WO2018199453A1 - Slurry composition for chemical mechanical polishing - Google Patents
Slurry composition for chemical mechanical polishing Download PDFInfo
- Publication number
- WO2018199453A1 WO2018199453A1 PCT/KR2018/002206 KR2018002206W WO2018199453A1 WO 2018199453 A1 WO2018199453 A1 WO 2018199453A1 KR 2018002206 W KR2018002206 W KR 2018002206W WO 2018199453 A1 WO2018199453 A1 WO 2018199453A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- slurry composition
- polishing
- weight
- film
- chemical
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 172
- 239000000203 mixture Substances 0.000 title claims abstract description 138
- 239000002002 slurry Substances 0.000 title claims abstract description 127
- 239000000126 substance Substances 0.000 title claims abstract description 12
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 48
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000004065 semiconductor Substances 0.000 claims abstract description 39
- -1 tertiary amine compound Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 31
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 10
- DORPKYRPJIIARM-UHFFFAOYSA-N Decaffeoylacteoside Natural products OC1C(O)C(O)C(C)OC1OC1C(O)C(OCCC=2C=C(O)C(O)=CC=2)OC(CO)C1O DORPKYRPJIIARM-UHFFFAOYSA-N 0.000 claims description 9
- DORPKYRPJIIARM-GYAWPQPFSA-N Verbasoside Chemical compound O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](O)[C@H](OCCC=2C=C(O)C(O)=CC=2)O[C@H](CO)[C@H]1O DORPKYRPJIIARM-GYAWPQPFSA-N 0.000 claims description 9
- 150000002484 inorganic compounds Chemical class 0.000 claims description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 239000001488 sodium phosphate Substances 0.000 claims description 9
- 150000001923 cyclic compounds Chemical class 0.000 claims description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- YDHWWBZFRZWVHO-UHFFFAOYSA-H [oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O YDHWWBZFRZWVHO-UHFFFAOYSA-H 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 150000004712 monophosphates Chemical class 0.000 claims description 4
- 239000001226 triphosphate Substances 0.000 claims description 4
- 235000011178 triphosphate Nutrition 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- NBSCHQHZLSJFNQ-GASJEMHNSA-N D-Glucose 6-phosphate Chemical compound OC1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H](O)[C@H]1O NBSCHQHZLSJFNQ-GASJEMHNSA-N 0.000 claims description 3
- VFRROHXSMXFLSN-UHFFFAOYSA-N Glc6P Natural products OP(=O)(O)OCC(O)C(O)C(O)C(O)C=O VFRROHXSMXFLSN-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- HXXFSFRBOHSIMQ-VFUOTHLCSA-N alpha-D-glucose 1-phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(O)=O)[C@H](O)[C@@H](O)[C@@H]1O HXXFSFRBOHSIMQ-VFUOTHLCSA-N 0.000 claims description 3
- 229950010772 glucose-1-phosphate Drugs 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 3
- UGQMRVRMYYASKQ-KQYNXXCUSA-N Inosine Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(O)=C2N=C1 UGQMRVRMYYASKQ-KQYNXXCUSA-N 0.000 claims 2
- 229930010555 Inosine Natural products 0.000 claims 2
- 229960003786 inosine Drugs 0.000 claims 2
- 239000011229 interlayer Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 10
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 10
- 229960000367 inositol Drugs 0.000 description 10
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 235000021317 phosphate Nutrition 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 description 3
- 235000019800 disodium phosphate Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- OOHOVWLWYJUPGP-UHFFFAOYSA-N 1-methylideneguanidine Chemical compound NC(=N)N=C OOHOVWLWYJUPGP-UHFFFAOYSA-N 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 101100396994 Drosophila melanogaster Inos gene Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- INAPMGSXUVUWAF-GCVPSNMTSA-N [(2r,3s,5r,6r)-2,3,4,5,6-pentahydroxycyclohexyl] dihydrogen phosphate Chemical compound OC1[C@H](O)[C@@H](O)C(OP(O)(O)=O)[C@H](O)[C@@H]1O INAPMGSXUVUWAF-GCVPSNMTSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 125000005340 bisphosphate group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229940098465 tincture Drugs 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a slurry composition for chemical-mechanical polishing, and more particularly, to a slurry composition for chemical-mechanical polishing, including a phosphate compound as a selectivity control agent, which enables to control the selection ratio of a polishing object and a polishing method using the same. .
- Semiconductor devices are highly integrated; As densification and multi-layer structure are made, finer pattern formation techniques are used, and thus, the surface structure of the semiconductor device is complicated, and the level of the interlayer films is further increased.
- a step occurs in the interlayer films, process defects may occur in a semiconductor device manufacturing process, so it is important to minimize the step. Therefore, in order to reduce the step difference of the interlayer films, a planarization technique of a semiconductor substrate is used.
- a reactive subsequent etching method or a chemical mechanical polishing method is used to remove a metal such as tungsten in a semiconductor process. Since the semi-ungionic ion etching method has a problem that residues are generated on the semiconductor substrate after the process, a chemical mechanical polishing method is more frequently used.
- a semiconductor substrate is polished using a water-soluble slurry composition containing an abrasive or the like.
- the slurry composition comprises an insulating film, a metal film, an insulating film and a metal film
- polishing rate ratio for each film to be polished is different.
- An object of the present invention is to provide a slurry composition for chemical-mechanical polishing, by including a specific polishing selectivity adjusting agent, it is possible to easily control the polishing rate of the insulating film of the semiconductor substrate than the conventional polishing selectivity.
- the present invention provides a method for polishing a semiconductor substrate using the slurry composition capable of polishing the insulating film and the metal film of the semiconductor substrate alone or simultaneously.
- a compound having at least one phosphate group selected from the group consisting of a) a cyclic compound having a phosphate group, an inorganic compound having a phosphate group and a metal compound having a phosphate group, b) a tertiary amine compound, and c) a mixture thereof
- a polishing selectivity regulator selected from the group.
- the polishing selectivity adjusting agent may be a cyclic compound having a phosphate group.
- the polishing selectivity adjusting agent may be a silicon nitride film polishing selector used to control the polishing rate of the silicon nitride film.
- C) may include the compound of a ) and b) the tertiary amine compound in an increase ratio of 1: 0.25 to 1: 5.
- the slurry composition according to an embodiment of the present invention may further include a catalyst.
- Slurry composition according to an embodiment of the present invention is one or more pH adjusters It may further include. .
- the slurry composition according to one embodiment of the present invention may further include one or more biosides.
- the slurry composition according to one embodiment of the present invention may further include one or more reaction agents.
- the slurry composition according to an embodiment of the present invention may further include water, alcohol or a mixture thereof.
- the slurry composition according to one embodiment of the present invention may further include one or more oxidizing agents.
- the ring compound having the phosphate group is monophosphate of inosi, biphosphate of inosi , triphosphate of inosi .
- Inosi may be one or more selected from the group consisting of pentakisphosphate inosi, nucleophosphate glucose 1-phosphate and glucose 6-phosphate.
- the tertiary amine compound may be at least one selected from the group consisting of trimethylamine, triethylamine, tributylamine and tripropylamine.
- the abrasive may comprise from 01 to 10% by weight based on the total weight of the total slurry composition.
- the catalyst may comprise 0.00001 to 1 weight percent based on the total weight of the total slurry composition.
- the polishing selectivity adjusting agent is whole. And from 0.0001 to 10% by weight based on the total weight of the slurry composition.
- the slurry composition for chemical-mechanical polishing is 0.01 to 10% by weight of the abrasive, 0.0001 to 10% by weight of the polishing selectivity adjusting agent based on the total weight of the total slurry composition. 0.00001 to 1 wt% of catalyst, 0.0005 to 5 wt% of pH adjuster, Bioside 0.00 . 01 to 0.01 weight% and the balance of water.
- the slurry composition may further include 0.0001 to 1% by weight of the reaction regulator based on the total weight of the entire slurry composition.
- the slurry composition is based on the total weight of the total slurry composition It may further comprise 0.005 to 10% by weight.
- the semiconductor substrate polishing method according to another embodiment of the present invention using the above-described chemical-mechanical polishing slurry composition.
- the insulating film may include a silicon nitride film, a silicon oxide film, or a silicon nitride film and a silicon oxide film.
- the metal film may be a tungsten film.
- a silicon nitride film or a silicon oxide film When the insulating film is a silicon nitride film or a silicon oxide film in the step b), a silicon nitride film or a silicon oxide film; And a polishing selectivity of the metal film; may be 1: 3 or more.
- the insulating film in the step b) comprises a silicon nitride film and a silicon oxide film.
- the polishing selectivity of the silicon nitride film: silicon oxide film: metal film may be 1: 0.5 to 2: 3 to 10.
- the slurry composition of the present invention is a metal containing an insulating film or tincture containing a silicon nitride film, a silicon oxide film, etc. of a semiconductor substrate by using a compound having a phosphate group or optionally further comprising a tertiary amine compound as a polishing selectivity control agent
- the film can be polished alone or simultaneously, and both can exhibit excellent effects. That is, using the slurry composition of the present invention, the compound having a phosphate group may selectively increase the polishing rate of the insulating film, in particular, the polishing rate of the silicon nitride film.
- the tertiary amine compound which can be used as the polishing selectivity adjusting agent in the present invention can further increase the polishing rate of the insulating film, in particular, the silicon oxide film polishing rate.
- the polishing target film consisting of three kinds such as silicon nitride film: silicon oxide film and tungsten can be simultaneously polished. These selection ratios can also be easily adjusted.
- CMP composition chemical-mechanical polishing slurry composition
- the present invention is to propose a slurry composition that can control the selectivity ratio and the method of other semiconductor substrate using the same.
- the insulating film or the metal film can be polished alone or at the same time.
- the insulating film is one kind of insulating film made of a silicon nitride film or a silicon oxide film formed on a semiconductor substrate, and made of a silicon nitride film and a silicon oxide film.
- the metal film may include at least one metal film, more specifically, a tungsten film formed on a semiconductor substrate.
- the present invention uses the compounds of a) to c) described above as polishing selectivity regulators in slurry compositions.
- the compound of a) uses a compound having a phosphate group, and specifically, at least one selected from three components is used as described above. More specifically, the most effective polishing selectivity modifier relative to the same content may be a ring compound having a phosphate group, which may include an aliphatic ring compound.
- the polishing selectivity adjusting agent of a) increases the silicon nitride film polishing rate more effectively among the insulating films.
- the polishing selectivity adjusting agent may be a silicon nitride film polishing selector used to control the polishing rate of the silicon nitride film.
- the selectivity control agent may further improve the polishing rate of the silicon nitride film according to the used content.
- the cyclic compound having a phosphate group may have 4 to 7 carbon atoms.
- the ring compound having a phosphate group used as the polishing selectivity adjusting agent may be an aliphatic ring compound. Specifically, inosi monophosphate, inosi biphosphate, inosi triphosphate, inosi tetraphosphate, inosi pentakiphosphate, inosi nucleophosphate, glucose 1-phosphate, and glucose 6 -At least one selected from the group consisting of phosphates:
- Inosi monophosphate inosi tol monophosphate
- Inosi bisphosphate inos i tol bi sphosphate, IP 2
- Inosi triphosphate inositol tr isphosphate, IP 3
- IP 4 Inositol tetraphosphate
- Inositol pent ak isphosphate.IP 5 Inosi hexaphosphate (inositol hexaphosphate, IP 6 ) (phytic acid or phytate)
- MAP monoammonium phosphate
- DSP diammonium phosphate
- TSP triammonium phosphate
- the metal compound having a phosphate group was monosodium phosphate (MSP), disodium phosphate (DSP), trisodium phosphate (TSP), and the like. Can be used.
- the polishing selectivity adjusting agent may use the tertiary amine compound of b).
- the polishing selectivity adjusting agent of the present invention may be selected from a compound compound having a) a phosphate group. It may be a mixture of one or more compounds and b) tertiary amines.
- the tertiary amine compound As a polishing selectivity control agent, it is possible to improve the removal rate of the silicon oxide film.
- the insulating film is made of a silicon nitride film and a silicon oxide film, it can exhibit an advantage of controlling the polishing rate of the silicon nitride film and the silicon oxide film at the same time.
- the tertiary amine compound includes trimethylamine, triethylamine, tributylamine, tripropylamine, and the like, and any one or more selected from these may be used.
- the primary amine compound or the secondary amine compound is used instead of the tertiary amine compound, it is difficult to increase the polishing rate of the metal film (eg, silicon oxide film) of the semiconductor substrate.
- the metal film eg, silicon oxide film
- the dispersibility of silica used as an abrasive may be lowered, thereby causing a problem of precipitation.
- c) may include a) a compound having a phosphate group and b) a tertiary amine compound in a weight ratio of 1: 0.25 to 1: 5.
- weight ratio of the compound having a phosphate group of a) and the tertiary amine compound of b) is 1: 0.25
- the selectivity of the polishing rate of the silicon oxide film is lower than that of the silicon nitride film.
- the ratio is out of 1: 5
- the selectivity of the smoke rate of the silicon oxide film to the silicon nitride film is excessively large, which may cause erosion.
- the ring compound having a phosphate group of a) and the primary tertiary amine compound of b) may be included in a weight ratio of 1: 0.7 to 1: 3.
- the selectivity ratio of the silicon oxide film to the silicon nitride film is 1: 0.5 to 2 I can regulate it.
- the above range is not satisfied, it is difficult to control the polishing selectivity of the silicon nitride film and the silicon oxide film.
- any one compound selected from inorganic compounds having a phosphate group and metal compounds having a phosphate group; And the tertiary amine compound may be included in a layer ratio of 1: 0.25 to 1: 5.
- the content of the polishing selectivity modifier may be 0.0001 to 10% by weight, specifically 0.0001 to 5% by weight, more specifically 0.0001 to 1% by weight and most specifically 0.0001 to 0.5% by weight, based on the total weight of the slurry composition. .
- the polishing selectivity adjusting agent when using the tertiary amine compound, it may be preferable to use from 0.0001 to 5% by weight based on the total weight of the total composition, and more preferably from 0.0001 to 0.5% by weight. If the content of the polishing selectivity adjusting agent is less than 0.0001% by weight, there is a problem that the polishing rate control effect is insufficient, and when the content of the polishing selector is outside 10% by weight, the polishing rate no longer increases.
- the slurry composition according to an embodiment of the present invention is a slurry composition further comprising an abrasive together with the above-described polishing selectivity adjusting agent.
- colloidal silica or fumed silica may be used among conventional abrasives that perform mechanical polishing.
- the amount of the abrasive may be from 0.01 to 10% by weight, specifically 1 to 8% by weight, based on the total weight of the total composition. If the content of the abrasive is less than 0.01% by weight, there is a problem that the polishing rate is lowered, and when the content is greater than 10% by weight, excessive scratches are generated.
- the slurry composition according to an embodiment of the present invention may further include a catalyst.
- the catalyst may improve the polishing rate of a metal film such as tungsten, and specifically, at least one selected from the group consisting of iron salts such as iron nitrate and iron chloride and nano ferrosilicon (FeSi) may be used.
- the content of the catalyst may be 0.00001 to 1% by weight, specifically 0.0001 to 0.5% by weight, based on the total weight of the slurry composition. If the content of the catalyst is less than 0.00001 weight 3 ⁇ 4>, there is a problem that the polishing rate of the metal film is lowered, and if the content of the catalyst exceeds 1% by weight, there is a problem that the polishing rate is uneven because of excessive chemical reactivity.
- the slurry composition according to an embodiment of the present invention may further include one or more pH adjusters.
- the pH, range of the slurry composition may be 1 to 4, specifically 1.5 to 3.5. Therefore, the present invention can adjust the pH of the slurry composition using an acidic or basic pH adjusting agent in reaction.
- the pH range of the slurry composition is lower than 1, the acidity is too low, so that there is a problem in handling. If the pH range is higher than 4, the polishing rate of some metal films may decrease.
- the pH adjusting agent (pH adj ust i ng agent) is used to adjust the pH of the slurry composition.
- pH adj ust i ng agent is used to adjust the pH of the slurry composition.
- any one selected from the group consisting of an acidic regulator and a basic regulator it can be adjusted to the above pH range having good handleability and excellent polishing rate.
- the acidic regulators include nitric acid, hydrochloric acid, sulfuric acid, and the like
- basic regulators include potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and more specifically tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and the like.
- kalm and natrum are metal impurity (meta l mpur i ty) management items, which can cause wafer contamination and defects, so the amount of use is limited.
- the content of the i) H regulator is based on the total weight of the slurry composition
- the slurry composition according to an embodiment of the present invention may further include at least one biocide (Bioc ide) ⁇
- the bioside is used to prevent microbial contamination, and for example, polynuclear methylene guanidine (PHMG) or isothiazolinone-based compound may be used.
- PHMG polynuclear methylene guanidine
- isothiazolinone-based compound examples include methyl isothiazolinone (MIT), chloromethyl isothiazolinone (CMIT), and 1,2-benzoisothiazole-3 (-one ((1 , 2- benzi sothi azol-3 (2 ⁇ )-one: Benzi sothiazol inone (BIT) can be used one or more selected from the group consisting of.
- the content of the bioside may be 0.0001 to 0.01 wt%, specifically 0.001 to 0.05 wt%, based on the total weight of the slurry composition. If the content of the bioside is less than 0.0001% by weight, microorganisms occur due to insufficient bactericidal action. There is a problem and there is a problem that the slurry performance may change if it exceeds 0.01% by weight.
- the slurry composition according to an embodiment of the present invention may further include at least one reaction agent.
- the reaction regulator malonic acid, phosphoric acid, potassium iodide, and the like may be used.
- the content of the reaction agent may be 0001 to 1% by weight, specifically 0.001 to 0.5% by weight, based on the total weight of the slurry composition. If the content of the reaction regulator is less than 0.0001% by weight there is a problem that the non-uniformity of the substrate is increased, if the content of more than 1% by weight has a problem that the polishing rate is lowered.
- the slurry composition according to an embodiment of the present invention may further include water, alcohol (R0H) or a combination thereof as the remaining components to satisfy 100% by weight of the composition, except for the above-described components.
- the slurry composition of the present invention may be a water-soluble composition. remind The alcohol may be a straight or branched alcohol having 2 to 10 carbon atoms.
- the slurry composition may further include an organic solvent as necessary. In this case, it can be used as a dissolution aid for components that are difficult to dissolve in water, or can be used to improve the wettability of the slurry composition on the film to be polished.
- the slurry composition according to an embodiment of the present invention may further include an oxidizing agent.
- the oxidant may further include when the polishing target includes tungsten.
- the oxidizing agent may be stored in a state contained in the slurry composition, or may be stored in the form of an additive liquid by dividing with the remaining slurry composition including the abrasive to prevent the stability of the slurry composition from deteriorating.
- the oxidizing agent may be blended with the remaining slurry composition prior to application to the polishing target film or applied to the polishing target film independently of the slurry composition during polishing.
- Specific examples that can be used as the oxidizing agent may be selected from, but are not limited to, hydrogen peroxide, potassium iodide, potassium permanganate, ammonia, amine compounds, ammonium compounds, nitrate compounds, and combinations thereof.
- the content of the oxidant may be 0.005 to 10% by weight, specifically 0.2 to 5% by weight, based on the total weight of the slurry composition.
- the chemical-mechanical polishing slurry composition may include 0.01 to 10% by weight of abrasive, 0.0001 to 10% by weight of polishing selectivity regulator, 0.00001 to 1% by weight of catalyst, H based on the total weight of the total slurry composition.
- a slurry composition for chemical-mechanical polishing comprising 0.0005-5% by weight of modifier, 0.0001-0. 1% by weight of bioside, and the balance of water can be provided.
- the slurry composition is a total increase in the total slurry composition On the basis of the reaction regulator may further comprise 0.0001 to 1% by weight.
- the slurry composition is based on the total amount of the total slurry composition of the oxidizing agent
- polishing selectivity control agent 0.0001 to 10% by weight
- catalyst 0.00001 to 1% by weight
- pH regulator 0.0005 to 5% by weight
- bioside 0.0001 to 0.01 weight reaction regulator 0.0001 by 1 weight
- a slurry composition for chemical-mechanical polishing comprising%, and the balance of water can be provided. Polishing method of semiconductor substrate
- the insulating film may include a silicon nitride film, a silicon oxide film, or a silicon nitride film and a silicon oxide film.
- the metal film may include a tungsten film.
- the catalyst and the oxidant may not be included in the polishing slurry composition.
- the chemical-mechanical polishing slurry composition of the present invention contains the above-described specific polishing selectivity regulator in a certain amount, and thus, the polishing rate is higher than conventional.
- the insulating film or metal film of one kind of semiconductor substrate may be polished to increase, or the insulating film and metal film of one or more types may be polished simultaneously.
- the slurry composition of the present invention is used to polish a selected one of a silicon nitride film, a silicon oxide film, or a tungsten film of a semiconductor substrate, or simultaneously polish an insulating film and a metal film composed of two or three selected ones, Can improve. At this time.
- the slurry composition is used to polish a metal film including a tungsten film, the above-mentioned oxidizing agent is used. May be added to the slurry composition immediately before
- the slurry composition for tungsten polishing may be manufactured and stored as a product with 100% of a composition containing no hydrogen peroxide, and additionally mixed with hydrogen peroxide immediately before polishing (CMP).
- CMP hydrogen peroxide immediately before polishing
- the polishing target is not limited, but each of an insulating film such as a silicon oxide film (Si0 2 ), a silicon nitride film (Si 3 N 4 ) or a metal film such as a tungsten (W) film forming a semiconductor substrate, Consisting of these
- Two or three kinds of films can be polished at the same time.
- the polishing selectivity is 1: 3 or more, or 1: 3 to
- the polishing selectivity of the silicon nitride film: silicon oxide film: metal film may be 1: 0.5 to 2: 3 to 10.
- polishing conditions and the polishing rate measuring method of the metal film of the semiconductor substrate for Examples and Comparative Examples are as follows.
- polishing equipment Mirra 3400 (Applied Materials)
- Polishing condition Proceed by the method of Table 1.
- Polishing Pad I C-1000 (Rohm & Haas)
- Thickness (Polishing Speed) Measuring Equipment (Thickness Unit: Angstrom, Symbol: A) Tungsten Film: CMT-2000 (4-point probe, Changmin Tech.)
- Polishing speed thickness before CMP-thickness after CMP
- Abrasives 200 nm humed silica
- catalysts iron nitrate, ferrosilicon
- polishing selectivity regulators components in Table 2
- biosides Metals in Table 2
- the pH of the slurry composition was adjusted to 2 using nitric acid and TMAH as pH adjusting agents. Then, before polishing the semiconductor film, 3% by weight of hydrogen peroxide at a concentration of 31% was further added to the pH-adjusted composition to prepare the slurry compositions of Examples 1-11.
- the content and composition of the abrasive and the polishing selectivity adjusting agent were as shown in Table 2 below.
- the structure which does not contain the polishing selectivity regulator was made into the comparative example 1.
- the slurry composition includes a compound having a phosphate group as the polishing selectivity regulator as in Examples 1 to 11, the silicon nitride film polishing rate was increased while the silicon nitride film polishing rate was increased as its content was increased. It did not affect speed.
- Examples 1 to 6 using the cyclic compound had the most excellent effect of improving the silicon nitride film polishing rate compared to the same content.
- Examples 7 to 11 using an inorganic compound having a phosphate group or a metal compound having a phosphate group similar improvement effects were exhibited at the same content.
- an inorganic compound is more preferable than a metal compound.
- Comparative Example 1 does not include the phosphate-containing compound of the present application showed that the polishing rate of the silicon nitride film is lower than the Example results. And, Comparative Examples 2 to 3 can be seen that the result is poor beyond the content range of the polishing selectivity control agent of the present invention.
- bioside Metal i sothi azo l inone
- distilled water distilled water
- the content of biosides in the slurry composition is 0.01% by weight.
- Abrasives 70 ⁇ colloidal silica
- catalysts iron nitrate, ferrosilicone
- polishing selectivity regulators K ingredient of Table 6
- biosides Metal i sothi azo l inone
- distilled water was mechanical stirrers (Mechani cal st i rrer) and stirred.
- the content of biosides in the slurry composition is 0.01% by weight.
- the pH of the slurry composition was adjusted to 3 using nitric acid and TMAH as the P H regulator. Then, by producing a 31% prior to grinding the semiconductor film is a common combined Comparative Examples 7 to 8 and Examples 12 to 18.
- the slurry composition of the "3% by weight aqueous hydrogen peroxide of concentration in addition to the above pH adjustment composition, the above-described The polishing experiment was carried out by the method. In addition, the slurry composition which did not use the grinding
- Example 12 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.015
- Example 16 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.3
- Example 18 Silica 2 phosphate ferrosilicon 0.004 3 triethylamine 0.18
- Table 7 shows the results of polishing rate and selectivity.
- a) at least one compound selected from the group consisting of a) a cyclic compound having a phosphate group, an inorganic compound having a phosphate group, and a metal compound having a phosphate group and b) a tertiary amine compound as a polishing selectivity adjusting agent is 1: 0.25.
- a weight ratio of 1: 1 it can be seen that exhibits an excellent effect.
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Abstract
The present invention relates to a slurry composition for chemical mechanical polishing. More particularly, the present invention relates to a slurry composition for chemical mechanical polishing which uses a compound having phosphate groups as a polishing selectivity regulator and optionally further uses a tertiary amine compound along with the polishing selectivity regulator, such that it is possible to polish, either alone or in combination, an insulating film such as a silicon nitride film or a metal film such as tungsten in contrast to the prior art, and particularly, to easily control the polishing rate thereof, thereby minimizing an interlayer step of a semiconductor element; and a method for polishing a semiconductor substrate using the same.
Description
【발명의 설명】 [Explanation of invention]
【발명의 명칭】 [Name of invention]
화학-기계적 연마용 슬러리 조성물 Slurry Composition for Chemical-Mechanical Polishing
【기술분야】 Technical Field
관련 출원 (돌)과의 상호 인용 Cross citation with related applications (stones)
본 출원은 2017년 4월 27일자 한국 특허 출원 제 10— 2017-0054609호 및 2018년 2월 21일자 한국 특허 출원 제 10-2018-0020654호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. This application claims the benefit of priority based on Korean Patent Application No. 10—2017-0054609 dated April 27, 2017 and Korean Patent Application No. 10-2018-0020654 dated February 21, 2018. All content disclosed in the literature is included as part of this specification.
본 발명은 화학-기계적 연마용 슬러리 조성물에 관한 것으로, 더욱 상세하게는 인산염 화합물을 선택비 조절제로 포함하여 연마 대상의 선택비 조절이 가능한 화학ᅳ기계적 연마용 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것이다. The present invention relates to a slurry composition for chemical-mechanical polishing, and more particularly, to a slurry composition for chemical-mechanical polishing, including a phosphate compound as a selectivity control agent, which enables to control the selection ratio of a polishing object and a polishing method using the same. .
【발명의 배경이 되는 기술】 [Technique to become background of invention]
반도체소자는 고집적화，. 고밀도화 및 다충 구조화됨에 따라 보다 미세한 패턴 형성 기술이 사용되고 있으며, 그에 따라 반도체 소자의 표면구조가 복잡해지고， 층간 막들의 단차도 더욱 커지고 있다. Semiconductor devices are highly integrated; As densification and multi-layer structure are made, finer pattern formation techniques are used, and thus, the surface structure of the semiconductor device is complicated, and the level of the interlayer films is further increased.
상기 층간 막들에서 단차가 발생되면 반도체 소자 제조 공정에서 공정 불량을 발생시키므로, 그 단차를 최소화하는 것이 중요하다. 따라서， 상기 층간 막들의 단차를 줄이기 위해, 반도체 기판의 평탄화 기술이 사용되고 있다. If a step occurs in the interlayer films, process defects may occur in a semiconductor device manufacturing process, so it is important to minimize the step. Therefore, in order to reduce the step difference of the interlayer films, a planarization technique of a semiconductor substrate is used.
상기 반도체 기판의 평탄화 기술에서 반도체 공정에서 텅스텐 등과 같은 금속을 제거하기 위해 반응성 이은 에칭 방법 또는 화학 기계적 연마 방법 연마 (chemi cal mechanical pol i shing: CMP) 등이 사용된다. 상기 반웅성 이온 에칭 방법은 공정 수행 후 반도체 기판 상에 잔류물이 발생되는 문제가 있으므로， 화학 기계적 연마 방법이 더 자주 사용되고 있다. In the planarization technology of the semiconductor substrate, a reactive subsequent etching method or a chemical mechanical polishing method (CMP) is used to remove a metal such as tungsten in a semiconductor process. Since the semi-ungionic ion etching method has a problem that residues are generated on the semiconductor substrate after the process, a chemical mechanical polishing method is more frequently used.
상기 화학 기계적 연마 방법은 연마제 등을 포함한 수용성 슬러리 조성물을 사용하여， 반도체 기판을 연마하고 있다. In the chemical mechanical polishing method, a semiconductor substrate is polished using a water-soluble slurry composition containing an abrasive or the like.
상기 슬러리 조성물로 절연막， 금속막, 절연막과 금속막올 포함하는
다층막을 연마하는 경우 각 연마 대상막에 대한 연마속도 비율이 다르다는 것이 문제된다 . The slurry composition comprises an insulating film, a metal film, an insulating film and a metal film When polishing a multilayer film, there is a problem that the polishing rate ratio for each film to be polished is different.
【발명의 내용】 [Content of invention]
【해결하고자 하는 과제】 Problem to be solved
본 발명의 목적은 특정 연마 선택비 조절제를 포함함으로써, 기존 보다 반도체 기판의 절연막의 연마 속도를 쉽게 조절할 수 있어 연마 선택비 조절이 가능한 화학-기계적 연마용 슬러리 조성물을 제공하는 것이다. An object of the present invention is to provide a slurry composition for chemical-mechanical polishing, by including a specific polishing selectivity adjusting agent, it is possible to easily control the polishing rate of the insulating film of the semiconductor substrate than the conventional polishing selectivity.
또한, 본 발명에서는 상기 반도체 기판의 절연막과 금속막을 단독으로 연마하거나 또는 이들을 동시에 연마할 수 있는 상기 슬러리 조성물을 이용한 반도체 기판의 연마 방법을 제공하는 것이다. In addition, the present invention provides a method for polishing a semiconductor substrate using the slurry composition capable of polishing the insulating film and the metal film of the semiconductor substrate alone or simultaneously.
【과제의 해결 수단】 [Measures of problem]
본 발명의 일 실시예에 따른 화학-기계적 연마용 슬러리 조성물은 Chemical-mechanical polishing slurry composition according to an embodiment of the present invention
1) 연마제 ; 및 1) abrasive; And
2) a) 인산염기를 갖는 고리 화합물， 인산염기를 갖는 무기 화합물 및 인산염기를 갖는 금속 화합물로 이루어진 군에서 선택된 1종 이상의 인산염기를 갖는 화합물, b) 3차 아민 화합물， 및 c) 이들의 흔합물로 이루어진 군에서 선택되는 연마 선택비 조절제；를 포함한다. 2) a compound having at least one phosphate group selected from the group consisting of a) a cyclic compound having a phosphate group, an inorganic compound having a phosphate group and a metal compound having a phosphate group, b) a tertiary amine compound, and c) a mixture thereof And a polishing selectivity regulator selected from the group.
또한, 더 구체적으로 상기 연마 선택비 조절제는 인산염기를 갖는 고리 화합물일 수 있다. Also, more specifically, the polishing selectivity adjusting agent may be a cyclic compound having a phosphate group.
이러한 상기 연마 선택비 조절제는 실리콘질화막의 연마속도를 조절하는데 사용되는 실리콘질화막 연마선택제일 수 있다. The polishing selectivity adjusting agent may be a silicon nitride film polishing selector used to control the polishing rate of the silicon nitride film.
이러한 경우 일 실시예에 따라, 상기 연마 선택비 조절제에서 C )는 a)의 화합물 및 b) 3차 아민 화합물을 1 : 0.25 내지 1 : 5의 증량비율로 포함할 수 있다. In this case, in the polishing selectivity adjusting agent, C) may include the compound of a ) and b) the tertiary amine compound in an increase ratio of 1: 0.25 to 1: 5.
본 발명의 일 실시예에 따른 슬러리 조성물은 촉매를 더 포함할 수 있다. The slurry composition according to an embodiment of the present invention may further include a catalyst.
본 발명의 일 실시예에 따른 슬러리 조성물은 1종 이상의 pH조절제를
더 포함할 수 있다. . Slurry composition according to an embodiment of the present invention is one or more pH adjusters It may further include. .
본 발명의 일 실시예에 따른 슬러리 조성물은 1종 이상의 바이오사이드를 더 포함할 수 있다. The slurry composition according to one embodiment of the present invention may further include one or more biosides.
본 발명의 일 실시예에 따른 슬러리 조성물은 1종 이상의 반웅 조절제를 더 포함할 수 있다. The slurry composition according to one embodiment of the present invention may further include one or more reaction agents.
본 발명의 일 실시예에 따른 슬러리 조성물은 물, 알코올 또는 이들의 흔합물을 더 포함할 수 있다. The slurry composition according to an embodiment of the present invention may further include water, alcohol or a mixture thereof.
본 발명의 일 실시예에 따른 슬러리 조성물은 1종 이상의 산화제를 더 포함할 수 있다. The slurry composition according to one embodiment of the present invention may further include one or more oxidizing agents.
상기 인산염기를 갖는 ᅵ고리 화합물은 이노시를 모노포스페이트， 이노시를 바이포스페이트， 이노시를 트리포스페이트，. 이노시를 테트라포스페이트. 이노시를 펜타키스포스페이트 이노시를 핵사포스페이트 글루코스 1-포스페이트 및 글루코스 6—포스페이트로 이루어진 군에서 선택된 1종 이상일 수 있다. The ring compound having the phosphate group is monophosphate of inosi, biphosphate of inosi , triphosphate of inosi . Inosi tetraphosphate. Inosi may be one or more selected from the group consisting of pentakisphosphate inosi, nucleophosphate glucose 1-phosphate and glucose 6-phosphate.
상기 3차 아민 화합물은 트리메틸아민， 트리에틸아민, 트리부틸아민 및 트리프로필아민으로 이루어진 군에서 선택된 1종 이상일 수 있다. The tertiary amine compound may be at least one selected from the group consisting of trimethylamine, triethylamine, tributylamine and tripropylamine.
본 발명에서, 상기 연마제는 전체 슬러리 조성물의 총 중량을 기준으로 으 01 내지 10 중량 %를 포함할 수 있다. In the present invention, the abrasive may comprise from 01 to 10% by weight based on the total weight of the total slurry composition.
상기 촉매는 전체 슬러리 조성물의 총 중량을 기준으로 0.00001 내지 1 중량 %를 포함할 수 있다. The catalyst may comprise 0.00001 to 1 weight percent based on the total weight of the total slurry composition.
상기 연마 선택비 조절제는 전체. 슬러리 조성물의 총 중량을 기준으로 0.0001 내지 10 증량 %를 포함할 수 있다. The polishing selectivity adjusting agent is whole. And from 0.0001 to 10% by weight based on the total weight of the slurry composition.
또한， 본 발명의 다른 실시예에 따른 화학-기계적 연마용 슬러리 조성물은 전체 슬러리 조성물의 총 중량을 기준으로 연마제 0.01 내지 10 중량 %， 연마 선택비 조절제 0.0001 내지 10 중량 %. 촉매 0.00001 내지 1 중량 % , pH 조절제 0.0005 내지 5 중량 %， 바이오 사이드 0.00.01 내지 0. 1 중량 % 및 잔부의 물올 포함한다. In addition, the slurry composition for chemical-mechanical polishing according to another embodiment of the present invention is 0.01 to 10% by weight of the abrasive, 0.0001 to 10% by weight of the polishing selectivity adjusting agent based on the total weight of the total slurry composition. 0.00001 to 1 wt% of catalyst, 0.0005 to 5 wt% of pH adjuster, Bioside 0.00 . 01 to 0.01 weight% and the balance of water.
그리고, 상기 슬러리 조성물은 전체 슬러리 조성물의 총 중량을 기준으로 반응 조절제 0.0001 내지 1 중량 %를 더 포함할 수 있다. 또한， 상기 슬러리 조성물은 전체 슬러리 조성물의 총 중량을 기준으로 산화제
0.005 내지 10 중량 %를 더 포함할 수 있다. In addition, the slurry composition may further include 0.0001 to 1% by weight of the reaction regulator based on the total weight of the entire slurry composition. In addition, the slurry composition is based on the total weight of the total slurry composition It may further comprise 0.005 to 10% by weight.
한편， 본 발명의 또 다른 실시예에 따른 반도체 기판의 연마 방법은 상술한 화학-기계적 연마용 슬러리 조성물을 사용하여. On the other hand, the semiconductor substrate polishing method according to another embodiment of the present invention using the above-described chemical-mechanical polishing slurry composition.
a) 반도체 기판에 형성된 절연막 또는 금속막을 연마하는 공정; 또는 b) 반도체 기판에 형성된 절연막 및 금속막을 동시에 연마하는 공정; 을 포함한다. a) polishing the insulating film or the metal film formed on the semiconductor substrate; Or b) simultaneously polishing the insulating film and the metal film formed on the semiconductor substrate; It includes.
상기 절연막은 실리콘 질화막, 실리콘 산화막， 또는 실리콘 질화막과 실리콘 산화막을 포함할 수 있다. 상기 금속막은 텅스텐막일 수 있다ᅳ The insulating film may include a silicon nitride film, a silicon oxide film, or a silicon nitride film and a silicon oxide film. The metal film may be a tungsten film.
상기 b) 공정에서 상기 절연막이 실리콘 질화막 또는 실리콘 산화막인 경우， 실리콘 질화막 또는 실리콘 산화막; 및 금속막；의 연마 선택비가 1 : 3이상일 수 있다. When the insulating film is a silicon nitride film or a silicon oxide film in the step b), a silicon nitride film or a silicon oxide film; And a polishing selectivity of the metal film; may be 1: 3 or more.
상기 b) 공정에서 상기 절연막이 실리콘 질화막과 실리콘 산화막을 포함하는 경우. 상기 실리콘 질화막: 실리콘 산화막: 금속막의 연마 선택비가 1 : 0.5 내지 2 : 3 내지 10일 수 있다. When the insulating film in the step b) comprises a silicon nitride film and a silicon oxide film. The polishing selectivity of the silicon nitride film: silicon oxide film: metal film may be 1: 0.5 to 2: 3 to 10.
【발명의 효과】 【Effects of the Invention】
본 발명의 슬러리 조성물은 인산염기를 갖는 화합물 또는 선택적으로 3차 아민 화합물을 더 포함하는 물질을 연마 선택비 조절제로 사용함으로써 반도체 기판의 실리콘 질화막, 실리콘 산화막 등을 포함하는 절연막 또는 팅스텐을 포함하는 금속막을 단독 또는 동시에 연마 가능하고， 모두 우수한 효과를 나타낼 수 있다. 즉, 본 발명의 슬러리 조성물을 이용하면 인산염기를 갖는 화합물이 선택적으로 절연막의 연마속도, 특히 실리콘 질화막의 연마속도를 더 증가시킬 수 있다. 또한， 본 발명에서 연마 선택비 조절제로 사용될 수 있는 3차 아민 화합물은 절연막의 연마속도， 특히 실리콘 산화막의 연마속도를 더 증가시킬 수 있다ᅳ 부가하여， 본 발명은 상기 연마 선택비 조절제의 함량을 적절히 조합함으로써， 실리콘질화막:실리콘산화막：텅스텐과 같은 3종으로 이루어진 연마 대상막에 대해서도 동시에 연마가 가능하므로. 이들의 선택비도 용이하게 조절할 수 있다.
【발명을 실시하기 위한 구체적인 내용】 The slurry composition of the present invention is a metal containing an insulating film or tincture containing a silicon nitride film, a silicon oxide film, etc. of a semiconductor substrate by using a compound having a phosphate group or optionally further comprising a tertiary amine compound as a polishing selectivity control agent The film can be polished alone or simultaneously, and both can exhibit excellent effects. That is, using the slurry composition of the present invention, the compound having a phosphate group may selectively increase the polishing rate of the insulating film, in particular, the polishing rate of the silicon nitride film. In addition, the tertiary amine compound which can be used as the polishing selectivity adjusting agent in the present invention can further increase the polishing rate of the insulating film, in particular, the silicon oxide film polishing rate. By properly combining, the polishing target film consisting of three kinds such as silicon nitride film: silicon oxide film and tungsten can be simultaneously polished. These selection ratios can also be easily adjusted. [Specific contents to carry out invention]
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 예시하고 상세하게 설명하고자 한다. 그러나， 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환， 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention.
단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다ᅳ 본 출원에서; "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자， 단계, 동작, 구성요소. 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지， 하나 또는 그 이상의 다른 특징들이나 숫자， 단계, 동작， 구성요소， 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. Singular expressions include plural expressions unless the context clearly indicates otherwise. Terms such as "comprise" or "have" refer to features, numbers, steps, actions, and components described in the specification. It is to be understood that the parts or combinations thereof are intended to be present and do not preclude the existence or addition of one or more other features or numbers, steps, operations, components, parts or combinations thereof in advance.
이하, 본 발명의 화학-기계적 연마용 슬러리 조성물 (CMP 조성물)과 이를 이용한 반도체 기판의 연마 방법에 대해 상세히 설명하도록 한다. 화학-기계적 연마용 슬러리 조성물 Hereinafter, a chemical-mechanical polishing slurry composition (CMP composition) of the present invention and a method of polishing a semiconductor substrate using the same will be described in detail. Slurry Composition for Chemical-Mechanical Polishing
본 발명의 일 실시예에 따라, 1) 연마제; 및 2) a) 인산염기를 갖는 고리 화합물, 인산염기를 갖는 무기 화합물 및 인산염기를 갖는. 금속 화합물로 이루어진 군에서 선택된 1종 이상의 인산염기를 갖는 화합물， b) 3차 아민 화합물， 및 c ) 이들의 혼합물로 이루어진 군에서 선택되는 연마 선택비 조절제；를 포함하는, 화학-기계적 연마용 슬러리 조성물이 제공될 수 있다. According to one embodiment of the invention, 1) an abrasive; And 2) a) a cyclic compound having a phosphate group, an inorganic compound having a phosphate group and a phosphate group. And a polishing selectivity regulator selected from the group consisting of a compound having at least one phosphate group selected from the group consisting of metal compounds, b) tertiary amine compounds, and c) mixtures thereof. This may be provided.
즉, 본 발명은 선택비 조절이 가능한 슬러리 조성물 및 이를 이용한 반도체기판의 딴마방법을 제시하는 것이다. That is, the present invention is to propose a slurry composition that can control the selectivity ratio and the method of other semiconductor substrate using the same.
또한 본 발명의 슬러리 조성물을 사용하면 절연막 또는 금속막을 단독으로 연마하거나, 이들을 동시에 연마할 수 있다. 이때. 상기 절연막은 반도체 기판에 형성되는 실리콘 질화막 또는 실리콘 산화막으로 이루어진 1종의 절연막과, 실리콘 질화막과 실리콘 산화막으로 이루어진 In addition, when the slurry composition of the present invention is used, the insulating film or the metal film can be polished alone or at the same time. At this time. The insulating film is one kind of insulating film made of a silicon nitride film or a silicon oxide film formed on a semiconductor substrate, and made of a silicon nitride film and a silicon oxide film.
2종의 절연막을 포함할 수 있다. 그리고 상기 금속막은 반도체 가판에 형성되는 1종 이상의 금속막, 더 구체적으로는 텅스텐막을 포함할 수 있다.
이를 위해， 본 발명은 슬러리 조성물에 연마 선택비 조절제로서, 상술한 a) 내지 c)의 화합물을 사용한다. Two kinds of insulating films may be included. The metal film may include at least one metal film, more specifically, a tungsten film formed on a semiconductor substrate. To this end, the present invention uses the compounds of a) to c) described above as polishing selectivity regulators in slurry compositions.
상기 a)의 화합물은 인산염기를 갖는 화합물을 사용하며, 구체적으로는 상술한 바대로 3개의 성분 중 선택된 1종 이상을 사용한다. 더 구체적으로는， 동일 함량 대비 가장 효과적인 연마 선택비 조절제는 인산염기를 갖는 고리 화합물일 수 있고， 이는 지방족 고리 화합물을 포함할 수 있다. The compound of a) uses a compound having a phosphate group, and specifically, at least one selected from three components is used as described above. More specifically, the most effective polishing selectivity modifier relative to the same content may be a ring compound having a phosphate group, which may include an aliphatic ring compound.
이러한 a)의 연마 선택비 조절제는， 절연막 중에서도 실리콘 질화막 연마속도를 더 효과적으로 증가시킨다. 따라서, 상기 연마 선택비 조절제는 실리콘질화막의 연마속도를 조절하는데 사용되는 실리콘질화막 연마선택제일 수 있다. 상기 연마. 선택비 조절제는 사용 함량에 따라 실리콘 질화막의 연마속도를 더욱 향상시킬 수 있다. The polishing selectivity adjusting agent of a) increases the silicon nitride film polishing rate more effectively among the insulating films. Thus, the polishing selectivity adjusting agent may be a silicon nitride film polishing selector used to control the polishing rate of the silicon nitride film. The polishing. The selectivity control agent may further improve the polishing rate of the silicon nitride film according to the used content.
이때. 상기 인산염기를 갖는 고리 화합물은 탄소수 4 내지 7의 탄소수를 가질 수 있다. 구체적인 예를 들면， 상기 연마 선택비 조절제로 사용되는 인산염기를 갖는 고리 화합물은, 지방족 고리 화합물일 수 있으며. 구체적으로 하가 구조의 이노시를 모노포스페이트, 이노시를 바이포스페이트， 이노시를 트리포스페이트， 이노시를 테트라포스페이트, 이노시를 펜타키스포스페이트， 이노시를 핵사포스페이트, 글루코스 1- 포스페이트 및 글루코스 6-포스페이트로 이루어진 군에서 선택된 1종 이상일 수 있다: At this time. The cyclic compound having a phosphate group may have 4 to 7 carbon atoms. For example, the ring compound having a phosphate group used as the polishing selectivity adjusting agent may be an aliphatic ring compound. Specifically, inosi monophosphate, inosi biphosphate, inosi triphosphate, inosi tetraphosphate, inosi pentakiphosphate, inosi nucleophosphate, glucose 1-phosphate, and glucose 6 -At least one selected from the group consisting of phosphates:
이노시를 모노포스페이트 ( inosi tol monophosphate , IP) Inosi monophosphate (inosi tol monophosphate, IP)
이노시를 바이포스페이트 ( inos i tol bi sphosphate , IP2)
Inosi bisphosphate (inos i tol bi sphosphate, IP 2 )
이노시를 트리포스페이트 (inositol tr isphosphate, IP3)
Inosi triphosphate (inositol tr isphosphate, IP 3 )
이노시를 테트라포스페이트 (inositol tetraphosphate, IP4)
Inositol tetraphosphate (IP 4 )
이노시를 펜타키스포스페이트 (inositol pent ak isphosphate. IP5)
이노시를 핵사포스페이트 (inositol hexaphosphate , IP6) (phytic acid or phytate) Inositol pent ak isphosphate.IP 5 Inosi hexaphosphate (inositol hexaphosphate, IP 6 ) (phytic acid or phytate)
hosphate) hosphate)
글루코스 6—포스페이트 (Glucose 6一 phosphate) Glucose 6—Phosphate
상기 인산염기를 갖는 금속 화합물은 제 1 인산 나트륨 (monosodium phosphate, MSP), 제 2 인산 나트륨 (Disodium phosphate, DSP), 제 3 인산 나트륨 (Trisodium phosphate. TSP) 등이 았으며， 이들은 1종 이상 선택하여
사용할 수 있다. 한편, 본 발명의 다른 실시예에 따라, 상기 연마 선택비 조절제는 b)의 3차 아민 화합물을 사용할 수 있다ᅳ 또한, 본 발명의 연마 선택비 조절제는 상술한 a) 인산염기를 갖는 화합물 증에서 선택된 1종 이상의 화합물과 b) 3차 아민의 혼합물이 될 수 있다. The metal compound having a phosphate group was monosodium phosphate (MSP), disodium phosphate (DSP), trisodium phosphate (TSP), and the like. Can be used. Meanwhile, according to another embodiment of the present invention, the polishing selectivity adjusting agent may use the tertiary amine compound of b). In addition, the polishing selectivity adjusting agent of the present invention may be selected from a compound compound having a) a phosphate group. It may be a mixture of one or more compounds and b) tertiary amines.
연마 선택비 조절제로서 3차 아민 화합물을 사용시, 실리콘 산화막의 연마속도를' 향상시킬 수 있다. 절연막이 실리콘 질화막과 실리콘 산화막으로 이루어진 경우에는 실리콘 질화막 및 실리콘 산화막의 연마속도를 동시에 조절할 수 있는 이점을 나타낼 수 있다. When using the tertiary amine compound as a polishing selectivity control agent, it is possible to improve the removal rate of the silicon oxide film. When the insulating film is made of a silicon nitride film and a silicon oxide film, it can exhibit an advantage of controlling the polishing rate of the silicon nitride film and the silicon oxide film at the same time.
상기 3차 아민 화합물은 트리메틸아민， 트리에틸아민， 트리부틸아민， 트리프로필아민 등이 있고， 이들 중에서 선택된 어느 하나 이상을 사용할 수 있다. The tertiary amine compound includes trimethylamine, triethylamine, tributylamine, tripropylamine, and the like, and any one or more selected from these may be used.
여기서 상기 3차 아민 화합물 대신, 1차 아민 화합물 또는 2차 아민 화합물을 사용하게 되면 반도체 기판의 금속막 (예를 들면， 실리콘 산화막)의 연마속도를 증가시키기 어렵다. 또한 3차 아민 화합물 대신， 폴리아민 화합물을 사용하면 연마제로 사용되는 실리카의 분산성을 저하시켜 침전이 발생하는 문제가 발생할 수 있다. If the primary amine compound or the secondary amine compound is used instead of the tertiary amine compound, it is difficult to increase the polishing rate of the metal film (eg, silicon oxide film) of the semiconductor substrate. In addition, if a polyamine compound is used instead of the tertiary amine compound, the dispersibility of silica used as an abrasive may be lowered, thereby causing a problem of precipitation.
또한, 본 발명의 일 실시예에 따라. 상기 연마 선택비 조절제에서 c)의 구성을 사용하는 경우, 상기 c)는 a)의 인산염기를 갖는 화합물 및 b) 3차 아민 화합물을 1:0.25 내지 1:5의 중량비율로 포함할 수 있다. 상기 a)의 인산염기를 갖는 화합물과 b)의 3차아민 화합물의 중량비가 1:0.25를 벗어나면 실리콘 질화막 대비 실리콘 산화막의 연마속도 선택비가 낮아지는 문제가 있다. 그리고, 그 비율이 1:5를 벗어나면 실리콘 질화막 대비 실리콘 산화막의 연막속도 선택비가 과하게 커져 이로견 (erosion)이 발생할 수 있다. Also, according to one embodiment of the present invention. When using the composition of c) in the polishing selectivity adjusting agent, c) may include a) a compound having a phosphate group and b) a tertiary amine compound in a weight ratio of 1: 0.25 to 1: 5. When the weight ratio of the compound having a phosphate group of a) and the tertiary amine compound of b) is 1: 0.25, the selectivity of the polishing rate of the silicon oxide film is lower than that of the silicon nitride film. And, if the ratio is out of 1: 5, the selectivity of the smoke rate of the silicon oxide film to the silicon nitride film is excessively large, which may cause erosion.
더 구체적으로， 상기 ' 연마 선택비 조절제가 C)인 경우， a)의 인산염기를 갖는 고리 화합물과 b)의 1 3차 아민 화합물은 1:0.7 내지 1:3의 중량비율로 포함할 수 있다. 상기 범위로 두 물질이 사용되는 경우에 상기 실리콘 질화막 대비 실리콘 산화막의 선택비가 1:0.5 내지 2가 되도톡
조절할 수 있다. 그러나, 상기 범위를 만족하지 못하면 실리콘 질화막과 실리콘 산화막의 연마 선택비를 조절하기 어려워진다. More specifically, when the ' polishing selectivity adjusting agent is C), the ring compound having a phosphate group of a) and the primary tertiary amine compound of b) may be included in a weight ratio of 1: 0.7 to 1: 3. When the two materials are used in the above range, the selectivity ratio of the silicon oxide film to the silicon nitride film is 1: 0.5 to 2 I can regulate it. However, if the above range is not satisfied, it is difficult to control the polishing selectivity of the silicon nitride film and the silicon oxide film.
그리.고， 상기 인산염기를 갖는 무기 화합물 및 인산염기를 갖는 금속화합물 중에서 선택된 어느 하나의 화합물; 및 3차 아민 화합물은 1:0.25 내지 1:5의 층량비율로 포함할 수 있다. 이러한 경우， 실리콘 질화막과 실리콘 산화막의 연마 선택비를 조절하기 용이하다. 또한， 연마 선택비 조절제의 함량은 슬러리 조성물의 총 중량을 기준으로 0.0001 내지 10 중량 %, 구체적으로 0.0001 내지 5 중량 %， 더 구체적으로 0.0001 내지 1 중량 가장 구체적으로는 0.0001 내지 0.5 중량 % 일 수 있다. 그리고, 연마 선택비 조절제를 사용시， 3차 아민 화합물을 사용할 경우는 전체 조성물의 총 중량을 기준으로 0.0001 내지 5 중량 %로 사용하는 것이 좋을 수 있고, 더 좋게는 0.0001 내지 0.5 중량 %로 사용한다. 상기 연마 선택비 조절제의 함량이 0.0001 증량 % 미만이면 연마속도 조절 효과가 부족한 문제가 있고, 10 중량 %를 벗어나면 연마속도자 더 이상 증가하지 않는 문제가 있다. 한편, 본 발명의 일 실시예에 따른 슬러리 조성물은 상술한 연마 선택비 조절제와 함께 연마제를 더욱 포함하는 슬러리 조성물이다. Not so. High, any one compound selected from inorganic compounds having a phosphate group and metal compounds having a phosphate group; And the tertiary amine compound may be included in a layer ratio of 1: 0.25 to 1: 5. In this case, it is easy to adjust the polishing selectivity of the silicon nitride film and the silicon oxide film. In addition, the content of the polishing selectivity modifier may be 0.0001 to 10% by weight, specifically 0.0001 to 5% by weight, more specifically 0.0001 to 1% by weight and most specifically 0.0001 to 0.5% by weight, based on the total weight of the slurry composition. . In addition, when using the polishing selectivity adjusting agent, when using the tertiary amine compound, it may be preferable to use from 0.0001 to 5% by weight based on the total weight of the total composition, and more preferably from 0.0001 to 0.5% by weight. If the content of the polishing selectivity adjusting agent is less than 0.0001% by weight, there is a problem that the polishing rate control effect is insufficient, and when the content of the polishing selector is outside 10% by weight, the polishing rate no longer increases. On the other hand, the slurry composition according to an embodiment of the present invention is a slurry composition further comprising an abrasive together with the above-described polishing selectivity adjusting agent.
이러한 본 발명의 슬러리 조성물에 사용되는, 상기 연마제 (Abrasive)는 기계적 연마를 수행하는 통상의 연마제 (Abrasive) 중에서도 콜로이달 실리카 (colloidal silica) 또는 훔드 실리카 (Fumed silica)가 사용될 수 있다. As the abrasive used in the slurry composition of the present invention, colloidal silica or fumed silica may be used among conventional abrasives that perform mechanical polishing.
상기 연마제의 함량은 전체 조성물의 총 중량을 기준으로 0.01 내지 10 중량 구체적으로는 으 1 내지 8 중량 % 가 될 수 있다. 연마제의 함량이 0.01 증량 % 미만이면 연마속도가 저하되는 문제가 있고, 10 증량 %를 초과하면 스크래치가 과도하게 발생되는 문제가 있다. 본 발명의 일 실시예에 따른 슬러리 조성물은 촉매를 더 포함할 수 있다.
상기 촉매는 텅스텐과 같은 금속막의 연마 속도를 향상시킬 수 있으며， 구체적으로 질산철， 염화철 등의 철염 및 나노 페로실리콘 (FeSi )로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다. The amount of the abrasive may be from 0.01 to 10% by weight, specifically 1 to 8% by weight, based on the total weight of the total composition. If the content of the abrasive is less than 0.01% by weight, there is a problem that the polishing rate is lowered, and when the content is greater than 10% by weight, excessive scratches are generated. The slurry composition according to an embodiment of the present invention may further include a catalyst. The catalyst may improve the polishing rate of a metal film such as tungsten, and specifically, at least one selected from the group consisting of iron salts such as iron nitrate and iron chloride and nano ferrosilicon (FeSi) may be used.
상기 촉매의 함량은 슬러리 조성물의 총 중량을 기준으로 0.00001 내지 1 중량 %ᅳ 구체적으로는 0.0001 내지 0. 5 중량 %일 수 있다. 상기 촉매의 함량이 0.00001 중량 ¾> 미만으로 너무 적으면 금속막의 연마속도가 저하되는 문제가 있고， 1 중량 %를 초과하면 화학적 반응성이 과도하여 연마속도가 불균일한 문제가 있다. 또한, 본 발명의 일실시예에 따른 슬러리 조성물은 1종 이상의 pH 조절제를 더 포함할 수 있다. The content of the catalyst may be 0.00001 to 1% by weight, specifically 0.0001 to 0.5% by weight, based on the total weight of the slurry composition. If the content of the catalyst is less than 0.00001 weight ¾>, there is a problem that the polishing rate of the metal film is lowered, and if the content of the catalyst exceeds 1% by weight, there is a problem that the polishing rate is uneven because of excessive chemical reactivity. In addition, the slurry composition according to an embodiment of the present invention may further include one or more pH adjusters.
본 발명에서 슬러리 조성물의 pH ,범위는 1 내지 4 , 구체적으로는 1.5 내지 3. 5일 수 있다. 따라서， 본 발명은 반웅 중 산성 또는 염기성의 pH 조절제를 사용하여 슬러리 조성물의 pH를 조절할 수 있다. 슬러리 조성물의 pH 범위는 1보다 낮으면 산성도가 너무 낮아서 취급의 문제가 있고， 4보다 높으면 일부 금속막의 연마속도가 감소할 수 있다. In the present invention, the pH, range of the slurry composition may be 1 to 4, specifically 1.5 to 3.5. Therefore, the present invention can adjust the pH of the slurry composition using an acidic or basic pH adjusting agent in reaction. When the pH range of the slurry composition is lower than 1, the acidity is too low, so that there is a problem in handling. If the pH range is higher than 4, the polishing rate of some metal films may decrease.
상기 pH 조절제 (pH adj ust i ng agent )는 슬러리 조성물의 pH를 조정 할 때 사용하는 것으로서. 산성 조절제 및 염기성 조절제로 이루어진 군에서 선택된 어느 하나를 사용하여, 취급성이 좋고 우수한 연마속도를 갖는 상기 pH 범위로 조절할 수 있다. The pH adjusting agent (pH adj ust i ng agent) is used to adjust the pH of the slurry composition. By using any one selected from the group consisting of an acidic regulator and a basic regulator, it can be adjusted to the above pH range having good handleability and excellent polishing rate.
상기 산성 조절제는 질산, 염산， 황산 등이 있고, 염기성 조절제는 수산화 칼륨, 수산화 나트륨， 수산화 테트라메틸암모늄， 수산화 테트라부틸암모늄 이며 , 더 구체적으로 수산화 테트라메틸암모늄, 수산화 테트라부틸암모늄 등이 있다. 반도체 재료에서 칼름, 나트룸은 금속 불순물 (meta l i mpur i ty) 관리 항목으로 웨이퍼 오염 및 불량을 유발할 수 있어서 사용량이 제한적이다. The acidic regulators include nitric acid, hydrochloric acid, sulfuric acid, and the like, and basic regulators include potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and more specifically tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and the like. In semiconductor materials, kalm and natrum are metal impurity (meta l mpur i ty) management items, which can cause wafer contamination and defects, so the amount of use is limited.
상기 i)H 조절제의 함량은 슬러리 조성물의 총 중량을 기준으로 The content of the i) H regulator is based on the total weight of the slurry composition
0.0005 내지 5 중량 % , 구체적으로는 0.001 내지 1 중량 % 일 수 있다. 상기 pH 조절제의 함량이 0.0005 중량 % 미만이면 pH 조절 효과가 부족할 문제가 있고， 5 중량 %를 초과하면 슬러리 성능이 변할 수 있는 문제가 있다.
또한， 본 발명의 일 실시예에 따른 슬러리 조성물은 1종 이상의 바이오사이드 (Bioc ide)를 더 포함할 수 있다ᅳ 0.0005 to 5% by weight, specifically 0.001 to 1% by weight. If the content of the pH regulator is less than 0.0005% by weight, there is a problem that the pH adjustment effect is insufficient, and when the content of the pH regulator exceeds 5% by weight there is a problem that the slurry performance may change. In addition, the slurry composition according to an embodiment of the present invention may further include at least one biocide (Bioc ide) ᅳ
상기 바이오사이드는 미생물의 오염을 방지하기 위해 사용하는 것으로서， 예를 들어 폴리핵사메틸렌 구아니딘 (PHMG) 또는 이소티아졸리논계 화합물 등이 사용될 수 있다. 상기 이소티나졸리논계 화합물로는， 메틸이소티아졸리논 (Methyl i sothi azol inone , MIT) , 클로로메틸 이소티아졸리논 (CMIT) 및 1，2-벤조이소티아졸 -3( -온 ( ( 1，2- benzi sothi azol-3(2^)-one : Benzi sothiazol inone , BIT)로 이루어진 군에서 선택된 1종 이상을 사용할 수 있다. The bioside is used to prevent microbial contamination, and for example, polynuclear methylene guanidine (PHMG) or isothiazolinone-based compound may be used. Examples of the isotinazolinone-based compound include methyl isothiazolinone (MIT), chloromethyl isothiazolinone (CMIT), and 1,2-benzoisothiazole-3 (-one ((1 ， 2- benzi sothi azol-3 (2 ^)-one: Benzi sothiazol inone (BIT) can be used one or more selected from the group consisting of.
상기 바이오사이드의 함량은 슬러리 조성물의 총 중량을 기준으로 0.0001 내지 0. 1 중량 % , 구체적으로는 0.001 내지 0.05 중량 % 일 수 있다. 상기 바이오사이드의 함량이 0.0001 중량 % 미만이면 살균작용이 부족하여 미생물이 발생할. 문제가 있고, 0. 1 중량 %를 초과하면 슬러리 성능이 변할 수 있는 문제가 있다. 또한， 본 발명의 일 실시예에 따른 슬러리 조성물은 1종 이상의 반웅 조절제를 더 포함할 수 있다. 상기 반웅 조절제로는 말론산， 인산， 요오드산칼륨 등이 사용될 수 있다. 상기 반웅 조절제의 함량은 슬러리 조성물의 총 중량을 기준으로 으 0001 내지 1 중량 %， 구체적으로는 0.001 내지 0.5 중량 %일 수 있다. 상기 반응 조절제의 함량이 0.0001 중량 % 미만이면 기판의 불균일성이 증가할 문제가 있고, 1 중량 %를 초과하면 연마속도가 저하될 문제가 있다. 또한， 본 발명의 일 실시예에 따른 슬러리 조성물은 상술한 성분들을 제외하고, 조성물의 100 중량 %를 충족하기 위한 나머지 성분으로 물, 알코올 (R0H) 또는 이들의 흔합물을 더 포함할 수 있다. 물을 포함할 경우， 이는 탈이온수， 이온 교환수, 초순수, 또는 증류수일 수 있고, 상기 증류수는 일반적으로 1 내지 3차 증류를 거쳐 얻은 것을 사용할 수 있다. 이 경우, 본 발명의 슬러리 조성물은 수용성 조성물일 수 있다. 상기
알코올은 탄소수 2 내지 10의 직쇄 또는 측쇄형 알코올이 사용 가능하다. 상기 슬러리 조성물은 필요에 따라 유기 용매를 더 포함할 수 있다. 이 경우 물에 용해하기 어려운 성분의 용해 보조제로 사용하거나 연마 대상막에 대한 슬러리 조성물의 젖음성 향상을 위해 사용할 수 있다. 또한， 본 발명의 일 실시예에 따른 슬러리 조성물은 산화제를 더 포함할 수 있다. The content of the bioside may be 0.0001 to 0.01 wt%, specifically 0.001 to 0.05 wt%, based on the total weight of the slurry composition. If the content of the bioside is less than 0.0001% by weight, microorganisms occur due to insufficient bactericidal action. There is a problem and there is a problem that the slurry performance may change if it exceeds 0.01% by weight. In addition, the slurry composition according to an embodiment of the present invention may further include at least one reaction agent. As the reaction regulator, malonic acid, phosphoric acid, potassium iodide, and the like may be used. The content of the reaction agent may be 0001 to 1% by weight, specifically 0.001 to 0.5% by weight, based on the total weight of the slurry composition. If the content of the reaction regulator is less than 0.0001% by weight there is a problem that the non-uniformity of the substrate is increased, if the content of more than 1% by weight has a problem that the polishing rate is lowered. In addition, the slurry composition according to an embodiment of the present invention may further include water, alcohol (R0H) or a combination thereof as the remaining components to satisfy 100% by weight of the composition, except for the above-described components. When water is included, it may be deionized water, ion-exchanged water, ultrapure water, or distilled water, and the distilled water may be generally one obtained through first to third distillation. In this case, the slurry composition of the present invention may be a water-soluble composition. remind The alcohol may be a straight or branched alcohol having 2 to 10 carbon atoms. The slurry composition may further include an organic solvent as necessary. In this case, it can be used as a dissolution aid for components that are difficult to dissolve in water, or can be used to improve the wettability of the slurry composition on the film to be polished. In addition, the slurry composition according to an embodiment of the present invention may further include an oxidizing agent.
상기 산화제는 연마대상이 텅스텐을 포함할 경우 추가로 더 포함할 수 있다. The oxidant may further include when the polishing target includes tungsten.
상기 산화제는 슬러리 조성물에 포함한 상태로 보존할 수도 있고， 슬러리 조성물의 안정성 저하를 방지하기 위해서 연마제를 포함하는 나머지 슬러리 조성물과 나누어 첨가액의 형태로 보존할 수 있다. 상기 산화제를 첨가액의 형태로 보존하는 경우에는 연마 대상막에 도포하기 이전에 나머지 슬러리 조성물에 배합하거나 또는 연마하는 동안에 슬러리 조성물과 독립적으로 연마 대상막에 도포될 수 있다. 상기 산화제로 사용될 수 있는 구체적인 예로는 과산화수소, 요오드산 칼륨， 칼륨 과망간산염 , 암모니아, 아민 화합물， 암모늄 화합물, 질산염 화합물 및 그 흔합물 중 1종 이상 선택 가능하지만 이에 한정되는 것은 아니다. The oxidizing agent may be stored in a state contained in the slurry composition, or may be stored in the form of an additive liquid by dividing with the remaining slurry composition including the abrasive to prevent the stability of the slurry composition from deteriorating. When the oxidizing agent is preserved in the form of an additive liquid, the oxidizing agent may be blended with the remaining slurry composition prior to application to the polishing target film or applied to the polishing target film independently of the slurry composition during polishing. Specific examples that can be used as the oxidizing agent may be selected from, but are not limited to, hydrogen peroxide, potassium iodide, potassium permanganate, ammonia, amine compounds, ammonium compounds, nitrate compounds, and combinations thereof.
상기 산화제의 함량은 슬러리 조성물의 총 중량을 기준으로 0.005 내지 10 중량 %， 구체적으로는 0.2 내지 5 중량%일 수 있다. The content of the oxidant may be 0.005 to 10% by weight, specifically 0.2 to 5% by weight, based on the total weight of the slurry composition.
상기 산화제의 함량이 0.005 중량 % 미만이면 금속막의 연마속도가 저하될 문제가 있고, 10 중량 %를 초과하면 화학적 반응성이 과도하여 금속막의 연마속도가 불균일한 문제가 있다. 본 발명의 다른 실시예에 따른 화학—기계적 연마용 슬러리 조성물은 전체 슬러리 조성물의 총 중량을 기준으로 연마제 0.01 내지 10 중량 %， 연마 선택비 조절제 0.0001 내지 10 중량 %， 촉매 0.00001 내지 1중량 %, H 조절제 0.0005 내지 5 증량 %， 바이오 사이드 0.0001 내지 0. 1 중량 %， 및 잔부의 물을 포함하는 화학-기계적 연마용 슬러리 조성물을 제공할 수 있다. 그리고， 상기 슬러리 조성물은 전체 슬러리 조성물의 총 증량을
기준으로 반응 조절제 0.0001 내지 1 중량 %를 더 포함할 수 있다. 또한, 상기 슬러리 조성물은 전체 슬러리 조성물의 총 증량을 기준으로 산화제If the content of the oxidizing agent is less than 0.005% by weight, there is a problem that the polishing rate of the metal film is lowered. If the content of the oxidizing agent is more than 10% by weight, the chemical reactivity is excessive, so that the polishing rate of the metal film is uneven. According to another embodiment of the present invention, the chemical-mechanical polishing slurry composition may include 0.01 to 10% by weight of abrasive, 0.0001 to 10% by weight of polishing selectivity regulator, 0.00001 to 1% by weight of catalyst, H based on the total weight of the total slurry composition. A slurry composition for chemical-mechanical polishing comprising 0.0005-5% by weight of modifier, 0.0001-0. 1% by weight of bioside, and the balance of water can be provided. And, the slurry composition is a total increase in the total slurry composition On the basis of the reaction regulator may further comprise 0.0001 to 1% by weight. In addition, the slurry composition is based on the total amount of the total slurry composition of the oxidizing agent
0.005 내지 10 중량 %를 더 포함할 수 있다. 이러한 경우, 본 발명은 연마제 0.01 내지 10 증량 연마 선택비 조절제 0.0001 내지 10 중량 % , 촉매 0.00001 내지 1중량 %， pH 조절제 0.0005 내지 5 증량 % , 바이오 사이드 0.0001 내지 0. 1 중량 반응 조절제 0.0001 내자 1 증량 % , 및 잔부의 물을 포함하는 화학-기계적 연마용 슬러리 조성물을 제공할 수 있다. 반도체 기판의 연마 방법 It may further comprise 0.005 to 10% by weight. In this case, the present invention is 0.01 to 10% by weight of the polishing selectivity control agent 0.0001 to 10% by weight, catalyst 0.00001 to 1% by weight, pH regulator 0.0005 to 5% by weight, bioside 0.0001 to 0.01 weight reaction regulator 0.0001 by 1 weight increase A slurry composition for chemical-mechanical polishing comprising%, and the balance of water can be provided. Polishing method of semiconductor substrate
본 발명의 또 다른 실시예에 따라， 상술한 화학-기계적 연마용 슬러리 조성물을 사용하여, a) 반도체 기판에 형성된 절연막 또는 금속막을 연마하는 공정; 또는 b) 반도체 기판에 형성된 절연막 및 금속막을 동시에 연마하는 공정;을 포함하는 반도체 기판의 연마방법이 제공된다. According to another embodiment of the present invention, using the above-described chemical-mechanical polishing slurry composition, a) polishing an insulating film or a metal film formed on a semiconductor substrate; Or b) simultaneously polishing the insulating film and the metal film formed on the semiconductor substrate.
상기 절연막은 실리콘 질화막, 실리콘 산화막， 또는 실리콘 질화막과 실리콘 산화막을 포함할 수 있다. 상기 금속막은 텅스텐막을 포함할 수 있다. The insulating film may include a silicon nitride film, a silicon oxide film, or a silicon nitride film and a silicon oxide film. The metal film may include a tungsten film.
그리고, 절연막을 단독으로 연마시에는 연마용 슬러리 조성물에 촉매와 산화제가 미포함될 수 있다. 또한, 절연막과 금속막을 동시에 연마하는 경우 슬러리 조성물에 촉매 및 산화제가 포함되는 것이 연마 효을 향상을 위해 더욱 유리할 수 있다. In addition, when polishing the insulating film alone, the catalyst and the oxidant may not be included in the polishing slurry composition. In addition, when polishing the insulating film and the metal film at the same time, it may be more advantageous to include a catalyst and an oxidizing agent in the slurry composition for improving the polishing effect.
또한， 본 발명의 화학-기계적 연마용 슬러리 조성물은 상술한 특정 연마 선택비 조절제를 일정 함량으로 포함하기 때문에， 기존보다 연마 속도를. 증가시켜 1종으로 이루어진 반도체 기판의 절연막 또는 금속막을 연마하거나， 또는 1종 이상으로 이루어진 절연막과 금속막을 동시에 연마할 수 있다. In addition, the chemical-mechanical polishing slurry composition of the present invention contains the above-described specific polishing selectivity regulator in a certain amount, and thus, the polishing rate is higher than conventional. The insulating film or metal film of one kind of semiconductor substrate may be polished to increase, or the insulating film and metal film of one or more types may be polished simultaneously.
따라서, 본 발명의 슬러리 조성물은 반도체 기판의 실리콘 질화막, 실리콘 산화막 또는 텅스텐막 중 선택된 1종을 연마하거나， 또는 이들 중 선택된 2종 또는 3종으로 이루어진 절연막과 금속막을 동시에 연마하는데 사용되어， 연마속도를 향상시킬 수 있다. 이때. 텅스텐막을 포함하는 금속막을 연마하는데 슬러리 조성물을 사용하는 경우 상술한 산화제는 사용
직전에 슬러리 조성물에 첨가될 수 있다ᅳ Therefore, the slurry composition of the present invention is used to polish a selected one of a silicon nitride film, a silicon oxide film, or a tungsten film of a semiconductor substrate, or simultaneously polish an insulating film and a metal film composed of two or three selected ones, Can improve. At this time. When the slurry composition is used to polish a metal film including a tungsten film, the above-mentioned oxidizing agent is used. May be added to the slurry composition immediately before
예를 들면， .텅스텐 연마용 슬러리 조성물의 경우 과산화수소 포함되지 않은 조성물을 100%으로 하여 제품으로 제조， 보관하며 연마 (CMP) 직전에 과산화수소를 추가로 흔합하여 사용할 수 있다. 그 이유는 과산화수소를 슬러리 조성물에 포함한 상태로 보존하게 되면 과산화수소가 분해되어 그 함량이 일정하게 유지되기 어려워 제품의 수명이 짧아질 수 있기 때문이다. For example, the. The slurry composition for tungsten polishing may be manufactured and stored as a product with 100% of a composition containing no hydrogen peroxide, and additionally mixed with hydrogen peroxide immediately before polishing (CMP). The reason is that when hydrogen peroxide is stored in the slurry composition, hydrogen peroxide is decomposed and its content is difficult to be kept constant, which may shorten the life of the product.
구체적으로, 상기 연마대상은 한정되지는 않지만， 주로 반도체 기판을 이루는 실리콘산화막 (Si02), 실리콘질화막 (Si3N4)과 같은 절연막 또는 텅스텐 (W)막과 같은 금속막의 각각을 연마하거나， 이들로 이루어진Specifically, the polishing target is not limited, but each of an insulating film such as a silicon oxide film (Si0 2 ), a silicon nitride film (Si 3 N 4 ) or a metal film such as a tungsten (W) film forming a semiconductor substrate, Consisting of these
2종 또는 3종의 막을 동시에 연마할 수 있다. Two or three kinds of films can be polished at the same time.
또한， 상기 b) 공정에서 상기 절연막이 실리콘 질화막인 경우, 실리콘 질화막; 및 금속막；의 연마 선택비는 1:3 이상， 혹은 1: 3 내지 Further, when the insulating film in the step b) is a silicon nitride film, a silicon nitride film; And a metal film; the polishing selectivity is 1: 3 or more, or 1: 3 to
10일 수 있고, 구체적으로 1:4 내지 8일 수 있다. 10, specifically 1: 4 to 8.
부가하여, 상기 b) 공정에서 상기 절연막이 실리콘 질화막과 실리콘 산화막을 포함하는 경우, 상기 실리콘 질화막: 실리콘 산화막: 금속막의 연마 선택비가 1: 0.5 내지 2: 3 내지 10일 수 있다. 이하, 발명의 구체적인 실시예를 통해. 발명의 작용 및 효과를 보다 상술하기로 다. 다만， 이러한 실시예는 발명의 예시로 제시된 것에 불과하며， 이에 의해 발명의 권리범위가 정해지는 것은 아니다. In addition, in the step b), when the insulating film includes a silicon nitride film and a silicon oxide film, the polishing selectivity of the silicon nitride film: silicon oxide film: metal film may be 1: 0.5 to 2: 3 to 10. Hereinafter, through specific embodiments of the invention. The operation and effects of the invention will be described in more detail. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.
[실시예] EXAMPLE
실시예 및 비교예에 대한， 반도체 기판의 금속막의 연마 조건과 연마 속도 측정방법은 다음과 같다. The polishing conditions and the polishing rate measuring method of the metal film of the semiconductor substrate for Examples and Comparative Examples are as follows.
1. 실험 Wafer: 텅스텐 OV) 8인치 blanket, 실리콘산화막 (PE-TE0S) 8인치 blanket, 실리콘질화막 (Si3N4) 8인치 blanket 1. Experiment Wafer: Tungsten OV) 8 inch blanket, Silicon oxide film (PE-TE0S) 8 inch blanket, Silicon nitride film (Si 3 N 4 ) 8 inch blanket
2. 연마 장비 (Polisher) ： Mirra 3400 (Applied Materials사) 2. Polishing equipment ： Mirra 3400 (Applied Materials)
3. 연마 조건 ： 표 1의 방법으로 진행 3. Polishing condition ： Proceed by the method of Table 1.
【표 1】
laten Head IC 압력 RR 압력 EC 압력 UC 압력 슬러리 유량 rpm Rpm psi psi psi psi m 1 / m i nTable 1 laten Head IC pressure RR pressure EC pressure UC pressure slurry flow rate rpm Rpm psi psi psi psi m 1 / min
84 78 3.6 10.4 5.2 5.2. 200 84 78 3.6 10.4 5.2 5.2. 200
4. 연마 패드 (Pad) ： I C- 1000 (Rohm & Haas사) 4. Polishing Pad ： I C-1000 (Rohm & Haas)
5. 두께 (연마속도) 측정 장비 (두께 단위 ： Angstrom, 기호: A) 텅스텐막 ： CMT-2000 (4— point probe, (주)창민 Tech.) 5. Thickness (Polishing Speed) Measuring Equipment (Thickness Unit: Angstrom, Symbol: A) Tungsten Film: CMT-2000 (4-point probe, Changmin Tech.)
실리콘산화막 및 실리콘질화막 ： Thermawave OPᅳ 2600 (KLA TENC0R) Silicon Oxide and Silicon Nitride ： Thermawave OP ᅳ 2600 (KLA TENC0R)
[식 1] [Equation 1]
연마속도 = CMP 전 두께 - CMP 후 두께 Polishing speed = thickness before CMP-thickness after CMP
6. particle size (입도) 분석 장비 6. Particle size analyzer
ELS-Z (Otsuka Electronics) ELS-Z (Otsuka Electronics)
7. pH 분석 장비 7. pH Analysis Equipment
Met r ohm 704 (Met r ohm) Met r ohm 704 (Met r ohm)
<비교예 1 내지 3 및 실시예 1 내지 11: 인산염기를 갖는 화합물을 포함하는 슬러리 제조 > <Comparative Examples 1 to 3 and Examples 1 to 11: Slurry Preparation comprising a compound having a phosphate group>
연마제 (200nm 훔드 실리카), 촉매 (질산철， 페로실리콘)， 연마 선택비 조절제 (표 2의 성분), 바이오사이드 (Methylisothiazolinone) 및 증류수를 흔합기에 넣고, 기계 교반기 (Mechanical stirrer)를 통해 교반하여 흔합하였다. Abrasives (200 nm humed silica), catalysts (iron nitrate, ferrosilicon), polishing selectivity regulators (components in Table 2), biosides (Methylisothiazolinone) and distilled water were added to the mixer and stirred through a mechanical stirrer. Mixed.
상기 교반이 완료되면, pH 조절제로서 질산과 TMAH를 사용하여 슬러리 조성물의 pH를 2로 조정하였다. 그리고， 반도체막을 연마하기 전에 31%의 농도의 과산화수소 3 중량 %를 상기 pH가 조정된 조성물에 추가로 첨가하여 실시예 1 내지 11의 슬러리 조성물을 제조하였다. When the stirring was completed, the pH of the slurry composition was adjusted to 2 using nitric acid and TMAH as pH adjusting agents. Then, before polishing the semiconductor film, 3% by weight of hydrogen peroxide at a concentration of 31% was further added to the pH-adjusted composition to prepare the slurry compositions of Examples 1-11.
이때 연마제 및 연마 선택비 조절제의 함량과 성분 구성은 하기 표 2와 같이하였다. 또한 연마 선택비 조절제가 포함되지 않는 구성은 비교예 1로 하였다. At this time, the content and composition of the abrasive and the polishing selectivity adjusting agent were as shown in Table 2 below. In addition, the structure which does not contain the polishing selectivity regulator was made into the comparative example 1.
또한， 연마 선택비 조절제의 함량이 본원의 범위를 벗어나는 경우 In addition, when the content of the polishing selectivity regulator is outside the scope of the present application
(0.0001 내지 10 중량 %)를 각각 비교예 2 및 3으로 하였다.
슬러리 조성물에서 바이오사이드의 함량은 0.01 중량 %이며, 연마제， 촉매 및 연마 선택비 조절제의 함량과 성분은 하기 표 2와 같이 하고， 질산과 TMAH는 슬러리 조성물의 pH가 2가 되도록 포함하였으며, 나머지 성분은 증류수의 함량이 되도록 조절하였다. (0.0001 to 10% by weight) were set as Comparative Examples 2 and 3, respectively. The content of biosides in the slurry composition is 0.01% by weight, and the amounts and components of the abrasive, the catalyst and the polishing selectivity adjusting agent are shown in Table 2 below, and nitric acid and TMAH are included so that the pH of the slurry composition is 2, and the remaining components are Was adjusted to the content of distilled water.
【표 2】 Table 2
실시예 9 7 0.05 0.005 2 카 phosphate 리콘 Example 9 7 0.05 0.005 2 Carphosphate Lycon
실시예 실리 Tr i sodi um 페로실 Examples Sily Tr i sodi um ferrocyl
7 0.05 0.005 2 10 카 phosphate 리콘 7 0.05 0.005 2 10 Carboxylic Phosphate
실시예 실리 Tr i sodi um Example Sily Tr i sodi um
7 0.05 . 질산철 0.06 2 11 카 phosphate 상기 비교예 1 내지 3 및 실시예 1 내지 11의 슬러리 조성물에 대하여， 상술한 방법으로 연마속도를 측정하고， 그 결과를 하기 표 3에 나타내었다. 7 0.05. Iron nitrate 0.06 2 11 car phosphate For the slurry compositions of Comparative Examples 1 to 3 and Examples 1 to 11, the polishing rate was measured by the method described above, and the results are shown in Table 3 below.
[표 3】 TABLE 3
선택비 Selectivity
No. Si.sN4 Si02 W No. Si. s N 4 Si0 2 W
Si3N4 Si02 w 비교예 1 145 310 1920 1.0 2. 1 13.2 비교예 2 150 322 1922 1.0 2. 1 12.8 비교예 3 699 308 2033 1.0 0.4 2.9 실시예 1 395 300 1907 1.0 0.8 4.8 실시예 2 390 304 1934 1.0 0.8 5.0 실시예 3 287 331 1897 1.0 1.2 6.6 실시예 4 395 311 1914 1.0 0.8 4.8 실시예 5 687 318 2095 1.0 0.5 3.0 실시예 6 379 , 318 1911 1.0 0.8 5.0 실시예 7 309 309 1927 1.0 1.0 6.2 실시예 8 315 328 1908 1.0 1.0 6. 1 실시예 9 327 317 1918 1.0 1.0 5.9 실시예 10 339 311 1999 1.0 0.9 5.9 . 실시예 11 322 315 1944 1.0 1.0 6.0
표 3의 결과를 보면, 실시예 1 내지 11과 같이 슬러리 조성물에 연마 선택비 조절제로 인산염기를 갖는 화합물을 포함하는 경우, 그 함량이 증가함에 따라 실리콘 질화막 연마속도가 증가하면서도 실리콘 산화막 및 렁스텐 연마속도에는 영향을 주지 않았다. Si 3 N 4 Si0 2 w Comparative Example 1 145 310 1920 1.0 2. 1 13.2 Comparative Example 2 150 322 1922 1.0 2. 1 12.8 Comparative Example 3 699 308 2033 1.0 0.4 2.9 Example 1 395 300 1907 1.0 0.8 4.8 Example 2 390 304 1934 1.0 0.8 5.0 Example 3 287 331 1897 1.0 1.2 6.6 Example 4 395 311 1914 1.0 0.8 4.8 Example 5 687 318 2095 1.0 0.5 3.0 Example 6 379, 318 1911 1.0 0.8 5.0 Example 7 309 309 1927 1.0 1.0 6.2 Example 8 315 328 1908 1.0 1.0 6. 1 Example 9 327 317 1918 1.0 1.0 5.9 Example 10 339 311 1999 1.0 0.9 5.9. Example 11 322 315 1944 1.0 1.0 6.0 As shown in Table 3, when the slurry composition includes a compound having a phosphate group as the polishing selectivity regulator as in Examples 1 to 11, the silicon nitride film polishing rate was increased while the silicon nitride film polishing rate was increased as its content was increased. It did not affect speed.
또한， 인산염기를 갖는 화합물 중에서도 고리화합물을 사용한 실시예 1 내지 6은 동일 함량 대비 실리콘 질화막 연마속도 향상 효과가 가장 우수하였다. 그리고, 인산염기를 갖는 무기화합물 .또는 인산염기를 갖는 금속화합물을 사용한 실시예 7 내지 11의 경우， 동일 함량에서 유사한 향상 효과를 나타내었다. 단, 금속오염을 줄이기 위해서는 금속화합물 보다 무기화합물이 더 바람직하다. In addition, among the compounds having a phosphate group, Examples 1 to 6 using the cyclic compound had the most excellent effect of improving the silicon nitride film polishing rate compared to the same content. In addition, in Examples 7 to 11 using an inorganic compound having a phosphate group or a metal compound having a phosphate group, similar improvement effects were exhibited at the same content. However, in order to reduce metal contamination, an inorganic compound is more preferable than a metal compound.
반면, 비교예 1의 경우 본원의 인산염 함유 화합물이 포함되지 않아 실시예 결과보다 실리콘 질화막의 연마속도가 낮게 나타났다. 그리고, 비교예 2 내지 3은 본원발명의 연마 선택비 조절제의 함량 범위를 벗어나 그 결과가 불량함을 알 수 있다. On the other hand, Comparative Example 1 does not include the phosphate-containing compound of the present application showed that the polishing rate of the silicon nitride film is lower than the Example results. And, Comparative Examples 2 to 3 can be seen that the result is poor beyond the content range of the polishing selectivity control agent of the present invention.
<비교예 4 내지 5 및 참고예 1 내지 6: 1차 내지 3차 아민 화합물 포함하는슬러리 제조 > <Slurry Preparation Comparing Comparative Examples 4 to 5 and Reference Examples 1 to 6: Primary to Tertiary Amine Compounds>
하기 표 4와 같이 연마 선택비 조절제로 1차, 2차, 3차 아민 화합물을 사용하는 경우에 대해 효과를 확인하기 위해 실험하였다. 연마제 (90nm 콜로이달 실리카) , 촉매 (페로실리콘) . 연마 선택비 조절제 (표 As shown in Table 4, the experiment was conducted to confirm the effect of the case of using the primary, secondary and tertiary amine compounds as the polishing selectivity adjusting agent. Abrasive (90 nm colloidal silica), catalyst (ferrosilicon). Polishing selectivity regulators (table
4의 성분) , 바이오사이드 (Methyl i sothi azo l inone) 및 증류수를 기계 교반기 (Mechani ca l st i rrer )에서 교반하여 흔합하였다. 슬러리 조성물에서 바이오사이드의 함량은 0.01 증량 % 이다. 4), bioside (Methyl i sothi azo l inone) and distilled water were mixed by stirring in a mechanical stirrer (Mechani ca st st). The content of biosides in the slurry composition is 0.01% by weight.
상기 교반이 완료되면. pH 조절제로 질산과 TMAH를 사용하여 슬러리 조성물의 pH를 2로 조정하였다. 그리고， 반도체막을 연마하기 전에 31%의 농도의 과산화수소 3 중량 %를 상기 pH가 조정된 조성물에 추가로 첨가하여 비교예 4 내지 5 및 참고예 1 내지 6의 슬러리 조성물을 제조하여， 상술한 방법으로 연마실험을 진행하였다. 또한. 연마 선택비 조절제로 1차 아민과 2차 아민을 사용한 경우를 각각 비교예 4 및 비교예 5로 하였다.
【표 4】 When the stirring is complete. The pH of the slurry composition was adjusted to 2 using nitric acid and TMAH as pH adjusters. Then, before polishing the semiconductor film, 3% by weight of hydrogen peroxide at a concentration of 31% was further added to the pH-adjusted composition to prepare the slurry compositions of Comparative Examples 4 to 5 and Reference Examples 1 to 6, by the method described above. Polishing experiment was conducted. Also. The case where primary amine and secondary amine were used as a polishing selectivity regulator was set as the comparative example 4 and the comparative example 5, respectively. Table 4
【표 5] [Table 5]
3차 아민 화합물의 함량을 증가시킴에 따라, 실리콘 산화막의 연마속도를 더욱 향상시켰다. <비교예 6 내지 8 및 실시예 12 내지 18: 인산염기를 갖는 화합물과As the content of the tertiary amine compound was increased, the polishing rate of the silicon oxide film was further improved. Comparative Examples 6 to 8 and Examples 12 to 18: a compound having a phosphate group
3차아민 화합물을 포함하는 슬러리 제조 > Slurry Preparation Containing Tertiary Amine Compounds>
상기 표 5의 결과를 통해, 슬러리 조성물에 연마 선택비 조절제로서 인산염기를 갖는 화합물에 3차 아민 화합물을 추가로 포함하는 경우 효과가 더 우수함을 입증하기 위한 실험을 진행하였다. Through the results of Table 5, an experiment was conducted to prove that the effect is better when the slurry composition further comprises a tertiary amine compound in the compound having a phosphate group as a polishing selectivity control agent.
연마제 (70誦 콜로이달 실리카)， 촉매 (질산철, 페로실리콘) , 연마 선택비 조절저 K표 6의 성분)， 바이오사이드 (Methyl i sothi azo l inone) 및 증류수를 기계 교반기 (Mechani cal st i rrer )에서 교반하여 혼합하였다. 슬러리 조성물에서 바이오사이드의 함량은 0.01 중량 % 이다. Abrasives (70 誦 colloidal silica), catalysts (iron nitrate, ferrosilicone), polishing selectivity regulators K ingredient of Table 6), biosides (Methyl i sothi azo l inone) and distilled water were mechanical stirrers (Mechani cal st i rrer) and stirred. The content of biosides in the slurry composition is 0.01% by weight.
상기 교반이 완료되면. PH 조절제로 질산과 TMAH를 사용.하여 슬러리 조성물의 pH를 3으로 조정하였다. .그리고, 반도체막을 연마하기 전에 31%의' 농도의 과산화수소 3 중량 %를 상기 pH가 조정된 조성물에 추가로 흔합하여 비교예 7 내지 8 및 실시예 12 내지 18의 슬러리 조성물을 제조하여, 상술한 방법으로 연마실험을 진행하였다. 또한, 연마 선택비 조절제를 사용하지 않은 슬러리 조성물을 비교예 6으로 하였다. When the stirring is complete. The pH of the slurry composition was adjusted to 3 using nitric acid and TMAH as the P H regulator. Then, by producing a 31% prior to grinding the semiconductor film is a common combined Comparative Examples 7 to 8 and Examples 12 to 18. The slurry composition of the "3% by weight aqueous hydrogen peroxide of concentration in addition to the above pH adjustment composition, the above-described The polishing experiment was carried out by the method. In addition, the slurry composition which did not use the grinding | polishing selectivity regulator was made into the comparative example 6.
【표 6】 Table 6
0.06 0.06
비교예 7 실리카 2 hexaphosphate 페로실리콘 0.004 3 트리부틸아민 0.012 Comparative Example 7 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.012
inositol inositol
0.06 0.06
비교예 8 실리카 2 hexaphosphate 페로실리콘 0.004 3 Comparative Example 8 Silica 2 hexaphosphate ferrosilicon 0.004 3
. 트리부틸아민 으.35 . Tributylamine E.35
inosi tol inosi tol
0.06 0.06
실시예 12 실리카 2 hexaphosphate 페로실리콘 0.004 3 트리부틸아민 0.015 Example 12 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.015
inosi tol inosi tol
0.06 0.06
실시예 13 실리카 2 hexaphosphate 페로실리콘 0.004 3 트리부틸아민 0.04 Example 13 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.04
inosi tol inosi tol
0.06 0.06
실시예 14 실리카 2 hexaphosphate 페로실리콘 0.004 3 트리부틸아민 0.06 Example 14 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.06
inosi tol inosi tol
0.06 0.06
실시예 15 실리카 2 hexaphosphate 페로실리콘 0.004 3 트리부틸아민' 0.18 Example 15 Silica 2 hexaphosphate Ferrosilicon 0.004 3 Tributylamine ' 0.18
inosi tol inosi tol
0.06 0.06
실시예 16 실리카 2 hexaphosphate 페로실리콘 0.004 3 트리부틸아민 0.3 Example 16 Silica 2 hexaphosphate ferrosilicon 0.004 3 tributylamine 0.3
monoainmon i urn monoainmon i urn
0.06 0.06
'실시예 17 실리카 2 phosphate 페로실리콘 0.004 3 트리에틸아민 0.18 '' Example 17 Silica 2 phosphate ferrosilicon 0.004 3 triethylamine 0.18
Tr i sod i um Tr i sod i um
0.06 0.06
실시예 18 실리카 2 phosphate 페로실리콘 0.004 3 트리에틸아민 0.18 상기 비교예 6 내지 8 및 실시예 12 내지 18의 슬러리 조성물에 대한
연마속도 및 선택비 측정 결과를 표 7에 나타내었다. Example 18 Silica 2 phosphate ferrosilicon 0.004 3 triethylamine 0.18 For the slurry compositions of Comparative Examples 6-8 and Examples 12-18 above Table 7 shows the results of polishing rate and selectivity.
【표 7】 Table 7
즉, 슬러리 조성물에서， 연마 선택비 조절제로서 a) 인산염기를 갖는 고리 화합물, 인산염기를 갖는 무기 화합물 및 인산염기를 갖는 금속화합물로 이루어진 군에서 선택된 1종 이상의 화합물 및 b) 3차 아민 화합물을 1 : 0.25 내지 1 : 5의 중량비율로 포함할 때， 우수한 효과를 나타냄을 알 수 있다.
That is, in the slurry composition, a) at least one compound selected from the group consisting of a) a cyclic compound having a phosphate group, an inorganic compound having a phosphate group, and a metal compound having a phosphate group and b) a tertiary amine compound as a polishing selectivity adjusting agent is 1: 0.25. When included in a weight ratio of 1: 1, it can be seen that exhibits an excellent effect.
Claims
【청구범위】 [Claim]
【청구항 11 [Claim 11
1) 연마제 ; 및 1) abrasive; And
2) a) 인산염기를 갖는 고리 화합물， 인산염기를 갖는 무기 화합물 및 인산염기를 갖는 금속 화합물로 이루어진 군에서 선택된 1종 이상의 인산염기를 갖는 화합물, b) 3차 아민 화합물， 및 c ) 이들의 흔합물로 이루어진 군에서 선택되는 연마 선택비 조절제; 2) a compound having at least one phosphate group selected from the group consisting of a) a cyclic compound having a phosphate group, an inorganic compound having a phosphate group and a metal compound having a phosphate group, b) a tertiary amine compound, and c) a mixture thereof Polishing selectivity modifiers selected from the group;
를 포함하는 화학-기계적 연마용 슬러리 조성물. 【청구항 2】 Chemical-mechanical polishing slurry composition comprising a. [Claim 2]
제 1항에 있어서, The method of claim 1,
상기 인산염기를 갖는 고리 화합물은 지방족 고리 화합물인 화학- 기계적 연마용 슬러리 조성물. 【청구항 3】 The ring compound having a phosphate group is an aliphatic ring compound. [Claim 3]
제 1항에 있어서ᅳ The method of claim 1
상기 인산염기를 갖는 고리 화합물은 이노시를 모노포스페이트, 이노시를 바이포스페이트. 이노시를 트리포스페이트， 이노시를 테트라포스페이트， 이노시를 펜타키스포스페이트, 이노시를 핵사포스페이트 글루코스 1-포스페이트 및 글루코스 6-포스페이트로 이루어진 군에서 선택된 1종 이상인 화학ᅳ기계적 연마용 슬러리 조성물. The cyclic compound having a phosphate group is monophosphate inosine, biphosphate inosine. A slurry composition for chemical mechanical polishing, which is at least one selected from the group consisting of inosi triphosphate, inosi tetraphosphate, inosi pentakiphosphate, and inosi nucleophosphate glucose 1-phosphate and glucose 6-phosphate.
【청구항 4] [Claim 4]
제 1항에 있어서, 상기 인산염기를 갖는 무기 화합물은 제 1인산암모늄， 제 2 인산 암모늄 및 제 3 인산 암모늄으로 이루어진 군에서 선택된 1종 이상인 화학-기계적 연마용 슬러리 조성물. The slurry composition for chemical-mechanical polishing according to claim 1, wherein the inorganic compound having a phosphate group is at least one selected from the group consisting of a first ammonium phosphate, a second ammonium phosphate, and a third ammonium phosphate.
【청구항 5】 [Claim 5]
저 U항에 있어서, 상기 인산염기를 갖는 금속 화합물은 제 1 인산 나트륨, 제 2 인산 나트륨 및 제 3 인산 나트륨으로 이루어진 군에서 선택된
1종 이상인 화학-기계적 연마용 슬러리 조성물. The metal compound having a phosphate group is selected from the group consisting of a first sodium phosphate, a second sodium phosphate and a third sodium phosphate. At least one chemical-mechanical polishing slurry composition.
【청구항 61 [Claim 61]
저 U항에 있어서 , In that U term,
상기 연마 선택비 조절제는 실리콘질화막의 연마속도를 조절하는 것인 화학-기계적 연마용 슬러리 조성물. The polishing selectivity adjusting agent is to adjust the polishing rate of the silicon nitride film chemical-mechanical polishing slurry composition.
【청구항 7】 [Claim 7]
제 1항에 있어서, The method of claim 1,
상기 3차 아민 화합물은 트리메틸아민, 트리에틸아민, 트리부틸아민 및 트리프로필아민으로 이루어진 군에서 선택된 1종 이상인 화학—기계적 연마용 슬러리 조성물. Wherein said tertiary amine compound is at least one member selected from the group consisting of trimethylamine, triethylamine, tributylamine and tripropylamine.
【청구항 8] [Claim 8]
제 1항에 있어서, The method of claim 1,
상기 연마 선택비 조절제에서 c)는 a)의 인산염기를 갖는 화합물 및 b) 3차 아민 화합물을 1 : 0.25 내지 1 : 5의 중량비율로 포함하는 화학-기계적 연마용 슬러리 조성물. 【청구항 9】 C) in the polishing selectivity adjusting agent comprises a) a compound having a phosphate group and b) tertiary amine compound in a weight ratio of 1: 0.25 to 1: 5 for a slurry composition for chemical-mechanical polishing. [Claim 9]
제 1항에 있어서, The method of claim 1,
상기 슬러리 조성물은 촉매를 더 포함하는 화학—기계적 연마용 슬러리 조성물. 【청구항 10】 Wherein said slurry composition further comprises a catalyst. [Claim 10]
제 9항에 있어서， The method of claim 9,
상기 촉매는 전체 슬러리 조성물의 총 중량을 기준으로 0.00001 내지 The catalyst is 0.00001 to 0.00 based on the total weight of the total slurry composition
1 증량 %를 포함하는 화학-기계적 연마용 슬러리 조성물. 【청구항 111
제 1항에 있어서, A slurry composition for chemical-mechanical polishing comprising 1% by weight increase. [Claim 111] The method of claim 1,
상기 슬러리 조성물은 1종 이상의 pH조절제를 더 포함하는 화학ᅳ 기계적 연마용 슬러리 조성물. 【청구항 12】 The slurry composition is a chemical mechanical polishing slurry composition further comprising at least one pH adjusting agent. [Claim 12]
제 1항에 있어서 , The method of claim 1,
상기 슬러리 조성물은 1종 이상의 바이오사이드를 더 포함하는 화학ᅳ 기계적 연마용 슬러리 조성물. 【청구항 13】 Wherein said slurry composition further comprises at least one bioside. [Claim 13]
제 1항에 있어서， The method of claim 1,
상기 슬러리 조성물은 1종 이상의 반웅 조절제를 더 포함하는 화학ᅳ 기계적 연마용 슬러리 조성물. 【청구항 14】 The slurry composition is a chemical chemical mechanical polishing slurry composition further comprises at least one reaction agent. [Claim 14]
제 1항에 있어서, The method of claim 1,
상기 슬러리 조성물은 물, 알코올 또는 이들의 흔합물을 더 포함하는 화학-기계적 연마용 슬러리 조성물. 【청구항 15】 The slurry composition further comprises a water, alcohol or a mixture thereof chemical-mechanical polishing slurry composition. [Claim 15]
제 1항에 있어서， The method of claim 1,
상기 슬러리 조성물은 1종 이상의 산화제를 더 포함하는 화학ᅳ기계적 연마용 슬러리 조성물. 【청구항 16】 Wherein said slurry composition further comprises at least one oxidizing agent. [Claim 16]
제 1항에 있어서. The method of claim 1.
상기 연마제는 전체 슬러리 조성물의 총 중량을 기준으로 0.01 내지 10 증량 %를 포함하는 화학—기계적 연마용 슬러리 조성물. 【청구항 17】
제 1항에 있어서， Wherein said abrasive comprises from 0.01 to 10% by weight, based on the total weight of the total slurry composition. [Claim 17] The method of claim 1,
상기 연마 선택'비. 조절제는 전체 슬러리 조성물의 총 중량을 기준으로 0.00이 내지 10 중량 %를 포함하는 화학-기계적 연마용 슬러리 조성물. The polishing selection ' B. Adjusting agent comprises 0.00 to 10% by weight based on the total weight of the total slurry composition.
【청구항 18】 [Claim 18]
전체 슬러리 조성물의 총 중량을 기준으로 연마제 0.01 내지 10 중량 %， 연마 선택비 조절제 0.0001 내지 10 중량 %， 촉메 0.00001 내지 1 중량 %， pH 조절제 0.0005 내지 5 증량 % , 바이오 사이드 0.0001 내지 0. 1 중량 % 및 잔부의 물을 포함하는 화학-기계적 연마용 슬러리 조성물. 0.01 to 10% by weight of abrasive, 0.0001 to 10% by weight of abrasive selectivity regulator, 0.00001 to 1% by weight of catalyst, 0.0005 to 5% by weight of pH regulator, 0.0001 to 0.1% by weight of bioside And a balance of water.
【청구항 19】 [Claim 19]
제 18항에 있어서, The method of claim 18,
전체 슬러리 조성물의 총 중량을 기준으로 반웅 조절제 0.0001 내지 1 중량 %를 더 포함하는 화학-기계적 연마용 슬러리 조성물. A slurry composition for chemical-mechanical polishing further comprising 0.0001 to 1% by weight of reaction modifier based on the total weight of the total slurry composition.
【청구항 20] [Claim 20]
제 18항에 있어서， The method of claim 18,
전체 슬러리 조성물의 총 중량을 기준으로 산화제 0.005 내지 10 중량 %를 더 포함하는 화학-기계적 연마용 슬러리 조성물. Slurry composition for chemical-mechanical polishing further comprising 0.005 to 10% by weight of oxidizing agent based on the total weight of the total slurry composition.
【청구항 21】 [Claim 21]
게 1항에 따른 화학-기계적 연마용 슬러리 조성물을 사용하여 , a) 반도체 기판에 형성된 절연막 또는 금속막을 연마하는 공정; 또는 b) 반도체 기판에 형성된 절연막 및 금속막을 동시에 연마하는 공정; 을 포함하는 반도체 기판의 연마 방법ᅳ A) polishing an insulating film or a metal film formed on a semiconductor substrate using the slurry composition for chemical-mechanical polishing according to claim 1; Or b) simultaneously polishing the insulating film and the metal film formed on the semiconductor substrate; Polishing method of a semiconductor substrate comprising a
【청구항 22】 [Claim 22]
제 21항에 있어서, The method of claim 21,
상기 절연막은 실리콘 질화막， 실리콘 산화막. 또는 실리콘 질화막과
실리콘 산화막을 포함하는 반도체 기판의 연마 방법. The insulating film is a silicon nitride film, a silicon oxide film. Or silicon nitride film A method of polishing a semiconductor substrate comprising a silicon oxide film.
【청구항 23】 [Claim 23]
제 21항에 있어서， The method of claim 21,
상기 금속막은 텅스텐막인， 반도체 기판의 연마 방법 . And said metal film is a tungsten film.
【청구항 24] [Claim 24]
제 21항에 있어서， The method of claim 21,
상기 b) 공정에서 상기 절연막이 실리콘 질화막 또는 실리콘 산화막인 경우， 실리콘 질화막 또는 실리콘 산화막; 및 금속막；의 연마 선택비가 1 : 3이상인 반도체 기판의 연마 방법 . When the insulating film is a silicon nitride film or a silicon oxide film in the step b), a silicon nitride film or a silicon oxide film; And a method of polishing a semiconductor substrate, wherein the polishing selectivity of the metal film is 1: 3 or more.
【청구항 25】 [Claim 25]
제 21항에 있어서， The method of claim 21,
상기 b) 공정에서 상기 절연막이 실리콘 질화막과 실리콘 산화막을 포함하는 경우， 상기 실리콘 질화막: 실리콘 산화막: 금속막의 연마 선택비가 1 : 0.5 내지 2 : 3 내지 10인 반도체 기판의 연마 방법.
And in the step b), when the insulating film comprises a silicon nitride film and a silicon oxide film, the polishing selectivity of the silicon nitride film: silicon oxide film: metal film is 1: 0.5 to 2: 3 to 10.
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| JP2004300348A (en) * | 2003-03-31 | 2004-10-28 | Fujimi Inc | Polishing composition |
| KR20090002501A (en) * | 2007-06-29 | 2009-01-09 | 제일모직주식회사 | Cmp slurry composition for the phase change memory materials and polishing method using the same |
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