KR102358801B1 - Surface treatment composition and surface treatment method using the same - Google Patents
Surface treatment composition and surface treatment method using the same Download PDFInfo
- Publication number
- KR102358801B1 KR102358801B1 KR1020190176991A KR20190176991A KR102358801B1 KR 102358801 B1 KR102358801 B1 KR 102358801B1 KR 1020190176991 A KR1020190176991 A KR 1020190176991A KR 20190176991 A KR20190176991 A KR 20190176991A KR 102358801 B1 KR102358801 B1 KR 102358801B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- acrylate
- surface treatment
- group
- treatment composition
- Prior art date
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000004094 surface-active agent Substances 0.000 claims abstract description 30
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims description 60
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 229920001577 copolymer Polymers 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 38
- 230000007547 defect Effects 0.000 claims description 35
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 239000004065 semiconductor Substances 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 22
- 238000005498 polishing Methods 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 20
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 16
- 229920003169 water-soluble polymer Polymers 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 239000000356 contaminant Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 10
- 229920005591 polysilicon Polymers 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001530 fumaric acid Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 claims description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 125000001174 sulfone group Chemical group 0.000 claims description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- BDMYQVMQTKUZNB-UHFFFAOYSA-N 4-methylpentyl prop-2-enoate Chemical compound CC(C)CCCOC(=O)C=C BDMYQVMQTKUZNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 claims description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 claims description 3
- HSFXEOPJXMFQHG-ARJAWSKDSA-N (z)-4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobut-2-enoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)\C=C/C(O)=O HSFXEOPJXMFQHG-ARJAWSKDSA-N 0.000 claims description 3
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 claims description 3
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004135 Bone phosphate Substances 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- ODBLHEXUDAPZAU-ZAFYKAAXSA-N D-threo-isocitric acid Chemical compound OC(=O)[C@H](O)[C@@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-ZAFYKAAXSA-N 0.000 claims description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- ODBLHEXUDAPZAU-FONMRSAGSA-N Isocitric acid Natural products OC(=O)[C@@H](O)[C@H](C(O)=O)CC(O)=O ODBLHEXUDAPZAU-FONMRSAGSA-N 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 3
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229940091181 aconitic acid Drugs 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 3
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims description 3
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 3
- 229940018557 citraconic acid Drugs 0.000 claims description 3
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
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- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
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- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 3
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
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- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- GJBRTCPWCKRSTQ-UHFFFAOYSA-N decanedioic acid Chemical compound OC(=O)CCCCCCCCC(O)=O.OC(=O)CCCCCCCCC(O)=O GJBRTCPWCKRSTQ-UHFFFAOYSA-N 0.000 claims description 2
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- 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
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- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02334—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment in-situ cleaning after layer formation, e.g. removing process residues
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Abstract
본 발명은, 표면처리 조성물 및 이를 이용한 표면처리 방법에 관한 것으로, 보다 구체적으로, 제미니형 계면활성제 및 pH 조절제를 포함하는 표면처리 조성물 및 이를 이용한 표면처리 방법에 관한 것이다. The present invention relates to a surface treatment composition and a surface treatment method using the same, and more particularly, to a surface treatment composition comprising a gemini-type surfactant and a pH adjuster, and a surface treatment method using the same.
Description
본 발명은, 표면 처리 조성물 및 이를 이용한 표면 처리 방법에 관한 것이다. The present invention relates to a surface treatment composition and a surface treatment method using the same.
마이크로전자 장치 웨이퍼는 집적 회로를 형성시키는데 사용된다. 마이크로전자 장치 웨이퍼는 규소와 같은 웨이퍼 포함하고, 웨이퍼 내로는 절연성, 전도성 또는 반전도성 특성을 갖는 상이한 물질들의 침착을 위한 영역들이 패턴화되어 있다. 정확한 패턴화를 얻기 위해서는, 웨이퍼 상에 층들을 형성시키는데 사용된 과량 물질이 제거되어야 한다. 또한, 기능성 및 신뢰성 회로를 제작하기 위해서, 후속 처리 이전에 평평하거나 평탄한 마이크로전자 웨이퍼 표면을 제조하는 것이 중요하다. 따라서, 마이크로전자 장치 웨이퍼의 특정 표면을 제거 및/또는 연마하는 것이 필요하다.Microelectronic device wafers are used to form integrated circuits. Microelectronic device wafers include wafers such as silicon, into which regions are patterned for deposition of different materials having insulating, conductive or semiconducting properties. In order to obtain accurate patterning, the excess material used to form the layers on the wafer must be removed. In addition, in order to fabricate functional and reliable circuits, it is important to prepare a flat or planar microelectronic wafer surface prior to subsequent processing. Accordingly, it is necessary to remove and/or polish certain surfaces of microelectronic device wafers.
화학 기계적 연마(Chemical Mechanical Polishing; CMP)는 임의 물질이 마이크로전자 장치 웨이퍼의 표면으로부터 제거되고, 그 표면이 연마와 같은 물리적 공정을 산화 또는 킬레이트화와 같은 화학 공정과 협력하여 연마되는 공정이다. 가장 기본적인 형태에서, CMP는 슬러리, 예를 들어, 연마제 및 활성 화합물의 용액을, 마이크전자 장치 웨이퍼의 표면을 버핑하여 제거, 평탄화 및 연마 공정을 달성하는 연마 패드에 도포하는 것을 수반한다. 집적 회로의 제작에서, CMP 슬러리는 또한 고도로 평탄한 표면이 후속 리소그래피 또는 패턴화, 에칭 및 박막 처리를 위해 생성될 수 있도록 금속과 다른 물질의 복합 층을 포함하는 필름을 우선적으로 제거하는 것이 가능해야 한다.Chemical Mechanical Polishing (CMP) is a process in which any material is removed from the surface of a microelectronic device wafer, and the surface is polished in cooperation with a chemical process such as oxidation or chelation by a physical process such as polishing. In its most basic form, CMP involves applying a slurry, eg, a solution of an abrasive and an active compound, to a polishing pad that buffs the surface of a microelectronic device wafer to achieve a removal, planarization and polishing process. In the fabrication of integrated circuits, CMP slurries should also be capable of preferentially removing films containing complex layers of metals and other materials so that highly planar surfaces can be created for subsequent lithography or patterning, etching and thin film processing. .
한편, 반도체 장치의 제조과정에서 발생하는 파티클, 금속원자, 유기물 등의 오염을 제거하고 장치의 신뢰성을 향상시키기 위하여, 세정 과정을 수행할 수 있다. 그러나, 일반적으로 연마 후 세정을 위해서 사용하는 세정액 조성물은, 알칼리성 수용액 중에서 OH-가 풍부하게 존재하기 때문에, 연마입자와 웨이퍼 표면을 대전하여, 전기적인 척력을 통한 연마입자의 제거가 용이해지지만, 세정 후의 웨이퍼 면의 금속 오염물, 유기 잔사 등의 불순물이 효과적으로 제거되지 않는 문제가 있다. 또한, 세정액 조성물의 pH가 8 이상으로 되면, 염기성 화합물에 의한 에칭 작용에 의해 웨이퍼 표면에 거칠기가 발생하기 쉬워진다. 따라서, 표면의 손상을 최소화하면서, 잔류입자, 유기 오염물 및 금속 오염물을 효과적으로 제거할 수 있는 세정공정 이전의 표면처리에 사용되는 조성물이 필요하다.On the other hand, in order to remove contamination of particles, metal atoms, organic matter, etc. generated in the manufacturing process of the semiconductor device and to improve the reliability of the device, a cleaning process may be performed. However, in general, the cleaning solution composition used for cleaning after polishing has an abundance of OH − in the alkaline aqueous solution, so that the abrasive particles and the wafer surface are charged, and the removal of the abrasive particles through electrical repulsion becomes easy, There is a problem in that impurities such as metal contaminants and organic residues on the wafer surface after cleaning are not effectively removed. In addition, when the pH of the cleaning liquid composition is 8 or higher, roughness tends to occur on the wafer surface due to the etching action of the basic compound. Accordingly, there is a need for a composition used for surface treatment prior to a cleaning process that can effectively remove residual particles, organic contaminants and metal contaminants while minimizing surface damage.
본 발명은, 상기 문제점을 해결하기 위해서, 반도체 디바이스용 웨이퍼의 화학기계적 연마 이후 수행하는 표면처리 공정에서 표면의 손상을 최소화하면서 표면 특성, 예를 들어, 표면 장력을 낮추어 후속 세정공정에서 잔류입자, 유기 오염물 및 금속 오염물을 효과적으로 제거하고, 결함을 낮출 수 있는 표면처리 조성물을 제공하는 것이다.The present invention, in order to solve the above problems, while minimizing the damage to the surface in the surface treatment process performed after chemical mechanical polishing of the wafer for semiconductor devices, the surface properties, for example, by lowering the surface tension, residual particles in the subsequent cleaning process, An object of the present invention is to provide a surface treatment composition capable of effectively removing organic contaminants and metal contaminants and lowering defects.
본 발명은, 본 발명에 의한 표면처리 조성물을 이용한 표면처리 방법을 제공하는 것이다. The present invention provides a surface treatment method using the surface treatment composition according to the present invention.
그러나, 본 발명이 해결하고자 하는 과제는 이상에서 언급한 것들로 제한되지 않으며, 언급되지 않은 또 다른 과제들은 아래의 기재로부터 해당 분야 통상의 기술자에게 명확하게 이해될 수 있을 것이다.However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.
본 발명의 일 실시예에 따라, 하기의 화학식 1로 표시되는 화합물, 하기의 화학식 2로 표시되는 화합물 또는 이 둘을 포함하는 제미니형 계면활성제; 및 pH 조절제를 포함하는 표면처리 조성물에 관한 것이다. According to an embodiment of the present invention, a compound represented by the following formula (1), a compound represented by the following formula (2), or a gemini-type surfactant comprising both; And it relates to a surface treatment composition comprising a pH adjusting agent.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
(상기 화학식 1 및 화학식 2에서 (In Formula 1 and Formula 2,
R1 내지 R6은, 각각, 수소, 할로겐, 선형(Linear) 또는 분지형(Branched) 탄소수 1 내지 20의 알킬기, 하이드록시기(-OH), 탄소수 1 내지 5의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A (R' 및 R''는, 각각, 탄소수 1 내지 5의 옥시알킬렌기에서 선택되고, R' 및 R''는, 서로 상이하며, A는 음이온기이며, m 및 n은, 각각, 1 내지 100에서 선택된다.)에서 선택될 수 있다. R 1 to R 6 are, respectively, hydrogen, halogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a hydroxy group (-OH), an oxyalkylene group having 1 to 5 carbon atoms, -(R ')m-(R'')n copolymer, -OA, and -R'-A (R' and R'' are each selected from an oxyalkylene group having 1 to 5 carbon atoms, R' and R'' is different from each other, A is an anionic group, and m and n are each selected from 1 to 100).
본 발명의 일 실시예에 따라, 상기 화학식 1 및 상기 화학식 2에서 R1, R2, R3 및 R4는, 각각, 수소, 선형 또는 분지형 탄소수 1 내지 20의 알킬기에서 선택되고, R5 및 R6은, 각각, 하이드록시기(-OH), 탄소수 1 내지 5의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A (R' 및 R''는, 각각, 탄소수 1 내지 5의 옥시알킬렌기에서 선택되고, R' 및 R''는, 서로 상이하며, A는, 술폰기, 황산기, 인산기 및 카르복실기에서 선택되고, m 및 n은, 각각, 1 내지 100에서 선택된다)에서 선택되는 것일 수 있다. According to an embodiment of the present invention, in Formula 1 and Formula 2, R 1 , R 2 , R 3 and R 4 are each selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, and R 5 and R 6 is, respectively, a hydroxy group (-OH), an oxyalkylene group having 1 to 5 carbon atoms, -(R')m-(R'')n copolymer, -OA, and -R'-A ( R' and R'' are each selected from an oxyalkylene group having 1 to 5 carbon atoms, R' and R'' are different from each other, A is selected from a sulfone group, a sulfuric acid group, a phosphoric acid group, and a carboxyl group, m and n, respectively, may be selected from 1 to 100).
본 발명의 일 실시예에 따라, 상기 화학식 1 및 상기 화학식 2에서 R5 및 R6은, 각각, 탄소수 2 내지 4의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A (R' 및 R''는 각각 탄소수 2 내지 4의 옥시알킬렌기에서 선택되고, A는 PO3 2-, SO3 -, COO- 및 CH3COO-에서 선택되고, m 및 n은, 각각, 1 내지 20에서 선택된다)에서 선택되는 것일 수 있다. According to an embodiment of the present invention, in Formula 1 and Formula 2, R 5 and R 6 are, respectively, an oxyalkylene group having 2 to 4 carbon atoms, -(R')m-(R'')n copolymer , -OA, and -R'-A (R' and R'' are each selected from an oxyalkylene group having 2 to 4 carbon atoms, and A is in PO 3 2- , SO 3 - , COO - and CH 3 COO - selected, and m and n are each selected from 1 to 20).
본 발명의 일 실시예에 따라, 상기 제미니형 계면활성제는, 상기 표면처리 조성물 중 0.001 중량% 내지 15 중량%인 것일 수 있다. According to an embodiment of the present invention, the gemini-type surfactant may be present in an amount of 0.001 wt% to 15 wt% of the surface treatment composition.
본 발명의 일 실시예에 따라, 상기 표면처리 조성물은, 수용성 중합체를 더 포함하고, 상기 수용성 중합체는, 아크릴레이트 계열의 모노머, 폴리머, 코폴리머 및 이들의 염 중 적어도 어느 하나를 포함하는 것일 수 있다.According to an embodiment of the present invention, the surface treatment composition may further include a water-soluble polymer, and the water-soluble polymer may include at least one of acrylate-based monomers, polymers, copolymers, and salts thereof. have.
본 발명의 일 실시예에 따라, 상기 수용성 중합체는, 아크릴레이트(acrylate), 메틸 아크릴레이트(Methyl acrylate), 에틸 아크릴레이트(Ethyl acrylate), 프로필 아크릴레이트(Propyl acrylate), 이소프로필 아크릴레이트(Isopropyl acrylate), 부틸 아크릴레이트(Butyl acrylate), 이소부틸 아크릴레이트(Isobutyl acrylate), 펜틸 아크릴레이트(Pentyl acrylate), 이소펜틸 아크릴레이(Isopentyl acrylate), 헥실 아크릴레이트(Hexyl acrylate), 이소헥실 아크릴레이트(Isohexyl acrylate), 헵틸 아크릴레이트(Heptyl acrylate), 옥틸 아크릴레이트(Octyl acrylate), 이소옥틸 아크릴레이트(Isooctyl acrylate), 노닐 아크릴레이트(Nonyl acrylate), 라우릴 아크릴레이트(Lauryl acrylate), 카르복시에틸 아크릴레이트(Carboxyethyl acrylate), 카르복시에틸 아크릴레이트 올리고머(Carboxyethyl acrylate oligomers), (메타크릴로일옥시)에틸 말레이에이트((Methacryloyloxy)ethyl maleate), (메타크릴로일옥시)에틸 숙시네이트((Methacryloyloxy)ethyl succinate), 및 암모늄 아크릴레이트(Ammonium acrylate)로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 모노머 또는 폴리머를 포함하는 것일 수 있다. According to an embodiment of the present invention, the water-soluble polymer is acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate (Isopropyl) acrylate), butyl acrylate, isobutyl acrylate, pentyl acrylate, isopentyl acrylate, hexyl acrylate, isohexyl acrylate ( Isohexyl acrylate, Heptyl acrylate, Octyl acrylate, Isooctyl acrylate, Nonyl acrylate, Lauryl acrylate, carboxyethyl acrylate (Carboxyethyl acrylate), Carboxyethyl acrylate oligomers, (Methacryloyloxy)ethyl maleate, (Methacryloyloxy)ethyl succinate ), and may include a monomer or polymer including at least one selected from the group consisting of ammonium acrylate.
본 발명의 일 실시예에 따라, 상기 수용성 중합체는, 말레산/아크릴레이트의 코폴리머(Copolymer of maleic acid/acrylate), 푸마르산/아크릴레이트의 코폴리머(Copolymer of fumaric acid/acrylate), 이타콘산/아크릴레이트의 코폴리머(Copolymer of itaconic acid/acrylate), 시트라콘산/아크릴레이트의 코폴리머(Copolymer of citraconic acid/acrylate), 아크릴산/아크릴레이트의 코폴리머(Copolymer of acrylic acid/acrylate), 메타아크릴산/아크릴레이트의 코폴리머(Copolymer of methacrylic acid/acrylate), 크로톤산/아크릴레이트의 코폴리머(Copolymer of crotonic acid/acrylate) 및 비닐아세트산/아크릴레이트의 코폴리머(Copolymer of vinylacetic acid/acrylate)로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.According to an embodiment of the present invention, the water-soluble polymer is a copolymer of maleic acid/acrylate, a copolymer of fumaric acid/acrylate, itaconic acid/ Copolymer of itaconic acid/acrylate, Copolymer of citraconic acid/acrylate, Copolymer of acrylic acid/acrylate, methacrylic acid /Consisting of a copolymer of methacrylic acid/acrylate, a copolymer of crotonic acid/acrylate and a copolymer of vinylacetic acid/acrylate It may include at least one selected from the group.
본 발명의 일 실시예에 따라, 상기 수용성 중합체는, 상기 표면처리 조성물 중 0.1 중량% 내지 20 중량%인 것일 수 있다. According to an embodiment of the present invention, the water-soluble polymer may be 0.1 wt% to 20 wt% of the surface treatment composition.
본 발명의 일 실시예에 따라, 상기 pH 조절제는, 유기산, 알킬아민 또는 이 둘을 포함하는 것일 수 있다. According to an embodiment of the present invention, the pH adjusting agent may include an organic acid, an alkylamine, or both.
본 발명의 일 실시예에 따라, 상기 유기산은, 1개의 카르복실기를 갖는 직쇄상의 포화 카르복실산, 포화 지방족 디카르복실산, 불포화 지방족 디카르복실산, 방향족 디카르복실산, 및 3개 이상의 카르복실기를 갖는 카르복실산으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,According to an embodiment of the present invention, the organic acid is a linear saturated carboxylic acid having one carboxyl group, a saturated aliphatic dicarboxylic acid, an unsaturated aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and three or more At least one selected from the group consisting of carboxylic acids having a carboxyl group,
상기 1개의 카르복실기를 갖는 직쇄상의 포화 카르복실산은, 포름산(formic acid), 아세트산(acetic acid), 프로피온산(propionic acid), 부티르산(butyric acid), 발레르산(valeric acid), 헥사노산(hexanoic acid), 헵타노산(heptanoic acid), 카프릴산(caprylic acid), 노나노산(nonanoic acid), 데카노산(decanoic acid), 운데실산(undecylenic acid), 라우릴산(lauric acid), 트리데실산(tridecylic acid), 미리스트산(myristic acid), 펜타데카노산(pentadecanoic acid) 및 팔미트산(palmitic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,The linear saturated carboxylic acid having one carboxyl group is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid ), heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid, tridecylic acid ( containing at least one selected from the group consisting of tridecylic acid, myristic acid, pentadecanoic acid, and palmitic acid,
상기 포화 지방족 디카르복실산은, 옥살산(oxalic acid), 말론산(malonic acid), 숙신산(succinic acid), 글루타르산(glutaric acid), 아디프산(adipic acid), 피멜산(pimelic acid), 수베르산(suberic acid), 아젤라산(azelaic acid) 및 세바식산(sebacic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,The saturated aliphatic dicarboxylic acid is, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid (suberic acid), azelaic acid (azelaic acid) and at least one selected from the group consisting of sebacic acid (sebacic acid),
상기 불포화 지방족 디카르복실산은, 말레인산(maleic acid), 푸마르산(fumaric acid), 글루타콘산(glutaconic acid), 트라우마트산(traumatic acid) 및 무콘산(muconic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,The unsaturated aliphatic dicarboxylic acid is at least one selected from the group consisting of maleic acid, fumaric acid, glutaconic acid, traumatic acid, and muconic acid. including,
상기 방향족 디카르복실산은, 프탈산(phthalic acid), 이소프탈산(isophthalic acid) 및 테레프탈산(terephthalic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고, The aromatic dicarboxylic acid includes at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid,
상기 3개 이상의 카르복실기를 갖는 카르복실산은, 시트르산(citric acid), 이소시트르산(isocitric acid), 아콘산(aconitic acid), 카르발릴산(carballylic acid), 트리베스산(tribasic acid) 및 멜리트산(mellitic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 것일 수 있다.The carboxylic acid having three or more carboxyl groups is citric acid, isocitric acid, aconitic acid, carballylic acid, tribasic acid, and mellitic acid ( mellitic acid) may include at least one selected from the group consisting of.
본 발명의 일 실시예에 따라, 상기 알킬아민은, 모노에탄올아민, 메틸에탄올아민, 메틸디에탄올아민, 에틸에탄올아민, 디에탄올아민, 디에틸에탄올아민, 트리에탄올아민, N-아미노-N-프로판올, 메틸아민, 디메틸아민, 트리메틸아민, 에틸아민, 디에틸아민, 트리에틸아민, 에틸렌디아민, 모노에탄올아민, N-(β아미노에틸)에탄올아민, 헥사메틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라아민, 모노이소프로판올아민, 디이소프로판올아민, 트리이소프로판올아민 및 테트라에틸렌펜타민으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 것일 수 있다. According to an embodiment of the present invention, the alkylamine is monoethanolamine, methylethanolamine, methyldiethanolamine, ethylethanolamine, diethanolamine, diethylethanolamine, triethanolamine, N-amino-N-propanol , methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetra It may include at least one selected from the group consisting of amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and tetraethylenepentamine.
본 발명의 일 실시예에 따라, 상기 표면처리 조성물의 pH가 2 내지 7인 것일 수 있다.According to an embodiment of the present invention, the surface treatment composition may have a pH of 2 to 7.
본 발명의 일 실시예에 따라, 상기 표면처리 조성물은, 실리콘 질화막, 실리콘 산화막. 폴리실리콘막 및 실리콘막으로 이루어진 군에서 선택되는 적어도 어느 하나의 막을 포함하는 반도체 디바이스용 웨이퍼 표면의 결함, 잔류물 및 오염물을 제거하는 것일 수 있다. According to an embodiment of the present invention, the surface treatment composition is a silicon nitride film, a silicon oxide film. Defects, residues and contaminants on the surface of a semiconductor device wafer including at least one film selected from the group consisting of a polysilicon film and a silicon film may be removed.
본 발명의 일 실시예에 따라, 상기 표면처리 조성물로 표면처리하였을 때, 실리콘 질화막, 실리콘 산화막. 폴리실리콘막 및 실리콘막 중 적어도 어느 하나의 막에 대한 결함 감소율이 50 % 이상인 것일 수 있다. According to an embodiment of the present invention, when the surface is treated with the surface treatment composition, a silicon nitride film, a silicon oxide film. The defect reduction rate for at least one of the polysilicon film and the silicon film may be 50% or more.
본 발명의 일 실시예에 따라, 표면처리 조성물을 사용하여, 반도체 디바이스용 웨이퍼의 화학기계적 연마 후의 반도체 디바이스용 웨이퍼를 표면처리하는 것인, 표면처리 방법에 관한 것이다. According to an embodiment of the present invention, it relates to a surface treatment method for surface treatment of a semiconductor device wafer after chemical mechanical polishing of the semiconductor device wafer using a surface treatment composition.
본 발명의 일 실시예에 따라, 상기 반도체 디바이스용 웨이퍼를 표면처리한 후에 불산 세정, SC1 세정 ((NH4OH 및 H2O2 포함하는 세정 용액) 및 상용 세정액을 이용한 세정으로 이루어진 군에서 선택되는 적어도 어느 하나의 후속 세정공정을 수행하는 것일 수 있다. According to an embodiment of the present invention, after surface treatment of the semiconductor device wafer, hydrofluoric acid cleaning, SC1 cleaning ((a cleaning solution containing NH 4 OH and H 2 O 2 ) and cleaning using a commercial cleaning solution is selected It may be to perform at least one subsequent cleaning process.
본 발명의 표면처리용 조성물은, 반도체 디바이스용 웨이퍼의 화학기계적 연마 후의 반도체 디바이스용 웨이퍼 표면 특성, 예를 들어, 표면 장력을 신속하게 낮추어 후속 세정공정에서의 세정 및 결함(Defect) 제거가 용이하고, 반도체 웨이퍼의 연마 후 잔류하는 연마입자, 유기물, 불순물 등의 오염물질을 효과적으로 제거할 수 있다. The composition for surface treatment of the present invention rapidly lowers the surface properties of the wafer for semiconductor devices, for example, surface tension, after chemical mechanical polishing of the wafer for semiconductor devices, so that cleaning and defect removal in the subsequent cleaning process are easy, and , it is possible to effectively remove contaminants such as abrasive particles, organic matter, and impurities remaining after polishing the semiconductor wafer.
도 1은, 본 발명의 일 실시예에 따라, 본 발명의 실시예의 농도에 따른 정적표면장력(Ciritical Micell Concentration) 그래프를 나타낸 것이다.
도 2는, 본 발명의 일 실시예에 따라, 본 발명의 실시예의 동적 표면장력 (Ciritical Micell Concentration)그래프를 나타낸 것이다. 1 shows a graph of Ciritical Micell Concentration according to concentration of an embodiment of the present invention, according to an embodiment of the present invention.
2 is a diagram showing a dynamic surface tension (Ciritical Micell Concentration) graph of an embodiment of the present invention, according to an embodiment of the present invention.
이하 본 발명의 실시예들을 상세히 설명한다. 본 발명을 설명함에 있어서, 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다. 또한, 본 명세서에서 사용되는 용어들은 본 발명의 바람직한 실시예를 적절히 표현하기 위해 사용된 용어들로서, 이는 사용자, 운용자의 의도 또는 본 발명이 속하는 분야의 관례 등에 따라 달라질 수 있다. 따라서, 본 용어들에 대한 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. Hereinafter, embodiments of the present invention will be described in detail. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms used in this specification are terms used to properly express a preferred embodiment of the present invention, which may vary depending on the intention of a user or operator or a custom in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification.
명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components.
이하, 본 발명의 표면 처리 조성물 및 이를 이용한 표면처리방법에 대하여 실시예를 참조하여 구체적으로 설명하도록 한다. 그러나, 본 발명이 이러한 실시예에 제한되는 것은 아니다.Hereinafter, the surface treatment composition of the present invention and a surface treatment method using the same will be described in detail with reference to Examples. However, the present invention is not limited to these examples.
본 발명은, 표면 처리 조성물에 관한 것으로, 본 발명의 일 실시예에 따라, 상기 표면 처리 조성물은, 제미니형 계면활성제 및 pH 조절제를 포함할 수 있다.The present invention relates to a surface treatment composition, and according to an embodiment of the present invention, the surface treatment composition may include a gemini type surfactant and a pH adjuster.
본 발명의 일 실시예에 따라, 상기 제미니형 계면활성제(Gemini surfactant)는, 주사슬 내에 다중결합(예를 들어, 탄소-탄소 이중결합, 탄소-탄소 삼중결합)을 가지며, 저기포성에 의한 기포 개선뿐만 아니라, 신속한 표면 흡착능력과 표면 장력을 개선시켜 세정 효과를 향상시킬 수 있다. According to an embodiment of the present invention, the Gemini surfactant has multiple bonds (eg, carbon-carbon double bond, carbon-carbon triple bond) in the main chain, and bubbles due to low foaming properties In addition to improvement, it is possible to improve the cleaning effect by improving the rapid surface adsorption ability and surface tension.
상기 제미니형 계면활성제는, 하기의 화학식 1, 하기의 화학식 2 또는 이 둘을 포함할 수 있다. The gemini-type surfactant may include the following Chemical Formula 1, the following Chemical Formula 2, or both.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
상기 화학식 1 및 화학식 2에서 R1 내지 R6은, 각각, 수소, 할로겐, 선형(Linear) 또는 분지형(Branched) 탄소수 1 내지 20의 알킬기, 하이드록시기(-OH), 탄소수 1 내지 5의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A 에서 선택될 수 있다. In Formulas 1 and 2, R 1 to R 6 are, respectively, hydrogen, halogen, linear or branched alkyl group having 1 to 20 carbon atoms, hydroxy group (-OH), and 1 to 5 carbon atoms an oxyalkylene group, -(R')m-(R'')n copolymer, -OA, and -R'-A.
여기서, R' 및 R''는, 각각, 탄소수 1 내지 5의 옥시알킬렌기에서 선택되고, R' 및 R''는, 서로 상이하며, A는, 음이온기이며, m 및 n은, 각각, 1 내지 100에서 선택될 수 있다. Here, R' and R'' are each selected from an oxyalkylene group having 1 to 5 carbon atoms, R' and R'' are different from each other, A is an anionic group, and m and n are each, It may be selected from 1 to 100.
상기 제미니형 계면활성제는, 한 분자 내에 친수성기 (hydrophilic group 또는 친수성 모이어티)와 소수성기(hydrophobic group 또는 소수성 모이어티)를 동시에 포함할 수 있고, 바람직하게는 두개 이상의 친수성기 및 두개 이상의 소수성기를 포함할 수 있다. 즉, 상기 제미니형 계면활성제는, 선형 계면활성화제(동일한 탄소수에서 선형 형태)에 비하여 낮은 CMC (Critical micelle concentration)를 나타내므로, 낮은 농도에서도 표면에 신속하게 흡착하여 표면 장력을 낮출 수 있고, 소수성기 (hydrophobic group)가 가지형태로 존재하기 때문에 기포성이 낮으면서 낮은 표면장력을 유지할 뿐만 아니라, 구조적으로 빨리 표면에 흡착하기 때문에 정적표면장력 뿐만 아니라 동적표면장력도 낮출 수 있다.The gemini-type surfactant may include a hydrophilic group or a hydrophilic moiety and a hydrophobic group or a hydrophobic group in one molecule, preferably, two or more hydrophilic groups and two or more hydrophobic groups. have. That is, the gemini surfactant exhibits a lower CMC (critical micelle concentration) than a linear surfactant (a linear form at the same number of carbon atoms), so it can be rapidly adsorbed to the surface even at a low concentration to lower the surface tension, and the hydrophobic group Because the hydrophobic group exists in the branched form, it not only maintains low surface tension with low foaming properties, but also structurally adsorbs to the surface quickly, so that not only the static surface tension but also the dynamic surface tension can be lowered.
예를 들어, 상기 화학식 1 및 상기 화학식 2에서 R1, R2, R3 및 R4는, 각각, 수소, 선형 또는 분지형 탄소수 1 내지 20; 탄소수 1 내지 15; 또는 탄소수 1 내지 12의 알킬기에서 선택될 수 있다.For example, in Formula 1 and Formula 2, R 1 , R 2 , R 3 and R 4 are, respectively, hydrogen, linear or branched carbon number of 1 to 20; 1 to 15 carbon atoms; Or it may be selected from an alkyl group having 1 to 12 carbon atoms.
예를 들어, 상기 화학식 1 및 상기 화학식 2에서 R5 및 R6은, 각각, 하이드록시기(-OH), 탄소수 1 내지 5의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A 에서 선택될 수 있다. For example, in Formula 1 and Formula 2, R 5 and R 6 are, respectively, a hydroxyl group (-OH), an oxyalkylene group having 1 to 5 carbon atoms, -(R')m-(R'') n copolymer, -OA, and -R'-A.
여기서, R' 및 R''는, 각각, 탄소수 1 내지 5의 옥시알킬렌기에서 선택되고, R' 및 R''는, 서로 상이한 것일 수 있다.Here, R' and R'' are each selected from an oxyalkylene group having 1 to 5 carbon atoms, and R' and R'' may be different from each other.
A는 음이온기이며, 예를 들어, 술폰기, 황산기, 인산기 및 카르복실기에서 선택될 수 있다.A is an anionic group, and may be selected from, for example, a sulfone group, a sulfuric acid group, a phosphoric acid group, and a carboxyl group.
m 및 n은, 각각, 1 내지 100; 1 내지 50; 또는 1 내지 20에서 선택되며 음의 값을 제외한 유리수이다. m and n are, respectively, 1 to 100; 1 to 50; or a rational number selected from 1 to 20 and excluding negative values.
바람직하게는 R5 및 R6은, 각각, 탄소수 2 내지 4의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A 에서 선택되고, 여기서 R' 및 R''는 각각 탄소수 2 내지 4의 옥시알킬렌기에서 선택되고, A는 PO3 2-, SO3 -, COO- 및 CH3COO-에서 선택되고, m 및 n은, 각각, 1 내지 20에서 선택될 수 있다. Preferably, R 5 and R 6 are each selected from an oxyalkylene group having 2 to 4 carbon atoms, -(R')m-(R'')n copolymer, -OA, and -R'-A, wherein R' and R'' are each selected from an oxyalkylene group having 2 to 4 carbon atoms, A is selected from PO 3 2- , SO 3 - , COO - and CH 3 COO - , m and n are each, It may be selected from 1 to 20.
상기 제미니형 계면활성제는, 상기 표면처리 조성물 중 0.001 중량% 내지 15 중량%이며, 상기 0.001 중량% 미만인 경우에 목적하는 표면 장력의 조절이 어렵고, 15 중량%를 초과할 경우에 반도체 웨이퍼의 연마 후 잔류하는 연마입자, 유기물, 불순물 등의 오염물질을 충분히 제거하는데 어려움이 있다. The gemini-type surfactant is 0.001 wt% to 15 wt% of the surface treatment composition, and when it is less than 0.001 wt%, it is difficult to control the desired surface tension, and when it exceeds 15 wt%, after polishing the semiconductor wafer It is difficult to sufficiently remove contaminants such as residual abrasive particles, organic matter, and impurities.
본 발명의 일 실시예에 따라, 상기 표면처리 조성물은, 수용성 중합체를 더 포함할 수 있다. 상기 잔류입자, 불순물 등의 제거에 용이하며, 금속막, 질화막, 산화막과 같은 친수성막에 대한 세정 및 결함을 개선시킬 수 있으며, 아크릴레이트 계열의 모노머, 폴리머, 코폴리머 및 이들의 염 중 적어도 어느 하나를 포함할 수 있다.According to an embodiment of the present invention, the surface treatment composition may further include a water-soluble polymer. It is easy to remove the residual particles and impurities, and it can improve cleaning and defects on hydrophilic films such as metal films, nitride films, and oxide films, and at least any of acrylate-based monomers, polymers, copolymers, and salts thereof. may contain one.
예를 들어, 상기 수용성 중합체는, 아크릴레이트(acrylate), 메틸 아크릴레이트(Methyl acrylate), 에틸 아크릴레이트(Ethyl acrylate), 프로필 아크릴레이트(Propyl acrylate), 이소프로필 아크릴레이트(Isopropyl acrylate), 부틸 아크릴레이트(Butyl acrylate), 이소부틸 아크릴레이트(Isobutyl acrylate), 펜틸 아크릴레이트(Pentyl acrylate), 이소펜틸 아크릴레이(Isopentyl acrylate), 헥실 아크릴레이트(Hexyl acrylate), 이소헥실 아크릴레이트(Isohexyl acrylate), 헵틸 아크릴레이트(Heptyl acrylate), 옥틸 아크릴레이트(Octyl acrylate), 이소옥틸 아크릴레이트(Isooctyl acrylate), 노닐 아크릴레이트(Nonyl acrylate), 라우릴 아크릴레이트(Lauryl acrylate), 카르복시에틸 아크릴레이트(Carboxyethyl acrylate), 카르복시에틸 아크릴레이트 올리고머(Carboxyethyl acrylate oligomers), (메타크릴로일옥시)에틸 말레이에이트((Methacryloyloxy)ethyl maleate), (메타크릴로일옥시)에틸 숙시네이트((Methacryloyloxy)ethyl succinate), 및 암모늄 아크릴레이트(Ammonium acrylate)로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 모노머 또는 폴리머를 포함할 수 있다. For example, the water-soluble polymer is acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylic Butyl acrylate, Isobutyl acrylate, Pentyl acrylate, Isopentyl acrylate, Hexyl acrylate, Isohexyl acrylate, heptyl Heptyl acrylate, Octyl acrylate, Isooctyl acrylate, Nonyl acrylate, Lauryl acrylate, Carboxyethyl acrylate, Carboxyethyl acrylate oligomers, (Methacryloyloxy)ethyl maleate, (Methacryloyloxy)ethyl succinate), and ammonium acrylic It may include a monomer or a polymer including at least one selected from the group consisting of ammonium acrylate.
예를 들어, 상기 수용성 중합체는, 말레산/아크릴레이트의 코폴리머(Copolymer of maleic acid/acrylate), 푸마르산/아크릴레이트의 코폴리머(Copolymer of fumaric acid/acrylate), 이타콘산/아크릴레이트의 코폴리머(Copolymer of itaconic acid/acrylate), 시트라콘산/아크릴레이트의 코폴리머(Copolymer of citraconic acid/acrylate), 아크릴산/아크릴레이트의 코폴리머(Copolymer of acrylic acid/acrylate), 메타아크릴산/아크릴레이트의 코폴리머(Copolymer of methacrylic acid/acrylate), 크로톤산/아크릴레이트의 코폴리머(Copolymer of crotonic acid/acrylate) 및 비닐아세트산/아크릴레이트의 코폴리머(Copolymer of vinylacetic acid/acrylate)로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the water-soluble polymer is a copolymer of maleic acid/acrylate, a copolymer of fumaric acid/acrylate, and a copolymer of itaconic acid/acrylate. (Copolymer of itaconic acid/acrylate), Copolymer of citraconic acid/acrylate, Copolymer of acrylic acid/acrylate, methacrylic acid/acrylate At least selected from the group consisting of a copolymer of methacrylic acid/acrylate, a copolymer of crotonic acid/acrylate, and a copolymer of vinylacetic acid/acrylate may include any one.
상기 수용성 중합체는, 상기 표면처리 조성물 중 0.1 중량% 내지 20 중량%이며, 상기 0.1 중량% 미만인 경우 반도체막의 오염 제거 능력을 발휘할 수 없을 수 있고, 20 중량％를 초과해도 그 이상의 효과는 얻어지지 않을 뿐만 아니라, 경제적인 측면에서도 비용이 보다 더 들게 된다.The water-soluble polymer is 0.1% to 20% by weight of the surface treatment composition, and when it is less than 0.1% by weight, it may not be able to exhibit the decontamination ability of the semiconductor film, and even if it exceeds 20% by weight, no further effect will be obtained. Not only that, it also costs more from an economic point of view.
상기 pH 조절제는, 유기산, 알킬아민 또는 이 둘을 포함할 수 있다. The pH adjusting agent may include an organic acid, an alkylamine, or both.
상기 유기산은, 연마 공정 이후에 잔류하는 연마 입자, 유기물, 불순물 등의 세정 효과를 제공할 수 있으며, 상기 유기산은, 1개의 카르복실기를 갖는 직쇄상의 포화 카르복실산, 포화 지방족 디카르복실산, 불포화 지방족 디카르복실산, 방향족 디카르복실산, 및 3개 이상의 카르복실기를 갖는 카르복실산으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. The organic acid may provide a cleaning effect of abrasive particles, organic substances, impurities, etc. remaining after the polishing process, and the organic acid is a linear saturated carboxylic acid having one carboxyl group, a saturated aliphatic dicarboxylic acid, It may include at least one selected from the group consisting of unsaturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and carboxylic acids having three or more carboxyl groups.
예를 들어, 상기 1개의 카르복실기를 갖는 직쇄상의 포화 카르복실산은, 포름산(formic acid), 아세트산(acetic acid), 프로피온산(propionic acid), 부티르산(butyric acid), 발레르산(valeric acid), 헥사노산(hexanoic acid), 헵타노산(heptanoic acid), 카프릴산(caprylic acid), 노나노산(nonanoic acid), 데카노산(decanoic acid), 운데실산(undecylenic acid), 라우릴산(lauric acid), 트리데실산(tridecylic acid), 미리스트산(myristic acid), 펜타데카노산(pentadecanoic acid) 및 팔미트산(palmitic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the linear saturated carboxylic acid having one carboxyl group is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexa hexanoic acid, heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid, It may include at least one selected from the group consisting of tridecyl acid (tridecylic acid), myristic acid (myristic acid), pentadecanoic acid (pentadecanoic acid) and palmitic acid (palmitic acid).
예를 들어, 상기 포화 지방족 디카르복실산은, 옥살산(oxalic acid), 말론산(malonic acid), 숙신산(succinic acid), 글루타르산(glutaric acid), 아디프산(adipic acid), 피멜산(pimelic acid), 수베르산(suberic acid), 아젤라산(azelaic acid) 및 세바식산(sebacic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the saturated aliphatic dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid ( pimelic acid), suberic acid, azelaic acid, and sebacic acid may include at least one selected from the group consisting of.
예를 들어, 상기 불포화 지방족 디카르복실산은, 말레인산(maleic acid), 푸마르산(fumaric acid), 글루타콘산(glutaconic acid), 트라우마트산(traumatic acid) 및 무콘산(muconic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the unsaturated aliphatic dicarboxylic acid is selected from the group consisting of maleic acid, fumaric acid, glutaconic acid, traumatic acid, and muconic acid. It may include at least any one of
예를 들어, 상기 방향족 디카르복실산은, 프탈산(phthalic acid), 이소프탈산(isophthalic acid) 및 테레프탈산(terephthalic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the aromatic dicarboxylic acid may include at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.
예를 들어, 상기 3개 이상의 카르복실기를 갖는 카르복실산은, 시트르산(citric acid), 이소시트르산(isocitric acid), 아콘산(aconitic acid), 카르발릴산(carballylic acid), 트리베스산(tribasic acid) 및 멜리트산(mellitic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the carboxylic acid having three or more carboxyl groups is citric acid, isocitric acid, aconitic acid, carballylic acid, tribasic acid) And it may include at least one selected from the group consisting of mellitic acid.
예를 들어, 상기 알킬아민은, 모노에탄올아민, 메틸에탄올아민, 메틸디에탄올아민, 에틸에탄올아민, 디에탄올아민, 디에틸에탄올아민, 트리에탄올아민, N-아미노-N-프로판올, 메틸아민, 디메틸아민, 트리메틸아민, 에틸아민, 디에틸아민, 트리에틸아민, 에틸렌디아민, 모노에탄올아민, N-(β-아미노에틸)에탄올아민, 헥사메틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라아민, 모노이소프로판올아민, 디이소프로판올아민, 트리이소프로판올아민 및 테트라에틸렌펜타민으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함할 수 있다. For example, the alkylamine is monoethanolamine, methylethanolamine, methyldiethanolamine, ethylethanolamine, diethanolamine, diethylethanolamine, triethanolamine, N-amino-N-propanol, methylamine, dimethyl Amine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, monoisopropanol It may include at least one selected from the group consisting of amine, diisopropanolamine, triisopropanolamine, and tetraethylenepentamine.
상기 표면처리 조성물의 pH가 2 내지 7일 수 있다. 상기 pH 범위 내에 포함되면, 화학기계적 연마(CMP)된 웨이퍼를 상기 표면처리 조성물로 처리한 경우 후속 세정공정에서 우수한 세정 효과 및 낮은 결함을 제공할 수 있다. 또한, 반도체 웨이퍼의 연마 후 잔류하는 연마입자, 유기물, 불순물 등의 오염물질을 충분히 제거할 수 있다.The surface treatment composition may have a pH of 2 to 7. When included in the pH range, when a chemical mechanical polishing (CMP) wafer is treated with the surface treatment composition, an excellent cleaning effect and low defects may be provided in a subsequent cleaning process. In addition, it is possible to sufficiently remove contaminants such as abrasive particles, organic matter, and impurities remaining after polishing the semiconductor wafer.
본 발명의 일 실시예에 따라, 상기 표면처리 조성물은, 용매를 포함하고, 상기 용매는, 물, 및/또는 유기용매를 포함할 수 있다. 표면처리 조성물 중의 물은, 표면 처리 조성물 중의 다른 성분을 용해 또는 분산시키는 작용을 한다. 물은, 다른 성분의 작용을 저해하는 불순물을 가능한 함유하지 않는 것이 바람직하다. 구체적으로는, 이온 교환수지를 사용하여 불순물 이온을 제거한 후에 필터를 통하여 이물을 제거한 이온 교환수, 또는 순수, 초순수, 탈이온수 또는 증류수가 바람직하다.According to an embodiment of the present invention, the surface treatment composition may include a solvent, and the solvent may include water and/or an organic solvent. Water in the surface treatment composition serves to dissolve or disperse other components in the surface treatment composition. It is preferable that water does not contain as much as possible an impurity which inhibits the action of other components. Specifically, ion-exchanged water from which foreign substances are removed through a filter after removing impurity ions using an ion-exchange resin, or pure water, ultrapure water, deionized water or distilled water is preferable.
상기 표면처리 조성물은, 실리콘 질화막, 실리콘 산화막. 폴리실리콘막 및 실리콘막으로 이루어진 군에서 선택되는 적어도 어느 하나의 막을 포함하는 반도체 디바이스용 웨이퍼 표면의 결함, 잔류물 및 오염물을 제거할 수 있다. The surface treatment composition is a silicon nitride film, a silicon oxide film. Defects, residues, and contaminants on the surface of a semiconductor device wafer including at least one film selected from the group consisting of a polysilicon film and a silicon film may be removed.
상기 잔류물은 CMP 연마 슬러리 유래 입자, CMP 연마 슬러리에 존재하는 화학물질, CMP 연마 슬러리의 반응 부산물, 탄소 농후 입자, 연마 패드 입자, 브러쉬 탈로딩 입자, 구성 입자의 장비 물질, 금속, 금속 산화물 및 이들의 조합으로 이루어진 군으로부터 선택된 물질을 포함하는 것일 수 있다.The residue may include particles from the CMP polishing slurry, chemicals present in the CMP polishing slurry, reaction byproducts of the CMP polishing slurry, carbon-enriched particles, polishing pad particles, brush unloading particles, equipment materials of the constituent particles, metals, metal oxides and It may include a material selected from the group consisting of combinations thereof.
상기 표면처리 조성물로 표면처리하였을 때, 본 발명의 표면처리 조성물을 사용하면, 실리콘 질화막, 실리콘 산화막, 폴리실리콘막 및 실리콘막 중 적어도 어느 하나의 막에 대해서도 결함 개선 효과가 우수하며, 즉, 결함 감소율이 50 % 이상; 또는 80 % 이상일 수 있다. 예를 들어, 실리콘 질화막에 대한 결함 감소율이 80 % 이상이고, 실리콘 산화막에 대한 결함 감소율이 80 % 이상이고, 폴리 실리콘막에 대한 결함 감소율이 50 % 이상인 것일 수 있다. 결함 감소율은 상기 표면처리 조성물로 표면처리한 후, 후속 세정공정을 진행했을 때의 결함을 기준으로 하며, 예를 들어, 불산세정 및 SC1 세정을 진행하였을 때, 실리콘 질화막에 대한 결함은, 표면처리를 진행하지 않고 불산 세정 및 SC1 세정만 진행했을 때의 결함을 기준으로 나타낸 것이고, 결함 감소율은 표면처리를 하지 않았을 때의 결함에 대해 표면처리를 하였을 때 결함이 어느 정도 수준으로 감소했는지를 나타내는 지표이다.When the surface treatment is performed with the surface treatment composition, when the surface treatment composition of the present invention is used, the defect improvement effect is excellent for at least any one of a silicon nitride film, a silicon oxide film, a polysilicon film, and a silicon film, that is, a defect. reduction of more than 50%; or 80% or more. For example, the defect reduction rate for the silicon nitride film may be 80% or more, the defect reduction rate for the silicon oxide film may be 80% or more, and the defect reduction rate for the polysilicon film may be 50% or more. The defect reduction rate is based on the defects when the subsequent cleaning process is performed after surface treatment with the surface treatment composition. For example, when hydrofluoric acid cleaning and SC1 cleaning are performed, defects on the silicon nitride film are surface treated It is shown based on the defects obtained when only hydrofluoric acid cleaning and SC1 cleaning were performed without performing the cleaning process. to be.
본 발명은, 본 발명에 의한 표면처리 조성물을 사용하여, 반도체 디바이스용 웨이퍼의 화학기계적 연마 후의 반도체 디바이스용 웨이퍼를 표면처리하는 표면처리 방법을 제공할 수 있다. The present invention can provide a surface treatment method for surface treatment of a semiconductor device wafer after chemical mechanical polishing of the semiconductor device wafer using the surface treatment composition according to the present invention.
즉, 표면처리 조성물을 이용하여 반도체 디바이스용 웨이퍼에 직접 접촉시켜 표면처리하는 것으로, 화학기계적 연마 후의 반도체 디바이스용 웨이퍼의 표면 장력을 낮추어 웨이퍼 표면에 대한 젖음성을 향상시키고, 후속 세정공정에서의 세정 및 결함 제거가 용이하도록 할 수 있고, 상기 표면처리 방법에 의하여, 화학기계적 연마 후 반도체 디바이스용 웨이퍼 표면특성을 변화시켜서 후속 세정공정에서 결함 제거가 용이하게 할 수 있다.That is, the surface treatment is performed by directly contacting the wafer for semiconductor devices using the surface treatment composition, thereby lowering the surface tension of the wafer for semiconductor devices after chemical mechanical polishing to improve wettability to the wafer surface, and cleaning and Defect removal can be facilitated, and the surface properties of the semiconductor device wafer can be changed after chemical mechanical polishing by the surface treatment method to facilitate defect removal in a subsequent cleaning process.
본 발명의 표면처리 조성물은, 통상의 웨이퍼의 표면처리에서 사용되는 것과 동일한 장치 및 조건에서 사용할 수 있다. 표면처리 장치에서 세정 모듈이 아닌 CMP 모듈에서 사용할 수 있다. 본 발명의 표면처리 방법에 의해 웨이퍼를 표면처리하는 경우, 표면처리 조성물의 사용 시의 온도는 특별히 한정되지 않지만, 5 ℃내지 60 ℃인 것일 수 있다.The surface treatment composition of the present invention can be used in the same apparatus and conditions as those used for surface treatment of ordinary wafers. It can be used in the CMP module instead of the cleaning module in the surface treatment device. In the case of surface treatment of the wafer by the surface treatment method of the present invention, the temperature at the time of using the surface treatment composition is not particularly limited, but may be 5°C to 60°C.
상기 표면처리 방법에 의한 웨이퍼의 표면처리는, 연마된 웨이퍼의 표면특성을 변화시키기 위한 표면처리일 수도 있고, 연마된 웨이퍼를 세정하기 위한 세정공정에 포함될 수도 있다. 표면처리 시간은 일반적으로 수초 내지 수분 동안 진행하며, 1 초 내지 10 분 이내에서 진행할 수 있다.The surface treatment of the wafer by the surface treatment method may be a surface treatment for changing the surface characteristics of the polished wafer, or may be included in a cleaning process for cleaning the polished wafer. The surface treatment time is generally performed for several seconds to several minutes, and may be performed within 1 second to 10 minutes.
상기 반도체 디바이스용 웨이퍼를 표면처리한 후에 건식 세정 및/또는 습식 세정에 의한 후속 세정공정을 수행하는 것일 수 있다. 예를 들어, 상기 건식 세정은, HF/H2O 기상 세정, UV/O3 세정, UV/Cl2 세정, H2/Ar 플라즈마 세정 등일 수 있으나, 이에 제한되지 않는다. After surface treatment of the semiconductor device wafer, a subsequent cleaning process by dry cleaning and/or wet cleaning may be performed. For example, the dry cleaning may be HF/H 2 O gas phase cleaning, UV/O 3 cleaning, UV/Cl 2 cleaning, H 2 /Ar plasma cleaning, etc., but is not limited thereto.
예를 들어, 상기 습식 세정은, 불산 세정, SC1 세정 및 상용 세정액을 이용한 세정으로 이루어진 군에서 선택되는 적어도 어느 하나를 이용하는 것으로, SC1 세정(SC-1(Standard cleaning-1, NH4OH:H2O2:H2O=1:1:5 to 1:2:7), SC2세정 (Standard cleaning-2, Standard cleaning-2, HCl:H2O2:H2O=1:1:5 to 1:2:8), SPM(Sulfuric acid peroxide mixture), HPM (Hydrochloric acid peroxide mixture), SPM (H2SO4/H2O2), DHF (HF/H2O), BHF (NH4F/HF/H2O), FPM (HF/H2O2), 불산, 오존불산 (HF/O3/H2O) 등일 수 있으나, 이에 제한되지 않는다. For example, the wet cleaning uses at least one selected from the group consisting of hydrofluoric acid cleaning, SC1 cleaning, and cleaning using a commercial cleaning solution, and SC1 cleaning (SC-1 (Standard cleaning-1, NH 4 OH:H) is used. 2 O 2 :H 2 O=1:1:5 to 1:2:7), SC2 cleaning (Standard cleaning-2, Standard cleaning-2, HCl:H 2 O 2 :H 2 O=1:1:5) to 1:2:8), SPM (Sulfuric acid peroxide mixture), HPM (Hydrochloric acid peroxide mixture), SPM (H 2 SO 4 /H 2 O 2 ), DHF (HF/H 2 O), BHF (NH 4 F/HF/H 2 O), FPM (HF/H 2 O 2 ), hydrofluoric acid, ozone hydrofluoric acid (HF/O 3 /H 2 O), etc., but is not limited thereto.
본 발명의 표면처리를 진행하는 경우, 종래에 통상적으로 사용하는 세정공정을 단순화시켜도 동등 이상의 효과를 나타낼 수 있다. 예를 들어, 표면처리 이후 불산 세정과 SC1 세정을 같이 적용하는 경우, 불산 세정을 진행하지 않고 SC1 세정만 단독 진행하여도 동등 효과를 기대할 수 있다.In the case of performing the surface treatment of the present invention, the same or more effects can be exhibited even by simplifying the conventionally used cleaning process. For example, when hydrofluoric acid cleaning and SC1 cleaning are applied together after surface treatment, the same effect can be expected even if only SC1 cleaning is performed without hydrofluoric acid cleaning.
이하, 실시예에 의하여 본 발명을 더욱 상세히 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.
실시예 1Example 1
삼중결합을 포함하고 말단에 하이드록시기를 갖는 제미니형 계면활성제, 및 아크릴산/아크릴레이트 공중합체를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing the gemini type surfactant including a triple bond and having a hydroxyl group at the terminal, and an acrylic acid/acrylate copolymer, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
실시예 2Example 2
삼중결합을 포함하고 말단에 에틸렌 옥사이드기를 갖는 제미니형 계면활성제, 및 폴리아크릴레이트를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a gemini type surfactant including a triple bond and having an ethylene oxide group at the terminal, and a polyacrylate, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
실시예 3Example 3
삼중결합을 포함하고 말단에 EO-PO기를 갖는 제미니형 계면활성제, 및 푸마르산/아크릴레이트 공중합체를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a gemini-type surfactant including a triple bond and having an EO-PO group at the terminal, and a fumaric acid/acrylate copolymer, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
실시예 4Example 4
삼중결합을 포함하고 말단에 OSO3 -를 갖는 제미니형 계면활성제, 및 이소부틸아크릴레이트를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a gemini-type surfactant including a triple bond and having OSO 3 − at the terminal, and isobutyl acrylate, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
실시예 5Example 5
삼중결합을 포함하고 말단에 에틸렌옥사이드와 술폰기를 동시에 갖는 제미니형 계면활성제, 및 메타아크릴산/아크릴레이트 공중합체를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a gemini-type surfactant containing a triple bond and having both ethylene oxide and a sulfone group at the terminal, and a methacrylic acid/acrylate copolymer, the pH is adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition prepared.
실시예 6Example 6
이중결합을 포함하고 말단에 하이드록시기를 갖는 제미니형 계면활성제, 및 카르복실에틸 아크릴레이트 올리고머를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a gemini type surfactant including a double bond and having a hydroxyl group at the terminal, and a carboxylethyl acrylate oligomer, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
실시예 7Example 7
이중결합를 포함하고 말단에 에틸렌 옥사이드기를 갖는 제미니형 계면활성제, 및 메타아크릴산/아크릴레이트의 수용성 중합체를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다. A surface treatment composition was prepared by mixing a Gemini-type surfactant containing a double bond and having an ethylene oxide group at the terminal, and a water-soluble polymer of methacrylic acid/acrylate, and then adjusting the pH to 3 using citric acid or monoethanolamine .
실시예 8Example 8
이중결합를 포함하고 말단에 EO-PO기를 갖는 제미니형 계면활성제, 및 폴리아크릴레이트 수용성 중합체를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.A surface treatment composition was prepared by mixing a gemini-type surfactant including a double bond and having an EO-PO group at the terminal, and a polyacrylate water-soluble polymer, and then adjusting the pH to 3 using citric acid or monoethanolamine.
실시예 9Example 9
이중결합을 포함하고 말단에 OSO3 -를 갖는 제미니형 계면활성제, 및 푸마르산/아크릴레이트의 코폴리머를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.A surface treatment composition was prepared by mixing a Gemini-type surfactant containing a double bond and having OSO 3 − at the terminal, and a copolymer of fumaric acid/acrylate, and then adjusting the pH to 3 using citric acid or monoethanolamine. .
실시예 10Example 10
이중결합을 포함하고 말단에 에틸렌옥사이드와 술폰기를 동시에 갖는 제미니형 계면활성제, 및 아크릴산/아크릴레이트의 코폴리머를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a gemini-type surfactant containing a double bond and having both ethylene oxide and a sulfone group at the terminal, and a copolymer of acrylic acid/acrylate, the pH is adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition prepared.
비교예 1 Comparative Example 1
선형의 EO기를 갖는 비이온성 계면활성제, 및 폴리아크릴레이트를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing the nonionic surfactant having a linear EO group and polyacrylate, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
비교예 2Comparative Example 2
친수기로 EO/BO를 가진 선형의 계면활성제, 및 폴리아크릴레이트를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a linear surfactant having EO/BO as a hydrophilic group, and polyacrylate, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
비교예 3Comparative Example 3
친수기로 EO/BO를 가진 분지형의 계면활성제, 및 말레산/아크릴레이트의 코폴리머를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 3으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a branched surfactant having EO/BO as a hydrophilic group and a copolymer of maleic acid/acrylate, the pH was adjusted to 3 using citric acid or monoethanolamine to prepare a surface treatment composition.
비교예 4Comparative Example 4
친수기로 EO/BO를 가진 선형의 계면활성제, 및 카르복실에틸아크릴레이트 올리고머를 혼합한 후, 시트르산 또는 모노에탄올아민을 이용하여 pH를 10으로 조절하여 표면 처리 조성물을 제조하였다.After mixing a linear surfactant having EO/BO as a hydrophilic group, and a carboxylethyl acrylate oligomer, the pH was adjusted to 10 using citric acid or monoethanolamine to prepare a surface treatment composition.
[표면장력 측정] [Measurement of surface tension]
실시예 1의 조성물에 대해 표면장력을 다음과 같이 측정하였다. For the composition of Example 1, the surface tension was measured as follows.
(1) 농도에 따른 표면 장력(1) Surface tension as a function of concentration
분석조건: Analysis conditions:
온도 21 ℃습도 20 %, 니들 두께 (Neddle Thickness: 1.8 mm), 용매 상 (Solvent Phase: DI-water)Temperature 21 ℃ Humidity 20%, Needle Thickness: 1.8 mm, Solvent Phase: DI-water
상기 분석 조건에서 “Pendant drop method (based on Young-Laplace equation)”로 “DSA 100”장비를 이용하여 농도에 따른 표면장력을 측정하였다. 농도에 따른 정적표면장력 그래프 (Ciritical Micell Concentration 그래프)는 도 1에 나타내었다.Under the above analysis conditions, the surface tension according to the concentration was measured using the “DSA 100” equipment with the “Pendant drop method (based on Young-Laplace equation)”. The static surface tension graph (Ciritical Micell Concentration graph) according to the concentration is shown in FIG. 1 .
(2) 동적 표면장력(2) dynamic surface tension
분석 조건: Analysis conditions:
온도 23 ℃ 습도 20 %, 캐필러리 물질(Capillary Material, Polypropylene), 샘플 밀도 (Sample Density, 약 1.00 g/cu·cm) 및 “Start at Bubble Age. 10 ms, Stop at Bubble Age. 16,000 ms, Value. 1000 및 Immersion Depth. 10 mm”Temperature 23 ℃ Humidity 20%, Capillary Material (Polypropylene), Sample Density (approx. 1.00 g/cu cm) and “Start at Bubble Age. 10 ms, Stop at Bubble Age. 16,000 ms, Value. 1000 and Immersion Depth. 10mm”
상기 분석 조건에서 “Maximum bubble pressure method”및 “BP2”장비를 이용하여 동적 표면장력을 측정하였다. 동적 표면장력 그래프 (Ciritical Micell Concentration 그래프)는 도 2에 나타내었다. Dynamic surface tension was measured using the “Maximum bubble pressure method” and “BP2” equipment under the above analysis conditions. A dynamic surface tension graph (Ciritical Micell Concentration graph) is shown in FIG. 2 .
도 1의 농도에 따른 표면 장력에서 낮은 농도에서 계면활성제가 최대로 흡착하여 표면장력이 떨어지는 것을 확인할 수 있다. 즉, 본 발명에 의한 표면 처리 조성물은 제미니형 계면활성제의 낮은 농도에서도 효과적으로 표면장력을 낮출 수 있다. In the surface tension according to the concentration of FIG. 1 , it can be confirmed that the surfactant is maximally adsorbed at a low concentration, thereby decreasing the surface tension. That is, the surface treatment composition according to the present invention can effectively lower the surface tension even at a low concentration of the gemini type surfactant.
도 2의 동적표면장력 측정 결과에서 본 발명에 의한 표면 처리 조성물은, 제미니형 계면활성제를 사용함으로써 빠른 시간내에 표면에 흡착되어 표면장력을 빨리 감소시키는 것을 확인할 수 있다. 즉, 본 발명에 의한 표면 처리 조성물은, 단시간 내에 젖음(Wetting) 능력을 향상시켜 세정에 효과적으로 적용할 수 있다. From the dynamic surface tension measurement result of FIG. 2 , it can be confirmed that the surface treatment composition according to the present invention is adsorbed to the surface within a short time by using the gemini type surfactant, thereby rapidly reducing the surface tension. That is, the surface treatment composition according to the present invention can be effectively applied to cleaning by improving the wetting ability within a short time.
[결함 제거율 측정] [Measurement of defect removal rate]
연마입자가 100 nm의 직경을 가진 슬러리 (pH 2)를 이용하여 웨이퍼를 1 psi 압력, 200 ml로 20초 동안 CMP 연마를 수행하였다. 연마된 웨이퍼를 표 1에 따른 조성물에 30초간 연마 정반(플래튼) 상에서 웨이퍼를 표면처리하였다. 이후, 1 % 불산을 이용하여 10초 동안 세정하고, SC1 용액을 이용하여 30초 동안 세정하였다. 여기서, SC1 용액은 암모니아 과산화수소 혼합물(ammonia and hydrogen peroxide mixture; APM) (NH4OH : H2O2 : H2O)을 사용하였다.Using a slurry (pH 2) having abrasive particles having a diameter of 100 nm, the wafer was subjected to CMP polishing at 1 psi pressure and 200 ml for 20 seconds. The polished wafer was treated with a composition according to Table 1 on a polishing platen (platen) for 30 seconds. Thereafter, washing was performed for 10 seconds using 1% hydrofluoric acid, and then washed with SC1 solution for 30 seconds. Here, the SC1 solution was an ammonia and hydrogen peroxide mixture (APM) (NH 4 OH : H 2 O 2 : H 2 O) was used.
웨이퍼를 표면처리 또는 세정한 후 결함 측정 장비 (KLA-Tencor社)로 측정하여 결함을 확인하였다. 결합 제거율은 하기의 식을 이용하여 계산하였고, 그 결과는 표 1에 나타내었다. After the wafer was surface-treated or cleaned, defects were confirmed by measuring it with a defect measuring device (KLA-Tencor). The bond removal rate was calculated using the following formula, and the results are shown in Table 1.
결함 제거율(%) = {1-(본 조성물을 사용하여 표면처리한 후 결함 개수/결함 평가 기준 웨이퍼 결함 개수)} ×100Defect removal rate (%) = {1-(number of defects after surface treatment using the present composition/number of wafer defects based on defect evaluation)} × 100
[결함 평가 기준][Defect Evaluation Criteria]
별도의 표면처리는 진행하지 않고, 1 % 불산을 이용하여 10 초 동안 세정하고, SC1 용액을 이용하여 30 초 동안 세정한 후, 폴리실리콘 웨이퍼 및 실리콘 질화막 웨이퍼 각각에 대해 측정된 결함을 기준으로 하였다. 실리콘 질화막 웨이퍼의 결함(≥52 nm)은 1995개, 실리콘 산화막 웨이퍼의 결함(≥63 nm)은 938개, 폴리실리콘 웨이퍼의 결함(≥63 nm)은 24개로 나타났다.Separate surface treatment was not performed, and after cleaning for 10 seconds using 1% hydrofluoric acid and cleaning for 30 seconds using SC1 solution, the defects measured for each of the polysilicon wafer and silicon nitride wafer were based on . There were 1995 defects (≥52 nm) in silicon nitride wafers, 938 defects (≥63 nm) in silicon oxide wafers, and 24 defects (≥63 nm) in polysilicon wafers.
표 1에서 R1 내지 R4는 각각 수소 또는 메틸기이고, EO(옥시에틸렌기)이고 PO(옥시프로필렌기)이다. In Table 1, R 1 to R 4 are each hydrogen or a methyl group, EO (oxyethylene group) and PO (oxypropylene group).
실시예 1 내지 5의 계면활성제는 탄소-탄소 3중결합이고, 실시예 6 내지 10은 탄소-탄소 2중 결합이다. The surfactants of Examples 1 to 5 are carbon-carbon triple bonds, and Examples 6 to 10 are carbon-carbon double bonds.
EO/PO는 -(EO)m-(PO)n 공중합체이다. EO/PO is a -(EO) m -(PO) n copolymer.
EO/BO는 -(EO)m-(BO)n 공중합체이다.EO/BO is a -(EO) m -(BO) n copolymer.
(m 및 n은 각각 1 내지 100의 정수이다.)(m and n are each an integer from 1 to 100.)
표 1에서 본 발명에 의한 표면 처리 조성물은, 비교예에 비하여 실리콘 질화막, 실리콘 산화막 및 폴리 실리콘막 각각에서 결함 감소율이 우수하고, 특히 실리콘 질화막 및 실리콘 산화막에서의 결함 감소율이 80 % 이상이면서, 폴리실리콘막에서의 결합 감소율이 50% 이상인 것을 확인할 수 있다. 즉, 본 발명에 의한 표면 처리 조성물은, 제미니 형태의 계면활성제를 적용함으로서, 빠른 시간 내에 표면에 흡착되어 표면장력을 감소시키고, 단시간 내에 젖음 능력을 향상시켜 세정 효과를 증대시킬 수 있으므로, 표면 처리 이후에 웨피어의 후속 세정공정에서 결함을 제거할 수 있다. In Table 1, the surface treatment composition according to the present invention has an excellent defect reduction rate in each of the silicon nitride film, the silicon oxide film and the polysilicon film compared to the comparative example, and in particular, the defect reduction rate in the silicon nitride film and the silicon oxide film is 80% or more, It can be seen that the reduction rate of bonding in the silicon film is 50% or more. That is, the surface treatment composition according to the present invention can be adsorbed to the surface within a short time by applying the Gemini type surfactant to reduce the surface tension and improve the wetting ability within a short time to increase the cleaning effect, so the surface treatment Thereafter, defects can be removed in a subsequent cleaning process of the wafer.
이상과 같이 실시예들이 비록 한정된 실시예와 도면에 의해 설명되었으나, 해당 기술분야에서 통상의 지식을 가진 자라면 상기의 기재로부터 다양한 수정 및 변형이 가능하다. 예를 들어, 설명된 기술들이 설명된 방법과 다른 순서로 수행되거나, 및/또는 설명된 구성요소들이 설명된 방법과 다른 형태로 결합 또는 조합되거나, 다른 구성요소 또는 균등물에 의하여 대치되거나 치환되더라도 적절한 결과가 달성될 수 있다. 그러므로, 다른 구현들, 다른 실시예들 및 특허청구범위와 균등한 것들도 후술하는 특허청구범위의 범위에 속한다.As described above, although the embodiments have been described with reference to the limited embodiments and drawings, various modifications and variations are possible from the above description by those skilled in the art. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.
Claims (16)
pH 조절제
를 포함하고,
수용성 중합체를 더 포함하고,
상기 수용성 중합체는, 아크릴레이트 계열의 모노머, 폴리머, 코폴리머 및 이들의 염 중 적어도 어느 하나를 포함하는 것인, 표면처리 조성물:
[화학식 1]
[화학식 2]
(상기 화학식 1 및 화학식 2에서
R1 내지 R6은, 각각, 수소, 할로겐, 선형(Linear) 또는 분지형(Branched) 탄소수 1 내지 20의 알킬기, 하이드록시기(-OH), 탄소수 1 내지 5의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A (R' 및 R''는, 각각, 탄소수 1 내지 5의 옥시알킬렌기에서 선택되고, R' 및 R''는, 서로 상이하며, A는 음이온기이며, m 및 n은, 각각, 1 내지 100에서 선택된다.)에서 선택된다.)
a compound represented by the following formula (1), a compound represented by the following formula (2), or a gemini-type surfactant comprising both; and
pH adjuster
including,
Further comprising a water-soluble polymer,
The water-soluble polymer, a surface treatment composition comprising at least one of acrylate-based monomers, polymers, copolymers, and salts thereof:
[Formula 1]
[Formula 2]
(In Formula 1 and Formula 2,
R 1 to R 6 are, respectively, hydrogen, halogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a hydroxy group (-OH), an oxyalkylene group having 1 to 5 carbon atoms, -(R ')m-(R'')n copolymer, -OA, and -R'-A (R' and R'' are each selected from an oxyalkylene group having 1 to 5 carbon atoms, R' and R'' is different from each other, A is an anionic group, and m and n are each selected from 1 to 100.)
상기 화학식 1 및 상기 화학식 2에서
R1, R2, R3 및 R4는, 각각, 수소, 선형 또는 분지형 탄소수 1 내지 20의 알킬기에서 선택되고,
R5 및 R6은, 각각, 하이드록시기(-OH), 탄소수 1 내지 5의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A (R' 및 R''는, 각각, 탄소수 1 내지 5의 옥시알킬렌기에서 선택되고, R' 및 R''는, 서로 상이하며, A는, 술폰기, 황산기, 인산기 및 카르복실기에서 선택되고, m 및 n은, 각각, 1 내지 100에서 선택된다)에서 선택되는 것인,
표면처리 조성물.
According to claim 1,
In Formula 1 and Formula 2,
R 1 , R 2 , R 3 and R 4 are each selected from hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms,
R 5 and R 6 are, respectively, a hydroxyl group (-OH), an oxyalkylene group having 1 to 5 carbon atoms, -(R')m-(R'')n copolymer, -OA, and -R'- A (R' and R'' are each selected from an oxyalkylene group having 1 to 5 carbon atoms, R' and R'' are different from each other, and A is selected from a sulfone group, a sulfuric acid group, a phosphoric acid group, and a carboxyl group; , m and n are each selected from 1 to 100),
surface treatment composition.
상기 화학식 1 및 상기 화학식 2에서
R5 및 R6은, 각각, 탄소수 2 내지 4의 옥시알킬렌기, -(R')m-(R'')n 공중합체, -O-A, 및 -R'-A (R' 및 R''는 각각 탄소수 2 내지 4의 옥시알킬렌기에서 선택되고, A는 PO3 2-, SO3 -, COO- 및 CH3COO-에서 선택되고, m 및 n은, 각각, 1 내지 20에서 선택된다)에서 선택되는 것인,
표면처리 조성물.
According to claim 1,
In Formula 1 and Formula 2,
R 5 and R 6 are, respectively, an oxyalkylene group having 2 to 4 carbon atoms, -(R')m-(R'')n copolymer, -OA, and -R'-A (R' and R'' are each selected from an oxyalkylene group having 2 to 4 carbon atoms, A is selected from PO 3 2 - , SO 3 - , COO - and CH 3 COO - , m and n are each selected from 1 to 20) which is selected from
surface treatment composition.
상기 제미니형 계면활성제는, 상기 표면처리 조성물 중 0.001 중량% 내지 15 중량%인 것인,
표면처리 조성물.
According to claim 1,
The gemini-type surfactant is 0.001 wt% to 15 wt% of the surface treatment composition,
surface treatment composition.
상기 수용성 중합체는, 아크릴레이트(acrylate), 메틸 아크릴레이트(Methyl acrylate), 에틸 아크릴레이트(Ethyl acrylate), 프로필 아크릴레이트(Propyl acrylate), 이소프로필 아크릴레이트(Isopropyl acrylate), 부틸 아크릴레이트(Butyl acrylate), 이소부틸 아크릴레이트(Isobutyl acrylate), 펜틸 아크릴레이트(Pentyl acrylate), 이소펜틸 아크릴레이(Isopentyl acrylate), 헥실 아크릴레이트(Hexyl acrylate), 이소헥실 아크릴레이트(Isohexyl acrylate), 헵틸 아크릴레이트(Heptyl acrylate), 옥틸 아크릴레이트(Octyl acrylate), 이소옥틸 아크릴레이트(Isooctyl acrylate), 노닐 아크릴레이트(Nonyl acrylate), 라우릴 아크릴레이트(Lauryl acrylate), 카르복시에틸 아크릴레이트(Carboxyethyl acrylate), 카르복시에틸 아크릴레이트 올리고머(Carboxyethyl acrylate oligomers), (메타크릴로일옥시)에틸 말레이에이트((Methacryloyloxy)ethyl maleate), (메타크릴로일옥시)에틸 숙시네이트((Methacryloyloxy)ethyl succinate), 및 암모늄 아크릴레이트(Ammonium acrylate)로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 모노머 또는 폴리머를 포함하는 것인,
표면처리 조성물.
According to claim 1,
The water-soluble polymer is acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate ), Isobutyl acrylate, Pentyl acrylate, Isopentyl acrylate, Hexyl acrylate, Isohexyl acrylate, Heptyl acrylate), octyl acrylate, isooctyl acrylate, nonyl acrylate, lauryl acrylate, carboxyethyl acrylate, carboxyethyl acrylate Carboxyethyl acrylate oligomers, (Methacryloyloxy)ethyl maleate, (Methacryloyloxy)ethyl succinate), and Ammonium acrylate ) comprising a monomer or polymer comprising at least one selected from the group consisting of
surface treatment composition.
상기 수용성 중합체는, 말레산/아크릴레이트의 코폴리머(Copolymer of maleic acid/acrylate), 푸마르산/아크릴레이트의 코폴리머(Copolymer of fumaric acid/acrylate), 이타콘산/아크릴레이트의 코폴리머(Copolymer of itaconic acid/acrylate), 시트라콘산/아크릴레이트의 코폴리머(Copolymer of citraconic acid/acrylate), 아크릴산/아크릴레이트의 코폴리머(Copolymer of acrylic acid/acrylate), 메타아크릴산/아크릴레이트의 코폴리머(Copolymer of methacrylic acid/acrylate), 크로톤산/아크릴레이트의 코폴리머(Copolymer of crotonic acid/acrylate) 및 비닐아세트산/아크릴레이트의 코폴리머(Copolymer of vinylacetic acid/acrylate)로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 것인,
표면처리 조성물.
According to claim 1,
The water-soluble polymer is a copolymer of maleic acid/acrylate, a copolymer of fumaric acid/acrylate, and a copolymer of itaconic acid/acrylate. acid/acrylate), copolymer of citraconic acid/acrylate, copolymer of acrylic acid/acrylate, copolymer of methacrylic acid/acrylate At least one selected from the group consisting of methacrylic acid/acrylate), a copolymer of crotonic acid/acrylate, and a copolymer of vinylacetic acid/acrylate that is,
surface treatment composition.
상기 수용성 중합체는, 상기 표면처리 조성물 중 0.1 중량% 내지 20 중량%인 것인,
표면처리 조성물.
According to claim 1,
The water-soluble polymer is 0.1 wt% to 20 wt% of the surface treatment composition,
surface treatment composition.
상기 pH 조절제는, 유기산, 알킬아민 또는 이 둘을 포함하는 것인,
표면처리 조성물.
According to claim 1,
The pH adjusting agent, which comprises an organic acid, an alkylamine, or both,
surface treatment composition.
상기 유기산은, 1개의 카르복실기를 갖는 직쇄상의 포화 카르복실산, 포화 지방족 디카르복실산, 불포화 지방족 디카르복실산, 방향족 디카르복실산, 및 3개 이상의 카르복실기를 갖는 카르복실산으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,
상기 1개의 카르복실기를 갖는 직쇄상의 포화 카르복실산은, 포름산(formic acid), 아세트산(acetic acid), 프로피온산(propionic acid), 부티르산(butyric acid), 발레르산(valeric acid), 헥사노산(hexanoic acid), 헵타노산(heptanoic acid), 카프릴산(caprylic acid), 노나노산(nonanoic acid), 데카노산(decanoic acid), 운데실산(undecylenic acid), 라우릴산(lauric acid), 트리데실산(tridecylic acid), 미리스트산(myristic acid), 펜타데카노산(pentadecanoic acid) 및 팔미트산(palmitic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,
상기 포화 지방족 디카르복실산은, 옥살산(oxalic acid), 말론산(malonic acid), 숙신산(succinic acid), 글루타르산(glutaric acid), 아디프산(adipic acid), 피멜산(pimelic acid), 수베르산(suberic acid), 아젤라산(azelaic acid) 및 세바식산(sebacic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,
상기 불포화 지방족 디카르복실산은, 말레인산(maleic acid), 푸마르산(fumaric acid), 글루타콘산(glutaconic acid), 트라우마트산(traumatic acid) 및 무콘산(muconic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,
상기 방향족 디카르복실산은, 프탈산(phthalic acid), 이소프탈산(isophthalic acid) 및 테레프탈산(terephthalic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하고,
상기 3개 이상의 카르복실기를 갖는 카르복실산은, 시트르산(citric acid), 이소시트르산(isocitric acid), 아콘산(aconitic acid), 카르발릴산(carballylic acid), 트리베스산(tribasic acid) 및 멜리트산(mellitic acid)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 것인,
표면처리 조성물.
10. The method of claim 9,
The organic acid is a linear saturated carboxylic acid having one carboxyl group, a saturated aliphatic dicarboxylic acid, an unsaturated aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, and a carboxylic acid having three or more carboxyl groups. At least one selected from
The linear saturated carboxylic acid having one carboxyl group is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid ), heptanoic acid, caprylic acid, nonanoic acid, decanoic acid, undecylenic acid, lauric acid, tridecylic acid ( containing at least one selected from the group consisting of tridecylic acid, myristic acid, pentadecanoic acid, and palmitic acid,
The saturated aliphatic dicarboxylic acid is, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid (suberic acid), azelaic acid (azelaic acid) and at least one selected from the group consisting of sebacic acid (sebacic acid),
The unsaturated aliphatic dicarboxylic acid is at least one selected from the group consisting of maleic acid, fumaric acid, glutaconic acid, traumatic acid, and muconic acid. including,
The aromatic dicarboxylic acid includes at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid,
The carboxylic acid having three or more carboxyl groups is citric acid, isocitric acid, aconitic acid, carballylic acid, tribasic acid, and mellitic acid ( mellitic acid) comprising at least one selected from the group consisting of,
surface treatment composition.
상기 알킬아민은, 모노에탄올아민, 메틸에탄올아민, 메틸디에탄올아민, 에틸에탄올아민, 디에탄올아민, 디에틸에탄올아민, 트리에탄올아민, N-아미노-N-프로판올, 메틸아민, 디메틸아민, 트리메틸아민, 에틸아민, 디에틸아민, 트리에틸아민, 에틸렌디아민, 모노에탄올아민, N-(β-아미노에틸)에탄올아민, 헥사메틸렌디아민, 디에틸렌트리아민, 트리에틸렌테트라아민, 모노이소프로판올아민, 디이소프로판올아민, 트리이소프로판올아민 및 테트라에틸렌펜타민으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 것인,
표면처리 조성물.
10. The method of claim 9,
The alkylamine is monoethanolamine, methylethanolamine, methyldiethanolamine, ethylethanolamine, diethanolamine, diethylethanolamine, triethanolamine, N-amino-N-propanol, methylamine, dimethylamine, and trimethylamine. , ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, monoisopropanolamine, diisopropanol That comprising at least one selected from the group consisting of amines, triisopropanolamine and tetraethylenepentamine,
surface treatment composition.
상기 표면처리 조성물의 pH가 2 내지 7인 것인,
표면처리 조성물.
According to claim 1,
The pH of the surface treatment composition is 2 to 7,
surface treatment composition.
상기 표면처리 조성물은, 실리콘 질화막, 실리콘 산화막. 폴리실리콘막 및 실리콘막으로 이루어진 군에서 선택되는 적어도 어느 하나의 막을 포함하는 반도체 디바이스용 웨이퍼 표면의 결함, 잔류물 및 오염물을 제거하는 것인,
표면처리 조성물.
According to claim 1,
The surface treatment composition is a silicon nitride film, a silicon oxide film. To remove defects, residues and contaminants on the surface of a semiconductor device wafer including at least one film selected from the group consisting of a polysilicon film and a silicon film,
surface treatment composition.
상기 표면처리 조성물로 표면처리하였을 때, 실리콘 질화막, 실리콘 산화막. 폴리실리콘막 및 실리콘막 중 적어도 어느 하나의 막에 대한 결함 감소율이 50 % 이상인 것인,
표면처리 조성물.
14. The method of claim 13,
When the surface is treated with the surface treatment composition, a silicon nitride film, a silicon oxide film. The defect reduction rate for at least one of the polysilicon film and the silicon film is 50% or more,
surface treatment composition.
표면처리 방법.
The surface treatment of the semiconductor device wafer after chemical mechanical polishing of the semiconductor device wafer using the surface treatment composition of claim 1,
Surface treatment method.
상기 반도체 디바이스용 웨이퍼를 표면처리한 후에 불산 세정, SC1 세정 (NH4OH 및 H2O2 포함하는 세정 용액) 및 상용 세정액을 이용한 세정으로 이루어진 군에서 선택되는 적어도 어느 하나의 후속 세정공정을 수행하는 것인,
표면처리 방법.16. The method of claim 15,
After surface treatment of the semiconductor device wafer, at least one subsequent cleaning process selected from the group consisting of hydrofluoric acid cleaning, SC1 cleaning (a cleaning solution containing NH 4 OH and H 2 O 2 ) and cleaning using a commercial cleaning solution is performed that is,
Surface treatment method.
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