TWI354016B - High rate barrier polishing composition - Google Patents
High rate barrier polishing composition Download PDFInfo
- Publication number
- TWI354016B TWI354016B TW093127065A TW93127065A TWI354016B TW I354016 B TWI354016 B TW I354016B TW 093127065 A TW093127065 A TW 093127065A TW 93127065 A TW93127065 A TW 93127065A TW I354016 B TWI354016 B TW I354016B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- salt
- hydrazine
- weight
- solution
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims description 73
- 230000004888 barrier function Effects 0.000 title claims description 61
- 239000000203 mixture Substances 0.000 title claims description 41
- -1 ferrous metal complex Chemical class 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- 150000002466 imines Chemical class 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000004475 Arginine Substances 0.000 claims description 11
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-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
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 210000003462 vein Anatomy 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 7
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001483 arginine derivatives Chemical class 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- YFHNDHXQDJQEEE-UHFFFAOYSA-N acetic acid;hydrazine Chemical compound NN.CC(O)=O YFHNDHXQDJQEEE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 206010036790 Productive cough Diseases 0.000 claims description 3
- RAESLDWEUUSRLO-UHFFFAOYSA-O aminoazanium;nitrate Chemical compound [NH3+]N.[O-][N+]([O-])=O RAESLDWEUUSRLO-UHFFFAOYSA-O 0.000 claims description 3
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 3
- PTYMQUSHTAONGW-UHFFFAOYSA-N carbonic acid;hydrazine Chemical compound NN.OC(O)=O PTYMQUSHTAONGW-UHFFFAOYSA-N 0.000 claims description 3
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 210000003802 sputum Anatomy 0.000 claims description 3
- 208000024794 sputum Diseases 0.000 claims description 3
- 159000000008 strontium salts Chemical class 0.000 claims description 3
- FNHMJTUQUPQWJN-UHFFFAOYSA-N 2,2-dimethylpropanimidamide Chemical compound CC(C)(C)C(N)=N FNHMJTUQUPQWJN-UHFFFAOYSA-N 0.000 claims description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 150000001454 anthracenes Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 210000004072 lung Anatomy 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims 2
- PZNODNZEMDPEQO-UHFFFAOYSA-N [Cl-].NN[NH3+] Chemical compound [Cl-].NN[NH3+] PZNODNZEMDPEQO-UHFFFAOYSA-N 0.000 claims 2
- 150000001720 carbohydrates Chemical class 0.000 claims 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- PSMULJKVDUDLTA-UHFFFAOYSA-O SCC=COCC[N+](C)(C)C Chemical compound SCC=COCC[N+](C)(C)C PSMULJKVDUDLTA-UHFFFAOYSA-O 0.000 claims 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims 1
- JMAKGYLSSLOOPO-UHFFFAOYSA-N [Bi].C=C Chemical compound [Bi].C=C JMAKGYLSSLOOPO-UHFFFAOYSA-N 0.000 claims 1
- 230000001133 acceleration Effects 0.000 claims 1
- 229940037003 alum Drugs 0.000 claims 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 150000001879 copper Chemical class 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims 1
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 claims 1
- 239000012493 hydrazine sulfate Substances 0.000 claims 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims 1
- 239000003617 indole-3-acetic acid Substances 0.000 claims 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 claims 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical class [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 claims 1
- XNEFVTBPCXGIRX-UHFFFAOYSA-N methanesulfinic acid Chemical compound CS(O)=O XNEFVTBPCXGIRX-UHFFFAOYSA-N 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 claims 1
- 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 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims 1
- SGGKDDZKMXGBEC-UHFFFAOYSA-N tetradecylhydrazine Chemical compound CCCCCCCCCCCCCCNN SGGKDDZKMXGBEC-UHFFFAOYSA-N 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 150000003535 tetraterpenes Chemical class 0.000 claims 1
- 235000009657 tetraterpenes Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 description 25
- 125000001424 substituent group Chemical group 0.000 description 20
- 239000012530 fluid Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 235000012431 wafers Nutrition 0.000 description 12
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 150000004767 nitrides Chemical class 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010455 vermiculite Substances 0.000 description 6
- 235000019354 vermiculite Nutrition 0.000 description 6
- 229910052902 vermiculite Inorganic materials 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical class NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur 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
- 125000004149 thio group Chemical group *S* 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- KUCWUAFNGCMZDB-UHFFFAOYSA-N 2-amino-3-nitrophenol Chemical compound NC1=C(O)C=CC=C1[N+]([O-])=O KUCWUAFNGCMZDB-UHFFFAOYSA-N 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical class CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- NRWCNEBHECBWRJ-UHFFFAOYSA-M trimethyl(propyl)azanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)C NRWCNEBHECBWRJ-UHFFFAOYSA-M 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N triphenylene Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- H01L21/04—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
- H01L21/31—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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- 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
- H01L21/04—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
-
- 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
- H01L21/04—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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- 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
- H01L21/04—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
- H01L21/31—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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
1354016 九、發明說明: 【發明所屬之技術領域】 本發明係關於抛光半導體基板,更特定言之,關於用 於移除障蔽層之拋光流體。 【先前技術】 半‘體裝置之電路互連可形成於排列多個渠溝之介電 層上。邊等互連係藉塗佈障蔽膜於下面介電層上,接著將 金屬層塗佈在該障蔽膜上的方式形成。形成具有足夠厚度 之金屬層以利用金屬填滿該等渠溝。該互連製造方法係包 括兩步驟化學機械拋光(CMP)方法之使用。 。CMP相當於一種利用拋光墊及拋光流體拋光半導體晶 圓之方法。在苐一拋光步驟中,自該下面障蔽層及該下面 =電層移除該金屬層。該金屬層係藉該拋光墊所施加之磨 知及與拋光流體之化學反應並伴隨化學反應產物之溶解而 移除。該第一拋光步驟移除該金屬層,在晶圓上留下一光 滑平坦已拋光表面並另外在該等渠溝中留下金屬以提供實 質上與該拋光表面一樣平坦之電路互連。例如,Lee等人 在EP專利公開案第! 072 662 A1號中揭示使用胍作為研 磨加速劑以加速研磨組合物有關金屬互連之介電移除率。 典型第一步驟拋光方法包括一拋光流體中具有氧化試 劑如〇〇3或札〇2以移除銅互連之水溶液。該銅金屬層係藉 氧化試劑氧化該金屬層並藉源自該拋光墊之磨損移除。此 外,該拋光墊磨損該金屬層以減少溶解氧化物自該溶液再 度沉積於欲拋光材料表面上。自下面障蔽膜,例如鈕(Ta)
(修正本)93060L 5 1354016 或氮化鈕(TaN)之障蔽膜移除銅。障蔽膜之耐磨性比銅高, 因此該障献膜係作為抛光終止層以終止銅之第一步驟抛 光。此外,以拋光流體氧化該障蔽膜表面將抑制第一步驟 拋光期間該膜之移除。 在第二拋光步驟中,自該下面介電層移除該障蔽層。 •第二步驟拋光可提供該介電層上一光滑、平坦已拋光表 •面。理想地,該第二拋光步驟不移除渠溝中過多金屬。在 該第二拋光步驟中移除過多金屬可能造成凹陷。 、凹陷是技術術語,其描述因移除渠溝中過多金屬所造 成電路互連中形成不想要的空洞。凹陷可能發生在該第一 拋光步驟及該第二拋光步驟中。電路互連必須具有精確尺 寸以決定如該電路互連所提供之訊號傳輪線的電阻抗。超 過可接受程度之凹陷在電路互連中造成尺寸缺陷,其可能 使電路互連所傳輸之電子訊號衰減。 該第二拋光步驟應造成最小腐#。射虫是技術術語, f描述因移除障蔽層下面之部分介電層所造成該介電層表 要的下降。緊鄰渠溝中之金屬所發生的腐姓造成 ”減5寸缺陷’其可能使電路互連所傳輸之電子訊 咸。為攻小化腐鞋,希望第二步驟拋光之拋光流體以 而於該介電層之移除率的移除率移除該障蔽膜。 弟一拋光步驟相對於該下 移除選擇性。移除選 τ〆/早敝層具有同 對照層(例如介金義為障蔽膜之移除率相對於 利說明書的目的姻性H之移、除率的比例。為達此專 、 ,丁、相虽於以每單位時間之距離(如 6
(修正本)93060L W分鐘)為單位之移除率的比例。因此,移除選擇性是一 項:除障蔽膜相對於移除介電層或金屬膜之測量。對於數 ,完整流程而*r係希望高移除選擇性。以相對於該介電声 現尚移除選擇性之拋光流體進行拋光可增加該障壁 車膜並降低該介電層之移除。因此希望抛光溶液i有 較而1¥敝層移除率及較低介電移除率。 【發明内容】 本發明提供—種適用於自半導體基板移除障蔽材料 :、之其包含0. 〇1至25重量%氧化劑、〇至15重量 遥屬之抑制劑、0至15重量%研磨劑、〇至重量%有色 士 = 剧、0.01至12重量%障蔽物移除劑及剩餘水, /章蔽物#除劑係選自亞胺衍生物化合物、肼衍生物> = : = =成之群;而且如以微孔聚胺基甲酸醋彳 β、 夕垂直於晶圓測量係等於或小於13. 8 kPa 比^:力測里4,該溶液之氮化钽對的選擇率至少為 徊特點中
, 今、钱%提供一種迺用於自半導髀其 板移除障蔽材料的溶液,其包含牛導體基 二◦重量%有色金屬之抑制劑、:至10重量:有。:::之。 .1至10重里%下式所形成之含有機録鹽
(修正本)93060L 7 1354016 R4 — N"1"— R2
I r3 (Rl R2、匕及R4是基團,h的碳鏈長度係少於15個碳原 子)及剩餘水,而且該溶液的pH係小於7, 料劑係選自乙脒、乙脒鹽、乙㈣生物、精胺 酉文鹽、精胺酸衍生物、甲腓、甲脒鹽、甲脉衍生物、脈衍 生物、胍鹽及其混合物組成之群。 在另一個本發明特點中,本發明提供一種自半導體晶 圓移除障蔽材料的方法,其包括下列步驟:令晶圓基板與 f光$液接觸,該晶圓基板包含障蔽材料、TE0S介電層及 第一"電層,該第二介電層具有低於TE〇s介電層之介電常 數,而該拋光溶液包含氧化劑及障蔽物移除劑,其中該障 敝物移除劑係選自包含亞胺魅物化合物、肼衍生物化合 八犯。物之群,以抛光墊拋光該晶圓基板以自晶圓基 板私除蔽材料;及以該拋光塾抛光該晶圓基 圓基板移除至少一邻分TF的人φ s廿切 J砟刀TE0S介電層並留下該第二介電層。 【實施方式】 /已發現調整pH值及氧化劑濃度可幫助提高含有亞胺 ,肼何生物化合物之拋光溶液的障蔽物移除率。而且,該 =液及方法提供未預期之移除障蔽材料選擇性及控制。該 溶液係依賴氧化鼓選自亞胺及肼衍生物化合物和其混合 物組成之群的障蔽物移除劑選擇性地移除障蔽材料,如含
(修正本)93060L 8 材料。該溶液係以較少介電腐⑽較少金屬 陷、腐Μ刮傷的方切除障蔽材料。再 ㈣::、1私除鈕障蔽材料而無低-k介電層自半導體晶圓 二5 a而且,该溶液對經矽酸四乙酯(TEOS)前驅物 沉積之二氧切所形成的硬罩幕具有經控制之漏移除 率。 、特別地’ 4,谷液包含一障蔽物移除劑以移除障蔽材 料,如鈕、氮化鈕、鈕一矽氮化物、鈦、氮化鈦、鈦—石夕氮 化物、鈦-鈦氮化物、鈦_鶴、鶴、氮化鶴及鶴氣化物。 雖然該溶液在酸性pH值下對含鈦障蔽材料是有效的。該溶 液對含鈕材料是特別有效的。為達本專利說明書的目的, 含鈕材料包括鈕、以钽為主之合金及鈕介金屬 (intermetallic) ’如碳化鈕、氮化鈕及氧化鈕。該泥漿對 移除已圖案化半導體晶圓之含鈕障蔽物是最有效的。 較佳亞胺衍生物包括式(I)化合物: 其中R1是-H或-腳2 ’ R2是-H、-腿2、烴基、胺基、羰基、 酸亞胺基、偶氮基、氰基、硫基或硒基及_〇R7,其中r7是 烴基。 較佳肼衍生物包括式(II)化合物: R3R4N-NR5R6 (Π)
(修正本)93060JL
9 1354016 其中R3、R4、R5及R6是獨立地_H、_〇r7、—·2、烴基、羰 基、醯亞胺基、偶氮基、氰基、硫基或硒基。 術語”含氮"相當於一含有兩或多個氮之物質。在含氮 物質中兩或多個氮原子可彼此鍵結或其可被其他原子分a 開。若含氮物質包含三或多個氮原子’部分氮原子可彼此 鍵結’而其餘則只鍵結在非氮原子上。含氮物質中的氮原 子可為該物質⑽學基的—部分,如絲1胺基、偶氮 基亞胺基醯亞胺基或肼基。含氮物質中氮原子最好係 呈還原態且不直接鍵結在氧原子上(即_N〇2 ; _N〇3)。 術。。烃基相當於經氫原子取代之碳原子的直鏈、支 鏈或環鏈並包括未練歧㈣代絲、㈣、快基、芳 基及雜《。絲最好包含β2(Μ@碳原子。烴基視情況 可經其他基團取代。碳原子間的鍵可獨立地選自單鍵、雙 鍵及卷鍵。 術”。烷基(或alkyl_或aiD相當於經取代或未經 取代、直鏈、支鏈或環烴鏈,其最好包含丨至2〇個碳原子。 料包括’例如甲基'乙基、丙基、異丙基、環丙基、丁 基、異丁基、第三丁基、第二丁基、環丁基、戊基、環戊 基、己基及環己基。 術°。烯基(或alkeny卜或alken-)相當於經取代或 未經取代、直鏈、支鏈或環煙鏈,其包含至少-個碳-碳雙 鍵且最好包含2至⑷固碳原子。烯基包括,例如乙稀基(或 乙婦基,-CH=Cii2) · 1 ;?; γ 计 n ,1-丙烯基;2-丙烯基(或烯丙基, -CH2-CH=CH2) ; 1 3-丁 - # # / 广口
’ 丁一烯基(-CH=CHCH=CH2) ; 1-丁烯基 (修正本)93060L 10 “54016 (CH-CHCH2CH3);己烯基;戊烯基;L 3, 5_己三烯基;環 己二烯基;環己烯基;環戊烯基;環辛烯基;環庚二烯基; 及環辛三烯基。 術^炔基(或alkynyl-或aikyn-)相當於經取代或 未經取代、直鏈、支鏈或環烴鏈,其包含至少一個碳—碳叁 鍵且最好包含2至20個碳原子。炔基包括,例如乙炔基(或 乙块基’ «Η2) ; 2-甲基-3一丁炔基;及己炔基。 術浯芳基"相當於任何最好包含3至2〇個碳原子之經 取代或未經取代芳族碳環基。芳基可為單環或多環。芳基 包括,例如苯基、萘基、聯苯基、苯甲基、甲苯基、二甲 苯基、苯基乙基、苯曱酸酯、烷基苯曱酸酯' 苯胺及N—烷 基苯胺基。 術語"雜環基"相當於飽和、不飽和或芳族環部分,其 匕έ或夕個雜原子且最好包含5至1 〇個,較佳係5至6 個環原子。術語”環原子”相#於併人該環結構之原子並排 除懸接於該環之其他原子。該環可為單、雙-或多環。雜環 基包含碳原子及U 3個雜原子,其中該雜原子係獨立地 選自由氮、氧及硫組成之群。雜環基也可為經取代或未經 =代’包括’例如苯并味唾、苯并嗟哇、咬喃、味峻、吲 °木、異喹啉、異噻唾、嗎福啉、派哄、吡哄、吡哇、吡啶、 嘧°疋、吡咯、喹啉、噻唑、噻吩、三嗪及三唑。 術語”經取代"用於描述一化學基時’其係相當於一包 含至少-個’較佳係i至5個取代基之化學部分。適合的 取代基包括,例如羥基(_0H)、胺基(_丽2)、氧基(_〇—)、
(修正本)93060L 11 羰基(>〇〇)、硫醇1基、隸 這些取代基可視情 均基方基及雜環基’ 術語,,鞍基相當於取代基取代。 團。例如,胺基可選自—ΝΗ2;其鍵結在物質上之基 基鞍基職)2);芳基胺^二基/基‘貌基);二燒 =組成之群。鍵結在該氮上之_最=: 20個碳原子,鍵纴名访土取灯匕si主 片子。-产美膝美之該等芳基包含3至20個礙 原子-坑基胺基中㈣基可為㈣或可為不同。 術έ吾幾基"相當於一 κ 基團並包括敌酸、酸二!;雙鍵鍵結在-氧原子上之 曰醛、酮、醋、羧酸鹵化 物及鹺胺。例如,羰基可具有通式(Ιπ)·· -c = o (ΙΠ);
I R8 其中 R8 是-Η、-〇H、-〇R9、-r1» R9、β1(1及R11係獨立地為包含i 、-NH2及-NH-C(=0)-Rn ; 至10個碳原子之烷基。 且 術語π醯亞胺基”相當於一碳原子雙鍵鍵結在一 NH基 上之基團。例如,醯亞胺基可具有通式(IV): (IV);
-C = NH I R12 其中R12是-Η、-NH2或含有1至10個碳原子之烷基。 術語”偶氮基π相當於一含有氮-氮雙鍵或-基單鍵 鍵結在另一 -ΝΗ基上之基團。例如,偶氮基可選自-ν3、
12 (修正本)93060L 1354016 卵 NH-NH3、-N=N-NH3、-j\j:=N~R13 n ,. 组成之群,其NH—㈣】6 個碳原子之録。 及1^獨立地為含有u10 ::"氰基"相當於一碳原子與一氮原子 戍-㈣子雙鍵鍵結在—氮原子 子如氧、硫…之基團。例如,氰基可 +oo、i〇s^N=G=Se 組叙^ 術語"硫基||相當於-硫原子單鍵鍵結在另—原子上之 基團。例如’硫基可選自|R' _S_S_R18、_s_c· _s⑽ 及-S0H組成之群,其令R"及Rl8係獨立地為含有i至1〇 個碳原子之烷基。 術語"硒基"相當於一硒原子單鍵鍵結在另一原子上之 基團。例如,硒基可選自_Se_Rl9、-Se_Se_R2Q及一Se_c_ 組成之群’其中"及R2°係獨立地為含有1至10個碳原子 之烧基。 亞胺衍生物之實例包括乙脒、乙脎鹽、乙脒衍生物、 淨月版Ssl、精胺酸鹽、精胺酸衍生物、曱肺、甲肺鹽、甲脎 知生物、胍衍生物、胍鹽及其混合物。較佳式(丨)亞胺衍生 物包括’例如氫氯化乙胨(acetamidine hydrochi〇ride)、 fee基-胍鹽酸鹽(amino_guanidine hydrochloride)、精胺 酸、甲脒、甲腓亞磺酸、曱脒乙酸鹽、13 —二苯基胍、卜 曱基-3-硝基胍、胍鹽酸鹽(gUanidine hydrochloride)、 四曱基胍、2, 2-偶氮基雙(二甲基-丙脒)二-HC1、胍硫酸 鹽、胍乙酸、胍碳酸鹽、胍硝酸鹽及其混合物。
13 (修正本)93060L 1354016 較佳式(11)之肼衍生物包括,例如卡骄 (carbohydrazide)、咪嗤、乙醯肼、氨基脲鹽酸鹽、丨,2_ 二甲醯基肼、甲基肼基-碳酸酯、乙二醯肼、二丙酮腙 (acetone azine)及甲醯肼和其混合物。 對於鹼性pH值,式(I)之亞胺衍生物化合物最好包含 推電子取代基如f或R2且無拉電子取代基。較佳係V與 R2中之一為推電子取代基,而另一取代基為氫或推電子取 代基。若兩推電子取代基存在於亞胺衍生物化合物中,該 等取代基可相同,或其可不同。 式(Π)之亞胺衍生物化合物最好包含一肼官能基 ON-NH2)及包含不超過一個拉電子取代基。當R3及R4皆為 氫時或R5及R6皆為氫時,具有肼官能基。 為達本專利說明書之目的,術語”推電子”相當於鍵結 在物負上之化學基,其可將電子密度轉移至該物質上。 F. A. Carey及R· J. Sundberg於高葶有機允學,义部:結 構輿及肩機禕,第三焱,紐約:Plenum出版社(199〇), 及546-561頁提供更多有關推電子取代基之細節描述。該 亞胺衍生物化合物具有可轉移足夠電子密度至該物質上以 建立一可測量部分正電荷於該取代基上之推電子取代基。 推電子取代基包括,例如胺基、羥基(_〇H)、烷基、經取代 烷基、烴基、經取代烴基、醯胺基及芳基。這些推電子取 代基加速含鈕障蔽材料之移除。 而且,研磨劑的添加可有效賦予亞胺及肼衍生物化合 物吸電子取代基。術語"吸電子"相當於鍵結在一物質上之
(修正本)93060L 14 1354016 化子基’其可將電子密度轉離該物質“及電子取代基可自 °亥物貝轉離足夠電子密度以建立-可測量部分負電荷於該 取代基上且不會加速障蔽物之移除。吸電子取代基包括, 例如-0-烷基、一鹵素、—c(=〇)H、—c( = )〇_烷基、_c(=〇川Η、 c(-〇)-烷基、m _s〇3H&_N〇2。拉電子之羰基不是醯 胺基。 A輯蔽物移除劑可為乙脉、乙脉鹽、乙肺衍生物、精 胺酸、精胺酸鹽、精胺酸衍生物、甲脉、甲懸、甲肺衍 勿胍衍生物、胍鹽及其混合物。這些障蔽物移除劑在 酉欠性pH值下對钽障蔽材料及含钽材料明顯具有強親和 ^此親和力明顯以有限研磨劑或視情況無使用任何研磨 =加速障蔽物移除率。此有限使料磨劑容許該拋光以比 介電及金屬互連大之速率移除該鈕障蔽物。特別有效的衍 及jm· U括虱氣化乙脉、胺基_脈鹽酸鹽、精胺酸、甲脎、 曱脒亞續酸、曱胨乙酸鹽、胍鹽酸鹽、脈硫酸鹽、胍乙酸、 胍碳酸鹽、胍硝酸鹽及其混合物。該溶液最好包含〇 〇1 至12重1 %障蔽物移除劑。為達本專利說明書之目的,所 有濃度值係以該拋光組合物之總重量計之重量百分比表 不,除非另外特別註明。最佳係該溶液包含0.丨至10重量 %障立蔽物移除劑’對大部分應用而·Τ,介於0.2與6重量% 之障蔽物移除劑濃度可提供足夠障蔽物移除率。 該障蔽物移除劑在寬廣ΡΗ範圍及所含剩餘為水的溶 液中提供效力。此溶液的可用ρΗ範圍至少從2延伸至12。 該溶液的pH最好介於2與7之間。最佳係該溶液的抑係
(修正本)93060L 15 1354016 介於5與6之間。典型用於向下調整pH之試劑包括硝酸、 硫酸、鹽酸、磷酸及有機酸。必要時,最佳係以氫氧化鉀 及硝酸提供最終pH調整。而且,該溶液最佳係依賴剩餘的 去離子水限制偶發不純物。 i組合物包含〇.〇1至25重量%氧化劑。該氧化劑在酸 it pH值下备許刼作之泥漿中是特別有效的。該溶液最好包 3 0. 01至15重里%氧化劑。最佳係該溶液包含〇· 至5 重量%氧化劑。該氧化劑至少是多種氧化化合物中之一種’ 如過氧化氫、單過硫酸鹽、礙酸鹽、過鄰苯二甲酸鎮、過 乙酸、過硫酸1酸鹽、過漠醆鹽、過氯酸鹽、過破酸鹽、 石肖酸鐵、鐵鹽、鈽_、f τ 了 τ、祿 / a Μη(ΠΙ)鹽、Μη(ίν)鹽及 Mn(VI)鹽、 此二::;鉻鹽、鈷鹽、鹵素、次氯酸鹽及其混合物。 ,使用氧化劑化合物之混合物經常是有助益的。 化劑最好是過氧化氬或蛾酸 氧化劑如過氧化氣時,使用;將含不安定的 疋取有助並的。在ρΗ值低於7 吊 移除障壁物。對於酸性 夜而要氧化劑幫助 適合用於該互連之金屬包二氧化劑是過氧化氨。 金合金、鎳、鋅八二!:括,例如銅、銅合金、金、 合金、鎢、鎢金眉 ·. 屬、鉑族金屬合金、銀、銀 互連金屬是銅。在利用氧化劑如過氧化合物。較佳 物及泥漿中,因為鋼之氧化作用 ς ·夂性抛先組合 飪刻速率是高的。在7政 啼初該鋼移除率及靜態 局了降低該互連全屬夕& 組合物使用腐鞋抑制劑。該等腐㈣率,錢光 和4係用於降低該互
(修正本)93060L 16 丄叶 連金屬之移除。這藉減少 能。 ^逆金屬凹陷幫助改善抛光性 該抑制劑一般係以〇至6重 代表該互連全屬之罝士⑴ 在—該抑制劑可 此範圍内’希望具有大於或等於⑽重 ==在 25重—量%之抑制劑量。在此範圍内,:希it 重量%’較佳係低於或等於1重量%之量。較 钱抑制劑是苯并三細Α)。在一具體實施例中 光組合物可包会相去士旦 D抛 率。在n 劑崎㈣互連移除 在TA浪度南於〇·25重量%時,可能不需要添加補充 腐蝕抑制劑。較佳ΒΤΑ濃度是〇.〇〇25至2重量%之量。 —拋光流體中視情況選用之錯合劑示範例係包括乙酸、 U:酉夂、乙酿乙酸乙醋、乙醇酸、乳酸、頻果酸、草酸' 水楊S文、一乙基二硫基胺基ρ酸鈉、琥珀酸、酒石酸、乙 硫醇酸、甘胺酸、丙胺酸、天冬胺酸、乙二胺、丙二胺、 =二酸、谷脫酸(glutericacid) ' 3_羥基丁酸、丙酸、鄰 苯二甲酸、間苯二甲酸、3_羥基水揚酸、3, 5_二羥基水揚 酸、〉又食子酸、葡萄糖酸、鄰苯二酚、五倍子酚、沒食子 酸、單争酸及其鹽。該拋光流體中所用的錯合劑最好是擰 檬酸。最佳係該拋光流體包含0至15重量%錯合劑。 雖然含氮拋光劑可提供有效的不含研磨劑之拋光流 體’但在某些應用中可能希望該添加研磨劑至拋光流體 中。該抛光組合物視情況可包含高達25重量%研磨劑以幫 助移除硬石或移除障蔽物與矽石之組合物_視完整流程而
17 (修正本)93060L 1354016 定,·該拋光組合物可用於{)移除該障壁層下面之罩幕層或 膜,·或ii)先移除障壁層,然後移除含氧化矽之層。該曰抱 光組合物視情況包括用於"機械"移除障壁層之研^劑:該 研磨劑最好是勝體研磨劑。研磨劑實例包括無機氧化物、 金屬硕化物、金屬碳化物、金屬氮化物、聚合物粒子及包 3至J -種上述化合物之混合物。適合的無機氧化物包 括,例如矽石(Sl〇2)、氧化紹Ul2〇3)、氧化錯、氧 化鈽(Ce〇2)、氧化錳(Mn〇〇或包含至少一種上述氧化物之 組合物。必要時,也可利用這些無機氧化物之改良形式如 包覆聚合物之無機氧化物粒子及包覆無機物之粒子。適人 的金屬碳化物、聽物及氮化物包括,例如碳切、氮= 石夕、碳氮切⑶⑻、魏厕、碳化km、職链、 碳化叙、碳化欽或包含至少一種上述金屬碳化物、观化物 及亂化物之組合物。必要時,也可利用鑽石作為研磨劑。 替代研磨劑也包括聚合物粒子及包覆聚合物之粒 研磨劑是矽石。 為限制腐蝕及凹陷,最好使用量低於5重量%之研磨 劑。利用低於i重量%之研磨劑可進一步幫助限制凹陷 蝕。最佳係該拋光流體不含研磨劑以進一步減少凹陷及 #。 肉 該研磨劑具有小於或等於15〇毫微米(nm)之平均粒徑 以防止過多金屬凹陷及介電腐#。為達本㈣說明書 的,粒徑相當於該研磨劑之平均粒徑。最好利用平二粒 小於或等於⑽毫微米,較佳係小於或等於5〇毫微米之ς
(修正本)93〇6〇L 18 1354016 體研磨齊卜最少介電腐钱及金屬㈤陷較佳係利用平均粒徑 小於或等於40宅微米之膠體矽石時發生。將該膠體研磨劑 之尺寸降低至小於或等於4〇毫微米傾向改善該拋光組合 物之選擇性;但其也易降低障蔽物移除率。而且,較佳膠 體研磨劑可包含添加劑,如分散劑、界面活性劑及緩衝液 以改善骖體研磨劑在酸性pH範圍之安定性。一此類膠體研 磨劑是購自法國PuteauXi C:lariant S A•的膠體矽石。 該化學機械拋光組合物也可視情況包含光澤劑,如氯化 銨、錯合劑、鉗合劑、pH緩衝液、抗微生物劑及消泡劑。 若拋光組合物不含研磨劑,然後拋光墊的選擇及調理 對化學機械平整(CMP)程序而言變得更重要。例如,對於某 些不含研磨劑之組合物,固定研磨墊可改善拋光性能。 已發現銨鹽可在酸性pH值下幫助含氧化矽層,如TE〇s 層之經控制移除率並因此可控制該含氧化矽材料的移除 率。此外,這些鹽可以對障蔽物移除率之最低不利影變移 除介電材料。該錢鹽係以包含下列結構之化合物所職的 有機銨鹽: R.
I
(修正本)93060L 19 1354016 氟化物及碘化物)' 檸檬酸鹽 '磷酸鹽、草酸鹽、蘋果酸鹽、 、 葡词糖酸鹽、氫氧化物、乙酸鹽、糊酸鹽、乳酸鹽、硫氰 k鹽、氰酸鹽、確酸鹽、石夕酸鹽、過鹵化物(如,過溴酸鹽、 過氣酸鹽及過碘酸鹽)、鉻酸鹽及包含至少一上述陰離子之· 混合物。這些銨鹽在小於7之钟值下係用於加速TE〇s移: 除率。可將該鹽直接加入該組合物中或於原處形成該鹽。 例如,將四甲基氫氧化銨加入pH為2·5之硝酸溶液中可-形成四甲基硝酸銨。 較佳銨鹽組合物係由四丁基氫氧化銨與氫氟酸反應所-籲 形成。此組合物在低ρΗ值下反應以形成四丁基氟化銨鹽。 雖然正確反應機制未知(氟化物鹽解離以提供溶液中之氟 化物離子),但是溶液中具有有機氟化銨鹽進一步加速 TE0S移除率。
Rl是碳鏈長度少於15個碳原子之有機基團。較佳係 h的碳鏈長度為2至1Q個碳原子。最佳係Ri的碳鏈長度
,2至5個碳原子。Rl之有機基團可為經取代或未經取代 芳基、烷基、芳烷基或烷芳基。 ^ 及L最好是有機化合物,如經取代或未經取 土烧基芳烧基或貌芳基;或氯。若1、1或匕是 機化口物然後„亥有機化合物的碳鍵長度最好少於1 $個 =^乂佳係其石厌鏈長度為2至個碳原子;最佳係其 鏈長為2至5個碳原子。
(修正本)93060L 20 1354016 基三乙基錄、二烯丙基二甲基鍵、甲基㈣酸二乙基胺基 ㈣、甲基㈣酸二甲基胺基㈣、甲基丙職氧基乙基 一甲基鉍、3-(甲基丙烯醯基醯胺基)丙基三甲基銨、三乙 四胺、四甲基胍、己基胺及包含至少—上述銨鹽之混合物。 特殊銨鹽包括四甲基硝酸銨、四甲基氯化銨、㈤曱基氟化 銨:四乙基硝酸銨、四丁基氟化銨、日乙基硝酸銨、四乙 f氟化銨、苯曱基三丁基氯化銨、苯甲基三曱基氣化銨、 苯f基三乙基氯化銨、二烯丙基二甲基氯化録、二婦丙基 二乙基氣化銨、甲基丙烯酸二乙基胺基乙g|、甲基丙稀酸 一甲基胺基乙酯、甲基丙稀酿氧基乙基三曱基硫酸銨、甲 基丙稀fe氧基乙基:甲基氯化銨、3_(?基丙稀酸基酿胺基) 丙基三甲基氯化銨、三乙四胺、甲基胍、己基胺及包含 至少一上述銨鹽之混合物。較佳銨鹽是四乙基銨鹽、四丁 基録鹽、苯甲基三丁基錄鹽、苯甲基三甲基銨鹽及苯甲基 二乙基録鹽。
、該等録鹽的存在量為0·001至1〇重量%。最佳係該溶 液包含G.G1至5重量%銨鹽。該拋綠合物的存在量最好 大於或等於0.02重量%,較佳係大於或等於〇 〇5重量%。 在此範圍内,也希望是低料等於5,較佳係低於或等於 2 ’更佳係低於或等於1重量%之量。 如以微孔聚胺基Τ酸酯拋光墊利用至少一垂直於曰 :量係等於或低於13.8kpa之拋光塾遷力測量時,該: 提供至少2比】之氮化㈣⑽的選擇率。對測定選擇 特別有用的拋光塾是IC1_™微孔聚胺基甲酸醋拋光墊 (修正本)93060L· 21 1354016 如以微孔聚胺基〒酸酯抛光塾利用至少一垂直於晶圓測量 料於或低於13.8kPa之抛光墊麼力測量時,該溶液最好 提供至少3比1之氮化组對CD〇的選擇率;最佳係此範圍 至少為5比1。調整pH、氧化劑濃度及鈕移除劑的濃度可. 調整該叙障蔽物移除率。調整該抑制劑、氧化劑、錯合;、; 研磨劑濃度、研磨劑尺寸及平整劑濃度可調整該^: 的蝕刻率。 虫蜀 實例 實例1至4之拋光條件如下:
拋光器: 拋光下壓力: 拋光壓平速度: 拋光載體速度: 泥滎流率: 拋光塾: 拋光時間:
Strasbaugh 6-EC™拋光器 2 psi(13. 8 kPa) 120 rpm Π4 rpm 200毫升/分鐘 icio〇〇™墊(Rodel,Inc.) 1分鐘
重旦…:二別註明,下列實例中所列所有泥漿包含 二里、立徑為25毫微米之矽石研磨劑並依賴硝 及^化钾以獲得目標pH值且剩餘為去離子水。在該等 :丨中;數字代表本發明實例,字母代表對。 貫例1 6 我們如表1所示比較四種在strasb 一 拋光|§拋光之、、
及1於去離子水中:二::及Cu移除率。泥漿A 乙吞0. 5 0重I %胍鹽酸。對照泥衆a不
(修正本)93060L 22 1354016 含氧化劑Ηζ〇2,而泥漿1包含〇. 5〇重量%之Η"〗。其餘對 泥漿,泥漿B及C不含任何胍鹽酸鹽。泥漿B不含h2〇2, 而泥聚C包含G. 3G重量%之H2()2。所有泥聚之pH值皆調整 至 5. 0。 表1
由比#父泥漿A及1之結果顯示胍鹽酸鹽與之結合 明顯增加Ta及TaN之移除率。該缺少胍與祕之組合:對 照泥漿A至C提供極低之Ta及TaN移除率。 實例2 此實例係比較如表2所示具有相同H2〇2氧化劑量但不 同胍鹽酸鹽濃度及pH值之泥漿的移除率。
(修正本)93060L 23 1354016 表2 泥漿 ΒΓΑ (4¾%) 研磨劑 (ti%) GHC (Μ%) m (重獨 ιίί Ta速率 (檢赠 TaN速率 Οα速率 鐵 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. 00 835 1463 37 E 0. 10 2.00 0. 00 0. 30 5. 00 1—一 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
在各pH值下,胍鹽酸鹽濃度的增加提高了 Ta及TaN 之移除率。而且,pH值對Ta及TaN移除率有影塑。 實例3 ^表3比較在PH5下具有〇.5重量%之相同胍鹽酸鹽濃度 里’但不同H2〇2氧化劑濃度之泥漿的移除率。 表3
Ta及TaN之移除率係隨ho2濃度而變 這些移除率的
(修正本)93060L 24 1354016 t S'力在約6重量。而且,CU移除率隨較高跳 艰度而i日加。這些幫助選擇所需Cu移除率以獲得 上述實例證實Ta與TaN之移除率係隨胍 ^辰度、㈣2濃度及pH值而變。因此,在任何較佳邱值 :胍鹽酸鹽及祕之微調濃度可提供所f Ta或—移除 實例4 而且,較佳pH值可最適化其他材料,如介電材料之移 除率。例如,經矽酸四乙酯(TE〇S)前驅物沉積之二氧化矽 也具有PH依賴性移除率。再者,其他化學添加劑,如 機銨鹽可選·_丽移除率以達到所f & 擇性。
在此貫例中,一系列具有不同四丁基硝,酸鐘⑽飾農 度、胍鹽酸鹽及H2〇2之濃度係固定在〇5重量%且邱固定 在^之泥漿說明移除率增加含有機錢鹽的能力。在 此貫例中,Strasbaugh 6-EC拋光器下壓力是i psi(69 kPa) ’研磨粒子濃度是2. 75重量%。
(修正本)93060L 25 1354016 當TBAN的濃度由0%增加至1%使TE0S的移除率由119 埃/分鐘增加至373埃/分鐘時,Ta移除率本質上固定。不 像TEOS,TBAN濃度本質上對購自Novellus公司(San Jose, CA)之CORAL摻碳氧化物(CD0)無影響。這容許以最低CDO 移除控制TE0S硬罩幕之移除。
26 (修正本)93060L
Claims (1)
- I 第93127065號專利申諳宏 卜、申請專舳®: .-種適用於自半導體基板移除障蔽材料的溶液,1包含 〇.〇1至25重量%氧化劑、〇幻5重量%有色金屬之抑制 劑、0至15重量%研磨劑、〇至2〇重量%有色金屬之錯 合劑、0.01至12重量%障蔽物移除劑及剩餘水,其令曰 該障蔽物移除劑係選自亞胺衍生物化合物、肼衍生物化 合物及其混合物組成之群,其中該亞胺衍生物化合物係 選自乙脎、乙脒鹽、乙脒衍生物、精胺酸、精胺酸鹽、 精胺酸衍生物、甲脒、甲脎鹽、尹肺衍生物、胍衍生物、 胍鹽及其混合物組成之群,該肼衍生物化合物係選自卡 肼、咪唑、乙醯肼、氨基脲鹽酸鹽、丨,2_二甲醯基肼、 甲基肼基-碳酸酯、乙二醯肼、二丙酮腙及甲醯肼和其 混合物組成之群;該溶液之pH係從2至12 ;而且如以 微孔聚胺基曱酸酯拋光墊利用至少一垂直於晶圓測量 係等於或小於13. 8 kPa之壓力測量時’該溶液之氮化 纽對CDO之選擇率至少為2比1。 如申請專利範圍第1項之溶液,其中該障蔽杨移除劑是 0. 1至10重量%亞胺衍生物化合物。 如申請專利範圍第1項之溶液,其中該氧化劑係選自過 氧化氫、單過硫酸鹽、碘酸鹽、過鄰苯二曱酸鎂、過乙 酸、過硫酸鹽、溴酸鹽、過溴酸鹽、過氯酸鹽、過埃酸 鹽、硝酸鐵、鐵鹽、鈽鹽、Mn(III)鹽、Mn(IV)鹽及Mn(VI) 鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽及其混 合物組成之群。 27 93606L修正版 ^54016 ' 第93127065號專利申請案 ' I 1〇〇年9月23日修正替換頁 4. 如申請專利範圍第1項之溶液,其中該亞胺衍生物化合 物係選自氫氯化乙胨、胺基_胍鹽酸鹽、精胺酸、甲脒、 甲脉亞磺酸、曱脒乙酸鹽、h 3一二苯基胍、甲基_3_ 硝基胍、胍鹽酸鹽、四曱基胍、2, 2-偶氮基雙(二甲基一 • 丙脒)二_HC1、胍硫酸鹽、胍乙酸、胍碳酸鹽、胍硝酸. 鹽及其混合物組成之群。 5. 種適用於自半導體基板移除障蔽材料的溶液,其包含 〇. 1至15重量%氧化劑、0至1〇重量%有色金屬之抑制 劑、0至10重量%有色金屬之錯合劑、〇1至1〇重量%籲 障蔽物移除劑、〇.〇1至10重量%下式所形成之含有機 銨鹽 R»—N1"—R2 I r3 (Ri、Rz、R3及R4是基團,Rl的碳鏈長度係少於15個碳 原子)及剩餘水,而且該溶液的PH係小於7,其中該障 蔽物移除劑係選自乙脒、乙脒鹽、乙脒衍生物、精胺酸、 精胺酸鹽、精胺酸衍生物、曱脉、甲脒鹽、甲肺衍生物、 脈衍生物、胍鹽及其混合物組成之群。 6. t申請專利範圍第5項之溶液,其中該_蔽物移除劑係 k自虱氣化乙脎、胺基-胍鹽酸鹽、精胺酸、甲牌、甲 脉亞~酸、甲脉乙酸鹽、丨,3 —二苯基胍、1-曱基-3-峭 基胍、胍鹽酸鹽、四曱基胍、2,2_偶氮基雙(二甲基— 93606L修正版 28 1354016 . 第93127065號專利申請案 100年9月23日修正替換頁 - 丙脒)二-HC1、胍硫酸鹽、胍乙酸、胍碳酸鹽、胍硝酸 鹽及其混合物組成之群 7·如申請專利範圍第5項之溶液,其中是包含2至5 個碳原子之經取代或未經取代芳基、烷基、芳烷基或烷 芳基。 8.如申請專利範圍第5項之溶液,其中該銨鹽係由選自包 含下列各物之群的化合物所形成:四甲基録、四乙基 銨、四丁基銨、苯曱基三丁基銨、笨甲基三曱基銨、笨 曱基二乙基銨、二烯丙基二曱基銨、甲基丙烯酸二乙基_ 胺基乙酯、甲基丙烯酸二曱基胺基乙酯、曱基丙烯醯氧 基乙基三曱基銨、3-(甲基丙烯醯基醯胺基)丙基三甲基 録、三乙四胺、四甲基胍、己基胺及其混合物。 9 · 一種自半導體晶圓移除障蔽材料之方法,其包含下列步 驟: 令晶圓基板與拋光溶液接觸,該晶圓基板包括障蔽 材料、TE0S介電層及第二介電層,該第二介電層具有 低於該TE0S介電層之介電常數,而該拋光溶液包括氧鬱 化劑务障蔽物移除劑,其中該障蔽物移除劑係選自包含 亞胺衍生物化合物、肼衍生物化合物及其混合物之群, 其中該亞胺衍生物化合物係選自乙脒、乙脒鹽、乙肺衍· 生物、精胺酸、精胺酸鹽、精胺酸衍生物、甲脎、甲脒 鹽、甲脒衍生物、胍衍生物、胍鹽及其混合物組成之群, §亥拼衍生物化合物係選自卡肼、咪唑、乙醯肼、氨基腺 鹽酸鹽、1,2-二甲醯基肼、甲基肼基—碳酸酯、乙二醯 29 93606L修正版 1354016 - 第93127065號專利申請案 100年9月23曰修正替換頁 • I 丨 丨_! 肼、二丙酮腙及曱醯肼和其混合物組成之群; 以拋光墊拋光該晶圓基板以自該晶圓基板移除該 障蔽材料;以及 以該拋光墊拋光該晶圓基板以自該晶圓基板移除 至少一部分該TE0S介電層並留下該第二介電層。 ^ 10.如申請專利範圍第9項之方法,其中該第二介電層是摻 、 碳氧化物層,該TE0S介電層覆蓋該摻碳氧化物,而該 拋光溶液包括在該拋光期間加速TE0S移除率之含有機 銨鹽。 30 93606L修正版
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