wt%、2.1wt%、2.2wt%、2.3wt%、2.4wt%、2.5wt%、2.6wt%、2.7wt%、2.8wt%、2.9wt%、3.0wt%、3.2wt%、3.5wt%、3.7wt%、3.9wt%、4.0wt%、4.2wt%、4.5wt%、5.0wt%、5.5wt%、6.5wt%、7.0wt%、8.2wt%、8.5wt%、9.0wt%、9.2wt%、9.5wt%、10.0wt%、10.5wt%、11.5wt%、12.5wt%、13.0wt%、14.0wt%、15.0wt%、16.0wt%、17.5wt%、20.0wt%、22.5wt%、25.0wt%、27.5wt%、30wt%、32.5wt%、35.0wt%、37.5wt%、39.0wt%、或39.5wt%。
优选地,在该清洗液中,该氟化盐的浓度为0.1wt%至30wt%。更优选地,在该清洗液中,该氟化盐的浓度为0.3wt%至25wt%。具体而言,在该清洗液中,该氟化铵的浓度为0.1wt%至30wt%。更优选地,在该清洗液中,该氟化铵的浓度为1wt%至25wt%。
优选地,在该清洗液中,该氟代烷的浓度为0.01wt%至10wt%。更优选地,在该清洗液中,该氟化烷的浓度为0.05wt%至8wt%。
优选地,在该清洗液中,该HFSA的浓度为0.1wt%至25wt%。更优选地,在该清洗液中,该HFSA的浓度为0.1wt%至20wt%。具体而言,在该清洗液中,该HFSA的浓度为1.0wt%至12wt%。
优选地,在该清洗液中,该六氟硅酸盐的浓度为0.1wt%至25wt%。更优选地,在该清洗液中,该六氟硅酸盐的浓度为0.1wt%至20wt%。
优选地,在该清洗液中,该HPF6的浓度为0.05wt%至10wt%。更优选地,在该清洗液中,该HPF6的浓度为0.1wt%至5wt%。
优选地,在该清洗液中,该六氟磷酸盐的浓度为0.05wt%至10wt%。更优选地,在该清洗液中,该六氟磷酸盐的浓度为0.1wt%至5wt%。
优选地,在该清洗液中,该HBF4的浓度为0.1wt%至20wt%。更优选地,在该清洗液中,该HBF4的浓度为0.8wt%至15wt%。
优选地,在该清洗液中,该氟硼酸盐的浓度为0.1wt%至20wt%。更优选地,在该清洗液中,该氟硼酸盐的浓度为0.8wt%至15wt%。
优选地,在该清洗液中,该三氟甲磺酸的浓度为0.05wt%至10wt%。更优选地,在该清洗液中,该三氟甲磺酸的浓度为0.1wt%至5wt%。
优选地,在该清洗液中,该三氟甲磺酸盐的浓度为0.05wt%至10wt%。更优选地,在该清洗液中,该三氟甲磺酸盐的浓度为0.1wt%至5wt%。
优选地,在该清洗液中,该氟磺酸的浓度为0.05wt%至10wt%。更优选地,在该清洗液中,该氟磺酸的浓度为0.1wt%至5wt%。
优选地,在该清洗液中,该氟磺酸盐的浓度为0.05wt%至10wt%。更优选地,在该清洗液中,该氟磺酸盐的浓度为0.1wt%至5wt%。
通过同时使用不同类型的含氟化合物,可调控该清洗液对去除蚀刻氮化硅产生的蚀刻残余物的去除速率。优选地,所述含氟化合物可同时包含六氟硅酸和氟化铵的组合、或同时包含氟硼酸和氟化铵的组合。
在一些实施例中,该清洗液可包含同一类型的两个以上的该氟化盐,例如氟化钠和氟化铵。
在一些实施例中,该清洗液主要由该含氟化合物和水所组成。
为了提高该清洗液的性能表现,优选地,该清洗液可还包含添加剂。所述添加剂可以是,但不限于,含硅化合物、卤素含氧酸(halogen oxyacid)、氢卤酸(halogen acid)、硝酸(HNO3)、硫酸(H2SO4)、亚硫酸(H2SO3)、磷酸(H3PO4)、碳酸(H2CO3)、氰酸(NCOH)、硼酸(H3BO3)、有机酸、有机酸盐、一级胺(primary amine)、二级胺(secondary amine)、三级胺(tertiary amine)、四级铵盐(quaternary ammonium salt)、烷基磺酸盐(alkylsulfonate salt)、烷基硫酸盐(alkyl sulfate salt)、烷基苯磺酸盐(alkylbenzenesulfonate salt)、烷基磷酸盐(alkyl phosphate salt)、烷基氧化胺(trialkylamineoxide)、和以上任一组合。
依据本发明,当所述添加剂可做为表面活性剂例如该烷基磺酸盐或该烷基硫酸盐时,其可调整该清洗液的表面张力。依据本发明,当所述添加剂可做为酸源例如该卤氧酸或该氢卤酸时,其可调整该表面活性剂和该清洗液的相容性(compatibility)。
优选地,所述添加剂选自:该四级铵盐、该烷基磺酸盐、该烷基硫酸盐、该烷基苯磺酸盐、该烷基磷酸盐、该烷基氧化胺、和以上任一组合。
优选地,以该清洗液的总重为基准,该添加剂的浓度为0.001wt%至30wt%;更优选地,该添加剂的浓度为0.003wt%至27wt%;再更优选地,该添加剂的浓度为0.005wt%至1.0wt%。在一些实施例中,该添加剂的浓度为0.0015wt%、0.002wt%、0.004wt%、0.005wt%、0.006wt%、0.0065wt%、0.007wt%、0.0075wt%、0.008wt%、0.0085wt%、0.009wt%、0.0095wt%、0.01wt%、0.011wt%、0.012wt%、0.013wt%、0.015wt%、0.017wt%、0.019wt%、0.02wt%、0.021wt%、0.022wt%、0.023wt%、0.024wt%、0.025wt%、0.026wt%、0.028wt%、0.03wt%、0.032wt%、0.035wt%、0.037wt%、0.039wt%、0.04wt%、0.045wt%、0.055wt%、0.065wt%、0.07wt%、0.082wt%、0.085wt%、0.09wt%、0.10wt%、0.2wt%、0.4wt%、0.5wt%、0.75wt%、0.9wt%、1.3wt%、2.0wt%、4wt%、6wt%、8wt%、11.0wt%、12.5wt%、13.0wt%、14.0wt%、15.0wt%、16.0wt%、17.5wt%、18.5wt%、19.6wt%、20.0wt%、22.5wt%、24.0wt%、25.0wt%、26.6wt%、27.5wt%、28.8wt%、或29.5wt%。
依据本发明,所述含硅化合物可如式(I)或式(II)所示的结构表示,但不限于此。
在式(I)和式(II)中,每个R各自独立为氢原子、羟基、胺基、碳数为1至5的烷基、碳数为2至5的烯基、碳数为2至5的炔基、碳数为1至5的烷氧基(alkoxy group)、碳数为1至5的烷基胺基(alkyl amino group)、磺酸基(sulfonate group)、磷酸基(phosphate group)、膦酰基(phosphono group)或硫醇基(thiol group)。每个R可相同或彼此不同。
在式(II)中,n为等于或大于0且等于或小于10的整数。
具体而言,所述含硅化合物可为3-氨基丙基三乙氧基硅烷((3-aminopropyl)triethoxysilane,APTES)、N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(N-[3-(trimethoxysilyl)propyl]ethylenediamine)、或氨基丙基倍半硅氧烷(aminopropylsilsesquioxane,例如由GELEST公司贩售的商品WSA-7011)。
优选地,以该清洗液的总重为基准,该清洗液中的含硅化合物的浓度为0.005wt%至10wt%。更优选地,该清洗液中的含硅化合物的浓度为0.005wt%至8wt%。
依据本发明,该卤素含氧酸可以是,但不限于,过氯酸(perchloric acid,HClO4)、溴酸(bromic acid,HBrO3)、碘酸(iodic acid,HIO3)或任一组合。
优选地,该清洗液中的卤素含氧酸的浓度为0.005wt%至10wt%。更优选地,该清洗液中的卤素含氧酸的浓度为0.005wt%至8wt%。
依据本发明,该氢卤酸可以是,但不限于,盐酸(HCl)、氢氟酸或其组合。
优选地,该清洗液中的氢卤酸的浓度为0.005wt%至10wt%。更优选地,该清洗液中的氢卤酸的浓度为0.005wt%至5wt%。优选地,该清洗液中的氢氟酸的浓度为0.005wt%至10wt%。更优选地,该清洗液中的氢氟酸的浓度为0.005wt%至5wt%。
依据本发明,该有机酸可以是,但不限于,具有碳数为1至10的有机酸;举例而言,该有机酸可以是醋酸(CH3COOH)、草酸(oxalic acid,H2C2O4)、辛酸(octanoic acid,O-acid,C8H16O2)、己酸(C6H12O2)或任一组合。
优选地,该清洗液中的有机酸的浓度为0.005wt%至10wt%。更优选地,该清洗液中的有机酸的浓度为0.005wt%至5wt%。优选地,该清洗液中的醋酸的浓度为0.005wt%至10wt%。更优选地,该清洗液中的醋酸的浓度为0.005wt%至5wt%。优选地,该清洗液中的辛酸的浓度为0.005wt%至10wt%。更优选地,该清洗液中的辛酸的浓度为0.005wt%至5wt%。
依据本发明,该有机酸盐可以是,但不限于,具有碳数为1至12的有机酸盐;举例而言,该有机酸盐可以甲酸钠(HCOONa)、丙酸钾(CH3CH2CO2K)、己酸钙(Ca(C6H11O2)2)、庚酸钠或任一组合。
优选地,该清洗液中的有机酸盐的浓度为0.005wt%至10wt%。更优选地,该清洗液中的有机酸盐的浓度为0.005wt%至5wt%。
依据本发明,该一级胺可以是,但不限于,具有碳数为4至16的一级胺;举例而言,该一级胺可以是正丁胺(CH3(CH2)3NH2)、正戊胺(CH3(CH2)4NH2)、正己胺(CH3(CH2)5NH2)、正庚胺(CH3(CH2)6NH2)、正辛胺(CH3(CH2)7NH2)或正癸胺(CH3(CH2)9NH2)。
优选地,该清洗液中的一级胺的浓度为0.005wt%至10wt%。更优选地,该清洗液中的一级胺的浓度为0.005wt%至5wt%。
依据本发明,该二级胺可以是,但不限于,具有碳数为4至24的二级胺;举例而言,该二级胺可以是二己胺([CH3(CH2)5]2NH)、二辛胺([CH3(CH2)7]2NH)或二癸胺([CH3(CH2)9]2NH)。
优选地,该清洗液中的二级胺的浓度为0.005wt%至10wt%。更优选地,该清洗液中的二级胺的浓度为0.005wt%至5wt%。
依据本发明,该三级胺可以是,但不限于,具有碳数为4至32的三级胺;举例而言,该三级胺可以是三戊胺([CH3(CH2)4]3N)、三己胺([CH3(CH2)5]3N)或三辛胺([CH3(CH2)6]3N)。
优选地,该清洗液中的三级胺的浓度为0.005wt%至10wt%。更优选地,该清洗液中的三级胺的浓度为0.005wt%至5wt%。
依据本发明,该四级铵盐可以是,但不限于,具有碳数为4至40的四级铵盐;举例而言,该四级铵盐可以是溴化十六烷基三甲铵(hexadecyl-trimethyl-ammonium bromide,简称CTAB)、溴化十二烷基三甲铵(dodecyl-trimethyl-ammonium bromide)或氯化十六烷基三甲铵(hexadecyl-trimethyl-ammonium chloride)。
优选地,该清洗液中的四级铵盐的浓度为0.005wt%至10wt%。更优选地,该清洗液中的四级铵盐的浓度为0.005wt%至5wt%。优选地,该清洗液中的CTAB的浓度为0.005wt%至10wt%。更优选地,该清洗液中的CTAB的浓度为0.005wt%至5wt%。
依据本发明,该烷基磺酸盐可以是,但不限于,具有碳数为4至16的烷基磺酸盐;举例而言,该烷基磺酸盐可以是十二烷基磺酸钠(sodium 1-dodecanesulfonate,CH3(CH2)11SO3Na)或1-庚烷基磺酸钠(sodium 1-heptanesulfonate,C7H15O3SNa)。
优选地,该清洗液中的烷基磺酸盐的浓度为0.005wt%至10wt%。更优选地,该清洗液中的烷基磺酸盐的浓度为0.005wt%至5wt%。
依据本发明,该烷基硫酸盐可以是,但不限于,具有碳数为4至16的烷基硫酸盐;举例而言,该烷基硫酸盐可以是十二烷基硫酸钠(sodium dodecyl sulfate,CH3(CH2)11OSO3Na,简称SDS)或辛基硫酸钠(CH3(CH2)7OSO3Na)。
优选地,该清洗液中的烷基硫酸盐的浓度为0.005wt%至10wt%。更优选地,该清洗液中的烷基硫酸盐的浓度为0.005wt%至5wt%。优选地,该清洗液中的SDS的浓度为0.005wt%至10wt%。更优选地,该清洗液中的SDS的浓度为0.005wt%至5wt%。
依据本发明,该烷基苯磺酸盐可以是,但不限于,具有碳数为4至16的烷基的烷基苯磺酸盐;举例而言,该烷基苯磺酸盐可以是十二烷基苯磺酸钠(CH3(CH2)11C6H4SO3Na,简称SDBS)。
优选地,该清洗液中的烷基苯磺酸盐的浓度为0.005wt%至10wt%。更优选地,该清洗液中的烷基苯磺酸盐的浓度为0.005wt%至5wt%。
依据本发明,该烷基磷酸盐可以是,但不限于,具有碳数为4至16的烷基磷酸盐;举例而言,该烷基磷酸盐可以是磷酸单十二烷基酯钠盐(sodium monododecyl phosphate)或单月桂基磷酸酯钾(potassium monolauryl phosphate,简称MLPK)。
优选地,该清洗液中的烷基磷酸盐的浓度为0.005wt%至10wt%。更优选地,该清洗液中的烷基磷酸盐的浓度为0.005wt%至5wt%。优选地,该清洗液中的MLPK的浓度为0.005wt%至10wt%。更优选地,该清洗液中的MLPK的浓度为0.005wt%至5wt%。
依据本发明,该烷基氧化胺可以是,但不限于,具有碳数为3至26的烷基氧化胺;举例而言,该烷基氧化胺可以是十二烷基二甲基氧化胺(N,N-dimethyldodecan-1-amineoxide,简称LDAO)。
优选地,该清洗液中的烷基氧化胺的浓度为0.005wt%至10wt%。更优选地,该清洗液中的烷基氧化胺的浓度为0.005wt%至5wt%。
在该清洗液中,可以同时使用不同类型的添加剂的组合。优选地,所述添加剂可以是该氢卤酸和该四级铵盐的组合、该氢卤酸和该烷基硫酸盐的组合、该氢卤酸和该烷基磺酸盐的组合、该氢卤酸和该烷基苯磺酸盐的组合、或该氢卤酸和该烷基磷酸盐的组合。具体而言,所述添加剂可以是HF和SDS的组合、HF和正辛胺(n-octylamine)的组合、或HF和辛酸(O-acid)的组合。
依据本发明,该清洗液的酸碱值(pH值)为0至8。在一些实施例中,该清洗液的pH值为0至3。在另一些实施例中,该清洗液的pH值为6.5至7.8。更具体而言,该清洗液的pH值可为0.1、0.3、0.5、0.75、1.0、1.3、1.5、1.7、1.9、2.2、2.6、3.0、3.5、4.0、4.4、4.9、5.2、5.5、6.0、6.5、6.8、7.2、7.5、7.8、或7.9。
具体地,当该含氟化合物包括氟化铵时,优选地,该清洗液的pH值为6.5至7.8。当该含氟化合物包括HFSA、HBF4和/或HPF6时,优选地,该清洗液的pH值为0至3。更优选地,当该含氟化合物包括HFSA、HBF4和/或HPF6时,优选地,该清洗液的pH值为0至1.25。
优选地,当所述SiNx/SiO2/Si晶片经过蚀刻程序后,可使用温度为10℃至90℃的去离子水清洗蚀刻后的SiNx/SiO2/Si晶片且以氮气干燥后,再将所述蚀刻后的SiNx/SiO2/Si晶片浸入前述清洗液中。
优选地,将所述蚀刻后的SiNx/SiO2/Si晶片浸入温度为10℃至80℃的前述清洗液中。更优选地,将所述蚀刻后的SiNx/SiO2/Si晶片浸入温度为10℃至40℃的前述清洗液中。
优选地,将所述蚀刻后的SiNx/SiO2/Si晶片浸于前述清洗液中1分钟至180分钟。更优选地,将所述蚀刻后的SiNx/SiO2/Si晶片浸于前述清洗液中20分钟至40分钟。
依据本发明,该清洗液具有一高于0.5埃/分钟的去除蚀刻残余物的去除速率。优选地,该清洗液的去除蚀刻残余物的去除速率为高于更优选地,该清洗液的去除蚀刻残余物的去除速率为高于再更优选地,该清洗液的去除蚀刻残余物的去除速率为高于
依据本发明,该清洗液具有一低于的蚀刻氧化硅层的蚀刻速率。优选地,该清洗液的蚀刻氧化硅层的蚀刻速率为低于 更优选地,该清洗液的蚀刻氧化硅层的蚀刻速率为低于 再更优选地,该清洗液的蚀刻氧化硅层的蚀刻速率为低于
依据本发明,该清洗液在蚀刻残余物(即通过蚀刻氮化硅后所产生的残余物)和氧化硅之间的去除选择率高于5。优选地,该清洗液在蚀刻残余物和氧化硅之间的去除选择率高于10。更优选地,该清洗液在蚀刻残余物和氧化硅之间的去除选择率高于12。再更优选地,该清洗液在蚀刻残余物和氧化硅之间的去除选择率高于15。
附图说明
图1为SiNx/SiO2/Si晶片的剖面示意图。
图2为本发明的实施例的蚀刻和清洗蚀刻残余物的流程示意图。
具体实施方式
在下文中,本领域技术人员可从以下实施例很轻易地理解本发明所能达到的优点及效果。因此,应当理解本文提出的叙述仅仅用于说明优选的实施方式而不是用于局限本发明的范围,在不悖离本发明的精神和范围的情况下,可以进行各种修饰、变更以便实施或应用本发明的内容。
制备例:
请参阅图2所示,齐备一厚度为的氮化硅层20’以及一厚度为的镀氧化层硅晶片(thermal oxide wafer)碎片10’。该镀氧化层硅晶片碎片10’包含一硅层和位于该硅层上的一氧化硅层。该氮化硅层20’和该镀氧化层硅晶片碎片10’具有相同的形状和尺寸。将两片密封胶带40分别贴附在该镀氧化层硅晶片碎片10’的两个相对的边缘,接着将该氮化硅层20’覆盖并贴附至该镀氧化层硅晶片碎片10’上,从而形成了一双层结构1。因此,该氮化硅层20’和该镀氧化层硅晶片碎片10’之间存在有一间隔,而该间隔的距离即为该密封胶带40的厚度,80微米(μm)。
首先,将该双层结构1浸泡于温度为155℃的蚀刻液50中20分钟;所述蚀刻液50包含85体积%的磷酸。在蚀刻过程中,该双层结构1的该氮化硅层20’会被蚀刻,因此,由蚀刻该氮化硅层20’而产生的蚀刻残余物201则持续地堆积在该镀氧化层硅晶片碎片10’的表面上,直至蚀刻残余物201累积的厚度至
接着,在室温下以去离子水洗涤所述蚀刻后的双层结构1;将所述氮化硅层20’和所述两片密封胶带40移除,从而获得测试样品1’。以椭圆偏振仪(spectroscopicellipsometer)量测所述测试样品1’的厚度。
实施例1至15:清洗液
实施例1至15的清洗液各自所包含的特定成份和其浓度都列于表1中。以实施例1为例,以所述清洗液的总重为基准,将0.875wt%的HFSA作为含氟化合物和99.125wt%的水混合,从而获得实施例1的清洗液。再以实施例3为例,以所述清洗液的总重为基准,将1.75wt%的HFSA作为含氟化合物、0.0084wt%的HF作为添加剂和98.2416wt%的水混合,从而获得实施例3的清洗液。
表1:实施例1至15(E1至E15)的清洗液的成份和其浓度、及各清洗液的pH值
比较例1至4:清洗液
比较例1至4的清洗液各自所包含的特定成份和其浓度都列于表2中。所述比较例1至4的清洗液通过与实施例1至15的清洗液相似的方法制备,主要差别在于比较例1至4的清洗液不包含本发明界定的特定的含氟化合物。
表2:比较例1至4(C1至C4)的清洗液的成份和其浓度、及各清洗液的pH值
分析1:去除蚀刻残余物的去除速率
如图2所示,将每个测试样品1’分别浸入实施例1至15和比较例1至4的清洗液60中一预定的去除时间。随后,再于室温下以去离子水洗涤经清洗液清洗的测试样品1’。然后,以椭圆偏振仪再次量测经清洗后的测试样品1’的厚度。因此,清洗前后的测试样品1’的厚度的差值,即为所述蚀刻残余物被去除的厚度。据此,根据上述得到的所述蚀刻残余物被去除的厚度除以去除所花的时间,即可计算得到蚀刻残余物的去除速率。
分析2:蚀刻氧化硅层的蚀刻速率
将各镀氧化层硅晶片以一由HF和水组成的氢氟酸水溶液清洗后,以椭圆偏振仪量测其厚度;其中,所述氢氟酸水溶液中的HF和水的体积比为200:1。然后,将清洗后的各镀氧化层硅晶片分别浸入实施例1至15和比较例1至4的清洗液中约20分钟,除非所述镀氧化层硅晶片于某一清洗液中会在少于20分钟的时间内被蚀刻光;然后,以椭圆偏振仪再次量测经清洗液浸泡后的各镀氧化层硅晶片的厚度。因此,浸泡清洗液前后的各镀氧化层硅晶片的厚度的差值,即为所述镀氧化层硅晶片被蚀刻掉的厚度。据此,根据上述得到的所述镀氧化层硅晶片被蚀刻掉的厚度除以浸泡于清洗液的时间,即可计算得到各清洗液蚀刻氧化硅层的蚀刻速率。
分析3:去除选择率
将各实施例1至15和比较例1至14的“去除蚀刻残余物的去除速率”除以“蚀刻氧化硅层的蚀刻速率”所获得的商值即定义为“去除选择率”。然而,在比较例1和3中,由于去除蚀刻残余物的去除速率太高以至于不能获得精确值,因此,比较例1和3的去除蚀刻残余物的去除速率仅估计其下限值。
表3实施例1至15、比较例1至4的去除蚀刻残余物的去除速率、蚀刻氧化硅层的蚀刻速率和去除选择率
实验结果讨论
每个蚀刻后的测试样品浸入本发明的各清洗液后,其沉积于氧化硅层上的蚀刻残余物确实都能被去除。另外,如表3所示,实施例1至15的清洗液所具有的去除选择率皆明显高于比较例1至4的清洗液所具有的去除选择率。由此可证,本发明的清洗液不仅可去除由蚀刻氮化硅层而产生的蚀刻残余物,还可具有良好的去除选择率。
此外,实施例1至15的清洗液对于氧化硅层的蚀刻速率皆明显低于比较例1至4的清洗液对于氧化硅层的蚀刻速率。由此可证,本发明的清洗液可以降低对氧化硅层的影响,从而可使氧化硅层具有更平坦的表面。
综上所述,本发明的清洗液因能在蚀刻残余物和氧化硅之间具有较高的去除选择率,从而具有更高的商业实施的潜力。
尽管前述说明已阐述本发明的诸多特征、优点及本发明的构成与特征细节,然而这仅属于示例性的说明。全部在本发明的权利要求的一般涵义所表示范围内,依据本发明原则所作的细节变化尤其是指形状、尺寸和元件设置的改变,均仍属于本发明的范围内。
Claims (12)
1.一种用于去除蚀刻残余物的清洗液,其包括含氟化合物;
其中,该含氟化合物选自:氟化盐、氟代烷、六氟硅酸、六氟硅酸盐、六氟磷酸、六氟磷酸盐、氟硼酸、氟硼酸盐、三氟甲磺酸、三氟甲磺酸盐、氟磺酸、氟磺酸盐、和以上任一组合。
2.根据权利要求1所述的用于去除蚀刻残余物的清洗液,其中,该清洗液还包括添加剂;其中,该添加剂选自:含硅化合物、卤素含氧酸、氢卤酸、硝酸、硫酸、亚硫酸、磷酸、碳酸、氰酸、硼酸、有机酸、有机酸盐、一级胺、二级胺、三级胺、四级铵盐、烷基磺酸盐、烷基硫酸盐、烷基苯磺酸盐、烷基磷酸盐、烷基氧化胺、和以上任一组合。
5.根据权利要求2所述的用于去除蚀刻残余物的清洗液,其中,该添加剂选自:该四级铵盐、该烷基磺酸盐、该烷基硫酸盐、该烷基苯磺酸盐、该烷基磷酸盐、该烷基氧化胺、和以上任一组合。
6.根据权利要求1至5中任一项所述的用于去除蚀刻残余物的清洗液,其中,该含氟化合物为该六氟硅酸、该六氟磷酸、或该氟硼酸。
7.根据权利要求1所述的用于去除蚀刻残余物的清洗液,其中,该清洗液还包括溶剂。
8.根据权利要求2至5中任一项所述的用于去除蚀刻残余物的清洗液,其中,该清洗液还包括溶剂。
9.根据权利要求7所述的用于去除蚀刻残余物的清洗液,其中,以该清洗液的总重为基准,该含氟化合物的浓度为0.1重量百分比至40重量百分比。
10.根据权利要求8所述的用于去除蚀刻残余物的清洗液,其中,以该清洗液的总重为基准,该含氟化合物的浓度为0.1重量百分比至40重量百分比,该添加剂的浓度为0.001重量百分比至30重量百分比。
11.根据权利要求1所述的用于去除蚀刻残余物的清洗液,其中,该清洗液具有一高于0.5埃/分钟的去除蚀刻残余物的去除速率。
12.根据权利要求1所述的用于去除蚀刻残余物的清洗液,其中,该清洗液具有一低于1.0埃/分钟的蚀刻氧化硅层的蚀刻速率。
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CN112592777A (zh) * | 2020-12-03 | 2021-04-02 | 湖北兴福电子材料有限公司 | 一种3d nand结构片干法蚀刻后的深沟槽清洗液 |
CN114276814A (zh) * | 2021-12-15 | 2022-04-05 | 湖北兴福电子材料有限公司 | 一种蚀刻硅片后清洗液 |
CN114395395A (zh) * | 2022-01-27 | 2022-04-26 | 广东粤港澳大湾区黄埔材料研究院 | 具有高选择比的氮化硅蚀刻液及其制备方法和应用 |
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