CN109690741A - Cmp用研磨液和研磨方法 - Google Patents
Cmp用研磨液和研磨方法 Download PDFInfo
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- CN109690741A CN109690741A CN201780048056.6A CN201780048056A CN109690741A CN 109690741 A CN109690741 A CN 109690741A CN 201780048056 A CN201780048056 A CN 201780048056A CN 109690741 A CN109690741 A CN 109690741A
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- Prior art keywords
- film
- metal
- lapping liquid
- grinding
- acid
- Prior art date
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- 238000000227 grinding Methods 0.000 title claims abstract description 117
- 239000007788 liquid Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 41
- 239000002184 metal Substances 0.000 claims abstract description 136
- 229910052751 metal Inorganic materials 0.000 claims abstract description 133
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 54
- 239000002245 particle Substances 0.000 claims abstract description 49
- 230000004888 barrier function Effects 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 35
- 238000005498 polishing Methods 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 12
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 10
- -1 polycyclic phenyl Chemical group 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 5
- 125000006353 oxyethylene group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 3
- 235000005979 Citrus limon Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 description 155
- 239000010949 copper Substances 0.000 description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 230000007547 defect Effects 0.000 description 12
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910000881 Cu alloy Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003002 pH adjusting agent Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000005368 silicate glass Substances 0.000 description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 101710171243 Peroxidase 10 Proteins 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000004520 agglutination Effects 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 150000003852 triazoles Chemical group 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 150000000177 1,2,3-triazoles Chemical class 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 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 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001362 Ta alloys Inorganic materials 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
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- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 150000007522 mineralic acids Chemical class 0.000 description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
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- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
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- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
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- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 description 1
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- FBQJKKPQBMSWEP-UHFFFAOYSA-N 1,3-diphenyl-1,3-diazinane-2,4,6-trione Chemical class O=C1CC(=O)N(C=2C=CC=CC=2)C(=O)N1C1=CC=CC=C1 FBQJKKPQBMSWEP-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- VBXZSFNZVNDOPB-UHFFFAOYSA-N 1,4,5,6-tetrahydropyrimidine Chemical compound C1CNC=NC1 VBXZSFNZVNDOPB-UHFFFAOYSA-N 0.000 description 1
- OTLPBSUQWCUNIG-UHFFFAOYSA-N 1-(4-aminopyrimidin-2-yl)ethanone Chemical compound CC(=O)C1=NC=CC(N)=N1 OTLPBSUQWCUNIG-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- AXINVSXSGNSVLV-UHFFFAOYSA-N 1h-pyrazol-4-amine Chemical compound NC=1C=NNC=1 AXINVSXSGNSVLV-UHFFFAOYSA-N 0.000 description 1
- BZYUMXXOAYSFOW-UHFFFAOYSA-N 2,3-dimethylthiophene Chemical compound CC=1C=CSC=1C BZYUMXXOAYSFOW-UHFFFAOYSA-N 0.000 description 1
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 description 1
- DPVIABCMTHHTGB-UHFFFAOYSA-N 2,4,6-trichloropyrimidine Chemical compound ClC1=CC(Cl)=NC(Cl)=N1 DPVIABCMTHHTGB-UHFFFAOYSA-N 0.000 description 1
- RJVAFLZWVUIBOU-UHFFFAOYSA-N 2,4,6-trimethoxypyrimidine Chemical compound COC1=CC(OC)=NC(OC)=N1 RJVAFLZWVUIBOU-UHFFFAOYSA-N 0.000 description 1
- OBSLLHNATPQFMJ-UHFFFAOYSA-N 2,4-Dimethylthiazole Chemical compound CC1=CSC(C)=N1 OBSLLHNATPQFMJ-UHFFFAOYSA-N 0.000 description 1
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- SYOANZBNGDEJFH-UHFFFAOYSA-N 2,5-dihydro-1h-triazole Chemical compound C1NNN=C1 SYOANZBNGDEJFH-UHFFFAOYSA-N 0.000 description 1
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- XCXKNNGWSDYMMS-UHFFFAOYSA-N 2-methyl-1-nitroguanidine Chemical compound CNC(N)=N[N+]([O-])=O XCXKNNGWSDYMMS-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JMFBVEWGVFCOKD-UHFFFAOYSA-N 2-n,4-n-bis(3-bromophenyl)-5-fluoropyrimidine-2,4-diamine Chemical compound N1=C(NC=2C=C(Br)C=CC=2)C(F)=CN=C1NC1=CC=CC(Br)=C1 JMFBVEWGVFCOKD-UHFFFAOYSA-N 0.000 description 1
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 description 1
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- VJEFVEHNRRGNQX-UHFFFAOYSA-N 3-(benzotriazol-1-yl)propane-1,1-diol Chemical compound C1=CC=C2N(CCC(O)O)N=NC2=C1 VJEFVEHNRRGNQX-UHFFFAOYSA-N 0.000 description 1
- NHLAPJMCARJFOG-UHFFFAOYSA-N 3-methyl-1,4-dihydropyrazol-5-one Chemical compound CC1=NNC(=O)C1 NHLAPJMCARJFOG-UHFFFAOYSA-N 0.000 description 1
- REGFWZVTTFGQOJ-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-amine Chemical compound NC1=NCCS1 REGFWZVTTFGQOJ-UHFFFAOYSA-N 0.000 description 1
- OUQMXTJYCAJLGO-UHFFFAOYSA-N 4-methyl-1,3-thiazol-2-amine Chemical compound CC1=CSC(N)=N1 OUQMXTJYCAJLGO-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
- FYTLHYRDGXRYEY-UHFFFAOYSA-N 5-Methyl-3-pyrazolamine Chemical compound CC=1C=C(N)NN=1 FYTLHYRDGXRYEY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- H—ELECTRICITY
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- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
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Abstract
本发明涉及一种研磨液,其为用于研磨至少包含阻挡金属、金属膜和二氧化硅膜的基板或至少包含阻挡金属、金属膜、二氧化硅膜和low‑k膜的基板的CMP用研磨液,所述研磨液含有研磨粒子、氧化金属溶解剂、氧化剂、水溶性高分子和碱金属离子,研磨时的所述研磨粒子和所述金属膜的表面电位为相同符号,所述研磨粒子的表面电位(mV)和所述金属膜的表面电位(mV)的乘积为250~10000,所述研磨液的pH为7.0~11.0。
Description
技术领域
本发明涉及CMP用研磨液和使用其的研磨方法。
背景技术
近年,随着半导体集成电路(以下,称为“LSI”。)的高集成化、高性能化,人们开发了新的微加工技术。化学机械研磨(以下,称为“CMP”。)法也是其中之一,是LSI制造工序,尤其是,多层布线形成工序中的绝缘膜的平坦化、金属插塞的形成、埋入式布线的形成中频繁使用的技术。例如在专利文献1中公开了该技术。
此外,最近,为了使LSI高性能化,人们尝试了使用铜或铜合金的金属膜作为形成布线材料的导电性物质。但是,对于铜或铜合金而言,难以实施基于频繁用于以往的铝合金布线的形成的干式蚀刻法而进行的微加工。
于是,主要采用所谓的镶嵌法(damascene method),即,在预先形成有沟槽的二氧化硅等的绝缘膜上堆积并埋入铜或铜合金的金属膜,通过CMP除去沟槽部以外的金属膜,形成埋入式布线。例如在专利文献2中公开了该技术。
另一方面,在铜或铜合金等金属膜的下层,作为用于防止金属扩散入绝缘膜中和提高密合性的阻挡金属,形成有由钽、钽合金、氮化钽等导体形成的层。因此,埋入铜或铜合金等的金属膜的布线部以外,需要通过CMP去除露出的阻挡金属。
但是,由于这些阻挡金属的硬度比铜或铜合金高,因此,即使组合铜或铜合金用的研磨材料来进行研磨也不能得到充分的研磨速度,且被研磨面的平坦性变差的情况多。于是,人们研究了由研磨金属膜的第1研磨工序和研磨阻挡金属的第2研磨工序构成的2步研磨方法。
图1显示基于一般的镶嵌工艺进行的布线形成的截面示意图。图1(a)表示研磨前的状态,具有在表面形成有沟槽的绝缘膜1、按照追随绝缘膜1的表面凹凸的方式形成的阻挡金属2、以填埋凹凸的方式堆积的铜或铜合金的布线部用金属3。
首先,如图1(b)所示,使用用于研磨布线部用金属的研磨液,研磨布线部用金属3直至阻挡金属2露出(第1研磨工序)。接着,使用阻挡金属2用的研磨液进行研磨直至绝缘膜1的凸部露出(第2研磨工序)。该第2研磨工序中,如图1(c)所示,常会出现进行了多余地研磨绝缘膜的过度研磨的情况。图1的(c)中,符号4表示第2研磨工序中的阻挡金属研磨前的图1(b)的状态。通过这样的过度研磨,可以提高研磨后的被研磨面的平坦性。
作为这样的阻挡金属用的研磨液,人们提出了下述的阻挡金属用研磨液的方案:其包含氧化剂、针对金属表面的保护膜形成剂、酸和水,pH为3以下,上述氧化剂的浓度为0.01~3质量%。(例如,参见专利文献3。)
此外,近年,随着布线间隔微细化,有时即便是非常微小的金属布线的腐蚀也会成为问题。有金属布线的腐蚀时,LSI的成品率恶化,因此,也寻求不引起金属布线的腐蚀的研磨液。此外,同样地从成品率的角度考虑,研磨后,金属布线和绝缘膜上的缺陷少也是必要的。
进一步地,随着近年的布线间隔微细化,会产生布线延迟的问题。集成电路中,将金属布线四处铺设好几层,由此传递信号,但随着微细化,布线彼此之间的距离变近,因此,邻近的布线间的布线间电容增大,与其成比例地产生信号延迟。由此,电路的动作速度不上升反而耗电增加的问题日益显著。
于是,为了克服该课题,作为降低布线间电容的手法之一,有时也会从以二氧化硅为主体的绝缘膜中使用低介电常数材料的绝缘膜(以下,称为“low-k膜”)的情况。作为low-k膜,可列举有机硅酸盐玻璃和全芳香环系low-k膜等。这些low-k膜与二氧化硅膜相比,具有机械强度低,吸湿性高,以及耐等离子体性和耐化学品性低的弱点。因此,第2研磨工序中有low-k膜的损伤、过度研磨、膜的剥離等问题。于是,为了克服上述的课题,人们也提出了设定为在low-k膜上覆盖二氧化硅膜的结构的方案。在绝缘膜部分含有覆盖层(cap layer)的二氧化硅膜时,受到二氧化硅的介电常数的影响,因此,作为绝缘膜整体,有效相对介电常数不会那么低。从该理由考虑,理想的是,在上述阻挡金属研磨时作为覆盖层的二氧化硅膜被迅速除去,最终形成仅由low-k膜形成的绝缘膜。
图2显示绝缘膜使用了low-k膜和覆盖层的布线形成的截面示意图。为了得到图2的(a)的结构,首先,在Si基板5上,以层叠结构方式将low-k膜6和由二氧化硅形成的覆盖层7成膜后,形成隆起部和沟槽部。在其上,按照追随表面的隆起部和沟槽部的方式形成有阻挡金属2,以填埋隆起部和沟槽部的方式形成有堆积于整体上的布线部用金属3。
与图1同样地,首先,从图2(a)所示的基板的状态至图2(b)所示的基板的状态,使用用于研磨布线部用金属的研磨液研磨布线部用金属3直至阻挡金属2露出(第1研磨工序)。接着,如图2(c)所示,使用阻挡金属用的研磨液研磨阻挡金属2,研磨至图2(c)所示的基板的状态,即直至至少由二氧化硅形成的覆盖层7被完全除去,low-k膜6露出为止(第2研磨工序)。
因此,第2研磨工序中,需要研磨阻挡金属、金属膜和二氧化硅膜,或者阻挡金属、金属膜、作为覆盖层的二氧化硅膜和low-k膜。由于low-k膜的机械强度和耐化学品性低等理由,low-k膜的研磨速度易于变大。与覆盖层不同,为了不过度地去除low-k膜,也需要对于low-k膜的研磨速度不过大。此外金属膜的研磨速度也过大时,埋入的金属布线的中央部分被各向同性地研磨而产生如碟状般下陷的现象(dishing),因此,需要金属膜的研磨速度也不过大。
现有技术文献
专利文献
【专利文献1】美国专利第4944836号说明书
【专利文献2】日本特开平02-278822号公报
【专利文献3】国际专利申请公报第01/13417号
发明内容
发明要解决的课题
如上所述,有时会出现使用阻挡金属用研磨液研磨阻挡金属、金属膜和二氧化硅膜,或者阻挡金属、金属膜、作为覆盖层的二氧化硅膜和low-k膜的情况。因此,在研磨液中,对于阻挡金属、金属膜、二氧化硅膜和low-k膜需要一定程度的均匀的研磨速度,特别是金属膜和low-k膜的研磨速度需要被适当控制(不过高)。但是,通常,由于阻挡金属和二氧化硅的机械强度相对增高,因此阻挡金属和二氧化硅膜的研磨速度易于降低,金属膜和low-k膜的研磨速度易于提高。因此,难以转而使用以各个膜作为研磨对象的CMP用研磨液,来得到对各膜的研磨速度的平衡。
本发明鉴于上述问题点而完成,目的在于提供:在研磨阻挡金属的第2研磨工序中可以抑制金属膜的腐蚀、金属膜和绝缘膜上的缺陷产生同时能够以均匀且高的研磨速度研磨阻挡金属、金属膜、二氧化硅膜和low-k膜的CMP用研磨液,以及使用该研磨液的研磨方法。
解决课题的手段
本发明涉及的研磨液为用于研磨至少包含阻挡金属、金属膜和二氧化硅膜的基板,或至少包含阻挡金属、金属膜、二氧化硅膜和low-k膜的基板的CMP用研磨液,其特征在于,该研磨液含有研磨粒子、氧化金属溶解剂、氧化剂、水溶性高分子和碱金属离子,研磨时的研磨粒子和金属膜的表面电位为相同符号,研磨粒子的表面电位(mV)和金属膜的表面电位(mV)的乘积为250~10000,该研磨液的pH为7.0~11.0。
本发明的一实施方式中,优选地,研磨粒子形成缔合粒子,缔合粒子的平均二次粒径为120nm以下。
本发明的一实施方式中,优选地,研磨粒子的含量为1~20质量%。
本发明的一实施方式中,优选地,研磨粒子包含二氧化硅粒子。
本发明的一实施方式中,优选地,氧化金属溶解剂包含选自柠檬酸、丙二酸、二甘醇酸、间苯二甲酸和甲基琥珀酸中的至少1种。
本发明的一实施方式中,优选地,水溶性高分子具有下述通式(1)的结构。
RO-Xn-Ym-H (1)
[式中,R表示碳数为6个以上的烷基、链烯基、苯基、多环苯基、烷基苯基或链烯基苯基,X和Y分别表示侧链可具有取代基的氧化乙烯基和氧化丙烯基。此外n和m分别表示0以上的整数,n+m为4以上的整数。]
本发明的一实施方式中,优选地,碱金属离子为钾离子。
此外,本发明的研磨方法,其特征在于,具备下述工序:在向研磨平台的研磨布上供给上述CMP用研磨液的同时,在将至少包含阻挡金属、金属膜和二氧化硅膜的基板,或至少包含阻挡金属、金属膜、二氧化硅膜和low-k膜的基板按压于研磨布的状态下,使研磨平台和基板相对移动。
发明效果
根据本发明可以提供:研磨阻挡金属的第2研磨工序中,可以抑制金属膜的腐蚀以及金属膜和绝缘膜上的缺陷的产生,同时,能够以均匀且高的研磨速度研磨阻挡金属、金属膜、二氧化硅膜和low-k膜的CMP用研磨液,以及使用了该研磨液的研磨方法。
附图说明
【图1】显示基于通常的镶嵌工艺进行的布线形成的截面示意图。
【图2】显示绝缘膜使用了low-k膜和覆盖层的布线形成的截面示意图。
符号说明
1…绝缘膜,2…阻挡金属,3…布线部用金属,5…Si基板,6…low-k膜,7…覆盖层。
具体实施方式
以下,说明本发明的优选实施方式。但是,本发明并不限定于下述实施方式。
(CMP用研磨液)
本实施方式涉及的CMP用研磨液含有研磨粒子、(作为化学成分的)氧化金属溶解剂、金属腐蚀抑制剂、氧化剂、水溶性高分子和碱金属离子。
(研磨粒子)
研磨粒子的一次粒径优选为80nm以下,更优选5~70nm,特别优选10~65nm,极其优选15~60nm。此外,研磨粒子可形成缔合粒子,该缔合粒子的平均二次粒径优选在120nm以下,更优选5~100nm,特别优选10~90nm,极其优选15~80nm。二次粒径超过120nm时,研磨速度倾向于恶化。另外,用光衍射散射型粒度分布计(例如,BECKMAN COULTER公司制造的N5)测定研磨粒子的二次粒径。
研磨粒子的含量(作为CMP用研磨液的总质量基准的含量。以下相同。)优选1~20质量%,更优选1.5~18质量%,特别优选2.0~15质量。该含量小于1质量%时,基于研磨粒子带来的机械性除去反应层能力不充分,二氧化硅膜和阻挡金属的研磨速度倾向于降低。
优选地,上述研磨粒子包含二氧化硅粒子。作为研磨粒子的材料,迄今为止,熟知有二氧化硅、氧化铝、铈土等,二氧化硅由于不易在研磨后在金属膜表面和绝缘膜上产生缺陷因而优选。另外,作为研磨粒子的材料,也可以进一步地使用二氧化硅类(在二氧化硅表面涂布了聚合物的粒子等)。
(氧化金属溶解剂)
作为氧化金属溶解剂,理想的为水溶性的氧化金属溶解剂,可列举例如丙二酸、柠檬酸、苹果酸、甘醇酸(二甘醇酸)、谷氨酸、葡萄糖酸、草酸、酒石酸、吡啶甲酸、烟酸、扁桃酸、吡啶甲酸、乙酸、甲酸、琥珀酸、己二酸、戊二酸、苯甲酸、喹哪啶酸、丁酸、戊酸、乳酸、邻苯二甲酸、富马酸、马来酸、氨基乙酸、水杨酸、甘油酸、庚二酸等有机酸,它们的有机酸酯,这些有机酸的盐;硫酸、硝酸、磷酸、乙酸、盐酸等无机酸,这些无机酸的盐;等。它们可以单独使用1种或混合2种以上使用。它们中,从阻挡金属和二氧化硅膜的研磨速度提高的角度考虑,优选柠檬酸、丙二酸、二甘醇酸、间苯二甲酸、甲基琥珀酸。它们可以单独使用1种或组合2种以上使用。
氧化金属溶解剂的含量优选为0.005~5质量%,更优选0.01~3质量%,特别优选0.1~2质量。该含量小于0.005质量%时,对于二氧化硅膜的研磨速度提高的效果低,此外该含量大于5质量%时,存在研磨粒子凝集,保存稳定性降低的倾向。
(水溶性高分子)
水溶性高分子优选具有下述通式(1)的结构。
RO-Xn-Ym-H (1)
式中,R表示碳数为6个以上的烷基、链烯基、苯基、多环苯基、烷基苯基或链烯基苯基。
式中,X表示氧化乙烯基,Y表示氧化丙烯基。氧化乙烯基或氧化丙烯基的侧链可键合有烷基、苯基等取代基。此外n、m表示氧化乙烯基、氧化丙烯基的重复结构的数量,分别为0以上的整数,n+m为4以上的整数。
水溶性高分子的重均分子量优选100~30000,进一步优选200~20000,特别优选300~10000。分子量小于100或者大于30000时,对于low-k膜的研磨速度的调节效果倾向于小。此外,其含量优选为0.001~0.5质量%,进一步优选0.002~0.3质量%,特别优选0.004~0.2质量%。含量小于0.001质量%时,对于low-k膜的研磨速度的调节效果小,含量大于0.5质量%时,研磨粒子凝集,保存稳定性倾向于降低。
(氧化剂)
本实施方式中,为了金属膜的研磨速度的调节,优选使用氧化剂。作为本实施方式中的金属膜的氧化剂,可列举过氧化氢(H2O2)、过碘酸钾、过硫酸铵、次氯酸、臭氧水等。它们可以单独使用1种或组合2种以上使用,但由于不希望由卤化物等引起的污染,因此,优选不含不挥发成分的氧化剂。其中,从稳定性的角度考虑,优选过氧化氢。
(CMP用研磨液的pH)
CMP用研磨液的pH优选7.0~11.0,进一步优选7.5~10.7,特别优选8.0~10.5。pH小于7时,或者大于11.0时,对金属膜的腐蚀倾向于易于产生。
(碱金属离子)
本实施方式的碱金属离子优选使用锂离子、钠离子、钾离子、铷离子,特别是,从不污染半导体装置的观点考虑优选钾离子。
碱金属离子作为pH调节剂被用于CMP用研磨液。作为包含碱金属离子的pH调节剂,可以适宜地使用氢氧化钾等。作为pH调节剂,也存在氨和有机胺类等,但是如果使用这些,就有这样的问题:金属膜的研磨速度显著恶化,或臭气易于产生。此外,也有包含碱土金属等的pH调节剂,但它们倾向于易于使研磨粒子凝集。
碱金属离子的含量优选0.01质量%以上,特别优选0.03质量%以上。从防止二氧化硅的凝集的角度考虑,优选小于2质量%,特别优选小于1.9质量%。
(表面电位)
用表面电位测定装置测得的、由CMP用研磨液所含的化学成分形成的金属膜的表面电位(mV)与研磨粒子的表面电位(mV)为相同符号,其乘积优选为250~10000,更优选300~10000,特别优选400~10000。两者的表面电位为相同符号,且其乘积在上述范围内,据此研磨粒子与金属膜和绝缘膜静电排斥,研磨后可以抑制源于研磨粒子的附着,同时,通过可以抑制研磨粒子的附着,从而对于金属膜表面、绝缘膜也可以抑制缺陷。
(金属腐蚀抑制剂)
本实施方式涉及的CMP用研磨液可含有金属腐蚀抑制剂等作为其他的添加剂。金属腐蚀抑制剂可以使用与金属生成螯合物、且能够形成防止金属被过度蚀刻的保护膜的化合物。作为这样的化合物,可以使用公知的化合物,可列举例如具有三唑骨架的化合物、具有咪唑骨架的化合物、具有嘧啶骨架的化合物、具有胍骨架的化合物、具有噻唑骨架的化合物、具有吡唑骨架的化合物。此外,这些金属腐蚀抑制剂可以1种单独使用或混合2种以上使用。
作为具有三唑骨架的化合物,可以例示1,2,3-三唑、1,2,4-三唑、3-氨基-1H-1,2,4-三唑、苯并三唑、1-羟基苯并三唑、1-二羟基丙基苯并三唑、2,3-二羧基丙基苯并三唑、4-羟基苯并三唑、4-羧基(-1H-)苯并三唑、4-羧基(-1H-)苯并三唑甲酯、4-羧基(-1H-)苯并三唑丁酯、4-羧基(-1H-)苯并三唑辛酯、5-己基苯并三唑、[1,2,3-苯并三唑基-1-甲基][1,2,4-三唑基-1-甲基][2-乙基己基]胺、甲苯三唑、萘并三唑(naphthotriazole)、双[(1-苯并三唑基)甲基]膦酸、3-氨基三唑、5-甲基苯并三唑等。
作为具有咪唑骨架的化合物,可列举2-甲基咪唑、2-乙基咪唑、2-异丙基咪唑、2-丙基咪唑、2-丁基咪唑、4-甲基咪唑、2,4-二甲基咪唑、2-乙基-4-甲基咪唑、2-十一烷基咪唑、2-氨基咪唑等。
作为具有嘧啶骨架的化合物,可列举嘧啶、1,2,4-三唑并[1,5-a]嘧啶、1,3,4,6,7,8-六氢化-2H-嘧啶并[1,2-a]嘧啶、1,3-二苯基-嘧啶-2,4,6-三酮、1,4,5,6-四氢嘧啶、2,4,5,6-四氨基嘧啶硫酸盐、2,4,5-三羟基嘧啶、2,4,6-三氨基嘧啶、2,4,6-三氯嘧啶、2,4,6-三甲氧基嘧啶、2,4,6-三苯基嘧啶、2,4-二氨基-6-羟基嘧啶、2,4-二氨基嘧啶、2-乙酰氨基嘧啶、2-氨基嘧啶、2-甲基-5,7-二苯基-(1,2,4)三唑并[1,5-a]嘧啶、2-甲硫基-5,7-二苯基-(1,2,4)三唑并[1,5-a]嘧啶、2-甲硫基-5,7-二苯基-4,7-二氢-(1,2,4)三唑并[1,5-a]嘧啶、4-氨基吡唑并[3,4-d]嘧啶等。
作为具有胍骨架的化合物,可列举1,3-二苯基胍、1-甲基-3-硝基胍等。
作为具有噻唑骨架的化合物,可列举2-巯基苯并噻唑、2-氨基噻唑、4,5-二甲基噻唑、2-氨基-2-噻唑啉、2,4-二甲基噻唑、2-氨基-4-甲基噻唑等。
作为具有吡唑骨架的化合物,可列举3,5-二甲基吡唑、3-甲基-5-吡唑啉酮、3-氨基-5-甲基吡唑、3-氨基-5-羟基吡唑、3-氨基-5-甲基吡唑等。
这些之中,从研磨速度和蚀刻速度的角度考虑,优选具有三唑骨架的化合物。进一步地,具有三唑骨架的化合物中,更优选1,2,3-三唑、1,2,4-三唑、3-氨基-1H-1,2,4-三唑、4-氨基-4H-1,2,4-三唑、苯并三唑、1-羟基苯并三唑、5-甲基苯并三唑。
从蚀刻的抑制变容易的角度考虑,金属腐蚀抑制剂的含量优选0.001质量%以上,更优选0.002质量%以上,进一步优选0.004质量%以上,此外,从可以得到实用水平的研磨速度的角度考虑,该含量优选1.0质量%以下,更优选0.5质量%以下,进一步优选0.3质量%以下。
(被研磨膜)
作为金属膜的材料,可列举以铜、铜合金、铜的氧化物或铜合金的氧化物、钴、钴合金、钨、钨合金、银、金等金属为主成分的金属膜材料。作为金属膜,可以使用通过公知溅射法、镀(敷)法等而成膜的膜。
为了防止布线金属的金属扩散到绝缘膜中,及为了提高绝缘膜和布线金属的密合性,因而形成阻挡金属。阻挡金属的组成优选选自钨、氮化钨、钨合金等钨化合物;钛、氮化钛、钛合金等钛化合物;钽、氮化钽、钽合金等钽化合物;钌、钌化合物;钴、钴化合物。阻挡金属可为由它们中的1种形成的单层结构,也可为由2种以上形成的层叠结构。
作为绝缘膜,具有二氧化硅膜和low-k膜。作为low-k膜,可列举硅系被膜及有机聚合物膜。作为low-k膜的硅系被膜,可列举以硅氧化膜、氟硅酸盐玻璃、以三甲基硅烷或二甲氧基二甲基硅烷为起始原料而得到的有机硅酸盐玻璃、多孔有机硅酸盐玻璃等二氧化硅系被膜。此外,作为low-k膜的有机聚合物膜,可列举全芳香族系低介电常数层间绝缘膜。另外,从消除布线延迟的角度考虑,优选它们的介电常数为2.9以下。这些中,特别是,可将氟硅酸盐玻璃、有机硅酸盐玻璃、多孔有机硅酸盐玻璃等用作为low-k膜。这些膜可通过CVD法、旋涂法、浸涂法或喷雾法成膜。
本实施方式的研磨方法为,通过在向研磨平台的研磨布上供给上述的CMP用研磨液的同时,在将具有被研磨膜的基板按压于研磨布的状态下,使研磨平台与基板相对移动,从而研磨被研磨膜的研磨方法。更具体地,本实施方式的研磨方法为具备下述工序的研磨方法:在向研磨平台的研磨布上供给上述的CMP用研磨液的同时,在将至少包含阻挡金属、金属膜和二氧化硅膜的基板,或至少包含阻挡金属、金属膜、二氧化硅膜和low-k膜的基板按压于研磨布的状态下使研磨平台和基板相对移动。作为研磨装置,可以使用例如,具有贴附有研磨布(衬垫)且安装有转速能够改变的电动机等的平台和保持基板的固定器的通常的研磨装置。作为研磨布,无特别制限,可以使用通常的无纺布、发泡聚氨酯、多孔质氟树脂等。研磨条件无特别制限,但优选将平台的旋转速度设定为200rpm以下的低旋转,以不使基板飞出。
具有被研磨膜的基板对研磨布的研磨压力优选3~100kPa,从研磨速度的基板面内均匀性和图案的平坦性的角度考虑,更优选5~50kPa。优选地,研磨时,用泵等连续地供给CMP用研磨液给研磨布。对该供给量无特别限制,但优选研磨布的表面始终被研磨液覆盖。优选地,为了使研磨布的表面状态始终如一而进行化学机械研磨,在研磨之前或在研磨中加入研磨布的调控工序。例如,使用具有金刚石粒子的修整器,用至少包含水的液体进行研磨布的调控。接着,实施本实施方式的研磨方法,优选地,进一步地,加入基板洗涤工序。
实施例
以下,通过实施例具体地说明本发明,但本发明并不限定于这些实施例。
(实施例1~4和比较例1~5)
作为研磨粒子,使用表1记载的二氧化硅。用BECKMAN COULTER公司制造的N5测定表1记载的二氧化硅(二氧化硅A、二氧化硅B)的平均二次粒径(缔合粒子的平均二次粒径)。测定法使用光子相关谱法,稀释含二氧化硅的材料以使其散射强度为5.0×104~1.0×106cps进而放入塑料池中,测定粒径。
【表1】
平均二次粒径(nm) | |
二氧化硅A | 66 |
二氧化硅B | 61 |
(实施例1)
将丙二酸0.4质量%、BTA(苯并三唑)0.0065质量%、聚氧乙烯十三烷基醚(上述通式(1)中的n=8、m=0。以下相同。)0.0065质量%加入去离子水中,向其中添加KOH 1.5质量%之后,加入7.5质量%的二氧化硅A,最后,加入过氧化氢0.1质量%,制造CMP用研磨液1。CMP用研磨液的pH为10。
(实施例2)
将二甘醇酸0.4质量%、HBTA(1-羟基苯并三唑)0.0065质量%、聚氧乙烯十三烷基醚0.0065质量%加入去离子水中,向其中添加KOH 1.26质量%之后,加入7.5质量%的二氧化硅A,最后,加入过氧化氢0.1质量%,制造CMP用研磨液2。CMP用研磨液的pH为10。
(实施例3)
将二甘醇酸0.22质量%、HBTA 0.0040质量%、聚氧乙烯十三烷基醚0.0065质量%加入去离子水中,向其中添加KOH 0.73质量%之后,加入5.0质量%的二氧化硅B,最后,加入过氧化氢0.1质量%,制造CMP用研磨液3。CMP用研磨液的pH为10。
(实施例4)
将丙二酸0.40质量%、聚氧乙烯十三烷基醚0.0065质量%加入去离子水中,向其中添加KOH 1.50质量%之后,加入7.5质量%的二氧化硅A,最后,加入过氧化氢0.1质量%,制造CMP用研磨液4。CMP用研磨液的pH为10。
(比较例1)
除了不加入作为氧化金属溶解剂的丙二酸、并将作为pH调节剂的KOH的添加量变更为0.35质量%以外,其余与实施例1同样地进行,制造CMP用研磨液5。CMP用研磨液5的pH为10。
(比较例2)
除了不加入作为有机化合物的聚氧乙烯十三烷基醚以外,其余与实施例1同样地进行,制造CMP用研磨液6。CMP用研磨液6的pH为10。
(比较例3)
除了碱金属离子源和将作为pH调节剂的KOH变更为单乙醇胺以外,其余与实施例1同样地进行,制造CMP用研磨液7。CMP用研磨液7的pH为10。
(比较例4)
除了不加入作为氧化剂的过氧化氢以外,其余与实施例1同样地进行,制造CMP用研磨液8。CMP用研磨液8的pH为10。
(比较例5)
将丙二酸0.4质量%、BTA 0.0065质量%、聚氧乙烯十三烷基醚0.0065质量%加入去离子水中,向其中添加KOH 0.05质量%之后,加入3.0质量%的二氧化硅A,最后,加入过氧化氢0.1质量%,制造CMP用研磨液9。CMP用研磨液9的pH为3.0。
(研磨条件)
研磨衬垫:H7000(富士纺株式会社)
研磨压力:10.3kPa
平台转速:90rpm
头部转速:87rpm
研磨液供给量:300ml
(研磨速度评价用基板)
金属膜:在硅基板上成膜有厚度1500nm的铜(Cu)的12英寸Cu基板
阻挡金属:在硅基板上成膜有厚度200nm的氮化钽(TaN)的12英寸TaN基板
low-k膜:在硅基板上成膜有厚度500nm的low-k膜的(应用材料公司制造,商品名“Black Diamond”)12英寸low-k基板
二氧化硅膜(覆盖膜):在硅基板上成膜有厚度1000nm的TEOS的12英寸TEOS基板
(研磨速度和选择比)
通过使用电阻测定器VR-120/08S(日立国际电气株式会社制造),将电阻值换算为Cu和TaN在CMP前后的膜厚度差,从而求得Cu研磨速度和TaN的研磨速度。此外,对于TEOS和low-k,通过使用作为光干渉式膜厚测定器的F80(Filmetrics,Inc.制造),根据研磨前后的膜厚度差从而求得。
另外,同一条件的CMP中,Cu/TaN/low-k/TEOS的研磨速度优选为(20~120nm/min)/(40~120nm/min)/(40~120nm/min)/(40~120nm/min)。
此外,作为研磨速度的选择比,Cu/TaN/low-k膜/TEOS的研磨速度比优选为(0.3~1.5)/1.0/(0.5~2.0)/(0.3~1.5)。
(Cu的腐蚀速度评价)
通过将切割为20mm见方的Cu基板贴附于搅拌叶片,使其以100rpm旋转,同时,将Cu基板浸渍入热浴至60℃的研磨液中5分钟,根据浸渍前后的膜厚度差和浸渍时间从而算出Cu的腐蚀速度。
(表面电位测定方法)
用BECKMAN COULTER公司制造的表面电位测定装置Delsa Nano C测定二氧化硅的表面电位。测定法通过使用激光多普勒多点检测方式电泳法,测定范围取±100mV而进行。稀释研磨液以使散射强度为1.0×104~5.0×104cps,将其加入稀薄溶液表面电位测定用石英池中,在25℃进行测定。
此外,因为认为在研磨时,由于氧化剂,Cu成为氧化铜,因此,Cu表面电位通过下述方法测定:将1质量%的氧化铜(II)粉末(关东化学株式会社制造)添加入不含研磨粒子的CMP用研磨液,静置5分钟时间,用移液管取其上清液,将3mL注入至测定池中进行测定。
(Cu(金属膜)和TEOS(绝缘膜)表面的缺陷评价)
使用日立电子工程(Hitachi Electronics Engineering)制造的LS6700,在下述条件下测定,进行Cu和TEOS的表面缺陷数的评价。且,算出研磨后的表面缺陷数/研磨前的表面缺陷数,2.0以上的情况判定为不好。
Cu表面的缺陷测定范围:0.200μm-0.370μm
TEOS表面的缺陷测定范围:0.200μm-0.808μm
对于实施例1~4和比较例1~5中的Cu、TaN、low-k、TEOS的研磨速度和研磨速度的选择比;Cu和二氧化硅的表面电位及其乘积;Cu的腐蚀速度;研磨前后的Cu和TEOS表面缺陷数的比,其评价结果如表2和表3所示。
【表2】
【表3】
(评价结果)
实施例1~4中,TaN、TEOS的研磨速度高,此外,Cu和low-k的研磨速度也与TaN、TEOS为同等程度,研磨速度和研磨速度的选择比均良好。此外,也无Cu的腐蚀,Cu和TEOS表面的缺陷也为低值。另一方面,未加入氧化金属溶解剂的比较例1的TEOS和TaN的研磨速度为非常低的值。此外,未加入水溶性高分子的比较例2的low-k的研磨速度为159nm/min的非常大的值。此外比较例3中,未使用作为钾离子源的pH调节剂的氢氧化钾,而使用了单乙醇胺,Cu的研磨速度显著增加。此外,比较例4中,未加入氧化剂,Cu的研磨速度为显著低的值。此外,比较例5中,表面电位的乘积为负值,对Cu的腐蚀速度高,进一步地TEOS表面的缺陷数也为高值。
根据以上结果,本发明的CMP用研磨液和研磨方法可以高速研磨TaN(阻挡金属)和TEOS(绝缘膜或者覆盖层),另一方面,能够恰当地(以研磨速度不变得过快的方式)控制Cu(金属膜)和low-k(低介电常数膜)的研磨速度。此外本发明的CMP用研磨液也没有对Cu(金属膜)的腐蚀,并且能够抑制Cu(金属膜)和TEOS(绝缘膜)表面的缺陷。
Claims (8)
1.一种研磨液,其为用于研磨至少包含阻挡金属、金属膜和二氧化硅膜的基板或至少包含阻挡金属、金属膜、二氧化硅膜和low-k膜的基板的CMP用研磨液,其特征在于,
所述研磨液含有研磨粒子、氧化金属溶解剂、氧化剂、水溶性高分子和碱金属离子,
研磨时的所述研磨粒子和所述金属膜的表面电位为相同符号,所述研磨粒子的表面电位(mV)和所述金属膜的表面电位(mV)的乘积为250~10000,
所述研磨液的pH为7.0~11.0。
2.根据权利要求1所述的研磨液,其中,所述研磨粒子形成缔合粒子,所述缔合粒子的平均二次粒径为120nm以下。
3.根据权利要求1或2所述的研磨液,其中,所述研磨粒子的含量为1~20质量%。
4.根据权利要求1~3中任一项所述的研磨液,其中,所述研磨粒子包含二氧化硅粒子。
5.根据权利要求1~4中任一项所述的研磨液,其中,所述氧化金属溶解剂包含选自柠檬酸、丙二酸、二甘醇酸、间苯二甲酸和甲基琥珀酸中的至少1种。
6.根据权利要求1~5中任一项所述的研磨液,其中,所述水溶性高分子具有下述通式(1)的结构,
RO-Xn-Ym-H(1)
式中,R表示碳数为6个以上的烷基、链烯基、苯基、多环苯基、烷基苯基或链烯基苯基,X和Y分别表示侧链具有取代基或不具有取代基的氧化乙烯基和氧化丙烯基,此外,n和m分别表示0以上的整数,n+m为4以上的整数。
7.根据权利要求1~6中任一项所述的研磨液,其中,所述碱金属离子为钾离子。
8.一种研磨方法,其具备下述工序:在向研磨平台的研磨布上供给权利要求1~7中任一项所述的CMP用研磨液的同时,在将至少包含阻挡金属、金属膜和二氧化硅膜的基板或至少包含阻挡金属、金属膜、二氧化硅膜和low-k膜的基板按压于所述研磨布的状态下使所述研磨平台和所述基板相对移动。
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- 2017-06-09 TW TW106119258A patent/TW201742900A/zh unknown
- 2017-06-09 WO PCT/JP2017/021482 patent/WO2017213255A1/ja active Application Filing
- 2017-06-09 KR KR1020187037654A patent/KR20190017815A/ko not_active IP Right Cessation
- 2017-06-09 US US16/308,009 patent/US20190256741A1/en not_active Abandoned
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US20210189179A1 (en) | 2021-06-24 |
JPWO2017213255A1 (ja) | 2019-05-16 |
US20190256741A1 (en) | 2019-08-22 |
WO2017213255A1 (ja) | 2017-12-14 |
US11359114B2 (en) | 2022-06-14 |
KR20190017815A (ko) | 2019-02-20 |
TW201742900A (zh) | 2017-12-16 |
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