CN114958207A - CMP slurry composition for polishing silicon oxide film - Google Patents
CMP slurry composition for polishing silicon oxide film Download PDFInfo
- Publication number
- CN114958207A CN114958207A CN202210166968.6A CN202210166968A CN114958207A CN 114958207 A CN114958207 A CN 114958207A CN 202210166968 A CN202210166968 A CN 202210166968A CN 114958207 A CN114958207 A CN 114958207A
- Authority
- CN
- China
- Prior art keywords
- polishing
- silicon oxide
- oxide film
- acid
- slurry composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 226
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 169
- 239000000203 mixture Substances 0.000 title claims abstract description 135
- 239000002002 slurry Substances 0.000 title claims abstract description 134
- 239000002270 dispersing agent Substances 0.000 claims abstract description 46
- 239000002245 particle Substances 0.000 claims abstract description 45
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 organic acid compound Chemical class 0.000 claims abstract description 18
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 11
- 239000012498 ultrapure water Substances 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 261
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 39
- 229920005591 polysilicon Polymers 0.000 claims description 38
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 37
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 37
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000003002 pH adjusting agent Substances 0.000 claims description 21
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 239000004310 lactic acid Substances 0.000 claims description 14
- 235000014655 lactic acid Nutrition 0.000 claims description 14
- 239000003607 modifier Substances 0.000 claims description 10
- 229940081066 picolinic acid Drugs 0.000 claims description 10
- 239000006061 abrasive grain Substances 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000007517 polishing process Methods 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- DTSDBGVDESRKKD-UHFFFAOYSA-N n'-(2-aminoethyl)propane-1,3-diamine Chemical compound NCCCNCCN DTSDBGVDESRKKD-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000007983 Tris buffer Substances 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- DGMPVYSXXIOGJY-UHFFFAOYSA-N Fusaric acid Chemical compound CCCCC1=CC=C(C(O)=O)N=C1 DGMPVYSXXIOGJY-UHFFFAOYSA-N 0.000 claims description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 claims description 4
- AXEYWFGSQDLHDX-UHFFFAOYSA-N hexane-1,3,6-triamine Chemical compound NCCCC(N)CCN AXEYWFGSQDLHDX-UHFFFAOYSA-N 0.000 claims description 4
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims description 3
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 claims description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 claims description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229960002510 mandelic acid Drugs 0.000 claims description 2
- 229960003512 nicotinic acid Drugs 0.000 claims description 2
- 235000001968 nicotinic acid Nutrition 0.000 claims description 2
- 239000011664 nicotinic acid Substances 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims 2
- 230000007547 defect Effects 0.000 abstract description 36
- 230000000052 comparative effect Effects 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- CEKXZSQLUFQAOG-UHFFFAOYSA-N barium(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Ba++] CEKXZSQLUFQAOG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The present invention relates to a CMP slurry composition for polishing a silicon oxide film, which can reduce the amount of dishing defects and scratches generated during a polishing or planarization process of a silicon oxide film by including abrasive particles (a), a dispersing agent (B), an auxiliary dispersing agent (C), a non-ionic additive (D), a pH adjustor (E), and residual ultrapure water (F), wherein the dispersing agent (B) includes an organic acid compound containing an aromatic ring and one or more carboxyl groups (-COOH), and the pH adjustor (E) includes an organic compound containing one or more hydroxyl groups (-OH) and one carboxyl group (-COOH).
Description
Technical Field
The present invention relates to a CMP slurry composition for polishing a silicon oxide film, and more particularly, to a CMP slurry composition for polishing a silicon oxide film, which can reduce the amount of dishing defects and scratches generated during a polishing or planarization process for a silicon oxide film.
Background
With the recent reduction in semiconductor design rules, the importance of the surface quality of polishing in the manufacture of submicron-sized semiconductor devices has become more apparent, and for this reason, a chemical mechanical polishing (hereinafter referred to as "CMP") process is required.
The CMP process refers to a planarization process in which a slurry composition is provided between a semiconductor substrate (wafer) and a polishing pad, and then the semiconductor substrate is pressed and rotated while being in contact with the polishing pad to polish the surface of the semiconductor substrate. At this time, the surface protrusions of the polishing pad and the polishing particles included in the slurry composition cause mechanical friction with the surface of the semiconductor substrate, thereby mechanically polishing the surface of the semiconductor substrate. In addition, the chemical components included in the slurry composition may selectively induce selective chemical reactions against the surface of the semiconductor substrate to selectively remove the surface of the substrate, thereby allowing for more optimal and extensive planarization.
As such, the polishing efficiency of the CMP process is determined by the chemical mechanical polishing apparatus, the composition of the slurry composition, and the type of polishing pad. In particular, the composition of the slurry composition has a significant effect on polishing efficiency. For example, for slurry compositions having the same composition, since the polishing rate may vary according to the properties of the film, the polishing degree of the film may be controlled by using the difference in polishing rate.
Further, in recent years, the CMP process is generally performed using a polishing speed difference between a silicon oxide film, a silicon nitride film, a polysilicon film, or a metal film widely used in semiconductor devices. In particular, slurry compositions having a high polishing speed for silicon oxide films and a low polishing speed for silicon nitride films or polysilicon films have been widely used.
However, when polishing a silicon oxide film using a silicon nitride film or a polysilicon film as a polishing stop layer, if a slurry composition having too high polishing selectivity with respect to the silicon oxide film is applied, there is a disadvantage in that: from the time when the silicon nitride film starts to be exposed, the silicon nitride film is hardly polished by the slurry, and only the silicon oxide film having a high polishing rate is excessively polished, so that an excessive dishing defect occurs. When a subminiaturized device is manufactured in which the trench line width is reduced to 50nm or less, such excessive dishing defects may generate a step between the active region and the field region, resulting in a reduction in the performance and reliability of the device.
[ Prior art documents ]
[ patent document ]
(patent document 1) Korean patent laid-open publication No.2019-
(patent document 2) Korean patent laid-open publication No.2019-0110662
Disclosure of Invention
An aspect of the present invention provides a CMP slurry composition for polishing a silicon oxide film, which can reduce the amount of dishing defects and scratches generated on the surface of the silicon oxide film by stopping a planarization process when the silicon oxide film is subjected to the planarization process using a silicon nitride film or a polysilicon film as a polishing stop layer by exposing the silicon nitride film or the polysilicon film.
Another aspect of the present invention provides a method for polishing a substrate, which can remove a high step of a silicon oxide film by performing a planarization process using a CMP slurry composition for polishing the silicon oxide film.
According to an aspect of the present invention, there is provided a CMP slurry composition for polishing a silicon oxide film, the CMP slurry composition comprising: abrasive grains (A); a dispersant (B); an auxiliary dispersant (C); a nonionic additive (D); a pH adjuster (E); and residual ultrapure water (F), wherein the dispersant (B) includes an organic acid compound having an aromatic ring and one or more carboxyl groups (-COOH), and the pH adjustor (E) may include an organic compound having one or more hydroxyl groups (-OH) and one carboxyl group (-COOH).
The CMP slurry composition for polishing a silicon oxide film may further include a silicon oxide film polishing rate modifier (G).
The CMP slurry composition for polishing a silicon oxide film may have a pH of 3 to 7 and a zeta potential of +30mV to less than +60 mV.
In addition, the CMP slurry composition for polishing a silicon oxide film may have a ratio of polishing selectivity (polishing rate) to a silicon nitride film to polishing selectivity (polishing rate) to a silicon oxide film of 1:100 to 1:300, and the CMP slurry composition for polishing a silicon oxide film may have a ratio of polishing selectivity (polishing rate) to a polysilicon film to polishing selectivity (polishing rate) to a silicon oxide film of 1:30 to 1: 100.
According to another aspect of the present invention, there is provided a method of polishing a substrate including a silicon oxide film, a silicon nitride film and a polysilicon film using a CMP slurry composition for polishing a silicon oxide film.
Advantageous effects
The CMP slurry composition for polishing a silicon oxide film of the present invention includes a specific dispersant and a pH adjustor in a specific ratio, so that a high step of the silicon oxide film can be removed by increasing the speed of polishing the silicon oxide film, and at the same time, by stopping the polishing process when the silicon nitride film or the polysilicon film as a polishing stop film is exposed, the amount of dishing defects and scratches generated on the surface of the silicon oxide film can be effectively suppressed. Therefore, in the case of applying the CMP slurry composition for polishing a silicon oxide film of the present invention, a more optimized and broader planarization effect of the silicon oxide film can be achieved in the manufacture of a miniaturized semiconductor device, thereby enabling the realization of a semiconductor device having improved performance and reliability.
Drawings
The following drawings attached hereto illustrate preferred embodiments of the present invention by way of example and serve to enable the technical idea of the invention to be further understood together with the detailed description of the invention given below, and the present invention should therefore not be construed as merely an item in such drawings.
Fig. 1 is a cross-sectional view illustrating a CMP process for Shallow Trench Isolation (STI) of a semiconductor device.
Detailed Description
Hereinafter, the present invention will be described in more detail.
It should be understood that the words or terms used in the specification and claims of this invention should not be construed as limited to having the meanings defined in commonly used dictionaries. It should be further understood that the words or terms should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the technical spirit of the present invention, based on the principle that the inventor can appropriately define the meaning of the words or terms that best explain the present invention.
In addition, in the present specification, "zeta potential" is an index representing the degree of surface charge of colloidal abrasive particles suspended or dispersed in a medium (water and/or an organic solvent). When an electric field is applied to the colloid from the outside, the colloidal particles migrate (move) in a direction opposite to the sign of the surface potential thereof, and the "zeta potential" is a numerical value calculated in consideration of the electric field intensity, hydrodynamic effects (viscosity of the solvent, dielectric constant), and the like, at which the moving speed is applied to the particles. That is, the zeta potential is the value of the electrostatic charge measured at the surface of an abrasive particle, the magnitude of which is a value representing the tendency of an abrasive particle to repel another particle or surface of similar charge. The larger the magnitude of zeta potential between the two materials, the stronger the repulsive force, resulting in increased dispersion and dispersion retention. In contrast, when the absolute value of the zeta potential approaches 0, the electrostatic attraction between the particles promotes aggregation and sedimentation, thereby making the particles easily aggregated with each other.
In the present specification, the zeta potential is obtained by measuring the surface potential by electroanalysis (ESA 9800; MATEC APPLIED SCIENCES), and the larger the absolute value of the measured value is, the larger the repulsive force between the particles is, and thus the better the stability is.
In addition, in the description of the present invention, unless otherwise specified, the pH can be measured at room temperature using a typical pH measuring device of Thermo limited, Orion StarA215 model.
CMP slurry composition for polishing silicon oxide film
The CMP slurry composition for polishing a silicon oxide film according to the present invention comprises: abrasive particles (A), a dispersing agent (B), an auxiliary dispersing agent (C), a non-ionic additive (D), a pH adjusting agent (E) and residual ultrapure water (F), wherein the dispersing agent (B) comprises an organic acid compound containing an aromatic ring and one or more carboxyl groups (-COOH), and the pH adjusting agent (E) comprises an organic compound containing one or more hydroxyl groups (-OH) and one carboxyl group (-COOH).
According to the studies of the present inventors, it has been found that it is possible to provide a CMP slurry composition for polishing a silicon oxide film, which can remove a high step of the silicon oxide film by including a specific dispersant and a pH adjustor in a specific ratio, thereby increasing the speed of polishing the silicon oxide film and can realize a multi-selectivity in which a polishing process is stopped when a silicon nitride film or a polysilicon film serving as a polishing stop layer is exposed. Further, it has been found that when the CMP slurry composition for polishing a silicon oxide film is applied during a process of polishing a substrate including a silicon oxide film, a silicon nitride film and a polysilicon film, the amount of dishing defects and scratches generated on the surface of the silicon oxide film can be effectively suppressed.
Hereinafter, the respective components of the CMP slurry composition for polishing a silicon oxide film of the present invention are described in more detail.
(A) Abrasive grain
The abrasive grains are components having a positive charge dispersed on the surface of the polishing target film, and may be at least one selected from metal oxides, metal oxides coated with an organic material or an inorganic material, metal oxides in a colloidal state. Specifically, the metal oxide may be at least one selected from the group consisting of silicon dioxide, cerium oxide, zirconium oxide, aluminum oxide, titanium dioxide, barium titanium dioxide, germanium dioxide, manganese dioxide, and magnesium oxide, wherein colloidal cerium oxide is most preferable, and the colloidal cerium oxide has the highest polishing rate of the silicon oxide film with respect to the content of the abrasive particles.
Average diameter (D) of abrasive grains 50 ) May be 50nm to 200nm, preferably, may be 50nm to 100 nm. When the size of the abrasive grains is less than 50nm, the polishing speed is reduced, so that efficiency in terms of productivity is low, and when it is more than 200nm, dispersion stability may be adversely affected, control of polishing rate and selectivity may be affected, and a large number of surface defects (e.g., dishing defects or scratches) may be caused on the surface of the silicon oxide film as the surface to be polished. Further, the size of the abrasive particles may have different meanings depending on the shape of the abrasive particles. For example, when the abrasive particles are in the shape of a sphere, the size of the abrasive particles refers to the diameter of the sphere, and when in the shape of an ellipse, the size of the abrasive particles may be the diameter of the major axis or the diameter of the minor axis of the ellipse.
The content of the abrasive particles may be 0.1 to 10 wt%, preferably 1 to 8 wt%, based on the total weight of the CMP slurry composition for polishing a silicon oxide film. When the content of the abrasive particles is less than 0.1 wt%, the slurry composition may not exhibit sufficient polishing performance, and when it exceeds 10 wt%, the number of abrasive particles remaining on the surface increases due to the increase in the number of abrasive particles, and a large number of scratches may be generated on the surface to be polished due to the large adsorption of such abrasive particles to the silicon oxide film.
(B) Dispersing agent
The dispersant is a component included for controlling dispersion stability of components contained in the slurry composition, a polishing rate and a zeta potential value of the silicon oxide film, and selectivity to the silicon nitride film when manufacturing the CMP slurry composition for polishing the silicon oxide film, and may include an organic acid compound containing an aromatic ring and one or more carboxyl groups (-COOH).
An aromatic ring structural part included in a molecular structure of the dispersant may be adsorbed onto the surface of the silicon oxide film to serve as a buffer pad for preventing dishing defects, and a carboxyl group (-COOH) structural part may be adsorbed onto the surface of the abrasive grains to increase a dispersion effect, so that polishing selectivity of the silicon oxide film with respect to the silicon nitride film or the polysilicon film during a polishing process may be improved.
Specifically, the dispersant may include at least one cationic organic acid compound selected from the group consisting of picolinic acid, nicotinic diacid, toluic acid, salicylic acid, nitrobenzoic acid, benzoic acid, phenylacetic acid, naphthoic acid, mandelic acid, pyridinedicarboxylic acid, nicotinic acid, isonicotinic acid, quinolinic acid, anthranilic acid, fusaric acid, phthalic acid, isophthalic acid, terephthalic acid, and picolinic acid, and more specifically, may include at least one of picolinic acid, nicotinic diacid, toluic acid, salicylic acid, and nitrobenzoic acid.
The dispersant may be contained in an amount of 0.1 to 10 wt%, preferably 5 to 10 wt%, based on the total weight of the CMP slurry composition for polishing a silicon oxide film. When the content of the dispersant is less than 0.1 wt%, dispersion stability is lowered, and when it is more than 10 wt%, a large number of scratches may be generated on the surface to be polished due to an excessive amount of the dispersant, and polishing efficiency may be lowered.
(C) Auxiliary dispersing agent
The auxiliary dispersant is a component capable of controlling dishing defects and defects on the surface of the polishing target film by lowering the zeta potential of the slurry composition, impairing the strong adsorption property of the semiconductor substrate and the pad, and specifically, the auxiliary dispersant may include an anionic polymer.
The anionic polymer may be selected from the group consisting of polyacrylic acid, polyacrylic acid ammonium salt, polymethacrylic acid ammonium salt, polyacrylic acid-styrene copolymer, polyacrylamide-acrylic acid copolymer, polyacrylic acid-sulfonic acid copolymer, and polyacrylic acid-maleic acid copolymer.
The content of the auxiliary dispersant may be 0.01 to 5 wt%, preferably 0.01 to 2 wt%, based on the total weight of the CMP slurry composition for polishing a silicon oxide film.
When the content of the auxiliary dispersant satisfies the above range, the amount of particles remaining on the surface of the polishing target film can be controlled, thereby preventing surface defects due to the adsorption property of the particles. When the content of the auxiliary dispersant is less than 0.01 wt%, there are disadvantages in that the effect of controlling the zeta potential is reduced and defects and scratches are increased, and when it is more than 5 wt%, dispersion stability is reduced due to an excessive amount of the auxiliary dispersant, and thus polishing efficiency may be reduced.
(D) Non-ionic additives
The nonionic additive is a component that imparts a polishing stop function to the polysilicon film, and specifically, the nonionic additive may include a nonionic linear polymer.
The nonionic linear polymer may include at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polybutylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol-polypropylene glycol copolymer.
The content of the nonionic additive may be 0.01 to 5 wt%, preferably 0.01 to 2 wt%, based on the total weight of the CMP slurry composition for polishing a silicon oxide film. When the content of the nonionic additive is less than 0.01 wt%, the polishing stop function of the polycrystalline silicon film is weakened so that high selectivity for a silicon oxide film cannot be ensured, and when it is more than 5 wt%, dispersion stability is lowered, and thus polishing efficiency may be lowered.
Further, the weight ratio of nonionic additive to auxiliary dispersant can be about 1:1 to 2: 1.
When the weight ratio of the nonionic additive and the auxiliary dispersant satisfies the above range, it is possible to secure polishing selectivity of the silicon oxide film to the silicon nitride film and the polysilicon film and prevent surface defects due to adsorption characteristics of particles on the surface of the polished film.
(E) pH regulator
The CMP slurry composition for polishing a silicon oxide film of the present invention may include an acid-based organic compound containing one or more hydroxyl groups (-OH) and one carboxyl group (-COOH) as a pH adjustor to control and achieve dispersion stability of abrasive particles and a proper polishing rate while keeping zeta potential constant.
Polishing properties vary according to the acid-based pH adjustor, and when an acid-based organic compound containing no carboxyl group (-COOH) is included as the pH adjustor, and when a polysilicon film and a silicon nitride film, which are polishing stopper films, are exposed, abrasive grains may be accumulated on the surface of the silicon oxide film, and thus dishing defects or scratches on the surface of the silicon oxide film may be aggravated. Further, when an acid-based organic compound containing two or more carboxyl groups (-COOH) (e.g., malic acid, citric acid, malonic acid, oxalic acid, succinic acid, tartaric acid, etc.) is included as a pH adjuster, the plurality of carboxyl groups (-COOH) increase attractive force between particles, leading to deterioration of dispersion characteristics of components included in the slurry composition, thereby leading to aggregation in the slurry composition, and thus there is a problem in that a target polishing rate is not secured because a polishing rate of a silicon oxide film is significantly reduced. Further, when an organic compound (for example, formic acid, acetic acid, propionic acid, malonic acid, succinic acid, etc.) not containing a hydroxyl group (-OH) but containing only a carboxyl group (-COOH) is included as a pH adjuster, the amount of dishing defect generated due to the strong acid ionic strength is significantly increased, and thus there is a problem in that polishing quality is significantly reduced.
Therefore, it is preferable that the CMP slurry composition for polishing a silicon oxide film of the present invention includes an acid-based organic compound having one or more hydroxyl groups (-OH) and one carboxyl group (-COOH) (i.e., lactic acid, glycolic acid, hydroxybutyric acid, etc.) as a pH adjustor, and more specifically, lactic acid may be used.
The pH adjuster may be used in an amount necessary to control the target pH.
The lower limit of the pH of the CMP slurry composition for polishing a silicon oxide film of the present invention is preferably 3 or more. That is, when the pH of the composition for polishing is 3 or less, the surface of the silicon oxide film as a polishing object of the slurry composition may be excessively etched.
In addition, the upper limit of the pH of the CMP slurry composition for polishing a silicon oxide film of the present invention is preferably 7 or less. That is, when the pH of the CMP slurry composition for polishing a silicon oxide film is more than 7, the zeta potential may move to the isoelectric point (IEP), and thus slurry aggregation may occur.
(F) Ultrapure water
In addition, the CMP slurry composition for polishing a silicon oxide film of the present invention may include ultrapure water in consideration of the removal of metal ions in the slurry composition and the safety of the dispersed abrasive particles.
At this time, unless otherwise specified, all weights except for the total content of the abrasive and other additive components in the total weight of the CMP slurry composition for polishing a silicon oxide film of the present invention may be the weight of ultrapure water.
(G) Silicon oxide film polishing rate modifier
The CMP slurry composition for polishing a silicon oxide film of the present invention may further comprise a silicon oxide film polishing rate modifier as an additive for controlling the polishing rate by adsorbing to the silicon oxide film as a polishing target film.
The silicon oxide film polishing rate modifier may generally include an amine compound.
The amine compound is not particularly limited as long as it is a compound that is generally used as an insulating film polishing conditioner in manufacturing a silicon oxide film slurry composition, and specifically, the amine compound may include a compound selected from the group consisting of Diethylenetriamine (DETA), triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), bis (hexamethylene) triamine, N- (3-aminopropyl) ethylenediamine, N '-bis (3-aminopropyl) ethylenediamine, N' -tris (3-aminopropyl) ethylenediamine, N-3-aminopropyl-1, 3-diaminopropane, N '-bis (3-aminopropyl) -1, 3-diaminopropane, N' -tris (3-aminopropyl) -1, at least one of 3-diaminopropane, bis- (3-aminopropyl) amine, dipropylenetriamine and tripropylenetetramine.
The content of the silicon oxide film polishing rate modifier may be 0.0001 wt% to 2 wt%, preferably 0.001 wt% to 1 wt%, based on the total weight of the CMP slurry composition for polishing a silicon oxide film. When the content of the silicon oxide film polishing rate modifier is less than 0.0001 wt%, it is difficult to control the polishing rate of the silicon oxide film, and when it exceeds 2 wt%, the polishing rate of the silicon oxide film is lowered, so that a desired polishing rate of the silicon oxide film cannot be secured.
Further, the CMP slurry composition for polishing a silicon oxide film of the present invention is a slurry composition exhibiting a positive charge, and due to the positively charged polishing particles, maintains high dispersion stability to prevent aggregation of abrasive particles, so that the generation of microscratches can be reduced.
Specifically, the zeta potential of the CMP slurry composition for polishing a silicon oxide film of the present invention may be from +30mV to less than +60 mV.
When the zeta potential absolute value of the CMP slurry composition for polishing a silicon oxide film of the present invention satisfies the above range, it is possible to ensure slurry dispersion stability and achieve desired polishing performance. If the absolute value of the zeta potential of the CMP slurry composition for polishing a silicon oxide film is less than +30mV, the amount of aggregates rapidly increases, so that a uniform polishing effect cannot be obtained. In addition, when the absolute value of zeta potential of the CMP slurry composition for polishing a silicon oxide film of the present invention is more than +60mV, there is a disadvantage in that a large amount of abrasive particles may be adsorbed on the surface of the negatively charged silicon oxide film, resulting in excessive defects or scratches on the polishing surface, and may be adsorbed on a polishing pad or a polishing disk to shorten the service life.
Furthermore, the zeta potential is obtained by measuring the surface potential by electroanalysis (ESA 9800; MATEC APPLIED SCIENCES), and the larger the absolute value of the measured value, the larger the repulsive force between the particles, and thus the better the stability.
The CMP slurry composition for polishing a silicon oxide film of the present invention can be used after being concentrated or diluted.
In addition, the CMP slurry composition for polishing a silicon oxide film of the present invention can be controlled so that the polishing selectivity (polishing rate) of the silicon oxide film to the silicon nitride film is 300 or less, and the polishing selectivity (polishing rate) of the silicon oxide film to the polysilicon film is 100 or less.
Specifically, the CMP slurry composition for polishing a silicon oxide film of the present invention can have a ratio of the polishing selectivity (polishing rate) of the silicon nitride film to the polishing selectivity (polishing rate) of the silicon oxide film of 1:100 to 1:300, more specifically 1:150 to 1: 300. In addition, the CMP slurry composition for polishing a silicon oxide film of the present invention may have a ratio of polishing selectivity (polishing rate) to a polysilicon film to polishing selectivity (polishing rate) to a silicon oxide film of 1:30 to 1:100, more specifically 1:50 to 1: 100.
Since the polishing selectivity of the CMP slurry composition for polishing a silicon oxide film of the present invention satisfies the above range, a high polishing selectivity of the silicon oxide film for a silicon nitride film and a polysilicon film can be achieved to stop the polishing process when the silicon nitride film or the polysilicon film is exposed, so that it is possible to ensure high dishing defect control of the surface of the silicon oxide film and effectively suppress the amount of scratches generated thereon.
The above-mentioned CMP slurry composition for polishing a silicon oxide film according to the present invention can control dishing defects on the surface of a silicon oxide film at a pattern density of 50% when polishing a substrate
Or less, and controlling the dishing defect of the silicon oxide film surface at a pattern density of 50% to 75%
Or less, and controlling the dishing defect of the silicon oxide film surface at a pattern density of 25% to 50%
Or smaller.
As described above, the CMP slurry composition for polishing a silicon oxide film of the present invention can be applied to, without limitation, all substrate polishing methods for polishing a substrate having a silicon oxide film formed thereon in the manufacture of a semiconductor device or a display device.
Specifically, such a substrate polishing method may include a Chemical Mechanical Polishing (CMP) process step in which at least one thin film among a silicon nitride film, a polysilicon film, and a mixed film in which the silicon nitride film and the polysilicon film are formed together is used as a polishing stop film, and a silicon oxide film is used as a polishing target film. The CMP process may be, for example, Shallow Trench Isolation (STI) CMP, Source Select Line (SSL) formation (separation) CMP, block-to-block separation CMP, world line planarization (world line planarization) CMP, Inter Layer Dielectrics (ILD) CMP, contact isolation CMP, or the like.
A substrate polishing method using the CMP slurry composition for polishing a silicon oxide film of the present invention can be described with reference to the STI CMP process of fig. 1.
That is, a liner silicon oxide film (not shown) and a liner silicon nitride film 3 are sequentially deposited on the silicon substrate 1, and a photolithography process using a device isolation mask is performed to sequentially and selectively etch the liner silicon nitride film 3 and the liner silicon oxide film (not shown), thereby forming an oxidation resistant film pattern (not shown).
Next, a polycrystalline polysilicon film 5 is deposited on the upper portion of the entire structure, and a silicon oxide film 7 filling the trench is deposited on the upper portion of the polysilicon film 5.
The polycrystalline polysilicon film may include an undoped polysilicon film, a polysilicon film doped with phosphorus (P), or both.
Thereafter, using the CMP slurry composition for polishing a silicon oxide film of the present invention, a CMP process is performed using the pad silicon nitride film 3 and the polycrystalline polysilicon film 5 as a polishing stop film and using the silicon oxide film 7 as a polishing target film, as shown in fig. 1.
At this time, when the pad silicon nitride film 3 and the polysilicon film 5 are simultaneously opened, high polishing selectivity of the silicon oxide film with respect to the pad silicon nitride film 3 and the polysilicon film 5 can be achieved, so that generation of dishing defects, scratches, and the like caused by abrasive grains and the like on the surface of the silicon oxide film can be reduced.
According to one embodiment of the inventionIt can be seen that after polishing the silicon nitride film or the polysilicon film, the amount of dishing defects generated in the silicon oxide film region is as much as
Or smaller. When the polishing slurry composition exhibits excessively high polishing selectivity, the silicon oxide region may be excessively polished, and thus, the amount of generated dishing defects may be increased, but the amount of generated dishing defects may be controlled to be small by including a specific pH adjustor. The CMP slurry composition for polishing a silicon oxide film of the invention has, when polishing is performed, a polishing slurry composition for a silicon oxide film having
Or more, and the polishing selectivity of the silicon oxide film/silicon nitride film is 100 or more, particularly 200 or more, and the polishing selectivity of the silicon oxide film/polysilicon film is 50 or more. In addition, the CMP slurry composition for polishing a silicon oxide film of the present invention has low defect characteristics and has excellent dishing defect properties despite the dispersion of cations.
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples. However, the technical spirit of the present invention is not limited or restricted thereto.
Examples of the invention
Example 1.
Colloidal ceria abrasive particles (2.5 wt%) having a particle size of 80nm were added to ultrapure water while stirring so as not to aggregate, thereby preparing a slurry precursor composition.
Thereafter, picolinic acid (7.5 wt%) as a dispersant, polyacrylic acid (0.4 wt%) as an auxiliary dispersant, and polyethylene glycol (0.5 wt%) as a nonionic additive were added to the slurry precursor composition while stirring, and then lactic acid was added thereto as a pH adjuster to produce a CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45 mV.
At this time, the zeta potential was measured by an electrical analysis method (ESA 9800; MATEC APPLIED SCIENCES), and the pH was measured by a pH measuring device of Orion StarA215 model of Thermo Co., Ltd.
Example 2.
Picolinic acid (7.5 wt%) as a dispersant, polyacrylic acid (0.4 wt%) as an auxiliary dispersant, polyethylene glycol (0.5 wt%) as a nonionic additive, and pentaethylenehexamine (0.005 wt%) as a silicon oxide film polishing rate modifier were mixed with the slurry precursor composition of example 1, and then lactic acid was added thereto as a pH modifier, to produce a CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45 mV.
Example 3.
A CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45mV was produced in the same manner as in example 2, except that glycolic acid was used instead of lactic acid as a pH adjuster.
Comparative example 1.
Colloidal ceria abrasive particles (2.5 wt%) having a particle size of 80nm were added to ultrapure water while stirring so as not to aggregate, thereby preparing a slurry precursor composition
Thereafter, picolinic acid (7.5 wt%) as a dispersant was added to the slurry precursor composition, and then lactic acid was added thereto as a pH adjuster to produce a CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +60 mV.
Comparative example 2.
Colloidal ceria abrasive particles (2.5 wt%) having a particle size of 80nm were added to ultrapure water while stirring so as not to aggregate, thereby preparing a slurry precursor composition.
Thereafter, picolinic acid (7.5 wt%) as a dispersant and polyacrylic acid (0.4 wt%) as an auxiliary dispersant were added to the slurry precursor composition, and lactic acid was then added thereto as a pH adjuster to produce a CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45 mV.
Comparative example 3.
Colloidal ceria abrasive particles (2.5 wt%) having a particle size of 80nm were added to ultrapure water while stirring so as not to aggregate, thereby preparing a slurry precursor composition.
Thereafter, picolinic acid (7.5 wt%) as a dispersant and polyethylene glycol (0.5 wt%) as a nonionic additive were added to the slurry precursor composition, and lactic acid was then added thereto as a pH adjuster to produce a CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +60 mV.
Comparative example 4.
A CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45mV was produced in the same manner as in example 2, except that formic acid was used as a pH adjuster instead of lactic acid.
Comparative example 5.
A CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45mV was produced in the same manner as in example 2, except that acetic acid was used instead of lactic acid as a pH adjuster.
Comparative example 6.
A CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45mV was produced in the same manner as in example 2, except that propionic acid was used instead of lactic acid as a pH adjuster.
Comparative example 7.
A CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45mV was produced in the same manner as in example 2, except that malic acid was used instead of lactic acid as a pH adjuster.
Comparative example 8.
A CMP slurry composition for polishing a silicon oxide film having a pH of 3.5 and a zeta potential of +45mV was produced in the same manner as in example 2, except that citric acid was used instead of lactic acid as a pH adjuster.
[ Table 1]
Examples of the experiments
Experimental example 1.
Using the CMP slurry compositions for polishing silicon oxide films of examples 1 to 3 and the CMP slurry compositions for polishing silicon oxide films of comparative examples 1 to 3 manufactured above, 300mm blanket wafers were polished at a pressure of 3.5psi, and the results are shown in table 2 below. At this time, the number of surface defects (defect, one) was measured using a surface defect analyzer (model SP-2 of KLA-Tencor, Inc.).
The common polishing conditions of examples 1 and 2 and comparative example 1 are as follows.
[ polishing Condition ]
1. Polishing machine: AP-300(CTS Co., Ltd.)
2. Lining: k7(Rohm & Hass Co., Ltd.)
3. Polishing time: 60s
4. Table RPM: 93
5. Spindle RPM: 87
6. Flow rate: 250ml/min
7. The wafers used were: PE-TEOS, Poly, SiN
8. Pressure: 3.5psi
[ Table 2]
Referring to table 2 above, in the case of the CMP slurry compositions for polishing a silicon oxide film of examples 1 to 3, which include an organic compound containing one or more hydroxyl groups (-OH) and one carboxyl group (-COOH) as a pH adjustor and an auxiliary dispersant and a nonionic additive, it was confirmed that the polishing rates for a silicon nitride film and a polysilicon film could be reduced to ensure that the polishing selectivity of the silicon oxide film to the silicon nitride film was 200 or more, the polishing selectivity of the silicon oxide film to the polysilicon film could be controlled in the range of 54 to 96, and the number of surface defects due to particle adsorption could be suppressed to 217 or less.
In contrast, in the case of the CMP slurry composition for polishing a silicon oxide film of comparative example 1 (not including a secondary dispersant or a nonionic additive as an additive), and in the case of the CMP slurry composition for polishing a silicon oxide film of comparative example 3 (not including a secondary dispersant but containing only a nonionic additive as an additive), it can be seen that the effect of improving the polishing selectivity of a silicon oxide film with respect to a silicon nitride film and a polysilicon film is reduced and the number of surface defects caused by particle adsorption is significantly increased when compared with the CMP slurry compositions for polishing a silicon oxide film of examples 1 to 3.
Further, in the case of the CMP slurry composition for polishing a silicon oxide film of comparative example 2 (not including a nonionic additive but including only an auxiliary dispersant as an additive), it can be seen that surface defects caused by particle adsorption are comparable to the CMP slurry composition for polishing a silicon oxide film of the present invention, and the effect of improving the polishing selectivity of a silicon oxide film with respect to a silicon nitride film and a polysilicon film is significantly deteriorated.
Experimental example 2.
Using the CMP slurry compositions for polishing silicon oxide films of examples 2 and 3 and the CMP slurry compositions for polishing silicon oxide films of comparative examples 4 to 8 manufactured above, 300mm blanket wafers were polished at a pressure of 3.5psi, and the results are shown in table 3 below. The common polishing conditions were the same as those of the above experimental example 1.
[ Table 3]
Referring to table 3, it can be confirmed that, when the CMP slurry compositions for polishing a silicon oxide film of examples 2 and 3 were used, the polishing selectivity of the silicon oxide film to the silicon nitride film can be achieved to 200 or more, the polishing selectivity of the silicon oxide film to the polysilicon film can be controlled to 60 or less, and the amount of dishing defects at the surface of the silicon oxide film can be reduced to about 60 or less
Or smaller.
In contrast, in the case of the CMP slurry compositions for polishing a silicon oxide film of comparative examples 4 to 6, which included an organic compound not containing a hydroxyl group (-OH) as a pH adjuster during the polishing process, it can be seen that the amount of dishing defects at the surface of the silicon oxide film was significantly increased to about the same level as that of the CMP slurry compositions for polishing a silicon oxide film of examples 2 and 3
Or more, the polishing quality is significantly reduced.
Further, in the case of the CMP slurry compositions for polishing a silicon oxide film of comparative examples 7 and 8, which included an acid-based organic compound containing two or more carboxyl groups (-COOH) as a pH adjuster, it can be seen that aggregation occurred in the slurry compositions and the polishing rate of the silicon oxide film was significantly reduced as the dispersion characteristics of the components included in the slurry compositions were deteriorated.
Claims (18)
1. A CMP slurry composition for polishing a silicon oxide film, comprising:
abrasive grains (A); a dispersant (B); an auxiliary dispersant (C); a nonionic additive (D); a pH adjuster (E); and residual ultrapure water (F), wherein:
the dispersant (B) includes an organic acid compound having an aromatic ring and one or more carboxyl groups (-COOH); and
the pH adjustor (E) includes an organic compound having one or more hydroxyl groups (-OH) and one carboxyl group (-COOH).
2. The CMP slurry composition according to claim 1, wherein the abrasive particles (a) comprise ceria.
3. The CMP slurry composition according to claim 1, wherein the dispersant (B) comprises: at least one of picolinic acid, nicotinic diacid, toluic acid, salicylic acid, nitrobenzoic acid, benzoic acid, phenylacetic acid, naphthoic acid, mandelic acid, dipicolinic acid, nicotinic acid, isonicotinic acid, quinolinic acid, anthranilic acid, fusaric acid, phthalic acid, isophthalic acid, terephthalic acid, and picolinic acid.
4. The CMP slurry composition according to claim 1, wherein the dispersant (B) is contained in an amount of 0.1 to 10 wt% based on the total weight of the CMP slurry composition for polishing a silicon oxide film.
5. The CMP slurry composition according to claim 1, wherein the auxiliary dispersant (C) includes at least one anionic copolymer selected from the group consisting of polyacrylic acid, polyacrylic acid ammonium salt, polymethacrylic acid ammonium salt, polyacrylic acid-styrene copolymer, polyacrylamide-acrylic acid copolymer, polyacrylic acid-sulfonic acid copolymer, and polyacrylic acid-maleic acid copolymer.
6. The CMP slurry composition according to claim 1, wherein the content of the auxiliary dispersant (C) is 0.01 to 5 wt% based on the total weight of the CMP slurry composition for polishing a silicon oxide film.
7. The CMP slurry composition according to claim 1, wherein the non-ionic additive (D) is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polybutylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol-polypropylene glycol copolymer.
8. The CMP slurry composition according to claim 1, wherein the non-ionic additive (D) is contained in an amount of 0.01 to 5 wt% based on the total weight of the CMP slurry composition for polishing a silicon oxide film.
9. The CMP slurry composition according to claim 1, wherein the pH-adjusting agent (E) includes at least one selected from the group consisting of lactic acid, glycolic acid, and hydroxybutyric acid.
10. The CMP slurry composition according to claim 1, further comprising a silicon oxide film polishing rate modifier (G).
11. The CMP slurry composition according to claim 10, wherein the silicon oxide film polishing rate modifier (G) is selected from the group consisting of Diethylenetriamine (DETA), triethylenetetramine (TETA), Tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), bis (hexamethylene) triamine, N- (3-aminopropyl) ethylenediamine, N ' -bis (3-aminopropyl) ethylenediamine, N ' -tris (3-aminopropyl) ethylenediamine, N-3-aminopropyl-1, 3-diaminopropane, N ' -bis (3-aminopropyl) -1, 3-diaminopropane, N ' -tris (3-aminopropyl) -1, 3-diaminopropane, N ' -tris (3-aminopropyl) -1, 3-diaminopropane, At least one amine compound selected from bis- (3-aminopropyl) amine, dipropylenetriamine and tripropylenetetramine.
12. The CMP slurry composition according to claim 10, wherein the silicon oxide film polishing rate modifier (G) is contained in an amount of 0.0001 to 2 wt% based on the total weight of the CMP slurry composition for polishing a silicon oxide film.
13. The CMP slurry composition according to claim 1, wherein the CMP slurry composition for polishing a silicon oxide film has a pH of 3 to 7.
14. The CMP slurry composition according to claim 1, wherein the zeta potential of the CMP slurry composition for polishing a silicon oxide film is from +30mV to less than +60 mV.
15. The CMP slurry composition according to claim 1, wherein the CMP slurry composition for polishing a silicon oxide film has a ratio of polishing selectivity (polishing rate) to a silicon nitride film to polishing selectivity (polishing rate) to a silicon oxide film of 1:100 to 1: 300.
16. The CMP slurry composition according to claim 1, wherein the CMP slurry composition for polishing a silicon oxide film has a ratio of polishing selectivity (polishing rate) to a polysilicon film to polishing selectivity (polishing rate) to a silicon oxide film of 1:30 to 1: 100.
17. A method for polishing a substrate having a silicon oxide film formed thereon, using the CMP slurry composition for polishing a silicon oxide film according to claim 1.
18. The method of claim 17, wherein the substrate polishing method comprises: the polishing process is performed using at least one thin film of a silicon nitride film, a polysilicon film, and a mixed film in which the silicon nitride film and the polysilicon film are formed together as a polishing stop film, and using a silicon oxide film as a polishing target film.
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