CN105264117B - 用于铜后化学机械平坦化的含水清洗组合物 - Google Patents
用于铜后化学机械平坦化的含水清洗组合物 Download PDFInfo
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- CN105264117B CN105264117B CN201480028326.3A CN201480028326A CN105264117B CN 105264117 B CN105264117 B CN 105264117B CN 201480028326 A CN201480028326 A CN 201480028326A CN 105264117 B CN105264117 B CN 105264117B
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- cleaning composition
- acid
- aqueous cleaning
- copper
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- 238000004140 cleaning Methods 0.000 title claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000000126 substance Substances 0.000 title claims abstract description 20
- 239000013110 organic ligand Substances 0.000 claims abstract description 35
- 150000007530 organic bases Chemical class 0.000 claims abstract description 24
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 methylene phosphonic acid Chemical compound 0.000 claims description 27
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- 239000004094 surface-active agent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007046 ethoxylation reaction Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000003009 phosphonic acids Chemical class 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical group OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical compound OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 3
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001231 choline Drugs 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- 229940031098 ethanolamine Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- LUKNLVTZDZMBOU-UHFFFAOYSA-N n-ethoxymethanamine Chemical compound CCONC LUKNLVTZDZMBOU-UHFFFAOYSA-N 0.000 claims description 3
- 229960003330 pentetic acid Drugs 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 2
- ZMRFRBHYXOQLDK-UHFFFAOYSA-N 2-phenylethanethiol Chemical compound SCCC1=CC=CC=C1 ZMRFRBHYXOQLDK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- NLBSQHGCGGFVJW-UHFFFAOYSA-N 2-carboxyethylphosphonic acid Chemical class OC(=O)CCP(O)(O)=O NLBSQHGCGGFVJW-UHFFFAOYSA-N 0.000 claims 1
- LJASZMIARXGOCH-UHFFFAOYSA-N 2-phosphanylethanamine Chemical compound NCCP LJASZMIARXGOCH-UHFFFAOYSA-N 0.000 claims 1
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical group CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 8
- 230000003746 surface roughness Effects 0.000 abstract description 6
- 238000011109 contamination Methods 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 230000008569 process Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 2
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000004690 coupled electron pair approximation Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- WGIAYBNWTYECJD-UHFFFAOYSA-N 1-ethoxypiperazine Chemical compound CCON1CCNCC1 WGIAYBNWTYECJD-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 1
- UTCHNZLBVKHYKC-UHFFFAOYSA-N 2-hydroxy-2-phosphonoacetic acid Chemical compound OC(=O)C(O)P(O)(O)=O UTCHNZLBVKHYKC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- WTBIAPVQQBCLFP-UHFFFAOYSA-N N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O Chemical compound N.N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O WTBIAPVQQBCLFP-UHFFFAOYSA-N 0.000 description 1
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- UZMAPBJVXOGOFT-UHFFFAOYSA-N Syringetin Natural products COC1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UZMAPBJVXOGOFT-UHFFFAOYSA-N 0.000 description 1
- 239000007997 Tricine buffer Substances 0.000 description 1
- SHPBBNULESVQRH-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[Zr+4] Chemical compound [O-2].[O-2].[Ti+4].[Zr+4] SHPBBNULESVQRH-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
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- KCFYHBSOLOXZIF-UHFFFAOYSA-N dihydrochrysin Natural products COC1=C(O)C(OC)=CC(C2OC3=CC(O)=CC(O)=C3C(=O)C2)=C1 KCFYHBSOLOXZIF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
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- 229960005102 foscarnet Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 238000001465 metallisation Methods 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical compound OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 description 1
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- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Classifications
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Abstract
提供用于铜后化学机械平坦化的含水清洗组合物。所述组合物包含有机碱、铜蚀刻剂、有机配体、腐蚀抑制剂、及水，其中该有机碱的浓度为至少200ppm，该铜蚀刻剂的浓度为至少200ppm，该有机配体的浓度为至少50ppm，且该腐蚀抑制剂的浓度为至少10ppm。当用于铜后化学机械平坦化清洗程序时，所述含水清洗组合物可有效地从晶片表面去除残余污染物和降低晶片表面上的缺陷数，同时赋予晶片以更好的表面粗糙度。
Description
技术领域
本发明涉及含水清洗组合物，特别是用于集成电路工艺中的铜后化学机械平坦化(CMP)(post copper chemical mechanical planarization)的含水清洗组合物。
背景技术
较新的半导体器件具有较小的线宽和较高的集成密度。然而，当最小线宽窄于0.25μm或更小时，金属线的电阻以及电介质寄生电容的RC延迟已使器件的运行(运算)速度减慢。为了改善器件的运行速度，铜线已使用低于0.13μm的高阶工艺代替常规的铝-铜合金线；该工艺由此称为“铜工艺”。
化学机械平坦化(CMP)将研磨剂颗粒例如二氧化硅、氧化铝、二氧化铈、或二氧化锆与化学助剂例如pH缓冲剂或氧化剂在研磨溶液中组合，以抛光表面材料。不平坦的表面的较高区域将处于较高的压力下且因此将以较高的移除速率抛光。同时，不均匀的表面的较低区域将处于较低的压力下且因此将以较低的移除速率抛光。实现全域性平坦化。将CMP技术应用于铜线工艺可解决由于蚀刻铜的困难所致的在晶片上限定图案的问题，而且可在研磨后形成具有全域性平坦性的平面，这有助于多层线结构化工艺。
在CMP工艺期间，研磨溶液内的细的研磨剂颗粒和化学助剂以及由研磨晶片所产生的切屑可附着到晶片表面上。在晶片的研磨之后产生的通常的污染物为金属离子、有机化合物、或研磨剂颗粒。如果没有有效的清洗程序来去除所述污染物，则后续工艺被妨碍并且器件的产率和可靠度将降低。因此，在CMP工艺之后的清洗程序已成为可否将CMP工艺成功地应用于半导体工艺领域的关键。
用于铜工艺的研磨溶液经常使用苯并三唑(简称BTA)或其衍生物作为腐蚀抑制剂。在铜工艺的研磨之后所产生的污染物之中，最难去除BTA有机残留物。主要原因是BTA有机残留物通过化学吸附键合至铜线。常规地，仅利用物理方式例如静电斥力、超声处理、和PVA刷洗去除BTA，不过不是成功地去除BTA。
此外，在CMP工艺之后，经常使用氨的水溶液、柠檬酸的水溶液和/或含氟化合物清洗金属间介电层(inter-metal dielectric layer)和W塞。然而，氨的水溶液不均匀地侵蚀铜表面，因此导致粗糙化。另外，柠檬酸的水溶液对铜具有差的溶解力且因此具有较低的污染物去除率。含氟化合物例如氢氟酸不仅使铜表面粗糙化，而且由于有害的化学品，处置起来是昂贵的。因此，以上清洗溶液不适合用于清洗具有铜线的晶片。
已提出用含N化合物的溶液来代替清洗组合物中的氨。Naghshineh等人的US 6,492,308公开了用于含铜的集成电路的清洗溶液，其包括C1-C10氢氧化季铵、极性有机胺和腐蚀抑制剂，其中该极性有机胺可选自单乙醇胺。Kolic等人的US2009/0162537 A1公开了用于清洗具有铜和介电镶嵌金属化层的基材的方法，其包括使用具有一种或多种胺例如醇胺的清洗溶液，其中至少一种胺可向该清洗溶液提供7至13的pH。Chen等人的US8,063,006公开了用于清洗集成电路工艺中的后CMP铜晶片的含水清洗组合物，其包含含N杂环有机碱、醇胺、和水。然而，现有技术中的由清洗组合物导致的在晶片表面上的粗糙度需要改善。尤其是对于具有铜线的晶片，难以控制胺对金属的蚀刻、减少在研磨晶片之后产生的污染物、以及降低晶片表面上具有不同组分的区域上的总缺陷数。
此外，随着半导体晶片工艺的发展，金属线的宽度已变窄到14nm，使得平坦化更加困难。例如，具有nm宽度的线的晶片的表面在所述工艺之后可为更粗糙的，且在线宽窄化之后铜线晶片的开/短路测试(open/short test)和可靠度测试的结果变差。因此，开发对于去除铜线晶片表面上的残留污染物和降低表面缺陷数比现有技术更有效的清洗组合物是重要的。
本发明通过提供用于铜后化学机械平坦化的含水清洗组合物而针对以上需求，所述用于铜后化学机械平坦化的含水清洗组合物可有效地去除残留污染物且降低晶片表面上的缺陷数，同时赋予晶片以较好的表面粗糙度。
发明内容
本发明的目的是提供用于铜后化学机械平坦化(post-Cu CMP)的含水清洗组合物，其包含有机碱、铜蚀刻剂、有机配体、腐蚀抑制剂、以及水，其中，该腐蚀抑制剂为酰肼化合物；该有机碱的浓度为至少200ppm；该铜蚀刻剂的浓度为至少200ppm；该有机配体的浓度为至少50ppm；且该腐蚀抑制剂的浓度为至少约10ppm。任选地，该含水清洗组合物可进一步包含络合剂和表面活性剂。
为了进一步说明本发明的目的、技术特征及优点，将根据若干实施方式详细地描述本发明。
实施方式
下文中，将详细地描述本发明的一些实施方式；然而，在不背离本发明的精神的情况下，本发明可以多种实施方式体现，且不应限于本说明书中描述的实施方式。此外，除非另外说明，本发明的说明书中(尤其是权利要求中)的表述“一种(个)(a)”和“该(所述)”等应包括单数及复数形式两者。
本发明人进行了研究且发现，在铜后CMP清洗程序中将有机碱、铜蚀刻剂、有机配体、和腐蚀抑制剂(酰肼化合物)组合可获得合乎需要的污染物去除率，有效地降低晶片表面上的缺陷数，并赋予晶片以较好的表面粗糙度。
因此，本发明提供含水清洗组合物，其包含有机碱、铜蚀刻剂、有机配体、腐蚀抑制剂以及水，其中该有机碱的浓度为200ppm至12,000ppm，该铜蚀刻剂的浓度为200ppm至10,000ppm，该有机配体的浓度为50ppm至10,000ppm，且该腐蚀抑制剂的浓度为10ppm至5,000ppm。
在不受理论限制的情况下，通常认为在本发明的清洗组合物中，所使用的有机碱可调整该清洗组合物的碱度，确保CMP工艺中所用的研磨剂颗粒与晶片表面保持有效的负的静电斥力，因此也移除研磨剂颗粒。而且，有机碱可提供轻微的金属蚀刻效果。此外，对于铜工艺，有机碱未遭受如当使用氨时所遇到的粗糙的铜表面。通常，有用的有机碱为季铵。季铵的例子可选自：氢氧化四甲基铵(TMAH)、氢氧化四乙基铵(TEAH)、氢氧化四丙基铵(TPAH)、氢氧化四丁基铵(TBAH)、氢氧化三(2-羟乙基)甲基铵(THEMAH)、氢氧化十六烷基三甲基铵(CTAH)、胆碱、及其组合，但不限于此。在以下实施例(working examples)中，举例说明的有机碱为TMAH、TEAH、THEMAH、CTAH、及胆碱。
在本发明的含水清洗组合物的实际使用中，有机碱的浓度通常为200ppm至12,000ppm，且优选400ppm至6,000ppm，以提供调整组合物的碱度的效果。然而，为了降低制造、运输及储存成本，含水清洗组合物的制造商经常将该组合物作为浓缩溶液提供。使用者可将该浓缩溶液稀释至期望的浓度。因此，本发明的含水清洗组合物可以浓缩形式提供，且在使用前稀释至期望的浓度。因此，本发明的含水清洗组合中的有机碱的浓度为至少200ppm，且优选至少400ppm。
本发明的含水清洗组合物还使用铜蚀刻剂，其经常可为含N化合物例如杂环胺、醇胺。在不受理论限制的情况下，认为当使用杂环胺时，该杂环胺的杂环中的氮原子的未共用电子对可与金属原子(如铜)形成配位共价键，因此，不仅提供所期望的移除研磨剂颗粒的效果，而且防止已脱离金属线的有机污染物再次化学吸附。此外，当使用醇胺时，其还均匀地蚀刻金属表面，使得经蚀刻的金属线的表面粗糙度未恶化。用于本发明中的铜蚀刻剂的例子可选自：哌嗪、1-(2-氨乙基)哌嗪、1-(2-羟乙基)哌嗪、2-(1-哌嗪基)乙醇、2-(1-哌嗪基)乙胺、2-(2-氨基乙氧基)乙醇、2-(2-氨乙基氨基)乙醇、2-氨基-1-丁醇、2-氨基-1-丙醇、2-氨基乙醇、2-二甲氨基乙醇、2-(N-甲氨基)乙醇、3-氨基-1-丙醇、乙醇胺、二乙醇胺、三乙醇胺、二亚乙基三胺、二异丙醇胺、异丙醇胺、N-甲基二乙醇胺、N-甲基乙醇胺、二甘醇胺(DGA)、N-二(羟乙基)甘氨酸、N-(三(羟甲基)甲基)甘氨酸(tricine)、三(羟甲基)氨基甲烷(Tris)、及其组合，但不限于此。在以下实施例中，举例说明的铜蚀刻剂可选自哌嗪、2-(2-氨基乙氧基)乙醇、2-氨基-1-丁醇、2-氨基-1-丙醇、3-氨基-1-丙醇、乙醇胺、二乙醇胺、三乙醇胺、二亚乙基三胺、N-甲基乙醇胺、N-二(羟乙基)甘氨酸、和Tris。
在实际使用中的本发明的含水清洗组合物中的铜蚀刻剂的浓度通常为200ppm至10,000ppm，优选300ppm至5,000ppm。如上所述，本发明的含水清洗组合物可以浓缩形式提供，且在使用之前稀释至期望的浓度。因此，本发明的含水清洗组合物中包含的铜蚀刻剂的浓度为至少200ppm，优选至少300ppm。
另外，本发明的清洗组合物还包含有机配体。本文中的“有机配体”是指可化学吸附或结合CMP工艺之后在晶片上的残留物例如BTA的有机物质。在不受理论限制的情况下，通常认为有机配体可提高有机物质例如BTA的饱和溶解度，并改善清洗效果。适合用于本发明的清洗组合物的有机配体的例子经常包括膦酸、羧酸、及其组合。该膦酸的例子可选自：二亚乙基三胺五(亚甲基膦酸)(DTPMP)、2-膦酰基丁烷-1,2,4-三羧酸(PBTCA)、六亚甲基二胺四(亚甲基膦酸)(HDTMP)、2-羟基膦酰基乙酸(HPAA)、2-羧基乙基膦酸(CEPA)、次膦酰基羧酸聚合物(phosphino carboxylic acid polymer，PCA)、多氨基多醚亚甲基膦酸(PAPEMP)、2-氨基乙基膦酸(AEPn)、N-(膦酰基甲基)亚氨基二乙酸(PMIDA)、氨基三(亚甲基膦酸)(ATMP)、及其组合，但不限于此。该羧酸的例子可选自：甘氨酸、氨基磺酸、二亚乙基三胺五乙酸(DTPA)、柠檬酸、L-半胱氨酸、乙醇酸、乙醛酸、及其组合，但不限于此。
在实际使用中，本发明的含水清洗组合物中包含的有机配体的浓度通常为50ppm至10,000ppm，优选100ppm至5,000ppm。如上所述，本发明的含水清洗组合物可以浓缩形式提供，且在使用之前稀释至期望的浓度。因此，本发明的含水清洗组合物中的有机配体的浓度为至少50ppm，优选至少100ppm。
在本发明的组合物中有用的另一组分为腐蚀抑制剂，即具有N-N共价键且四个取代基的至少一个取代基为酰基的酰肼化合物。通常，酰肼化合物具有下式：
其中，
R2和R3独立地为氢；
R1和R4独立地为氢、-NHNH2、-C(O)NHNH2、C1-C8烷基、C1-C8烷氧基、-(CH2)nCN、-(CH2)nC(O)NHNH2、-(CH2)nC(O)O(CH2)n、-NHNHC6H5、-(CH2)nC6H5、-C6H5、-C10H7，其中-C6H5与-C10H7为未取代的或独立地被选自卤素、羟基、氨基、-NO2、C1-C4烷基和C1-C4烷氧基的一个或多个取代基取代，且n为1至3。优选地，R1为H或-NHNH2，且R4为H。根据本发明的一些实施方式，使用碳酰肼作为本发明的组合物中的腐蚀抑制剂。
在不受理论限制的情况下，通常认为选自酰肼化合物的腐蚀抑制剂可保护晶片表面上的金属层且防止金属层溶解于清洗溶液中，因此，有助于降低晶片表面上的缺陷数并维持较好的粗糙度。
在实际使用中，本发明的含水清洗组合物中包含的酰肼化合物的浓度通常为10ppm至5,000ppm，优选50ppm至2,500ppm。如上所述，本发明的含水清洗组合物可以浓缩形式提供，且在使用之前稀释至期望的浓度。因此，本发明的含水清洗组合物中包含的酰肼化合物的浓度为至少10ppm，优选至少50ppm。
除有机碱、铜蚀刻剂、有机配体、以及腐蚀抑制剂之外，本发明的清洗组合物可任选地进一步包含表面活性剂。
在不受理论限制的情况下，通常认为表面活性剂可在清洗期间提供晶片表面的充分润湿。用于本发明的组合物中的表面活性剂为由式H(OCH2CH2)nSR5表示的乙氧基化硫醇，其中R5为烃基且n为1至100。“烃基”可为例如，但不限于，烷基、烯基、炔基、环烷基、芳基、芳烷基以及烷芳基；前述基团可为支链的、直链的、取代或未取代的。在上式中，R5优选为C1-C30烷基、C2-C30烯基、C2-C30炔基、C3-C30环烷基、C5-C30芳基、C6-C30芳烷基、或C6-C30烷芳基，且n优选为4至20。更优选地，R5为C6-C18烷基、或C6-C18芳烷基，且n为4至12。
适合用于本发明的清洗组合物的表面活性剂的例子可选自：乙氧基化叔十二烷基硫醇、乙氧基化正十二烷基硫醇、乙氧基化2-苯基乙基硫醇、及其组合，但不限于此。适合用于本发明的组合物的表面活性剂的市售产品为例如来自Shibley Chemicals(Elyria,OH)的Alcodet 260、Alcodet SK以及Alcodet 218。在以下实施例中，举例说明的表面活性剂为Alcodet 218。实际使用中的包含于本发明的含水清洗组合物中的表面活性剂的浓度通常为50ppm至3,000ppm，优选100ppm至1,000ppm。
此外，本发明的含水清洗组合物的pH值优选高于9，更优选高于10。
本发明的清洗组合物可在室温下使用。例如，将本发明的清洗组合物与铜半导体晶片接触一段对于去除晶片表面上的污染物且维持铜线的合乎需要的表面粗糙度是有效的时间。通常，当使用的浓度较低时，需要较长的接触时间(1至3分钟)，且当使用的浓度较高时，需要较短的接触时间(短于1分钟)。在实际使用时，使用者可根据需要调整时间。
在本发明的含水清洗组合物的实际使用中，可在CMP机台上使用本发明的清洗组合物以清洗经平坦化的晶片表面，且可在独立的清洗机台上使用本发明的清洗组合物以清洗经平坦化的晶片表面。
以下实施例进一步说明本发明，且不意图限制本发明的范围。可由本领域技术人员容易地实现的任何变型和改变被覆盖在本发明范围内。
实施例
表1中所列的有机配体主要可购自山东泰和水处理有限公司(Shandong TaiheWater Treatment Co.,Ltd)(中国)，且其它化学品可以高于99％的纯度购自Sigma-Aldrich、Alfa Aesar、MERCK、Showa Chemical、Tokyo Chemical Industry(TCI)。
表1
| 缩写 | 化学品 | 分类 |
| TMAH | 氢氧化四甲基铵 | 有机碱 |
| THEMAH | 氢氧化三(2-羟乙基)甲基铵 | 有机碱 |
| TEAH | 氢氧化四乙基铵 | 有机碱 |
| CTAH | 氢氧化十六烷基三甲基铵 | 有机碱 |
| Tris | 三(羟甲基)氨基甲烷 | 铜蚀刻剂 |
| DTPMP | 二亚乙基三胺五(亚甲基膦酸) | 有机配体 |
| PMIDA | N-(膦酰基甲基)亚氨基二乙酸 | 有机配体 |
| PAPEMP | 多氨基多醚亚甲基膦酸 | 有机配体 |
| ATMP | 氨基三(亚甲基膦酸) | 有机配体 |
| PCA | 次膦酰基羧酸聚合物 | 有机配体 |
| HEDP | 1-羟基亚乙基-1,1-二膦酸 | 有机配体 |
| EDTMPA | 亚乙基二胺四(亚甲基膦酸) | 有机配体 |
| TDTMP | 四亚甲基二胺四(亚甲基膦酸) | 有机配体 |
| HDTMP | 六亚甲基二胺四(亚甲基膦酸) | 有机配体 |
| HPAA | 2-羟基膦酰基羧酸 | 有机配体 |
| CEPA | 2-羧基乙基膦酸 | 有机配体 |
| PBTCA | 2-膦酰基丁烷-1,2,4-三羧酸 | 有机配体 |
| AEPn | 2-氨基乙基膦酸 | 有机配体 |
| EDTA | 亚乙基二胺四乙酸 | 有机配体 |
| DTPA | 二亚乙基三胺五乙酸 | 有机配体 |
| EDDS | 亚乙基二胺-N,N'-二丁二酸 | 有机配体 |
表面活性剂Alcodet 218由Rhodia(美国)提供，其组成为乙氧基化十二烷基硫醇(CAS.No.：9004-83-5)。
根据表2中所列的组分和量制备清洗组合物。在实施例中，使用的空白(毯覆式，blanket)铜晶片购自SKW Associates,Inc.(美国)，具有1.5μm厚的铜膜。空白TEOS晶片购自SVTC Technologies,L.L.C.(美国)，具有1.0μm厚的膜。
使用由Cabot Microelectronics Coporation(美国)生产的C8908铜研磨浆料将空白铜晶片抛光20秒，然后使用由Cabot Microelectronics Coporation(美国)生产的B7601阻挡物浆料抛光60秒，以将铜膜移除0.2μm的厚度。然后，将经研磨溶液污染的空白铜晶片置于Entrepix,Inc.(美国)的OnTrak清洗机台上，并使用下表中所列的组合物进行清洗。使用由Cabot Microelectronics Coporation(美国)生产的B7601阻挡物浆料将空白TEOS晶片抛光60秒，以将TEOS膜移除300至的厚度。然后，将经研磨溶液污染的空白TEOS晶片置于Entrepix,Inc.(美国)的OnTrak清洗机台上，并使用下表中所列的组合物进行清洗。清洗时间持续2分钟，清洗组合物的流速为1500毫升/分钟。在清洗后，以原子力显微镜(AFM)测量表面粗糙度，并以KLA-Tencor SP1测量晶片表面缺陷数。结果描绘于表2中。
表2结果显示，将特定的有机碱、铜蚀刻剂、有机配体、以及腐蚀抑制剂组合的组合物(实施例1至37)与包括其它组分的组合物(比较例L至T)或不具有某一组分的组合物(比较例A至G和K)相比总体上可更有效地消除各种缺陷。此外，添加特定的表面活性剂可进一步减少铜晶片缺陷数(实施例38与比较例U和V)。
以上实施例被用于举例说明本发明的优选实施方式，且不意图限制本发明。任何根据本说明书和权利要求书的公开内容的修饰和变化被涵盖在本发明的范围内。
Claims (9)
1.用于铜后化学机械平坦化(post-Cu CMP)的含水清洗组合物，其包含：
有机碱；
铜蚀刻剂；
有机配体；
腐蚀抑制剂，其为酰肼化合物；以及
水；
其中，该有机碱的浓度为至少200ppm，该铜蚀刻剂的浓度为至少200ppm，该有机配体的浓度为至少50ppm，且该腐蚀抑制剂的浓度为至少10ppm，
其中该有机配体选自：膦酸、及膦酸与羧酸的组合，
其中该膦酸选自：二亚乙基三胺五(亚甲基膦酸)(DTPMP)、2-膦酰基丁烷-1,2,4-三羧酸(PBTCA)、六亚甲基二胺四(亚甲基膦酸)(HDTMP)、2-羟基膦酰基乙酸(HPAA)、2-羧基乙基膦酸(CEPA)、次膦酰基羧酸聚合物(PCA)、多氨基多醚亚甲基膦酸(PAPEMP)、2-氨基乙基膦酸(AEPn)、N-(膦酰基甲基)亚氨基二乙酸(PMIDA)、氨基三(亚甲基膦酸)(ATMP)、及其组合；且该羧酸选自：甘氨酸、氨基磺酸、二亚乙基三胺五乙酸(DTPA)、柠檬酸、L-半胱氨酸、乙醇酸、乙醛酸、及其组合，
其中该有机碱为选自如下的季铵：氢氧化四甲基铵(TMAH)、氢氧化四乙基铵(TEAH)、氢氧化四丙基铵(TPAH)、氢氧化四丁基铵(TBAH)、氢氧化三(2-羟乙基)甲基铵(THEMAH)、氢氧化十六烷基三甲基铵(CTAH)、胆碱、及其组合，和
其中该铜蚀刻剂为选自如下的含N化合物：哌嗪、2-(2-氨基乙氧基)乙醇、2-氨基-1-丁醇、3-氨基-1-丙醇、乙醇胺、二乙醇胺、三乙醇胺、二亚乙基三胺、N-甲基乙醇胺、N-二(羟乙基)甘氨酸、三(羟甲基)氨基甲烷(Tris)、及其组合。
2.权利要求1的含水清洗组合物，其中该有机碱的浓度为至少400ppm。
3.权利要求1的含水清洗组合物，其中该铜蚀刻剂的浓度为至少300ppm。
4.权利要求1的含水清洗组合物，其中该有机配体的浓度为至少100ppm。
5.权利要求1的含水清洗组合物，其中该酰肼化合物具有下式：
其中，
R2和R3独立地为氢；
R1和R4独立地为氢、-NHNH2、-C(O)NHNH2、C1-C8烷基、C1-C8烷氧基、-(CH2)nCN、-(CH2)nC(O)NHNH2、-(CH2)nC(O)O(CH2)n、-NHNHC6H5、-(CH2)nC6H5、-C6H5、-C10H7，其中-C6H5和-C10H7为未取代的或独立地被选自卤素、羟基、氨基、-NO2、C1-C4烷基、和C1-C4烷氧基的一个或多个取代基取代，且n为1至3；以及
该酰肼化合物的浓度为至少50ppm。
6.权利要求5的含水清洗组合物，其中R1为H或-NHNH2，且R4为H。
7.权利要求6的含水清洗组合物，其中该酰肼化合物为碳酰肼。
8.权利要求1至7中任一项的含水清洗组合物，其进一步包含表面活性剂，该表面活性剂为由式H(OCH2CH2)nSR5表示的乙氧基化硫醇，其中R5为烃基且n为1至100，且该表面活性剂的浓度为至少50ppm。
9.权利要求8的含水清洗组合物，其中该乙氧基化硫醇选自：乙氧基化叔十二烷基硫醇、乙氧基化正十二烷基硫醇、乙氧基化2-苯基乙基硫醇、及其组合，且该乙氧基化硫醇的浓度为至少100ppm。
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| EP2971248B1 (en) | 2021-10-13 |
| KR102237745B1 (ko) | 2021-04-09 |
| JP6751015B2 (ja) | 2020-09-02 |
| JP2016519423A (ja) | 2016-06-30 |
| US20140264151A1 (en) | 2014-09-18 |
| EP2971248A1 (en) | 2016-01-20 |
| TW201435145A (zh) | 2014-09-16 |
| TWI515339B (zh) | 2016-01-01 |
| CN105264117A (zh) | 2016-01-20 |
| KR20150127278A (ko) | 2015-11-16 |
| WO2014151361A1 (en) | 2014-09-25 |
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