TWI743026B - 無胺之化學機械研磨後(post cmp)組成物及其使用方法 - Google Patents
無胺之化學機械研磨後(post cmp)組成物及其使用方法 Download PDFInfo
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- TWI743026B TWI743026B TW104135783A TW104135783A TWI743026B TW I743026 B TWI743026 B TW I743026B TW 104135783 A TW104135783 A TW 104135783A TW 104135783 A TW104135783 A TW 104135783A TW I743026 B TWI743026 B TW I743026B
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- Prior art keywords
- acid
- composition
- ammonium
- ether
- oxide
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 170
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 54
- 239000010941 cobalt Substances 0.000 claims abstract description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 48
- 238000004377 microelectronic Methods 0.000 claims abstract description 47
- 239000000356 contaminant Substances 0.000 claims abstract description 39
- 239000000126 substance Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007800 oxidant agent Substances 0.000 claims description 27
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000008139 complexing agent Substances 0.000 claims description 22
- -1 peroxyphthalate Chemical compound 0.000 claims description 22
- 150000001412 amines Chemical class 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 17
- 150000007514 bases Chemical class 0.000 claims description 14
- 239000011877 solvent mixture Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 11
- 239000004471 Glycine Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 239000003082 abrasive agent Substances 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical group O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 claims description 10
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 claims description 9
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 9
- 235000018417 cysteine Nutrition 0.000 claims description 9
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 9
- 238000007517 polishing process Methods 0.000 claims description 9
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 claims description 8
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 7
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 7
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-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
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 4
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 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 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-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
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- NVLADMORQQMDKF-UHFFFAOYSA-N 1-ethyl-1-oxidopyrrolidin-1-ium Chemical compound CC[N+]1([O-])CCCC1 NVLADMORQQMDKF-UHFFFAOYSA-N 0.000 claims description 3
- YIZTVEDOQDZLOH-UHFFFAOYSA-N 1-methyl-1-oxidopyrrolidin-1-ium Chemical compound C[N+]1([O-])CCCC1 YIZTVEDOQDZLOH-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- 241000208340 Araliaceae Species 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims description 3
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- KBKZYWOOZPIUJT-UHFFFAOYSA-N azane;hypochlorous acid Chemical compound N.ClO KBKZYWOOZPIUJT-UHFFFAOYSA-N 0.000 claims description 3
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 3
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940000635 beta-alanine Drugs 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- HCAJEUSONLESMK-UHFFFAOYSA-N cyclohexylsulfamic acid Chemical compound OS(=O)(=O)NC1CCCCC1 HCAJEUSONLESMK-UHFFFAOYSA-N 0.000 claims description 3
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 3
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 3
- 235000008434 ginseng Nutrition 0.000 claims description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 3
- LFMTUFVYMCDPGY-UHFFFAOYSA-N n,n-diethylethanamine oxide Chemical compound CC[N+]([O-])(CC)CC LFMTUFVYMCDPGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229960001922 sodium perborate Drugs 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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Abstract
本發明係關於一種保護含鈷材料層及/或自其上具有化學機械研磨(CMP)後殘留物及污染物之微電子裝置清除該等殘留物及污染物之高pH組成物及方法。該等組成物達成含鈷材料層之高度有效的保護及自微電子裝置表面清除CMP後殘留物及污染物材料,而不會損壞低k介電材料、銅互連材料、或含鈷材料。
Description
本發明係關於用於自其上具有殘留物及/或污染物之微電子裝置實質且有效率地清除該等物質之無胺之組成物。本發明進一步關於保護含鈷材料層。
熟知積體電路(IC)製造商已針對先進微電子應用以銅取代鋁及鋁合金,因銅具有較高的傳導性,其等同於互連效能的顯著改良。此外,基於銅之互連體提供較鋁佳之電遷移抗性(electromigration resistance),因而改良互連可靠性。亦即,銅之實施面臨特定的挑戰。舉例來說,銅(Cu)對二氧化矽(SiO2)及對其他介電材料之黏著力一般不佳。不良的黏著會導致Cu於製程期間自鄰接薄膜脫層。此外,Cu離子易於電偏壓下擴散至SiO2中,且即使係在介電質內之極低Cu濃度下亦會增加Cu線間的介電漏電。此外,如銅擴散至主動裝置所處的下層矽中,則裝置效能會退化。
銅於二氧化矽(SiO2)及於其他金屬間介電質(IMD)/層間介電質(ILD)中之高擴散性的問題仍保持極度相關。為處理此問題,必需將積體電路基板塗布適當的阻障層,其囊封銅及阻止銅原子之擴散。通常將包含傳導性及非傳導性材料兩者之阻障層形成於圖案化介電層上,隨後再沈積銅。阻障層之典型材料包括鉭(Ta)、
氮化鉭(TaNx)、鎢(W)、鈦(Ti)、氮化鈦(TiN)、釕(Ru)、鈷(Co)、鉬(Mo)、錸(Rh)、及其合金。
在深次微米半導體之製造中,使用銅鑲嵌製程來在低k介電層中形成傳導銅線及通孔。鑲嵌製程的一重要步驟係銅化學機械研磨(CMP)以移除在介電層表面上方的過剩銅。CMP製程涉及在CMP漿液之存在下在受控壓力及溫度下使半導體裝置之薄且平坦的基板抵靠經潤濕的研磨墊固持且旋轉。該等漿液包含研磨材料及適用於特定CMP製程及需求的化學添加劑。在CMP製程後,由來自研磨漿液之顆粒、添加至漿液之化學物質、及研磨漿液之反應副產物組成之污染物殘留於晶圓表面上。必需在微電子裝置製程中之任何進一步步驟之前將所有污染物移除,以避免裝置可靠性退化及將瑕疵引入至裝置中。此等污染物之顆粒通常小於0.3微米。
在此方面的一特定問題係在CMP加工後殘留於微電子裝置基板上之殘留物。此等殘留物包括CMP材料及腐蝕抑制劑化合物諸如苯并三唑(BTA)。若未經移除,則此等殘留物會導致損壞銅線或使銅金屬化嚴重變粗糙,以及導致CMP後塗覆層於裝置基板上之不良黏著。銅金屬化之嚴重粗糙化尤其成為問題,因過度粗糙的銅會導致產物微電子裝置之不良電效能。為此,已發展出CMP後移除組成物來移除CMP後殘留物及污染物。
習知之清潔技術使用清潔溶液(例如,基於氫氧化銨之鹼性溶液)於晶圓表面上之流體流動組合超音波振盪、噴射或刷洗來移除污染物。該等清潔溶液藉由在自晶圓移除脫落的污染物之前侵蝕晶圓表面或與污染物反應來移除污染物。一些污染物可能不利地對清潔溶液中之化學成分呈化學惰性。此外,技藝中已知之含
胺清潔溶液有臭味且會釋放會破壞光阻劑的胺蒸氣至廠中。
提供用於微電子裝置之CMP後清潔、用於自該裝置之表面實質上無瑕疵且實質上無刮痕地移除CMP殘留物及污染物之改良的不含胺之組成物在技藝中將係一項顯著進步。該等水性組成物達成自裝置表面實質的殘留物及污染物移除,而不會損壞經暴露的低k介電材料及互連及通孔材料(例如,含銅及/或鋁之材料)。
本發明大致係關於用於自其上具有殘留物及/或污染物之微電子裝置清除該等殘留物及污染物之無胺的組成物及方法。該殘留物可包括CMP後殘留物。
在一態樣中,描述一種相對於微電子裝置上之含銅材料層保護含鈷材料層的方法,該方法包括使微電子裝置與包含至少一種氧化劑之高pH組成物接觸,其中該高pH組成物之pH係大於約10。
在另一態樣中,描述一種用來自表面清除殘留物及污染物之組成物,該組成物包括至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、水、至少一種氧化劑,其中該至少一種鹼性化合物包含選自由下列所組成之群之物質:(a)KOH、CsOH、氫氧化銨、及其組合,其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料,及(b)氫氧化四級鏻鹼,其中該組成物中之至少一組分具有至少一個氮原子,其中該pH係大於約10,且其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料。
在又另一態樣中,描述一種自其上具有殘留物及污染
物之微電子裝置清除該等殘留物及污染物之方法,該方法包括使微電子裝置與組成物接觸足以自微電子裝置至少部分地清除該等殘留物及污染物之時間,其中該組成物包括至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、水、至少一種氧化劑,其中該至少一種鹼性化合物包含選自由下列所組成之群之物質:(a)KOH、CsOH、氫氧化銨、及其組合,其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料,及(b)氫氧化四級鏻鹼,其中該組成物中之至少一組分具有至少一個氮原子,其中該pH係大於約10,且其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料。
本發明之其他態樣、特徵及優點將可由隨後之揭示內容及隨附之申請專利範圍而更完整明瞭。
圖1繪示銅及鈷在與實施例1之組成物接觸後之電流腐蝕的塔菲爾圖(Tafel plot)。
圖2A繪示銅及鈷在與調配物B接觸後之電流腐蝕的塔菲爾圖。
圖2B繪示銅及鈷在與調配物C接觸後之電流腐蝕的塔菲爾圖。
圖2C繪示銅及鈷在與調配物D接觸後之電流腐蝕的塔菲爾圖。
圖3A繪示銅及鈷在與調配物E接觸後之電流腐蝕的塔菲爾圖。
圖3B繪示銅及鈷在與調配物F接觸後之電流腐蝕的塔菲爾圖。
圖3C繪示銅及鈷在與調配物G接觸後之電流腐蝕的塔菲爾圖。
圖4繪示銅及鈷在與實施例4之組成物接觸後之電流腐蝕的塔菲爾圖。
圖5繪示銅及鈷在與實施例5之組成物接觸後之電流腐蝕的塔菲爾圖。
圖6繪示銅及鈷在與實施例6之組成物接觸後之電流腐蝕的塔菲爾圖。
本發明大致係關於自其上具有CMP後殘留物及污染物之微電子裝置清除該等殘留物及污染物之無胺的組成物。該等清潔組成物可與經暴露的材料相容,同時自微電子裝置之表面實質上地移除該等CMP後殘留物及污染物。該等清潔組成物有利地與含鈷材料層高度相容。此外,本發明大致係關於保護含鈷材料。
為容易參考起見,「微電子裝置」係對應於經製造用於微電子、積體電路、或電腦晶片應用中之半導體基板、平板顯示器、相變記憶體裝置、太陽能面板及包括太陽能基板、光伏打元件、及微機電系統(MEMS)的其他產品。應瞭解術語「微電子裝置」不具任何限制意味,且包括任何最終將成為微電子裝置或微電子組件的基板。
如本文所用之「殘留物」係相當於在微電子裝置之製造期間(包括,但不限於,電漿蝕刻、灰化、化學機械研磨、濕式
蝕刻、及其組合)產生的顆粒。
如本文所用之「污染物」係相當於存在於CMP漿液中之化學物質,例如,苯并三唑(BTA)、研磨漿液之反應副產物、存在於濕式蝕刻組成物中之化學物質、濕式蝕刻組成物之反應副產物、及任何其他作為CMP製程、濕式蝕刻、電漿蝕刻或電漿灰化製程之副產物的材料。
如本文所用之「CMP後殘留物」係相當於來自研磨漿液之顆粒(例如,含矽石顆粒)、存在於漿液中之化學物質、研磨漿液之反應副產物、富碳顆粒、研磨墊顆粒、刷的卸載顆粒、設備的構造材料顆粒、銅、銅之氧化物、有機殘留物、及任何其他作為CMP製程之副產物的物質。
如本文所定義之「低k介電材料」係相當於任何在層狀微電子裝置中使用作為介電材料的材料,其中該材料具有小於約3.5之介電常數。低k介電材料較佳包括低極性材料諸如含矽有機聚合物、含矽之有機/無機混合材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽、摻碳氧化物(CDO)玻璃、購自Novellus Systems,Inc.之CORALTM、購自Applied Materials,Inc.之BLACK DIAMONDTM、購自Dow Corning,Inc.之SiLKTM、及Nanopore,Inc.之NANOGLASSTM、及其類似物。應明瞭低k介電材料可具有不同密度及不同孔隙度。
如本文所定義之「無胺之清潔組成物」係相當於在即將與其上具有CMP後及/或污染物之微電子裝置接觸前之無胺之組成物。
如本文所定義,「錯合劑」包括熟悉技藝人士理解為
錯合劑、鉗合劑及/或螯合劑的該等化合物。錯合劑將與待使用本發明之組成物移除的金屬原子及/或金屬離子化學結合或以物理方式將其固持住。
如本文所定義,術語「阻障材料」係相當於任何在技藝中用來密封金屬線(例如,銅互連體),以使該金屬(例如,銅)之擴散至介電材料中減至最小的材料。習知的阻障層材料包括組或鈦、其氮化物及矽化物、及其合金。可用作可直接電鍍擴散阻障之候選材料包括釕(Ru)、鈷(Co)、鎢(W)、鉬(Mo)、錸(Rh)、及其合金,包括,但不限於,純鈷、CoWP、CoWB、鈷之氮化物(包括含有諸如Ta或Li之額外元素的鈷之氮化物)、CoW、CoP、CoSi、及矽化鈷。
如本文所定義之「含鈷材料層」係相當於包含鈷及鈷合金的金屬層。
如本文所定義之「含銅材料層」係相當於包含銅及銅合金的金屬層。
如本文所使用之「約」係意指相當於所述值之±5%。
「實質上不含」在本文係定義為小於2重量%,較佳小於1重量%,更佳小於0.5重量%,再更佳小於0.1重量%,及最佳0重量%。
如本文所定義,「蝕刻後殘留物」係相當於在氣相電漿蝕刻製程(例如,BEOL雙重鑲嵌加工)後殘留的材料。蝕刻後殘留物之性質可為有機、有機金屬、有機矽、或無機,例如,含矽材料、碳基有機材料、及蝕刻氣體殘留物(包括,但不限於,氧及氟)。文中所使用之「灰化後殘留物」係相當於在用來移除硬化光阻劑及
/或底部抗反射塗層(BARC)材料之氧化或還原電漿灰化後殘留的材料。灰化後殘留物之性質可為有機、有機金屬、有機矽、或無機。
熟悉技藝人士當明瞭當組成物為水性時,氫氧化銨(NH4OH)可與氨(NH3)交替使用。
關於本發明,「胺」係定義為至少一種一級、二級、或三級胺,其限制條件為(i)醯胺基、(ii)同時包括羧酸基及胺基之物質(例如,胺基酸)、(iii)氨(亦稱為氫氧化銨)、(iv)包括胺基之界面活性劑、及(v)胺-N-氧化物不被視為根據此定義之「胺」。胺之化學式可以NR1R2R3表示,其中R1、R2及R3可彼此相同或不同且係選自由氫、直鏈或分支鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、己基)、C6-C10芳基(例如,苄基)、直鏈或分支鏈C1-C6烷醇(例如,甲醇、乙醇、丙醇、丁醇、戊醇、己醇)、及其組合所組成之群,其限制條件為R1、R2及R3不可皆為氫。氫氧化四級銨化合物具有通式R1R2R3R4NOH,其中R1、R2、R3及R4係彼此相同或不同且係氫、C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基或己基)、及經取代或未經取代之C6-C10芳基(例如,苄基);及烷醇胺。
如本文所定義,氫氧化四級鏻鹼係相當於具有式R1R2R3R4POH之化合物,其中R1、R2、R3及R4係彼此相同或不同且係氫、C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基或己基)、及經取代或未經取代之C6-C10芳基(例如,苄基)。氫氧化四級鏻鹼包括氫氧化四甲鏻、氫氧化四乙鏻、氫氧化四丙鏻、氫氧化四丁鏻(TBPH)、氫氧化十四烷基三丁基鏻、氫氧化苯基三甲鏻、氫氧化苯基三乙鏻及氫氧化苄基三甲鏻、對應的陰離子(例如,鹵化物)、及
其組合。
如本文所用,「適用」於自其上具有殘留物及污染物之微電子裝置清除該等殘留物及污染物係相當於自該微電子裝置至少部分移除該等殘留物/污染物。清潔效力係藉由在微電子裝置上的物體減少來評定。舉例來說,可使用原子力顯微鏡來進行清潔前及清潔後分析。可將樣品上之顆粒登錄為一像數範圍。可應用直方圖(例如,Sigma Scan Pro)來過濾特定強度(例如,231-235)中之像素,且計算顆粒數目。顆粒減少可使用下式來計算:
值得注意地,清潔效力之測定方法僅係提供作為實例,而不意欲對其造成限制。或者,可將清潔效力視為經顆粒物質覆蓋之總表面的百分比。舉例來說,AFM可經程式化以執行z平面掃描,來識別高於一特定高度臨限值之相關形貌面積,然後再計算經該等相關面積覆蓋之總表面面積。熟悉技藝人士當可輕易明瞭在清潔後經該等相關面積覆蓋的面積愈小,清潔組成物就愈有效。較佳地,使用文中所述之組成物自微電子裝置移除至少75%之殘留物/污染物,更佳至少90%,再更佳至少95%,及最佳移除至少99%之殘留物/污染物。
本發明之組成物可以如更完整說明於下文之相當多樣的特定調配物具體實施。
在所有此等組成物中,當參照包括零下限之重量百分比範圍論述組成物之特定組分時,當明瞭在組成物之各種特定具體例中可存在或不存在此等組分,且在存在此等組分之情況中,其可
以基於其中使用此等組分之組成物之總重量計低至0.001重量百分比之濃度存在。
在第一態樣中,本發明係關於一種用來清除CMP後殘留物及污染物之無胺之組成物,該無胺之組成物包括至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、至少一種氧化劑、及水。視情況,該無胺之組成物可進一步包括至少一種緩衝劑。
在一具體例中,該無胺之組成物包含以下組分,由其所組成,或基本上由其所組成:至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、至少一種氧化劑、及水,其中該至少一種鹼性化合物包括KOH、CsOH、氫氧化銨、及其組合,較佳為KOH,視情況之至少一種緩衝劑。該無胺之組成物之濃縮物中的組分係基於組成物之總重量以以下之重量百分比範圍存在,
如熟悉技藝人士所可輕易明瞭,當經稀釋時,無胺之濃縮組成物中的組分之重量百分比值將隨稀釋倍數而改變。文中所述之組成物有利地相對於含銅材料層保護含鈷材料層。水較佳係經去離子。應明瞭當意欲存在至少一種氧化劑時,其可在清潔裝置之上游處或
在清潔裝置處才添加。
在又另一具體例中,該無胺之組成物包含以下組分,由其所組成,或基本上由其所組成:至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、至少一種氧化劑、及水,其中該至少一種鹼性化合物包括氫氧化四級鏻鹼及視情況之至少一種緩衝劑,其中該組成物中之至少一組分具有至少一個氮原子。該無胺之組成物之濃縮物中的組分係基於組成物之總重量以以下之重量百分比範圍存在,
如熟悉技藝人士所可輕易明瞭,當經稀釋時,無胺之濃縮組成物中的組分之重量百分比值將隨稀釋倍數而改變。文中所述之組成物有利地相對於含銅材料層保護含鈷材料層。水較佳係經去離子。應明瞭當意欲存在至少一種氧化劑時,其可在清潔裝置之上游處或在清潔裝置處才添加。熟悉技藝人士應明瞭由於該等組成物意欲為「無胺」,因而「該組成物中之至少一組分具有至少一個氮原子」包括含有氮原子的非胺化合物,例如,胺基酸、胺基聚羧酸、包含氮原子的離子化合物等。
文中所述之組成物可有用於包括,但不限於,下列應用中:蝕刻後殘留物移除、灰化後殘留物移除表面製備、電鍍後清潔、CMP後殘留物移除、銅晶種蝕刻/清潔、穿透矽通孔(through silicon via;TSV)清潔、MEMS清潔、及鈷及鈷合金表面清潔及保護。
文中涵蓋的錯合劑包括於其鹽中包含至少一個COOH基團或羧酸根基團的有機酸,包括,但不限於,乳酸、順丁烯二酸、抗壞血酸、蘋果酸、檸檬酸、苯甲酸、反丁烯二酸、琥珀酸、草酸、丙二酸、苯乙醇酸、順丁烯二酸酐、酞酸、戊二酸、羥乙酸、乙醛酸、甘油、乙醯丙酮、柳異羥肟酸、其鹽、或其之部分中和形式,苯乙酸、奎尼酸(quinic acid)、1,2,4,5-苯四甲酸、酒石酸、對苯二甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、葡萄糖酸、甘油酸、甲酸、乙酸、丙酸、丙烯酸、己二酸、衣康酸、葡萄糖醛酸、胺基酸(例如,甘胺酸、離胺酸、β-丙胺酸、組胺酸、苯基丙胺酸、半胱胺酸、白胺酸、絲胺酸、精胺酸、天冬胺酸、麩胺酸)、8-羥基喹啉、2,4-戊二酮、苯四羧酸、丙酮酸、單寧酸、對胺苯磺酸、2-羥基膦醯羧酸(HPAA)、鄰苯二酚、五倍子酚、五倍子酸、單寧酸、乙二胺四乙酸(EDTA)、二伸乙三胺五乙酸(DTPA)、(1,2-伸環己基二氮基)四乙酸(CDTA)、亞胺二乙酸、2-膦醯丁烷-1,2,4-三羧酸(PBTCA)、其他脂族及芳族羧酸、其鹽以及前述酸之組合。可作為替代物或附加物涵蓋的其他錯合劑包括膦酸及其衍生物(例如,1,5,9-三吖環十二烷-N,N’,N”-參(亞甲基膦酸)(DOTRP)、1,4,7,10-四吖環十二烷-N,N’,N”,N’”-肆(亞甲基膦酸)(DOTP)、氮基參(亞甲基)三膦酸、二伸乙三胺五(亞甲基膦酸)(DETAP)、胺基三(亞甲基膦
酸)、1-羥亞乙基-1,1-二膦酸(HEDP)、雙(六亞甲基)三胺膦酸、1,4,7-三吖環壬烷-N,N’,N”-參(亞甲基膦酸)(NOTP)、乙二胺四(亞甲基膦酸(EDTMP))、水楊酸、對甲苯磺酸、5-磺基水楊酸及其衍生物、及其任何組合。較佳地,用於無胺之組成物之錯合劑包含5-磺基水楊酸、CDTA、胺基酸諸如甘胺酸、半胱胺酸、或組胺酸、及其任何組合。一些錯合劑可有利地使包含至少一種氧化劑之無胺之組成物穩定。舉例來說,僅添加約0.001重量%至約0.1重量% CDTA至包含氧化劑(例如,尿素過氧化氫)之無胺之組成物將使該組成物穩定,實質上降低氧化劑隨時間之分解。
涵蓋的氧化劑包括臭氧、硝酸、鼓泡空氣、環己胺基磺酸、過氧化氫(H2O2)、FeCl3(包括水合及未水合)、發氧方(oxone,2KHSO5˙KHSO4˙K2SO4)、多原子銨鹽(例如,過氧單硫酸銨、亞氯酸銨(NH4ClO2)、氯酸銨(NH4ClO3)、碘酸銨(NH4IO3)、過硼酸銨(NH4BO3)、過氯酸銨(NH4ClO4)、過碘酸銨(NH4IO3)、過硫酸銨((NH4)2S2O8)、次氯酸銨(NH4ClO)、過硼酸鈉(NaBO3)、多原子鈉鹽(例如,過硫酸鈉(Na2S2O8)、次氯酸鈉(NaClO))、多原子鉀鹽(例如,碘酸鉀(KIO3)、過錳酸鉀(KMnO4)、過硫酸鉀、過硫酸鉀(K2S2O8)、次氯酸鉀(KClO))、多原子四甲銨鹽(例如,亞氯酸四甲銨((N(CH3)4)ClO2)、氯酸四甲銨((N(CH3)4)ClO3)、碘酸四甲銨((N(CH3)4)IO3)、過硼酸四甲銨((N(CH3)4)BO3)、過氯酸四甲銨((N(CH3)4)ClO4)、過碘酸四甲銨((N(CH3)4)IO4)、過硫酸四甲銨((N(CH3)4)S2O8))、多原子四丁銨鹽(例如,過氧單硫酸四丁銨)、過氧單硫酸、硝酸鐵(Fe(NO3)3)、胺-N-氧化物(例如,N-甲基啉-N-氧化物(NMMO)、三甲胺-N-氧化物、三乙胺-N-氧化物、吡啶-N-
氧化物、N-乙基啉-N-氧化物、N-甲基吡咯啶-N-氧化物、N-乙基吡咯啶-N-氧化物)、尿素過氧化氫((CO(NH2)2)H2O2)、過乙酸(CH3(CO)OOH)、過碘酸、重鉻酸鉀、氯酸鉀、2-硝基酚、1,4-苯醌、過氧苯甲酸、過氧酞酸鹽、釩之氧化物(例如,VO2、V6O13)、偏釩酸銨、鎢酸銨、硝酸鈉、硝酸鉀、硝酸銨、硝酸鍶、硫酸、及其組合。較佳地,用於無胺之組成物之氧化劑包含過氧化氫、NMMO、尿素過氧化氫、及其組合。
涵蓋的溶劑合劑包括,但不限於,2-吡咯啶酮、1-(2-羥乙基)-2-吡咯啶酮(HEP)、甘油、1,4-丁二醇、四亞甲碸(四氫噻吩碸)、二甲碸、乙二醇、丙二醇、二丙二醇、二甘醇單甲醚、三甘醇單甲醚、二甘醇單乙醚、三甘醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二甘醇單丁醚(即丁基卡必醇)、三甘醇單丁醚、乙二醇單己醚、二甘醇單己醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(TPGME)、二丙二醇二甲基醚、二丙二醇乙基醚、丙二醇正丙基醚、二丙二醇正丙基醚(DPGPE)、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、三丙二醇正丁基醚、丙二醇苯基醚、及其組合。較佳地,用於無胺之組成物的溶劑合劑包括四氫噻吩碸(四亞甲碸)、1-(2-羥乙基)-2-吡咯啶酮、及其組合。
當存在時,緩衝劑係經添加以在稀釋及製造期間穩定無胺之組成物以及達成適當的組成物pH值,其係如熟悉技藝人士所可輕易決定。涵蓋的緩衝劑包括,但不限於,磷酸二鉀、碳酸鉀、硼酸、離胺酸、脯胺酸、β-丙胺酸、乙二胺四乙酸(EDTA)、二伸乙三胺五乙酸(DTPA)、二甲基乙二肟(dimethyl glyoxime)、二鹼式
磷酸鹽(例如,(NH4)H2PO4、K2HPO4)、三鹼式磷酸鹽(例如,(NH4)3PO4、K3PO4)、二鹼式及三鹼式磷酸鹽之混合物(例如,K2HPO4/K3PO4)、二鹼式及三鹼式碳酸鹽之混合物(例如,K2CO3/KHCO3)、羥基亞乙基二膦酸(HEDP)、及其組合。當存在時,較佳的緩衝劑包括二鹼式磷酸鹽(例如,(NH4)H2PO4、K2HPO4)、三鹼式磷酸鹽(例如,(NH4)3PO4、K3PO4)、二鹼式及三鹼式磷酸鹽之混合物(例如,K2HPO4/K3PO4)、及其組合。
文中所述之無胺之組成物較佳實質上不含通常用於化學機械研磨製程中之研磨材料(在開始清潔之前)、含氟化物來源、胺、四級銨鹼、及其任何組合。四級銨鹼包括具有式NR1R2R3R4OH之化合物,其中R1、R2、R3及R4可彼此相同或不同且係選自由下列所組成之群:氫、直鏈或分支鏈C1-C6烷基(例如,甲基、乙基、丙基、丁基、戊基、及己基)、及經取代或未經取代之C6-C10芳基(例如,苄基),其限制條件為R1、R2、R3或R4中之至少一者需為除氫外之組分。
在一較佳具體例中,無胺之組成物包含以下組分,由其所組成,或基本上由其所組成:(i)包含選自由過氧化氫、尿素過氧化氫、NMMO、及其組合所組成之群之物質之至少一種氧化劑,(ii)包含KOH之至少一種鹼性化合物,(iii)包含選自由5-磺基水楊酸及其衍生物、CDTA、甘胺酸、組胺酸、半胱胺酸、及其組合所組成之群之物質之至少一種錯合劑,(iv)選自由四氫噻吩碸、1-(2-羥乙基)-2-吡咯啶酮、及其組合所組成之群之至少一種溶劑合劑,及(v)水,其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料,其中該pH係在約7至
約13之範圍內。在另一較佳具體例中,無胺之組成物包含以下組分,由其所組成,或基本上由其所組成:(i)包含選自由過氧化氫、尿素過氧化氫、NMMO、及其組合所組成之群之物質之至少一種氧化劑,(ii)包含TBPH之至少一種鹼性化合物,(iii)包含選自由5-磺基水楊酸及其衍生物、CDTA、甘胺酸、組胺酸、半胱胺酸、及其組合所組成之群之物質之至少一種錯合劑,(iv)選自由四氫噻吩碸、1-(2-羥乙基)-2-吡咯啶酮、及其組合所組成之群之至少一種溶劑合劑,及(v)水,其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料,其中該pH係大於10,且其中該組成物中之至少一組分具有至少一個氮原子。較佳地,該無胺之組成物具有小於5埃/分鐘(Å min-1)之銅蝕刻速率,小於5埃/分鐘之鈷蝕刻速率,及大於20%、更佳大於30%、及最佳大於40%之BTA移除效率。文中所述之組成物有利地相對於含銅材料層保護含鈷材料層。
在第一態樣之一具體例中,提供一種可經稀釋用作清潔溶液之濃縮的無胺之組成物。濃縮組成物或「濃縮物」有利地容許使用者(例如,CMP製程工程師)在使用點將濃縮物稀釋至期望濃度及酸度。濃縮的無胺之組成物之稀釋可在約1:1至約2500:1,較佳約10:1至約100:1之範圍內,其中無胺之組成物係在工具處或工具之前方才用溶劑(例如,去離子水)稀釋。
文中所述之無胺之組成物的一重要特徵係非水性成分(除水外之成分)係少量地存在於組成物中,通常少於約20重量%。此具經濟優勢,因可更經濟地調配有效的無胺之組成物,由於無胺之CMP後組成物係被大量地使用,因此此點極具重要性。再
者,由於無胺之組成物係為水基,因此文中所述之無胺之組成物更容易處置。值得注意地,無胺之組成物之壽命僅取決於顆粒負載量,因此,無胺之組成物係可回收。
在第二態樣中,文中所述無胺之組成物包含以下組分,由其所組成,或基本上由其所組成:至少一種錯合劑、至少一種鹼性化合物、至少一種緩衝劑、水、視需要之至少一種氧化劑、視需要之至少一種還原劑、視需要之至少一種溶劑合劑、殘留物及/或污染物。應注意,該等殘留物及污染物可溶解及/或懸浮於文中所述無胺之組成物中。較佳地,該殘留物包括CMP後殘留物。
文中所述無胺之組成物係經由簡單地添加各別成分及混合至均勻狀態而容易地調配得。此外,可輕易地將無胺之組成物調配為單一包裝調配物或在使用點處或使用點前混合的多份調配物,例如,可將多份調配物之個別份於工具處或於工具上游之儲槽中混合。在本發明之寬廣實務中,各別成分的濃度可在無胺之組成物的特定倍數內寬廣地改變,即更稀或更濃,且當明瞭無胺之組成物可變化及替代地包含與本文之揭示內容一致之成分的任何組合,由其所組成,或基本上由其所組成。
因此,另一態樣係關於一種套組,其包括存於一或多個容器中之一或多種適於形成本發明第一態樣之組成物的組分。套組較佳包括用於在工廠或使用點處與額外的水及至少一種氧化劑結合之存於一或多個容器中之至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、水、視需要之至少一種緩衝劑。套組之容器必需適於儲存及運送該第一組成物組分,例如,NOWPak®容器(Advanced Technology Materials,Inc.,Danbury,Conn.,USA)。
在第三態樣中,文中所述無胺之組成物可有效用於自微電子裝置之表面清除CMP後殘留物及污染物。無胺之組成物應不會損壞低k介電材料,不會實質上地腐蝕裝置表面上的金屬互連體(例如,銅),且不會實質上地腐蝕含鈷材料層。文中所述之組成物有利地相對於電流對中之含銅材料層保護含鈷材料層。較佳地,無胺之組成物移除在殘留物移除前存在於裝置上之殘留物的至少85%,更佳至少90%,再更佳至少95%,及最佳至少99%。
在CMP後殘留物及污染物清潔應用中,無胺之組成物可配合相當多樣之習知清潔工具諸如超音波震盪(megasonics)及刷洗使用,其包括,但不限於,Verteq單晶圓超音波震盪Goldfinger、OnTrak系統DDS(雙面洗滌器)、SEZ單晶圓噴霧洗滌、Applied Materials Mirra-MesaTM/ReflexionTM/Reflexion LKTM、及Megasonic批式濕式台面系統。
在使用無胺之組成物於自其上具有CMP後殘留物及污染物之微電子裝置清除該等物質時,通常使無胺之組成物與裝置在約20℃至約50℃範圍內之溫度下接觸約5秒至約10分鐘之時間(較佳約15秒至5分鐘)。此等接觸時間及溫度係為說明性,可採用任何其他可有效於自裝置至少部分地清除CMP後殘留物/污染物的適當時間及溫度條件。「至少部分地清除」及「實質移除」皆係相當於移除在殘留物移除前存在於裝置上之殘留物的至少85%,更佳至少90%,再更佳至少95%,及最佳至少99%。
於達成期望的清潔作用後,可輕易地將無胺之組成物自其先前經施用的裝置移除,此可能係在本發明組成物之指定最終應用中所需且有效。沖洗溶液較佳包括去離子水。其後可使用氮氣
或旋轉乾燥循環乾燥裝置。
另一態樣係關於一種包含如文中所述之濃縮的無胺組成物之經稀釋的清潔組成物,其係以約1:1至約2500:1,較佳約10:1至約100:1之範圍稀釋,其中該無胺之組成物係在工具處或工具之前方才用溶劑(例如,去離子水)稀釋。
又另一態樣係關於根據本文所述方法製得之改良的微電子裝置,及含有該等微電子裝置之產品。
另一態樣係關於一種經再循環的無胺之組成物。該無胺之組成物可經再利用直至殘留物及/或污染物載入量達到各別組成物所可容納之最大量為止,此係可由熟悉技藝人士輕易地決定。
又再一態樣係關於製造包含微電子裝置之物件的方法,該方法包括使微電子裝置與無胺之組成物接觸足夠的時間,以自其上具有CMP後殘留物及污染物之微電子裝置清除該等殘留物及污染物,及將該微電子裝置併入至該物件中。
另一態樣係關於一種相對於微電子裝置上之含銅材料層保護含鈷材料層之方法,該方法包括使微電子裝置與文中所述之無胺之組成物接觸。
另一態樣係關於一種保護微電子裝置上之含鈷材料層之方法,該方法包括使微電子裝置與文中所述之無胺之組成物接觸。
又另一態樣係關於一種保護微電子裝置上之含鈷材料層之方法,該方法包括使微電子裝置與包含至少一種氧化劑之高pH溶液接觸,其中該溶液之pH係大於約10。驚人地發現包含至
少一種氧化劑之具高pH之溶液可保護含鈷材料層。該至少一種氧化劑可係任何該等前文於第一態樣中所述者且其含量係在約0.01重量%至約5重量%之範圍內。接觸時間可係約15秒至約5分鐘且接觸溫度係在約20℃至約50℃之範圍內,此係如熟悉技藝人士所可輕易地決定。為提供大於約10之pH值,組成物可包含至少一種選自由下列所組成之群之鹼:氫氧化鈉、氫氧化鉀、氫氧化銫、氫氧化銣、至少一種胺、至少一種氫氧化四級銨(例如,氫氧化四甲基銨(TMAH)、氫氧化四丙基銨(TPAH)、氫氧化四丁基銨、氫氧化四乙基銨、氫氧化苄基三乙基銨、氫氧化苄基三甲基銨、氫氧化三丁基甲基銨、氫氧化膽鹼、氫氧化銨、氫氧化(2-羥乙基)三甲基銨、氫氧化(2-羥乙基)三乙基銨、氫氧化(2-羥乙基)三丙基銨、氫氧化(1-羥丙基)三甲基銨、氫氧化乙基三甲基銨、氫氧化二乙基二甲基銨(DEDMAH)、氫氧化三烷基-羥烷基銨、氫氧化二烷基-雙(羥烷基)銨、氫氧化參(羥烷基)烷基銨、至少一種如文中所定義之氫氧化四級鏻、及其任何組合。熟悉技藝人士當明瞭應添加多少該至少一種鹼來達到大於約10之pH。該溶液可進一步包含如文中所定義之至少一種錯合劑、至少一種溶劑合劑、及水。值得注意地,該溶液較佳實質上不含含氟化物來源及通常用於化學機械研磨製程中之研磨材料。
本發明之特徵及優點由以下論述的說明性實施例作更完整展示。
製備包含10-20重量%四氫噻吩碸-W、0.01-2重量%二水合5-磺基水楊酸、0.01-2重量%甘胺酸、0.01-5重量% KOH、
0.001-1重量% CDTA、及0.01-5重量%尿素過氧化氫、其餘之水、pH大約10-12之組成物且測得銅及鈷之腐蝕速率分別為0.153埃/分鐘及0.098埃/分鐘。銅及鈷之電流腐蝕的塔菲爾圖顯示於圖1,其中可見鈷相對於電流對中之銅受到保護。
製備10-20重量%四氫噻吩碸-W、0.01-2重量%二水合5-磺基水楊酸、0.01-2重量%半胱胺酸、0.01-5重量% KOH、其餘之水、pH大約10-12之組成物,下文稱為調配物B。製備10-20重量%四氫噻吩碸-W、0.01-2重量%二水合5-磺基水楊酸、0.01-2重量%半胱胺酸、0.01-5重量% KOH、0.1-5重量%尿素過氧化氫、其餘之水、pH大約10-12之第二組成物,下文稱為調配物C。製備10-20重量%四氫噻吩碸-W、0.01-2重量%二水合5-磺基水楊酸、0.01-2重量%半胱胺酸、0.01-5重量% KOH、0.1-5重量%尿素過氧化氫、其餘之水、pH大約10-12之第三組成物,下文稱為調配物D。調配物D中尿素過氧化氫之濃度較調配物C中者大。銅及鈷之電流腐蝕的塔菲爾圖顯示於圖2A(調配物B)、2B(調配物C)及2C(調配物D),其中可見當尿素過氧化氫之濃度增加時,鈷相對於電流對中之銅受到保護。
製備20-40重量% 1-(2-羥乙基)-2-吡咯啶酮、0.01-2重量%酒石酸、0.01-2重量%甘胺酸、0.1-5重量%組胺酸、0.01-5重量% KOH、其餘之水、pH大約10-12之組成物,下文稱為調配物E。製備20-40重量%1-(2-羥乙基)-2-吡咯啶酮、0.01-2重量%酒石酸、0.01-2重量%甘胺酸、0.1-5重量%組胺酸、0.01-5重量%
KOH、0.1-5重量%尿素過氧化氫、其餘之水、pH大約10-12之第二組成物,下文稱為調配物F。製備20-40重量%1-(2-羥乙基)-2-吡咯啶酮、0.01-2重量%酒石酸、0.01-2重量%甘胺酸、0.1-5重量%組胺酸、0.01-5重量% KOH、0.1-5重量%尿素過氧化氫、其餘之水、pH大約10-12之第三組成物,下文稱為調配物G。調配物G中尿素過氧化氫之濃度較調配物F中者大。銅及鈷之電流腐蝕的塔菲爾圖顯示於圖3A(調配物E)、3B(調配物F)及3C(調配物G),其中可見當尿素過氧化氫之濃度增加時,鈷相對於電流對中之銅受到保護。
製備包含10-20重量%四氫噻吩碸-W、0.01-2重量%二水合5-磺基水楊酸、0.01-2重量%甘胺酸、2-12重量% TBPH、0.001-1重量% CDTA、及0.01-5重量%尿素過氧化氫、其餘之水、pH大約10-12之組成物且測得銅及鈷之蝕刻速率分別為約11-12埃/分鐘及<1埃/分鐘。銅及鈷之電流腐蝕的塔菲爾圖顯示於圖4,其中可見鈷相對於電流對中之銅受到保護。
製備10-20重量%四氫噻吩碸-W、0.01-2重量%二水合5-磺基水楊酸、0.01-2重量%半胱胺酸、1-7重量% TBPH、其餘之水、pH大約10-12之組成物且測得銅及鈷之蝕刻速率皆為約1埃/分鐘。銅及鈷之電流腐蝕的塔菲爾圖顯示於圖5,其中可見鈷未相對於電流對中之銅受到保護。預期當將氧化劑添加至此調配物時(例如,如同實施例2),保護作用將會轉換。
製備20-40重量%1-(2-羥乙基)-2-吡咯啶酮、0.01-2重量%酒石酸、0.01-2重量%甘胺酸、0.1-5重量%組胺酸、12-25重量% TBPH、其餘之水、pH大約10-12之組成物且測得銅及鈷之蝕刻速率分別為約2埃/分鐘及20埃/分鐘。銅及鈷之電流腐蝕的塔菲爾圖顯示於圖6,其中可見鈷未相對於電流對中之銅受到保護。預期當將氧化劑添加至此調配物時(例如,如同實施例3),保護作用將會轉換。
雖然本發明已參照說明具體例及特徵以不同方式揭示於文中,但當明瞭前文所述之具體例及特徵並非要限制本發明,且熟悉技藝人士當可基於文中之揭示內容明白其他的變化、修改及其他具體例。因此,本發明係應廣泛解釋為涵蓋在後文所述之申請專利範圍之精神及範疇內的所有此等變化、修改及替代具體例。
Claims (10)
- 一種保護微電子裝置上之含鈷材料層之方法,該方法包括使微電子裝置與包含至少一種氧化劑及至少一氫氧化四級鏻鹼之高pH組成物接觸,其中該高pH組成物之pH係大於10。
- 如請求項1之方法,其中,該至少一種氧化劑包括選自由下列所組成之群之物質:臭氧、硝酸、鼓泡空氣、環己胺基磺酸、過氧化氫、FeCl3、發氧方(oxone,2KHSO5˙KHSO4˙K2SO4)、過氧單硫酸銨、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、次氯酸銨、過硼酸鈉、過硫酸鈉、次氯酸鈉、碘酸鉀、過錳酸鉀、過硫酸鉀、次氯酸鉀、亞氯酸四甲銨、氯酸四甲銨、碘酸四甲銨、過硼酸四甲銨、過氯酸四甲銨、過碘酸四甲銨、過硫酸四甲銨、過氧單硫酸四丁銨、過氧單硫酸、硝酸鐵、N-甲基啉-N-氧化物、三甲胺-N-氧化物、三乙胺-N-氧化物、吡啶-N-氧化物、N-乙基啉-N-氧化物、N-甲基吡咯啶-N-氧化物、N-乙基吡咯啶-N-氧化物、尿素過氧化氫、過乙酸、過碘酸、重鉻酸鉀、氯酸鉀、2-硝基酚、1,4-苯醌、過氧苯甲酸、過氧酞酸鹽、釩之氧化物、偏釩酸銨、鎢酸銨、硝酸鈉、硝酸鉀、硝酸銨、硝酸鍶、硫酸、及其組合。
- 如請求項1或2之方法,其中該組成物中之至少一組分具有至少一個氮原子,且其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料。
- 如請求項3之方法,其中,該組成物進一步包括至少一種錯合劑、至少一種溶劑合劑、及水。
- 一種用來自表面清除殘留物及污染物之組成物,該組成物包括至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、水及至少 一種氧化劑,其中該至少一種鹼性化合物包含氫氧化四級鏻鹼,其中該組成物中之至少一組分具有至少一個氮原子,其中該組成物具有大於約10之pH,且其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料。
- 如請求項5之組成物,其中,該氫氧化四級鏻鹼包括氫氧化四甲鏻、氫氧化四乙鏻、氫氧化四丙鏻、氫氧化四丁鏻(TBPH)、氫氧化十四烷基三丁基鏻、氫氧化苯基三甲鏻、氫氧化苯基三乙鏻或氫氧化苄基三甲鏻或其組合。
- 如請求項5之組成物,其中,該至少一種錯合劑包括選自由下列所組成之群之物質:乳酸、順丁烯二酸、抗壞血酸、蘋果酸、檸檬酸、苯甲酸、反丁烯二酸、琥珀酸、草酸、丙二酸、苯乙醇酸、順丁烯二酸酐、酞酸、天冬胺酸、麩胺酸、戊二酸、羥乙酸、乙醛酸、甘油、乙醯丙酮、柳異羥肟酸、柳異羥肟酸之鹽、或柳異羥肟酸之部分中和形式,苯乙酸、奎尼酸(quinic acid)、1,2,4,5-苯四甲酸、酒石酸、對苯二甲酸、1,2,4-苯三甲酸、1,3,5-苯三甲酸、葡萄糖酸、甘油酸、甲酸、乙酸、丙酸、丙烯酸、己二酸、衣康酸、葡萄糖醛酸、甘胺酸、離胺酸、β-丙胺酸、組胺酸、苯基丙胺酸、半胱胺酸、白胺酸、絲胺酸、8-羥基喹啉、2,4-戊二酮、苯四羧酸、丙酮酸、單寧酸、對胺苯磺酸、2-羥基膦醯羧酸(HPAA)、鄰苯二酚、五倍子酚、五倍子酸、單寧酸、乙二胺四乙酸(EDTA)、二伸乙三胺五乙酸(DTPA)、(1,2-伸環己基二氮基)四乙酸(CDTA)、亞胺二乙酸、2-膦醯丁烷-1,2,4-三羧酸(PBTCA)、膦酸、1,5,9-三吖環十二烷-N,N’,N”-參(亞甲基膦酸)(DOTRP)、1,4,7,10-四吖環十二烷-N,N’,N”,N’”-肆(亞甲基膦酸)(DOTP)、氮基參(亞甲基)三膦酸、二伸乙三胺五(亞甲基膦酸)(DETAP)、胺基三(亞甲基膦酸)、 1-羥亞乙基-1,1-二膦酸(HEDP)、雙(六亞甲基)三胺膦酸、1,4,7-三吖環壬烷-N,N’,N”-參(亞甲基膦酸)(NOTP)、乙二胺四(亞甲基膦酸)(EDTMP)、水楊酸、對甲苯磺酸、5-磺基水楊酸及其衍生物、及其任何組合。
- 如請求項5之組成物,其中,該至少一種氧化劑包括選自由下列所組成之群之物質:臭氧、硝酸、鼓泡空氣、環己胺基磺酸、過氧化氫、FeCl3、發氧方(2KHSO5˙KHSO4˙K2SO4)、過氧單硫酸銨、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、次氯酸銨、過硼酸鈉、過硫酸鈉、次氯酸鈉、碘酸鉀、過錳酸鉀、過硫酸鉀、次氯酸鉀、亞氯酸四甲銨、氯酸四甲銨、碘酸四甲銨、過硼酸四甲銨、過氯酸四甲銨、過碘酸四甲銨、過硫酸四甲銨、過氧單硫酸四丁銨、過氧單硫酸、硝酸鐵、N-甲基啉-N-氧化物、三甲胺-N-氧化物、三乙胺-N-氧化物、吡啶-N-氧化物、N-乙基啉-N-氧化物、N-甲基吡咯啶-N-氧化物、N-乙基吡咯啶-N-氧化物、尿素過氧化氫、過乙酸、過碘酸、重鉻酸鉀、氯酸鉀、2-硝基酚、1,4-苯醌、過氧苯甲酸、過氧酞酸鹽、釩之氧化物、偏釩酸銨、鎢酸銨、硝酸鈉、硝酸鉀、硝酸銨、硝酸鍶、硫酸、及其組合。
- 如請求項5之組成物,其中,該至少一種溶劑合劑包括選自由下列所組成之群之物質:2-吡咯啶酮、1-(2-羥乙基)-2-吡咯啶酮、甘油、1,4-丁二醇、四亞甲碸(四氫噻吩碸)、二甲碸、乙二醇、丙二醇、二丙二醇、二甘醇單甲醚、三甘醇單甲醚、二甘醇單乙醚、三甘醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二甘醇單丁醚、三甘醇單丁醚、乙二醇單己醚、二甘醇單己醚、乙二醇苯基醚、丙二醇甲基醚、二丙二醇甲基醚(DPGME)、三丙二醇甲基醚(TPGME)、二丙二醇二甲基醚、二 丙二醇乙基醚、丙二醇正丙基醚、二丙二醇正丙基醚(DPGPE)、三丙二醇正丙基醚、丙二醇正丁基醚、二丙二醇正丁基醚、三丙二醇正丁基醚、丙二醇苯基醚、及其組合。
- 一種自其上具有殘留物及污染物之微電子裝置清除該等殘留物及污染物之方法,該方法包括使微電子裝置與組成物接觸足以自微電子裝置至少部分地清除該等殘留物及污染物之時間,其中該組成物包括至少一種錯合劑、至少一種鹼性化合物、至少一種溶劑合劑、水及至少一種氧化劑,其中該至少一種鹼性化合物包含氫氧化四級鏻鹼,其中該組成物中之至少一組分具有至少一個氮原子,其中該組成物具有大於約10之pH,且其中該組成物實質上不含胺、四級鹼、含氟化物來源、及通常用於化學機械研磨製程中之研磨材料。
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