TWI683896B - Polishing composition - Google Patents
Polishing composition Download PDFInfo
- Publication number
- TWI683896B TWI683896B TW105127883A TW105127883A TWI683896B TW I683896 B TWI683896 B TW I683896B TW 105127883 A TW105127883 A TW 105127883A TW 105127883 A TW105127883 A TW 105127883A TW I683896 B TWI683896 B TW I683896B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing
- polishing composition
- silicon
- water
- silicon nitride
- Prior art date
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 276
- 239000000203 mixture Substances 0.000 title claims abstract description 149
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 68
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 56
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 52
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 229920005591 polysilicon Polymers 0.000 claims description 32
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 19
- -1 silica Chemical class 0.000 description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 229910052710 silicon Inorganic materials 0.000 description 26
- 239000010703 silicon Substances 0.000 description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 24
- 235000012431 wafers Nutrition 0.000 description 21
- 229910021529 ammonia Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 description 9
- 239000011164 primary particle Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 229910052814 silicon oxide Inorganic materials 0.000 description 6
- 239000006061 abrasive grain Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000000116 mitigating effect Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229940078492 ppg-17 Drugs 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- UPMCDOMOBNMTPH-UHFFFAOYSA-N 6-phenyl-5,6-dihydroimidazo[2,1-b][1,3]thiazole Chemical compound N1=C2SC=CN2CC1C1=CC=CC=C1 UPMCDOMOBNMTPH-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N C[N+](C)(C)c1ccccc1 Chemical compound C[N+](C)(C)c1ccccc1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 244000147568 Laurus nobilis Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 1
- 229960001950 benzethonium chloride Drugs 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- FXJNQQZSGLEFSR-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride;hydrate Chemical compound O.[Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 FXJNQQZSGLEFSR-UHFFFAOYSA-M 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VWTINHYPRWEBQY-UHFFFAOYSA-N denatonium Chemical compound [O-]C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C[N+](CC)(CC)CC(=O)NC1=C(C)C=CC=C1C VWTINHYPRWEBQY-UHFFFAOYSA-N 0.000 description 1
- 229960001610 denatonium benzoate Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NVTNQIBQPLGHGE-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;hydrate Chemical compound [OH-].CCCC[NH+](CCCC)CCCC NVTNQIBQPLGHGE-UHFFFAOYSA-N 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical class C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ICTMDIORIDZWQN-UHFFFAOYSA-M triethyl(phenyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)C1=CC=CC=C1 ICTMDIORIDZWQN-UHFFFAOYSA-M 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
本發明提供一種研磨用組成物，其係多晶矽及非晶矽的研磨速度相對於氮化矽的研磨速度之比大，多晶矽及非晶矽的研磨速度大，且氮化矽的研磨速度小。研磨用組成物含有磨粒、在構造中具有苯環的四級銨鹽、與水溶性高分子及界面活性劑之至少一者。此研磨用組成物係用於具有多晶矽及非晶矽之至少一者與氮化矽的研磨對象物之研磨。 The invention provides a polishing composition, which is a ratio of the polishing speed of polycrystalline silicon and amorphous silicon to the polishing speed of silicon nitride is large, the polishing speed of polycrystalline silicon and amorphous silicon is large, and the polishing speed of silicon nitride is small. The polishing composition contains at least one of abrasive particles, a quaternary ammonium salt having a benzene ring in the structure, a water-soluble polymer, and a surfactant. This polishing composition is used to polish at least one of polycrystalline silicon and amorphous silicon and the polishing object of silicon nitride.
Description
本發明關於研磨用組成物。 The present invention relates to a composition for polishing.
藉由化學機械研磨(Chemical Mechanical Polishing；CMP)將半導體基板的表面予以平坦化時，有在比較容易研磨的多晶矽膜或非晶矽膜之下層配置比較難以研磨的氮化矽膜，將此氮化矽膜當作停止層，進行多晶矽膜或非晶矽膜之研磨。於如此的研磨中，理想上為高效率地研磨多晶矽膜或非晶矽膜，而且幾乎不研磨氮化矽膜。 When the surface of the semiconductor substrate is planarized by chemical mechanical polishing (CMP), there is a silicon nitride film that is more difficult to polish under the polysilicon film or amorphous silicon film that is easier to polish. The siliconized film is used as a stop layer to grind the polycrystalline silicon film or amorphous silicon film. In such polishing, it is desirable to efficiently polish the polycrystalline silicon film or the amorphous silicon film, and hardly polish the silicon nitride film.
因此，於如此之研磨所用的研磨用組成物中，要求多晶矽膜及非晶矽膜的研磨速度相對於氮化矽膜的研磨速度之比(藉由將多晶矽膜或非晶矽膜的研磨速度除以氮化矽膜的研磨速度而算出)大、多晶矽膜及非晶矽膜的研磨速度大、及氮化矽膜的研磨速度接近零。 Therefore, in the polishing composition used for such polishing, the ratio of the polishing speed of the polycrystalline silicon film and the amorphous silicon film to the polishing speed of the silicon nitride film (by combining the polishing speed of the polycrystalline silicon film or the amorphous silicon film Calculated by dividing by the polishing speed of the silicon nitride film), the polishing speed of the polycrystalline silicon film and the amorphous silicon film is large, and the polishing speed of the silicon nitride film is close to zero.
例如於專利文獻1中，揭示多晶矽膜的研磨速度相對於氮化矽膜的研磨速度之比大，且多晶矽膜的研磨速度大之研磨用組成物。然而，專利文獻1中揭示的研
磨用組成物不能說是氮化矽膜的研磨速度為充分小。因此，於多晶矽膜的研磨完成後，若沒有準確地結束研磨作業，則有研磨到作為停止層的氮化矽膜之虞。
For example,
[專利文獻1]日本發明專利公開公報2004年第266155號 [Patent Document 1] Japanese Invention Patent Publication No. 266155 of 2004
因此，本發明係解決如上述的習知技術所具有的問題點，課題在於提供一種研磨用組成物，其係多晶矽及非晶矽的研磨速度相對於氮化矽的研磨速度之比大，多晶矽及非晶矽的研磨速度大，且氮化矽的研磨速度小。 Therefore, the present invention solves the problems of the above-mentioned conventional technology, and the object is to provide a polishing composition that has a large ratio of the polishing speed of polycrystalline silicon and amorphous silicon to the polishing speed of silicon nitride. And amorphous silicon has a high polishing speed, and silicon nitride has a low polishing speed.
為了解決前述問題，本發明之一態樣的研磨用組成物係用於具有多晶矽及非晶矽之至少一者與氮化矽的研磨對象物之研磨的研磨用組成物，要旨為含有磨粒、在構造中具有苯環的四級銨鹽、與水溶性高分子及界面活性劑之至少一者。 In order to solve the aforementioned problems, the polishing composition according to one aspect of the present invention is a polishing composition for polishing at least one of polycrystalline silicon and amorphous silicon and an object to be polished of silicon nitride. 1. At least one of a quaternary ammonium salt having a benzene ring in the structure, a water-soluble polymer and a surfactant.
本發明之研磨用組成物係多晶矽及非晶矽的研磨速度相對於氮化矽的研磨速度之比大，多晶矽及非晶矽的研磨速度大，且氮化矽的研磨速度小。 The polishing composition of the present invention is a ratio of the polishing speed of polycrystalline silicon and amorphous silicon relative to the polishing speed of silicon nitride, the polishing speed of polycrystalline silicon and amorphous silicon is large, and the polishing speed of silicon nitride is small.
1‧‧‧矽基板 1‧‧‧Si substrate
2‧‧‧氧化矽膜 2‧‧‧Silicon oxide film
3‧‧‧氮化矽膜 3‧‧‧Silicon nitride film
4‧‧‧多晶矽膜 4‧‧‧Polycrystalline silicon film
4a‧‧‧階差 4a‧‧‧step difference
圖1係說明矽晶圓的構成之剖面圖。 FIG. 1 is a cross-sectional view illustrating the structure of a silicon wafer.
以下詳細說明本發明之一實施形態。再者，本實施形態係表示本發明之一例，本發明不受本實施形態所限定。又，可對於本實施形態加以各種的變更或改良，加有如此的變更或改良之形態亦可包含於本發明中。例如，於本實施形態中，說明用於具有多晶矽及氮化矽的研磨對象物之研磨的研磨用組成物，但此研磨用組成物亦可用於具有非晶矽及氮化矽的研磨對象物之研磨或具有多晶矽與非晶矽與氮化矽的研磨對象物之研磨。 Hereinafter, an embodiment of the present invention will be described in detail. In addition, this embodiment shows an example of the present invention, and the present invention is not limited to this embodiment. In addition, various changes or improvements can be added to this embodiment, and modes with such changes or improvements can also be included in the present invention. For example, in the present embodiment, a polishing composition for polishing an object to be polished with polycrystalline silicon and silicon nitride is described, but this polishing composition can also be used for an object to be polished with amorphous silicon and silicon nitride Lapping or polishing objects with polysilicon, amorphous silicon and silicon nitride.
本實施形態之研磨用組成物係用於具有多晶矽及氮化矽的研磨對象物之研磨的研磨用組成物，含有磨粒、在構造中具有苯環的四級銨鹽、與水溶性高分子及界面活性劑之至少一者。 The polishing composition of the present embodiment is a polishing composition for polishing an object to be polished with polycrystalline silicon and silicon nitride, and contains abrasive particles, a quaternary ammonium salt having a benzene ring in the structure, and a water-soluble polymer And at least one of surfactants.
如此的本實施形態之研磨用組成物係在相同條件下進行研磨時，多晶矽的研磨速度相對於氮化矽的研磨速度之 比(以下亦記載為「研磨速度比」)大，具有多晶矽的研磨速度大且氮化矽的研磨速度小之性能。再者，當研磨對象物具有非晶矽時，亦可將「多晶矽」換成「非晶矽」之措辭(以下亦同樣)。 When the polishing composition of this embodiment is polished under the same conditions, the polishing rate of polysilicon is relative to the polishing rate of silicon nitride The ratio (hereinafter also referred to as "grinding speed ratio") is larger, and has the performance of a higher polysilicon polishing speed and a lower silicon nitride polishing speed. In addition, when the object to be polished has amorphous silicon, the expression "polycrystalline silicon" may be replaced with "amorphous silicon" (the same applies hereinafter).
詳細說明的話，本實施形態之研磨用組成物由於具有高的水解性，可有效率地研磨多晶矽。因此，若使用本實施形態之研磨用組成物進行研磨，則多晶矽的研磨速度變大。又，四級銨鹽的陽離子由於吸附於帶負電的氮化矽，而抑制氮化矽之研磨。因此，若使用本實施形態之研磨用組成物進行研磨，則氮化矽的研磨速度變小。而且，由於多晶矽的研磨速度係保持大，研磨速度比變大(即，研磨的選擇性高)、研磨速度比可成為250以上。 In detail, since the polishing composition of this embodiment has high hydrolyzability, polysilicon can be polished efficiently. Therefore, if the polishing composition of the present embodiment is used for polishing, the polishing rate of polysilicon increases. In addition, the cations of the quaternary ammonium salt are adsorbed on the negatively charged silicon nitride, thereby inhibiting the grinding of silicon nitride. Therefore, if the polishing composition of the present embodiment is used for polishing, the polishing rate of silicon nitride is reduced. Moreover, since the polishing rate of polysilicon is kept high, the polishing rate ratio becomes larger (that is, the polishing selectivity is high), and the polishing rate ratio can be 250 or more.
因此，若使用本實施形態之研磨用組成物進行具有多晶矽及氮化矽的研磨對象物之研磨，則可效率且選擇地研磨多晶矽而去除。又，氮化矽由於難以被研磨，即使於多晶矽的研磨完成後沒有立即地使研磨作業結束，也氮化矽的研磨量為稍微。例如，當在氮化矽膜之上堆積有多晶矽膜之附膜的矽晶圓為研磨對象物時，可有效率且選擇地研磨多晶矽膜而去除。另外，即使於多晶矽膜的研磨完成後沒有立即地使研磨作業結束，也作為停止層的氮化矽膜幾乎沒有被研磨。 Therefore, if the polishing composition having polysilicon and silicon nitride is polished using the polishing composition of the present embodiment, polysilicon can be efficiently and selectively polished and removed. In addition, since silicon nitride is difficult to be polished, even if the polishing operation is not completed immediately after the polishing of polysilicon is completed, the polishing amount of silicon nitride is a little. For example, when a silicon wafer with an attached film of a polycrystalline silicon film deposited on the silicon nitride film is an object to be polished, the polycrystalline silicon film can be efficiently and selectively polished and removed. In addition, even if the polishing operation is not completed immediately after the polishing of the polycrystalline silicon film is completed, the silicon nitride film as the stop layer is hardly polished.
再者，水溶性高分子係具有吸附於多晶矽而抑制研磨之作用。當多晶矽之表面有階差時，在構成階差的凸部上所吸附的水溶性高分子由於係藉由研磨去除，而 維持多晶矽的研磨速度，另一方面，構成階差的凹部之水溶性高分子係不被去除而抑制研磨。因此，若使用本實施形態之研磨用組成物進行研磨，則在多晶矽的表面之凸部與凹部的研磨速度發生差異，結果多晶矽的表面之階差係容易被緩和。 In addition, the water-soluble polymer has an effect of being adsorbed on polysilicon and inhibiting grinding. When there is a step difference on the surface of polysilicon, the water-soluble polymer adsorbed on the convex part constituting the step difference is removed by grinding, and While maintaining the polishing rate of polysilicon, on the other hand, the water-soluble polymer constituting the recessed portion of the step is not removed to suppress polishing. Therefore, when the polishing composition of the present embodiment is used for polishing, the polishing speeds of the convex portions and the concave portions on the surface of the polycrystalline silicon are different, and as a result, the step difference on the surface of the polycrystalline silicon is easily alleviated.
再者，作為水溶性高分子，若使用在其構造中具有氮的含氮水溶性高分子，則促進凸部的研磨速度，故可得到特別良好的階差緩和性能。茲認為此係因為在多晶矽的表面上所吸附的水溶性高分子之表面上由於氮原子存在，藉由氮原子所具有正電荷及親水性作用之影響，而與親水性且具有負電荷的磨粒與多晶矽之表面的親和性升高，促進磨粒所致的刮取。 In addition, as a water-soluble polymer, if a nitrogen-containing water-soluble polymer having nitrogen in its structure is used, the polishing speed of the convex portion is promoted, so that particularly good step relaxation performance can be obtained. It is believed that this is due to the presence of nitrogen atoms on the surface of the water-soluble polymer adsorbed on the surface of the polysilicon, due to the positive charge and hydrophilic effect of the nitrogen atom, and the hydrophilic and negative charge grinding The affinity of the particles and the surface of polysilicon increases, which promotes scraping caused by abrasive particles.
以下，更詳細地說明本實施形態之研磨用組成物。 Hereinafter, the polishing composition of the present embodiment will be described in more detail.
於使用本實施形態之研磨用組成物的研磨中，可適用的研磨對象物只要是具有多晶矽及氮化矽者，則沒有特別的限定，例如可舉出在基體的表面上形成有多晶矽膜及氮化矽膜者。基體之材質係沒有特別的限定，可舉出單質矽、矽化合物、金屬、陶瓷、樹脂等。 In the polishing using the polishing composition of the present embodiment, applicable polishing objects are not particularly limited as long as they have polysilicon and silicon nitride. For example, a polysilicon film formed on the surface of the substrate and Those with silicon nitride films. The material of the substrate is not particularly limited, and examples include elemental silicon, silicon compounds, metals, ceramics, and resins.
作為單質矽，例如可舉出單晶矽、多晶矽(多結晶矽)、非晶矽等。又，作為矽化合物，例如可舉出氮化矽、二氧化矽(例如，使用四乙氧基矽烷(TEOS)而形成 的二氧化矽層間絕緣膜)、碳化矽等。 Examples of elemental silicon include single crystal silicon, polycrystalline silicon (polycrystalline silicon), and amorphous silicon. In addition, examples of the silicon compound include silicon nitride and silicon dioxide (for example, formed using tetraethoxysilane (TEOS)) Silicon dioxide interlayer insulating film), silicon carbide, etc.
又，作為金屬，例如可舉出鎢、銅、鋁、鉿、鈷、鎳、鈦、鉭、金、銀、鉑、鈀、銠、釕、銥、鋨等。此等之金屬亦可以合金或金屬化合物之形態含有。 In addition, examples of the metal include tungsten, copper, aluminum, hafnium, cobalt, nickel, titanium, tantalum, gold, silver, platinum, palladium, rhodium, ruthenium, iridium, and osmium. These metals may also be contained in the form of alloys or metal compounds.
作為如此的研磨對象物之具體例，可舉出在氮化矽膜之上堆積有多晶矽膜之附膜的矽晶圓。 As a specific example of such an object to be polished, a silicon wafer with an attached film of a polycrystalline silicon film deposited on the silicon nitride film can be cited.
本實施形態之研磨用組成物中所含有的磨粒之種類係沒有特別的限定，例如可為無機粒子、有機粒子及有機無機複合粒子之任一者。作為無機粒子之具體例，例如可舉出由矽石、氧化鋁、氧化鈰、氧化鈦等之金屬氧化物所成的粒子及由氮化矽、碳化矽、氮化硼等之陶瓷所成的粒子。作為有機粒子之具體例，例如可舉出聚甲基丙烯酸甲酯(PMMA)粒子。此等之磨粒係可單獨使用1種，也可組合2種以上使用。 The type of abrasive particles contained in the polishing composition of the present embodiment is not particularly limited, and for example, it may be any of inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include particles made of metal oxides such as silica, alumina, cerium oxide, and titanium oxide, and ceramics made of silicon nitride, silicon carbide, and boron nitride. particle. Specific examples of the organic particles include polymethyl methacrylate (PMMA) particles. One type of these abrasive particles may be used alone, or two or more types may be used in combination.
於此等具體例之中，較佳為矽石。作為矽石之具體例，可舉出膠態矽石、煙薰矽石、溶膠凝膠法矽石等，於此等矽石之中，更佳為膠態矽石，於膠態矽石之中，更佳為繭形(例如，以長軸為中心使橢圓旋轉而得之旋轉體的形狀)的膠態矽石。再者，亦可將有機酸固定化於矽石之表面。有機酸對於矽石之固定化係藉由使有機酸的官能基化學地鍵結於矽石之表面而進行。作為有機酸之例，可舉出磺酸、羧酸、亞磺酸及膦酸。 Among these specific examples, silica is preferred. Specific examples of silica include colloidal silica, fumed silica, sol-gel silica, etc. Among these silicas, colloidal silica is more preferable, and colloidal silica Among them, colloidal silica in the shape of a cocoon (for example, a shape of a rotating body obtained by rotating an ellipse around the long axis) is more preferable. Furthermore, organic acids can also be immobilized on the surface of silica. The organic acid is immobilized on silica by chemically bonding the functional group of the organic acid to the surface of silica. Examples of organic acids include sulfonic acid, carboxylic acid, sulfinic acid, and phosphonic acid.
研磨用組成物中的磨粒之含量係可設為0.1質量%以上，較佳為0.5質量%以上，更佳為1質量%以上。隨著磨粒含量變多，研磨用組成物所致的研磨對象物之去除速度(研磨速度)升高。 The content of the abrasive particles in the polishing composition can be 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more. As the content of abrasive particles increases, the removal rate (polishing rate) of the object to be polished by the polishing composition increases.
又，研磨用組成物中的磨粒之含量可設為15質量%以下，較佳為10質量%以下，更佳為5質量%以下，尤佳為3質量%以下，特佳為2.3質量%以下。隨著磨粒含量變少，可抑制研磨用組成物之材料成本，而且磨粒的凝集難以發生。 In addition, the content of abrasive grains in the polishing composition can be set to 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, and particularly preferably 2.3% by mass the following. As the content of the abrasive particles becomes smaller, the material cost of the polishing composition can be suppressed, and the aggregation of the abrasive particles hardly occurs.
磨粒的平均一次粒徑係可設為5nm以上，較佳為10nm以上，尤佳為30nm以上。隨著磨粒的平均一次粒徑變大，研磨用組成物所致的研磨對象物之研磨速度升高。 The average primary particle size of the abrasive particles can be set to 5 nm or more, preferably 10 nm or more, and particularly preferably 30 nm or more. As the average primary particle size of the abrasive particles becomes larger, the polishing rate of the object to be polished by the polishing composition increases.
又，磨粒的平均一次粒徑係可設為200nm以下，較佳為100nm以下，更佳為50nm以下。隨著磨粒的平均一次粒徑變小，藉由使用研磨用組成物來研磨研磨對象物，容易得到表面缺陷少的被研磨面。 In addition, the average primary particle size of the abrasive particles can be 200 nm or less, preferably 100 nm or less, and more preferably 50 nm or less. As the average primary particle size of the abrasive grains becomes smaller, by polishing the object to be polished using the polishing composition, it is easy to obtain a surface to be polished with fewer surface defects.
再者，磨粒的平均一次粒徑之值例如可以使用氮氣等的BET法所測定的磨粒之比表面積為基礎而計算。再者，於繭形的膠態矽石等之非球狀的磨粒時，由於以BET法所測定的磨粒之比表面積為基礎來計算假想的球狀粒子之平均一次粒徑，故將此假想的球狀粒子之平均一次粒徑當作非球狀的磨粒之平均一次粒徑。 In addition, the value of the average primary particle diameter of an abrasive particle can be calculated based on the specific surface area of the abrasive particle measured by the BET method, such as nitrogen, for example. Furthermore, in the case of non-spherical abrasive particles such as cocoon-shaped colloidal silica, the average primary particle size of the virtual spherical particles is calculated based on the specific surface area of the abrasive particles measured by the BET method. The average primary particle size of the hypothetical spherical particles is regarded as the average primary particle size of the non-spherical abrasive particles.
於本實施形態之研磨用組成物中，添加在構造中具有苯環的四級銨鹽(以下，亦僅記載為「四級銨鹽」)。四級銨鹽之種類只要是在其構造中具有苯環，則沒有特別的限定，例如可舉出四級銨鹽的銨離子為以下述化學式1表示者。
In the polishing composition of the present embodiment, a quaternary ammonium salt having a benzene ring in its structure (hereinafter, also simply referred to as "quaternary ammonium salt") is added. The type of the quaternary ammonium salt is not particularly limited as long as it has a benzene ring in its structure. For example, the ammonium ion of the quaternary ammonium salt is represented by the following
再者，下述化學式1中的x為1以上15以下之整數，y、z及w各自獨立為0以上4以下之整數。惟，x、y、z、及w愈小愈佳。
In addition, in the following
作為以上述化學式1表示之具有銨離子的四級銨鹽之例，可舉出下述各化學式2~4中所示的氯化苄基三甲基銨、氯化苄基三乙基銨、氯化苄基三丁基銨等。
Examples of the quaternary ammonium salt having ammonium ions represented by the
又，作為以上述化學式1表示者以外之具有銨離子的四級銨鹽之例，可舉出下述各化學式5~12中所示的氯化苄基二甲基十四基銨水合物、氯化苄基二甲基苯基銨、氯化三甲基苯基銨、氯化三乙基苯基銨、氯化本索寧(benzethonium chloride)、氯化苯甲醯基膽鹼、氯化苄烷胺(benzalkonium chloride)、苯酸苄銨醯胺(denatonium benzoate)等。
In addition, examples of quaternary ammonium salts having ammonium ions other than those represented by the above
此等之四級銨鹽係可單獨使用1種，也可組合2種以上使用。 These quaternary ammonium salts can be used alone or in combination of two or more.
再者，化學式2~12中所示的四級銨鹽係銨離子與氯化物離子或苯甲酸離子之鹽，但亦可為銨離子與氫氧化物離子、氟化物離子、溴化物離子、碘化物離子或有機酸離子之鹽。
Furthermore, the quaternary ammonium salt shown in
又，為了提高多晶矽的研磨速度及多晶矽的研磨速度相對於氮化矽的研磨速度之比，四級銨鹽的銨離子係化學式1所示者比其他化學式所示之四級銨鹽的銨離子更佳。
In addition, in order to increase the polishing rate of polycrystalline silicon and the ratio of the polishing rate of polycrystalline silicon to the polishing rate of silicon nitride, the ammonium ion of the quaternary ammonium salt is represented by the
再者，作為四級銨鹽的陰離子，從研磨後表面的陰離子殘留之觀點來看，最佳為氫氧化物離子。 In addition, as anions of the quaternary ammonium salt, from the viewpoint of remaining anions on the surface after polishing, the hydroxide ions are most preferable.
研磨用組成物中的四級銨鹽之含量係可設為0.0001質量%以上，較佳為0.001質量%以上，更佳為0.01質量%以上，尤佳為0.03質量%以上。隨著四級銨鹽之含量變高，研磨用組成物所致之多晶矽的研磨速度及多晶矽的研磨速度相對於氮化矽的研磨速度之比升高。 The content of the quaternary ammonium salt in the polishing composition can be 0.0001 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and particularly preferably 0.03 mass% or more. As the content of the quaternary ammonium salt becomes higher, the ratio of the polishing speed of the polycrystalline silicon and the polishing speed of the polycrystalline silicon relative to the polishing speed of the silicon nitride due to the polishing composition increases.
又，研磨用組成物中的四級銨鹽之含量係可設為1質量%以下，較佳為0.5質量%以下，更佳為0.3質量%以下。藉此，得到優異的階差緩和性能。 In addition, the content of the quaternary ammonium salt in the polishing composition can be set to 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. By this, excellent step difference mitigation performance is obtained.
於本實施形態之研磨用組成物中，添加水溶性高分子及界面活性劑之至少一者。水溶性高分子之種類係沒有特別的限定，例如可舉出甲基纖維素、甲基羥乙基纖維素、甲基羥丙基纖維素、羥乙基纖維素、羥丙基纖維素、羧甲基纖維素、羧乙基纖維素、羧甲基羥乙基纖維素等之纖維素類，或殼聚糖等之多糖類，或聚乙二醇、聚乙烯亞胺、聚-N-乙烯吡咯啶酮、聚乙烯醇、聚丙烯酸(或其鹽)、聚丙烯醯胺、聚環氧乙烷等之聚合物類。此等之水溶性高分子係可單獨使用1種，也可組合2種以上使用。 In the polishing composition of this embodiment, at least one of a water-soluble polymer and a surfactant is added. The type of water-soluble polymer is not particularly limited, and examples thereof include methyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxyl. Cellulose such as methyl cellulose, carboxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, or polysaccharide such as chitosan, or polyethylene glycol, polyethyleneimine, poly-N-ethylene Polymers such as pyrrolidone, polyvinyl alcohol, polyacrylic acid (or its salt), polyacrylamide, polyethylene oxide, etc. These water-soluble polymers can be used alone or in combination of two or more.
於此等水溶性高分子之中，較佳為在其構造中具有氮的含氮水溶性高分子。含氮水溶性高分子之單體所具有的氮原子之數係可為1個或複數。又，含氮水溶性高分子係可在其主鏈中具有氮原子，也可在側鏈中具有氮原子。再者，含氮水溶性高分子亦可具有氮原子作為胺基、亞胺基、醯胺基、醯亞胺基、碳二亞胺基、醯肼基或胺基甲酸酯基。 Among these water-soluble polymers, a nitrogen-containing water-soluble polymer having nitrogen in its structure is preferred. The number of nitrogen atoms possessed by the monomer of the nitrogen-containing water-soluble polymer may be one or plural. In addition, the nitrogen-containing water-soluble polymer system may have a nitrogen atom in the main chain or a nitrogen atom in the side chain. Furthermore, the nitrogen-containing water-soluble polymer may also have a nitrogen atom as an amine group, imine group, amide group, amide imine group, carbodiimide group, hydrazide group, or urethane group.
再者，含氮水溶性高分子亦可具有氮原子作為由氮陽離子與其他陰離子所形成之鹽(例如銨鹽)。作為具有鹽的構造之含氮水溶性高分子，例如可舉出水溶性尼龍等之聚縮合系聚醯胺、水溶性聚酯等之聚縮合系聚酯、聚加成系聚胺、聚加成系聚亞胺、聚加成系(甲基)丙烯醯胺、於烷基主鏈的至少一部分具有氮原子的水溶性高分子、於側鏈的至少一部分具有氮原子的水溶性高分子等。 Furthermore, the nitrogen-containing water-soluble polymer may have a nitrogen atom as a salt (for example, an ammonium salt) formed by a nitrogen cation and other anions. Examples of the nitrogen-containing water-soluble polymer having a salt structure include polycondensation-based polyamides such as water-soluble nylons, polycondensation-based polyesters such as water-soluble polyesters, polyaddition-based polyamines, and polyadditions. Synthetic polyimine, polyaddition-based (meth)acrylamide, water-soluble polymer having a nitrogen atom in at least part of the alkyl main chain, water-soluble polymer having a nitrogen atom in at least part of the side chain, etc. .
作為聚加成系的含氮水溶性高分子之具體例，可舉出聚乙烯基咪唑、聚乙烯基咔唑、聚-N-乙烯吡咯啶酮、聚乙烯基己內醯胺、聚乙烯基哌啶。又，含氮水溶性高分子亦可部分地具有乙烯醇構造、甲基丙烯酸構造、乙烯基磺酸構造、乙烯醇羧酸酯構造、氧化烯構造等之具有親水性的構造。另外，亦可為具有此等之二嵌段型或三嵌段型、無規型、交替型之複數種的構造之聚合物。 Specific examples of the polyaddition-based nitrogen-containing water-soluble polymer include polyvinylimidazole, polyvinylcarbazole, poly-N-vinylpyrrolidone, polyvinylcaprolactam, and polyvinyl. Piperidine. In addition, the nitrogen-containing water-soluble polymer may partially have a hydrophilic structure such as a vinyl alcohol structure, a methacrylic acid structure, a vinyl sulfonic acid structure, a vinyl alcohol carboxylate structure, and an alkylene oxide structure. In addition, it may be a polymer having a plurality of structures of these diblock type or triblock type, random type, and alternating type.
再者，含氮水溶性高分子係可為在分子中之一部分或全部具有陽離子者、具有陰離子者、具有陰離子與陽離子之兩方者、具有非離子者之任一個。 In addition, the nitrogen-containing water-soluble polymer system may be any one having a cation in part or all of the molecule, having an anion, having both an anion and a cation, or having a non-ion.
於此等含氮水溶性高分子之中，更佳為聚-N-乙烯吡咯啶酮、聚乙烯亞胺、聚丙烯醯胺。 Among these nitrogen-containing water-soluble polymers, poly-N-vinylpyrrolidone, polyethyleneimine, and polypropyleneamide are more preferred.
水溶性高分子之重量平均分子量係可設為5000以上，較佳為10000以上，更佳為30000以上，尤佳為40000以上。藉此，研磨用組成物所致之多晶矽的研磨速度及多晶矽的研磨速度相對於氮化矽的研磨速度之比係升高。 The weight average molecular weight of the water-soluble polymer can be set to 5,000 or more, preferably 10,000 or more, more preferably 30,000 or more, and particularly preferably 40,000 or more. As a result, the ratio of the polishing rate of the polycrystalline silicon and the polishing rate of the polycrystalline silicon to the polishing rate of silicon nitride due to the polishing composition is increased.
又，水溶性高分子之重量平均分子量係可設為300萬以下，較佳為100萬以下，更佳為10萬以下，尤佳為6萬以下。藉此，得到優異的階差緩和性能。 In addition, the weight average molecular weight of the water-soluble polymer can be 3 million or less, preferably 1 million or less, more preferably 100,000 or less, and particularly preferably 60,000 or less. By this, excellent step difference mitigation performance is obtained.
再者，研磨用組成物中的水溶性高分子之含量係可設為0.0001質量%以上，較佳為0.001質量%以上，更佳為0.01質量%以上，尤佳為0.03質量%以上。藉此，得到優異的階差緩和性能。 In addition, the content of the water-soluble polymer in the polishing composition can be 0.0001 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and particularly preferably 0.03 mass% or more. By this, excellent step difference mitigation performance is obtained.
還有，研磨用組成物中的水溶性高分子之含量係可設為1質量%以下，較佳為0.5質量%以下，更佳為0.3質量%以下，尤佳為0.1質量%以下。藉此，研磨用組成物所致之多晶矽的研磨速度及多晶矽的研磨速度相對於氮化矽的研磨速度之比係升高。 In addition, the content of the water-soluble polymer in the polishing composition can be set to 1% by mass or less, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less. As a result, the ratio of the polishing rate of the polycrystalline silicon and the polishing rate of the polycrystalline silicon to the polishing rate of silicon nitride due to the polishing composition is increased.
再者，研磨用組成物中的水溶性高分子之含量與磨粒之含量之比([磨粒之含量]/[水溶性高分子之含量])係可設為250以下，較佳為150以下，更佳為100以下，尤佳為50以下。 Furthermore, the ratio of the content of the water-soluble polymer in the polishing composition to the content of the abrasive particles ([content of abrasive particles]/[content of water-soluble polymer]) can be 250 or less, preferably 150 Below, more preferably 100 or less, particularly preferably 50 or less.
還有，研磨用組成物中的水溶性高分子之含量與四級 銨鹽之含量之比([四級銨鹽之含量]/[水溶性高分子之含量])係可設為1以上，較佳為2以上。 In addition, the content of water-soluble polymer in the polishing composition The ratio of ammonium salt content ([quaternary ammonium salt content]/[water-soluble polymer content]) can be set to 1 or more, preferably 2 or more.
於本實施形態之研磨用組成物中，添加水溶性高分子及界面活性劑之至少一者。作為界面活性劑，可使用陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑及非離子性界面活性劑之任一者。 In the polishing composition of this embodiment, at least one of a water-soluble polymer and a surfactant is added. As the surfactant, any of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants can be used.
作為陰離子性界面活性劑之具體例，聚氧乙烯烷基醚醋酸、聚氧乙烯烷基硫酸酯、烷基硫酸酯、聚氧乙烯烷基硫酸、烷基硫酸、烷基苯磺酸、烷基磷酸酯、聚氧乙烯烷基磷酸酯、聚氧乙烯磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯基醚二磺酸、或此等之鹽(例如月桂基硫酸銨)。 As specific examples of the anionic surfactant, polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl sulfate, alkyl sulfate, polyoxyethylene alkyl sulfuric acid, alkyl sulfuric acid, alkylbenzenesulfonic acid, alkyl Phosphate, polyoxyethylene alkyl phosphate, polyoxyethylene sulfosuccinic acid, alkyl sulfosuccinic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, or salts of these (e.g. laurel Ammonium sulfate).
又，作為陽離子性界面活性劑之具體例，可舉出烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、烷基胺鹽。 In addition, specific examples of the cationic surfactant include alkyltrimethylammonium salt, alkyldimethylammonium salt, alkylbenzyldimethylammonium salt, and alkylamine salt.
還有，作為兩性界面活性劑之具體例，可舉出烷基甜菜鹼、烷基胺氧化物。 In addition, specific examples of amphoteric surfactants include alkyl betaines and alkylamine oxides.
再者，作為非離子性界面活性劑之具體例，可舉出聚氧乙烯烷基醚、聚氧化烯烷基醚、山梨醇酐脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷基胺、烷基烷醇醯胺。 In addition, specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, Polyoxyethylene alkylamine, alkyl alkanolamide.
此等之界面活性劑係可單獨使用1種，也可組合2種 以上使用。 These surfactants can be used alone or in combination of two Used above.
於本實施形態之研磨用組成物中，為了提高其性能，視需要亦可更添加一般的研磨用組成物中所含有之眾所周知的添加劑。例如，可添加pH調整劑、氧化劑、防蝕劑、螯合劑、分散助劑、防腐劑、防黴劑等之各種添加劑。 In the polishing composition of the present embodiment, in order to improve its performance, a well-known additive contained in a general polishing composition may be added as needed. For example, various additives such as pH adjusting agents, oxidizing agents, corrosion inhibitors, chelating agents, dispersing aids, preservatives, mold inhibitors, etc. may be added.
於本實施形態之研磨用組成物中，為了將pH調整至所欲之值，視需要亦可添加pH調整劑。所使用的pH調整劑係可為酸及鹼之任一者，而且可為無機化合物及有機化合物之任一者。作為pH調整劑，例如可使用硝酸、磷酸、鹽酸、硫酸、檸檬酸等。 In the polishing composition of the present embodiment, in order to adjust the pH to a desired value, a pH adjuster may be added as necessary. The pH adjuster used may be any of acid and alkali, and may be any of inorganic compound and organic compound. As the pH adjuster, for example, nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid, citric acid and the like can be used.
本實施形態之研磨用組成物的pH係沒有特別的限定，但可設為7以上11以下。 The pH of the polishing composition of this embodiment is not particularly limited, but can be set to 7 or more and 11 or less.
於本實施形態之研磨用組成物中，為了將研磨對象物之表面予以氧化，視需要亦可添加氧化劑。氧化劑係具有將研磨對象物之表面予以氧化之作用，當於研磨用組成物中加有氧化劑時，有研磨用組成物所致的研磨速度之提高效果。 In the polishing composition of the present embodiment, in order to oxidize the surface of the object to be polished, an oxidizing agent may be added as necessary. The oxidizing agent has the effect of oxidizing the surface of the object to be polished. When an oxidizing agent is added to the polishing composition, the polishing speed by the polishing composition is improved.
可使用的氧化劑例如為過氧化物。作為過氧化物之具體例，可舉出過氧化氫、過乙酸、過碳酸鹽、過氧化脲、過氯酸、過硫酸鹽(例如過硫酸鈉、過硫酸鉀、過硫酸銨)等。 Oxidizing agents that can be used are, for example, peroxides. Specific examples of the peroxide include hydrogen peroxide, peracetic acid, percarbonate, urea peroxide, perchloric acid, and persulfate (for example, sodium persulfate, potassium persulfate, and ammonium persulfate).
於本實施形態之研磨用組成物中，為了抑制研磨對象物的表面之腐蝕，視需要亦可添加防蝕劑。作為防蝕劑之具體例，可舉出胺類、吡啶類、四苯基鏻鹽、苯并三唑類、三唑類、四唑類、苯甲酸等。 In the polishing composition of the present embodiment, in order to suppress corrosion of the surface of the object to be polished, an anticorrosive agent may be added as necessary. Specific examples of the corrosion inhibitor include amines, pyridines, tetraphenylphosphonium salts, benzotriazoles, triazoles, tetrazoles, and benzoic acid.
於本實施形態之研磨用組成物中，藉由捕捉研磨系中的金屬雜質成分而形成錯合物，可抑制研磨對象物的金屬污染，視需要亦可添加螯合劑。作為螯合劑之具體例，可舉出羧酸、胺、有機膦酸、胺基酸等。 In the polishing composition of the present embodiment, by capturing metal impurity components in the polishing system to form a complex, metal contamination of the object to be polished can be suppressed, and a chelating agent can be added as necessary. Specific examples of chelating agents include carboxylic acids, amines, organic phosphonic acids, amino acids, and the like.
於本實施形態之研磨用組成物中，為了使磨粒的疑集體之再分散成為容易，視需要亦可添加分散助劑。作為分散助劑之具體例，可舉出焦磷酸鹽或六偏磷酸鹽等之縮合磷酸鹽等。 In the polishing composition of the present embodiment, in order to facilitate the redispersion of the abrasive particles, a dispersion aid may be added as necessary. Specific examples of the dispersion aid include condensed phosphates such as pyrophosphate and hexametaphosphate.
於本實施形態之研磨用組成物中，視需要亦可添加防腐劑或防黴劑。作為防腐劑及防黴劑，例如可舉出2-甲基-4-異噻唑啉-3-酮、5-氯-2-甲基-4-異噻唑啉-3-酮等之異噻唑啉系防腐劑、或對羥基苯甲酸酯類、或苯氧基乙醇。 In the polishing composition of this embodiment, a preservative or mold inhibitor may be added as needed. Examples of the preservatives and mold inhibitors include isothiazolines such as 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. Preservatives, or parabens, or phenoxyethanol.
本實施形態之研磨用組成物亦可含有水、有機溶劑等之液狀介質。液狀介質係具有作為將研磨用組成物的各成分(磨粒、在構造中具有苯環的四級銨鹽、水溶性高分子、界面活性劑、添加劑等)分散或溶解用之分散介質或溶劑的機能。 The polishing composition of this embodiment may contain a liquid medium such as water or an organic solvent. The liquid medium is a dispersion medium for dispersing or dissolving the components of the polishing composition (abrasive particles, quaternary ammonium salt having a benzene ring in the structure, water-soluble polymer, surfactant, additives, etc.) or The function of the solvent.
作為液狀介質，可舉出水、有機溶劑，可單獨使用1種，也可混合2種以上使用，較佳為含有水。惟，從將阻礙各成分的作用者予以抑制之觀點來看，較佳為使用儘可能不含雜質的水。具體而言，較佳為以離子交換樹脂去除雜質離子後，通過過濾器去除異物後之純水或超純水或蒸餾水。 Examples of the liquid medium include water and organic solvents. One type may be used alone, or two or more types may be used in combination. It is preferable to contain water. However, from the viewpoint of suppressing the agent that hinders each component, it is preferable to use water containing as little impurities as possible. Specifically, it is preferable to use pure water, ultrapure water, or distilled water after removing impurity ions with an ion exchange resin and removing foreign matter through a filter.
本實施形態之研磨用組成物之製造方法係沒有特別的限定，例如可藉由在水等之液狀介質中攪拌、混合磨粒、四級銨鹽、與水溶性高分子及界面活性劑之至少一者、與依所欲的各種添加劑而製造。混合時的溫度係沒有特別的限定，但較佳為10℃以上40℃以下，為了提高溶解速 度，亦可加熱。又，混合時間亦沒有特別的限定。 The manufacturing method of the polishing composition of this embodiment is not particularly limited. For example, it can be agitated in a liquid medium such as water and mixed with abrasive particles, quaternary ammonium salt, water-soluble polymer and surfactant. At least one of them is manufactured with various additives as desired. The temperature during mixing is not particularly limited, but it is preferably 10°C or higher and 40°C or lower. In order to increase the dissolution rate It can also be heated. Also, the mixing time is not particularly limited.
使用本實施形態之研磨用組成物來將研磨對象物予以研磨之方法或條件係沒有特別的限定，可適宜選擇一般的研磨之方法、於條件之範圍內適合研磨對象物的研磨之方法，適宜選擇條件而進行研磨。例如，可藉由使研磨用組成物介於研磨對象物(例如，於氮化矽膜之上堆積有多晶矽膜之附膜的矽晶圓)與研磨墊之間存在，使用研磨裝置(單面研磨裝置、雙面研磨裝置等)，於一般的研磨條件下進行研磨，而進行研磨對象物之研磨。 The method or conditions for polishing the object to be polished using the polishing composition of the present embodiment are not particularly limited, and a general method of polishing can be appropriately selected, and a method suitable for polishing the object to be polished within the range of conditions is suitable Select the conditions and polish. For example, a polishing device (single-sided) can be used by interposing the polishing composition between the object to be polished (for example, a silicon wafer with a polysilicon film deposited on the silicon nitride film) and the polishing pad (Grinding device, double-sided polishing device, etc.), polishing is performed under general polishing conditions, and the object to be polished is polished.
例如，將於氮化矽膜之上堆積有多晶矽膜之附膜的矽晶圓當作研磨對象物，使用單面研磨裝置進行研磨時，使用被稱為載體的保持具來保持矽晶圓，將貼附有研磨墊的壓盤推壓至矽晶圓的單面，藉由一邊供給研磨用組成物一邊使壓盤旋轉，而研磨矽晶圓的單面。 For example, when a silicon wafer with a polysilicon film deposited on top of the silicon nitride film is used as the object to be polished, when a single-sided polishing device is used for polishing, a silicon holder is used to hold the silicon wafer. The platen to which the polishing pad is attached is pushed to one side of the silicon wafer, and the single side of the silicon wafer is polished by rotating the platen while supplying the polishing composition.
又，使用雙面研磨裝置來研磨矽晶圓時，使用被稱為載體的保持具來保持矽晶圓，將貼附有研磨墊的壓盤從矽晶圓的兩側分別推壓至矽晶圓的雙面，藉由一邊供給研磨用組成物一邊使兩側的壓盤旋轉，而研磨矽晶圓的雙面。 In addition, when using a double-sided polishing device to polish a silicon wafer, a holder called a carrier is used to hold the silicon wafer, and the platens with the polishing pad attached are pushed to the silicon crystals from both sides of the silicon wafer. The double sides of the round are polished on both sides of the silicon wafer by rotating the platens on both sides while supplying the polishing composition.
研磨墊之種類係沒有特別的限定，可為發泡體，也可為布、不織布等之非發泡體，可使用一般的不織布、發泡聚胺基甲酸酯、多孔質氟樹脂等。又，於研磨墊，亦可施予形成如研磨用組成物積留的溝之溝加工。作 為研磨墊之材質，可使用聚胺基甲酸酯、丙烯酸、聚酯、丙烯酸酯共聚物、聚四氟乙烯、聚丙烯、聚乙烯、聚4-甲基戊烯、纖維素、纖維素酯、聚醯胺(尼龍、芳香族聚醯胺等)、聚醯亞胺、聚醯亞胺醯胺、聚矽氧烷共聚物、環氧乙烷化合物、酚樹脂、聚苯乙烯、聚碳酸酯、環氧樹脂等之樹脂。 The type of polishing pad is not particularly limited, and it may be a foam, or a non-foamed body such as cloth or non-woven fabric, and general non-woven fabric, foamed polyurethane, porous fluororesin, etc. may be used. In addition, the polishing pad may also be processed to form grooves where the polishing composition is accumulated. Make As the material of the polishing pad, polyurethane, acrylic, polyester, acrylate copolymer, polytetrafluoroethylene, polypropylene, polyethylene, poly 4-methylpentene, cellulose, cellulose ester can be used , Polyamide (Nylon, Aromatic Polyamide, etc.), Polyimide, Polyimideamide, Polysiloxane Copolymer, Ethylene Oxide Compound, Phenolic Resin, Polystyrene, Polycarbonate , Epoxy resin and other resins.
還有，本實施形態之研磨用組成物係在使用於研磨對象物之研磨後回收，可再使用於研磨對象物之研磨。作為再使用研磨用組成物的方法之一例，可舉出在桶槽中回收自研磨裝置所排出的研磨用組成物，再度使循環到研磨裝置內而使用於研磨之方法。若循環使用研磨用組成物，則由於可減少作為廢液所排出的研磨用組成物之量.而可減低環境負荷。又，由於可減少所使用的研磨用組成物之量，故可抑制研磨對象物之研磨所需要的製造成本。 In addition, the polishing composition of the present embodiment is recovered after polishing the object to be polished, and can be used again to polish the object to be polished. As an example of a method of reusing the polishing composition, a method of recovering the polishing composition discharged from the polishing device in a barrel tank and circulating it into the polishing device again for polishing can be mentioned. If the polishing composition is recycled, the amount of the polishing composition discharged as waste liquid can be reduced, and the environmental load can be reduced. In addition, since the amount of the polishing composition used can be reduced, the manufacturing cost required for polishing the object to be polished can be suppressed.
再使用本實施形態之研磨用組成物時，可將因使用於研磨而消耗、損失的磨粒、四級銨鹽、水溶性高分子、界面活性劑、添加劑等之一部分或全部作為組成調整劑添加後，再使用。作為組成調整劑，可使用磨粒、四級銨鹽、水溶性高分子、界面活性劑、添加劑等以任意的混合比率所混合者。藉由追加地添加組成調整劑，可調整至適合研磨用組成物再使用的組成，進行適宜的研磨。組成調整劑中所含有的磨粒、四級銨鹽、水溶性高分子、界面活性劑、添加劑之濃度為任意，並沒有特別的限定，可 按照桶槽之大小或研磨條件來適宜調整。 When the polishing composition of this embodiment is used again, part or all of the abrasive particles, quaternary ammonium salt, water-soluble polymer, surfactant, additives, etc. that are consumed and lost due to polishing may be used as a composition modifier Use it after adding it. As the composition adjuster, abrasive grains, quaternary ammonium salts, water-soluble polymers, surfactants, additives, etc., which are mixed at an arbitrary mixing ratio, can be used. By additionally adding a composition modifier, the composition can be adjusted to a composition suitable for reuse of the polishing composition, and suitable polishing can be performed. The concentration of the abrasive particles, quaternary ammonium salt, water-soluble polymer, surfactant, and additives contained in the composition adjuster is arbitrary, and is not particularly limited, but may be According to the size of the barrel tank or grinding conditions to adjust appropriately.
又，本實施形態之研磨用組成物係可為一液型，也可為將研磨用組成物的成分之一部分或全部以任意之比率所混合的二液型等之多液型。再者，本實施形態之研磨用組成物係可將原液直接使用於研磨，也可將原液以水等的液狀介質稀釋，將所得之研磨用組成物的稀釋物用於研磨。 In addition, the polishing composition of the present embodiment may be a one-liquid type or a multi-liquid type such as a two-liquid type in which a part or all of the components of the polishing composition are mixed at an arbitrary ratio. In addition, in the polishing composition of this embodiment, the stock solution may be directly used for polishing, or the stock solution may be diluted with a liquid medium such as water, and the resulting diluted composition of the polishing composition may be used for polishing.
以下顯示實施例及比較例，更具體地說明本發明。 Examples and comparative examples are shown below to explain the present invention more specifically.
混合磨粒、四級銨鹽、水溶性高分子及水，而製造研磨用組成物(參照表1)。磨粒為平均一次粒徑35nm之繭形的膠態矽石，研磨用組成物中的磨粒之濃度為2.0質量%。四級銨鹽為氫氧化苄基三甲基銨(以下記載為「BTMAH」)，研磨用組成物中的BTMAH之濃度為0.05質量%。水溶性高分子為重量平均分子量(Mw)45000之聚-N-乙烯吡咯啶酮(以下記載為「PVP」)，研磨用組成物中的PVP之濃度為0.02質量%。又，此研磨用組成物之pH為10.0。 The abrasive grains, quaternary ammonium salt, water-soluble polymer and water are mixed to produce a polishing composition (see Table 1). The abrasive particles are cocoon-shaped colloidal silica with an average primary particle size of 35 nm, and the concentration of abrasive particles in the polishing composition is 2.0% by mass. The quaternary ammonium salt is benzyltrimethylammonium hydroxide (hereinafter referred to as "BTMAH"), and the concentration of BTMAH in the polishing composition is 0.05% by mass. The water-soluble polymer is poly-N-vinylpyrrolidone (hereinafter referred to as "PVP") having a weight average molecular weight (Mw) of 45,000, and the concentration of PVP in the polishing composition is 0.02% by mass. In addition, the pH of the polishing composition was 10.0.
除了使研磨用組成物中之磨粒、BTMAH及PVP之濃度以及PVP之重量平均分子量(Mw)成為如表1中所示之點以外，與實施例1同樣地製造研磨用組成物。此等研磨用組成物之pH係如表1中所示。 The polishing composition was produced in the same manner as in Example 1, except that the abrasive particles in the polishing composition, the concentration of BTMAH and PVP, and the weight average molecular weight (Mw) of PVP were as shown in Table 1. The pH of these polishing compositions is shown in Table 1.
除了代替作為水溶性高分子的PVP，使用重量平均分子量500000之聚乙烯基甲基酮(以下記載為「PVMK」)，使研磨用組成物中的PVMK之濃度成為0.05質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 In addition to replacing PVP as a water-soluble polymer, polyvinyl methyl ketone with a weight average molecular weight of 500,000 (hereinafter referred to as "PVMK") was used to make the concentration of PVMK in the polishing composition 0.05% by mass, and Example 2 produced the polishing composition in the same manner. The pH of this polishing composition was 10.0.
除了代替作為水溶性高分子的PVP，使用重量平均分子量216000之甲基乙烯基醚/馬來酸酐交替共聚物(以下記載為「PMVEMA」)，使研磨用組成物中的PMVEMA之濃度成為0.05質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 Instead of using PVP as a water-soluble polymer, a methyl vinyl ether/maleic anhydride alternating copolymer with a weight average molecular weight of 216000 (hereinafter referred to as "PMVEMA") was used to make the concentration of PMVEMA in the polishing composition 0.05 mass Except for the% point, the polishing composition was produced in the same manner as in Example 2. The pH of this polishing composition was 10.0.
此實施例係使用界面活性劑代替水溶性高分子之例。除了代替水溶性高分子，使用界面活性劑的月桂基硫酸銨 (以下記載為「ALS」)，使研磨用組成物中的ALS之濃度成為0.10質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 This embodiment is an example in which a surfactant is used instead of a water-soluble polymer. In addition to replacing water-soluble polymers, ammonium lauryl sulfate using surfactants (Hereinafter referred to as "ALS") The polishing composition was produced in the same manner as in Example 2 except that the concentration of ALS in the polishing composition was 0.10% by mass. The pH of this polishing composition was 10.0.
除了代替作為四級銨鹽的BTMAH，使用氫氧化三甲銨(以下記載為「TMAH」)，使研磨用組成物中的TMAH之濃度成為0.07質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.4。 Polishing was carried out in the same manner as in Example 2 except that instead of BTMAH, which is a quaternary ammonium salt, trimethylammonium hydroxide (hereinafter referred to as "TMAH") was used to adjust the concentration of TMAH in the polishing composition to 0.07 mass%. Composition. The pH of this polishing composition was 10.4.
除了代替作為四級銨鹽的BTMAH，使用氫氧化三乙銨(以下記載為「TEAH」)，使研磨用組成物中的TEAH之濃度成為0.08質量%之點以外，與實施例4同樣地製造研磨用組成物。此研磨用組成物之pH為10.2。 It was manufactured in the same manner as in Example 4 except that instead of BTMAH, which is a quaternary ammonium salt, triethylammonium hydroxide (hereinafter referred to as "TEAH") was used to adjust the concentration of TEAH in the polishing composition to 0.08% by mass. Composition for polishing. The pH of this polishing composition was 10.2.
除了代替作為四級銨鹽的BTMAH，使用氫氧化三丁銨(以下記載為「TBAH」)，使研磨用組成物中的TBAH之濃度成為0.12質量%之點以外，與實施例4同樣地製造研磨用組成物。此研磨用組成物之pH為10.1。 It was manufactured in the same manner as in Example 4 except that instead of BTMAH, which is a quaternary ammonium salt, tributylammonium hydroxide (hereinafter referred to as "TBAH") was used to make the concentration of TBAH in the polishing composition 0.12% by mass. Composition for polishing. The pH of this polishing composition was 10.1.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物 中的氨之濃度成為0.07質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 In addition to replacing the quaternary ammonium salt, ammonia is used as the base to make the polishing composition The polishing composition was produced in the same manner as in Example 2 except that the concentration of ammonia in was 0.07% by mass. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點以外，與實施例4同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 The polishing composition was produced in the same manner as in Example 4 except that instead of the quaternary ammonium salt, ammonia was used as the base and the concentration of ammonia in the polishing composition was 0.07% by mass. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點以外，與實施例6同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 The polishing composition was produced in the same manner as in Example 6, except that instead of the quaternary ammonium salt, ammonia was used as the base and the concentration of ammonia in the polishing composition was 0.07% by mass. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點以外，與實施例10同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 A polishing composition was produced in the same manner as in Example 10 except that instead of the quaternary ammonium salt, ammonia was used as the base and the concentration of ammonia in the polishing composition was 0.07% by mass. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點以外，與實施例11同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 The polishing composition was produced in the same manner as in Example 11 except that instead of the quaternary ammonium salt, ammonia was used as the base and the concentration of ammonia in the polishing composition was 0.07 mass%. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點，代替作為水溶性高分子的PVP，使用重量平均分子量40000之聚乙烯醇(以下記載為「PVA」)，使研磨用組成物中的PVA之濃度成為0.10質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 In addition to replacing the quaternary ammonium salt, ammonia is used as the base, so that the ammonia concentration in the polishing composition becomes 0.07% by mass. Instead of PVP, which is a water-soluble polymer, polyvinyl alcohol with a weight average molecular weight of 40,000 (described below) is used. "PVA"), except that the concentration of PVA in the polishing composition is 0.10% by mass, the polishing composition is produced in the same manner as in Example 2. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點，與代替作為水溶性高分子的PVP，使用重量平均分子量250000之羥乙基纖維素(以下記載為「HEC」)，使研磨用組成物中的HEC之濃度成為0.04質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 In addition to replacing the quaternary ammonium salt, ammonia is used as the base, so that the ammonia concentration in the polishing composition becomes 0.07% by mass, and instead of PVP as the water-soluble polymer, hydroxyethyl cellulose with a weight average molecular weight of 250,000 is used. (Hereinafter referred to as "HEC") The polishing composition was produced in the same manner as in Example 2 except that the concentration of HEC in the polishing composition was 0.04% by mass. The pH of this polishing composition was 10.0.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點，與代替作為水溶性高分子的PVP，使用重量平均分子量1100之聚氧乙烯(3)聚氧丙烯(17)二醇(以下記載為「POEPOP」)，使研磨用組成物中的POEPOP之濃度成為0.10質量%之點以外，與實施例2同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 In addition to replacing the quaternary ammonium salt, ammonia is used as the base, so that the ammonia concentration in the polishing composition becomes 0.07% by mass, and instead of PVP, which is a water-soluble polymer, polyoxyethylene with a weight average molecular weight of 1100 (3 ) Polyoxypropylene (17) diol (hereinafter referred to as "POEPOP"), except that the concentration of POEPOP in the polishing composition was 0.10% by mass, the polishing composition was produced in the same manner as in Example 2. The pH of this polishing composition was 10.0.
還有，聚氧乙烯(3)聚氧丙烯(17)二醇之「(3)」係意 指氧乙烯單位的平均重複數為3。同樣地，「(17)」係指氧丙烯單位的平均重複數為17。 In addition, polyoxyethylene (3) polyoxypropylene (17) glycol "(3)" means Refers to an average repeat number of oxyethylene units of 3. Similarly, "(17)" means that the average repeat number of oxypropylene units is 17.
除了代替四級銨鹽，使用氨作為鹼，使研磨用組成物中的氨之濃度成為0.07質量%之點以外，與實施例12同樣地製造研磨用組成物。此研磨用組成物之pH為10.0。 A polishing composition was produced in the same manner as in Example 12, except that instead of the quaternary ammonium salt, ammonia was used as the base and the concentration of ammonia in the polishing composition was 0.07% by mass. The pH of this polishing composition was 10.0.
接著，使用此等之研磨用組成物，進行研磨對象物之研磨。首先，將在表面上具有多晶矽膜的矽晶圓(SVM公司製)及在表面上具有氮化矽膜的矽晶圓(SVM公司製)當作研磨對象物，以相同的研磨方法、研磨條件，各自進行研磨，分別算出多晶矽及氮化矽的研磨速度。然後，自所算出之多晶矽的研磨速度與氮化矽的研磨速度，算出多晶矽的研磨速度相對於氮化矽的研磨速度之比(研磨速度比)。 Next, using these polishing compositions, the object to be polished is polished. First, a silicon wafer (manufactured by SVM) with a polysilicon film on the surface and a silicon wafer (manufactured by SVM) with a silicon nitride film on the surface were treated as the objects to be polished, using the same polishing method and polishing conditions , Respectively grinding, calculate the grinding speed of polysilicon and silicon nitride. Then, from the calculated polysilicon polishing rate and silicon nitride polishing rate, the ratio of the polysilicon polishing rate to the silicon nitride polishing rate (polishing rate ratio) is calculated.
表1中顯示各研磨速度及研磨速度比之值。研磨速度係藉由將矽晶圓的多晶矽膜或氮化矽膜在研磨前後的膜厚差除以研磨時間而算出。因此，研磨速度之單位為nm/min。多晶矽膜或氮化矽膜之膜厚係使用KLA-Tencor股份有限公司製之膜厚測定裝置ASET-F5x(商品名)進行測定。 Table 1 shows the values of each polishing speed and the polishing speed ratio. The polishing speed is calculated by dividing the film thickness difference of the polycrystalline silicon film or the silicon nitride film of the silicon wafer before and after polishing by the polishing time. Therefore, the unit of the polishing rate is nm/min. The film thickness of the polycrystalline silicon film or the silicon nitride film was measured using a film thickness measuring device ASET-F5x (trade name) manufactured by KLA-Tencor Co., Ltd.
研磨條件係如下述。 The polishing conditions are as follows.
研磨裝置：股份有限公司荏原製作所製之CMP裝置F-REX300E(商品名) Grinding device: CMP device F-REX300E (trade name) manufactured by Ebara Corporation
研磨墊：DOW電子材料公司製之研磨墊IC1010(商品名) Polishing pad: Polishing pad IC1010 (trade name) manufactured by DOW Electronic Materials
研磨荷重：10.3kPa Grinding load: 10.3kPa
壓盤旋轉速度：60rpm Platen rotation speed: 60rpm
載體旋轉速度：65rpm Carrier rotation speed: 65rpm
研磨時間：1分鐘 Grinding time: 1 minute
研磨用組成物之供給速度：300mL/分鐘(溢流使用) Supply rate of polishing composition: 300mL/min (for overflow)
接著，將形成有配線的矽晶圓(參照圖1)當作研磨對象物，使用實施例1~12及比較例1~12之研磨用組成物，各自進行研磨。首先，關於研磨對象物的矽晶圓之構成，邊參照圖1邊說明。此矽晶圓係Advanced Materials Technology股份有限公司製之直徑300mm的晶圓，於矽基板1上形成有氧化矽膜2、氮化矽膜3及多晶矽膜4者。
Next, using the silicon wafer (see FIG. 1) on which the wiring is formed as the object to be polished, each of the polishing compositions of Examples 1 to 12 and Comparative Examples 1 to 12 was used for polishing. First, the configuration of the silicon wafer to be polished will be described with reference to FIG. 1. This silicon wafer is a 300 mm diameter wafer manufactured by Advanced Materials Technology Co., Ltd., and a
詳細說明的話，於矽基板1上形成藉由熱氧化所造成的氧化矽膜2(膜厚12.5nm)，再於氧化矽膜2之上形成藉由減壓化學氣相蒸鍍法所造成的氮化矽膜3(膜厚70.0nm)。然後，去除氧化矽膜2及氮化矽膜3之一部分，形成複數的溝狀之溝槽(最小寬度0.18μm)。再者，於氮化矽膜3之上堆積多晶矽膜4(膜厚152.5nm)，亦以多晶矽埋入溝槽內。
In detail, a silicon oxide film 2 (thickness 12.5 nm) caused by thermal oxidation is formed on the
於如此的矽晶圓之表面(多晶矽膜4之表面)的溝槽之上方部分，形成有階差(階梯)4a。此階差4a的階梯高度為70nm。然後，使用實施例1~12及比較例1~12之研磨用組成物，各自研磨此矽晶圓之表面，測定研磨後
殘留的階差4a之階梯高度。
A step (step) 4a is formed on the upper part of the trench on the surface of the silicon wafer (the surface of the polysilicon film 4). The step height of this
研磨條件係如下述。 The polishing conditions are as follows.
研磨裝置：日本ENGIS股份有限公司製的研磨裝置EJ-380IN(商品名) Grinding device: Grinding device EJ-380IN (trade name) manufactured by Japan ENGIS Co., Ltd.
研磨墊：DOW電子材料公司製之研磨墊IC1010(商品名) Polishing pad: Polishing pad IC1010 (trade name) manufactured by DOW Electronic Materials
研磨荷重：6.9kPa Grinding load: 6.9kPa
壓盤旋轉速度：70rpm Platen rotation speed: 70rpm
研磨時間：1分鐘 Grinding time: 1 minute
研磨用組成物之供給速度：100mL/分鐘(溢流使用) Supply rate of polishing composition: 100mL/min (for overflow)
又，於階梯高度之測定中，使用KLA-Tencor股份有限公司製之高分解能力表面地形描繪系統HRP340(商品名)。表1中顯示結果。於表1中，研磨後殘留的階差4a之階梯高度未達8nm時係以「A」表示，8nm以上且未達12nm時係以「B」表示，超過12nm時係以「C」表示。
In addition, in the measurement of the step height, a high resolution surface topography drawing system HRP340 (trade name) manufactured by KLA-Tencor Co., Ltd. was used. Table 1 shows the results. In Table 1, the step height of the remaining
如由表1可知，於使用實施例1~12之研磨用組成物的研磨中，研磨速度比大，多晶矽的研磨速度大，而且氮化矽的研磨速度小。又，階梯高度為A或B，研磨後殘留的階差4a小。
As can be seen from Table 1, in the polishing using the polishing compositions of Examples 1 to 12, the polishing rate ratio is large, the polysilicon polishing rate is large, and the silicon nitride polishing rate is small. In addition, the step height is A or B, and the remaining
相對於其，於使用比較例1~12之研磨用組成物的研磨中，雖然有多晶矽的研磨速度大或氮化矽的研磨速度小者，但皆研磨速度比小，未達250。又，關於階梯高度，亦有A或B者，但也有C者(研磨後殘留的階差4a大)。
In contrast, in the polishing using the polishing compositions of Comparative Examples 1 to 12, although the polishing rate of polycrystalline silicon is high or the polishing rate of silicon nitride is low, the polishing rate is lower than 250. In addition, regarding the step height, there are A or B, but there are also C (the remaining
1‧‧‧矽基板 1‧‧‧Si substrate
2‧‧‧氧化矽膜 2‧‧‧Silicon oxide film
3‧‧‧氮化矽膜 3‧‧‧Silicon nitride film
4‧‧‧多晶矽膜 4‧‧‧Polycrystalline silicon film
4a‧‧‧階差 4a‧‧‧step difference
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-182197 | 2015-09-15 | ||
| JP2015182197A JP6533439B2 (en) | 2015-09-15 | 2015-09-15 | Polishing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201726880A TW201726880A (en) | 2017-08-01 |
| TWI683896B true TWI683896B (en) | 2020-02-01 |
Family
ID=58288965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW105127883A TWI683896B (en) | 2015-09-15 | 2016-08-30 | Polishing composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6533439B2 (en) |
| TW (1) | TWI683896B (en) |
| WO (1) | WO2017047307A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110462797B (en) * | 2017-03-31 | 2023-09-22 | 福吉米株式会社 | Polishing composition |
| WO2019069370A1 (en) * | 2017-10-03 | 2019-04-11 | 日立化成株式会社 | Polishing liquid, polishing liquid set, polishing method, and defect inhibition method |
| JP7133414B2 (en) | 2018-09-20 | 2022-09-08 | 株式会社フジミインコーポレーテッド | Polishing composition |
| US11621171B2 (en) | 2018-09-25 | 2023-04-04 | Nissan Chemical Corporation | Method for polishing silicon wafer with reduced wear on carrier, and polishing liquid used therein |
| US20220348788A1 (en) | 2021-04-27 | 2022-11-03 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Polishing composition and method of polishing a substrate having enhanced defect reduction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101568615A (en) * | 2006-12-28 | 2009-10-28 | 花王株式会社 | Polishing liquid composition |
| CN103492519A (en) * | 2011-04-15 | 2014-01-01 | 嘉柏微电子材料股份公司 | Compositions and methods for selective polishing of silicon nitride materials |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004266155A (en) * | 2003-03-03 | 2004-09-24 | Jsr Corp | Water dispersed element for chemical mechanical polishing and chemical mechanical polishing method using the same and method for manufacturing semiconductor device |
| JP2004247542A (en) * | 2003-02-14 | 2004-09-02 | Kao Corp | Method for manufacturing substrate for precision component |
| US7018560B2 (en) * | 2003-08-05 | 2006-03-28 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Composition for polishing semiconductor layers |
| US7446046B2 (en) * | 2005-01-06 | 2008-11-04 | Intel Corporation | Selective polish for fabricating electronic devices |
| KR20100014849A (en) * | 2007-02-27 | 2010-02-11 | 히다치 가세고교 가부시끼가이샤 | Cmp slurry for silicon film |
| US8431490B2 (en) * | 2010-03-31 | 2013-04-30 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Method of chemical mechanical polishing a substrate with polishing composition adapted to enhance silicon oxide removal |
| JP2016017149A (en) * | 2014-07-09 | 2016-02-01 | 日立化成株式会社 | Abrasive, abrasive set, and substrate polishing method |
-
2015
- 2015-09-15 JP JP2015182197A patent/JP6533439B2/en active Active
-
2016
- 2016-08-12 WO PCT/JP2016/073745 patent/WO2017047307A1/en active Application Filing
- 2016-08-30 TW TW105127883A patent/TWI683896B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101568615A (en) * | 2006-12-28 | 2009-10-28 | 花王株式会社 | Polishing liquid composition |
| CN103492519A (en) * | 2011-04-15 | 2014-01-01 | 嘉柏微电子材料股份公司 | Compositions and methods for selective polishing of silicon nitride materials |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017047307A1 (en) | 2017-03-23 |
| TW201726880A (en) | 2017-08-01 |
| JP2017057263A (en) | 2017-03-23 |
| JP6533439B2 (en) | 2019-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI683896B (en) | Polishing composition | |
| JP6581198B2 (en) | Composite abrasive particles for chemical mechanical planarization compositions and methods of use thereof | |
| JP6023125B2 (en) | Chemical mechanical polishing slurry composition and method for copper using it and through silicon via application | |
| JP6542761B2 (en) | Polishing composition of mixed abrasives | |
| TWI398473B (en) | Compositions for polishing aluminum/copper and titanium in damascene structures | |
| TWI718998B (en) | Polishing composition | |
| JP4614981B2 (en) | Chemical mechanical polishing aqueous dispersion and semiconductor device chemical mechanical polishing method | |
| JP6603234B2 (en) | Composition and method for CMP of tungsten material | |
| JP7148506B2 (en) | Polishing composition and polishing method using the same | |
| TWI730970B (en) | Polishing method, composition for removing impurities, substrate and manufacturing method thereof | |
| TW200811276A (en) | Polishing composition containing polyether amine | |
| JP2008091524A (en) | Polishing solution for metal | |
| TWI787329B (en) | Chemical mechanical polishing method for cobalt | |
| JP2011508423A (en) | Halide anion for controlling metal removal rate | |
| JPWO2014103725A1 (en) | Chemical mechanical polishing aqueous dispersion and chemical mechanical polishing method | |
| WO2017126268A1 (en) | Polishing composition and method for polishing silicon substrate | |
| TW201518489A (en) | Abrasive agent, abrasive agent set and method for polishing substrate | |
| US10526508B2 (en) | Slurry composition for CMP and polishing method using same | |
| JP6697362B2 (en) | Surface treatment composition, surface treatment method using the same, and method for manufacturing semiconductor substrate | |
| TW201915133A (en) | Chemical mechanical polishing method for cobalt | |
| JP2016069522A (en) | Composition | |
| TW201139633A (en) | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing method using same, and kit for preparing aqueous dispersion for chemical mechanical polishing | |
| JP2017107905A (en) | Cleaning fluid and cleaning method | |
| JP7356932B2 (en) | Polishing composition and polishing method | |
| JP6349852B2 (en) | Abrasive, stock solution for abrasive, and polishing method |