KR20080044637A - Cleaning solution composition for electronic material and cleaning method using the same - Google Patents
Cleaning solution composition for electronic material and cleaning method using the same Download PDFInfo
- Publication number
- KR20080044637A KR20080044637A KR1020060113717A KR20060113717A KR20080044637A KR 20080044637 A KR20080044637 A KR 20080044637A KR 1020060113717 A KR1020060113717 A KR 1020060113717A KR 20060113717 A KR20060113717 A KR 20060113717A KR 20080044637 A KR20080044637 A KR 20080044637A
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- group
- compound
- ammonium
- cleaning
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 238000004140 cleaning Methods 0.000 title claims description 99
- 238000000034 method Methods 0.000 title claims description 51
- 239000012776 electronic material Substances 0.000 title claims description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 49
- 239000010703 silicon Substances 0.000 claims abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005260 corrosion Methods 0.000 claims abstract description 43
- 230000007797 corrosion Effects 0.000 claims abstract description 42
- -1 peroxide compound Chemical class 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 50
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 16
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 15
- 150000002222 fluorine compounds Chemical class 0.000 claims description 14
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 13
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000004973 liquid crystal related substance Substances 0.000 claims description 9
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 claims description 3
- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 claims description 3
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 claims description 3
- 125000000565 sulfonamide group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- MRCKRGSNLOHYRA-UHFFFAOYSA-N (2-nitrophenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1[N+]([O-])=O MRCKRGSNLOHYRA-UHFFFAOYSA-N 0.000 claims description 2
- DWVNLBRNGAANPI-UHFFFAOYSA-N 1,2-dimethoxy-3-nitrobenzene Chemical compound COC1=CC=CC([N+]([O-])=O)=C1OC DWVNLBRNGAANPI-UHFFFAOYSA-N 0.000 claims description 2
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 claims description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 2
- HJRJRUMKQCMYDL-UHFFFAOYSA-N 1-chloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 HJRJRUMKQCMYDL-UHFFFAOYSA-N 0.000 claims description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 2
- BSMKYQUHXQAVKG-UHFFFAOYSA-N 1-nitro-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1[N+]([O-])=O BSMKYQUHXQAVKG-UHFFFAOYSA-N 0.000 claims description 2
- IVOMCIOXYNVSEW-UHFFFAOYSA-N 2,3,4-trinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1[N+]([O-])=O IVOMCIOXYNVSEW-UHFFFAOYSA-N 0.000 claims description 2
- MCIDYUGTJBLEST-UHFFFAOYSA-N 2,3-dinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1[N+]([O-])=O MCIDYUGTJBLEST-UHFFFAOYSA-N 0.000 claims description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims description 2
- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 claims description 2
- KAQBNBSMMVTKRN-UHFFFAOYSA-N 2,4,6-trinitrobenzoic acid Chemical compound OC(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O KAQBNBSMMVTKRN-UHFFFAOYSA-N 0.000 claims description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 claims description 2
- CVYZVNVPQRKDLW-UHFFFAOYSA-N 2,4-dinitroanisole Chemical compound COC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CVYZVNVPQRKDLW-UHFFFAOYSA-N 0.000 claims description 2
- OVOJUAKDTOOXRF-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O OVOJUAKDTOOXRF-UHFFFAOYSA-N 0.000 claims description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 claims description 2
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- QBVBOBWTOSGVEN-UHFFFAOYSA-N 2-chloro-3,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1Cl QBVBOBWTOSGVEN-UHFFFAOYSA-N 0.000 claims description 2
- QBGLHYQUZJDZOO-UHFFFAOYSA-N 2-chloro-3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1Cl QBGLHYQUZJDZOO-UHFFFAOYSA-N 0.000 claims description 2
- FMXDVBRYDYFVGS-UHFFFAOYSA-N 2-methoxy-1,3,5-trinitrobenzene Chemical compound COC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O FMXDVBRYDYFVGS-UHFFFAOYSA-N 0.000 claims description 2
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 claims description 2
- GNDKYAWHEKZHPJ-UHFFFAOYSA-N 2-nitrobenzenesulfonimidic acid Chemical compound NS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O GNDKYAWHEKZHPJ-UHFFFAOYSA-N 0.000 claims description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims description 2
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical class [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 claims description 2
- GZJIQNJINXQYTG-UHFFFAOYSA-N 2-nitrooxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O[N+]([O-])=O GZJIQNJINXQYTG-UHFFFAOYSA-N 0.000 claims description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 2
- YAVVHVRMNIDVOQ-UHFFFAOYSA-N 3,4-dinitrobenzene-1,2-diol Chemical compound OC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1O YAVVHVRMNIDVOQ-UHFFFAOYSA-N 0.000 claims description 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 claims description 2
- FGMRHNYMZYMARX-UHFFFAOYSA-N 3-amino-2-nitrobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1[N+]([O-])=O FGMRHNYMZYMARX-UHFFFAOYSA-N 0.000 claims description 2
- JFOWATROJMCOHF-UHFFFAOYSA-N 3-ethyl-2-nitrobenzoic acid Chemical compound CCC1=CC=CC(C(O)=O)=C1[N+]([O-])=O JFOWATROJMCOHF-UHFFFAOYSA-N 0.000 claims description 2
- RITQAMSEQYWFML-UHFFFAOYSA-N 3-methoxy-2-nitroaniline Chemical compound COC1=CC=CC(N)=C1[N+]([O-])=O RITQAMSEQYWFML-UHFFFAOYSA-N 0.000 claims description 2
- YHKWFDPEASWKFQ-UHFFFAOYSA-N 3-nitrobenzene-1,2-diol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1O YHKWFDPEASWKFQ-UHFFFAOYSA-N 0.000 claims description 2
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DGDAVTPQCQXLGU-UHFFFAOYSA-N 5437-38-7 Chemical compound CC1=CC=CC(C(O)=O)=C1[N+]([O-])=O DGDAVTPQCQXLGU-UHFFFAOYSA-N 0.000 claims description 2
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims description 2
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 claims description 2
- PFDHBJNLFOINAY-UHFFFAOYSA-N [chloro(dinitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)([N+]([O-])=O)C1=CC=CC=C1 PFDHBJNLFOINAY-UHFFFAOYSA-N 0.000 claims description 2
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 claims description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- IGTXUDQEBIVUOK-UHFFFAOYSA-N dinitro(phenyl)methanol Chemical compound [O-][N+](=O)C([N+]([O-])=O)(O)C1=CC=CC=C1 IGTXUDQEBIVUOK-UHFFFAOYSA-N 0.000 claims description 2
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 2
- QQHJCXBRTFLRQV-UHFFFAOYSA-N n-chloro-n-(2-nitrophenyl)nitramide Chemical compound [O-][N+](=O)N(Cl)C1=CC=CC=C1[N+]([O-])=O QQHJCXBRTFLRQV-UHFFFAOYSA-N 0.000 claims description 2
- LHHIALSOMNPUOW-UHFFFAOYSA-N n-chloro-n-phenylnitramide Chemical compound [O-][N+](=O)N(Cl)C1=CC=CC=C1 LHHIALSOMNPUOW-UHFFFAOYSA-N 0.000 claims description 2
- LZGUHMNOBNWABZ-UHFFFAOYSA-N n-nitro-n-phenylnitramide Chemical compound [O-][N+](=O)N([N+]([O-])=O)C1=CC=CC=C1 LZGUHMNOBNWABZ-UHFFFAOYSA-N 0.000 claims description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 2
- 229950002929 trinitrophenol Drugs 0.000 claims description 2
- 239000000015 trinitrotoluene Substances 0.000 claims description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims 2
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 claims 1
- 239000004114 Ammonium polyphosphate Substances 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- JXQXIMDCEZOPKT-UHFFFAOYSA-N C(C)(=O)NC1=CC=CC=C1.[N+](=O)([O-])CCCONC1=CC=CC=C1 Chemical compound C(C)(=O)NC1=CC=CC=C1.[N+](=O)([O-])CCCONC1=CC=CC=C1 JXQXIMDCEZOPKT-UHFFFAOYSA-N 0.000 claims 1
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims 1
- 229920001276 ammonium polyphosphate Polymers 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 22
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- 125000003161 (C1-C6) alkylene group Chemical group 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
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- 150000001412 amines Chemical class 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
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- 239000010937 tungsten Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000005536 corrosion prevention Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000001312 dry etching Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 5
- 238000001039 wet etching Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 239000011575 calcium Substances 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 description 2
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WMKGMCCZGTXXQU-UHFFFAOYSA-N 2,3-benzodioxine-1,4-dione Chemical compound C1=CC=C2C(=O)OOC(=O)C2=C1 WMKGMCCZGTXXQU-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- KNDAEDDIIQYRHY-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(piperazin-1-ylmethyl)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CN1CCNCC1 KNDAEDDIIQYRHY-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
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- ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 2-nitrobenzene-1,3-diol Chemical compound OC1=CC=CC(O)=C1[N+]([O-])=O ZLCPKMIJYMHZMJ-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- AELXREXQYKNSPY-UHFFFAOYSA-N P(O)(O)=O.[N+](=O)([O-])C1=CC=CC=C1 Chemical compound P(O)(O)=O.[N+](=O)([O-])C1=CC=CC=C1 AELXREXQYKNSPY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 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 1
- QMKKLDSVLASQEF-UHFFFAOYSA-N n-(3-nitropropoxy)aniline Chemical compound [O-][N+](=O)CCCONC1=CC=CC=C1 QMKKLDSVLASQEF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 235000013842 nitrous oxide Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
Description
본 발명은 전자 재료용 세정액 조성물 및 이를 이용한 세정 방법에 관한 것이다. 보다 상세하게는, 전자 재료의 제조공정에 있어서, 실리콘 및 실리콘 이외의 금속의 부식을 억제하며, 전자 재료 표면에 부착되어 있는 미세한 오염 입자, 습식 또는 건식 식각 공정, 드라이 에싱 공정 후 발생하는 변질, 경화된 포토레지스트 및 폴리머 잔류물을 제거하기 위한 전자 재료용 세정액 및 이를 이용한 세정 방법에 관한 것이다. The present invention relates to a cleaning liquid composition for an electronic material and a cleaning method using the same. More specifically, in the electronic material manufacturing process, the corrosion of metals other than silicon and silicon is suppressed, and fine contaminant particles adhering to the surface of the electronic material, wet or dry etching processes, deterioration occurring after a dry ashing process, A cleaning liquid for electronic materials for removing cured photoresist and polymer residues and a cleaning method using the same.
반도체 소자의 제조 공정 중에는, 소자의 제조 시 영향을 줄 수 있는 파티클(particle)이나 오염물질을 제거하고, 표면을 다른 불순물로부터 보호하기 위한 표면 세척 공정이 있는데, 이를 통상 세정 공정이라 한다. 상기 오염물질은 탄소 및 그 계열로서, 폴리머, 포토레지스트, 왁스, 오일 등이 그 원인이 되는 유기성 잔류물과, 산화물, 질화물, 케미칼 자체에서 함유한 파티클, 기타 장비 파티클 등이 원인이 되는 무기성 잔류물, 및 대기, 수중에서 저절로 성장한 자연 산화막, 알 루미늄(Al), 바륨(Ba), 카드뮴(Cd), 칼슘(Ca), 크롬(Cr), 코발트(Co), 구리(Cu), 철(Fe), 납(Pb), 리튬(Li), 마그네슘(Mg), 망간(Mn), 니켈(Ni), 칼륨(K), 나트륨(Na), 스트론튬(Sr), 주석(Sn), 아연(Zn) 등으로 케미칼 자체에서 함유한 경우 또는 장비 소스 등이 원인이 되는 금속 불순물로 나눌 수 있다. In the manufacturing process of the semiconductor device, there is a surface cleaning process to remove particles or contaminants that may affect the manufacturing of the device, and to protect the surface from other impurities, which is commonly referred to as a cleaning process. The contaminants are carbon and its series, and organic residues caused by polymers, photoresists, waxes, oils, etc., and inorganic matters caused by particles contained in oxides, nitrides, chemicals, and other equipment particles. Residues and natural oxide films grown naturally in air, water, aluminum (Al), barium (Ba), cadmium (Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), nickel (Ni), potassium (K), sodium (Na), strontium (Sr), tin (Sn), zinc (Zn) or the like can be divided into metal impurities caused by the chemical itself or the source of the equipment.
상기 오염 물질을 세척하지 않고 방치할 경우, 이는 소자 불량의 원인이 되는데, 이는 오염 물질의 종류에 따라 그 불량 내용도 달라지게 된다. 유기 물질의 경우는 결정 결함 및 핀 홀, 콘택 통전 불량의 발생 원인이고, 무기 물질의 경우는 배선 단선, 저항 증대 등에 의한 패턴 불량 및 스팟(Spot) 이상돌기의 발생 원인이며, 금속 불순물의 경우는 접합 누설전류(Junction Leakage)의 발생, 수명감소 및 문턱전압(Threshold Voltage)의 이전 등의 불량을 일으키는 원인이 되며, 또한 자연 산화막의 경우는 막의 특성을 열화시키는 불량을 야기한다. 따라서, 이러한 오염물질의 제거를 위한 세정 공정은 소자의 특성의 향상을 위하여 필수적인 공정이다. If the contaminants are left unwashed, this may cause device defects, which will vary depending on the type of contaminants. In the case of organic materials, crystal defects, pinholes, and poor contact energization are caused.Inorganic materials are causes of pattern defects and spot abnormalities due to disconnection of wires, increased resistance, and the like. It causes defects such as generation of junction leakage, reduced lifespan and transfer of threshold voltage, and in the case of natural oxide film, it causes defects that deteriorate the characteristics of the film. Therefore, the cleaning process for removing such contaminants is an essential process for improving the characteristics of the device.
종래부터, 반도체용 실리콘기판, 액정용 유리기판, 포토 마스크용 석영기판 등의 표면 세정은 주로, 과산화수소수와 황산의 혼합액(SPM), 과산화수소수와 암모니아수와 물의 혼합액(SC-1), 과산화수소수와 염산과 물의 혼합액(SC-2), 희석 불산(DHF) 등의 농후한 약액을 사용해서 고온에서 세정한 후에 초순수에 의해 헹구는, 소위 RCA(Radio Corporation of America) 세정법에 의해서 각각의 오염원인에 대해 행하여져 왔다. RCA세정법에 있어서, 황산과 과산화수소수를 1:4로 혼합하여 제조하는 SPM 약액은 유기 오염 물질의 제거에 효과적이며, SC-1, SC-2는 각각 염 기성과 산성 용액으로 산화물 내의 파티클과 금속 오염 물질의 제거에 효과적이다.Background Art [0002] Conventionally, surface cleaning of silicon substrates for semiconductors, glass substrates for liquid crystals, quartz substrates for photo masks, and the like is mainly carried out with a mixture of hydrogen peroxide and sulfuric acid (SPM), a mixture of hydrogen peroxide and ammonia and water (SC-1), and hydrogen peroxide. Each of the causes of contamination by the so-called RCA (Radio Corporation of America) cleaning method, which is washed with ultrapure water after washing at high temperature with a concentrated chemical solution such as hydrochloric acid and water (SC-2) and diluted hydrofluoric acid (DHF). Has been done. In the RCA cleaning method, SPM chemicals prepared by mixing sulfuric acid and hydrogen peroxide at 1: 4 are effective for removing organic contaminants, and SC-1 and SC-2 are basic and acidic solutions, respectively. Effective for removing contaminants
반도체, LCD, 포토마스크 등의 제조 공정 중에 사용되는 포토레지스트는 유기 고분자 화합물(Organic polymer)이고, 이를 분해하려면 강산이나 강염기 또는 강한 산화제가 필요하다. 통상 포토레지스트를 제거하기 위하여 황산과 과산화수소수가 혼합된 SPM을 사용하며, 이는 탈수소화 반응과 산화 반응을 통하여 유기 화합물을 이산화탄소와 수분으로 분해한다. 또한, 금속 성분을 제거하기 위해서는 통상 염산과 과산화수소수와 물의 혼합액인 SC-2를 사용하는데, 이는 Cl 라디칼과 금속이 반응하여 염산을 형성하여 금속 오염 물질을 제거한다. Photoresists used during the manufacturing process of semiconductors, LCDs, photomasks, and the like are organic polymers, and strong acids, strong bases, or strong oxidizing agents are required to decompose them. In order to remove photoresist, SPM, which is a mixture of sulfuric acid and hydrogen peroxide water, is used, which decomposes organic compounds into carbon dioxide and water through dehydrogenation and oxidation. In addition, SC-2, which is a mixture of hydrochloric acid, hydrogen peroxide and water, is generally used to remove metal components, which react with Cl radicals and metals to form hydrochloric acid to remove metal contaminants.
그러나, 상기의 RCA세정법은 피식각층 패턴이 금속 패턴인 경우에는 무기용매의 조성에 의해 금속이 심하게 손상되고, 부식되어 패턴 프로파일이 불량하게 되고, 또한, 불순물을 제거하는 과정이 섭씨 50 내지 120도 정도의 고온에서 이루어져야 하므로, 불산, 암모니아수, 황산 및 과산화수소수 등과 같은 물질을 세정액으로 사용하는 경우에는 많은 주의가 필요하다. However, in the above RCA cleaning method, when the etched layer pattern is a metal pattern, the metal is severely damaged and corroded by the composition of the inorganic solvent, so that the pattern profile is poor, and the process of removing impurities is 50 to 120 degrees Celsius. Since it should be made at a high temperature, much care must be taken when using substances such as hydrofluoric acid, aqueous ammonia, sulfuric acid, and hydrogen peroxide as the cleaning liquid.
이상에 대한 해결책을 제안하고 있는 문헌들의 예는 다음과 같다. Examples of documents suggesting a solution to the above are as follows.
한국 특허공개공보 제 2003-0041092호는 (A) 치환기를 가질 수도 있는 탄화수소기와, 폴리옥시에틸렌기를 동일 분자 구조 내에 갖는 에틸렌옥사이드 부가형 계면활성제로, 이 탄화수소기에 함유되는 탄소수(m)와 폴리옥시에틸렌기 중의 옥시에틸렌기의 수(n)의 비율(m/n)이 m/n=1.5인 것을 특징으로 하는 것, (B) 알칼리성분, (C) 과산화수소, (D) 물의 조성을 갖고, pH가 9이상, (C)의 함유량이 0.01중 량% 이상 4중량% 이하인 것을 특징으로 하는 기판표면 세정액을 개시한다. Korean Patent Laid-Open Publication No. 2003-0041092 is an ethylene oxide addition type surfactant having (A) a hydrocarbon group which may have a substituent and a polyoxyethylene group in the same molecular structure, wherein the carbon number (m) and polyoxyethylene contained in the hydrocarbon group The ratio (m / n) of the number (n) of the oxyethylene groups in the group is m / n = 1.5, characterized by the composition of (B) an alkali component, (C) hydrogen peroxide, and (D) water, Disclosed is a substrate surface cleaning liquid, characterized in that the content of 9 or more and (C) is 0.01% by weight or more and 4% by weight or less.
한국 특허공개공보 제 2000-0023187호는 염산-과산화수소계(HPM) 또는 황산-과산화수소계(SPM)의 용액에 미량의 불산을 혼합한 HPFM또는 SPFM으로 구성되어 있어, 상기 실리콘계 절연막 상에 부착하는 백금족 금속(예컨대, Pt 또는 Ir) 오염물질을 1×1010atoms/cm2미만으로 저감시킬 수 있는 세정액 조성물을 개시한다. Korean Patent Laid-Open Publication No. 2000-0023187 is composed of HPFM or SPFM in which a small amount of hydrofluoric acid is mixed with a solution of hydrochloric acid-hydrogen peroxide (HPM) or sulfuric acid-hydrogen peroxide (SPM), and is deposited on the silicon-based insulating film. Disclosed is a cleaning liquid composition capable of reducing metal (eg, Pt or Ir) contaminants to less than 1 × 10 10 atoms / cm 2 .
한국 특허공개공보 제 1999-0067948호는 불화수소 및 수소가스, 불화수소 및 산소가스, 불화수소, 염화수소 또는 질산 및 수소가스, 또는 불화수소, 염화수소 또는 질산 및 산소가스, 또는 불화수소, 과산화수소 및 산소가스를 용해한 수용액으로 이루어진 것을 특징으로 하는 전자 재료용 세정수와 이들 전자 재료용 세정수에 초음파 진동을 전달하면서 세정을 행하는 것을 특징으로 하는 세정 방법을 개시한다. Korean Patent Publication No. 1999-0067948 discloses hydrogen fluoride and hydrogen gas, hydrogen fluoride and oxygen gas, hydrogen fluoride, hydrogen chloride or nitric acid and hydrogen gas, or hydrogen fluoride, hydrogen chloride or nitric acid and oxygen gas, or hydrogen fluoride, hydrogen peroxide and oxygen Disclosed is a cleaning method comprising washing with electronic ultrasonic cleaning to an electronic material cleaning water characterized by consisting of an aqueous solution in which a gas is dissolved, and ultrasonic vibration to these cleaning materials for electronic materials.
한국 특허공개공보 제 1998-048608호는 웨이퍼 상에 발생된 유기물, 자연 산화막 및 불순물 입자를 황산, 암모니아, 과산화수소수 및 순수로 이루어진 암모니아 혼합 용액을 사용하여 세정하여, 웨이퍼 표면의 청결을 유지하는 방법을 개시한다. Korean Patent Laid-Open Publication No. 1998-048608 discloses a method for cleaning organic surface, natural oxide film, and impurity particles generated on a wafer by using ammonia mixed solution composed of sulfuric acid, ammonia, hydrogen peroxide, and pure water to maintain clean wafer surface. Initiate.
한국 등록특허공보 제 10-0255168호는 5℃ 내지 10℃ 정도의 저온 오존수를 이용하여 금속적 불순물을 완전히 제거한 후, 저함량 불산 계열 화학약품으로 자연 산화막을 효과적으로 제거하여, 측벽의 스페이서 산화막 손실을 최소화 할 수 있는 세정 방법을 개시한다. Korean Patent Publication No. 10-0255168 completely removes metallic impurities using low temperature ozone water of about 5 ° C to 10 ° C, and then effectively removes the natural oxide film with a low-fluoric acid chemical, thereby minimizing the loss of spacer oxide on the sidewalls. The cleaning method which can be performed is disclosed.
유럽 특허공보 제 0742282호는 0.1 내지 4%의 불산과 RfCOONH4(Rf는 불소가 포함된 탄소수가 5 내지 9인 탄화수소기)가 50 내지 1500ppm 또는 Rf'O(CH2CH2O)nR 혹은 Rf'(CH2CH2O)nR(Rf'는 불소가 포함된 탄소수가 5 내지 15인 탄화수소기, R은 수소 혹은 탄소수가 1 내지 4인 탄화수소기, n은 5 내지 20)가 50 내지 100000ppm로 구성된 실리콘 표면을 세정하는 세정액을 개시한다. EP 0742282 discloses 0.1 to 4% of hydrofluoric acid and RfCOONH 4 (Rf is a hydrocarbon group having 5 to 9 carbon atoms containing fluorine) 50 to 1500 ppm or Rf'O (CH 2 CH 2 O) n R or Rf '(CH 2 CH 2 O) n R (Rf' is a hydrocarbon group having 5 to 15 carbon atoms containing fluorine, R is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, n is 5 to 20) 50 to A cleaning liquid for cleaning a silicon surface composed of 100000 ppm is disclosed.
미국 특허공보 제 5705089호는 포스폰산계의 킬레이트제와 HOCH2-(CHOH)n-CH2OH(n=0 내지 10)의 다가 알코올을 포함하는 산성 혹은 알칼리성의 과산화수소 세정액을 개시한다. US Patent No. 5705089 discloses an acidic or alkaline hydrogen peroxide cleaning liquid comprising a phosphonic acid chelating agent and a polyhydric alcohol of HOCH 2- (CHOH) n -CH 2 OH (n = 0 to 10).
미국 특허공보 제 4857225호는 0.005 내지 10g/L의 과산화산 또는 과산화물과, 황산, 인산, 질산 중 하나 이상을 포함하는 산성계의 알루미늄 표면 세정액을 개시한다. US Patent No. 4857225 discloses an acidic aluminum surface cleaning liquid comprising from 0.005 to 10 g / L peroxide or peroxide and at least one of sulfuric acid, phosphoric acid and nitric acid.
일본 공개특허공보 제 2002-176022호는 실리콘 기판 등의 기판에 부착된 오염 물질, 특히 구리 혹은 구리 합금 등의 미립자 또는 원자, 이온 등을 충분히 제거할 수 있는, 5 내지 20%의 황산, 20 내지 50%의 과산화수소수(30% 수용액), 0.5 내지 5%의 불산 혹은 질산을 포함한 세정액과 세정법을 개시한다.Japanese Laid-Open Patent Publication No. 2002-176022 discloses 5 to 20% sulfuric acid, 20 to 20, which can sufficiently remove contaminants attached to a substrate such as a silicon substrate, particularly fine particles or atoms, ions, etc., such as copper or a copper alloy. A cleaning solution containing 50% hydrogen peroxide solution (30% aqueous solution), 0.5 to 5% hydrofluoric acid or nitric acid and a cleaning method are disclosed.
일본 공개특허공보 제 2001-207281호는 디아릴알킬렌디아민 공중합체 0.1 내지 50000mg/L를 포함하는 산성계 세정액을 개시한다. Japanese Laid-Open Patent Publication No. 2001-207281 discloses an acidic cleaning liquid containing 0.1 to 50000 mg / L of a diarylalkylenediamine copolymer.
일본 공개특허공보 평9-279189호는 암모니아, 염산, 황산 또는 불산으로 이루어진 군에서 선택되어지는 물질 0.01 내지 85%와, 차아염소산, 아질산, 퍼옥소질산, 질산암모늄 또는 일산화이질소로 이루어진 군에서 선택되어지는 하나의 물질 0.01 내지 15%로 이루어진 반도체 기판용 세정액을 개시한다. Japanese Patent Application Laid-Open No. 9-279189 is selected from the group consisting of 0.01 to 85% of a substance selected from the group consisting of ammonia, hydrochloric acid, sulfuric acid, or hydrofluoric acid, and hypochlorous acid, nitrous acid, peroxonitrate, ammonium nitrate or dinitrogen monoxide. Disclosed is a cleaning liquid for a semiconductor substrate, which is composed of 0.01 to 15% of a single substance.
일본 공개특허공보 평7-115077호는 실리콘 표면 불순물 금속 및 부착 미립자를 제거하는, 0.005중량% 이상 0.05중량% 미만의 불산과 0.3중량% 이상 20.0중량% 이하의 과산화수소수를 포함하며, pH가 1이상 5미만인 산성 세정액을 개시한다. Japanese Patent Application Laid-Open No. 7-115077 includes at least 0.005% by weight and less than 0.05% by weight of hydrofluoric acid and at least 0.3% by weight and at least 20.0% by weight of hydrogen peroxide, which removes silicon surface impurity metal and adhered fine particles. The acidic washing liquid which is less than 5 is started.
그러나, 이러한 선행기술에서 제안된 세정액을 사용한 경우, 실리콘 및 실리콘 이외의 금속을 부식을 효과적으로 방지하지 못하는 문제가 있으며, 포토레지스 트 및 폴리머 잔류물에 대한 박리 능력이 충분하지 못하고, 포토레지스트를 이루는 고분자물질에 대한 용해력이 충분하지 못하여 박리된 포토레지스트 잔류물이 반도체기판 또는 유리기판 등에 재부착하거나, 부가적인 용제 부산물을 생성할 뿐만 아니라, 공정 조건이 고온이어서 환경적 측면과 처리 비용 면에서 유리하지 않는 문제점이 있다. 또한, 상기 종래의 박리액 조성물에서는, 금속 배선과 무기재료가 형성된 기판의 부식 방지와, 포토레지스트 및 변질된 포토레지스트에 대한 박리성 모두를 균형 있게 달성하지 못하였다. However, when the cleaning solution proposed in the prior art is used, there is a problem in that it does not effectively prevent the corrosion of silicon and metals other than silicon, and the peeling ability of the photoresist and the polymer residue is insufficient, and the photoresist is formed. Insufficient dissolvability to the polymer material causes the photoresist residue to be re-adhered to a semiconductor substrate or a glass substrate, or to generate additional solvent by-products. There is a problem that does not. In addition, in the above conventional peeling liquid composition, the corrosion prevention of the substrate on which the metal wiring and the inorganic material are formed and the peelability to the photoresist and the altered photoresist have not been achieved in a balanced manner.
따라서, 본 발명의 목적은 실리콘 및 실리콘 이외의 금속의 부식을 억제하며, 반도체소자 표면에 부착되어 있는 미세한 오염 입자, 습식 또는 건식 식각공정, 드라이 에싱 공정 후 발생하는 변질, 경화된 포토레지스트 및 폴리머 잔류물을 용이하게 제거할 수 있는 세정액 조성물을 제공하는 것이다. Accordingly, it is an object of the present invention to suppress the corrosion of silicon and metals other than silicon, and to remove fine contaminant particles, wet or dry etching processes, dry alteration processes, and cured photoresists and polymers adhered to the surface of semiconductor devices. It is to provide a cleaning liquid composition that can easily remove the residue.
본 발명의 또 다른 목적은 상기 세정액을 사용하여, 변질, 경화된 포토레지스트 및 폴리머 잔류물을 제거하는 방법을 제공하는 것이다. It is another object of the present invention to provide a method for removing altered, cured photoresist and polymer residues using the cleaning solution.
상기 목적을 달성하기 위해서, 본 발명은 황산, 과산화 화합물, 불소화합물, 인산암모늄염, 하기 구조식 1로 표시되는 금속 부식 방지 화합물, 하기 구조식 2로 표시되는 실리콘 부식 방지 화합물 및 탈이온수를 포함하는 전자 재료용 세정제 조 성물을 제공한다. In order to achieve the above object, the present invention is an electronic material comprising sulfuric acid, peroxide compound, fluorine compound, ammonium phosphate salt, metal corrosion protection compound represented by the following structural formula 1, silicon corrosion preventing compound represented by the following structural formula 2 and deionized water Provide a detergent composition.
[구조식 1] [Formula 1]
상기 구조식 1에서, A 및 B는 각각 독립적으로 수소 또는 NR1R2이며, 상기 식의 R1, R2 및 R3는 각각 독립적으로 수소, 알킬, 히드록시알킬, 아릴, -(CH2)m-COOH, -P(=O)(OH)2, 및 -(CH2)n-P(=O)(OH)2 (식 중, m과 n은 각각 독립적으로 1 내지 6의 정수이다)로 이루어진 군에서 선택될 수 있으며, R5 및 R6는 각각 독립적으로 직쇄 또는 분지된 탄소수 1 내지 6의 알킬렌, 모노옥시알킬렌, 또는 폴리옥시알킬렌이며, 이는 비치환이거나, 히드록실, 히드록시알킬, 아릴, -(CH2)p-COOH, -P(=O)(OH)2, 및 -(CH2)q-P(=O)(OH)2 로 이루어진 군에서 선택된 적어도 하나의 치환기로 치환될 수 있고, 이 경우에, p 및 q는 각각 독립적으로 0 내지 6의 정수이고, a'는 0내지 2의 정수이다. In Formula 1, A and B are each independently hydrogen or NR 1 R 2 , wherein R 1 , R 2 And R 3 are each independently hydrogen, alkyl, hydroxyalkyl, aryl,-(CH 2 ) m -COOH, -P (= 0) (OH) 2 , and-(CH 2 ) n -P (= 0) (OH) 2 (wherein m and n are each independently an integer from 1 to 6), and R 5 and R 6 are each independently straight or branched alkyl having 1 to 6 carbon atoms Ethylene, monooxyalkylene, or polyoxyalkylene, which is unsubstituted or hydroxyl, hydroxyalkyl, aryl,-(CH 2 ) p -COOH, -P (= 0) (OH) 2 , and- (CH 2 ) q -P (= O) (OH) 2 , and may be substituted with at least one substituent selected from the group consisting of p, q in this case, each independently, an integer of 0 to 6, a ' Is an integer between 0 and 2.
[구조식 2] [Formula 2]
상기 구조식 2에서, R1 내지 R5는 각각 독립적으로, 수소원자, 할로겐원자, 니트로기, 알킬기, 수산기, 히드록시알킬기, 아민기, 카르복실기, 술폰산기, 술폰아미드기, 알콕실기, 알데히드기, 아세톡실기, 포스폰산기, 머캅토기, 알릴기, 아릴기, 알데히드기, 아밀기 등의 관능기, 또는 이러한 관능기의 알킬화 유도체, 아세틸화 유도체, 할로겐화 유도체, 또는 이것들의 염을 나타낸다.In Formula 2, R1 to R5 are each independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a hydroxyl group, a hydroxyalkyl group, an amine group, a carboxyl group, a sulfonic acid group, a sulfonamide group, an alkoxyl group, an aldehyde group, an acetoxyl group And functional groups such as phosphonic acid group, mercapto group, allyl group, aryl group, aldehyde group and amyl group, or alkylated derivatives, acetylated derivatives, halogenated derivatives of these functional groups, or salts thereof.
상기 조성물은 황산 0.5 내지 20중량%, 과산화 화합물 1 내지 20중량%, 불소화합물 0.01 내지 0.1중량%, 인산암모늄염 0.01 내지 30중량%, 상기 구조식 1로 표시되는 금속 부식 방지 화합물 0.0005 내지 0.1중량%, 상기 구조식 2로 표시되는 실리콘 부식 방지 화합물 0.0001 내지 5중량% 및 전체 세정제 조성물이 100중량%가 되도록 하는 잔량의 탈이온수를 포함한다.The composition is 0.5 to 20% by weight sulfuric acid, 1 to 20% by weight peroxide compound, 0.01 to 0.1% by weight fluorine compound, 0.01 to 30% by weight ammonium phosphate salt, 0.0005 to 0.1% by weight of the metal corrosion protection compound represented by the formula (1), 0.0001 to 5% by weight of the silicon corrosion protection compound represented by the formula 2 and the remaining amount of deionized water to 100% by weight of the total detergent composition.
또한, 본 발명은 반도체 디바이스 및 액정표시장치를 포함하는 전자 재료 제조 시 상기한 세정제 조성물을 이용하여 세정을 실시하는 것을 특징으로 하는 세정 방법을 제공한다. In addition, the present invention provides a cleaning method characterized in that the cleaning is performed using the above-described cleaning composition in the manufacture of an electronic material including a semiconductor device and a liquid crystal display device.
이하에서 본 발명을 자세히 설명한다. Hereinafter, the present invention will be described in detail.
본 발명은 황산, 과산화 화합물, 불소화합물, 인산암모늄염, 금속 부식 방지 화합물, 실리콘 부식 방지 화합물 및 탈이온수를 포함하는 전자 재료용 세정액 조성물을 제공한다. The present invention provides a cleaning liquid composition for an electronic material containing sulfuric acid, a peroxide compound, a fluorine compound, an ammonium phosphate salt, a metal corrosion preventing compound, a silicon corrosion preventing compound, and deionized water.
본 발명의 황산, 과산화 화합물 및 불소화합물은 폴리머들을 효과적으로 제거하는 역할을 한다. Sulfuric acid, peroxide compounds and fluorine compounds of the present invention serve to effectively remove polymers.
상기 황산, 과산화 화합물 및 불소화합물을 포함하는 세정액 조성물의 pH가 0.1 미만이면 잔류하는 폴리머들의 세정능력은 우수하나 실리콘 및 실리콘 이외의 금속이 부식되는 문제점이 발생한다. 또한, 상기 세정액 조성물의 pH가 4를 초과하면, 잔류하는 폴리머들의 세정능력이 저하된다. 따라서, 상기 세정액 조성물의 pH는 0.1 내지 4인 것이 바람직하고, 보다 바람직하게는 약 0.5 내지 2의 pH를 갖는다. If the pH of the cleaning liquid composition including sulfuric acid, peroxide compound and fluorine compound is less than 0.1, the remaining polymers have excellent cleaning ability, but silicon and non-silicon metals are corroded. In addition, when the pH of the cleaning liquid composition exceeds 4, the cleaning ability of the remaining polymers is lowered. Therefore, the pH of the cleaning liquid composition is preferably 0.1 to 4, more preferably has a pH of about 0.5 to 2.
본 발명의 조성물에 있어서, 상기 황산은 산성 수용액의 산도 (pH)를 증가시켜 상기 세정액 조성물 중에 포함되어 있는 불소화합물이 세정액 조성물 내에서 빨리 해리될 수 있도록 하여 폴리머들이 보다 용이하게 제거될 수 있도록 하는 촉매 역할을 한다. In the composition of the present invention, the sulfuric acid increases the acidity (pH) of the acidic aqueous solution so that fluorine compounds contained in the cleaning liquid composition can be quickly dissociated in the cleaning liquid composition so that the polymers can be more easily removed. It acts as a catalyst.
본 발명의 조성물 중 황산의 함량은 조성물 총 중량에 대하여 0.5 내지 20중량%로 포함되는 것이 바람직하며, 더욱 바람직하게는 1 내지 10 중량%이다. 황산의 함량이 0.5중량% 미만이면, 폴리머 잔류물이 제거되지 않는 문제가 발생하며, 20중 량%를 초과하면, 실리콘 및 실리콘 이외의 금속이 부식되는 문제점이 발생한다. 상기 사용되는 황산은 그 농도에 따라서 상기 세정액 조성물에 포함되는 황산의 함량이 달라질 수 있으며, 바람직하게는 상기 세정액 조성물은 황산(100%로 환산한 것)을 0.5 내지 20중량%를 함유한다. The content of sulfuric acid in the composition of the present invention is preferably included in 0.5 to 20% by weight, more preferably 1 to 10% by weight relative to the total weight of the composition. If the content of sulfuric acid is less than 0.5% by weight, there is a problem that the polymer residue is not removed, if more than 20% by weight, the problem of corrosion of metals other than silicon and silicon. The sulfuric acid used may vary in the content of sulfuric acid included in the cleaning liquid composition according to its concentration, and preferably, the cleaning liquid composition contains 0.5 to 20% by weight of sulfuric acid (converted to 100%).
본 발명의 조성물 중 과산화 화합물의 함량은 조성물 총 중량에 대하여 1 내지 20중량%로 포함되는 것이 바람직하다. 과산화 화합물의 함량이 1중량% 미만이면, 폴리머 잔류물이 제거되지 않는 문제가 발생하며, 20중량%를 초과하면, 실리콘 및 실리콘 이외의 금속이 부식되는 문제점이 발생한다. 상기 사용되는 과산화 화합물은 그 농도에 따라서 상기 세정액 조성물에 포함되는 과산화 화합물의 함량이 달라질 수 있다.The content of the peroxide compound in the composition of the present invention is preferably included in 1 to 20% by weight based on the total weight of the composition. If the content of the peroxide compound is less than 1% by weight, there is a problem that the polymer residues are not removed, and if it exceeds 20% by weight, silicon and non-silicon metals are corroded. The peroxide compound used may vary in content of the peroxide compound included in the cleaning liquid composition according to its concentration.
상기 과산화 화합물의 구체적인 예로는 과산화수소수, 오존, 과산화황산, 과산화붕산, 과산화인산, 과산화아세트산, 과산화벤조산, 과산화프탈산 및 이들의 염으로 이루어진 군으로부터 1종 이상 선택된 화합물을 들 수 있다. Specific examples of the peroxide compound include at least one compound selected from the group consisting of hydrogen peroxide, ozone, sulfur peroxide, boric peroxide, phosphoric acid peroxide, acetic acid peroxide, benzoic peroxide, phthalic peroxide and salts thereof.
본 발명의 조성물 중 불소화합물의 함량은 조성물 총 중량에 대하여 0.01 내지 0.1중량%로 포함되는 것이 바람직하다. 불소화합물의 함량이 0.01중량% 미만이면, 폴리머 잔류물이 제거되지 않는 문제가 발생하며, 0.1중량%를 초과하면, 실리콘 및 실리콘 이외의 금속이 부식되는 문제점이 발생한다. The content of the fluorine compound in the composition of the present invention is preferably included in 0.01 to 0.1% by weight based on the total weight of the composition. If the content of the fluorine compound is less than 0.01% by weight, there is a problem that the polymer residue is not removed. If the content of the fluorine compound exceeds 0.1% by weight, silicon and non-silicon metals are corroded.
상기 불소화합물의 구체적인 예로는 불산(Fluoric acid), 불화 암모늄(Ammonium fluoride), 테트라메틸암모늄 플루오르화물(Tetramethylammonium fluoride), 불화수소 암모늄(Ammonium hydrogen fluoride), 불화붕소 산(Fluoboric acid) 및 테트라메틸암모늄 테트라플루오로붕산염(Tetramethylammonium tetrafluoroborate)으로 이루어진 군으로부터 1종 이상 선택된 화합물을 들 수 있다. Specific examples of the fluorine compound include fluoric acid, ammonium fluoride, tetramethylammonium fluoride, ammonium hydrogen fluoride, fluoroboric acid, and tetramethylammonium tetra And at least one compound selected from the group consisting of fluoroborate (Tetramethylammonium tetrafluoroborate).
본 발명의 조성물에 있어서, 상기 인산암모늄염은 인산 이온 또는 폴리(poly) 인산 이온과 암모늄 이온염 화합물을 의미하고, 상기 염 화합물에서 인산 성분은 알루미늄 혹은 알루미늄 합금에 대한 부식 방지에 우수한 효과가 있다. 또한 암모늄 성분은 기판 위의 유기오염물이나 파티클 제거에 우수한 효과가 있다. In the composition of the present invention, the ammonium phosphate salt means a phosphate ion or a poly (phosphate) ion and an ammonium ion salt compound, and the phosphoric acid component in the salt compound has an excellent effect on corrosion protection against aluminum or an aluminum alloy. In addition, the ammonium component is excellent in removing organic contaminants and particles on the substrate.
본 발명의 조성물 중 인산암모늄염의 함량은 조성물 총 중량에 대하여 바람직하게는 0.01 내지 30중량%, 더욱 바람직하게는 0.1 내지 20중량%이다. 인산암모늄염의 함량이 0.01중량% 미만이면, 세정액 조성물의 금속에 대한 부식 방지력이 저하되고, 30중량%를 초과하면, 부식 방지효과는 더 이상 비례하여 증가하지 않고 인산염이 기판 표면에 잔존할 수 있다. The content of ammonium phosphate salt in the composition of the present invention is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight based on the total weight of the composition. If the content of ammonium phosphate salt is less than 0.01% by weight, the corrosion protection of the cleaning liquid composition against the metal is lowered, and if it exceeds 30% by weight, the corrosion protection effect no longer increases proportionally and phosphate may remain on the substrate surface. have.
상기 인산암모늄염의 구체적인 예로는 인산 일수소 암모늄, 인산 이수소 암모늄, 인산 삼암모늄, 차인산 암모늄, 오르쏘인산 암모늄, 오르쏘인산 이수소 암모늄, 오르쏘인산 일수소 암모늄, 차아인산 암모늄, 오르쏘아인산 이수소 암모늄 및 Wn +2PnO3n +1(W=NH4, n=2이상의 정수)로 표시되는 폴리인산암모늄염 및 이들의 혼합물로 이루어진 군으로부터 1종 이상 선택되는 화합물을 사용하는 것이 바람직하다. 특히 이들 가운데 인산 이수소 암모늄을 포함하는 것이 보다 바람직하다. Specific examples of the ammonium phosphate salt include ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium orthophosphate, ammonium orthophosphate, ammonium monophosphate, ammonium hypophosphite, ortho Using at least one compound selected from the group consisting of ammonium dihydrogen phosphate and poly ammonium phosphate represented by W n +2 P n O 3n +1 (W = NH 4 , n = 2 integer) and mixtures thereof It is preferable. Among these, it is more preferable to include ammonium dihydrogen phosphate.
본 발명의 조성물에 있어서, 금속 부식 방지 화합물은 세정액 조성물 내에 존재하다가 전자 재료의 금속과 흡착반응 (킬레이트 반응)하여 상기 금속의 부식을 억제하는 부식 방지막을 형성하고, 상기 부식 방지막은 상기 세정액 조성물에 포함된 산성 수용액이 금속 반응하는 속도를 늦추는 역할을 하여 세정 공정 동안에 금속의 부식을 최소화하는 역할을 한다. 상기 본 발명의 세정액 조성물에 포함된 금속 부식 방지 화합물은 바람직하게는 하기 구조식 1로 나타낸다. In the composition of the present invention, the metal corrosion protection compound is present in the cleaning liquid composition and then adsorbed with the metal of the electronic material (chelating reaction) to form a corrosion prevention film that suppresses corrosion of the metal, and the corrosion protection film is applied to the cleaning liquid composition. The acidic aqueous solution contained serves to slow down the rate at which the metal reacts, thereby minimizing the corrosion of the metal during the cleaning process. The metal corrosion prevention compound contained in the cleaning liquid composition of the present invention is preferably represented by the following structural formula (1).
[구조식 1] [Formula 1]
상기 구조식 1에서, A 및 B는 각각 독립적으로 수소 또는 NR1R2이며, 상기 식의 R1, R2 및 R3는 각각 독립적으로 수소, 알킬, 히드록시알킬, 아릴, -(CH2)m-COOH, -P(=O)(OH)2, 및 -(CH2)n-P(=O)(OH)2 (식 중, m과 n은 각각 독립적으로 1 내지 6의 정수이다)로 이루어진 군에서 선택될 수 있으며, R5 및 R6는 각각 독립적으로 직쇄 또는 분지된 탄소수 1 내지 6의 알킬렌, 모노옥시알킬렌, 또는 폴리옥시알킬렌이며, 이는 비치환이거나, 히드록실, 히드록시알킬, 아릴, -(CH2)p-COOH, -P(=O)(OH)2, 및 -(CH2)q-P(=O)(OH)2 로 이루어진 군에서 선택된 적어도 하나의 치환기로 치환될 수 있고, 이 경우에, p 및 q는 각각 독립적으로 0 내지 6의 정수이고, a'는 0내지 2의 정수이다. In Formula 1, A and B are each independently hydrogen or NR 1 R 2 , wherein R 1 , R 2 and R 3 are each independently hydrogen, alkyl, hydroxyalkyl, aryl,-(CH 2 ) m- COOH, -P (= O) (OH) 2 , and-(CH 2 ) n -P (= O) (OH) 2 , wherein m and n are each independently an integer from 1 to 6 It may be selected from the group consisting of, R 5 and R 6 are each independently straight or branched alkylene, monooxyalkylene, or polyoxyalkylene having 1 to 6 carbon atoms, which is unsubstituted, hydroxyl, At least one selected from the group consisting of hydroxyalkyl, aryl,-(CH 2 ) p -COOH, -P (= 0) (OH) 2 , and-(CH 2 ) q -P (= 0) (OH) 2 It may be substituted with the substituent of, In this case, p and q are each independently an integer of 0 to 6, a 'is an integer of 0 to 2.
본 발명의 조성물 중 금속 부식 방지 화합물의 함량은 조성물 총 중량에 대하여 바람직하게는 0.0005 내지 0.1중량%이다. 금속 부식 방지 화합물의 함량이 0.0005중량% 미만이면, 실리콘 및 실리콘 이외의 금속이 부식되는 문제점이 발생하며, 0.1중량%를 초과하면, 잔류하는 폴리머들의 세정능력이 저하된다. The content of the metal corrosion preventing compound in the composition of the present invention is preferably 0.0005 to 0.1% by weight based on the total weight of the composition. If the content of the metal corrosion preventing compound is less than 0.0005% by weight, the problem of corrosion of metals other than silicon and silicon occurs, and if it exceeds 0.1% by weight, the cleaning ability of the remaining polymers is lowered.
본 발명의 실리콘 이외의 금속은 바람직하게는 알루미늄 또는 텅스텐을 포함한다.Metals other than silicon of the invention preferably comprise aluminum or tungsten.
상기 구조식 1로 표기되는 화합물의 구체적인 예로는 펜타메틸디에틸렌트리아민(PMDETA), 테트라메틸에틸렌디아민(TMEDA), 에틸렌디아민테트라아세트산(EDTA), 디에틸렌트리아민펜타아세트산(DTPA), 히드록시에틸에틸렌디아민아세트산(HEDTA), 글리콜에테르디아민테트라아세트산(GEDTA), 트리에틸렌테트라아민헥사아세트산(TTHA), 1,3-프로판디아민테트라아세트산(PDTA), 1,3-디아미노-2-히드록시프로판테트라아세트산(DPTA-OH), 아미노트리메틸렌포스폰산(ATMPA), 에틸렌디아민테트라메틸렌포스폰산(EDTMPA), 디에틸렌트리아민펜타메틸렌포스폰산(DTPMPA), 헥사메틸렌디아민테트라메틸렌포스폰산(HDTMPA), 니트릴로트리메틸렌포스폰산(NTMP) 및 그 염으로 이루어진 군으로부터 1종 이상 선택되는 화합물을 사용하는 것이 바 람직하다. Specific examples of the compound represented by Structural Formula 1 include pentamethyldiethylenetriamine (PMDETA), tetramethylethylenediamine (TMEDA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyl Ethylenediamineacetic acid (HEDTA), glycol etherdiaminetetraacetic acid (GEDTA), triethylenetetraaminehexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropane Tetraacetic acid (DPTA-OH), aminotrimethylenephosphonic acid (ATMPA), ethylenediaminetetramethylenephosphonic acid (EDTMPA), diethylenetriaminepentamethylenephosphonic acid (DTPMPA), hexamethylenediaminetetramethylenephosphonic acid (HDTMPA), It is preferred to use a compound selected from the group consisting of nitrilotrimethylenephosphonic acid (NTMP) and salts thereof.
상기 구조식 1로 표기되는 화합물은 구입하여 사용할 수 있다. 구입할 수 있는 구체적인 제품의 상품명으로는, Chelest PH-210, Chelest PH-212, Chelest PH-214, Chelest PH-320, Chelest PH-325(이상 CHELEST CORPORATION, Japan), DequestTM 2040, DequestTM 2041, DequestTM 2046, DequestTM 2050, DequestTM 2054, DequestTM 2060, DequestTM 2060S, DequestTM 2066, DequestTM 2066A (이상 Solutia, Inc., USA) 등을 들 수 있다. The compound represented by Structural Formula 1 can be purchased and used. Specific names of specific products that can be purchased include Chelest PH-210, Chelest PH-212, Chelest PH-214, Chelest PH-320, Chelest PH-325 (above CHELEST CORPORATION, Japan), Dequest TM 2040, Dequest TM 2041, Dequest ™ 2046, Dequest ™ 2050, Dequest ™ 2054, Dequest ™ 2060, Dequest ™ 2060S, Dequest ™ 2066, Dequest ™ 2066A (above Solutia, Inc., USA) and the like.
본 발명의 조성물에 있어서, 실리콘 부식 방지 화합물은 세정액 조성물에 함유되어 세정 공정 동안 실리콘의 부식을 최소화하는 역할을 한다. 상기 본 발명의 세정액 조성물에 포함된 실리콘 부식 방지 화합물은, 분자 중에 적어도 하나 이상의 니트로기를 포함하는 화합물이며, 바람직하게는 하기 구조식 2로 나타낸다. In the composition of the present invention, the silicon corrosion preventing compound is contained in the cleaning liquid composition and serves to minimize the corrosion of the silicon during the cleaning process. The silicon corrosion protection compound contained in the cleaning liquid composition of the present invention is a compound containing at least one nitro group in a molecule, preferably represented by the following structural formula (2).
[구조식 2] [Formula 2]
상기 구조식 2에서, R1 내지 R5는 각각 독립적으로, 수소원자, 할로겐원자, 또는 니트로기, 알킬기, 수산기, 히드록시알킬기, 아민기, 카르복실기, 술폰산기, 술폰아미드기, 알콕실기, 알데히드기, 아세톡실기, 포스폰산기, 머캅토기, 알릴기, 아릴기, 알데히드기, 아밀기 등의 관능기, 또는 이러한 관능기의 알킬화 유도체, 아세틸화 유도체, 할로겐화 유도체, 또는 이것들의 염을 나타낸다.In Formula 2, R1 to R5 are each independently a hydrogen atom, a halogen atom, or a nitro group, an alkyl group, a hydroxyl group, a hydroxyalkyl group, an amine group, a carboxyl group, a sulfonic acid group, a sulfonamide group, an alkoxyl group, an aldehyde group, an acetok Functional groups, such as a real group, a phosphonic acid group, a mercapto group, an allyl group, an aryl group, an aldehyde group, an amyl group, or an alkylated derivative, an acetylated derivative, a halogenated derivative of these functional groups, or salts thereof are shown.
본 발명의 조성물 중 실리콘 부식 방지 화합물의 함량은 조성물 총 중량에 대하여 바람직하게는 0.0001 내지 5중량%, 더욱 바람직하게는 0.001 내지 1중량%이다. 실리콘 부식 방지 화합물의 함량이 0.0001중량% 미만이면, 실리콘 및 실리콘 이외의 금속이 부식되는 문제점이 발생하며, 5중량%를 초과하면, 세정액 중 실리콘 부식 방지 화합물의 용해도가 낮아지는 결과를 초래한다. The content of the silicone corrosion preventing compound in the composition of the present invention is preferably 0.0001 to 5% by weight, more preferably 0.001 to 1% by weight based on the total weight of the composition. If the content of the silicon anticorrosion compound is less than 0.0001% by weight, the problem of corrosion of metals other than silicon and silicon occurs, and if it exceeds 5% by weight, the solubility of the silicon anticorrosion compound in the cleaning solution is lowered.
상기 구조식 2로 표기되는 구체적인 화합물로서는, 니트로벤젠, 디니트로벤젠, 트리니트로벤젠, 니트로클로로벤젠, 디니트로클로로벤젠, 트리니트로클로로벤젠, 니트로톨루엔, 디니트로톨루엔, 트리니트로톨루엔, 니트로클로로톨루엔, 디니트로클로로톨루엔, 트리니트로클로로톨루엔, 니트로자일렌, 이소프로필니트로벤젠, 니트로페놀, 디니트로페놀, 트리니트로페놀, 니트로카테콜, 디니트로카테콜, 니트로레졸시놀, 니트로클로로페놀, 디니트로클로로페놀, 트리니트로클로로페놀, 니트로살리실산, 니트로벤질알코올, 디니트로벤질알콜, 트리니트로벤질알콜, 니트로아닐린, 디니트로아닐린, 트리니트로아닐린, 니트로클로로아닐린, 디니트로클로로아닐린, 트리니트로클로로아닐린, 니트로프로폭시아닐린, 니트로아세트아닐리드, 니트로페니렌디아민, 니트로안식향산, 디니트로안식향산, 트리니트로안식향산, 니트로안식향산메틸, 니트로안식향산에틸, 아미노니트로안식향산, 니트로프탈산, 니트 로벤젠술폰산, 디니트로벤젠술폰산, 트리니트로벤젠술폰산, 니트로벤젠술폰아미드, 디니트로벤젠술폰아미드, 트리니트로벤젠술폰아미드, 니트로아니솔, 디니트로아니솔, 트리니트로아니솔, 아미노니트로아니솔, 디메톡시니트로벤젠, 니트로벤조알데히드, 디니트로벤조알데히드, 트리니트로벤조알데히드, 초산니트로페닐, 니트로톨루이디엔 및 니트로벤조일클로라이드로 이루어진 군으로부터 1종 이상 선택되는 화합물을 사용하는 것이 바람직하다. 한편, 이러한 화합물에 있어서, 니트로기에 대한 관능기 등의 위치 관계는 오르쏘(O-), 메타(m-), 파라(p-)의 어느 위치에 존재하고 있어도 좋다. Specific examples of the compound represented by Structural Formula 2 include nitrobenzene, dinitrobenzene, trinitrobenzene, nitrochlorobenzene, dinitrochlorobenzene, trinitrochlorobenzene, nitrotoluene, dinitrotoluene, trinitrotoluene, nitrochlorotoluene, and dinitrochloro Toluene, trinitrochlorotoluene, nitroxylene, isopropylnitrobenzene, nitrophenol, dinitrophenol, trinitrophenol, nitrocatechol, dinitrocatechol, nitroresorcinol, nitrochlorophenol, dinitrochlorophenol, trinitrochloro Phenol, nitrosalicylic acid, nitrobenzyl alcohol, dinitrobenzyl alcohol, trinitrobenzyl alcohol, nitroaniline, dinitroaniline, trinitroaniline, nitrochloroaniline, dinitrochloroaniline, trinitrochloroaniline, nitropropoxyaniline, nitroacenitrile, Nitrophenyrendi Min, nitro benzoic acid, dinitro benzoic acid, trinitro benzoic acid, methyl nitro benzoic acid, ethyl nitro benzoic acid, amino nitro benzoic acid, nitrophthalic acid, nitrobenzene sulfonic acid, dinitrobenzene sulfonic acid, trinitrobenzene sulfonic acid, nitrobenzene sulfonamide, dinitrobenzene sulfone Amide, trinitrobenzenesulfonamide, nitroanisole, dinitroanisole, trinitroanisole, aminonitroanisole, dimethoxynitrobenzene, nitrobenzoaldehyde, dinitrobenzoaldehyde, trinitrobenzoaldehyde, nitrophenyl acetate, nitrotoluyi Preference is given to using at least one compound selected from the group consisting of dienes and nitrobenzoyl chlorides. In addition, in such a compound, the positional relationship, such as a functional group, with respect to a nitro group may exist in any position of ortho (O-), meta (m-), and para (p-).
상기 니트로기 함유 화합물 중 보다 바람직한 구체 예로서는, 니트로벤젠, 니트로아닐린, 니트로톨루엔, 니트로아니솔, 니트로벤질알콜 및 니트로아세트아닐리드 등을 들 수 있다. As a more preferable specific example among the said nitro group containing compounds, nitrobenzene, nitroaniline, nitrotoluene, nitroanisole, nitrobenzyl alcohol, nitroacetanilide, etc. are mentioned.
본 발명의 세정액 조성물에서 사용할 수 있는 실리콘 부식 방지 화합물은, 세정액에 함유시킴으로써, 실리콘에 대한 부식성이 없는 세정액을 제공할 수 있다. By containing in the washing | cleaning liquid the silicone corrosion prevention compound which can be used by the washing | cleaning liquid composition of this invention can provide the washing | cleaning liquid which is not corrosive to silicone.
본 발명의 세정액 조성물에 함유되는 상기 실리콘 부식 방지 화합물은, 단일화합물이라도 좋고, 복수의 화합물을 함유시켜도 좋다. The said silicon corrosion prevention compound contained in the washing | cleaning liquid composition of this invention may be a single compound, and may contain a some compound.
또한, 본 발명의 전자 재료용 세정액 조성물은 본 발명의 효과에 악영향을 미치지 않는 한, 당 업계에서 통상적으로 사용되는 첨가제를 함유할 수 있다. Moreover, the cleaning liquid composition for electronic materials of this invention may contain the additive normally used in the art, as long as it does not adversely affect the effect of this invention.
본 발명의 전자 재료용 세정액 조성물을 수득하기 위하여, 상술한 화합물은 소정의 양으로 유리하게 혼합될 수 있으며, 혼합 방법은 특별히 제한되는 것이 아니며, 여러 가지 공지 방법을 적용할 수 있다. In order to obtain the cleaning liquid composition for an electronic material of the present invention, the above-mentioned compounds can be advantageously mixed in a predetermined amount, and the mixing method is not particularly limited, and various known methods can be applied.
본 발명에 따른 전자 재료용 세정액 조성물을 사용할 경우에는, 후속의 린스공정에서 이소프로필 알코올, 디메틸 설폭사이드와 같은 유기용제를 사용할 필요 없이, 물만으로 린스가 가능하다. In the case of using the cleaning liquid composition for an electronic material according to the present invention, it is possible to rinse only with water without using organic solvents such as isopropyl alcohol and dimethyl sulfoxide in the subsequent rinsing step.
또한, 본 발명의 전자 재료용 세정액 조성물은 단결정 실리콘, 비결정(amorphous) 실리콘, 다결정 실리콘 등의 실리콘 및 산화실리콘 절연막, 또한 실리콘 이외의 금속, 예를 들어 알루미늄, 텅스텐 등에 대한 부식성을 억제한 세정액이므로, 액정디스플레이, 실리콘기판을 사용한 집적회로 디바이스 등의 전자부품의 세정공정에 적용이 가능하다. In addition, the cleaning liquid composition for an electronic material of the present invention is a cleaning liquid that suppresses the corrosiveness to silicon and silicon oxide insulating films, such as monocrystalline silicon, amorphous silicon, polycrystalline silicon, and metals other than silicon such as aluminum, tungsten, and the like. It is applicable to the cleaning process of electronic components, such as a liquid crystal display and an integrated circuit device using a silicon substrate.
본 발명의 전자 재료용 세정액 조성물은 실리콘 및 실리콘 이외의 금속, 예를 들어 알루미늄, 텅스텐, 티타늄 등과 같은 물질에 대하여 매우 낮은 부식성을 가지며, 특히 알루미늄, 텅스텐을 포함하는 금속 막질에 우수한 방식성을 가진다. 또한, 반도체소자 표면에 부착되어 있는 미세한 오염 입자, 습식 또는 건식 식각공정, 드라이 에싱 공정 후 발생하는 변질, 경화된 포토레지스트 및 폴리머 잔류물에 대하여 침적, 분무법, 매엽 방식에 의하여 저온에서, 단시간 내에 용이하게 세정하여 제거할 수 있으며, 반도체소자 및 액정표시소자를 구성하고 있는 금속막, 산화막과 같은 무기재료 물질에 대하여 부식성이 매우 낮으며, 결과적으로 반도체소자 및 액정표시소자의 제조 공정 중 세정 공정에서 사용될 수 있다. The cleaning liquid composition for an electronic material of the present invention has very low corrosiveness to silicon and metals other than silicon, such as aluminum, tungsten, titanium, and the like, and particularly has excellent anticorrosive property to metal films including aluminum and tungsten. . In addition, in a short time at low temperature by depositing, spraying, or sheeting method on fine contaminant particles, wet or dry etching process, dry de-essing process, and dried photoresist and polymer residue adhering to the surface of semiconductor device. It can be easily cleaned and removed, and it has very low corrosiveness to inorganic material materials such as metal films and oxide films constituting semiconductor devices and liquid crystal display devices, and as a result, cleaning process during the manufacturing process of semiconductor devices and liquid crystal display devices. Can be used in
또한, 본 발명은 본 발명의 세정제 조성물을 이용하여 반도체 디바이스 및 액정표시장치를 포함하는 전자 재료 제조 시 세정을 실시하는 것을 특징으로 하는 세정 방법을 제공한다. In addition, the present invention provides a cleaning method using the cleaning composition of the present invention for cleaning the electronic material including the semiconductor device and the liquid crystal display device.
본 발명의 세정 방법은 바람직하게는 실리콘 및 실리콘 이외의 금속, 바람직하게는 알루미늄, 텅스텐 금속의 부식을 억제하며, 반도체소자 표면에 부착되어 있는 미세한 오염 입자, 습식 또는 건식 식각공정, 드라이 에싱 공정 후 발생하는 변질, 경화된 포토레지스트 및 폴리머 잔류물을 제거하는데 사용할 수 있다. The cleaning method of the present invention preferably suppresses corrosion of metals other than silicon and silicon, preferably aluminum and tungsten metals, and after fine contaminating particles, wet or dry etching processes, and dry ashing processes adhered to the surface of the semiconductor device. It can be used to remove the resulting deterioration, cured photoresist and polymer residues.
세정 방법은 당 업계에 통상적으로 알려진 세정 방법에 의하여 수행할 수 있으며, 세정액 조성물과, 포토레지스트 및 폴리머 잔류물이 형성되어 있는 기판이 접촉할 수 있는 방법이면, 양호한 결과를 얻을 수 있다. 본 발명에 따른 세정 방법으로는, 침적, 분무법, 매엽 방식 및 에어 나이프 방식을 이용한 방법 등이 적용된다. 침적, 분무법, 매엽 방식 및 에어 나이프 방식에 의하여 세정하는 경우, 세정 조건으로서 온도는 대개 10 내지 100℃, 바람직하게는 20 내지 50℃이고, 침적 및 분무시간은 대개 10초 내지 30분, 바람직하게는 30초 내지 10분이지만, 본 발명에 있어서 엄밀하지 않으며, 당업자에 의해 용이하게 적합화 될 수 있다. The cleaning method can be carried out by cleaning methods commonly known in the art, and good results can be obtained as long as the cleaning liquid composition and the substrate on which the photoresist and the polymer residue are formed can contact each other. As a washing | cleaning method which concerns on this invention, the method using the immersion, the spraying method, the sheet | leaf method, the air knife system, etc. are applied. In the case of cleaning by dip, spray, sheetfed and air knife methods, the temperature is usually 10 to 100 ° C., preferably 20 to 50 ° C., and the deposition and spraying time is usually 10 seconds to 30 minutes, preferably Is 30 seconds to 10 minutes, but is not exact in the present invention and can be easily adapted by those skilled in the art.
이하, 본 발명을 실시예를 통해 더욱 상세히 설명하고자 한다. 그러나 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.
세정액 조성물의 제조Preparation of Cleaning Liquid Composition
실시예Example 1 One
세정액 조성물 100중량%에 대하여 황산 1중량%, 과산화수소수 5중량%, 불산(HF) 0.05중량%, 인산이수소암모늄 10중량%, 디에틸렌트리아민펜타메틸렌포스폰산 0.05중량%, 니트로벤젠 0.05중량% 및 잔량의 탈이온수를 혼합하여 세정액 조성물을 제조하였다. 이때, 상기 황산, 과산화수소수 및 불산은 100% 순수한 물질로 환산하여 첨가하였다.1% by weight sulfuric acid, 5% by weight hydrogen peroxide, 0.05% by weight hydrofluoric acid (HF), 10% by weight ammonium dihydrogen phosphate, 0.05% by weight diethylenetriaminepentamethylenephosphonic acid, 0.05% by weight nitrobenzene % And the remaining amount of deionized water were mixed to prepare a cleaning liquid composition. At this time, the sulfuric acid, hydrogen peroxide and hydrofluoric acid were added in terms of 100% pure material.
실시예Example 2~19 2 ~ 19
상기 실시예 1과 동일한 방법으로 세정액 조성물을 제조하되, 그 조성비를 하기 표 1에 도시된 바와 같은 조성 (단위: 중량%)으로 변경하여 제조하였다. To prepare a cleaning solution composition in the same manner as in Example 1, was prepared by changing the composition ratio of the composition (unit: weight%) as shown in Table 1 below.
비교예Comparative example 1~3 1 to 3
상기 실시예 1과 동일한 방법으로 세정액 조성물을 제조하되, 그 조성비를 하기 표 1에 도시된 바와 같은 조성 (단위: 중량%)으로 변경하여 제조하였다. 구체적으로, 비교예 1의 경우 인산암모늄염, 금속부식 방지 화합물 및 실리콘 부식 방지 화합물을 모두 첨가하지 않았고, 비교예 2 및 3의 경우 인산암모늄염은 모두 첨가하지 않았으며, 금속부식 방지 화합물 또는 실리콘 부식 방지 화합물을 선택적으로 첨가하지 않았다. To prepare a cleaning solution composition in the same manner as in Example 1, was prepared by changing the composition ratio of the composition (unit: weight%) as shown in Table 1 below. Specifically, in the case of Comparative Example 1, all of the ammonium phosphate salt, the metal corrosion preventing compound and the silicon corrosion preventing compound were not added, and in Comparative Examples 2 and 3, all the ammonium phosphate salt was not added, and the metal corrosion preventing compound or the silicon corrosion preventing No compound was added selectively.
실험예Experimental Example . 방식효과 및 . Anticorrosion effect and 폴리머Polymer 제거력Removal 평가 evaluation
텅스텐(W) 또는 알루미늄 (Al) 금속막이 형성된 기판, 보로포스포실리케이트 글라스 (borophosphatesilicate glass, BPSG) 또는 다결정실리콘 (poly-Si) 하부층이 각각 형성된 기판을 상온의 상기 실시예 1 내지 19 및 비교예 1 내지 3의 세정액 조성물에 5분간 침지하고 탈이온수로 린스 한 후, 주사전자현미경(SEM, HITACHI, S-4700)으로 관찰하고, 금속층 및 하부층에 대한 부식 방지 능력과 폴리머 제거능을 평가하여, 표 2에 나타내었다. SEM 관찰결과의 평가 기준은 하기와 같다. A substrate on which a tungsten (W) or aluminum (Al) metal film was formed, a borophosphatesilicate glass (BPSG) or a polycrystalline silicon (poly-Si) lower layer, respectively, was formed. After immersing for 5 minutes in the cleaning solution composition of 1 to 3 and rinsed with deionized water, observed with a scanning electron microscope (SEM, HITACHI, S-4700), and evaluated the anti-corrosion ability and the polymer removal ability to the metal layer and the lower layer, 2 is shown. Evaluation criteria of SEM observation results are as follows.
○ : 우수 ○: excellent
X : 불량 X: bad
표 2에 나타난 바와 같이, 실시예 1 내지 19의 세정액 조성물은 금속막 및 하부층의 부식이 없고, 폴리머 제거 효율이 양호한 세정 결과를 나타내었다. As shown in Table 2, the cleaning liquid compositions of Examples 1 to 19 were free from corrosion of the metal film and the lower layer, and showed good cleaning results with good polymer removal efficiency.
그러나, 비교예 1의 세정액 조성물을 이용하여 기판의 세정 공정을 수행한 경우, 금속막 및 하부층 모두 부식이 발생하였다. 비교예 2의 세정액 조성물을 이용하여 기판의 세정 공정을 수행한 경우, 텅스텐 막을 제외한 알루미늄, BPSG 및 다결정실리콘막에 부식이 발생하였다. 또한, 비교예 3의 세정액 조성물을 이용하여 기판의 세정 공정을 수행한 경우, BPSG막 및 다결정실리콘막을 제외한 알루미늄, 텅스텐 막에 부식이 발생하였다.However, when the cleaning process of the substrate was performed using the cleaning liquid composition of Comparative Example 1, corrosion occurred in both the metal film and the lower layer. When the substrate cleaning process was performed using the cleaning liquid composition of Comparative Example 2, corrosion occurred in the aluminum, BPSG, and polycrystalline silicon films except for the tungsten film. In addition, when the substrate cleaning process was performed using the cleaning liquid composition of Comparative Example 3, corrosion occurred in the aluminum and tungsten films except for the BPSG film and the polycrystalline silicon film.
이상에서 설명한 바와 같이, 본 발명의 전자 재료용 세정액 조성물은 실리콘 및 실리콘 이외의 금속의 부식을 억제하며, 반도체소자 표면에 부착되어 있는 미세한 오염 입자, 습식 또는 건식 식각공정, 드라이 에싱 공정 후 발생하는 변질, 경화된 포토레지스트 및 폴리머 잔류물의 제거성능이 우수하고, 반도체소자 및 액정표시소자를 구성하고 있는 금속막, 산화막과 같은 무기재료 물질에 대하여 부식성이 매우 낮으며, 결과적으로 반도체소자 및 액정표시소자의 제조 공정 중 세정 공정에서 사용될 수 있다. As described above, the cleaning liquid composition for an electronic material of the present invention suppresses corrosion of silicon and metals other than silicon, and is generated after fine contaminating particles, wet or dry etching, and dry ashing processes adhered to the surface of a semiconductor device. Excellent removal performance of deteriorated, cured photoresist and polymer residue, very low corrosiveness to inorganic materials such as metal film and oxide film constituting semiconductor device and liquid crystal display device, and consequently, semiconductor device and liquid crystal display It can be used in the cleaning process of the device manufacturing process.
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| KR20160062410A (en) | 2014-11-25 | 2016-06-02 | 이호규 | Battery cleaner composition |
| JP2019057524A (en) * | 2017-09-19 | 2019-04-11 | 株式会社フジミインコーポレーテッド | Surface treatment composition, method for producing surface treatment composition, method for surface treatment, and method for producing semiconductor substrate |
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| KR20160062410A (en) | 2014-11-25 | 2016-06-02 | 이호규 | Battery cleaner composition |
| JP2019057524A (en) * | 2017-09-19 | 2019-04-11 | 株式会社フジミインコーポレーテッド | Surface treatment composition, method for producing surface treatment composition, method for surface treatment, and method for producing semiconductor substrate |
| TWI775910B (en) * | 2017-09-19 | 2022-09-01 | 日商福吉米股份有限公司 | Surface treatment composition, method for producing surface treatment composition, method for surface treatment, and method for producing semiconductor substrate |
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