TWI781379B - 用來移除表面殘餘物的清洗調配物及使用其之方法 - Google Patents
用來移除表面殘餘物的清洗調配物及使用其之方法 Download PDFInfo
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- TWI781379B TWI781379B TW109107107A TW109107107A TWI781379B TW I781379 B TWI781379 B TW I781379B TW 109107107 A TW109107107 A TW 109107107A TW 109107107 A TW109107107 A TW 109107107A TW I781379 B TWI781379 B TW I781379B
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- Taiwan
- Prior art keywords
- weight
- acid
- composition
- group
- benzotriazole
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 141
- 238000004140 cleaning Methods 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 70
- 238000009472 formulation Methods 0.000 title description 19
- 239000000758 substrate Substances 0.000 claims abstract description 68
- 239000002738 chelating agent Substances 0.000 claims abstract description 61
- 239000004065 semiconductor Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 150000001298 alcohols Chemical class 0.000 claims abstract description 14
- 239000002265 redox agent Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000012964 benzotriazole Substances 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 9
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims abstract description 5
- -1 4-isopropylbenzotriazole Triazole Chemical compound 0.000 claims description 71
- 125000003118 aryl group Chemical group 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 150000001565 benzotriazoles Chemical class 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 238000004380 ashing Methods 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229920005646 polycarboxylate Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229960003330 pentetic acid Drugs 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
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 3
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical class C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-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
- SJBOEHIKNDEHHO-UHFFFAOYSA-N 2-[2-aminoethyl(carboxymethyl)amino]acetic acid Chemical compound NCCN(CC(O)=O)CC(O)=O SJBOEHIKNDEHHO-UHFFFAOYSA-N 0.000 claims description 2
- ZIMXAFGAUMQPMG-UHFFFAOYSA-N 2-[4-[bis(carboxymethyl)amino]butyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCCN(CC(O)=O)CC(O)=O ZIMXAFGAUMQPMG-UHFFFAOYSA-N 0.000 claims description 2
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 claims description 2
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 2
- PHFUGYFADPADDV-UHFFFAOYSA-N 4-(2-methylpropyl)-2h-benzotriazole Chemical compound CC(C)CC1=CC=CC2=NNN=C12 PHFUGYFADPADDV-UHFFFAOYSA-N 0.000 claims description 2
- DNJANJSHTMOQOV-UHFFFAOYSA-N 4-bromo-2h-benzotriazole Chemical compound BrC1=CC=CC2=C1N=NN2 DNJANJSHTMOQOV-UHFFFAOYSA-N 0.000 claims description 2
- IPIVUPVIFPKFTG-UHFFFAOYSA-N 4-butyl-2h-benzotriazole Chemical compound CCCCC1=CC=CC2=C1N=NN2 IPIVUPVIFPKFTG-UHFFFAOYSA-N 0.000 claims description 2
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 claims description 2
- ALDDXGSQUCGTDT-UHFFFAOYSA-N 4-fluoro-2h-benzotriazole Chemical compound FC1=CC=CC2=NNN=C12 ALDDXGSQUCGTDT-UHFFFAOYSA-N 0.000 claims description 2
- OKFSBQOGHYYGRZ-UHFFFAOYSA-N 4-hexyl-2h-benzotriazole Chemical compound CCCCCCC1=CC=CC2=C1N=NN2 OKFSBQOGHYYGRZ-UHFFFAOYSA-N 0.000 claims description 2
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical compound [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 claims description 2
- TVOIATIUZOHKFY-UHFFFAOYSA-N 4-pentyl-2h-benzotriazole Chemical compound CCCCCC1=CC=CC2=NNN=C12 TVOIATIUZOHKFY-UHFFFAOYSA-N 0.000 claims description 2
- VXDLXVDZTJOKAO-UHFFFAOYSA-N 4-propyl-2h-benzotriazole Chemical compound CCCC1=CC=CC2=C1N=NN2 VXDLXVDZTJOKAO-UHFFFAOYSA-N 0.000 claims description 2
- YQTFAYALFNXJFA-UHFFFAOYSA-N 5-(2,4-dimethylpentan-2-yl)-2H-benzotriazole Chemical compound CC(C)CC(C)(C)c1ccc2[nH]nnc2c1 YQTFAYALFNXJFA-UHFFFAOYSA-N 0.000 claims description 2
- JQSSWPIJSFUBKX-UHFFFAOYSA-N 5-(2-methylpropyl)-2h-benzotriazole Chemical compound C1=C(CC(C)C)C=CC2=NNN=C21 JQSSWPIJSFUBKX-UHFFFAOYSA-N 0.000 claims description 2
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 claims description 2
- BQCIJWPKDPZNHD-UHFFFAOYSA-N 5-bromo-2h-benzotriazole Chemical compound C1=C(Br)C=CC2=NNN=C21 BQCIJWPKDPZNHD-UHFFFAOYSA-N 0.000 claims description 2
- ZCFMGIGLXOKMJC-UHFFFAOYSA-N 5-butyl-2h-benzotriazole Chemical compound C1=C(CCCC)C=CC2=NNN=C21 ZCFMGIGLXOKMJC-UHFFFAOYSA-N 0.000 claims description 2
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 claims description 2
- ZWTWLIOPZJFEOO-UHFFFAOYSA-N 5-ethyl-2h-benzotriazole Chemical compound C1=C(CC)C=CC2=NNN=C21 ZWTWLIOPZJFEOO-UHFFFAOYSA-N 0.000 claims description 2
- SYGGDXKMRDPIKQ-UHFFFAOYSA-N 5-fluoro-2h-benzotriazole Chemical compound C1=C(F)C=CC2=NNN=C21 SYGGDXKMRDPIKQ-UHFFFAOYSA-N 0.000 claims description 2
- GAHAURRLKFPBCQ-UHFFFAOYSA-N 5-hexyl-2h-benzotriazole Chemical compound CCCCCCC1=CC=C2NN=NC2=C1 GAHAURRLKFPBCQ-UHFFFAOYSA-N 0.000 claims description 2
- SUPSFAUIWDRKKZ-UHFFFAOYSA-N 5-methoxy-2h-benzotriazole Chemical compound C1=C(OC)C=CC2=NNN=C21 SUPSFAUIWDRKKZ-UHFFFAOYSA-N 0.000 claims description 2
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 claims description 2
- CEKGSUMCMSBKNQ-UHFFFAOYSA-N 5-octyl-2h-benzotriazole Chemical compound C1=C(CCCCCCCC)C=CC2=NNN=C21 CEKGSUMCMSBKNQ-UHFFFAOYSA-N 0.000 claims description 2
- WXSBVEKBZGNSDY-UHFFFAOYSA-N 5-phenyl-2h-benzotriazole Chemical compound C1=CC=CC=C1C1=CC2=NNN=C2C=C1 WXSBVEKBZGNSDY-UHFFFAOYSA-N 0.000 claims description 2
- MBSXHYDCWYCSME-UHFFFAOYSA-N 5-propan-2-yl-2h-benzotriazole Chemical compound C1=C(C(C)C)C=CC2=NNN=C21 MBSXHYDCWYCSME-UHFFFAOYSA-N 0.000 claims description 2
- CCBSHAWEHIDTIU-UHFFFAOYSA-N 5-propyl-2h-benzotriazole Chemical compound CCCC1=CC=C2NN=NC2=C1 CCBSHAWEHIDTIU-UHFFFAOYSA-N 0.000 claims description 2
- JLGADKXBPJXIOQ-UHFFFAOYSA-N 5-tert-butyl-2h-benzotriazole Chemical compound C1=C(C(C)(C)C)C=CC2=NNN=C21 JLGADKXBPJXIOQ-UHFFFAOYSA-N 0.000 claims description 2
- MKBUQYWFFBCMFG-UHFFFAOYSA-N acetic acid propane-1,1-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CCC(N)N MKBUQYWFFBCMFG-UHFFFAOYSA-N 0.000 claims description 2
- HSANJBZMPJBTRT-UHFFFAOYSA-N acetic acid;1,4,7,10-tetrazacyclododecane Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.C1CNCCNCCNCCN1 HSANJBZMPJBTRT-UHFFFAOYSA-N 0.000 claims description 2
- JCXKHYLLVKZPKE-UHFFFAOYSA-N benzotriazol-1-amine Chemical compound C1=CC=C2N(N)N=NC2=C1 JCXKHYLLVKZPKE-UHFFFAOYSA-N 0.000 claims description 2
- ANHXKSXTBQIUAZ-UHFFFAOYSA-M benzyl(tributyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 ANHXKSXTBQIUAZ-UHFFFAOYSA-M 0.000 claims description 2
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 claims description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 2
- UVSNFZAOYHOOJO-UHFFFAOYSA-N chembl1343456 Chemical compound OC1=CC=C2N=NNC2=C1 UVSNFZAOYHOOJO-UHFFFAOYSA-N 0.000 claims description 2
- 229960003260 chlorhexidine Drugs 0.000 claims description 2
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- OKQVTLCUHATGDD-UHFFFAOYSA-N n-(benzotriazol-1-ylmethyl)-2-ethyl-n-(2-ethylhexyl)hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1 OKQVTLCUHATGDD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims 1
- QGCDUBGOXJTXIU-UHFFFAOYSA-N 3-(2h-benzotriazol-4-yl)propane-1,1-diol Chemical compound OC(O)CCC1=CC=CC2=NNN=C12 QGCDUBGOXJTXIU-UHFFFAOYSA-N 0.000 claims 1
- KBBWYWHFFVVLQK-UHFFFAOYSA-N 4-(4-methylphenyl)-2h-benzotriazole Chemical compound C1=CC(C)=CC=C1C1=CC=CC2=NNN=C12 KBBWYWHFFVVLQK-UHFFFAOYSA-N 0.000 claims 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 claims 1
- YZTYEGCWRPJWEE-UHFFFAOYSA-N 5-(benzotriazol-2-yl)pentan-1-amine Chemical compound C1=CC=CC2=NN(CCCCCN)N=C21 YZTYEGCWRPJWEE-UHFFFAOYSA-N 0.000 claims 1
- XUVUONUBXHYGCD-UHFFFAOYSA-N 6-chlorohexan-1-amine Chemical compound NCCCCCCCl XUVUONUBXHYGCD-UHFFFAOYSA-N 0.000 claims 1
- VPZZQWGLNIXULB-UHFFFAOYSA-N N1N=NC=C1.C(CCCC)C1=CC2=C(NN=N2)C=C1 Chemical compound N1N=NC=C1.C(CCCC)C1=CC2=C(NN=N2)C=C1 VPZZQWGLNIXULB-UHFFFAOYSA-N 0.000 claims 1
- 150000005215 alkyl ethers Chemical class 0.000 claims 1
- QVIOQZLYHBYECF-UHFFFAOYSA-M azanium diethyl(dimethyl)azanium dihydroxide Chemical compound [OH-].[NH4+].C(C)[N+](C)(C)CC.[OH-] QVIOQZLYHBYECF-UHFFFAOYSA-M 0.000 claims 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims 1
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- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 abstract description 16
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- 238000012360 testing method Methods 0.000 description 27
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- 230000000052 comparative effect Effects 0.000 description 15
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- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 12
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 12
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- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 9
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- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
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- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
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- ZHZCYWWNFQUZOR-UHFFFAOYSA-N pent-4-en-2-ol Chemical compound CC(O)CC=C ZHZCYWWNFQUZOR-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
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- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
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- NNNVXFKZMRGJPM-KHPPLWFESA-N sapienic acid Chemical compound CCCCCCCCC\C=C/CCCCC(O)=O NNNVXFKZMRGJPM-KHPPLWFESA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 description 1
- FDXKBUSUNHRUIZ-UHFFFAOYSA-M tetramethylazanium;chlorite Chemical compound [O-]Cl=O.C[N+](C)(C)C FDXKBUSUNHRUIZ-UHFFFAOYSA-M 0.000 description 1
- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- APIBROGXENTUGB-ZUQRMPMESA-M triphenyl-[(e)-3-phenylprop-2-enyl]phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C\C=C\C1=CC=CC=C1 APIBROGXENTUGB-ZUQRMPMESA-M 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- LXNOENXQFNYMGT-UHFFFAOYSA-N xi-5-Hydroxydodecanoic acid Chemical compound CCCCCCCC(O)CCCC(O)=O LXNOENXQFNYMGT-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
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Abstract
本揭露係有關於一種清洗組成物,其含有1)至少一氧化還原劑,2)至少一第一螯合劑,此第一螯合劑係一聚胺基聚羧酸,3)至少一第二螯合劑,其係不同於第一螯合劑,此第二螯合劑含有至少二個含氮基團,4)至少一金屬腐蝕抑制劑,此金屬腐蝕抑制劑係一經取代或未經取代之苯并三唑,5)至少一有機溶劑,其係選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚所組成之族群,6)水,及7)選擇性之至少一pH調整劑,此pH調整劑係無金屬離子之一鹼。本揭露亦係有關於一種使用上述組成物清洗半導體基材之方法。
Description
本申請案主張於2014年2月7日申請之美國臨時申請案序號第61/936,999號案,及於2013年12月6日申請之美國臨時申請案序號第61/912,697號案之優先權,此等案之內容在此被完整併入以供參考。
本揭露係有關於一種用於半導體基材之新穎清洗組成物及一種清洗半導體基材之方法。更特別地,本揭露係有關於一種用於在電漿蝕刻沉積於基材上之金屬層或介電材料層後移除形成於半導體基材上之電漿蝕刻殘餘物及於經由一電漿灰化方法移除大量阻劑後移除留於基材上之殘餘物之清洗組成物。
於製造積體電路裝置,光阻劑係作為一中間遮罩,其係用於藉由一系列之光微影術及電漿蝕刻步驟使一標線片之原始遮蔽圖案轉移至基材上。積體電路裝置製造方法之基本步驟之一係自晶圓基材移除圖案化之光阻劑膜。一般,此步驟係藉由二方法之一實行。
一方法包含一濕剝除步驟,其中,經光阻劑覆蓋之基材與主要由一有機溶劑及一胺組成之一光阻劑剝除劑溶液接觸。但是,剝除劑溶液不能完全及可靠地移除光阻劑膜,特別是若於製造期間光阻劑膜已曝露於紫外線輻射及電漿處理。一些光阻劑膜藉由此等處理變成高度交聯,且更難溶於剝除劑溶液中。此外,用於此等傳統濕剝除方法之化學品有時對於在以含鹵素之氣體電漿蝕刻金屬或氧化物層期間形成之無機或有機金屬殘餘材料之移除係無效。
移除光阻劑膜之一另外方法包含於一稱為電漿灰化之方法中使一經光阻劑塗覆之晶圓曝露於以氧為主之電漿以便使光阻劑膜自基材燃燒掉。但是,電漿灰化於移除如上所示之電漿蝕刻副產物亦不是有效。反而,移除此等電漿蝕刻副產物典型上係藉由其後使經處理之金屬及介電薄膜曝露於某些清洗溶液中而完成。
金屬基材一般係易腐蝕。例如,諸如鋁、銅、鋁銅合金、氮化鎢、鎢(W)、鈷(Co)、氧化鈦、其它金屬及金屬氮化物之基材會輕易腐蝕,且介電質[ILD,ULK]會藉由使用傳統清洗化學蝕刻。此外,積體電路裝置製造
商容忍之腐蝕量變得愈來愈小,因為此裝置之幾何形狀縮小。
同時,因為殘餘物變得更難以移除且腐蝕需控制於更低程度,清洗溶液需為使用安全且對環境友善。
因此,清洗溶液對於移除電漿蝕刻及電漿灰殘餘物需為有效,且亦需對於所有曝露之基材材料不具腐蝕性。
本揭露係有關於一種非腐蝕性清洗組成物,其可主要用於作為一多步驟製造方法中之一中間步驟而自一半導體基材移除殘餘物(例如,電漿蝕刻及/或電漿灰化殘餘物)。此等殘餘物包含一系列之相對較不可溶之諸如殘餘光阻劑、有機金屬化合物、金屬氧化物之有機化合物的混合物,其等係自曝露之諸如鋁、鋁/銅合金、銅、鈦、鉭、鎢、鈷之金屬,諸如氮化鈦及氮化鎢之金屬氮化物,及其它材料以反應副產物而形成。此處所述之清洗組成物的一優點係其可清洗一廣大範圍之所遭遇的殘餘物,且對於曝露之基材材料(例如,曝露之諸如鋁、鋁/銅合金、銅、鈦、鉭、鎢、鈷之金屬,及諸如氮化鈦及氮化鎢之金屬氮化物)一般係不具腐蝕性。
於一方面,本揭露特徵係一種清洗組成物,含有1)至少一氧化還原劑,2)至少一第一螯合劑,此第一螯合劑係一聚胺基聚羧酸,3)至少一第二螯合劑,其係不
同於第一螯合劑,此第二螯合劑含有至少二個含氮基團,4)至少一金屬腐蝕抑制劑,此金屬腐蝕抑制劑係一經取代或未經取代之苯并三唑,5)至少一有機溶劑,其係選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚所組成之族群,6)水,及7)選擇性之至少一pH調整劑,此pH調整劑係無金屬離子之一鹼。於某些實施例,清洗組成物之pH係於約6與約11之間(例如,約6與約9.5之間)。於某些實施例,清洗組成物係一均勻溶液。
例如,清洗組成物可含有:1)約0.5重量%至約20重量%之至少一氧化還原劑;2)約0.01重量%至約1重量%之至少一第一螯合劑;3)約0.01重量%至約1.8重量%之至少一第二螯合劑;;4)約0.05重量%至約1重量%之至少一金屬腐蝕抑制劑;5)約1重量%至約30重量%之至少一有機溶劑;6)約78%至約98%之水,及7)選擇性之至少一pH調整劑。
本揭露亦係有關於一種自一半導體基材清洗殘餘物之方法。此方法包含使含有蝕刻後殘餘物及/或灰化後殘餘物之一半導體基材與此處所述之一清洗組成物接觸。例如,此方法包含步驟:(A)提供含有蝕刻後及/或灰化後的殘餘物之一半導體基材;(B)使該半導體基材與此處所述之一清洗組成物接觸;(C)以一適合沖洗溶劑沖洗該半導體基材;及
(D)選擇性地藉由移除沖洗溶劑且不會連累該半導體基材完整性之任何手段乾燥該半導體基材。
如此處所定義,除其它註記外,表示之所有百分率應瞭解係相對於清洗組成物總重量之重量百分率。除其它註記外,環境溫度係定義為約攝氏16與約27度(℃)之間。
於此處定義時,一“水溶性”物質(例如,一水溶性之醇、酮、酯,或醚)係指於25℃之水中具有至少5重量%溶解度之一物質。
本揭露之一實施例係有關於一種非腐蝕性清洗組成物,包含:1)約0.5重量%至約20重量%之至少一氧化還原劑;2)約0.01重量%至約1重量%之至少一第一螯合劑;此第一螯合劑係一聚胺基聚羧酸;3)約0.01重量%至約1.8重量%之不同於至少一第一螯合劑之第二螯合劑,此第二螯合劑含有至少二個含氮基團,4)約0.05重量%至約1重量%之至少一金屬腐蝕抑制劑,其係選自由經取代及未經取代之苯并三唑類所組成之族群;5)約1重量%至約30重量%之至少一有機溶劑,其係選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚類所組成之族群;6)約78%至約98%之水,及
7)選擇性之至少一至少一pH調整劑,此pH調整劑係無金屬離子之一鹼,且使清洗組成物之pH調整至約6與約9.5之間。
本揭露之組成物含有至少一氧化還原劑,其助於溶解半導體表面上之殘餘物,諸如,光阻劑殘餘物金屬殘餘物,及金屬氧化物殘餘物。於此處使用時,術語“氧化還原劑”係指可於一半導體清洗方法中誘發氧化及還原之一化合物。一適合氧化還原劑之一例子係羥基胺。於某些實施例,氧化還原劑不含有過氧化物(例如,過氧化氫)。
於某些實施例,本揭露之組成物含有至少約0.5重量%(例如,至少約1重量%,至少約2重量%,至少約3重量%,或至少約5重量%)及/或至多約20重量%(例如,至多約17重量%,至多約15重量%,至多約12重量%,或至多約10重量%)之氧化還原劑。
本揭露之組成物含有至少一第一螯合劑,其可為一聚胺基聚羧酸。為了本揭露之目的,一聚胺基聚羧酸係指具有多數個胺基基團及多數個羧酸基團之一化合物。適合種類之聚胺基聚羧酸螯合劑不受限地包含單或聚伸烷基聚胺聚羧酸類、聚胺基烷聚羧酸類、聚胺基醇聚羧酸類,及羥基烷基醚聚胺聚羧酸類。
適合聚胺基聚羧酸螯合劑不受限地包含丁二胺四乙酸、二伸乙基三胺五乙酸(DTPA)、乙二胺四丙酸、三伸乙基四胺六乙酸、1,3-二胺基-2-羥基丙烷-N,N,N',N'-四乙酸、丙二胺四乙酸、乙二胺四乙酸
(EDTA)、反-1,2-二胺基環己烷四乙酸、乙二胺二乙酸、乙二胺二丙酸、1,6-六伸甲基-二胺-N,N,N',N'-四乙酸、N,N-雙(2-羥基苯甲基)乙二胺-N,N-二乙酸、二胺基丙烷四乙酸、1,4,7,10-四氮雜環十二烷-四乙酸、二胺基丙醇四乙酸,及(羥基乙基)乙二胺三乙酸。
於某些實施例,本揭露之組成物含有至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之聚胺基聚羧酸螯合劑。
一般,本揭露之組成物可含有至少一具有至少2個含氮基團(例如,具有螯合能力之含氮基團)之第二螯合劑。適合之含氮基團的例子包含一級胺基、二級胺基、咪唑基、三唑基、苯并三唑基、哌基、吡咯基、吡咯啶基、吡唑基、哌啶基、胍基、雙胍基、carbazatyl、醯肼基、半卡巴肼基,及胺基胍基。具有此等基團之任二或更多者之組合的化合物係被考慮。具有至少2個含氮基團之第二螯合劑可以本身化合物,或以其經中和之鹽添加。於某些實施例,第二螯合劑係選擇性地於本揭露之組成物中。
為了本揭露之目的,聚胺基聚羧酸係自第二螯合劑排除。換言之,第二螯合劑係不同於第一螯合劑。但是,於某些實施例,第二螯合劑可含有一或多個羧酸基團。
例如,第二螯合劑可為含有一個一級或二級
胺基基團及至少一另外的含氮鹼性基團之一單羧酸化合物。為了本揭露之目的,所需之一級或二級胺基基團不直接鍵結至另外的含氮鹼性基團(例如,NH2、H2NC(=X),或H2NNHC(=X),其中,X=O、S,或NR,R係H或C1-C4烷基)之部份。換言之,NH2NH-、H2NC(=X)NH-,或H2NNHC(=X)NH-不被認為係本揭露中之一級或二級胺基基團。因此,僅含有此一鹼性基團(例如,NH2NH-、H2NC(=X)NH-,或H2NNHC(=X)NH-)之一單羧酸不含有一個一級或二級胺基基團,因此係自本揭露中所述之含有一個一級或二級胺基基團及至少一另外的含氮衍生鹼性基團之單羧酸化合物排除。此等被排除之單羧酸類的例子包含胍基乙酸及4-胍基丁酸。
適合種類之含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之單羧酸化合物係含有一個一級或二級胺基基團及選自由下述所組成族群之下列含氮鹼性基團之至少一者的單羧酸化合物:咪唑基、三唑基、苯并三唑基、哌基、吡咯基、吡咯啶基、吡唑基、哌啶基、胍基、carbazatyl、醯肼基、半卡巴肼基、胺基胍基、一級胺基(例如,C1-C10一級胺基),及二級胺基(例如,C1-C10二級胺基)。此等基團可以例如較低烷基基團之取代基進一步取代,但二級胺基基團除外。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外之含氮鹼性基團之至少一單羧酸化合物係選自以一般性結構(I)描述之化合物:
(R3NH)C(R1)(R2)CO2H (I),其中,R1及R2之每一者獨立地係一氫原子、C1-C4烷基,或具有至少一含氮鹼性基團之一基團(例如,一C1-C10基團);且R3係一氫原子、C1-C10烷基,或具有至少一含氮鹼性基團之一基團(例如,一C1-C10基團);其中,R1、R2,及R3之至少一者係具有至少一含氮鹼性基團之一基團。
於某些實施例,R1可為具有至少一含氮鹼性基團之一基團,其中,具有至少一含氮鹼性基團之基團係以胺基、胍基或咪唑基取代且選擇性地以OH進一步取代之C1-C10烷基。於此等實施例,R2可為H或C1-C10烷基,且R3可為H、C1-C10烷基,或具有至少一含氮鹼性基團之一基團,其中,具有至少一含氮鹼性基團之基團係選擇性以胺基、胍基,或咪唑基取代且選擇性以OH進一步取代之C1-C10烷基。
於某些實施例,R3可為具有至少一今氮鹼基團之一基團,其中,具有至少一今氮鹼基團之基團係以胺基、胍基,或咪唑基取代且選擇性以OH進一步取代之C1-C10烷基。於此等實施例,R1及R2之每一者獨立地可為H或C1-C4烷基。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之至少一單羧酸化合物係選自以上述結構(I)描述之化合物,其中,R1係具有至少一含氮鹼性基團之一基團,且R2及R3之每一者係一氫原子。具有此結構之化合物的例子不受限地包含2,3-二
胺基丁酸、2,4-二胺基丁酸、鳥胺酸、2,3-二胺基丙酸、2,6-二胺基庚酸、4-甲基離胺酸、3-甲基離胺酸、5-羥基離胺酸、3-甲基-L-精胺酸、精胺酸、高精胺酸、N5-單甲基-L-精胺酸、N5-[亞胺基(甲基胺基)甲基]-D-鳥胺酸、刀豆胺酸,及組胺酸。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之至少一單羧酸化合物係係選自以上述結構(I)描述之化合物,其中,R1及R2之每一者係一氫原子,且R3係含有一具有至少一含氮鹼性基團之基團的一C1-C10基團。具有此結構之化合物的例子不受限地包含N-(2-胺基乙基)甘胺酸及N-(2-胺基丙基)甘胺酸。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之至少一單羧酸化合物係係選自以上述結構(I)描述之化合物,其中,R1係具有至少一含氮鹼性基團之一基團,R2係一氫原子,且R3係一C1-C10烷基基團。具有此結構之化合物的例子不受限地包含N2-甲基離胺酸,及N2-甲基-L-精胺酸。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之至少一單羧酸化合物係係選自以上述結構(I)描述之單羧酸化合物,其中,R1係具有至少一含氮鹼性基團之一基團,R2係一氫原子,且R3係具有至少一含氮鹼性基團之一基團。具有此結構之化合物的例子不受限地包含N2-(2-胺基乙基)-D-精胺
酸,及N2-(2-胺基乙基)-L-精胺酸。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之至少一單羧酸化合物係係選自以上述結構(I)描述之單羧酸化合物,其中,R1係一C1-C4烷基,R2係至少一含氮鹼性基團之一基團,且R3係一氫原子。具有此結構之化合物的例子不受限地包含2-甲基離胺酸及2-甲基-L-精胺酸。
於本揭露之某些實施例,含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之至少一單羧酸化合物係係選自具有其中所需之一級或二級胺基基團不與和羧基基團相同的碳鍵結之一結構之單羧酸化合物。具有此結構之化合物的例子不受限地包含3,4-二胺基丁酸及3-胺基-5-[(胺基亞胺基甲基)甲基胺基]戊酸。
於某些實施例,第二螯合劑可含有雙胍基團。例如,第二螯合劑可具有下列結構(II):
其中,R10、R11、R12,及R13係獨立地選自由氫、經取代或未經取代之芳基、經取代或未經取代之C3-C10環烷基,及經取代或未經取代之C1-C10線性或分支烷基所組成之族群;且R14係氫或與R13一起形成一咪唑環之一單鍵結;只要R10、R11、R12,及R13之至少一者係一芳基基團或含有
一芳基取代基,R10、R11、R12,及R13之至少二者係氫。於某些實施例,R11及R13係氫。於某些實施例,R13及R14係氫。
用於R10-R13之適合芳基基團的例子不受限地包含苯基、萘基,及蒽基。適合之取代基不受限地包含鹵素(例如,Cl、Br,或F)、C1-C10線性或分支烷基、C3-C10環烷基、C1-C10線性或分支烷氧基、C3-C10環烷氧基、硝基、SH、間二氧雜環戊烯基,及經取代或未經取代之苯基。
用於R10-R13之適合的經取代或未經取代之C3-C10環烷基之例子不受限地包含環丁基、環戊基、環己基、環庚基,及二環系統,諸如,降莰基及經完全氫化之萘。適合之取代基不受限地包含鹵素(例如,Cl、Br,或F)、C1-C10線性或分支烷基、C3-C10環烷基、鹵素(例如,Cl、Br,或F),及經取代或未經取代之苯基。
用於R10-R13之適合的經取代或未經取代之C1-C10線性或分支烷基之例子不受限地包含甲基、乙基、丙基、丁基、戊基、己基、辛基、異丙基、異丁基、第三丁基、辛基、1,1,2,2-四甲基丙基,及癸基。適合之取代基不受限地包含鹵素(例如,Cl、Br,或F)、C1-C10線性或分支烷氧基、C1-C10線性或分支氟烷氧基、C3-C10環烷氧基,及經取代或未經取代之芳基。
具有一經取代或未經取代之芳基的雙胍之例子不受限地包含1-苯基雙胍、1-(鄰-甲苯基)雙胍、1-(3-甲基苯基)雙胍、1-(4-甲基苯基)雙胍、1-(2-氯苯基)雙胍、
1-(4-氯苯基)雙胍、1-(2,3-二甲基苯基)雙胍、1-(2,6-二甲基苯基)雙胍、1-(1-萘基)雙胍、1-(4-甲氧基苯基)雙胍、1-(4-硝基苯基)雙胍、1,1-二苯基雙胍、1,5-二苯基雙胍、1,5-雙(4-氯苯基)雙胍、1,5-雙(3-氯苯基)雙胍、1-(4-氯)苯基-5-(4-甲氧基)苯基雙胍、1,1-雙(3-氯-4-甲氧基苯基)雙胍、1,5-雙(3,4-二氯苯基)雙胍、1,5-雙(3,5-二氯苯基)雙胍、1,5-雙(4-溴苯基)雙胍。
具有一經取代或未經取代之芳基基團及一經取代或未經取代之C1-C10線性或分支烷基基團之雙胍的例子不受限地包含1-苯基-1-甲基雙胍、1-(4-氯苯基)-5-(1-甲基乙基)雙胍(氯胍)、1-(3,4-二氯苯基)-5-(1-甲基乙基)雙胍、1-(4-甲基苯基)-5-辛基雙胍、1-(4-氯苯基)-2-(N'-丙-2-基脒基)胍、二甲苯基雙胍、二萘基雙胍,及二苯甲基雙胍。
具有一經取代或經取代之C1-C10線性或分支烷基之雙胍的例子不受限地包含4-氯二苯甲基雙胍、1-苯并[1,3]間二氧雜環戊烯-5-基甲基雙胍、1-苯甲基-5-(吡啶-3-基)甲基雙胍、1-苯甲基雙胍、4-氯苯甲基雙胍、1-(2-苯基乙基)雙胍、1-己基-5-苯甲基雙胍、1,1-二苯甲基雙胍、1,5-二苯甲基雙胍、1-(苯乙基)-5-丙基雙胍,及1,5-雙(苯乙基)雙胍。
具有一經取代或未經取代之C3-C10環烷基之雙胍的例子不受限地包含1-環己基-5-苯基雙胍、1-(4-苯基環己基)雙胍、1-(4-甲基)環己基-5-苯基雙胍,及1-
環戊基-5-(4-甲氧基苯基)雙胍、降莰基雙胍、二降莰基雙胍、金剛烷基雙胍、二金剛烷基雙胍、二環己基雙胍。
其中R14係與R13一起形成一咪唑烷之一單鍵結的結構(II)之例子不受限地包含2-胍基苯并咪唑、5-甲基-2-胍基苯并咪唑、4,6-二甲基-2-胍基苯并咪唑、5,6-二甲基-2-胍基苯并咪唑、5-氯-2-胍基苯并咪唑、4,5-二氯-2-胍基苯并咪唑、4,6-二氯-2-胍基苯并咪唑、5-溴-2-胍基苯并咪唑、5-苯基-2-胍基苯并咪唑,及5-甲氧基-2-胍基苯并咪唑。
於某些實施例,第二螯合劑含有多數個多數個雙胍基團。於某些實施例,第二螯合劑含有二個雙胍基團。此等第二螯合劑於此處稱為聯雙胍或二雙胍。於某些實施例,含有多數個雙胍基團之第二螯合劑係一聚合雙胍。被考慮之聚合雙胍包含其中雙胍部份係包含於此聚合物主鏈內之聚合物,與含有側雙胍部份之聚合物。
含有二個雙胍基團之第二螯合劑的一例子係具有結構(III)之一化合物:
其中,R20、R21、R22,及R23係獨立地選自由氫、經取代或未經取代之芳基、經取代或未經取代之C3-C10環烷基,及經取代或未經取代之C1-C10線性或分支烷基所組成之族
群;每一R24係獨立地選自由氫、經取代或未經取代之芳基、經取代或未經取代之苯基乙基,或經取代或未經取代之苯甲基烷基所組成之族群;且m係從1至10之整數,只要R20、R21、R22、R23及R24之至少一者係一芳基基團或含有一芳基取代基且R20、R21、R22,及R23之至少二者係氫。
具有結構(III)之聯雙胍的例子不受限地包含乙二雙胍、丙二雙胍、四伸甲基二雙胍、五伸甲基二雙胍、六伸甲基二雙胍、七伸甲基二雙胍、八伸甲基二雙胍、1,6-雙-(4-氯苯甲基二胍基)-己烷(氟己啶(R))、1,1'-六伸甲基雙(5-(對-氯苯基)雙胍)(氯己啶)、2-(苯甲氧基甲基)戊烷-1,5-雙(5-己基雙胍)、2-(苯硫基甲基)戊烷-1,5-雙(5-苯乙基雙胍)、3-(苯硫基)己基-1,6-雙(5-己基雙胍)、3-(苯硫基)己烷-1,6-雙(5-環己基雙胍)、3-(苯甲硫基)己烷-1,6-雙(5-己基雙胍,及3-(苯甲硫基)己烷-1,6-雙(5-環己基雙胍)。
於某些實施例,含有二個雙胍基團之第二螯合劑不受限地包含苯二雙胍、萘二雙胍、吡啶二雙胍、哌二雙胍、酞二雙胍、1,1'-[4-(十二烷氧基)-間-伸苯基]
聯雙胍、2-(癸硫基甲基)戊烷-1,5-雙(5-異丙基雙胍),及2-(癸硫基甲基)戊烷-1,5-雙(5,5-二乙基雙胍)。
於某些實施例,含有多數個雙胍基團之第二螯合劑係一聚合物雙胍。考慮作為此處所述組成物之一組份的例示聚合物雙胍具有結構(IV):
-其中,n係至少2之整數;每一R25獨立地係H或C1-C6烷基;且每一R26獨立地係選擇性經取代之C1-C20伸烷基(例如,C4-C10伸烷基)。
於此處使用時,“伸烷基”係指一個二價有機基團。二價伸烷基部份之例子不受限地包含-CH2-、-CH2CH2-、-CH2CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-等。於某些實施例,R26係-CH2CH2CH2CH2CH2CH2-。
於某些實施例,C1-C20伸烷基係選擇性經取代。適合取代基不受限地包含C1-C10線性或分支烷基、C3-C10環烷基、經取代或未經取代之苯基、C1-C10線性或分支烷氧基、C3-C10環烷氧基、硝基、羥基、SH、鹵素、胺基、間二氧雜環戊烯基、二胍基、氰基、羧基、酯、醯胺、醚、硫化物、二硫化物、亞碸,及碸。
於某些實施例,此處所述之伸烷基部份的至少一伸甲基單元係以諸如-O-、-NH-、-S-等之一雜原子替
代。
於某些實施例,n係從2至6000之整數。於某些實施例,n係從3至3000之整數。於某些實施例,n係從3至1000之整數。於某些實施例,n係從5至300之整數。於某些實施例,n係從5至50之整數。於某些實施例,n係從10至20之整數(例如,12或15)。
於某些實施例考慮作為此處所述組成物之組份的聚合物雙胍具有上述結構,其中,R25係H,R26係C6伸烷基,且n係12或15。
除了如上所示之聚合物雙胍外,帶有側雙胍部份之聚合物雙胍被考慮。此等實施例的例子不受限地包含經二胍基取代之α-烯烴單體的聚合產物,諸如,聚(乙烯基雙胍)、聚(N-乙烯基雙胍)、聚(烯丙基雙胍),此等之共聚物。需瞭解經二胍基取代之α-烯烴單體可與各種烯烴單體共聚合,使得每一聚合鏈的側二胍基部份的數量可廣泛改變。
此處揭露之雙胍與各種有機及無機酸類輕易形成鹽類。被考慮用於此處所述之組成物中之雙胍的無機酸鹽類不受限地包含氫氯酸、氫氟酸、氫溴酸、氫碘酸、膦酸、磷酸、磺酸、硫酸等。被考慮用於此處所述組成物中之雙胍的有機酸鹽類不受限地包含選擇性經取代之羧酸類,諸如,戊酸、己酸、辛酸、2-辛烯酸、十二酸、5-十二烯酸、十四酸、十五酸、十六酸、十八烯酸、十八酸、二十酸、十七酸、十六烯酸、蓖麻酸、12-羥基十八酸、
16-羥基十六酸、2-羥基己酸、12-羥基十二酸、5-羥基十二酸、5-羥基癸酸、4-羥基癸酸、十二烷二酸、十一烷二酸、癸二酸、苯甲酸、氫苯甲酸、對苯二酸等。
其它適合第二螯合劑之例子包含伸烷基二胺類,諸如,乙二胺、丙二胺、丁二胺、己二胺、二伸乙基三胺、三伸乙基四胺,及具有至少2個含氮基團之聚乙二亞胺。
於某些實施例,本揭露之組成物含有至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,至少約0.3重量%,或至少約0.4重量%)及/或至多約1.8重量%(例如,至多約1.5重量%,至多約1.3重量%,至多約1.1重量%,至多約1重量%,至多約0.8重量%,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之第二螯合劑。
本揭露之組成物含有至少一選自經取代或未經取代之苯并三唑的金屬腐蝕抑制劑。適合種類之經取代的苯并三唑不受限地包含以烷基基團、芳基基團、鹵素基團、胺基基團、硝基基團、烷氧基基團,及羥基基團取代之苯并三唑。經取代之苯并三唑亦包含以一或多個芳基(例如,苯基)或雜芳基基團稠合者。為了本揭露之目的,用語“經取代或未經取代之苯并三唑類”被定義係排除同時含有一羧基基團及一個一級或二級胺基基團二者之任何苯并三唑化合物。
作為一金屬腐蝕抑制劑之適合苯并三唑類
不受限地包含苯并三唑(BTA)、1-羥基苯并三唑、5-苯基硫醇-苯并三唑、5-氯苯并三唑、4-氯苯并三唑、5-溴苯并三唑、4-溴苯并三唑、5-氟苯并三唑、4-氟苯并三唑、萘并三唑、甲苯基三唑、5-苯基-苯并三唑、5-硝基苯并三唑、4-硝基苯并三唑、3-胺基-5-巰基-1,2,4-三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-苯并三唑、5-甲基-1H-苯并三唑、苯并三唑-5-羧酸、4-甲基苯并三唑、4-乙基苯并三唑、5-乙基苯并三唑、4-丙基苯并三唑、5-丙基苯并三唑、4-異丙基苯并三唑、5-異丙基苯并三唑、4-正丁基苯并三唑、5-正丁基苯并三唑、4-異丁基苯并三唑、5-異丁基苯并三唑、4-戊基苯并三唑、5-戊基苯并三唑、4-己基苯并三唑、5-己基苯并三唑、5-甲氧基苯并三唑、5-羥基苯并三唑、二羥基丙基苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]-苯并三唑、5-第三丁基苯并三唑、5-(1',1'-二甲基丙基)-苯并三唑、5-(1',1',3'-三甲基丁基)苯并三唑、5-正辛基苯并三唑,及5-(1',1',3',3'-四甲基丁基)苯并三唑。
於某些實施例,本揭露之組成物含有至少約0.05重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之金屬腐蝕抑制劑。
本揭露之組成物含有至少一選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚類(例如,二醇二醚類)所組成族群之有機溶劑。
水溶性醇類種類不受限地包含烷二醇類(不受限地包含伸烷基二醇類)、二醇類、烷氧基醇類(不受限地包含二醇單醚類)、飽和脂族單羥醇類、不飽和非芳香族單羥醇類,及含有一環結構之低分子量醇類。
水溶性烷二醇類之例子不受限地包含2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇、頻哪醇,及伸烷基二醇類。
水溶性伸烷基二醇類之例子不受限地包含乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇,及四乙二醇。
水溶性烷氧基醇類之例子不受限地包含3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇,及水溶性二醇單醚類。
水溶性二醇單醚類之例子不受限地包含乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單丁醚、1-甲氧基-2-丙醇、2-甲氧基-1-丙醇、1-乙氧基-2-丙醇、2-乙氧基-1-丙醇、丙二醇單正丙醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、三丙二醇單乙醚、三丙二醇單甲醚,及乙二醇單苯甲醚、二乙二醇單苯甲醚。
水溶性飽和脂族單羥醇類之例子不受限地
包含甲醇、乙醇、正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、第三丁醇、2-戊醇、第三戊醇,及1-己醇。
水溶性不飽和非芳香族單羥醇類之例子不受限地包含烯丙醇、炔丙醇、2-丁烯醇、3-丁烯醇,及4-戊烯-2-醇。
含有一環結構之水溶性低分子量醇類的例子不受限地包含四氫糠醇、糠醇,及1,3-環戊二醇。
水溶性酮類之例子不受限地包含丙酮、丙酮、環丁酮、環戊酮、環己酮、二丙酮醇、2-丁酮、5-己二酮、1,4-環己二酮、3-羥基丙乙酮、1,3-環己二酮,及環己酮。
水溶性酯類之例子不受限地包含乙酸乙酯、二醇單酯類,諸如,乙二醇單乙酸酯、二乙二醇單乙酸酯,及二醇單醚單酯類,諸如,丙二醇單甲醚乙酸酯、乙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、乙烯及二醇單乙醚乙酸酯。
於某些實施例,本揭露之組成物含有至少約1重量%(例如,至少約5重量%,至少約8重量%,或至少約10重量%)及/或至多約30重量%(例如,至多約25重量%,至多約20重量%,或至多約15重量%)之有機溶劑。
本揭露之清洗組成物進一步含有水。較佳地,水係經去離子及超純,不含有有機污染物,且具有約4至約17百萬歐姆(mega Ohm)之最小電阻。更佳地,水之電阻係至少17百萬歐姆。
於某些實施例,本揭露之組成物含有至少約78重量%(例如,至少約80重量%,至少約83重量%,或至少約85重量%)及/或至多約98重量%(例如,至多約95重量%,至多約93重量%,或至多約90重量%)之水。
本揭露之組成物選擇性地含有至少一pH調整劑,使pH控制於約6至約11之間。於某些實施例,本揭露之組成物可具有至少約6(例如,至少約6.5,至少約7,或至少約7.5)至至多約11(例如,至多約10,至多約9.5,至多約9,至多約8.5)之pH。雖不欲受理論限制,但相信具有高於11的pH之一清洗組成物使電漿蝕刻殘餘物清洗減至對於完全清洗係不能實施之程度,且低於6之pH會使W之蝕刻速率增至一不合需要之程度。有效之pH會依用於此處所述組成物中之成份的型式及量而改變。
所需pH調整劑(若有)的量可於其它組份之濃度於不同調配物改變時改變,特別是羥基胺、第一螯合劑聚胺基聚羧酸,及第二螯合劑(或其經中和化之鹽),及為使用之特定pH調整劑之分子量的函數。一般,pH調整劑濃度範圍係從約0.1%至約3%。於某些實施例,本揭露之清洗組成物含有至少約0.1重量%(例如,至少約0.5重量%,至少約1重量%,或至少約1.5重量%)及/或至多約3重量%(例如,至多約2.5重量%,至多約2重量%,或至多約1.5重量%)之pH調整劑。
一般,pH調整劑係無任何金屬離子(除了一微量之金屬離子雜質外)。適合之無金屬離子之pH調整劑
包含氫氧化銨、四級銨氫氧化物類、單胺類(包含醇胺類)、亞胺類(諸如,1,8-二氮雜二環[5.4.0]-7-十一烯,及1,5-二氮雜二環[4.3.0]-5-壬烯),及胍鹽類(諸如,碳酸胍)。
適合四級銨氫氧化物類之例子不受限地包含氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、二甲基二乙基氫氧化銨、膽鹼、四乙醇氫氧化銨、苯甲基三甲基氫氧化銨、苯甲基三乙基氫氧化銨,及苯甲基三丁基氫氧化銨。
適合單胺類之例子不受限地包含三乙胺、三丁胺、三戊胺、乙醇胺、二乙醇胺、二乙胺、丁胺、二丁胺,及苯甲胺。
於某些實施例,本揭露之非腐蝕性清洗組成物係含有下述,由下述所組成,或基本上由下述所述成:至少約0.5重量%(例如,至少約1重量%,至少約2重量%,至少約3重量%,或至少約5重量%)及/或至多約20重量%(例如,至多約17重量%,至多約15重量%,至多約12重量%,或至多約10重量%)之氧化還原劑;至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之第一螯合劑(即,一聚胺基聚羧酸);至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,至少約0.3重量%,或至少約0.4重量%)及/或至多約1.8重量%(例如,至多約1.5重量%,至多約1.3重量%,至多約1.1重量%,至多約1重量%,至
多約0.8重量%,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之第二螯合劑;至少約0.05重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之選自由經取代及未經取代之苯并三唑類的金屬腐蝕抑制劑;至少約1重量%(例如,至少約5重量%,至少約8重量%,或至少約10重量%)及/或至多約30重量%(例如,至多約25重量%,至多約20重量%,或至多約15重量%)之有機溶劑;至少約78重量%(例如,至少約80重量%,至少約83重量%,或至少約85重量%)及/或至多約98重量%(例如,至多約95重量%,至多約93重量%,或至多約90重量%)之水;及選擇性之約0.1%至約3%之一無金屬離子之pH調整劑;其中,此非腐蝕性清洗組成物之pH係從至少6(例如,至少約6.5,至少約7,或至少約7.5)至至多約11(例如,至多約10,至多約9.5,至多約9,至多約8.5)。
於某些實施例,本揭露之非腐蝕性清洗組成物係含有下述,由下述所組成,或基本上由下述所述成:至少約0.5重量%(例如,至少約1重量%,至少約2重量%,至少約3重量%,或至少約5重量%)及/或至多約20重量%(例如,至多約17重量%,至多約15重量%,至多約12重量%,或至多約10重量%)之羥基胺;至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多
約0.6重量%,或至多約0.5重量%)之第一螯合劑(即,一聚胺基聚羧酸);至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,至少約0.3重量%,或至少約0.4重量%)及/或至多約1.8重量%(例如,至多約1.5重量%,至多約1.3重量%,至多約1.1重量%,至多約1重量%,至多約0.8重量%,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之選自由具有至少二個選自由一級胺基、二級胺基、咪唑基、三唑基、苯并三唑基、哌基、吡咯基、吡咯啶基、吡唑基、哌啶基、胍基、二胍基、carbazatyl、醯肼基、半卡巴肼基,及胺基胍基所組成之族群的含氮基團之化合物所組成之族群的第二螯合劑;至少約0.05重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之選自由經取代及未經取代之苯并三唑類所組成之族群的金屬腐蝕抑制劑;至少約1重量%(例如,至少約5重量%,至少約8重量%,或至少約10重量%)及/或至多約30重量%(例如,至多約25重量%,至多約20重量%,或至多約15重量%)之選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚類所組成之族群的有機溶劑;至少約78重量%(例如,至少約80重量%,至少約83重量%,或至少約85重量%)及/或至多約98重量%(例如,至多約95重量%,至多約93重量%,或至多約90重量%)之水;及選擇性之約0.1%至約3%之一無金屬離子之pH調整劑;其中,非腐蝕性清洗組成物之pH
係從至少6(例如,至少約6.5,至少約7,或至少約7.5)至至多約11(例如,至多約10,至多約9.5,至多約9,至多約8.5)。
於某些實施例,本揭露之非腐蝕性清洗組成物係含有下述,由下述所組成,或基本上由下述所述成:至少約0.5重量%(例如,至少約1重量%,至少約2重量%,至少約3重量%,或至少約5重量%)及/或至多約20重量%(例如,至多約17重量%,至多約15重量%,至多約12重量%,或至多約10重量%)之羥基胺;至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之第一螯合劑(即,一聚胺基聚羧酸);至少約0.01重量%(例如,至少約0.1重量%,至少約0.2重量%,至少約0.3重量%,或至少約0.4重量%)及/或至多約1.8重量%(例如,至多約1.5重量%,至多約1.3重量%,至多約1.1重量%,至多約1重量%,至多約0.8重量%,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之選自由含有一個一級或二級胺基基團及至少一另外的含氮鹼性基團之一單羧酸化合物、具有化學式II之一雙胍化合物,及一具有多數個雙胍基團之化合物所組成之族群的第二螯合劑;至少約0.05重量%(例如,至少約0.1重量%,至少約0.2重量%,或至少約0.3重量%)及/或至多約1重量%(例如,至多約0.7重量%,至多約0.6重量%,或至多約0.5重量%)之選自由經取代及未經取代之苯并三唑
類所組成之族群的金屬腐蝕抑制劑;至少約1重量%(例如,至少約5重量%,至少約8重量%,或至少約10重量%)及/或至多約30重量%(例如,至多約25重量%,至多約20重量%,或至多約15重量%)之選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚類所組成之族群的有機溶劑;至少約78重量%(例如,至少約80重量%,至少約83重量%,或至少約85重量%)及/或至多約98重量%(例如,至多約95重量%,至多約93重量%,或至多約90重量%)之水;及選擇性之約0.1%至約3%之一無金屬離子之pH調整劑;其中,非腐蝕性清洗組成物之pH係從至少6(例如,至少約6.5,至少約7,或至少約7.5)至至多約11(例如,至多約10,至多約9.5,至多約9,至多約8.5)。
此外,於某些實施例,本揭露之清洗組成物可含有添加劑,諸如,另外之pH調整劑、另外之腐蝕抑制劑、界面活性劑、另外之有機溶劑、殺生物劑,及消泡劑作為選擇性之組份。
適合消泡劑之例子包含聚矽氧烷脫泡劑(例如,聚二甲基矽氧烷)、聚乙二醇甲醚聚合物、環氧乙烷/環氧丙烷共聚物,及經縮水甘油醚封蓋之乙炔二醇乙氧基化物(諸如,於美國專利第6,717,019號案中所述者,此案在此被併入以供參考)。
於某些實施例,本揭露之清洗組成物可特別排除以任何組合(若多於一種)之一或多種添加劑組份。此等組份係自由下所所組成之族群:氧清除劑、四級銨氫氧
化物類、胺類、鹼金屬及鹼土鹼類(諸如,NaOH、KOH、LiOH、氫氧化鎂,及氫氧化鈣)、除脫泡劑外之界面活性劑類、含氟化物之化合物、氧化劑類(例如,過氧化物類、過氧化氫、硝酸鐵、碘酸鉀、過錳酸鉀、硝酸、亞氯酸銨、氯酸銨、碘酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、四甲基亞氯酸銨、四甲基氯酸銨、四甲基碘酸銨、四甲基過硼酸銨、四甲基過氯酸銨、四甲基過碘酸銨、四甲基過硫酸銨、尿素過氧化氫,及過乙酸)、磨料類、矽酸鹽類、羥基羧酸類、無胺基基團之羧酸類及聚羧酸類、非唑之腐蝕抑制劑、胍、胍鹽類、無機酸類(例如,磺酸類、硫酸、亞硫酸、硝酸、亞硝酸、亞磷酸,及磷酸)、吡咯啶酮、聚乙烯基吡咯啶酮、金屬鹵化物類、具有化學式WzMXy之金屬鹵化物類,其中,W係選自H、一鹼金屬或鹼土金屬,及一無金屬離子之氫氧化物鹼部份;M係選自由Si、Ge、Sn、Pt、P、B、Au、Ir、Os、Cr、Ti、Zr、Rh、Ru及Sb所組成族群之一金屬;y係從4至6;且z係1、2,或3,及除於此揭露中所述者外之腐蝕抑制劑。
一般,本揭露之清洗組成物並非特別設計用以自半導體基材移除大量光阻劑膜。相反地,本揭露之清洗組成物一般係設計用以於藉由乾式或濕式剝除方法移除大量阻劑後移除所有殘餘物。因此,本揭露之清洗方法較佳係於一乾式或濕式光阻劑剝除方法後使用。此光阻劑剝除方法一般係藉由一圖案轉移方法進行,諸如,一蝕刻或移植方法,或其被進行以於圖案轉移前更正遮罩誤差。殘
餘物之化學成份會依進行清洗步驟之方法而定。
任何適合之乾式剝除方法可用以自半導體基材移除大量阻劑。適合乾式剝除方法之例子包含以氧為主之電漿灰化,諸如,氟/氧電漿或N2/H2電漿、臭氧氣相處理;氟電漿處理、熱H2氣體處理(諸如,於美國專利第5,691,117號案中所述者,其在此被完整併入以供參考)等。此外,熟習此項技藝者所知之任何傳統有機濕式剝除溶液可被用以自半導體基材移除大量阻劑。
與本揭露之清洗方法組合之一較佳剝除方法係一乾式剝除方法。較佳地,此乾式剝除方法係以氧為主之電漿灰化方法。此方法係藉由於高溫(典型上係250℃)於真空條件(即,1托耳)藉由施加一反應性氧氛圍自半導體基材移除大部份光阻劑。有機材料係藉由此方法氧化,且以處理氣體移除。但是,此方法並未自半導體基材移除無機或有機金屬污染物。其後以本揭露之清洗組成物清洗半導體基材對於移除此等殘餘物典型上係必需。
本揭露之一實施例係一種自半導體基材清洗殘餘物之方法,其包含使含有蝕刻後殘餘物及/或灰化後殘餘物之一半導體基材以此處所述之一清洗組成物接觸。此方法可進一步包含於接觸步驟後使半導體基材以一沖洗溶劑沖洗,及/或於沖洗步驟後乾燥此半導體基材。
於某些實施例,清洗方法包含步驟:(A)提供一半導體基材,其含有蝕刻後及/或灰化後之殘餘物;
(B)使該半導體基材與此處所述之一清洗組成物接觸;(C)以一適合沖洗溶劑沖洗該半導體基材;及(D)選擇性地藉由移除沖洗溶劑且不會連累該半導體基材的完整性之任何手段乾燥該半導體基材。
於某些實施例,清洗方法進一步包含自藉由上述方法獲得之半導體基材形成一半導體裝置(例如,一積體電路裝置,諸如,一半導體晶片)。
欲於此方法清洗之半導體基材可含有有機及有機金屬殘餘物,且另外地,含有一系列需被移除之金屬氧化物。半導體基材典型上係由矽、矽鍺、如GaAs之第III-V族化合物,或此等之任何組合所構成。半導體基材可另外含有露出之積體電路結構,諸如,互連結構(interconnect feature),如金屬線,及介電材料。用於互連結構之金屬及金屬合金不受限地包含鋁、與銅摻合之鋁、銅、鈦、鉭、鈷,及矽、氮化鈦、氮化鉭,及鎢。該半導體基材亦可含有層間介電物、氧化矽、氮化矽、碳化矽、氧化鈦,及以碳摻雜之氧化矽之層。
半導體基材可藉由任何適合方法與一清洗組成物接觸,諸如,使清洗組成物置於一槽內及使半導體基材沉浸及/或浸沒於清洗組成物內,使清洗組成物噴灑於半導體基材上,使清洗組成物蒸烘至半導體基材上,或此等之任何組合。較佳地,半導體基材係沉浸於清洗組成物內。
本揭露之清洗組成物可有效地用於最高達約90℃之溫度。較佳地,清洗組成物可於從約25℃至約80℃使用。更佳地,清洗組成物可用於從約30℃至約60℃之溫度範圍使用,且最佳係約40℃至約60℃之溫度範圍。
相似地,清洗時間可依使用之特定清洗方法及溫度於一廣範圍改變。當於一沉浸批式型式方法中清洗,一適合時間範圍係,例如,最高達約60分鐘。用於批式型式方法之一較佳範圍係從約1分鐘至約60分鐘。用於批式型式方法之一更佳時間範圍係從約3分鐘至約20分鐘。用於批式型式清洗方法之最佳時間範圍係從約4分鐘至約15分鐘。
用於單一晶圓方法之清洗時間範圍可為從約10秒至約5分鐘。用於單一晶圓方法之一較佳清洗時間範圍可為從約15秒至約4分鐘。用於單一晶圓方法之一更佳清洗時間範圍可為從約15秒至約3分鐘。用於單一晶圓方法之一最佳清洗時間範圍可為從約20秒至約2分鐘。
為進一步增進本揭露之清洗組成物之清洗能力,機械式攪拌手段可被使用。適合攪拌手段之例子包含清洗組成物於基材上循環.使清洗組成物蒸烘或噴灑於基材上,於清洗方法期間超音波或兆音波攪拌。半導體基材相對於地面之方向可為任何角度。水平或垂直方向係較佳。
本揭露之清洗組成物可用於熟習此項技藝者所知之傳統清洗工具中。本揭露之組成物的一顯著優點
係其等整體及部份含有相對較非毒性、非腐蝕性,及非反應性之組份,因此,此等組成物係適於廣範圍之溫度及處理時間。本揭露之組成物係與用於建構用於批式及單一晶圓清洗的現存及提議之半導體晶清洗方法工具的實質上所有材料係化學上相容。
清洗後,半導體基材以一適合沖洗溶劑沖洗約5秒至最高達約5分鐘,其係具有或不具有攪拌手段。適合沖洗溶劑之例子不受限地包含去離子(DI)水、甲醇、乙醇、異丙醇、N-甲基吡咯啶酮、γ-丁內酯、二甲基亞碸、乳酸乙酯,及丙二醇單甲醚乙酸酯。另外,具有pH>8之水性沖洗液(諸如,稀的水性氫氧化銨)可被使用。沖洗溶劑之較佳例子不受限地包含稀的水性氫氧化銨、去離子水、甲醇、乙醇,及異丙醇。更佳沖洗溶劑係稀的水性氫氧化銨、去離子水,及異丙醇。最佳沖洗溶劑係稀的水性氫氧化銨及去離子水。溶劑可使用與用於施用此處所述之清洗組成物者相似之手段施用。清洗組成物可於沖洗步驟開始前自半導體基材移除,或可於沖洗步驟開始時仍與半導體基材接觸。較佳地,沖洗步驟使用之溫度係16℃與27℃之間。
選擇性地,半導體基材於沖洗步驟後乾燥。此項技藝所知之任何適合乾燥段可被使用。適合乾燥手段之例子包含旋轉乾燥、使一乾燥氣體流過半導體基材,以一加熱裝置(諸如,一熱板或紅外線燈)加熱半導體基材、馬蘭葛尼式(Marangoni)乾燥、旋轉移動式(rotagoni)乾
燥、IPA乾燥,或此等之任何組合。乾燥時間會依使用之特定方法而定,但典型上係於30秒至最高達數分鐘之等級。
於某些實施例,使用此處所述之一清洗組成物製造積體電露之一方法可包含下列步驟。第一,一光阻劑層漆敷於一半導體基材。然後,因而獲得之半導體基材可進行一圖案轉移方法,諸如,一蝕刻或移植方法,形成一積體電路。然後,大量之光阻劑可藉由一乾式或濕式剝除方法(例如,一以氧為主之電漿灰化方法)移除。半導體基材上之留下的殘餘物可使用此處所述之一清洗組成物以上述方式移除。半導體基材其後被加工於基材上形成一或多個另外電路,或可藉由,例如,組合(例如,切割及結合)及封裝(例如,晶片密封)加工形成一半導體晶片。
本揭露參考下列範例作更詳細例示,此等範例係用於例示目的且不應被作為限制本揭露之範圍而闡釋。除非其它特定,列示之任何百分率係以重量(重量%)。除非它其註記,測試期間之控制式攪拌係以一1英吋攪拌棒以300rpm進行。
一般程序1
調配摻合
清洗組成物之樣品係藉由於攪拌時對計算量之超純去離子水(DIW)添加除了無金屬離子之pH調整劑外之清洗配製物的組份而製備。於一均勻溶液達成後,
若有使用時,添加選擇性之添加劑。組成物之調配藉由添加pH調整劑而完成。使溶液平衡,且若要的話,取得清洗組成物之pH。
若要的話,pH測量係於所有組份完全溶解後於環境溫度(17-25℃)進行。Beckman Coulter Φ 400系列之手持式計器可被用於此等pH測量。使用之所有組份係可購得且具高純度。
一般程序2
以燒杯測試之清洗評估
自一基材清洗PER(蝕刻後殘餘物)係以所述之清洗組成物使用已藉由微影術圖案化,於一電漿金屬蝕刻劑中蝕刻,及其後以氧電漿灰化完全移除上光阻劑層之具有光阻劑/TiOx/SiN/Co/ILD(ILD=層間介電物)或光阻劑/TiOx/SiN/W/ILD之一多層式基材進行。
測試片係使用4”長塑膠鎖鑷固定,因此,測試片其後可懸浮於含有約200毫升之本揭露的蝕刻組成物之一500毫升體積之玻璃燒杯。使測試片沉浸於蝕刻組成物內之前,組成物預熱至合意之測試條件溫度(如註記般,典型上係40℃或60℃)並且控制式攪拌。然後,清洗測試藉由以測試片之含有PER層之一側面向攪拌棒之方式,使藉由塑膠鑷固定之測試片置於經加熱之組成物內而實行。測試片於蝕刻組成物中保持靜止一段時間(典型上係2至5分鐘),同時組成物係於控制式攪拌下保持於測試溫度。當合意之清洗時間完全時,測試片自蝕刻快速移除,且置於
以約400毫升之於環境溫度(~17℃)的去離子水填充之一500毫升塑膠燒杯內,並且溫和攪拌。測試片於具去離子水之燒杯內約30秒,然後,快速移除,且於環溫溫度之一去離子水流下沖洗約30秒。測試片立即曝露於來自一手持式吹氮氣槍之一氮氣流,此造成測試片表面上之任何滴液自測試片吹走,且進一步,使測試片裝置表面完全乾燥。此最終氮氣乾燥步驟後,測試片自塑膠鑷固定器移除,且置於一經覆蓋之塑膠載具內,且使此裝置側向上,以供短期貯存不大於約2小時。然後,經清洗之測試片裝置表面之主要結構(key feature)之掃瞄式電子顯微術(SEM)影像被收集。
一般程序3
以燒杯測試之材料相容性評估
於矽基材上之覆蓋Co、矽基材上之W、於矽基材上之SiO2上之TiOx、於矽基材上之SiN、於矽基材上之ILD被切割成約1英吋x 1英吋之方形測試片,以供材料相容性測試。測試片被起始測量厚度或片電阻,對於金屬膜(Co、W)係藉由4點探針,CDE Resmap 273,或對於介電膜(TiOx、SiN及ILD)係藉由橢圓偏光術且用一Woollam M-2000X。然後,測試片安裝於4”長之塑膠鎖鑷上,且以一般程序3中之清洗程序所述般處理,且測試片之含有Co、W、TiOx、SiN,或ILD層之側係面向攪拌棒,持續10分鐘。
最終氮氣乾燥步驟後,測試片自塑膠鑷固定
器移除,且置於一經覆蓋之塑膠載具內。然後,後厚度或片電阻於加工後測試片表面上收集,對於金屬膜(Co及W)係使用4-點探針,CDE Resmap 273,或對於介電膜(TiOx、SiN及ILD)係藉由橢圓偏光術且使用一Woollam M-2000X。
調配範例FE-1-FE-5與比較調配例CFE-1-CFE-4
表1含有藉由一般程序1製備之調配物FE-1-FE-5與比較調配物CFE-1-CFE-4。
範例1-5與比較例CE1-CE4
清洗劑與露出金屬之相容性
調配例FE-1-FE-5與比較調配例CFE-1-CFE-4係依據一般程序2測試清洗及依據一般程序3測試材料相容性,其係於65℃持續4分鐘。Co、W、TiOx、SiN、SiC、TEOS(四乙基-正矽酸鹽),及ILD於清洗組成物中之蝕刻速率(埃/分鐘)係顯示於表2。
表2中之數據顯示本揭露之調配物(即,FE-1-FE-5)清洗蝕刻後殘餘物且不會顯著蝕刻典型上於半導體裝置中發現之半導體材料(諸如,Co、W、TiOx、SiN、SiC、TEOS,及ILD)。另一方面,具有高於9.5之pH的比較調配物CFE-1及CFE-2形成差的清洗。此外,不具有第二螯合劑之比較調配物CFE-3於被測試之半導體基
材展現顯著蝕刻掉鎢。相似地,含有過氧化氫以替代羥基胺之比較調配物CFE-4於半導體基材中亦展現顯著蝕刻掉鎢。
調配範例FE-6-FE-13與比較調配例CFE-5及CFE-6
表3詳述調配物FE-6-FE-13與比較調配物CFE-5及CFE-6,其等係藉由一般程序1製備。
範例6-13與比較例CE-5及CE-6
清洗劑與露出金屬之相容性
調配範例FE-6-FE-13與比較調配例CFE-5及CFE-6係依據一般程序2測試清洗能力及依據一般程序3測試材料相容性,其係於65℃持續4分鐘。清洗組成物之Co、W、TiOx、SiN、SiC,及ILD(若可用)蝕刻速率(埃/分鐘)係顯示於表4。
表4中之所有調配物顯示優異清洗能力。但是,比較調配物CFE-5(無雙胍)及CFE-6(二烷基雙胍)顯示不可接受高之W蝕刻速率。調配範例FE-6-FE13顯示顯著減少之W蝕刻速率,同時對於其它材料維持可接受之蝕刻速率且具有優異清洗。
範例14-17與比較例CE-7及CE-8;
清洗劑與露出金屬之相容性
調配範例FE-14至FE-17與比較調配例CFE-7及CFE-8係依據一般程序2測試清洗能力,及依據一般程序3測試材料相容性,其係於65℃持續4分鐘。表陳述此等清洗組成物。表5中所述之“Pol-BG”係指聚六伸甲基雙胍,氫氯酸鹽(見如下之結構,n=12)。
此等清洗組成物之Co、W、TiOx、SiN、SiC,及ILD(若
可用)蝕刻速率(埃/分鐘)係顯示於表6中。
表6中之所有調配物顯示優異清洗能力。但是,比較調配物CFE-7及CFE-8顯示不可接受高之W蝕刻
速率。調配範例FE-14至FE17顯示顯著減少之W蝕刻速率,同時對其它材料維持可接受之蝕刻速率且具有優異清洗。
調配範例18-38
為對本揭露之組成物進一步詳細說明,另外之清洗組成物係描述於表7中。表7中之“第二螯合劑7係指具有結構(IV)之聚合物雙胍(即,如下之聚合物1-8)或含有側雙胍基團之聚合物雙胍(即,如下之聚合物9-12)。特別地,聚合物1-8係具有結構(IV)者,其中,n、R25及R26係如下定義。
Claims (24)
- 一種清洗組成物,其包含:1)至少一氧化還原劑;2)至少一第一螯合劑,該第一螯合劑係一聚胺基聚羧酸;3)至少一金屬腐蝕抑制劑,該金屬腐蝕抑制劑係一經取代或未經取代之苯并三唑;4)至少一有機溶劑,其係選自由水溶性醇類、水溶性酮類、水溶性酯類,及水溶性醚類所組成之族群;5)至少一四級銨氫氧化物;及6)水。
- 如請求項1之組成物,其中,該組成物之pH係約6與約11之間。
- 如請求項1之組成物,其中,該至少一氧化還原劑包含羥基胺。
- 如請求項1之組成物,其中,該至少一氧化還原劑係佔該組成物之約0.5重量%至約20重量。
- 如請求項1之組成物,其中,該聚胺基聚羧酸係選自由單或聚伸烷基聚胺聚羧酸類、聚胺基烷聚羧酸類、聚胺基醇聚羧酸類,及羥基烷基醚聚胺聚羧酸類所組成之族群。
- 如請求項1之組成物,其中,該聚胺基聚羧酸係選自由丁二胺四乙酸、二伸乙基三胺五乙酸、乙二胺四丙酸、三伸乙基四胺六乙酸、1,3-二胺基-2-羥基丙 烷-N,N,N',N'-四乙酸、丙二胺四乙酸、乙二胺四乙酸、反-1,2-二胺基環己烷四乙酸、乙二胺二乙酸、乙二胺二丙酸、1,6-六伸甲基-二胺-N,N,N',N'-四乙酸、N,N-雙(2-羥基苯甲基)乙二胺-N,N-二乙酸、二胺基丙烷四乙酸、1,4,7,10-四氮雜環十二烷-四乙酸、二胺基丙醇四乙酸,及(羥基乙基)乙二胺三乙酸所組成之族群。
- 如請求項1之組成物,其中,該至少一第一螯合劑包含二伸乙基三胺五乙酸。
- 如請求項1之組成物,其中,該至少一第一螯合劑係佔該組成物之約0.01重量%至約1重量%。
- 如請求項1之組成物,其中,該至少一金屬腐蝕抑制劑包含選擇性以選自由烷基基團、芳基基團、鹵素基團、胺基基團、硝基基團、烷氧基基團,及羥基基團所組成之族群的至少一取代基取代之苯并三唑。
- 如請求項1之組成物,其中,該至少一金屬腐蝕抑制劑係選自由苯并三唑、1-羥基苯并三唑、5-苯基硫醇-苯并三唑、5-氯苯并三唑、4-氯苯并三唑、5-溴苯并三唑、4-溴苯并三唑、5-氟苯并三唑、4-氟苯并三唑、萘并三唑、甲苯基三唑、5-苯基-苯并三唑、5-硝基苯并三唑、4-硝基苯并三唑、3-胺基-5-巰基-1,2,4-三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-苯并三唑、5-甲基-1H-苯并三唑、苯并三唑-5-羧酸、4-甲基苯并三唑、4-乙基苯并三唑、5-乙基苯并三唑、4-丙基苯并三唑、5-丙基苯并三唑、4-異丙基苯并三唑、5-異丙基苯并三唑、4-正丁基 苯并三唑、5-正丁基苯并三唑、4-異丁基苯并三唑、5-異丁基苯并三唑、4-戊基苯并三唑、5-戊基苯并三唑、4-己基苯并三唑、5-己基苯并三唑、5-甲氧基苯并三唑、5-羥基苯并三唑、二羥基丙基苯并三唑、1-[N,N-雙(2-乙基己基)胺基甲基]-苯并三唑、5-第三丁基苯并三唑、5-(1',1'-二甲基丙基)-苯并三唑、5-(1',1',3'-三甲基丁基)苯并三唑、5-正辛基苯并三唑,及5-(1',1',3',3'-四甲基丁基)苯并三唑所組成之族群。
- 如請求項1之組成物,其中,該至少一金屬腐蝕抑制劑包含5-甲基-1H-苯并三唑。
- 如請求項1之組成物,其中,該至少一金屬腐蝕抑制劑係佔該組成物之約0.05重量%至約1重量%。
- 如請求項1之組成物,其中,該至少一四級銨氫氧化物包含氫氧化四甲銨、氫氧化四乙銨、氫氧化四丙銨、氫氧化四丁銨、二甲基二乙基氫氧化銨、膽鹼、四乙醇氫氧化銨、苯甲基三甲基氫氧化銨、苯甲基三乙基氫氧化銨,或苯甲基三丁基氫氧化銨。
- 如請求項1之組成物,其中,該至少一四級銨氫氧化物包含氫氧化四乙銨或氫氧化四丁銨。
- 如請求項1之組成物,其中,該至少一四級銨氫氧化物係佔該組成物之約0.1重量%至約3重量%。
- 如請求項1之組成物,其中,該至少一 有機溶劑係佔該組成物之約1重量%至約30重量%。
- 如請求項1之組成物,其中,該水係佔該組成物之約78重量%至約98重量%。
- 一種清洗方法,其包含:使含有蝕刻後殘餘物及/或灰化後殘餘物之一半導體基材與如請求項1之清洗組成物接觸。
- 一種組成物,其包含羥基胺、二伸乙基三胺五乙酸、氯己啶鹽、5-甲基-1H-苯并三唑、氫氧化四丁銨、乙二醇丁醚,及水。
- 如請求項19之組成物,其中,該組成物包含:約0.5至20重量%之羥基胺;約0.01至1重量%之二伸乙基三胺五乙酸;約0.01至1.8重量%之氯己啶鹽;約0.05至1重量%之5-甲基-1H-苯并三唑;約0.1至3重量%之氫氧化四丁銨;約1至30重量%之乙二醇丁醚;及約78至98重量%之水。
- 如請求項1之組成物,其進一步包含不同於該第一螯合劑之至少一第二螯合劑,該第二螯合劑包含至少二個含氮基團。
- 如請求項21之組成物,其中,該至少一第二螯合劑包含氯己啶或其鹽。
- 如請求項21之組成物,其中,該至少一第二螯合劑係佔該組成物之約0.01重量%至約1.8重量%。
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