CN101760355A - 用于CoWP和多孔电介质的湿清洁组合物 - Google Patents
用于CoWP和多孔电介质的湿清洁组合物 Download PDFInfo
- Publication number
- CN101760355A CN101760355A CN200911000051A CN200911000051A CN101760355A CN 101760355 A CN101760355 A CN 101760355A CN 200911000051 A CN200911000051 A CN 200911000051A CN 200911000051 A CN200911000051 A CN 200911000051A CN 101760355 A CN101760355 A CN 101760355A
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- Prior art keywords
- acid
- preparaton
- cowp
- amine
- ether
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000008367 deionised water Substances 0.000 claims abstract description 54
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 54
- 238000004140 cleaning Methods 0.000 claims abstract description 44
- 238000005530 etching Methods 0.000 claims abstract description 35
- 150000007524 organic acids Chemical class 0.000 claims abstract description 33
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 32
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 74
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 70
- 235000011187 glycerol Nutrition 0.000 claims description 37
- 238000009472 formulation Methods 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- -1 organic acid salt Chemical class 0.000 claims description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 239000012964 benzotriazole Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 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
- 239000002904 solvent Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229960004418 trolamine Drugs 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- IHPYMWDTONKSCO-UHFFFAOYSA-N 2,2'-piperazine-1,4-diylbisethanesulfonic acid Chemical compound OS(=O)(=O)CCN1CCN(CCS(O)(=O)=O)CC1 IHPYMWDTONKSCO-UHFFFAOYSA-N 0.000 claims description 4
- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 4
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical group S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 claims description 2
- RJLKIAGOYBARJG-UHFFFAOYSA-N 1,3-dimethylpiperidin-2-one Chemical compound CC1CCCN(C)C1=O RJLKIAGOYBARJG-UHFFFAOYSA-N 0.000 claims description 2
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 claims description 2
- RQUBQBFVDOLUKC-UHFFFAOYSA-N 1-ethoxy-2-methylpropane Chemical compound CCOCC(C)C RQUBQBFVDOLUKC-UHFFFAOYSA-N 0.000 claims description 2
- FVRSWMRVYMPTBU-UHFFFAOYSA-M 1-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCC(O)[N+](C)(C)C FVRSWMRVYMPTBU-UHFFFAOYSA-M 0.000 claims description 2
- OMAFFHIGWTVZOH-UHFFFAOYSA-O 1-methyl-2h-tetrazol-1-ium Chemical compound C[N+]1=CN=NN1 OMAFFHIGWTVZOH-UHFFFAOYSA-O 0.000 claims description 2
- NAFPAOUIKZHXDV-UHFFFAOYSA-N 1-propan-2-yloxy-2-(2-propan-2-yloxypropoxy)propane Chemical compound CC(C)OCC(C)OCC(C)OC(C)C NAFPAOUIKZHXDV-UHFFFAOYSA-N 0.000 claims description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002184 metal Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- 230000001066 destructive effect Effects 0.000 description 2
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- 239000003352 sequestering agent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
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- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
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- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
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- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
Images
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
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- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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Abstract
本发明涉及用于CoWP和多孔电介质的湿清洁组合物。本发明是一种用于从具有CoWP特征的半导体基片上湿清洁除去蚀刻后和灰残留物的配制剂,包括:去离子水;有机酸;胺和/或氢氧化季铵;其中,所述配制剂与所述CoWP特征相容,并且,或者(a)胺和/或氢氧化季铵与有机酸的摩尔比提供在7-14的范围的pH值;或者(b)所述配制剂包括缓蚀剂。还描述了使用所述配制剂的方法。
Description
对相关申请的交叉引用
本申请要求2008年12月17日提交的序列号为61/138244的美国临时专利申请的权益。
技术领域
本申请涉及用于CoWP和多孔电介质的湿清洁组合物。
背景技术
在集成电路(IC)的连续剥离(scaling)中面临的诸多挑战之一是使Cu互连达到可接受的电迁移(EM)可靠性。解决这一挑战的一种方法是在Cu上界面上沉积金属覆盖层。钴钨磷化物(cobalt tungsten phosphide,CoWP)的无电沉积作为Cu金属化的覆盖层看来是最有希望的候选。
CoWP的成功执行不仅依赖于优化的沉积,而且依赖于完全CoWP相容的集成(integration)处理,其包括湿清洁处理。但是,普通的半水性氟化物剥离剂(semi-aqueous fluoride strippers)和稀释的氢氟酸(DHF)剥离剂与CoWP不相容,其在湿清洁过程中完全地除去CoWP层。
参见J.Lauerhaas,Reduced Oxygen Cleaning Process for Advanced Cu/Low-kIntegration,SEMATECH Surface Preparation and Cleaning Conference,March23-25,2009。
本发明公开了在保持CoWP完整性的同时,表现出善于对CoWP暴露的图案化晶片进行清洁的湿清洁配制剂,其将更完整地公开如下。
发明内容
本发明是用于从具有CoWP特征(feature)的半导体基片(semiconductorsubstrate)上除去蚀刻后和灰残留物(post etch and ash residue)的湿清洁配制剂,其包括:
去离子水;
有机酸;
胺和/或氢氧化季铵;
其中,所述配制剂与所述CoWP特征相容,和,(a)胺和/或氢氧化季铵与有机酸的摩尔比提供在7-14的范围的pH值,或者(b)所述配制剂包括缓蚀剂(corrosioninhibitor)。
本发明也是用于从具有CoWP特征的半导体基片上湿清洁除去蚀刻后和灰残留物的方法,其包括:
提供具有CoWP特征的半导体基片;
使所述基片与配制剂接触,该配制剂包括:
去离子水;
有机酸;
胺和/或氢氧化季铵;
其中,所述配制剂与所述CoWP特征相容,和,(a)胺和/或氢氧化季铵与有机酸的摩尔比提供在7-14的范围的pH值,或者(b)所述配制剂包括缓蚀剂。
附图说明
图1是在接触任何清洁化学品之前具有CoWP覆盖层的图案化晶片的扫描电镜照片(SEM)。1是铜层,2是CoWP覆盖层,3是ILD层,4是通孔,以及5表示蚀刻后/灰残留物。
图2是采用包括实施例2AW21028-85G的本发明配制剂在25℃和2分钟的接触清洁后具有CoWP覆盖层的图案化晶片的SEM。1是铜层,2是CoWP覆盖层,3是ILD层,4是通孔,以及5表示蚀刻后/灰残留物。
图3是采用包括实施例3AW21028-85H的本发明配制剂在25℃和2分钟的接触清洁后具有CoWP覆盖层的图案化晶片的SEM。1是铜层,2是CoWP覆盖层,3是ILD层,4是通孔,以及5表示蚀刻后/灰残留物。
图4是采用包括实施例6AW21028-67E的本发明配制剂在25℃和2分钟的接触清洁后具有CoWP覆盖层的图案化晶片的SEM。1是铜层,2是CoWP覆盖层,3是ILD层,4是通孔,以及5表示蚀刻后/灰残留物。
图5是采用包括对比例2DHF(800∶1)的对比技术配制剂在25℃和30秒的接触清洁后具有CoWP覆盖层的图案化晶片的SEM。1是铜层,2是CoWP覆盖层,3是ILD层,4是通孔,以及5表示蚀刻后/灰残留物。
具体实施方式
普通的半水性氟化物剥离剂(semi-aqueous fluoride strippers)和DHF剥离剂具有高CoWP蚀刻速度和严重的CoWP/Cu原电池腐蚀(galvanic corrosion)。相反,本发明公开了湿清洁配制剂,其有效地最小化CoWP蚀刻和CoWP/Cu原电池腐蚀(共同地CoWP相容),表现出善于对具有和不具有CoWP特征的Cu/低-k图案化晶片进行清洁和对多孔低-k电介质具有最小的影响。优选地,CoWP相容性表示CoWP蚀刻速度不大于
本发明公开了适合用于IC集成工艺,特别是CoWP集成工艺中的蚀刻后和灰残留物清洁的非氟化物湿清洁配制剂(non-fluoride wet cleaning formulations)。所述配制剂包括去离子水(DIW),有机酸和/或其盐,胺和/或氢氧化季铵和溶剂。组合物的pH为7-14,优选7-11。作为选择,如果存在缓蚀剂,则可以使用更低的pH值。
通过控制所述配制剂pH、溶剂和溶剂/水比率,可使CoWP蚀刻速度和CoWP/Cu原电池腐蚀最小化。
所述组合物可通过在室温顺序添加:DIW、有机酸、胺和/或氢氧化季铵、和溶剂而混合。有机酸和胺和/或氢氧化季铵的盐可原位形成。胺和/或氢氧化季铵与有机酸的摩尔比等于或大于1或者足够保持pH为7-14。
所述组合物的实施例为:
实施例1:AW21028-83H
去离子水 46.36wt%
乙酸 0.84wt%
TEA 2.8wt%
甘油 50wt%
(TEA=三乙醇胺)
实施例2:AW21028-85G
去离子水 55.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
实施例3:AW21028-85H
去离子水 57.27wt%
乙酸 0.63wt%
TEA 2.1wt%
甘油 40wt%
实施例4:AW21028-90A
去离子水 47.86wt%
乙酸 0.84wt%
NMEA 1.3wt%
甘油 50wt%
(NMEA=N-甲基单乙醇胺)
实施例5:AW21028-66F
去离子水 96.69wt%
乙酸 0.42wt%
TMAH(25%)3.16wt%
(TMAH(25%)=氢氧化四甲基铵,25%水溶液)
实施例6:AW21028-67E
去离子水 65.41wt%
辛酸 2wt%
TEA 2.59wt%
甘油 30wt%
实施例7:AW21656-29G
去离子水 55.93wt%
抗坏血酸 2.52wt%
TEA 1.55wt%
甘油 40wt%
实施例8:AW21656-29H
去离子水 54.89wt%
抗坏血酸 2.52wt%
TEA 2.59wt%
甘油 40wt%
实施例9:AW21656-29F
去离子水 53.98wt%
抗坏血酸 2.52wt%
TEA 3.50wt%
甘油 40wt%
优选范围:
去离子水 7-99.7wt%
有机酸 0.2-5wt%
胺/氢氧化季铵 0.5-20wt%
溶剂 0-70wt%
最优选范围:
去离子水 7-99.7wt%
有机酸 0.5-3wt%
胺/氢氧化季铵 1.5-10wt%
溶剂 25-55wt%
典型的有机酸:
有机酸的例子可以是脂肪族/芳香族羧酸、氨基羧酸、磺酸和氨基磺酸。典型的羧酸包括但不限于:乙酸、丙酸、丁酸、戊酸、3-甲基丁酸、己酸、庚酸、辛酸、壬酸、癸酸、十二烷酸、十三烷酸、十四烷酸、十五烷酸、十六烷酸、十七烷酸、十八烷酸、十二烷二酸、2-甲基庚酸、2-己基癸酸、草酸、丙二酸、马来酸、富马酸、琥珀酸、衣康酸、戊二酸、己二酸、苹果酸、酒石酸、丙烯酸、甲基丙烯酸、柠檬酸、乳酸、羟基乙酸、抗坏血酸、邻氨基苯甲酸、没食子酸、苯甲酸、异酞酸、邻苯二甲酸、苯偏三酸、均苯四甲酸、水杨酸、2,4-二羟基苯甲酸和其它。典型的氨基羧酸包括但不限于:氨基乙酸、二羟基乙基氨基乙酸、丙氨酸、缬氨酸、亮氨酸、天冬酰胺、谷氨酰胺、天门冬氨酸、戊二酸、赖氨酸、精氨酸、亚氨基二乙酸、次氮基三乙酸、乙二胺四乙酸、1,2-环己二胺四乙酸、二亚乙基三胺五乙酸和其它。典型的磺酸/氨基磺酸包括但不限于:苄磺酸、对甲苯磺酸、2-(N-吗啉代)乙磺酸、N-(2-羟乙基)哌嗪-N’-(乙磺酸)、3-[N,N-双(2-羟乙基)氨基]-2-羟基丙磺酸、4-(N-吗啉代)丁磺酸、N-(2-羟乙基)哌嗪-N’-(2-羟基丙磺酸)、N-(2-羟乙基)哌嗪-N’-(3-丙磺酸)、2-(N-环己基氨基)乙磺酸,和其它。
典型的胺:
胺的例子可以是脂肪族/芳香族伯、仲、叔胺、二胺和三胺、链烷醇胺、脂环胺、杂环胺和羟胺类。胺的例子包括甲胺、乙胺、丙胺、丁胺、单乙醇胺、单异丙醇胺、2-(2-氨基乙氧基)乙醇、二甲胺、二乙胺、二丙胺、二丁胺、二乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、三甲胺、三乙胺、三丙胺、三丁胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、三乙醇胺、环己胺、二环己胺、吡咯、吡咯烷、吡啶、吗啉、吡嗪、哌啶、苄胺、二苄胺、N-甲基苄胺、N-乙基苄胺和其它。可用于这里描述的清洁组合物的羟胺类的例子包括:羟胺或羟胺的烷基-取代衍生物,例如,非限定的,羟胺、N-甲基羟胺、N,N-二甲基羟胺、N,N-二乙基羟胺和其它。
典型的氢氧化季铵:
氢氧化季铵的例子可以是具有以下化学式的那些化合物:[N-R1R2R3R4]+OH-,其中R1、R2、R3和R4各自独立地为烷基,羟烷基,和它们的组合。这里使用的术语“烷基”指的是1至20个碳原子的直链或支链的未取代烃基,或优选1至8个碳原子,或更优选1至4个碳原子。
合适的烷基的例子包括:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基。
这里使用的术语“羟烷基”指的是包含1至20个碳原子,或优选1至8个碳原子,或更优选1至4个碳原子的烃基的直链或支链的未取代羟烷基。
合适的羟烷基的例子包括羟乙基和羟丙基。
合适的氢氧化季铵化合物的例子包括:氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵和氢氧化苄基三甲基铵。
典型的溶剂:
这里公开的配制剂可含有至少一种有机极性溶剂,其优选是水溶性的。有机极性溶剂的例子可以是酰胺和亚砜。有机极性溶剂的例子包括但不限于:二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、四亚甲基砜、二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、二甲基-2-哌啶酮(DMPD)和其它酰胺、醇或亚砜、或多官能化合物,例如羟基酰胺类或氨基醇。
所述有机极性溶剂的进一步的例子包括二元醇和多元醇,例如(C2-C20)烷二醇和(C3-C20)烷三醇,环状醇和取代的醇。这些有机溶剂的特定的例子是乙二醇、丙二醇、甘油、四氢糠醇,双丙酮醇和1,4-环己烷二甲醇。
上面列举的非水溶剂可单独使用或两种或更多种溶剂结合使用。
在特定的具体实施方式中,所述有机极性溶剂可包含二醇醚。二醇醚的例子包括乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙二醇单苯醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丙醚、二乙二醇单异丙醚、二乙二醇单丁醚、二乙二醇单异丁醚、二乙二醇单苄醚、二乙二醇二甲醚、二乙二醇二乙醚、三乙二醇单甲醚、三乙二醇二甲醚、聚乙二醇单甲醚、二乙二醇甲基乙基醚、三乙二醇单甲基醚乙酸酯、乙二醇单乙基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇单甲醚、丙二醇二甲醚、丙二醇单丁醚、丙二醇单丙醚、二丙二醇单甲醚、二丙二醇单丙醚、二丙二醇单异丙醚、二丙二醇单丁醚、二丙二醇二异丙醚、三丙二醇单甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇和2-(2-丁氧基乙氧基)乙醇。
比较例:
比较例1DHF(100∶1)
去离子水99wt%
HF(49%)1wt%
比较例2DHF(800∶1)
去离子水799wt%
HF(49%)1wt%
表1和2中提供了Co、CoWP和Cu的蚀刻速度(“ER”)的总结。在测定Co和Cu蚀刻速度时,晶片具有沉积在其上面的已知厚度的盖层(blanket layer)。晶片的初始厚度使用CDE ResMap 273 Four Point Probe来测定。测定初始厚度后,将测试晶片浸入湿清洁配制剂中。五分钟后,将测试晶片从湿清洁配制剂中移出,用去离子水漂洗三分钟,然后在氮气下完全干燥。测量每个晶片的厚度。在10、20、40和60分钟的暴露时间重复该程序。厚度测量在每个时间间隔进行测定,并且利用“最小二乘法拟合”模型对每个清洁配制剂的结果作图。每种组合物的“最小二乘法拟合”模型的计算斜率就是得到的蚀刻速度,单位为埃/分钟在测定CoWP蚀刻速度时,膜厚度不容易用传统的椭圆偏光法(ellipsometric method)来测量,因为CoWP膜非常薄并且下面的Cu导致入射光束的反射。作为替代,作为在湿清洁配制剂中的浸没时间的函数,测定CoWP层的开路电压(OCP)。将覆层CoWP基片(blanket CoWP substrate)(1×4cm2)浸入500ml空气饱和的湿清洁配制剂中,并随着时间监控电压。CoWP膜的OCP与下面的Cu明显不同。当CoWP被完全蚀刻时,开路电压与Cu相似。通过记下达到Cu OCP花费的时间和已知CoWP层的初始厚度,就可确定CoWP蚀刻速度。在测定CoWP和Cu电偶(couple)的动电电流(galvanic current)时,当与各种湿清洁配制剂接触时,进行电压极化来确定在与Cu的电偶中CoWP的腐蚀电流。在环境温度在空气饱和的条件下,伴随强烈的搅动(600RPM),使覆层CoWP或Cu基片(2×2cm2)浸入500ml湿清洁配制剂中。然后,相对于Ag/AgCl参比电极,以10mV/s的扫描速度从-1V至0.1V施加阴极电流。将极化曲线绘制成Tafel图(Tafel plots)。外推至零电流密度,得出腐蚀电压(Ecorr)。CoWP和Cu极化曲线交点处的电流密度给出CoWP和Cu电偶的电动电流密度。
表1显示出本发明的湿清洁配制剂相对于比较例1DHF(100∶1),对Co、CoWP和Cu具有更低的蚀刻速度和更低的电动电流密度。表1和表2显示出本发明的所有湿清洁配制剂在CoWP上都具有优异的低蚀刻速度,这对于CoWP集成是必要的。
表1:覆层CoWP晶片的CoWP相容性数据以及Co和Cu蚀刻速度
NA:不可得到
pH测定是在环境温度使用5%水溶液进行的。
表2:在覆层Co、CoWP和Cu晶片上的蚀刻速度数据
表3中提供了清洁数据以及暴露温度和时间的总结。测试晶片是在Cu/CoWP/ILD叠层中以沟槽和通孔为特征的具有蚀刻后残余物和灰的图案化晶片。在这个过程中,将一个或更多测试晶片放入含有400ml的每种湿清洁配制剂的600毫升(ml)烧杯中。所述的600ml烧杯进一步包括以每分钟400转旋转的1”搅拌棒。然后在表3提供的温度和时间加热其中包含晶片的湿清洁配制剂。在暴露于湿清洁配制剂后,用去离子水漂洗晶片,并用氮气干燥。劈开晶片以提供边缘,然后使用电子扫描显微镜(SEM)对晶片上多个预定位置进行检查,并视觉解释清洁性能和CoWP相容性结果。表3显示出比较例2DHF(800∶1)在25℃/30秒完全清除掉残留物和除去CoWP层。这清楚地证明DHF与CoWP覆盖层不相容。在这种情况下本发明的湿清洁配制剂包含:实施例2AW21028-85G和实施例6AW21028-67E,在25℃/2min完全清除掉残留物而没有底切(undercutting)CoWP层。这些结果证明了本发明的湿清洁配制剂的良好的清洁效率和CoWP相容性。
表3:图案化的CoWP晶片的清洁性能
表4和表5中提供了覆层多孔ILD(blanket porous ILD)相容性数据的总结。使用Precision 5000集成沉积平台沉积基于二乙氧基甲基硅烷(DEMS)的多孔有机硅酸盐玻璃(organosilicate glass,OSG)膜。使用DEMS和致孔剂(porogen)作为化学前体来把复合膜沉积到<100>Si 8-12 ohm/cm 200mm晶片上。UV固化所述膜以制备介电常数为2.5的最终多孔膜。该电介质膜的厚度和折射率使用SCIFilm TekTM 2000反射仪来测定。k值和FTIR(傅立叶变换红外光谱)光谱分别使用MSI电子汞探针(Model Hg-401)和NEXUS 470 FT-IR光谱仪获得。
表4总结了本发明的湿清洁配制剂与基于DEMS的多孔OSG(k=2.5)的电介质相容性(dielectric compatibility)。在25℃,在湿清洁配制剂:实施例1AW21028-83H、实施例2AW21028-85G和实施例3AW21028-85H中处理k值为2.5的原始(pristine)ILD晶片2分钟。处理后膜厚度、折射率或k值均无改变。表5的FTIR数据显示C-H/SiO2和Si-CH3/SiO2的键保持率(bond retention)几乎不变,表明对表面Si-CH3键和SiO2网络没有破坏。这些结果表明本发明的湿清洁配制剂对覆层多孔ILD电介质没有负面影响。
表4:覆层多孔ILD PDEMS 2.5相容性
表5:覆层多孔ILD PDEMS 2.5相容性:FTIR
多孔OSG电介质上的图案化沟槽特征被用于确定所述湿清洁配制剂对蚀刻破坏的电介质侧壁的影响。图案化晶片是基于90nm设计规则制备的。在图案化的晶片工艺期间,在具有多孔OSG电介质的基片上涂覆光刻胶层。使用照相平版印刷法在光刻胶层上限定图案。然后,所述图案化的光刻胶层经受等离子体蚀刻,由此将图案转移到基片上。随后对图案化的基片进行蚀刻和灰化,以形成所需的沟槽特征。在用湿清洁配制剂处理后,通过SEM测量电介质沟槽(M1沟槽)的CD(临界尺寸)变化,并提供在表6中。
表6显示了在包含实施例2AW21028-8G的本发明的湿清洁配制剂中在25℃处理2分钟后,非常小的CD变化(0.03μm,3%)。相反,在对比例1DHF(100∶1)中在25℃处理20秒后,观察到严重的CD变化(0.21μm,21%)。这些结果表明本发明的湿清洁配制剂与蚀刻破坏的多孔低-k电介质相容。
表6:图案化多孔ILD PDEMS 2.5相容性
清洁配制剂 | 温度(℃) | 时间(秒) | CD变化(μm) | CD变化(%) |
比较例1DHF(100∶1) | 25 | 20 | 0.21 | 21 |
实施例2AW21028-85G | 25 | 120 | 0.03 | 3 |
从上述数据可以看出,本发明公开了有效地防止CoWP蚀刻和CoWP/Cu原电池腐蚀的湿清洁配制剂,证实了对具有和不具有CoWP的Cu/低-k图案化晶片的良好清洁作用并且对多孔低-k电介质具有极小的影响。
所述湿清洁配制剂还可含有一种或多种下述添加剂:缓蚀剂(corrosioninhibitors)、O2清除剂、和其它添加剂。所述一种或多种添加剂可以添加至它们对组合物的pH范围产生和/或不产生不利影响的程度。使用缓蚀剂和/或O2清除剂添加剂,胺和/或氢氧化季铵与有机酸的摩尔比可以是:(a)等于、(b)大于、或(c)小于1。
组合物的实施例为:
实施例10:AW21656-16D
去离子水 53.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
苯并三唑 2wt%
实施例11:AW21656-16E
去离子水 54.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
苯并三唑 1wt%
实施例12:AW21656-16F
去离子水 54.95wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
苯并三唑 0.5wt%
实施例13:AW21656-19A
去离子水 55.35wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
苯并三唑 0.1wt%
实施例14:AW21656-18A
去离子水 54.95wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
甲苯并三唑 0.5wt%
实施例15:AW21656-19B
去离子水 55.35wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
甲苯并三唑 0.1wt%
实施例16:AW21656-18G
去离子水 53.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
1,2,4-三唑 2wt%
实施例17:AW21656-18C
去离子水 54.95wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
1,2,4-三唑 0.5wt%
实施例18:AW21656-19C
去离子水 55.35wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
1,2,4-三唑 0.1wt%
实施例19:AW21656-19D
去离子水 50.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
抗坏血酸 5wt%
实施例20:AW21656-18H
去离子水 53.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
抗坏血酸 2wt%
实施例21:AW21656-18D
去离子水 54.95wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
抗坏血酸 0.5wt%
实施例22:AW21656-18F
去离子水 53.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
碳酰肼 2wt%
实施例23:AW21656-18B
去离子水 54.95wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
碳酰肼 0.5wt%
实施例24:AW21656-16A
去离子水 50.45wt%
乙酸 1.05wt%
TEA 3.5wt%
甘油 40wt%
邻苯二酚 5wt%
实施例25:AW21656-29A
去离子水 64.91wt%
辛酸 2wt%
TEA 2.59wt%
甘油 30wt%
抗坏血酸 0.5wt%
实施例26:AW21656-30D
去离子水 56.9wt%
乙酸 1.05wt%
TEA 1.55wt%
甘油 40wt%
苯并三唑 0.5wt%
实施例27:AW21656-30E
去离子水 55.86wt%
乙酸 1.05wt%
TEA 2.59wt%
甘油 40wt%
苯并三唑 0.5wt%
实施例28:AW21656-30H
去离子水 56.9wt%
乙酸 1.05wt%
TEA 1.55wt%
甘油 40wt%
甲苯并三唑 0.5wt%
实施例29:AW21656-30I
去离子水 55.86wt%
乙酸 1.05wt%
TEA 2.59wt%
甘油 40wt%
甲苯并三唑 0.5wt%
实施例30:AW21656-30F
去离子水 56.9wt%
乙酸 1.05wt%
TEA 1.55wt%
甘油 40wt%
1,2,4-三唑 0.5wt%
实施例31:AW21656-30G
去离子水 55.86wt%
乙酸 1.05wt%
TEA 2.59wt%
甘油 40wt%
1,2,4-三唑 0.5wt%
优选范围:
去离子水 7-99.7wt%
有机酸 0.2-5wt%
胺/氢氧化季铵 0.5-20wt%
溶剂 0-70wt%
缓蚀剂和/或O2清除剂 0.01-10wt%
接触时间 0.1-5min。
最优选范围:
去离子水 7-99.7wt%
有机酸 0.5-3wt%
胺/氢氧化季铵 1.5-10wt%
溶剂 25-55wt%
缓蚀剂和/或O2清除剂 0.1-5wt%
接触时间 0.5-2min。
典型的有机缓蚀剂和O2清除剂:
本公开的组合物还可任选的含有最高约10wt%,或约0.1wt%至约5wt%的缓蚀剂和/或氧清除剂(oxygen scavenger)来进一步减少对Cu、Co和CoWP的侵蚀。缓蚀剂的例子可以是三唑类,例如1,2,4-三唑,或由诸如C1-C8烷基、氨基、硫醇、巯基、亚氨基、羧基和硝基的取代基取代的三唑,例如苯并三唑、5-羧酸苯并三唑(5-carboxylic acid benzotriazole)、甲苯并三唑(tolyltriazole)、5-苯基-苯并三唑、5-硝基-苯并三唑、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇苯并三唑(5-phenylthiolbenzotriazole)、萘并三唑(naphthotriazole),和噻唑类、四唑类、咪唑类、磷酸酯/盐类、硫醇类和吖嗪类,例如2-巯基苯并咪唑、2-巯基-苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基四唑、5-氨基-1,3,4-噻二唑-2-硫醇、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑啉酮(imidazolidinone)、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、巯基苯并噻唑、咪唑啉硫酮(imidazoline thione)、巯基苯并咪唑、4-甲基-4H-1,2,4-三唑-3硫醇、5-氨基-1,3,4-噻二唑-2硫醇、苯并噻唑、磷酸三甲苯酯、苯并异二唑(indiazole)等。合适的缓蚀剂进一步包括有机酸、有机酸盐、酚、羟胺类或其酸式盐。特别的缓蚀剂的例子包括柠檬酸、邻氨基苯甲酸、水杨酸、乳酸、亚氨基二乙酸、苯甲酸、异酞酸、马来酸、富马酸、D,L-苹果酸、丙二酸、邻苯二甲酸、马来酸酐、邻苯二甲酸酐、间苯二酚、二乙基羟胺和其乳酸及柠檬酸盐等。合适的缓蚀剂的其它例子包括果糖、硫代硫酸铵、甘氨酸、四甲基胍、苯胍胺、三聚氰胺、鸟嘌呤、腺嘌呤、硫代甘油、水杨酰胺、和二甲基乙酰乙酰胺。在缓蚀剂是有机酸的具体实施方式中,所述有机酸可以与溶液中使用的有机酸相同。
典型的氧清除剂包括抗坏血酸、邻苯二酚、碳酰肼、没食子酸、对苯二酚、连苯三酚、环己二酮、肼、亚硫酸盐(sulfite)、酸式硫酸盐(bisulfate)、和/或亚硝酸盐(nitrilte)。
所述组合物还可包括一种或多种以下添加剂:表面活性剂、螯合剂、化学改性剂、染料、杀生物剂、和其它添加剂。所述一种或多种添加剂可以添加到不对组合物的pH范围产生不利影响的程度。一些代表性的添加剂例子包括炔醇(acetylenics alcohols)及其衍生物,炔二醇(acetylenics diols)(非离子烷氧基化的和/或可自乳化的炔二醇表面活性剂)及其衍生物,醇,季胺和二胺,酰胺(包括非质子溶剂,例如二甲基甲酰胺和二甲基乙酰胺),烷基链烷醇胺(例如二乙醇乙基胺),和螯合剂,例如β-二酮类,β-酮亚胺类,羧酸,基于苹果酸和酒石酸的酯和二酯及其衍生物,和叔胺、二胺和三胺。具体的炔二醇包括从Air Products andChemicals,Inc.,Allentown,Pennsylvania,USA获得的Surfynol 465表面活性剂。Surfynol 465是2,4,7,9-四甲基-5-癸炔-4,7-二醇,其被10个环氧乙烷单元乙氧基化。见美国专利6,717,019的第9栏第46行。
比较例:
比较例3AW21656-30B
去离子水 57.40wt%
乙酸 1.05wt%
TEA 1.55wt%
甘油 40wt%
比较例4AW21656-30C
去离子水 56.36wt%
乙酸 1.05wt%
TEA 2.59wt%
甘油 40wt%
表7和8总结了具有另外的缓蚀剂和/或O2清除剂的湿清洁配制剂的金属蚀刻速度数据。所述缓蚀剂和/或O2清除剂,和/或两种或更多种的缓蚀剂和/或O2清除剂的结合,在pH>7或pH<7可用于改进所述组合物与金属的相容性。
表7:覆层Co、CoWP和Cu晶片的蚀刻速度数据
表8:覆层Co、CoWP和Cu晶片的蚀刻速度数据
Claims (29)
1.用于从具有CoWP特征的半导体基片除去蚀刻后和灰残留物的非氟化物湿清洁配制剂,基本上由以下组成:
去离子水;
有机酸;
胺和/或氢氧化季铵;
任选的一种或更多种缓蚀剂;非水有机极性溶剂和氧清除剂;
其中所述配制剂与所述CoWP特征相容,并且,(a)胺和/或氢氧化季铵与有机酸的摩尔比提供在7-14的范围的pH值;或者(b)所述配制剂包括缓蚀剂。
2.权利要求1的配制剂,其中pH值保持在7-11的范围。
3.权利要求1的配制剂,包括非水有机极性溶剂。
4.权利要求1的配制剂,其中所述有机酸是有机酸的盐。
5.权利要求1的配制剂,其中所述有机酸选自:脂肪族或芳香族羧酸、氨基酸、磺酸、乙酸、丙酸、丁酸、戊酸、3-甲基丁酸、己酸、庚酸、辛酸、壬酸、癸酸、十二烷酸、十三烷酸、十四烷酸、十五烷酸、十六烷酸、十七烷酸、十八烷酸、十二烷二酸、2-甲基庚酸、2-己基癸酸、草酸、丙二酸、马来酸、富马酸、琥珀酸、衣康酸、戊二酸、己二酸、苹果酸、酒石酸、丙烯酸、甲基丙烯酸、柠檬酸、乳酸、羟基乙酸、抗坏血酸、邻氨基苯甲酸、没食子酸、苯甲酸、异酞酸、邻苯二甲酸、苯偏三酸、均苯四甲酸、水杨酸、2,4-二羟基苯甲酸、氨基乙酸、二羟基乙基氨基乙酸、丙氨酸、缬氨酸、亮氨酸、天冬酰胺、谷氨酰胺、天门冬氨酸、戊二酸、赖氨酸、精氨酸、亚氨基二乙酸、次氮基三乙酸、乙二胺四乙酸、1,2-环己二胺四乙酸、二亚乙基三胺五乙酸、苄磺酸、对甲苯磺酸、2-(N-吗啉代)乙磺酸、N-(2-羟乙基)哌嗪-N’-(乙磺酸)、3-[N,N-双(2-羟乙基)氨基]-2-羟基丙磺酸、4-(N-吗啉代)丁磺酸、N-(2-羟乙基)哌嗪-N’-(2-羟基丙磺酸)、N-(2-羟乙基)哌嗪-N’-(3-丙磺酸)、2-(N-环己基氨基)乙磺酸及它们的混合物。
6.权利要求1的配制剂,其中所述胺选自:脂肪族或芳香族伯、仲、叔胺、二胺和三胺、链烷醇胺、脂环胺、杂环胺、羟胺类、甲胺、乙胺、丙胺、丁胺、单乙醇胺、单异丙醇胺、2-(2-氨基乙氧基)乙醇、二甲胺、二乙胺、二丙胺、二丁胺、二乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、三甲胺、三乙胺、三丙胺、三丁胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、三乙醇胺、环己胺、二环己胺、吡咯、吡咯烷、吡啶、吗啉、吡嗪、哌啶、苄胺、二苄胺、N-甲基苄胺、N-乙基苄胺、羟胺、N-甲基羟胺、N,N-二甲基羟胺、N,N-二乙基羟胺、N-甲基单乙醇胺及它们的混合物。
7.权利要求1的配制剂,其中所述氢氧化季铵具有下式:[N-R1R2R3R4]+OH-,其中R1、R2、R3和R4各自独立地为烷基、羟烷基、及它们的组合,其中烷基是1至20个碳原子的直链或支链的未取代的烃基;其中羟烷基是1至20个碳原子的直链或支链的未取代的含羟基烃基。
8.权利要求7的配制剂,其中所述氢氧化季铵的烷基具有1至8个碳原子。
9.权利要求7的配制剂,其中所述氢氧化季铵的烷基具有1至4个碳原子。
10.权利要求7的配制剂,其中所述氢氧化季铵的羟烷基具有1至8个碳原子。
11.权利要求7的配制剂,其中所述氢氧化季铵的羟烷基具有1至4个碳原子。
12.权利要求7的配制剂,其中所述氢氧化季铵的烷基选自:甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基及它们的混合物。
13.权利要求7的配制剂,其中所述氢氧化季铵的羟烷基选自:羟乙基、羟丙基及它们的混合物。
14.权利要求1的配制剂,其中所述氢氧化季铵选自:氢氧化四甲基铵(TMAH)、氢氧化四乙基铵、氢氧化四丁基铵(TBAH)、氢氧化四丙基铵、氢氧化三甲基乙基铵、氢氧化(2-羟乙基)三甲基铵、氢氧化(2-羟乙基)三乙基铵、氢氧化(2-羟乙基)三丙基铵、氢氧化(1-羟丙基)三甲基铵、氢氧化乙基三甲基铵、氢氧化二乙基二甲基铵、氢氧化苄基三甲基铵及它们的混合物。
15.权利要求3的配制剂,其中所述非水有机极性溶剂选自:二甲基乙酰胺(DMAC)、N-甲基吡咯烷酮(NMP)、二甲基亚砜(DMSO)、四亚甲基砜、二甲基甲酰胺、N-甲基甲酰胺、甲酰胺、二甲基-2-哌啶酮(DMPD)、四氢糠醇、甘油、乙二醇、羟基酰胺类、氨基醇、二元醇、多元醇、(C2-C20)烷二醇、(C3-C20)烷三醇、环状醇、取代的醇、丙二醇、双丙酮醇和1,4-环己烷二甲醇、二醇醚、乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙二醇单苯醚、乙二醇二甲醚、乙二醇二乙醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丙醚、二乙二醇单异丙醚、二乙二醇单丁醚、二乙二醇单异丁醚、二乙二醇单苄醚、二乙二醇二甲醚、二乙二醇二乙醚、三乙二醇单甲醚、三乙二醇二甲醚、聚乙二醇单甲醚、二乙二醇甲基乙基醚、三乙二醇单甲基醚乙酸酯、乙二醇单乙基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇单甲醚、丙二醇二甲醚、丙二醇单丁醚、丙二醇单丙醚、二丙二醇单甲醚、二丙二醇单丙醚、二丙二醇单异丙醚、二丙二醇单丁醚、二丙二醇二异丙醚、三丙二醇单甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基丁醇和2-(2-丁氧基乙氧基)乙醇及它们的混合物。
16.权利要求1的配制剂,其含有选自以下的缓蚀剂:三唑、1,2,4-三唑、苯并三唑、5-羧酸苯并三唑、甲苯并三唑、5-苯基-苯并三唑、5-硝基-苯并三唑3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、羟基苯并三唑、2-(5-氨基-戊基)-苯并三唑、1-氨基-1,2,3-三唑、1-氨基5-甲基-1,2,3-三唑、3-氨基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、5-苯基硫醇苯并三唑、萘并三唑、噻唑类、四唑类、咪唑类、磷酸酯、硫醇类、吖嗪类、2-巯基苯并咪唑、2-巯基-苯并噻唑、4-甲基-2-苯基咪唑、2-巯基噻唑啉、5-氨基四唑、5-氨基-1,3,4-噻二唑-2-硫醇、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑啉酮、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、二氨基甲基三嗪、巯基苯并噻唑、咪唑啉硫酮、巯基苯并咪唑、4-甲基4H-1,2,4-三唑-3-硫醇、5-氨基-1,3,4-噻二唑-2-硫醇、苯并噻唑、磷酸三甲苯酯、苯并异二唑、有机酸、有机酸盐、苯酚、羟胺、柠檬酸、邻氨基苯甲酸、水杨酸、乳酸、亚氨基二乙酸、苯甲酸、异酞酸、马来酸、富马酸、D,L-苹果酸、丙二酸、邻苯二甲酸、马来酸酐、邻苯二甲酸酐、间苯二酚、二乙基羟胺、果糖、硫代硫酸铵、甘氨酸、四甲基胍、苯胍胺、三聚氰胺、鸟嘌呤、腺嘌呤、硫代甘油、水杨酰胺、二甲基乙酰乙酰胺及它们的混合物。
17.权利要求1的配制剂,其含有选自以下的氧清除剂:抗坏血酸、邻苯二酚、碳酰肼、没食子酸、对苯二酚、连苯三酚、环己二酮、肼、亚硫酸盐、酸式硫酸盐、亚硝酸盐及它们的混合物。
18.权利要求1的配制剂,其具有以下的组成范围:
去离子水 7-99.7wt%
有机酸 0.2-5wt%
胺/氢氧化季铵 0.5-20wt%
溶剂 0-70wt%。
19.权利要求1的配制剂,其具有以下的组成范围:
去离子水 7-99.7wt%
有机酸 0.5-3wt%
胺/氢氧化季铵 1.5-10wt%
溶剂 25-55wt%。
20.权利要求1的配制剂,其中胺和/或氢氧化季铵与有机酸的摩尔比等于或大于1。
21.权利要求1的配制剂,其中所述CoWP相容性包含不大于的CoWP蚀刻速度。
22.一种用于从具有CoWP特征的半导体基片上除去蚀刻后和灰残留物的非氟化物湿清洁配制剂,基本上由以下组成:
去离子水;
乙酸;
选自三乙醇胺和N-甲基单乙醇胺的胺;
甘油;
任选的一种或更多种缓蚀剂和氧清除剂;
其中所述配制剂与所述CoWP特征相容,并且,(a)胺与有机酸的摩尔比提供在7-14的范围的pH值,或者(b)所述配制剂包括缓蚀剂。
23.一种用于从具有CoWP特征的半导体基片上除去蚀刻后和灰残留物的非氟化物湿清洁配制剂,基本上由以下组成:
去离子水;
辛酸;
三乙醇胺;
甘油;
任选的一种或更多种缓蚀剂和氧清除剂;
其中所述配制剂与所述CoWP特征相容,并且,(a)胺与有机酸的摩尔比提供在7-14的范围的pH值,或者(b)所述配制剂包括缓蚀剂。
24.一种用于从具有CoWP特征的半导体基片上除去蚀刻后和灰残留物的非氟化物湿清洁配制剂,基本上由以下组成:
去离子水;
抗坏血酸;
三乙醇胺;
甘油。
25.一种从具有CoWP特征的半导体基片上湿清洁除去蚀刻后和灰残留物的方法,包括:
提供具有CoWP特征的半导体基片;
使所述基片与湿清洁配制剂接触,所述配制剂包含:
去离子水;
有机酸;
胺和/或氢氧化季铵;
其中,所述配制剂与所述CoWP特征相容,并且,(a)胺和/或氢氧化季铵与有机酸的摩尔比提供在7-14的范围的pH值,或者(b)所述配制剂包括缓蚀剂。
26.权利要求25的方法,其中所述CoWP特征临近铜金属特征。
27.权利要求25的方法,其中所述基片包括多孔低介电特征。
28.权利要求25的方法,其中在接触过程中的温度在20至45℃的范围。
29.权利要求25的方法,其中所述接触进行0.1至5分钟的时间。
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US (1) | US8361237B2 (zh) |
EP (1) | EP2199379B1 (zh) |
JP (1) | JP5096447B2 (zh) |
KR (1) | KR101131228B1 (zh) |
CN (1) | CN101760355B (zh) |
SG (1) | SG162680A1 (zh) |
TW (1) | TWI461525B (zh) |
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- 2009-12-17 KR KR1020090126151A patent/KR101131228B1/ko active IP Right Grant
- 2009-12-17 JP JP2009286368A patent/JP5096447B2/ja not_active Expired - Fee Related
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EP2199379A1 (en) | 2010-06-23 |
JP2010147476A (ja) | 2010-07-01 |
TW201024404A (en) | 2010-07-01 |
KR101131228B1 (ko) | 2012-04-12 |
EP2199379B1 (en) | 2013-07-17 |
JP5096447B2 (ja) | 2012-12-12 |
CN101760355B (zh) | 2012-08-22 |
SG162680A1 (en) | 2010-07-29 |
US20100152086A1 (en) | 2010-06-17 |
KR20100070308A (ko) | 2010-06-25 |
TWI461525B (zh) | 2014-11-21 |
US8361237B2 (en) | 2013-01-29 |
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