CN1616574A - 高速阻挡层抛光组合物 - Google Patents
高速阻挡层抛光组合物 Download PDFInfo
- Publication number
- CN1616574A CN1616574A CNA2004100118194A CN200410011819A CN1616574A CN 1616574 A CN1616574 A CN 1616574A CN A2004100118194 A CNA2004100118194 A CN A2004100118194A CN 200410011819 A CN200410011819 A CN 200410011819A CN 1616574 A CN1616574 A CN 1616574A
- Authority
- CN
- China
- Prior art keywords
- solution
- salt
- polishing
- acid
- guanidine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 230000004888 barrier function Effects 0.000 title claims abstract description 41
- 238000005498 polishing Methods 0.000 title claims description 78
- -1 hydrazine derivative compounds Chemical class 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 150000002466 imines Chemical class 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 230000000903 blocking effect Effects 0.000 claims description 28
- GETQZCLCWQTVFV-UHFFFAOYSA-N anhydrous trimethylamine Natural products CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 26
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 24
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 23
- 150000003863 ammonium salts Chemical class 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000001721 carbon Chemical class 0.000 claims description 15
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004475 Arginine Substances 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 8
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 8
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- UBDZFAGVPPMTIT-UHFFFAOYSA-N 2-aminoguanidine;hydron;chloride Chemical compound [Cl-].NC(N)=N[NH3+] UBDZFAGVPPMTIT-UHFFFAOYSA-N 0.000 claims description 4
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 claims description 4
- BMFMQGXDDJALKQ-BYPYZUCNSA-N Argininic acid Chemical class NC(N)=NCCC[C@H](O)C(O)=O BMFMQGXDDJALKQ-BYPYZUCNSA-N 0.000 claims description 4
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- XPOLVIIHTDKJRY-UHFFFAOYSA-N acetic acid;methanimidamide Chemical compound NC=N.CC(O)=O XPOLVIIHTDKJRY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001483 arginine derivatives Chemical class 0.000 claims description 4
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 4
- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 claims description 4
- MJFQUUWPZOGYQT-UHFFFAOYSA-O diaminomethylideneazanium;nitrate Chemical compound NC(N)=[NH2+].[O-][N+]([O-])=O MJFQUUWPZOGYQT-UHFFFAOYSA-O 0.000 claims description 4
- WCQOBLXWLRDEQA-UHFFFAOYSA-N ethanimidamide;hydrochloride Chemical compound Cl.CC(N)=N WCQOBLXWLRDEQA-UHFFFAOYSA-N 0.000 claims description 4
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 claims description 4
- 150000002357 guanidines Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- LLYCMZGLHLKPPU-UHFFFAOYSA-M perbromate Chemical compound [O-]Br(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-M 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- XCXKNNGWSDYMMS-UHFFFAOYSA-N 2-methyl-1-nitroguanidine Chemical compound CNC(N)=N[N+]([O-])=O XCXKNNGWSDYMMS-UHFFFAOYSA-N 0.000 claims description 3
- UJTTUOLQLCQZEA-UHFFFAOYSA-N 9h-fluoren-9-ylmethyl n-(4-hydroxybutyl)carbamate Chemical compound C1=CC=C2C(COC(=O)NCCCCO)C3=CC=CC=C3C2=C1 UJTTUOLQLCQZEA-UHFFFAOYSA-N 0.000 claims description 3
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 claims description 3
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 150000001409 amidines Chemical class 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 3
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 3
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 3
- WFJRIDQGVSJLLH-UHFFFAOYSA-N methyl n-aminocarbamate Chemical class COC(=O)NN WFJRIDQGVSJLLH-UHFFFAOYSA-N 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 239000008139 complexing agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 36
- 239000002002 slurry Substances 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- 239000010949 copper Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 229910052715 tantalum Inorganic materials 0.000 description 15
- 239000012530 fluid Substances 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 14
- 235000012431 wafers Nutrition 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 13
- 239000012964 benzotriazole Substances 0.000 description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 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
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000003636 chemical group Chemical group 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 229960000789 guanidine hydrochloride Drugs 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000006413 ring segment Chemical group 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 101150065749 Churc1 gene Proteins 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-M gallate Chemical compound OC1=CC(C([O-])=O)=CC(O)=C1O LNTHITQWFMADLM-UHFFFAOYSA-M 0.000 description 2
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
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- QHOKENWFMZXSEU-UHFFFAOYSA-N tetrabutylazanium;nitrate Chemical compound [O-][N+]([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC QHOKENWFMZXSEU-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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Abstract
适用于从半导体衬底上去除阻挡层材料的溶液。该溶液包含:0.01至25wt%的氧化剂,0至15wt%的非铁金属抑制剂,0至15wt%的研磨剂,0至20wt%该非铁金属的配位剂,0.01至12wt%的阻挡层去除剂,和余量的水;该阻挡层去除剂选自亚胺衍生化合物,肼衍生化合物和它们的混合物。
Description
技术领域
本发明涉及抛光半导体衬底且更具体地,涉及去除阻挡层的抛光流体。
背景技术
可以通过在电介质层中布置多个沟槽来形成半导体器件的电路互连。该互连是通过在下层的电介质层上镀覆阻挡层薄膜,然后在该阻挡层薄膜上镀覆金属层形成。形成的金属层必需具有足够的厚度以便使金属充满沟槽。该互连制造工艺包括两步化学机械抛光(CMP)过程的使用。
CMP是指用抛光垫或抛光流体抛光半导体晶片的工艺。在第一步的抛光中,从下层的阻挡层薄膜和下层的电介质层上除去金属层。该金属层的去除既是通过抛光垫所施加的摩擦作用,也是通过与该抛光流体的化学反应以及伴随的化学反应产物的溶解作用。第一步抛光可去除金属层,并在晶片上留下光滑平坦的抛光表面,并进一步在沟槽中留下金属以便提供与抛光表面基本平齐的电路互连。例如Lee等人在欧洲专利公开1 072 662 A1中公开了使用胍作为研磨加速剂以便相对于金属互连提高研磨组合物的电介质去除速率。
典型的第一步抛光过程包括在抛光流体中使用含有氧化剂例如KNO3或H2O2的水溶液以便去除铜互连。该铜金属层的去除是通过氧化剂对金属层的氧化作用和抛光垫产生的研磨。此外,抛光垫磨蚀该金属层从而最大程度上减少溶解氧化物从溶液中再次沉积到抛光材料的表面。从下层的阻挡层薄膜例如钽(Ta)或氮化钽(TaN)上去除铜。该阻挡层薄膜比铜具有更大的研磨抵抗性,因此阻挡层起到使第一步的铜抛光停止的抛光停止作用。此外,抛光流体对阻挡层薄膜表面的氧化会抑制其在第一步抛光过程中的去除。
在第二抛光步骤中,从下面的电介质层上去除阻挡层薄膜。第二步抛光能够在电介质层上提供光滑,平坦的抛光表面。理想情况下,该第二抛光步骤不会过多地除去沟槽中的金属。在第二抛光步骤中过度的金属去除会导致凹陷。
凹陷是描述由于除去沟槽中过多的金属从而在电路互连中形成的不良孔穴的技术术语。凹陷既可以发生在第一步抛光中也可以发生在第二抛光步骤中。要求该电路互连具有精确的尺寸,该尺寸决定了电路互连所提供的信号传输线路的电阻。超过许可水平的凹陷会在电路互连中引起尺度缺陷,这会导致该电路互连所传输的电信号的减弱。
该第二抛光步骤应当只引起最小程度的腐蚀。腐蚀是描述由于除去阻挡层薄膜下面的一些电介质层而引起的电介质层表面的不良降低的技术术语。发生在接近沟槽中的金属处的腐蚀会在该电路互连中引起尺度缺陷,该缺陷会导致该电路互连所传输的电信号的减弱。为了最大程度上减小腐蚀,希望第二步抛光的抛光流体能以比电介质层的去除速率更高的去除速率去除该阻挡层薄膜。
该第二抛光步骤应具有高的阻挡层相对于下层的去除选择性。去除选择性定义为阻挡层薄膜的去除速率与相对层如电介质层或金属层的去除速率的比值。对本说明书而言,选择性是指以每单位时间的距离例如埃每分钟表示的去除速率的比值。因此,去除选择性是阻挡层薄膜相对于电介质层或金属层的去除的量度。高的去除选择性对于一些集成方案是较为理想的。使用表现出高的相对于电介质层的去除选择性的抛光流体进行的抛光可增加阻挡层式薄膜的去除并减少电介质层的去除。存在对具有提高的阻挡层去除速率和减小的电介质去除速率的抛光液的需求。
发明内容
本发明提供了用于从半导体衬底上去除阻挡层材料的溶液,该溶液包含:0.01至25wt%的氧化剂,0至15wt%的非铁金属抑制剂,0至15wt%的研磨剂,0至20wt%该非铁金属的配位剂,0.01至12wt%选自亚胺衍生化合物,肼衍生化合物和它们的混合物的阻挡层去除剂,和余量的水;而且如使用至少一个等于或小于13.8kPa的垂直于晶片测量的微孔聚氨酯抛光垫压力所测,该溶液具有至少2比1的氮化钽相对于CDO的选择性。
另一个方面,本发明提供了用于从半导体衬底上去除阻挡层材料的溶液,该溶液包含0.1至15wt%的氧化剂,0至10wt%的非铁金属抑制剂,0至10wt%该非铁金属的配位剂,0至10wt%的氧化剂,0.1至10wt%选自乙脒,乙脒盐,乙脒衍生物,精氨酸,精氨酸盐,精氨酸衍生物,甲脒,甲脒盐,甲脒衍生物,胍衍生物,胍盐和它们的混合物的阻挡层去除剂,0.01至10wt%与
构成的包含有机物的铵盐,R1,R2,R3和R4是基团,R1具有小于15个碳原子的碳链长度且余量为水而且该溶液具有小于7的pH。
本发明的另一个方面,本发明提供了从半导体晶片上去除阻挡层材料的方法,该方法包括如下步骤:使晶片衬底与抛光溶液接触,该晶片衬底包含阻挡层材料,TEOS电介质层和第二电介质层,该第二电介质层具有低于TEOS电介质层的介电常数而且该抛光溶液包含氧化剂和阻挡层去除剂,该阻挡层去除剂选自亚胺衍生化合物,肼衍生化合物和它们的混合物;使用抛光垫对晶片衬底进行抛光以便从该晶片衬底上去除阻挡层材料;使用抛光垫对该晶片衬底进行抛光以便从晶片衬底上去除至少一部分的TEOS电介质层并留下第二电介质层。
具体实施方式
已发现调节pH的水平和氧化剂的浓度有利于提高包含亚胺和肼衍生化合物的抛光溶液的阻挡层去除速率。此外,对于去除阻挡层材料,该溶液和方法可提供意想不到的选择性和控制。该溶液依靠氧化剂和选自亚胺和肼衍生化合物以及它们的混合物的阻挡层去除剂来选择性去除阻挡层材料,如包含钽和包含钛的电介质。该溶液可去除阻挡层材料,同时具有减小的电介质腐蚀和减少的互连金属例如铜的凹陷,腐蚀和划痕。此外,该溶液可去除钽阻挡层材料而不会使低k电介质层从半导体晶片上剥落或分层。此外,对于由原硅酸四乙酯(TEOS)前体沉积的二氧化硅形成的硬掩模,该溶液具有受控制的TEOS去除速率。
特别地,该溶液包含阻挡层去除剂以便去除例如钽,氮化钽,钽-氮化硅,钛,氮化钛,钛-氮化钛,钛-氮化硅,钛-钨,钨,氮化钨和钨-氮化硅的阻挡层材料。虽然该溶液对于含钛阻挡层材料在酸性pH水平有效。对于含钽材料该溶液具有特别的效力。对本说明书而言,含钽材料包括钽,钽基合金和钽的金属间化合物,例如钽的碳化物,氮化物和氧化物。对于从具有图案的半导体晶片上去除含钽阻挡层该浆料最为有效。
优选的亚胺衍生物包括式(I)的化合物:
其中R1是-H或-NH2而R2是-H,-NH2,烃基,氨基,羰基,亚氨基,偶氮基,氰基,硫基,或硒基和其中R7是烃基的-OR7。
优选的肼衍生物包括式(II)的化合物:
R3R4N-NR5R6 (II)
其中R3,R4,R5,和R6独立地是-H,-OR7,-NH2,烃基,羰基,亚氨基,偶氮基,氰基,硫基,或硒基。
术语“含氮”是指包含两个或多个氮原子的物质。在含氮物质中两个或多个氮原子可以互相结合,或者可以被其它原子隔开。如果含氮物质包含三个或更多的氮原子,这些氮原子其中的一些可以互相结合而其它氮原子可以只与非氮原子结合。含氮物质中的氮原子可以是该物质中的化学基团例如氨基,酰胺基,偶氮基、亚氨基(imino),亚氨基(imido),或肼基的一部分。优选地,含氮物质中的氮原子处于它们的还原态且不与氧原子直接结合(即-NO2;-NO3)。
术语“烃基”是指用氢原子取代的直链,支链或环状碳原子链,且包括未取代和取代烷基,烯基,炔基,芳基,和杂环基。优选地,烃基包含1至20个碳原子。可选用其它基团取代烃基。碳原子之间的键可独立地选自单键,双键,和三键。
术语“烷基”(或烷基-)是指取代或未取代直链,支链或环状烃链,该烃链优选包含1至20个碳原子。烷基包括,例如甲基,乙基,丙基,异丙基,环丙基,丁基,异丁基,叔丁基,仲丁基,环丁基,戊基,环戊基,己基和环己基。
术语“烯基”(或烯基-)是指至少包含一个碳-碳双键的取代或未取代直链,支链或环状烃链,且该烃链优选包含2至20个碳原子。烯基包括,例如乙烯基(-CH=CH2);1-丙稀基;2-丙稀基(或烯丙基,CH2-CH=CH2);1,3-丁二烯基(-CH=CHCH=CH2);1-丁烯基(-CH=CHCH2CH3);己烯基;戊烯基;1,3,5-己三烯基;环己二烯基;环己烯基;环戊烯基;环辛烯基;环庚二烯基;和环辛三烯基。
术语“炔基”(或炔基-)是指包含至少一个碳-碳三键的取代或未取代直链,支链或环状烃链,且该烃链优选包含2至20个碳原子。炔基包括,例如乙炔基(-C≡CH);2-甲基-3丁炔基;和己炔基。
术语“芳基”是指取代或未取代芳香碳环基,该碳环基优选包含3至20个碳原子。芳基可以是单环或者多环。芳基包括,例如苯基,萘基,二苯基,苯甲基,甲苯基,二甲苯基,苯乙基,苯甲酸盐,烷基苯甲酸盐,苯胺基,和N-烷基苯氨基。
术语“杂环基”是指包含一个或多个杂原子的饱和,非饱和,或芳香环组成部分,且该部分优选包含5至10个环上原子,且更优选包含5至6个环上原子。术语“环上原子”是指包含在环结构中的原子而不包括悬挂在该环上的其它原子。该环可以是单环,双环或多环。杂环基包含碳原子和1至3个独立地选自氮,氧,和硫的杂原子。杂环基也可以是取代或未取代的,其中包括例如苯并咪唑,苯并三唑,呋喃,咪唑,吲哚,异喹啉,异噻唑,吗啉,哌嗪,吡嗪,吡唑,吡啶,嘧啶,吡咯,喹啉,噻唑,噻吩,三嗪和三唑。
当用来描述化学基团时,术语“取代”是指包含至少一个,优选1至5个取代基的化学组成部分。适合的取代基包括,例如羟基(-OH),氨基(-NH2),氧(-O-),羰基(>C=O),硫氢基(thiol),烷基,卤素,硝基,芳基和杂环基。可选用1至5个取代基进一步取代这些取代基。
术语“氨基”是指通过氮原子与本体结合的基团。例如,氨基可选自如下基团:-NH2;烷基氨基(-NH-烷基);二烷基氨基(-N-(烷基)2);芳氨基(-NH-芳基)和它们的取代衍生物。优选地,与氮结合的烷基包含1至20个碳原子,而与氮结合的芳基包含3至20个碳原子。二烷基氨基中的烷基可以相同也可以不同。
术语“羰基”是指包含与氧原子双键结合的碳原子的基团,且包括羧酸,酸酐,碳酸盐,醛,酮,酯,羧酸卤化物,和酰胺。例如,羰基可以具有通式(III):
其中R8是-H,-OH,-OR9,-R10,-NH2,和-NH-C(=O)-R11,且R9,R10,和R11独立地是包含1至10个碳原子的烷基。
术语“亚氨基”是指包含与-HN基双键结合的碳原子的基团。例如,亚氨基可以具有下面的通式(IV):
其中R12是-H,-NH2,或包含1至10个碳原子的烷基。
术语“偶氮基”是指包含氮氮双键,或一个-NH基与另一个-NH基单键结合的基团。例如,偶氮基可以选自-N3;-NH-NH-NH3;-N=N-NH3;-N=N-R13;-R14=N-N=R15;和-NH-NH-R16;其中R13,R14,R15,和R16独立地是包含1至10个碳原子的烷基。
术语“氰基”是指包含碳氮三键,或碳原子与氮原子双键结合并同时与另一个杂原子如氧,硫,或硒双键结合的基团。例如,氰基可以选自-C≡N;-N≡C;-N-C=O;-N=C=S;和-N=C=Se。
术语“硫基”是指包含与另一个原子单键结合的硫原子的基团。例如,硫基可以选自-S-R17;-S-S-R18;-S-C≡N;-SO2H;和-SOH;其中R17和R18独立地是包含1至10个碳原子的烷基。
术语“硒基”是指包含与另一个原子单键结合的硒原子的基团。例如,硒基可以选自-Se-R19;-Se-Se-R20;-Se-C≡N;其中R19和R20独立地是包含1至10个碳原子的烷基。
亚胺衍生物的实例包括,乙脒,乙脒盐,乙脒衍生物,精氨酸,精氨酸盐,精氨酸衍生物,甲脒,甲脒盐,甲脒衍生物,胍衍生物,胍盐和它们的混合物。优选的式(I)的亚胺衍生物包括,例如盐酸乙脒,盐酸氨基胍,精氨酸,甲脒,甲脒亚磺酸,甲脒乙酸盐,1,3-二苯胍,1-甲基-3-硝基胍,盐酸胍,四甲基胍,2,2-偶氮基二(二甲基-丙脒)二-HCl,硫酸胍,乙酸胍,碳酸胍,硝酸胍和它们的混合物。
优选的式(II)的肼衍生物包括,例如碳酰肼,咪唑,乙酰肼,盐酸氨基脲,1,2-二甲酰肼,甲基肼基-羧酸盐,草酸二酰肼,丙酮吖嗪和甲酰肼和它们的混合物。
对于碱性pH水平,式(I)的亚胺衍生化合物优选包含给电子取代基如R1或R2,而不含吸电子取代基。更优选地,R1和R2中的一个是给电子取代基,而另一个取代基是氢或者给电子取代基。如果亚胺衍生化合物中存在两个给电子取代基时,该取代基可以相同或者也可以不同。
式(II)的亚胺衍生化合物优选包含肼官能团(>N-NH2)且不包含多于一个的吸电子取代基。当R3和R4均为氢,或者当R5和R6均为氢时可提供肼官能团。
对本说明书而言,术语“给电子”是指可向本体转移电子密度的与本体结合的化学基团。F.A.Carey和R.J.Sundberg在AdvancedOrganic Chemistry,Part A:Structure and Mechanisms,3rd EditionNew York:Plenum Press(1990),p.208和546-561中提供了更详细的给电子取代基的描述。该亚胺衍生化合物具有能够向本体转移足够的电子密度从而在该取代基上形成可测量的局部正电荷的给电子取代基。给电子取代基包括,例如氨基,羟基(-OH),烷基,取代烷基,烃基,取代烃基,酰胺基,和芳基。这些给电子取代基可促进含钽阻挡层材料的去除。
此外,研磨添加剂可使亚胺和肼衍生化合物与吸电子取代基作用。术语“吸电子”是指可以将电子密度从该本体转移出的与基体结合的化学基团。吸电子取代基可从本体上转移出足够的电子密度从而在该取代基上建立可测量的局部负电荷而不会促进阻挡层的去除。吸电子取代基包括,例如-O-烷基;-卤素;-C(=O)H;-C(=)O-烷基;-C(=O)OH;-C(=O)-烷基;-SO2H;-SO3H;和-NO2。该吸电子羰基不是酰胺基。
该钽阻挡层去除剂可以是乙脒,乙脒盐,乙脒衍生物,精氨酸,精氨酸盐,精氨酸衍生物,甲脒,甲脒盐,甲脒衍生物,胍衍生物,胍盐和它们的混合物。这些阻挡层去除剂在酸性pH水平下显出对钽阻挡层材料和含钛材料具有强烈的亲合力。这种亲合力可以在使用有限的研磨剂或可选的在无需使用任何研磨剂的情况下提高阻挡层的去除速率。这种有限的研磨剂使用允许该抛光以大于对电介质和金属互连的速率去除该钽阻挡层。特别有效的衍生物和盐包括盐酸乙脒,盐酸氨基胍,精氨酸,甲脒,甲脒亚磺酸,甲脒乙酸盐,盐酸胍,硫酸胍,乙酸胍,碳酸胍,硝酸胍和它们的混合物。优选地,该溶液包含0.01至12wt%的阻挡层去除剂。对本说明书而言,除非特别说明,所有的浓度值均以抛光组合物总重量的重量百分比表示。最优选地,该溶液包含0.1至10wt%的阻挡层去除剂并且对于大多数应用,介于0.2至6重量百分比之间的阻挡层去除剂的浓度可提供足够的阻挡层去除速率。
在包含余量水的溶液中,该钽去除剂可在宽的pH范围上提供效力。该溶液有用的pH范围可以至少为2至12。优选地,该溶液具有介于2和7之间的pH。最优选地,该溶液的pH介于5和6之间。用于调节降低pH的典型试剂包括硝酸,硫酸,盐酸,磷酸和有机酸。最优选地,氢氧化钾和硝酸可按照需要提供最终的pH调节。此外,该溶液最优选依靠余量的去离子水来限制附带的杂质。
该组合物包含0.01至25wt%的氧化剂。该氧化剂在允许对该浆料在酸性pH水平上进行操作的情形中特别有效。优选地,该溶液包含0.01至15wt%的氧化剂。最优选地,该溶液包含0.01至5wt%的氧化剂。该氧化剂可以是许多氧化性化合物中的至少一种,例如过氧化氢,单过硫酸盐,碘酸盐,过邻苯二甲酸镁,过乙酸,过硫酸盐,溴酸盐,过溴酸盐,高氯酸盐,高碘酸盐,硝酸铁,铁盐,铈盐,Mn(III)盐,Mn(IV)盐和Mn(VI)盐,银盐,铜盐,铬盐,钴盐,卤素,次氯酸盐和它们的混合物。此外,通常优选使用氧化剂化合物的混合物。优选地,该氧化剂是过氧化氢或碘酸盐。当该抛光浆料包含不稳定氧化剂例如过氧化氢时,通常最优选在使用时将该氧化剂混入浆料。在低于7的pH水平,该溶液需要氧化剂以便促进阻挡层的去除。对于酸性pH水平,最有利的氧化剂是过氧化氢。
适用于该互连的金属包括,例如铜,铜合金,金,金合金,镍,镍合金,铂族金属,铂族金属合金,银,银合金,钨,钨合金和包含前述金属中至少一种的混合物。优选的互连金属是铜。在使用氧化剂如过氧化氢的酸性抛光组合物和浆料中,主要由于铜的氧化,铜的去除速率和静态腐蚀速率两者都较高。为了降低互连金属的去除速率,该抛光组合物使用了腐蚀抑制剂。腐蚀抑制剂的作用是减少该互连金属的去除。这可以通过减少互连金属的凹陷从而促进抛光性能的提高。
该抑制剂的典型存在量是0至6wt%——该抑制剂可以是单一抑制剂或者是互连金属抑制剂的混合物。在这个范围内,希望抑制剂含量大于或等于0.0025wt%,优选大于或等于0.25wt%。在这个范围内还希望其含量小于或等于4wt%,优选小于或等于1wt%。优选的腐蚀抑制剂是苯并三唑(BTA)。在一个实施方案中,该抛光组合物可以包含相对大量的BTA腐蚀抑制剂以便降低互连的去除速率。在大于0.25wt%的BTA浓度下,无需添加额外的腐蚀抑制剂。优选的BTA浓度是0.0025至2wt%的量。
可选用于该抛光流体的示例性配位剂包括乙酸,柠檬酸,乙酰乙酸乙酯,羟基乙酸,乳酸,苹果酸,草酸,水扬酸,二乙基二硫代氨基甲酸钠,丁二酸,酒石酸,疏基乙酸,甘氨酸,丙氨酸,天冬氨酸,乙二胺,三甲基二胺,丙二酸,谷氨酸(gluteric acid),3-羟基丁酸,丙酸,邻苯二甲酸,间苯二甲酸,3-羟基水杨酸,3,5-二羟基水杨酸,棓酸,葡萄糖酸,邻苯二酚,连苯三酚,棓酸,丹宁酸,和它们的盐。优选地,该抛光流体中使用的配位剂是柠檬酸。最优选地,该抛光流体包含0至15wt%的配位剂。
虽然该含氮抛光试剂可提供有效的无研磨剂抛光流体,但是在一些应用希望向该抛光流体中添加研磨剂。该抛光组合物可选包含最高25wt%的研磨剂以便促进二氧化硅的去除或阻挡层和二氧化硅一起的去除——取决于该集成方案,该抛光组合物可用于i)去除掩模层或阻挡层下面的薄膜;或ii)首先去除阻挡层然后去除含氧化硅的层。该抛光组合物可选包含用于“机械”去除阻挡层的研磨剂。该研磨剂优选为胶态研磨剂。典型的研磨剂包括无机氧化物,金属硼化物,金属碳化物,金属氮化物,聚合物颗粒和包含前述研磨剂其中至少一种的混合物。适合的无机氧化物包括,例如二氧化硅(SiO2),氧化铝(Al2O3),氧化锆(ZrO2),氧化铈(CeO2),氧化锰(MnO2),或包含前述氧化物中至少一种的组合。如果需要也可以使用这些无机氧化物的改良形式,例如聚合物包覆无机氧化物颗粒和无机包覆颗粒。适合的金属碳化物,硼化物和氮化物包括,例如碳化硅,氮化硅,碳氮化硅(SiCN),碳化硼,碳化钨,碳化锆,硼化铝,碳化钽,碳化钛,或包含前述金属碳化物,硼化物,氮化物中至少一种的组合。如果需要也可以使用金刚石作为研磨剂。可选的研磨剂还包括聚合物颗粒和包覆聚合物颗粒。优选的研磨剂是二氧化硅。
为了限制腐蚀和凹陷,研磨剂的用量优选小于5wt%。使用小于1wt%的研磨剂有利于进一步限制凹陷和腐蚀。最优选地,该抛光流体不包含研磨剂以便进一步减少凹陷和腐蚀。
该研磨剂具有小于或等于150纳米(nm)的平均颗粒尺寸以便防止过度的金属凹陷和电介质腐蚀。对本说明书而言,颗粒尺寸是指该研磨剂的平均颗粒尺寸。希望使用具有小于或等于100nm,优选小于或等于50nm的平均颗粒尺寸的胶态研磨剂。当使用具有小于或等于40nm的平均颗粒尺寸的胶态二氧化硅时可产生最少的电介质腐蚀和金属凹陷。将该胶态研磨剂的尺寸减小到小于或等于40nm时,趋向于提高该抛光组合物的选择性;但其仍趋向于降低阻挡层的去除速率。此外,优选的胶态研磨剂可以包含添加剂,例如分散剂,表面活性剂和缓冲剂以便在酸性pH范围内提高该胶态研磨剂的稳定性。一种这样的胶态研磨剂是法国Clariant S.A.,Puteaux生产的胶态二氧化硅。该化学机械平坦化组合物还可选包含光亮剂如氯化铵,配位剂,螯合剂,pH缓冲剂,杀菌剂和消泡剂。
如果该抛光组合物不包含研磨剂,这时对于化学机械平坦化(CMP)工艺垫的选择和调整变得更为重要。例如,对于一些不含研磨剂的组合物,固定研磨剂垫可改善抛光性能。
已发现铵盐有利于在酸性pH水平上控制含氧化硅层如TEOS层的去除速率,从而容许控制该含氧化硅材料的去除速率。此外,这些盐允许电介质的去除而对阻挡层的去除速率没有多少有害影响。该铵盐是与化合物构成的有机铵盐且包含下列结构:
R1,R2,R3和R4可以是相同或者不同的基团。该组合物在酸性pH下起作用,这时该铵化合物发生离子化。阴离子的实例包括,硝酸根,硫酸根,卤化物(例如溴化物,氯化物,氟化物和碘化物),柠檬酸根,磷酸根,草酸根,苹果酸根,葡萄糖酸根,氢氧化物,乙酸根,硼酸根,乳酸根,硫氰酸根,氰酸根,磺酸根,硅酸根,过卤化物(例如过溴酸根,高氯酸根和高碘酸根),铬酸根,和包含至少一种前述阴离子的混合物。这些铵盐在小于7的pH水平下起作用以便提高TEOS的去除速率。可以将该盐直接加入该组合物或者在原位形成该盐。例如,将氢氧四甲铵加入pH为2.5的硝酸溶液中可形成硝酸四甲铵。
优选的铵盐组合是氢氧四丁铵与氢氟酸反应形成的。这种组合在低pH水平发生反应从而形成氟化四丁铵盐。虽然不清楚确切的机制(该氟化物盐在溶液中离解从而提供氟离子),但溶液中包含有机氟化铵盐可进一步提高TEOS的去除速率。
R1是具有小于15个碳原子的碳链长度的有机物。更优选地,R1具有2到10的碳链长度。最优选地,R1具有2到5个碳原子的碳链长度。该有机物R1可以是取代或非取代芳基,烷基,芳烷基,或烷芳基。
优选地,R2,R3和R4是有机化合物,例如取代或非取代芳基,烷基,芳烷基,或烷芳基;或氢。如果R2,R3或R4是有机化合物,这时该有机化合物优选具有小于15个碳原子的碳链长度;更优选地,该化合物具有2至10个碳原子的碳链长度;且最优选地该化合物具有2到5个碳原子的碳链长度。
适用于形成铵盐的化合物包括四甲铵,四乙铵,四丁铵,苄基三丁铵,苄基三甲铵,苄基三乙铵,二烯丙基二甲铵,甲基丙稀酸二乙基氨基乙酯,甲基丙稀酸二甲基氨基乙酯,甲基丙烯酰氧基乙基三甲铵,3-(甲基丙烯酰氨基)丙基三甲铵,三亚乙基四胺,四甲基胍,己胺和包含至少一种前述铵盐的混合物。具体的铵盐包括硝酸四甲铵,氯化四甲铵,氟化四甲铵,硝酸四乙铵,氟化四丁铵,硝酸四乙铵,氟化四乙铵,氯化苄基三丁铵,氯化苄基三甲铵,氯化苄基三乙铵,氯化二烯丙基二甲铵,氯化二烯丙基二乙胺,甲基丙烯酸二乙基氨基乙酯,甲基丙稀酸二甲基氨基乙酯,硫酸甲基丙烯酰氧基乙基三甲铵,氯化甲基丙烯酰氧基乙基三甲铵,氯化3-(甲基丙烯酰氨基)丙基三甲铵,三亚乙基四胺,四甲基胍,己胺和包含至少一种前述铵盐的混合物。优选的铵盐是四乙铵盐,四丁铵盐,苄基三丁铵盐,苄基三甲铵盐和苄基三乙铵盐。
该铵盐存在的量是0.001wt%至10wt%。最优选地,该溶液包含0.01至5wt%的铵盐。优选地,该抛光组合物以大于或等于0.02wt%的量存在,且优选大于或等于0.05wt%。此外该范围内同时希望其量小于或等于5wt%,优选小于或等于2wt%,且更优选小于或等于1wt%。
如使用至少一个等于或小于13.8kPa的垂直于晶片测量的微孔聚氨酯抛光垫压力所测,该溶液可提供至少2比1的氮化钽相对于CDO的选择性。特别适用于测定选择性的抛光垫是IC1000TM微孔聚氨酯抛光垫。优选地,该溶液可提供至少3比1的氮化钽相对于CDO的选择性,如使用至少一个等于或小于13.8kPa的垂直于晶片测量的微孔聚氨酯抛光垫压力所测;且最优选地,该范围是至少5比1。调节pH,氧化剂的浓度和钽去除剂的浓度可调整钽阻挡层的去除速率。调整抑制剂,氧化剂,配位剂,研磨剂浓度,研磨剂尺寸和均平剂的浓度可以调节互连金属的腐蚀速率。
实施例
用于实施例1至4的抛光条件如下:
抛光机: Strasbaugh 6-ECTM抛光机
抛光下压力: 2psi(13.8kPa)
抛光工作台转速: 120rpm
抛光托架转速: 114rpm
浆料流速: 200ml/min
抛光垫: IC 1000TM垫板(Rodel,Inc.)
抛光时间: 1分钟
除非另外明确说明,下面的实施中列出的所有浆料均包含2wt%的二氧化硅研磨剂,且该研磨剂具有25nm的重均颗粒尺寸并依靠硝酸和氢氧化钾获得目标pH水平,且余量为去离子水。在这些实施例中,以数字代表本发明的实施例而用字母代表对照浆料。
实施例1
在这个实施例中,我们使用四种浆料在Strasbaugh-EC抛光机上进行抛光并比较四种浆料对Ta,TaN和Cu的去除速率,如表1所示。浆料A和1在去离子水中包含0.50wt%的盐酸胍。对照浆料A不包含氧化剂H2O2,然而浆料1包含0.50wt%的H2O2。剩余的对照浆料B和C不包含任何盐酸胍。浆料B不包含剂H2O2,而浆料C包含0.30wt%的H2O2。将所有浆料的pH水平调节至5.0。
表1
浆料 | BTA(wt%) | 研磨剂(wt%) | GHC(wt%) | H202(wt%) | pH | Ta(/min) | TaN(/min) | Cu(/min) |
A | 0.10 | 2.00 | 0.50 | 0.00 | 5.00 | 60 | 260 | 120 |
B | 0.10 | 2.00 | 0.00 | 0.00 | 5.00 | 0 | 368 | 33 |
C | 0.10 | 2.00 | 0.00 | 0.30 | 5.00 | 35 | 101 | 126 |
1 | 0.10 | 2.00 | 0.50 | 0.5 | 5.00 | 700 | 1537 | 107 |
比较浆料A和1所得的结果显示盐酸胍和H2O2的组合可显著提高Ta和TaN的去除速率。缺少盐酸胍和H2O2组合的对照浆料A至C只能提供非常低的Ta和TaN去除速率。
实施例2
这个实施例对于具有相同量的H2O2氧化剂,而盐酸胍浓度和pH水平不同的浆料进行比较,如表2所示。
表2
浆料 | BTA(wt%) | 研磨剂(wt%) | GHC(wt%) | H2O2(wt%) | pH | Ta(/min) | TaN(/min) | Cu(/min) |
D | 0.10 | 2.00 | 0.00 | 0.30 | 3.00 | 178 | 322 | 85 |
2 | 0.10 | 2.00 | 0.50 | 0.30 | 3.00 | 599 | 1513 | 58 |
3 | 0.10 | 2.00 | 1.00 | 0.30 | 3.00 | 8 35 | 1463 | 37 |
E | 0.10 | 2.00 | 0.00 | 0.30 | 5.00 | 35 | 101 | 126 |
4 | 0.10 | 2.00 | 0.50 | 0.30 | 5.00 | 530 | 1373 | 190 |
5 | 0.10 | 2.00 | 1.00 | 0.30 | 5.00 | 604 | 1620 | 37 |
F | 0.10 | 2.00 | 0.00 | 0.30 | 7.00 | 35 | 34 | 149 |
6 | 0.10 | 2.00 | 1.00 | 0.30 | 7.00 | 426 | 1071 | 128 |
在每个pH水平,盐酸胍浓度的增加可提高Ta和TaN的去除速率。此外,pH水平对Ta和TaN的去除速率有影响。
实施例3
表3对具有相同量的盐酸胍浓度0.5wt%且pH为5而氧化剂H2O2浓度不同的浆料进行了比较。
表3
浆料 | BTA(wt%) | 研磨剂(wt%) | GHC(wt%) | H2O2(wt%) | pH | Ta(/min) | TaN(/min) | Cu(/min) |
G | 0.10 | 2.00 | 0.50 | 0 | 5.00 | 60 | 260 | 120 |
7 | 0.10 | 2.00 | 0.50 | 0.3 | 5.00 | 530 | 1373 | 190 |
8 | 0.10 | 2.00 | 0.50 | 0.6 | 5.00 | 700 | 1537 | 107 |
9 | 0.10 | 2.00 | 0.50 | 2 | 5.00 | 551 | 1158 | 554 |
10 | 0.10 | 2.00 | 0.50 | 4 | 5.00 | 459 | 1125 | 1390 |
Ta和TaN两者的去除速率均为H2O2浓度的函数。这些去除速率在约0.6wt%H2O2时具有最大值。此外,Cu的去除速率随H2O2浓度的增加而增加。这有利于选择需要的Cu去除速率以便获得所需的Ta∶Cu选择比。以上实施例证明Ta和TaN的去除速率是盐酸胍浓度,H2O2浓度和pH水平的函数。因此,在任何优选的pH水平下对盐酸胍和H2O2的浓度进行细致的调节可以提供所需的Ta或TaN去除速率。
实施例4
此外,优选的pH水平可以优化其它材料例如电介质材料的去除速率。例如,由原硅酸四乙酯(TEOS)前体沉积的二氧化硅也具有与pH相关的去除速率。此外,另外的化学添加剂,例如包含有机物的铵盐可以有选择地影响TEOS的去除速率从而获得所需的Ta∶TEOS选择比。
在这个实施例中,一系列浆料具有不同浓度的硝酸四丁铵(TBAN),而盐酸胍和H2O2的浓度固定为0.5wt%,且pH固定为5.0,这些浆料说明了包含有机物的铵盐提高TEOS的去除速率的能力。在这个实施例中,Strasbaugh 6-EC抛光机的下压力是1psi(6.9kPa)而研磨剂颗粒的浓度是2.75wt%。
表4
浆料 | BTA(wt%) | 研磨剂(wt%) | GHC(wt%) | H2O2(wt%) | TBAN(wt%) | 最终pH | Ta RR(/min) | TEOS(/min) | CDO(/min) |
11 | 0.15 | 2.75 | 0.50 | 0.5 | 0.00 | 5.00 | 357 | 119 | 71 |
12 | 0.15 | 2.75 | 0.50 | 0.5 | 0.10 | 5.00 | 356 | 109 | 47 |
13 | 0.15 | 2.75 | 0.50 | 0.5 | 0.25 | 5.00 | 377 | 179 | 45 |
14 | 0.15 | 2.75 | 0.50 | 0.5 | 0.50 | 5.00 | 367 | 265 | 46 |
15 | 0.15 | 2.75 | 0.50 | 0.5 | 1.00 | 5.00 | 420 | 373 | 48 |
当TBAN的浓度从0%增加到1%时,Ta的去除速率基本不变而TEOS的去除速率从119/min增加到373/min。与TEOS不同,TBAN的浓度对Novellus Corporation(San Jose,CA)生产的CORAL碳掺杂氧化物(CDO)基本没有影响。这允许TEOS硬质掩模的可控去除并同时具有最小程度的CDO去除。
Claims (10)
1.用于从半导体衬底上去除阻挡层材料的溶液,该溶液包含:0.01至25wt%的氧化剂,0至15wt%的非铁金属抑制剂,0至15wt%的研磨剂,0至20wt%该非铁金属的配位剂,0.01至12wt%选自亚胺衍生化合物,肼衍生化合物和它们的混合物的阻挡层去除剂,和余量的水;而且如使用至少一个等于或小于13.8kPa的垂直于晶片测量的微孔聚氨酯抛光垫压力所测,该溶液具有至少2比1的氮化钽相对于CDO的选择性。
2.权利要求1的溶液,其中该阻挡层去除剂是0.1至10wt%的亚胺衍生化合物。
3.权利要求1的溶液,其中该氧化剂选自过氧化氢,单过硫酸盐,碘酸盐,过邻苯二甲酸镁,过乙酸,过硫酸盐,溴酸盐,过溴酸盐,高氯酸盐,高碘酸盐,硝酸铁,铁盐,铈盐,Mn(III)盐,Mn(IV)盐和Mn(VI)盐,银盐,铜盐,铬盐,钴盐,卤素,次氯酸盐和它们的混合物。
4.权利要求1的溶液,其中该亚胺衍生化合物选自盐酸乙脒,盐酸氨基胍,精氨酸,甲脒,甲脒亚磺酸,甲脒乙酸盐,1,3-二苯胍,1-甲基-3-硝基胍,盐酸胍,四甲基胍,2,2-偶氮基二(二甲基-丙脒)二-HCl,硫酸胍,乙酸胍,碳酸胍,硝酸胍和它们的混合物而且该肼衍生化合物选自碳酰肼,咪唑,乙酰肼,盐酸氨基脲,1,2-二甲酰肼,甲基肼基-羧酸盐,草酸二酰肼,丙酮吖嗪和甲酰肼和它们的混合物。
6.权利要求5的溶液,其中该亚胺衍生化合物选自盐酸乙脒,盐酸氨基胍,精氨酸,甲脒,甲脒亚磺酸,甲脒乙酸盐,1,3-二苯胍,1-甲基-3-硝基胍,盐酸胍,四甲基胍,2,2-偶氮基二(二甲基-丙脒)二-HCl,硫酸胍,乙酸胍,碳酸胍,硝酸胍和它们的混合物而该肼衍生化合物选自碳酰肼,咪唑,乙酰肼,盐酸氨基脲,1,2-二甲酰肼,甲基肼基-羧酸盐,草酸二酰肼,丙酮吖嗪和甲酰肼和它们的混合物,且该阻挡层去除剂的含量是0.2至6wt%。
7.权利要求5的溶液,其中R1是包含2至5个碳原子的取代或非取代芳基,烷基,芳烷基,或烷芳基。
8.权利要求5的溶液,其中该铵盐是与选自下列的化合物形成的:四甲铵,四乙铵,四丁铵,苄基三丁铵,苄基三甲铵,苄基三乙铵,二烯丙基二甲铵,甲基丙稀酸二乙基氨基乙酯,甲基丙稀酸二甲基氨基乙酯,甲基丙烯酰氧基乙基三甲铵,3-(甲基丙烯酰氨基)丙基三甲铵,三亚乙基四胺,四甲基胍,己胺和它们的混合物。
9.用于从半导体晶片上去除阻挡层材料的方法,该方法包括下列步骤:
使晶片衬底与抛光溶液接触,该晶片衬底包含阻挡层材料,TEOS电介质层和第二个电介质层,该第二电介质层具有低于TEOS电介质层的介电常数而且该抛光溶液包含氧化剂和阻挡层去除剂,该阻挡层去除剂选自亚胺衍生化合物,肼衍生化合物和它们的混合物;
使用抛光垫对晶片衬底进行抛光以便从该晶片衬底上去除阻挡层材料;
使用抛光垫对该晶片衬底进行抛光以便从晶片衬底上去除至少一部分的TEOS电介质层并留下第二电介质层。
10.权利要求9的方法,其中该第二电介质层是碳掺杂氧化物层,该TEOS电介质层覆盖在该碳掺杂氧化物层上而该抛光溶液含有可以在抛光过程中提高TEOS去除速率的包含有机物的铵盐。
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-
2004
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- 2004-09-14 EP EP04255560A patent/EP1520893B1/en not_active Ceased
- 2004-09-22 CN CNB2004100118194A patent/CN100462415C/zh not_active Expired - Lifetime
- 2004-09-23 KR KR1020040076320A patent/KR101109002B1/ko active IP Right Grant
- 2004-09-27 JP JP2004279440A patent/JP4761748B2/ja not_active Expired - Lifetime
Cited By (7)
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CN101302405B (zh) * | 2007-05-08 | 2012-02-01 | 罗门哈斯电子材料Cmp控股股份有限公司 | 碱性阻挡层抛光浆液 |
CN102559062A (zh) * | 2010-09-20 | 2012-07-11 | 罗门哈斯电子材料Cmp控股股份有限公司 | 稳定的、可浓缩的化学机械抛光组合物和抛光基材的方法 |
CN103619982A (zh) * | 2011-06-29 | 2014-03-05 | 三洋化成工业株式会社 | 研磨液用中和盐、电子材料用研磨液、研磨方法和电子材料的制造方法 |
CN103619982B (zh) * | 2011-06-29 | 2015-09-30 | 三洋化成工业株式会社 | 研磨液用中和盐、电子材料用研磨液、研磨方法和电子材料的制造方法 |
CN103773244A (zh) * | 2012-10-17 | 2014-05-07 | 安集微电子(上海)有限公司 | 一种碱性化学机械抛光液 |
CN103773244B (zh) * | 2012-10-17 | 2017-08-11 | 安集微电子(上海)有限公司 | 一种碱性化学机械抛光液 |
CN113913115A (zh) * | 2021-10-20 | 2022-01-11 | 博力思(天津)电子科技有限公司 | 一种硅通孔阻挡层碱性抛光液 |
Also Published As
Publication number | Publication date |
---|---|
TW200514843A (en) | 2005-05-01 |
JP4761748B2 (ja) | 2011-08-31 |
KR20050030577A (ko) | 2005-03-30 |
US20050066585A1 (en) | 2005-03-31 |
US7300480B2 (en) | 2007-11-27 |
EP1520893B1 (en) | 2011-05-18 |
TWI354016B (en) | 2011-12-11 |
CN100462415C (zh) | 2009-02-18 |
EP1520893A1 (en) | 2005-04-06 |
JP2005167199A (ja) | 2005-06-23 |
KR101109002B1 (ko) | 2012-02-08 |
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