JPH1094955A - Abrasive composed of surface modified secondary cerium oxide particles, and polishing method - Google Patents
Abrasive composed of surface modified secondary cerium oxide particles, and polishing methodInfo
- Publication number
- JPH1094955A JPH1094955A JP19695597A JP19695597A JPH1094955A JP H1094955 A JPH1094955 A JP H1094955A JP 19695597 A JP19695597 A JP 19695597A JP 19695597 A JP19695597 A JP 19695597A JP H1094955 A JPH1094955 A JP H1094955A
- Authority
- JP
- Japan
- Prior art keywords
- polishing
- oxide particles
- cerium
- ammonium
- ceric oxide
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 174
- 238000005498 polishing Methods 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims description 26
- 229910000420 cerium oxide Inorganic materials 0.000 title abstract description 26
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title abstract description 26
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 49
- 230000001590 oxidative effect Effects 0.000 claims abstract description 40
- 150000001450 anions Chemical class 0.000 claims abstract description 22
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 87
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 84
- 229940044927 ceric oxide Drugs 0.000 claims description 83
- 239000012736 aqueous medium Substances 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 15
- 125000000129 anionic group Chemical group 0.000 claims description 14
- 239000004065 semiconductor Substances 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 239000007788 liquid Substances 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 229910052760 oxygen Inorganic materials 0.000 description 24
- 239000000725 suspension Substances 0.000 description 22
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 16
- 125000001453 quaternary ammonium group Chemical group 0.000 description 16
- 239000013078 crystal Substances 0.000 description 15
- 229910052814 silicon oxide Inorganic materials 0.000 description 15
- -1 rare earth compound Chemical class 0.000 description 14
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical class [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 13
- 239000011261 inert gas Substances 0.000 description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910052761 rare earth metal Inorganic materials 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 8
- 239000000908 ammonium hydroxide Substances 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003082 abrasive agent Substances 0.000 description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 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
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- BSVSPZGXUSFFEG-UHFFFAOYSA-N dihydroxy(oxo)silane;tetrakis(2-hydroxyethyl)azanium Chemical compound O[Si](O)=O.OCC[N+](CCO)(CCO)CCO BSVSPZGXUSFFEG-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000501754 Astronotus ocellatus Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 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
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- CKMNQZXKOURUMB-UHFFFAOYSA-N cerium dimer Chemical compound [Ce]#[Ce] CKMNQZXKOURUMB-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- QIICBUVIQUVXPN-UHFFFAOYSA-N cerium(4+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[Ce+4] QIICBUVIQUVXPN-UHFFFAOYSA-N 0.000 description 1
- LQCIDLXXSFUYSA-UHFFFAOYSA-N cerium(4+);tetranitrate Chemical compound [Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LQCIDLXXSFUYSA-UHFFFAOYSA-N 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- DPUCLPLBKVSJIB-UHFFFAOYSA-N cerium;tetrahydrate Chemical compound O.O.O.O.[Ce] DPUCLPLBKVSJIB-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本願発明は、酸化第二セリウ
ム粒子、又はセリウムを主成分とする希土類元素を含む
組成物を焼成と粉砕する事によって得られた酸化第二セ
リウムを主成分とする粒子の粒子表面を改質する事と、
その表面改質された粒子を用いた研磨剤及び研磨方法に
関する。The present invention relates to ceric oxide particles or particles containing cerium oxide as a main component obtained by firing and pulverizing a composition containing a rare earth element containing cerium as a main component. Modifying the particle surface of
The present invention relates to an abrasive and a polishing method using the surface-modified particles.
【０００２】[0002]
【従来の技術】酸化セリウム粒子、又は酸化セリウムを
主体とした組成物の粒子は、無機ガラス、水晶、石英ガ
ラスの研磨剤として性能が良いことが証明されている。
特開昭５８−５５３３４号公報は、酸化セリウム（IV）
水和物を塩の存在下において加熱し、酸化セリウム（I
V）水和物中の凝集された微結晶を解体させてセリウム
化合物を含有する分散性生成物の製造方法が開示されて
いる。上記公報では、塩として金属硝酸塩、金属塩化
物、金属過塩素酸塩に加えて硝酸アンモニウムも使用す
ることが開示されている。その実施態様として、酸化セ
リウム（IV）水和物と硝酸アンモニウムを含有する溶液
を１０５℃で乾燥し、更に３００℃で加熱して酸化第二
セリウムと硝酸塩を含む生成物を得て、この生成物を水
に分散してゾルを得た事が記載されている。しかし、こ
れらのゾルの具体的な用途については記載されていな
い。2. Description of the Related Art Cerium oxide particles or particles of a composition mainly composed of cerium oxide have been proved to have good performance as an abrasive for inorganic glass, quartz and quartz glass.
JP-A-58-55334 discloses cerium (IV) oxide.
The hydrate is heated in the presence of a salt to give cerium oxide (I
V) A method for producing a dispersible product containing a cerium compound by dissolving aggregated microcrystals in a hydrate is disclosed. The publication discloses that ammonium nitrate is used as a salt in addition to metal nitrate, metal chloride, and metal perchlorate. In one embodiment, a solution containing cerium (IV) oxide hydrate and ammonium nitrate is dried at 105 ° C. and heated at 300 ° C. to obtain a product containing ceric oxide and nitrate. Is dispersed in water to obtain a sol. However, no specific use of these sols is described.
【０００３】特開平５−２６２５１９号公報は、水性媒
体中で蓚酸塩、希土類化合物、及びアンモニウム塩を混
合し、３０〜９０℃で生成した沈殿を分離し、得られた
蓚酸希土類アンモニウム複塩を６００〜１２００℃で焼
成する希土類酸化物の製法が開示されている。上記公報
では、アンモニウム塩として硝酸アンモニウム、塩化ア
ンモニウム、酢酸アンモニウム等を使用し、希土類化合
物として硝酸セリウムを使用する事が記載されている。JP-A-5-262519 discloses an oxalate, a rare earth compound, and an ammonium salt in an aqueous medium, and the precipitate formed at 30 to 90 ° C. is separated to obtain a rare earth ammonium oxalate double salt. A method for producing a rare earth oxide fired at 600 to 1200 ° C. is disclosed. The above publication describes using ammonium nitrate, ammonium chloride, ammonium acetate, or the like as an ammonium salt, and using cerium nitrate as a rare earth compound.
【０００４】[0004]
【発明が解決しようとする課題】半導体デバイスのシリ
コン酸化膜（ＳｉＯ2膜）、フォトマスク用石英ガラ
ス、水晶発振器の水晶片等は高い平坦性を有する研磨面
が求められるようになり、その為にサブミクロン以下の
粒子径を有する研磨剤を使用する必要性がある。これら
の研磨において、使用する研磨剤の粒子径を小さくする
と機械的な研磨力が低下するため研磨速度が遅くなり、
研磨工程の生産性の低下により製品の価格上昇等を招
く。研磨剤粒子の粒子径を変えずに研磨速度を向上する
ことが出来れば、研磨工程の生産性が向上する。A silicon oxide film (SiO 2 film) of a semiconductor device, a quartz glass for a photomask, a crystal piece of a crystal oscillator, and the like require a polished surface having high flatness. It is necessary to use an abrasive having a particle diameter of submicron or less. In these polishing, if the particle diameter of the abrasive used is reduced, the polishing rate is reduced because the mechanical polishing force is reduced,
A decrease in the productivity of the polishing process causes an increase in the price of the product. If the polishing rate can be improved without changing the particle size of the abrasive particles, the productivity of the polishing step will be improved.
【０００５】一方、半導体デバイスの層間膜の平坦化に
おいて、シリコン酸化膜（ＳｉＯ2膜）をストッパー
（研磨を停止する層）とした場合に、有機樹脂膜等の軟
らかい膜の研磨が進行しシリコン酸化膜（ＳｉＯ2膜）
等の硬い膜の部分で研磨が停止する様に、シリコン酸化
膜（ＳｉＯ2膜）等の硬い膜を研磨せずに有機樹脂膜等
の軟らかい膜のみを研磨できれば微細な加工技術への展
開が期待できる。On the other hand, when a silicon oxide film (SiO 2 film) is used as a stopper (a layer for stopping polishing) in flattening an interlayer film of a semiconductor device, polishing of a soft film such as an organic resin film progresses and silicon Oxide film (SiO 2 film)
If polishing can be stopped only at a soft film such as an organic resin film without polishing a hard film such as a silicon oxide film (SiO 2 film) so that polishing stops at a portion of a hard film such as Can be expected.
【０００６】本願発明は、酸化第二セリウム粒子、又は
セリウムを主成分とする希土類元素を含む組成物を焼成
と粉砕する事によって得られた酸化第二セリウムを主成
分とする粒子を、アンモニウム塩の存在下に水性媒体中
で５０〜２５０℃の温度で加熱処理した酸化第二セリウ
ム粒子、又は酸化第二セリウムを主成分とする粒子から
なる研磨剤を提供するものである。この研磨剤は表面改
質された酸化第二セリウム粒子であって、表面改質に用
いる薬剤の種類により得られる酸化第二セリウム粒子か
らなる研磨剤は、研磨速度の制御や研磨面の性質に合わ
せた研磨方法が可能である。The present invention relates to a method for producing ceric oxide particles or particles containing cerium oxide as a main component obtained by firing and pulverizing a composition containing a rare earth element containing cerium as a main component. The present invention provides an abrasive comprising ceric oxide particles heat-treated in an aqueous medium at a temperature of 50 to 250 ° C. in the presence of cerium oxide or particles containing ceric oxide as a main component. This abrasive is ceric oxide particles whose surface has been modified, and the abrasive composed of ceric oxide particles obtained by the type of the agent used for surface modification can control the polishing rate and improve the properties of the polished surface. A combined polishing method is possible.
【０００７】[0007]
【課題を解決するための手段】本願発明は、アンモニウ
ム塩の存在下に水性媒体中で５０〜２５０℃の温度で加
熱処理した酸化第二セリウム粒子からなる研磨剤であ
る。また、本願発明はアンモニウム塩の存在下に水性媒
体中で５０〜２５０℃の温度で加熱処理した酸化第二セ
リウム粒子からなる研磨剤を使用する研磨方法である。SUMMARY OF THE INVENTION The present invention is an abrasive comprising ceric oxide particles heat-treated at 50 to 250 ° C. in an aqueous medium in the presence of an ammonium salt. Further, the present invention is a polishing method using an abrasive made of ceric oxide particles which has been heat-treated at a temperature of 50 to 250 ° C. in an aqueous medium in the presence of an ammonium salt.
【０００８】[0008]
【発明の実施の形態】原料として用いる酸化第二セリウ
ム粒子は特別に制限はなく、公知の方法で製造された酸
化第二セリウム粒子を用いることが出来る。例えば、水
酸化第一セリウム、水酸化第二セリウム、硝酸第一セリ
ウム、塩基性硝酸セリウム（IV）、塩化第一セリウム、
塩化第二セリウム、炭酸第一セリウム、炭酸第二セリウ
ム、塩基性硫酸第一セリウム、塩基性硫酸第二セリウ
ム、蓚酸第一セリウム、蓚酸第二セリウム等のセリウム
塩や、これらを主成分とする希土類化合物を１０００℃
で焼成した後、粉砕、分級する乾式法で製造した粒子径
０．０５〜５μｍの結晶性酸化第二セリウム粒子を使用
することが出来る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The ceric oxide particles used as a raw material are not particularly limited, and ceric oxide particles produced by a known method can be used. For example, cerous hydroxide, ceric hydroxide, cerous nitrate, basic cerium (IV) nitrate, cerous chloride,
Cerium salts such as ceric chloride, cerous carbonate, ceric carbonate, basic ceric sulfate, basic ceric sulfate, ceric oxalate, ceric oxalate, etc. 1000 ℃ of rare earth compound
After sintering, crystalline ceric oxide particles having a particle diameter of 0.05 to 5 μm and manufactured by a dry method of pulverizing and classifying can be used.
【０００９】特に原料として用いる酸化第二セリウム粒
子は、不活性ガス雰囲気下に水性媒体中でセリウム（II
I）塩とアルカリ性物質を３〜３０の（ＯＨ）／（Ｃｅ
3+）モル比で反応させて水酸化セリウム（III）の懸濁
液を生成した後、直ちに該懸濁液に大気圧下、１０〜９
５℃の温度で酸素又は酸素を含有するガスを吹き込む方
法で製造された０．００５〜５μｍ（ミクロンメート
ル）の粒子径を有する結晶性酸化第二セリウム粒子を使
用することが好ましい。In particular, ceric oxide particles used as a raw material are prepared in an aqueous medium under an inert gas atmosphere.
I) The salt and the alkaline substance are mixed with 3 to 30 (OH) / (Ce)
3+ ) to produce a suspension of cerium (III) hydroxide by molar ratio and immediately add
It is preferable to use crystalline ceric oxide particles having a particle size of 0.005 to 5 μm (micrometer) manufactured by a method of blowing oxygen or a gas containing oxygen at a temperature of 5 ° C.
【００１０】上記原料として用いる酸化第二セリウム粒
子の製造方法（原料粒子の製法）では第１工程として、
不活性ガス雰囲気下に水性媒体中でセリウム（III）塩
とアルカリ性物質を３〜３０の（ＯＨ）／（Ｃｅ3+）モ
ル比で反応させて水酸化セリウム（III）、即ち水酸化
第一セリウムの懸濁液を生成する事である。不活性ガス
雰囲気下での反応とは、例えばガス置換可能な撹拌機と
温度計を装備した反応容器を用いて、水性媒体中でセリ
ウム（III）塩とアルカリ性物質を反応させるものであ
る。水性媒体とは、通常、水が用いられるが、少量の水
溶性有機溶媒を含有させることもできる。ガス置換は水
性媒体中に細管状のガス導入口を水没させて、不活性ガ
スを水性媒体中に吹き込み反応容器の水性媒体上部に取
り付けられた排出口よりガスを流出させて、反応容器内
に不活性ガスを充満させる。不活性ガスの置換が終了後
に反応を開始することが好ましい。この反応容器はステ
ンレス鋼、グラスライニング等の材質を使用する事が出
来る。この時、反応容器内は大気圧下とする事が望まし
く、従ってガスの流入量と流出量はほぼ同一量である事
が好ましい。ガスの流入量及び流出量は、反応槽の容積
１リットルに対して０．０１〜２０リットル／分とする
事が好ましい。In the method for producing ceric oxide particles used as the raw material (the method for producing the raw material particles), as a first step,
Cerium (III) hydroxide, that is, a cerium (III) hydroxide, i.e., a hydroxide having a molar ratio of 3 to 30 (OH) / (Ce3 + ) in an aqueous medium under an inert gas atmosphere, is reacted. To produce a cerium suspension. The reaction in an inert gas atmosphere is, for example, a reaction between a cerium (III) salt and an alkaline substance in an aqueous medium using a reaction vessel equipped with a gas-replaceable stirrer and a thermometer. The aqueous medium is usually water, but may contain a small amount of a water-soluble organic solvent. Gas replacement involves submerging a tubular gas inlet in an aqueous medium, blowing an inert gas into the aqueous medium, and allowing the gas to flow out from an outlet attached to the upper portion of the aqueous medium in the reaction vessel, and into the reaction vessel. Fill with inert gas. It is preferable to start the reaction after the replacement of the inert gas is completed. The reaction vessel can be made of a material such as stainless steel or glass lining. At this time, it is desirable that the inside of the reaction vessel is under atmospheric pressure. Therefore, it is preferable that the inflow amount and outflow amount of the gas are substantially the same. The gas inflow and outflow are preferably 0.01 to 20 liters / minute with respect to 1 liter of the volume of the reaction tank.
【００１１】不活性ガスとしては、窒素ガス、アルゴン
ガス等が挙げられるが、特に窒素ガスが好ましい。原料
粒子の製法ではセリウム（III）塩として、例えば、硝
酸第一セリウム、塩化第一セリウム、硫酸第一セリウ
ム、炭酸第一セリウム、硝酸アンモニウムセリウム（II
I）等が挙げられる。上記のセリウム（III）塩は、単独
または混合物として使用することができる。Examples of the inert gas include a nitrogen gas and an argon gas, and a nitrogen gas is particularly preferable. In the production method of the raw material particles, as a cerium (III) salt, for example, cerous nitrate, cerous chloride, cerous sulfate, cerous carbonate, cerium ammonium nitrate (II)
I) and the like. The above cerium (III) salts can be used alone or as a mixture.
【００１２】原料粒子の製法ではアルカリ性物質とし
て、水酸化ナトリウム、水酸化カリウム等のアルカリ金
属水酸化物またはアンモニア、アミン、水酸化第四級ア
ンモニウム等の有機塩基が挙げられるが、特にアンモニ
ア、水酸化ナトリウム、水酸化カリウムが好ましく、こ
れらを単独または混合物として使用することができる。
上記のセリウム（III）塩及びアルカリ性物質を水性媒
体に添加して反応容器中で反応させることもできるが、
セリウム（III）塩水溶液とアルカリ性物質水溶液を作
成して、この両水溶液を混合して反応する事もできる。
セリウム（III）塩は水性媒体中で１〜５０重量％濃度
で使用することが好ましい。In the method for producing the raw material particles, examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and organic bases such as ammonia, amine and quaternary ammonium hydroxide. Sodium oxide and potassium hydroxide are preferred, and these can be used alone or as a mixture.
The cerium (III) salt and the alkaline substance described above can be added to an aqueous medium and reacted in a reaction vessel.
A cerium (III) salt aqueous solution and an alkaline substance aqueous solution can be prepared, and the two aqueous solutions can be mixed and reacted.
The cerium (III) salt is preferably used in an aqueous medium at a concentration of 1 to 50% by weight.
【００１３】原料粒子の製法ではセリウム（III）塩と
アルカリ性物質の割合は、（ＯＨ）／（Ｃｅ3+）モル比
で３〜３０、好ましくは６〜１２である。（ＯＨ）／
（Ｃｅ 3+）モル比が３より小さい場合は、セリウム（II
I）塩が完全に水酸化セリウム（III）に中和されず、一
部セリウム（III）塩として懸濁液中に残存する為に好
ましくない。このセリウム（III）塩は、水酸化セリウ
ム（III）よりもセリウム（IV）への酸化反応速度が非
常に遅いため、水酸化セリウム（III）とセリウム（II
I）塩が共存した場合、結晶性酸化第ニセリウムの核生
成速度及び結晶成長速度の制御ができなくなるため、粒
子径分布が広くなり粒子径が均一にならないので好まし
くない。また、（ＯＨ）／（Ｃｅ3+）モル比が３０より
大きい場合は、得られる結晶性酸化第ニセリウム粒子の
結晶性が低下し、研磨剤として利用した場合は研磨速度
の低下が起こるので好ましくない。また、得られる粒子
の粒子径分布が広くなり粒子径が均一にならないので好
ましくない。In the method for producing the raw material particles, a cerium (III) salt is used.
The ratio of the alkaline substance is (OH) / (Ce3+) Molar ratio
And 3 to 30, preferably 6 to 12. (OH) /
(Ce 3+) When the molar ratio is less than 3, cerium (II
I) The salt is not completely neutralized by cerium (III) hydroxide,
Cerium (III) salt to remain in suspension
Not good. This cerium (III) salt is
Oxidation rate to cerium (IV) is lower than
Cerium (III) hydroxide and cerium (II
I) Nucleation of crystalline ceric oxide in the presence of salt
Since the growth rate and crystal growth rate cannot be controlled,
Preferred because the particle size distribution is wide and the particle size is not uniform
I don't. Also, (OH) / (Ce3+) More than 30 molar ratio
If it is large, the resulting crystalline ceric oxide particles
When the crystallinity is reduced and used as an abrasive, the polishing rate
Is undesirably reduced. Also, the resulting particles
Particle size distribution is wide and the particle size is not uniform.
Not good.
【００１４】原料粒子の製法では上記第１工程での反応
時間は、仕込量の大きさにより異なり概ね１分〜２４時
間である。上記の第１工程で、不活性ガスの代わりに、
空気等の酸素を含有するガス中でセリウム（III）塩と
アルカリ性物質を反応させると、生成した水酸化セリウ
ム（III）が酸素と接触し、次々にセリウム（IV）塩や
酸化第二セリウムに変化するために、水性媒体中に酸化
第二セリウムの核が多数発生して、得られる酸化第二セ
リウム粒子の粒子径分布が広くなり粒子径が均一になら
ないので好ましくない。In the method for producing the raw material particles, the reaction time in the first step varies depending on the amount of the charge and is generally about 1 minute to 24 hours. In the above first step, instead of the inert gas,
When a cerium (III) salt reacts with an alkaline substance in an oxygen-containing gas such as air, the produced cerium (III) hydroxide comes into contact with oxygen, and then cerium (IV) salt and ceric oxide one after another. Due to the change, a large number of cerium oxide nuclei are generated in the aqueous medium, and the particle size distribution of the obtained ceric oxide particles is widened, and the particle size is not uniform, which is not preferable.
【００１５】原料粒子の製法では、その第２工程とし
て、第１工程で生成した懸濁液に大気圧下、１０〜９５
℃の温度で酸素又は酸素を含有するガスを吹き込むこと
によって０．００５〜５μｍの粒子径を有する結晶性酸
化第二セリウム粒子を製造するものである。第１工程で
得られた懸濁液中の水酸化セリウム（III）を酸素又は
酸素を含有するガスの存在下に、セリウム（IV）塩を経
て結晶性の高い酸化第二セリウム粒子を製造する工程で
ある。酸素又は酸素を含有するガスとは、ガス状の酸
素、又は空気、若しくは酸素と不活性ガスとの混合ガス
が挙げられる。不活性ガスは窒素、アルゴン等が挙げら
れる。混合ガスを用いる場合は混合ガス中での酸素の含
有量は１体積％以上が好ましい。その第２工程では製法
上の容易さから特に空気を用いることが好ましい。In the method for producing the raw material particles, as a second step, the suspension produced in the first step is added under atmospheric pressure to 10 to 95%.
By blowing oxygen or a gas containing oxygen at a temperature of ° C., crystalline ceric oxide particles having a particle size of 0.005 to 5 μm are produced. Cerium (III) hydroxide in the suspension obtained in the first step is produced through cerium (IV) salt in the presence of oxygen or a gas containing oxygen to produce highly crystalline ceric oxide particles. It is a process. The oxygen or the gas containing oxygen includes gaseous oxygen, air, or a mixed gas of oxygen and an inert gas. Examples of the inert gas include nitrogen and argon. When a mixed gas is used, the content of oxygen in the mixed gas is preferably 1% by volume or more. In the second step, it is particularly preferable to use air from the viewpoint of easiness in the production method.
【００１６】原料粒子の製法の上記第２工程は第１工程
に続きその同じ反応容器内で行われ、第１工程の不活性
ガスの導入に続き、その不活性ガスを直ちに酸素又は酸
素を含有するガスに代えて連続してガスを導入するもの
である。即ち、第１工程で得られた懸濁液中に、該懸濁
液中に水没した細管状のガス導入口から酸素又は酸素を
含有するガスを吹き込むことによって行われる。The second step of the method for producing raw material particles is carried out in the same reaction vessel following the first step, and following the introduction of the inert gas in the first step, the inert gas is immediately replaced with oxygen or oxygen-containing gas. The gas is introduced continuously instead of the gas to be used. That is, oxygen or a gas containing oxygen is blown into the suspension obtained in the first step from a thin gas inlet port submerged in the suspension.
【００１７】原料粒子の製法の第２工程は大気圧下で行
われる為に、懸濁液中に導入された量とほぼ同量のガス
が反応容器内の懸濁液上部に取り付けられた排出口より
排出される。原料粒子の製法の第２工程では、懸濁液中
に吹き込む酸素又は酸素を含有するガスの総量は、水酸
化セリウム（III）を酸化第二セリウムに変化させる事
が可能な量であり、（Ｏ2 ）／（Ｃｅ3+）のモル比で１
以上とする事が好ましい。上記モル比が１未満の場合は
懸濁液中に水酸化セリウム(III）が残り、これが第２工
程の終了後の洗浄中に空気中の酸素に接触することで、
微小粒子が生成する事があり、得られる酸化第二セリウ
ム粒子の粒子径分布が広くなり粒子径が均一と成らない
ので好ましくない。Since the second step of the method for producing the raw material particles is carried out under atmospheric pressure, almost the same amount of gas as the amount introduced into the suspension is discharged from the upper part of the suspension in the reaction vessel. It is discharged from the exit. In the second step of the method for producing the raw material particles, the total amount of oxygen or oxygen-containing gas blown into the suspension is an amount capable of converting cerium (III) hydroxide to ceric oxide, O 2 ) / (Ce 3+ ) molar ratio of 1
It is preferable to make the above. When the molar ratio is less than 1, cerium (III) hydroxide remains in the suspension, which comes into contact with oxygen in the air during washing after the completion of the second step,
Fine particles may be formed, and the obtained ceric oxide particles are not preferable because the particle size distribution of the obtained ceric oxide particles is widened and the particle size is not uniform.
【００１８】原料粒子の製法の第２工程でガスの単位時
間当たりの流入量及び流出量は、反応槽の容積１リット
ルに対して０．０１〜５０リットル／分とする事が好ま
しい。原料粒子の製法の第１工程での不活性ガスの吹き
込みと第２工程での酸素又は酸素を含有するガスの吹き
込みとが時間的に連続していない場合は、第１工程で得
られた懸濁液の表面が空気と接触することになり、表面
層に粒子径が大小さまざまな酸化第二セリウム粒子を含
む層が生成するので、その後行われる第２工程で得られ
る酸化第二セリウム粒子の粒子径が均一にならないので
好ましくない。In the second step of the process for producing the raw material particles, the inflow and outflow of gas per unit time are preferably 0.01 to 50 liter / min per 1 liter of the volume of the reaction vessel. If the blowing of the inert gas in the first step of the method for producing the raw material particles and the blowing of oxygen or a gas containing oxygen in the second step are not temporally continuous, the suspension obtained in the first step may be used. The surface of the suspension will come into contact with air, and a layer containing ceric oxide particles of various sizes will be generated in the surface layer. It is not preferable because the particle diameter is not uniform.
【００１９】この第２工程は、懸濁液中に酸素又は酸素
を含有するガスが均一に存在するように懸濁液をディス
パー等の撹拌機で撹拌しながら行うことが好ましい。ガ
スの吹き込みによって懸濁液自体が撹拌される場合は、
撹拌機での撹拌は必ずしも必要ではない。原料粒子の製
法での水酸化セリウム（III）を酸化して結晶性酸化第
二セリウム粒子を生成させることは、結晶性酸化第二セ
リウム粒子の核生成とその結晶成長が行われることであ
り、核生成速度及び結晶成長速度は、セリウム塩の濃
度、アルカリ性物質の濃度、反応温度、酸化性水溶液の
濃度及び供給量などで制御することができる。また上記
方法では、核生成及び結晶成長時のセリウム塩の濃度、
アルカリ性物質の濃度、反応温度、酸化性水溶液の濃度
及び供給量などを互いに自由に変えることができる。こ
れらの要因を調整することにより、０．００５〜５μｍ
の粒子径範囲で任意に粒子径を制御することが出来る。This second step is preferably carried out while stirring the suspension with a stirrer such as a disper so that oxygen or a gas containing oxygen is uniformly present in the suspension. If the suspension itself is agitated by gas injection,
Stirring with a stirrer is not necessary. Oxidizing cerium (III) hydroxide in the method of producing the raw material particles to produce crystalline cerium oxide particles means that nucleation and crystal growth of crystalline cerium oxide particles are performed, The nucleation rate and crystal growth rate can be controlled by the concentration of the cerium salt, the concentration of the alkaline substance, the reaction temperature, the concentration of the oxidizing aqueous solution, the supply amount, and the like. In the above method, the concentration of cerium salt during nucleation and crystal growth,
The concentration of the alkaline substance, the reaction temperature, the concentration and the supply amount of the oxidizing aqueous solution can be freely changed. By adjusting these factors, 0.005 to 5 μm
The particle diameter can be arbitrarily controlled within the particle diameter range described above.
【００２０】原料粒子の製法の第２工程での反応温度は
粒子径の制御に大きく寄与する。例えば、３０℃の温度
で核生成及び結晶成長を行った場合、５ｎｍ〜１０ｎｍ
（ナノメートル）の粒子径を有する結晶性酸化第二セリ
ウム粒子が得られ、また８０℃の温度で核生成及び結晶
成長を行った場合は、８０ｎｍ〜１００ｎｍの粒子径を
有する結晶性酸化第二セリウム粒子が得られる。そし
て、更に８０ｎｍ〜１００ｎｍの粒子径を有する結晶性
酸化第二セリウム粒子を種結晶にして、滋養物として水
酸化セリウム（III）を供給しながら結晶成長させるこ
とにより、１μｍ〜３μｍの結晶性酸化第二セリウム粒
子が得られる。即ち、第１工程で原料を仕込む際に、８
０ｎｍ〜１００ｎｍの粒子径を有する結晶性酸化第二セ
リウム粒子を最初から添加して第１工程に続き第２工程
を行うものである。The reaction temperature in the second step of the process for producing the raw material particles greatly contributes to the control of the particle size. For example, when nucleation and crystal growth are performed at a temperature of 30 ° C., 5 nm to 10 nm
(Nanometer) crystalline cerium oxide particles having a particle diameter of 80 nm are obtained, and when nucleation and crystal growth are performed at a temperature of 80 ° C., the crystalline cerium oxide particles having a particle diameter of 80 nm to 100 nm are obtained. Cerium particles are obtained. Further, the crystalline cerium oxide particles having a particle diameter of 80 nm to 100 nm are used as seed crystals, and the crystals are grown while supplying cerium (III) hydroxide as a nutrient, whereby the crystalline oxidized particles of 1 μm to 3 μm are formed. Cerium cerium particles are obtained. That is, when charging the raw materials in the first step, 8
The second step is performed after the first step by adding crystalline cerium oxide particles having a particle diameter of 0 nm to 100 nm from the beginning.
【００２１】原料粒子の製法において、水酸化セリウム
（III）の懸濁液を空気などの酸化剤を用いて常圧下で
１０〜９５℃の温度で反応する代わりに、硝酸等の酸化
性物質を含有する水酸化セリウム（III）の懸濁液を１
００℃以上の温度で水熱処理した場合は、所望とする粒
子径範囲以下（例えば、３０ｎｍ以下）の結晶性酸化第
ニセリウム粒子しか得られず、そして硝酸等の酸化性物
質を含有する水酸化セリウム（III）の懸濁液を１００
℃以下の温度で処理した場合は、反応が不十分で未反応
物が残る。In the method of producing the raw material particles, instead of reacting a suspension of cerium (III) hydroxide with an oxidizing agent such as air under normal pressure at a temperature of 10 to 95 ° C., an oxidizing substance such as nitric acid is used. The cerium (III) hydroxide suspension containing
When the hydrothermal treatment is performed at a temperature of 00 ° C. or more, only crystalline nissium oxide particles having a particle size of a desired particle size or less (eg, 30 nm or less) can be obtained, and cerium hydroxide containing an oxidizing substance such as nitric acid can be obtained. 100 ml of the suspension of (III)
When the treatment is performed at a temperature of not more than ℃, the reaction is insufficient and unreacted substances remain.
【００２２】また、酸化性物質を含有しない水酸化セリ
ウム（III）の懸濁液を１００℃以上で水熱処理した場
合、結晶性酸化第ニセリウム粒子は得られない。原料粒
子の製法において得られた酸化第ニセリウム粒子は、反
応装置よりスラリーとして取り出し、限外濾過法または
フィルタープレス洗浄法などにより洗浄することによ
り、不純物を除去することが出来る。When a suspension of cerium (III) hydroxide containing no oxidizing substance is subjected to hydrothermal treatment at 100 ° C. or higher, crystalline nissium oxide particles cannot be obtained. The ceric oxide particles obtained in the method for producing the raw material particles can be removed as a slurry from the reactor and washed by an ultrafiltration method or a filter press washing method to remove impurities.
【００２３】上記原料粒子の製法によって得られる酸化
第二セリウム粒子は、透過型電子顕微鏡（ＴＥＭ）観察
を行ったところ０．００５〜５μｍの粒子径であり、ま
た酸化第二セリウム粒子を１１０℃で乾燥して、Ｘ線回
折装置により回折パターンを測定したところ、回折角度
２θ＝２８．６°、４７．５°、及び５６．４°、に主
ピークを有し、ＡＳＴＭカードＮｏ３４−３９４に記載
の立方晶系の結晶性の高い酸化第二セリウム粒子であ
る。またこの酸化第二セリウム粒子のガス吸着法（ＢＥ
Ｔ法）による比表面積値は、２〜２００ｍ2／ｇであ
る。The ceric oxide particles obtained by the above method for producing the raw material particles have a particle size of 0.005 to 5 μm when observed by a transmission electron microscope (TEM). And the diffraction pattern was measured by an X-ray diffractometer. As a result, it was found that ASTM cards No. 34-394 had main peaks at diffraction angles 2θ = 28.6 °, 47.5 °, and 56.4 °. It is a cubic cerium oxide particle having high crystallinity according to the above description. In addition, the gas adsorption method for the ceric oxide particles (BE)
The specific surface area value by T method) is 2 to 200 m 2 / g.
【００２４】本願発明の水性媒体とは、通常、水が用い
られるが、少量の水溶性有機媒体を含有させることが出
来る。本願発明に用いるアンモニウム塩は、陰イオン成
分が非酸化性成分のアンモニウム塩を使用する事が出来
る。この非酸化性の陰イオン成分を有するアンモニウム
塩は、炭酸アンモニウム、炭酸水素アンモニウムが最も
好ましく、これらを単独又は混合物として使用すること
が出来る。As the aqueous medium of the present invention, water is usually used, but a small amount of a water-soluble organic medium can be contained. As the ammonium salt used in the present invention, an ammonium salt whose anionic component is a non-oxidizing component can be used. The ammonium salt having a non-oxidizing anion component is most preferably ammonium carbonate or ammonium hydrogen carbonate, and these can be used alone or as a mixture.
【００２５】上記の非酸化性の陰イオン成分を有するア
ンモニウム塩は、水性媒体中の〔ＮＨ4 +〕／〔Ｃｅ
Ｏ2〕モル比として０．１〜３０が好ましく、また水性
媒体中での上記アンモニウム塩の濃度は１〜３０重量％
とする事が好ましい。陰イオン成分が非酸化性成分のア
ンモニウム塩を用い水性媒体中で加熱する場合は、５０
〜２５０℃、好ましくは５０〜１８０℃の温度で加熱処
理して、表面改質された結晶性酸化第二セリウム粒子が
得られる。加熱時間は１０分〜４８時間とする事が出来
る。加熱処理温度が１００℃以下の場合は開放系の反応
容器を用いて行われるが、１００℃を越える温度ではオ
ートクレーブ装置や超臨界処理装置を用いて行われる。
加熱処理された酸化第二セリウム粒子は処理層よりスラ
リーとして取り出し、限外濾過法やフィルタープレス法
により洗浄し、不純物を取り除くことが出来る。The above ammonium salt having a non-oxidizing anion component can be obtained by mixing [NH 4 + ] / [Ce in an aqueous medium.
O 2 ] molar ratio is preferably 0.1 to 30, and the concentration of the ammonium salt in the aqueous medium is 1 to 30% by weight.
It is preferable that When an anionic component is heated in an aqueous medium using an ammonium salt of a non-oxidizing component, 50
Heat treatment at a temperature of from about 250 ° C. to about 250 ° C., preferably from about 50 ° C. to 180 ° C., gives surface-modified crystalline ceric oxide particles. The heating time can be 10 minutes to 48 hours. When the heat treatment temperature is 100 ° C. or lower, the heat treatment is performed using an open reaction vessel. When the heat treatment temperature exceeds 100 ° C., the heat treatment is performed using an autoclave apparatus or a supercritical processing apparatus.
The heat-treated ceric oxide particles can be taken out of the treatment layer as a slurry and washed by an ultrafiltration method or a filter press method to remove impurities.
【００２６】非酸化性の陰イオン成分を有するアンモニ
ウム塩の存在下に加熱処理して表面改質された酸化第二
セリウム粒子は、容易に水性媒体に分散して研磨液とす
る事が出来る。この水性媒体は水を使用する事が好まし
い。非酸化性の陰イオン成分を有するアンモニウム塩の
存在下に水性媒体中で加熱処理して表面改質された酸化
第二セリウム粒子を含有するゾルは、洗浄により不純物
を取り除いた後、第４級アンモニウムイオン（ＮＲ4 +、
但しＲは有機基である。）を、（ＮＲ4 +）／（Ｃｅ
Ｏ2）のモル比で０．００１〜１の範囲に含有させる事
により研磨液の安定性が向上するので好ましい。第４級
アンモニウムイオンは、第４級アンモニウムシリケー
ト、ハロゲン化第４級アンモニウム、水酸化第４級アン
モニウム、又はこれらの混合物を添加する事によって与
えられ、特に第４級アンモニウムシリケート、水酸化第
４級アンモニウムの添加が好ましい。Ｒはメチル基、エ
チル基、プロピル基、ヒドロキシエチル基、及びベンジ
ル基等が挙げられる。この第４級アンモニウム化合物と
しては、例えばテトラメチルアンモニウムシリケート、
テトラエチルアンモニウムシリケート、テトラエタノー
ルアンモニウムシリケート、モノエチルトリエタノール
アンモニウムシリケート、トリメチルベンジルアンモニ
ウムシリケート、水酸化テトラメチルアンモニウム、水
酸化テトラエチルアンモニウムが挙げられる。The ceric oxide particles surface-modified by heat treatment in the presence of an ammonium salt having a non-oxidizing anionic component can be easily dispersed in an aqueous medium to form a polishing liquid. This aqueous medium preferably uses water. The sol containing cerium oxide particles surface-modified by heat treatment in an aqueous medium in the presence of an ammonium salt having a non-oxidizing anionic component is subjected to quaternary elimination after removing impurities by washing. Ammonium ion (NR 4 + ,
However, R is an organic group. ) To (NR 4 + ) / (Ce
O 2 ) is preferably contained in a molar ratio of 0.001 to 1 because the stability of the polishing liquid is improved. The quaternary ammonium ion is provided by adding a quaternary ammonium silicate, a quaternary ammonium halide, a quaternary ammonium hydroxide, or a mixture thereof, particularly a quaternary ammonium silicate, a quaternary ammonium hydroxide. The addition of quaternary ammonium is preferred. R includes a methyl group, an ethyl group, a propyl group, a hydroxyethyl group, a benzyl group and the like. Examples of the quaternary ammonium compound include tetramethylammonium silicate,
Examples include tetraethylammonium silicate, tetraethanolammonium silicate, monoethyltriethanolammonium silicate, trimethylbenzylammonium silicate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide.
【００２７】また、少量の酸又は塩基を含有することも
できる。研磨液のｐＨは、２〜１２が好ましい。上記研
磨液（ゾル）は、水溶性酸を〔Ｈ+〕／〔ＣｅＯ2〕モル
比で０．００１〜１の範囲に含有させることにより酸性
研磨液（ゾル）にする事が出来る。この酸性ゾルは２〜
６のｐＨを持つ。上記水溶性酸は、例えば塩化水素、硝
酸等の無機酸、蟻酸、酢酸、蓚酸、酒石酸、クエン酸、
乳酸等の有機酸、これらの酸性塩、又はこれらの混合物
が挙げられる。また、水溶性塩基を〔ＯＨ-〕／〔Ｃｅ
Ｏ2〕モル比で０．００１〜１の範囲に含有させる事に
よりアルカリ性ゾルにする事が出来る。このアルカリ性
研磨液（ゾル）は、８〜１２のｐＨを持つ。上記水溶性
塩基は、上記記載の第４級アンモニウムシリケート、及
び水酸化第４級アンモニウムの他に、モノエタノールア
ミン、ジエタノールアミン、トリエタノールアミン、ア
ミノエチルエタノールアミン、Ｎ，Ｎ−ジメチルエタノ
ールアミン、Ｎ−メチルエタノールアミン、モノプロパ
ノールアミン、及びモルホリン等のアミン類や、アンモ
ニアが挙げられる。Further, it may contain a small amount of acid or base. The pH of the polishing liquid is preferably from 2 to 12. The polishing liquid (sol) can be made an acidic polishing liquid (sol) by containing a water-soluble acid in a molar ratio of [H + ] / [CeO 2 ] in the range of 0.001 to 1. This acidic sol is
It has a pH of 6. The water-soluble acids include, for example, inorganic acids such as hydrogen chloride and nitric acid, formic acid, acetic acid, oxalic acid, tartaric acid, citric acid,
Examples thereof include organic acids such as lactic acid, acid salts thereof, and mixtures thereof. Further, the water-soluble base is changed to [OH − ] / [Ce
An alkaline sol can be obtained by including the compound in an O 2 ] molar ratio of 0.001 to 1. This alkaline polishing liquid (sol) has a pH of 8 to 12. The water-soluble base may be, in addition to the quaternary ammonium silicate and the quaternary ammonium hydroxide described above, monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, N, N-dimethylethanolamine, N Amines such as methylethanolamine, monopropanolamine and morpholine, and ammonia.
【００２８】研磨液は室温に放置して１年以上の長期に
わたり安定である。上記の非酸化性の陰イオン成分を有
するアンモニウム塩の存在下に加熱処理して表面改質さ
れた酸化第二セリウムを含有する研磨剤を用いて行う研
磨方法では、半導体デバイスのシリコン酸化膜（ＳｉＯ
2膜）の研磨や無機ガラス、水晶（例えば、水晶発振器
の水晶片）、石英ガラスの研磨において、従来品の同じ
粒子径の酸化第二セリウム粒子を用いた場合に比べて高
い研磨速度を達成することが出来る。これらの理由とし
ては、酸化第二セリウム粒子は機械的な研磨作用と同時
に化学的な研磨作用を有していて、非酸化性の陰イオン
成分を有するアンモニウム塩の存在下に水性媒体中で加
熱処理を施すことにより酸化第二セリウム粒子表面に水
酸基（≡Ｃｅ−ＯＨ）が多く生成し、この（≡Ｃｅ−Ｏ
Ｈ）基がシリコン酸化膜表面の水酸基（≡Ｓｉ−ＯＨ）
に化学的な作用を及ぼし研磨速度が向上したと考えられ
る。非酸化性の陰イオン成分を有するアンモニウム塩は
酸化第二セリウム粒子の表面に対して、還元的な作用を
及ぼすと考えられる。The polishing liquid is stable at room temperature for a long period of one year or more. In the above-mentioned polishing method using a polishing agent containing cerium oxide surface-modified by heat treatment in the presence of an ammonium salt having a non-oxidizing anion component, a silicon oxide film of a semiconductor device ( SiO
Higher polishing speed in polishing of 2 films), polishing of inorganic glass, crystal (for example, crystal chips of crystal oscillators), and quartz glass than in the case of using ceric oxide particles of the same particle size as conventional products You can do it. For these reasons, ceric oxide particles have a chemical polishing effect at the same time as a mechanical polishing effect, and are heated in an aqueous medium in the presence of an ammonium salt having a non-oxidizing anionic component. By performing the treatment, a large amount of hydroxyl groups (≡Ce-OH) is generated on the surface of the ceric oxide particles, and this (≡Ce-O)
H) groups are hydroxyl groups (≡Si-OH) on the silicon oxide film surface
It is considered that the polishing rate was improved by exerting a chemical action on the polishing. It is considered that the ammonium salt having a non-oxidizing anion component exerts a reducing action on the surface of the ceric oxide particles.
【００２９】本願発明では上記の非酸化性の陰イオン成
分を有するアンモニウム塩の存在下に水性媒体中で加熱
処理する代わりに、ヒドラジン、亜硝酸アンモニウム等
の水溶性還元性物質の存在下に水性媒体中で加熱処理し
た酸化第二セリウム粒子を研磨剤として用いても、上記
（高い研磨速度が得られる）効果を達成することが出来
る。しかし、ヒドラジンや亜硝酸アンモニウムは取り扱
い上、爆発等の危険を伴う為に上記の非酸化性の陰イオ
ン成分を有するアンモニウム塩を使用する事が好まし
い。In the present invention, instead of performing the heat treatment in an aqueous medium in the presence of the above-mentioned ammonium salt having a non-oxidizing anionic component, the aqueous medium is added in the presence of a water-soluble reducing substance such as hydrazine or ammonium nitrite. Even if ceric oxide particles heat-treated in the medium are used as an abrasive, the above-described effect (a high polishing rate can be obtained) can be achieved. However, hydrazine and ammonium nitrite are associated with danger of explosion and the like in handling, so that it is preferable to use the above-mentioned ammonium salt having a non-oxidizing anion component.
【００３０】また、上記の非酸化性の陰イオン成分を有
するアンモニウム塩を使用せずに単なる純水中で加熱処
理しても、研磨速度は原料の酸化第二セリウム粒子を用
いた場合の研磨剤と同じ研磨速度となり効果が期待でき
ない。研磨剤は研磨工程で使用されると、徐々に研磨速
度が低下することが知られている。ひとたび研磨速度の
低下した（即ち、研磨能力の低下した）研磨剤は、研磨
工程での生産性の低下につながるので、その様な研磨剤
は研磨剤自体を廃棄処分することになる。ところが本願
発明では使用済みの研磨能力の低下した酸化第二セリウ
ム粒子を、非酸化性の陰イオン成分を有するアンモニウ
ム塩の存在下で水性媒体中で５０〜２５０℃の温度で加
熱処理することにより、再度研磨能力を回復し、研磨速
度が向上した研磨剤とする事が出来る。Further, even if the heat treatment is carried out in pure water without using the ammonium salt having a non-oxidizing anion component, the polishing rate in the case of using the raw material ceric oxide particles is reduced. The polishing rate is the same as that of the agent and the effect cannot be expected. It is known that the polishing rate gradually decreases when an abrasive is used in a polishing step. Once the polishing rate has been reduced (i.e., the polishing ability has been reduced), the polishing agent leads to a decrease in productivity in the polishing process, and such a polishing agent discards the polishing agent itself. However, in the present invention, the used ceric oxide particles having reduced polishing ability are subjected to a heat treatment at a temperature of 50 to 250 ° C. in an aqueous medium in the presence of an ammonium salt having a non-oxidizing anion component. In addition, the polishing ability can be recovered again and the polishing rate can be improved.
【００３１】他方、本願発明に用いるアンモニウム塩
は、陰イオン成分が酸化性成分のアンモニウム塩を使用
する事が出来る。この酸化性の陰イオン成分を有するア
ンモニウム塩は、硝酸アンモニウム、スルファミン酸ア
ンモニウムが最も好ましく、これらを単独又は混合物と
して使用することが出来る。上記の酸化性の陰イオン成
分を有するアンモニウム塩は、水性媒体中の〔ＮＨ 4 +〕
／〔ＣｅＯ2〕モル比として０．１〜３０が好ましく、
また水性媒体中での上記アンモニウム塩の濃度は１〜３
０重量％とする事が好ましい。On the other hand, the ammonium salt used in the present invention
Uses ammonium salt whose anion component is oxidizing component
You can do it. This oxidizing anion component has
Ammonium salts are ammonium nitrate and sulfamic acid
Most preferred, and these may be used alone or in mixtures.
Can be used. The above oxidizing anion component
Ammonium salt having an amount of [NH Four +]
/ [CeOTwo0.1 to 30 are preferable as the molar ratio,
The concentration of the ammonium salt in the aqueous medium is 1 to 3
It is preferably 0% by weight.
【００３２】陰イオン成分が酸化性成分のアンモニウム
塩を用い水性媒体中で加熱する場合は、５０〜２５０
℃、好ましくは１００〜２５０℃の温度で加熱処理し
て、表面改質された酸化第二セリウム粒子が得られる。
加熱時間は１０分〜９６時間とする事が出来る。加熱処
理温度が１００℃以下の場合は開放系の反応容器を用い
て行われるが、１００℃を越える温度ではオートクレー
ブ装置や超臨界処理装置を用いて行われる。加熱処理さ
れた酸化第二セリウム粒子は処理層よりスラリーとして
取り出し、限外濾過法やフィルタープレス法により洗浄
し、不純物を取り除くことが出来る。When the anion component is heated in an aqueous medium using an ammonium salt of an oxidizing component, it is preferably 50 to 250.
C., preferably 100 to 250.degree. C., to obtain surface-modified ceric oxide particles.
The heating time can be from 10 minutes to 96 hours. When the heat treatment temperature is 100 ° C. or lower, the heat treatment is performed using an open reaction vessel. When the heat treatment temperature exceeds 100 ° C., the heat treatment is performed using an autoclave apparatus or a supercritical processing apparatus. The heat-treated ceric oxide particles can be taken out of the treatment layer as a slurry and washed by an ultrafiltration method or a filter press method to remove impurities.
【００３３】酸化性の陰イオン成分を有するアンモニウ
ム塩の存在下に加熱処理して表面改質された酸化第二セ
リウム粒子は、容易に水性媒体に分散して研磨液とする
事が出来る。この水性媒体は水を使用する事が出来る。
酸化性の陰イオン成分を有するアンモニウム塩の存在下
に水性媒体中で加熱処理して表面改質された酸化第二セ
リウム粒子を含有するゾルは、洗浄により不純物を取り
除いた後、第４級アンモニウムイオン（ＮＲ4 +、但しＲ
は有機基である。）を、（ＮＲ4 +）／（ＣｅＯ2）のモ
ル比で０．００１〜１の範囲に含有させる事により研磨
液の安定性が向上し、上記（シリコン酸化膜等の硬い膜
を研磨せずに有機樹脂膜等の軟らかい膜のみを研磨す
る）効果がより向上するので好ましい。第４級アンモニ
ウムイオンは、第４級アンモニウムシリケート、ハロゲ
ン化第４級アンモニウム、水酸化第４級アンモニウム、
又はこれらの混合物を添加する事によって与えられ、特
に第４級アンモニウムシリケート、水酸化第４級アンモ
ニウムの添加が好ましい。Ｒはメチル基、エチル基、プ
ロピル基、ヒドロキシエチル基、及びベンジル基等が挙
げられる。この第４級アンモニウム化合物としては、例
えばテトラメチルアンモニウムシリケート、テトラエチ
ルアンモニウムシリケート、テトラエタノールアンモニ
ウムシリケート、モノエチルトリエタノールアンモニウ
ムシリケート、トリメチルベンジルアンモニウムシリケ
ート、水酸化テトラメチルアンモニウム、水酸化テトラ
エチルアンモニウムが挙げられる。The ceric oxide particles whose surface has been modified by heat treatment in the presence of an ammonium salt having an oxidizing anion component can be easily dispersed in an aqueous medium to form a polishing liquid. This aqueous medium can use water.
The sol containing cerium oxide particles surface-modified by heat treatment in an aqueous medium in the presence of an ammonium salt having an oxidizing anion component is washed with quaternary ammonium hydroxide after removing impurities. Ion (NR 4 + , where R
Is an organic group. ) Is contained in a molar ratio of (NR 4 + ) / (CeO 2 ) in the range of 0.001 to 1, thereby improving the stability of the polishing liquid and polishing the hard film such as the above (silicon oxide film). Polishing only a soft film such as an organic resin film) is more preferred. Quaternary ammonium ions include quaternary ammonium silicate, quaternary ammonium halide, quaternary ammonium hydroxide,
Alternatively, it is provided by adding a mixture thereof, particularly preferably a quaternary ammonium silicate or a quaternary ammonium hydroxide. R includes a methyl group, an ethyl group, a propyl group, a hydroxyethyl group, a benzyl group and the like. Examples of the quaternary ammonium compound include tetramethylammonium silicate, tetraethylammonium silicate, tetraethanolammonium silicate, monoethyltriethanolammonium silicate, trimethylbenzylammonium silicate, tetramethylammonium hydroxide, and tetraethylammonium hydroxide.
【００３４】また、少量の塩基を含有することもでき
る。研磨液のｐＨは、８〜１２が好ましい。上記研磨液
（ゾル）は、水溶性塩基を〔ＯＨ-〕／〔ＣｅＯ2〕モル
比で０．００１〜１の範囲に含有させる事によりアルカ
リ性ゾルにする事が出来る。このアルカリ性研磨液（ゾ
ル）は、８〜１２のｐＨを持つ。上記水溶性塩基は、上
記記載の第４級アンモニウムシリケート、及び水酸化第
４級アンモニウムの他に、モノエタノールアミン、ジエ
タノールアミン、トリエタノールアミン、アミノエチル
エタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミ
ン、Ｎ−メチルエタノールアミン、モノプロパノールア
ミン、及びモルホリン等のアミン類や、アンモニアが挙
げられる。Further, a small amount of a base can be contained. The pH of the polishing liquid is preferably from 8 to 12. The polishing liquid (sol) can be made an alkaline sol by including a water-soluble base in a molar ratio of [OH − ] / [CeO 2 ] in the range of 0.001 to 1. This alkaline polishing liquid (sol) has a pH of 8 to 12. The water-soluble base may be, in addition to the quaternary ammonium silicate and the quaternary ammonium hydroxide described above, monoethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine, N, N-dimethylethanolamine, N Amines such as methylethanolamine, monopropanolamine and morpholine, and ammonia.
【００３５】研磨液は室温に放置して１年以上の長期に
わたり安定である。酸化性の陰イオン成分を有するアン
モニウム塩の存在下に加熱処理して表面改質された酸化
第二セリウム粒子を研磨剤に用いて行う研磨方法では、
半導体デバイスの層間膜の平坦化に使用することが出来
る。例えば、シリコン酸化膜（ＳｉＯ2膜）をストッパ
ー（研磨を停止する層）とした場合に、有機樹脂膜等の
軟らかい膜の研磨が進行しシリコン酸化膜（ＳｉＯ
2膜）等の硬い膜の部分で研磨が停止する様に、シリコ
ン酸化膜（ＳｉＯ2膜）等の硬い膜を研磨せずに有機樹
脂膜等の軟らかい膜のみを研磨できれば微細な加工が施
せる。即ち、シリコン酸化膜（ＳｉＯ2膜）の研磨速度
が低い研磨剤である。これらの理由としては、酸化第二
セリウム粒子は機械的な研磨作用と同時に化学的な研磨
作用を有していて、酸化第二セリウム粒子表面の水酸基
（≡Ｃｅ−ＯＨ）はシリコン酸化膜表面の水酸基（≡Ｓ
ｉ−ＯＨ）に化学的な作用を及ぼし研磨速度が向上する
と考えられるが、酸化性の陰イオン成分を有するアンモ
ニウム塩の存在下に水性媒体中で加熱処理を施すことに
より酸化第二セリウム粒子表面の水酸基（≡Ｃｅ−Ｏ
Ｈ）が減少し、酸化第二セリウム粒子の持つ化学的な研
磨作用が低下した為と考えられる。酸化性の陰イオン成
分を有するアンモニウム塩は酸化第二セリウム粒子の表
面に対して、酸化的な作用を及ぼすと考えられる。The polishing liquid is stable at room temperature for one year or more. In a polishing method performed by using a cerium oxide particles surface-modified by heat treatment in the presence of an ammonium salt having an oxidizing anion component as an abrasive,
It can be used for flattening an interlayer film of a semiconductor device. For example, when a silicon oxide film (SiO 2 film) is used as a stopper (a layer for stopping polishing), polishing of a soft film such as an organic resin film proceeds, and the silicon oxide film (SiO 2 film)
In order to stop polishing at a hard film portion such as ( 2 film), fine processing can be performed if only a soft film such as an organic resin film can be polished without polishing a hard film such as a silicon oxide film (SiO 2 film). . That is, it is a polishing agent having a low polishing rate for the silicon oxide film (SiO 2 film). For these reasons, the ceric oxide particles have a chemical polishing effect at the same time as the mechanical polishing effect, and the hydroxyl groups (≡Ce-OH) on the surface of the ceric oxide particles are Hydroxyl group (≡S
Although it is considered that the polishing rate is improved by chemically acting on i-OH), the surface of the ceric oxide particles is subjected to heat treatment in an aqueous medium in the presence of an ammonium salt having an oxidizing anion component. Hydroxyl group (≡Ce-O
It is considered that H) decreased, and the chemical polishing action of the ceric oxide particles decreased. The ammonium salt having an oxidizing anion component is considered to exert an oxidative effect on the surface of the ceric oxide particles.
【００３６】例えば、半導体デバイスの層間膜の平坦化
においては、非酸化性の陰イオン成分を有するアンモニ
ウム塩の存在下に水性媒体中で加熱処理した酸化第二セ
リウム粒子を含有する研磨剤と、酸化性の陰イオン成分
を有するアンモニウム塩の存在下に水性媒体中で加熱処
理した酸化第二セリウム粒子を含有する研磨剤を、交互
に使用して研磨することにより研磨速度を自由にコント
ロールする事ができる。この研磨方法により硬いシリコ
ン酸化膜（ＳｉＯ2膜）部分と軟らかい有機樹脂膜部分
が混在する研磨体を、２種類の研磨剤で使い分けてより
精密な研磨を達成することが出来る。この方法で交互に
とは、研磨面に対してそれぞれの研磨剤を別々に少なく
とも１回使用することである。For example, in planarizing an interlayer film of a semiconductor device, an abrasive containing ceric oxide particles heat-treated in an aqueous medium in the presence of an ammonium salt having a non-oxidizing anionic component; The polishing rate can be freely controlled by alternately using abrasives containing ceric oxide particles that have been heat-treated in an aqueous medium in the presence of an ammonium salt having an oxidizing anion component. Can be. According to this polishing method, a polishing body in which a hard silicon oxide film (SiO 2 film) portion and a soft organic resin film portion coexist can be selectively used with two types of polishing agents to achieve more precise polishing. Alternating in this manner means that each abrasive is separately used at least once for the polished surface.
【００３７】本願発明において、非酸化性の陰イオン成
分を有するアンモニウム塩、又は酸化性の陰イオン成分
を有するアンモニウム塩の存在下に水性媒体中で５０〜
２５０℃の温度で加熱処理した酸化第二セリウム粒子
は、乾燥してＸ線回折装置により回折パターンを測定し
たところ、回折角度２θ＝２８．６°、４７．５°、及
び５６．４°に主ピークを有し、ＡＳＴＭカードＮｏ３
４−３９４に記載の立方晶系の結晶性の高い酸化第二セ
リウム粒子である。In the present invention, 50 to 50% of an ammonium salt having a non-oxidizing anionic component or an ammonium salt having an oxidizing anionic component in an aqueous medium.
The ceric oxide particles heat-treated at a temperature of 250 ° C. were dried and the diffraction pattern was measured by an X-ray diffractometer. The diffraction angles were 28.6 °, 28.6 °, 47.5 °, and 56.4 °. ASTM card No3 with main peak
4-394 is a cubic ceric oxide particle having high crystallinity.
【００３８】[0038]
実施例１ ２リットルのセパラブルフラスコにＮＨ4ＯＨ／Ｃｅ3+
モル比が６に相当する量の９重量％のアンモニア水溶液
７４０ｇを仕込み、液温を３０℃に保持しながらガラス
製のノズルより２リットル／分の窒素ガスを吹き込み窒
素ガスでフラスコ内を置換した。そして、フラスコに硝
酸セリウム（III）２１６ｇを純水５００ｇに溶解させ
た溶液を徐々に添加して水酸化セリウム（III）の懸濁
液を得た。続いてこの懸濁液を８０℃まで昇温させた
後、ガラス製のノズルからの吹き込みを窒素から４リッ
トル／分の空気に切り替えてセリウム（III）をセリウ
ム（IV）にする酸化反応を開始した。３時間で酸化反応
が終了し、淡黄色の酸化第二セリウム粒子を有するｐＨ
７．２の反応液が得られた。この酸化第二セリウム粒子
を原料粒子として用いた。Example 1 NH 4 OH / Ce 3+ was placed in a 2-liter separable flask.
740 g of a 9% by weight aqueous ammonia solution corresponding to a molar ratio of 6 was charged, and nitrogen gas was blown in at a rate of 2 L / min from a glass nozzle while maintaining the liquid temperature at 30 ° C., and the inside of the flask was replaced with nitrogen gas. . Then, a solution of 216 g of cerium (III) nitrate dissolved in 500 g of pure water was gradually added to the flask to obtain a suspension of cerium (III) hydroxide. Subsequently, after the temperature of the suspension is raised to 80 ° C., the blowing reaction from the glass nozzle is switched from nitrogen to air at 4 liters / minute to start an oxidation reaction for converting cerium (III) to cerium (IV). did. Oxidation reaction is completed in 3 hours, and pH with pale yellow ceric oxide particles
A reaction liquid of 7.2 was obtained. The ceric oxide particles were used as raw material particles.
【００３９】反応液より上記原料粒子となる酸化第二セ
リウム粒子を濾別し、洗浄した後、透過型電子顕微鏡
（ＴＥＭ）で観察したところ粒子径８０〜１００ｎｍの
粒子であった。また、粒子を乾燥して粉末Ｘ線回折を測
定したところ、回折角度２θ＝２８．６°、４７．５°
及び５６．４°に主ピークを有し、ＡＳＴＭカードＮｏ
３４−３９４に記載の立方晶系の結晶性酸化第二セリウ
ムの特性ピークと一致した。The ceric oxide particles serving as the raw material particles were separated from the reaction solution by filtration, washed, and observed by a transmission electron microscope (TEM) to find that the particles had a particle diameter of 80 to 100 nm. Further, when the particles were dried and powder X-ray diffraction was measured, the diffraction angles 2θ = 28.6 ° and 47.5 °
And a main peak at 56.4 °, and the ASTM card No.
34-394, which was in agreement with the characteristic peak of cubic crystalline ceric oxide.
【００４０】１０重量％の炭酸アンモニウム水溶液１５
００ｇを３リットルのセパラブルフラスコに仕込み、そ
の後上記に得られた原料粒子である酸化第二セリウム粒
子１５０ｇをフラスコに入れ９５℃で８時間の加熱処理
を行った。加熱処理したスラリーを濾別して、洗浄した
後、透過型電子顕微鏡（ＴＥＭ）で観察したところ表面
改質前と同じ８０〜１００ｎｍであった。得られた表面
改質された粒子を乾燥して粉末Ｘ線回折を測定したとこ
ろ立方晶系の酸化第二セリウムであった。再度濾過、洗
浄した表面改質した結晶性酸化第二セリウム粒子にテト
ラメチルアンモニウムシリケート水溶液を〔Ｎ（Ｃ
Ｈ3）4 +／ＣｅＯ2〕モル比で０．０１になる様に添加し
て、ＣｅＯ2濃度を２０重量％、ｐＨを１０．３に調製
した。この２０重量％の結晶性酸化第二セリウムゾル７
５０ｇを研磨液として作製した。A 10% by weight aqueous solution of ammonium carbonate 15
00 g was charged into a 3-liter separable flask, and then 150 g of ceric oxide particles, which were the raw material particles obtained above, were placed in the flask and heated at 95 ° C. for 8 hours. The heat-treated slurry was separated by filtration, washed, and then observed with a transmission electron microscope (TEM). The result was 80 to 100 nm, the same as before surface modification. The obtained surface-modified particles were dried and subjected to powder X-ray diffraction measurement to find that they were cubic ceric oxide. An aqueous tetramethylammonium silicate solution was added to the surface-modified crystalline cerium oxide particles, which were again filtered and washed [N (C
[H 3 ) 4 + / CeO 2 ] The molar ratio was adjusted to 0.01 to adjust the CeO 2 concentration to 20% by weight and the pH to 10.3. This 20% by weight crystalline ceric oxide sol 7
50 g was prepared as a polishing liquid.
【００４１】実施例２ １０重量％の炭酸アンモニウム水溶液１５００ｇを３リ
ットルのグラスライニング製の高圧容器に仕込み、実施
例１と同様に製造された原料粒子となる酸化第二セリウ
ム粒子１５０ｇを高圧容器に入れ１５０℃で２０時間の
水熱処理を行った。加熱処理したスラリーを濾別して、
洗浄した後、透過型電子顕微鏡（ＴＥＭ）で観察したと
ころ表面改質前と同じ８０〜１００ｎｍであった。得ら
れた表面改質された粒子を乾燥して粉末Ｘ線回折を測定
したところ立方晶系の酸化第二セリウム粒子であった。
再度濾過、洗浄した表面改質した結晶性酸化第二セリウ
ム粒子にテトラメチルアンモニウムシリケート水溶液を
〔Ｎ（ＣＨ3）4 +／ＣｅＯ2〕モル比で０．０１になる様
に添加して、ＣｅＯ2濃度を２０重量％、ｐＨを１０．
３に調製した。この２０重量％の結晶性酸化第二セリウ
ムゾル７５０ｇを研磨液として作製した。Example 2 1500 g of a 10% by weight aqueous solution of ammonium carbonate was charged into a 3 liter glass-lined high-pressure vessel, and 150 g of ceric oxide particles as raw material particles produced in the same manner as in Example 1 were placed in a high-pressure vessel. Hydrothermal treatment was performed at 150 ° C. for 20 hours. Filter the heated slurry,
After washing, it was observed with a transmission electron microscope (TEM) and found to be 80 to 100 nm as before the surface modification. The obtained surface-modified particles were dried and subjected to powder X-ray diffraction measurement to find that they were cubic ceric oxide particles.
An aqueous solution of tetramethylammonium silicate is added to the surface-modified crystalline ceric oxide particles, which have been filtered and washed again, so that the molar ratio of [N (CH 3 ) 4 + / CeO 2 ] becomes 0.01, and CeO is added. 2. 20% by weight concentration and 10.
3 was prepared. 750 g of this 20 wt% crystalline ceric oxide sol was prepared as a polishing liquid.
【００４２】実施例３ １０重量％の硝酸アンモニウム水溶液１５００ｇを３リ
ットルのグラスライニング製の高圧容器に仕込み、実施
例１と同様に製造された原料粒子となる酸化第二セリウ
ム粒子１５０ｇを高圧容器に入れ１５０℃で２０時間の
水熱処理を行った。加熱処理したスラリーを濾別して、
洗浄した後、透過型電子顕微鏡（ＴＥＭ）で観察したと
ころ表面改質前と同じ８０〜１００ｎｍであった。得ら
れた表面改質された粒子を乾燥して粉末Ｘ線回折を測定
したところ立方晶系の酸化第二セリウム粒子であった。
再度濾過、洗浄して表面改質した結晶性酸化第二セリウ
ム粒子を純水に分散させて、さらに水酸化テトラメチル
アンモニウム水溶液を〔Ｎ（ＣＨ3）4 +／ＣｅＯ2〕モル
比で０．０１になる様に添加して、ｐＨを１０．３とし
て安定化し、２０重量％の結晶性酸化第二セリウムゾル
７５０ｇを研磨液として作製した。Example 3 1500 g of a 10% by weight aqueous solution of ammonium nitrate was charged into a 3 liter glass-lined high-pressure vessel, and 150 g of ceric oxide particles as raw material particles produced in the same manner as in Example 1 were placed in the high-pressure vessel. Hydrothermal treatment was performed at 150 ° C. for 20 hours. Filter the heated slurry,
After washing, it was observed with a transmission electron microscope (TEM) and found to be 80 to 100 nm as before the surface modification. The obtained surface-modified particles were dried and subjected to powder X-ray diffraction measurement to find that they were cubic ceric oxide particles.
The crystalline ceric oxide particles whose surface was modified by filtration and washing again were dispersed in pure water, and an aqueous solution of tetramethylammonium hydroxide was added at a molar ratio of [N (CH 3 ) 4 + / CeO 2 ] of 0.1. 01, and the pH was stabilized at 10.3 to prepare 750 g of a crystalline ceric oxide sol of 20% by weight as a polishing liquid.
【００４３】実施例４ １０重量％の炭酸アンモニウム水溶液１５００ｇを３リ
ットルのセパラブルフラスコに仕込み、市販のセリウム
を主成分として含む希土類化合物を焼成と粉砕する事で
得られた研磨剤粒子（粒子径は１μｍ、ＣｅＯ2含有量
は８８重量％、Ｌａ2Ｏ3含有量は７重量％、ＳｉＯ2含
有量は５重量％）１５０ｇをセパラブルフラスコに入れ
９５℃で８時間加熱処理して粒子の表面改質を行った。
加熱処理したスラリーを濾別して、洗浄した後、透過型
電子顕微鏡（ＴＥＭ）で観察したところ表面改質前と同
じ１μｍであった。得られた表面改質された粒子を乾燥
して粉末Ｘ線回折を測定したところ、立方晶系の酸化第
二セリウムのピークを含むものであった。再度濾過、洗
浄した表面改質した上記研磨剤粒子にテトラメチルアン
モニウムシリケート水溶液を〔Ｎ（ＣＨ3）4 +／Ｃｅ
Ｏ2〕モル比で０．０１になる様に添加して、ＣｅＯ2濃
度を２０重量％、ｐＨを１０．３に調製した。この２０
重量％の上記研磨剤粒子の分散液７５０ｇを研磨液とし
て作製した。Example 4 1500 g of a 10% by weight aqueous solution of ammonium carbonate was charged into a 3-liter separable flask, and commercially available rare earth compounds containing cerium as a main component were calcined and pulverized to obtain abrasive particles (particle size). Is 1 μm, the content of CeO 2 is 88% by weight, the content of La 2 O 3 is 7% by weight, the content of SiO 2 is 5% by weight) 150 g is placed in a separable flask and heated at 95 ° C. for 8 hours to obtain particles. Surface modification was performed.
The heat-treated slurry was separated by filtration, washed, and observed with a transmission electron microscope (TEM). The obtained surface-modified particles were dried and subjected to powder X-ray diffraction measurement. As a result, the particles contained a cubic ceric oxide peak. An aqueous tetramethylammonium silicate solution [N (CH 3 ) 4 + / Ce
[O 2 ] molar ratio was adjusted to 0.01 to adjust the CeO 2 concentration to 20% by weight and the pH to 10.3. This 20
A polishing liquid was prepared using 750 g of a dispersion of the above-mentioned abrasive particles in a weight%.
【００４４】比較例１ 実施例１と同様に製造された原料粒子となる粒子径８０
〜１００ｎｍの酸化第二セリウム粒子を、アンモニウム
塩の存在下での加熱処理による表面改質を行わずに、純
水に分散してテトラメチルアンモニウムシリケート水溶
液を〔Ｎ（ＣＨ 3）4 +／ＣｅＯ2〕モル比で０．０１にな
る様に添加して、ＣｅＯ2濃度を２０重量％、ｐＨを１
０．３に調製した。この２０重量％の結晶性酸化第二セ
リウムゾル７５０ｇを研磨液として作製した。Comparative Example 1 The particle diameter of the raw material particles produced in the same manner as in Example 1 was 80
~ 100 nm ceric oxide particles were treated with ammonium
Without surface modification by heat treatment in the presence of salt, pure
Disperse in water to dissolve tetramethylammonium silicate in water
The solution was added to [N (CH Three)Four +/ CeOTwo] In a molar ratio of 0.01.
CeOTwoConcentration 20% by weight, pH 1
It was adjusted to 0.3. This 20% by weight crystalline second oxide
750 g of lithium sol was prepared as a polishing liquid.
【００４５】比較例２ 市販のセリウムを主成分として含む希土類化合物を焼成
と粉砕する事で得られた研磨剤粒子（粒子径は１μｍ、
ＣｅＯ2含有量は８８重量％、Ｌａ2Ｏ3含有量は７重量
％、ＳｉＯ2含有量は５重量％）を、アンモニウム塩の
存在下での加熱処理による表面改質を行わずに、純水に
分散してテトラメチルアンモニウムシリケート水溶液を
〔Ｎ（ＣＨ3）4 +／ＣｅＯ2〕モル比で０．０１になる様
に添加して、ＣｅＯ2濃度を２０重量％、ｐＨを１０．
３に調製した。この２０重量％の結晶性酸化第二セリウ
ムゾル７５０ｇを研磨液として作製した。Comparative Example 2 Abrasive particles obtained by baking and pulverizing a commercially available rare earth compound containing cerium as a main component (particle diameter is 1 μm,
The CeO 2 content was 88% by weight, the La 2 O 3 content was 7% by weight, and the SiO 2 content was 5% by weight). Dispersed in water, an aqueous tetramethylammonium silicate solution was added so that the molar ratio of [N (CH 3 ) 4 + / CeO 2 ] became 0.01, the CeO 2 concentration was 20% by weight, and the pH was 10.
3 was prepared. 750 g of this 20 wt% crystalline ceric oxide sol was prepared as a polishing liquid.
【００４６】実施例１〜４及び比較例１〜２の研磨剤
を、市販のオスカー型レンズ研磨機を用い、下記の研磨
条件で研磨を行った。研磨速度は、石英ガラスに溝を付
け、溝の深さを触針式表面粗さ測定装置で測定する事に
より求め、その結果を表１に示した。 ａ．研磨布：フッ素樹脂（φ２５０ｍｍ）又は発泡ポリ
ウレタン（φ２５０ｍｍ） ｂ．被研磨物：石英ガラス（φ２５ｍｍ） ｃ．回転数：３０ｒｐｍ、及び ｄ．研磨圧力：２７０ｇ／ｃｍ2 The abrasives of Examples 1 to 4 and Comparative Examples 1 and 2 were polished using a commercially available Oscar lens polisher under the following polishing conditions. The polishing rate was determined by forming a groove in quartz glass and measuring the depth of the groove with a stylus type surface roughness measuring device. The results are shown in Table 1. a. Polishing cloth: fluororesin (φ250mm) or polyurethane foam (φ250mm) b. Object to be polished: quartz glass (φ25 mm) c. Rotation speed: 30 rpm, and d. Polishing pressure: 270 g / cm 2
【００４７】[0047]
【表１】 表１ 研磨速度（ｎｍ／分） （研磨布として （研磨布として 研磨剤 フッ素樹脂） 発泡ポリウレタン） 実施例１ ４８ ９０ 実施例２ ４０ ８３ 実施例３ １ −− 実施例４ −− ５０２ 比較例１ ２１ ３８ 比較例２ −− ４３８ 非酸化性の陰イオン成分を有するアンモニウム塩の存在
下に水性媒体中で加熱処理を行い表面改質された酸化第
二セリウム粒子からなる実施例１〜２の研磨剤は、全く
表面改質されていない酸化第二セリウム粒子からなる比
較例１の研磨剤に比べて、同一の研磨条件で比較してほ
ぼ２倍の研磨速度を有する。実施例１〜２で示される様
な研磨速度が向上した研磨剤は、半導体デバイスのシリ
コン酸化膜（ＳｉＯ2膜）の硬い膜の研磨や、無機ガラ
ス、水晶（例えば、水晶発振器の水晶片）、石英ガラス
等の硬質物質の研磨において、従来品の同じ粒子径の酸
化第二セリウム粒子を用いた研磨剤に比べて高い研磨速
度が得られる。 Table 1 Polishing rate (nm / min) (As a polishing cloth (abrasive fluororesin as a polishing cloth ) foamed polyurethane) Example 1 48 90 Example 2 40 83 Example 3 1 −− Example 4 −− 502 Comparative Example 1 21 38 Comparative Example 2 --- 438 Example 1 comprising ceric oxide particles surface-modified by heat treatment in an aqueous medium in the presence of an ammonium salt having a non-oxidizing anionic component. The polishing agents No. to No. 2 have almost twice the polishing rate under the same polishing conditions as compared with the polishing agent of Comparative Example 1 consisting of ceric oxide particles whose surface is not modified at all. Polishing agents with improved polishing rates as shown in Examples 1 and 2 are used for polishing hard silicon oxide films (SiO 2 films) of semiconductor devices, inorganic glass, and quartz (for example, quartz pieces of quartz oscillators). In polishing a hard substance such as quartz glass, a higher polishing rate can be obtained as compared with a conventional polishing agent using ceric oxide particles having the same particle diameter as conventional products.
【００４８】この様な実施例１〜２の研磨剤と比較例１
の研磨剤との関係は、原料粒子を市販のセリウムを主成
分として含む希土類化合物を焼成と粉砕する事で得られ
た研磨剤粒子に置き換えても、実施例４の研磨剤と比較
例２の関係の通り、表面改質された粒子からなる研磨剤
は研磨速度が高い。一方、酸化性の陰イオン成分を有す
るアンモニウム塩の存在下に水性媒体中で加熱処理を行
い表面改質された酸化第二セリウム粒子からなる実施例
３の研磨剤は、全く表面改質されていない酸化第二セリ
ウム粒子からなる比較例１の研磨剤に比べて、同一の研
磨条件で比較して１／２０という極端に研磨速度が低く
なる。この実施例３の研磨剤の使用方法としては、例え
ばＣＭＰを用いた層間膜平坦化において、ＬＳＩ表面上
の凹凸に硬いＳｉＯ2膜をストッパーとして、その上部
に軟らかい膜（有機樹脂膜や不純物が含有されたＳｉＯ
2膜）を被覆して有る場合に、本願の実施例３で示され
る研磨剤で研磨する事を想定すると、まず凸部表面に形
成された軟らかい膜が研磨され凸部に表れた硬いＳｉＯ
2膜の部分で研磨が停止され、選択的に軟らかい膜のみ
を研磨する事が出来る。The abrasives of Examples 1 and 2 and Comparative Example 1
The relationship between the abrasive of Example 4 and the abrasive of Comparative Example 2 was obtained by replacing the raw material particles with abrasive particles obtained by baking and pulverizing a commercially available rare earth compound containing cerium as a main component. As is related, the polishing agent composed of the surface-modified particles has a high polishing rate. On the other hand, the abrasive of Example 3 comprising ceric oxide particles surface-modified by heat treatment in an aqueous medium in the presence of an ammonium salt having an oxidizing anion component is completely surface-modified. As compared with the polishing agent of Comparative Example 1 comprising no ceric oxide particles, the polishing rate is extremely reduced to 1/20 under the same polishing conditions. As a method of using the polishing agent of the third embodiment, for example, in the planarization of an interlayer film using CMP, a SiO 2 film having unevenness on the LSI surface is used as a stopper, and a soft film (organic resin film or impurities SiO contained
2 ), it is assumed that polishing is performed with the abrasive shown in Example 3 of the present application.
The polishing is stopped at the portion of the two films, and only the soft film can be selectively polished.
【００４９】また、ＬＳＩ表面上の凹凸に軟らかい膜
（有機樹脂膜や不純物が含有されたＳｉＯ2膜）が被覆
して有り、その上部に硬いＳｉＯ2膜を被覆して有る場
合に、本願の実施例１〜２の研磨剤と実施例３の研磨剤
を組み合わせて研磨する事を想定すると、まず凸部表面
の硬いＳｉＯ2膜を実施例１〜２の研磨剤で研磨して、
次に凸部に表れた軟らかい膜を実施例３の研磨剤で研磨
して、次第に凸部の山が低くなり凹部の硬いＳｉＯ2膜
部分（ストッパー）に達した時に研磨が停止し、ＬＳＩ
表面の平坦化が達成される。Further, in the case where a soft film (an organic resin film or an SiO 2 film containing impurities) is coated on the unevenness on the LSI surface and a hard SiO 2 film is coated thereon, Assuming that polishing is performed by combining the polishing agents of Examples 1 and 2 and the polishing agent of Example 3, first, a hard SiO 2 film on the surface of the convex portion is polished with the polishing agent of Examples 1 and 2,
Next, the soft film appearing on the convex portion was polished with the abrasive of Example 3, and when the peak of the convex portion gradually decreased and reached the hard SiO 2 film portion (stopper) of the concave portion, polishing was stopped, and the LSI was removed.
Surface planarization is achieved.
【００５０】[0050]
【発明の効果】本願発明は、酸化第二セリウム粒子、又
はセリウムを主成分とする希土類元素を含む組成物を焼
成と粉砕する事によって得られた酸化第二セリウムを主
成分とする粒子を、アンモニウム塩の存在下に水性媒体
中で５０〜２５０℃の温度で加熱して得られる酸化第二
セリウム粒子、又は酸化第二セリウムを主成分とする粒
子からなる研磨剤であり、この研磨剤は表面改質された
酸化第二セリウム粒子であって、表面改質に用いる薬剤
（アンモニウム塩）の種類により得られる酸化第二セリ
ウム粒子の研磨剤としての性質は異なる。According to the present invention, ceric oxide particles or particles containing cerium oxide as a main component obtained by firing and pulverizing a composition containing a rare earth element containing cerium as a main component, A ceric oxide particle obtained by heating at a temperature of 50 to 250 ° C. in an aqueous medium in the presence of an ammonium salt, or an abrasive comprising particles containing ceric oxide as a main component, The properties of the ceric oxide particles obtained from the surface-modified ceric oxide particles as abrasives differ depending on the type of the agent (ammonium salt) used for the surface modification.
【００５１】非酸化性の陰イオン成分を有するアンモニ
ウム塩の存在下に水性媒体中で加熱処理を行い表面改質
された酸化第二セリウム粒子からなる研磨剤を用いるこ
とによって、半導体デバイスのシリコン酸化膜（ＳｉＯ
2膜）の硬い膜の研磨や、無機ガラス、水晶（例えば、
水晶発振器の水晶片）、石英ガラス等の硬質物質の研磨
において、従来品の同じ粒子径の酸化第二セリウム粒子
を用いた場合に比べて高い研磨速度を達成する事が出来
る。By using an abrasive composed of ceric oxide particles whose surface has been modified by heat treatment in an aqueous medium in the presence of an ammonium salt having a non-oxidizing anionic component, the silicon oxide of a semiconductor device can be reduced. Film (SiO
Polishing of hard film of 2 ), inorganic glass, crystal (for example,
In polishing a hard substance such as a crystal piece of a quartz oscillator) and quartz glass, a higher polishing rate can be achieved as compared with a conventional product using ceric oxide particles having the same particle diameter.
【００５２】また、酸化性の陰イオン成分を有するアン
モニウム塩の存在下に水性媒体中で加熱処理を行い表面
改質された酸化第二セリウム粒子からなる研磨剤を用い
ることによって、シリコン酸化膜（ＳｉＯ2膜）の硬い
膜等の研磨において従来品の同じ粒子径の酸化第二セリ
ウム粒子を用いた場合に比べて極端に研磨速度が低くな
る。In addition, by using a polishing agent composed of cerium oxide particles whose surface has been modified by heat treatment in an aqueous medium in the presence of an ammonium salt having an oxidizing anion component, a silicon oxide film ( In the polishing of a hard film such as a SiO 2 film, the polishing rate is extremely lower than that of a conventional product using ceric oxide particles having the same particle diameter.
【００５３】この様に２種類の研磨剤をそれぞれ単独で
使用する事で幅広い用途の研磨が可能であるが、この２
種類の研磨剤を組み合わせる事で半導体デバイスの分野
では選択的研磨が可能である。As described above, by using two types of polishing agents independently, polishing for a wide range of applications is possible.
By combining various types of abrasives, selective polishing is possible in the field of semiconductor devices.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西村 透 千葉県船橋市坪井町722番地１ 日産化学 工業株式会社中央研究所内 (72)発明者 谷本 健二 富山県婦負郡婦中町笹倉635 日産化学工 業株式会社富山工場内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toru Nishimura 722-1 Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Industry Co., Ltd. Central Research Laboratory (72) Inventor Kenji Tanimoto 635 Sasakura, Funaka-cho, Onuma-gun, Toyama Nissan Chemical Inside Toyama Factory
Claims (9)
５０〜２５０℃の温度で加熱処理した酸化第二セリウム
粒子からなる研磨剤。1. An abrasive comprising ceric oxide particles heat-treated at a temperature of 50 to 250 ° C. in an aqueous medium in the presence of an ammonium salt.
化性成分である請求項１に記載の研磨剤。2. The abrasive according to claim 1, wherein the anionic component of the ammonium salt is a non-oxidizing component.
ニウム塩が、炭酸アンモニウム、炭酸水素アンモニウ
ム、又はこれらの混合物である請求項２に記載の研磨
剤。3. The abrasive according to claim 2, wherein the ammonium salt having a non-oxidizing anionic component is ammonium carbonate, ammonium hydrogen carbonate, or a mixture thereof.
性成分である請求項１に記載の研磨剤。4. The abrasive according to claim 1, wherein the anionic component of the ammonium salt is an oxidizing component.
ウム塩が、硝酸アンモニウム、スルファミン酸アンモニ
ウム、又はこれらの混合物である請求項４に記載の研磨
剤。5. The abrasive according to claim 4, wherein the ammonium salt having an oxidizing anion component is ammonium nitrate, ammonium sulfamate, or a mixture thereof.
５０〜２５０℃の温度で加熱処理した酸化第二セリウム
粒子からなる研磨剤を使用する研磨方法。6. A polishing method using an abrasive made of ceric oxide particles which has been heat-treated in an aqueous medium at a temperature of 50 to 250 ° C. in the presence of an ammonium salt.
ム、又はこれらの混合物の存在下に水性媒体中で５０〜
２５０℃の温度で加熱処理した酸化第二セリウム粒子か
らなる研磨剤を使用する研磨方法。7. An aqueous medium in the presence of ammonium carbonate, ammonium bicarbonate, or a mixture thereof.
A polishing method using an abrasive made of ceric oxide particles heat-treated at a temperature of 250 ° C.
モニウム、又はこれらの混合物の存在下に水性媒体中で
１００〜２５０℃の温度で加熱処理した酸化第二セリウ
ム粒子からなる研磨剤を使用する半導体デバイスの研磨
方法。8. A method for polishing a semiconductor device using a polishing agent comprising ceric oxide particles heat-treated at a temperature of 100 to 250 ° C. in an aqueous medium in the presence of ammonium nitrate, ammonium sulfamate, or a mixture thereof. .
の研磨剤を交互に使用する半導体デバイスの研磨方法。9. A method for polishing a semiconductor device, wherein the polishing agent according to claim 3 and the polishing agent according to claim 5 are used alternately.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19695597A JP3918241B2 (en) | 1996-08-01 | 1997-07-23 | Polishing agent and polishing method comprising surface-modified ceric oxide particles |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-203450 | 1996-08-01 | ||
| JP20345096 | 1996-08-01 | ||
| JP19695597A JP3918241B2 (en) | 1996-08-01 | 1997-07-23 | Polishing agent and polishing method comprising surface-modified ceric oxide particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1094955A true JPH1094955A (en) | 1998-04-14 |
| JP3918241B2 JP3918241B2 (en) | 2007-05-23 |
Family
ID=26510082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19695597A Expired - Fee Related JP3918241B2 (en) | 1996-08-01 | 1997-07-23 | Polishing agent and polishing method comprising surface-modified ceric oxide particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3918241B2 (en) |
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| WO2006049197A1 (en) * | 2004-11-08 | 2006-05-11 | Asahi Glass Company, Limited | METHOD FOR PRODUCING CeO2 FINE PARTICLES AND POLISHING SLURRY CONTAINING SUCH FINE PARTICLES |
| JPWO2006049197A1 (en) * | 2004-11-08 | 2008-05-29 | 旭硝子株式会社 | Method for producing CeO2 fine particles and polishing slurry containing the fine particles |
| US7381232B2 (en) | 2004-11-08 | 2008-06-03 | Asahi Glass Company, Limited | Process for producing CeO2 fine particles and polishing slurry containing such fine particles |
| JP2008105168A (en) * | 2006-04-28 | 2008-05-08 | Asahi Glass Co Ltd | Manufacturing method of glass substrate for magnetic disk and magnetic disk |
| JP2015120844A (en) * | 2013-12-24 | 2015-07-02 | 旭硝子株式会社 | Manufacturing method of polishing agent, polishing method, and manufacturing method of semiconductor integrated circuit device |
| JP2016092343A (en) * | 2014-11-11 | 2016-05-23 | 富士通株式会社 | Manufacturing method of semiconductor device |
| WO2023032930A1 (en) * | 2021-08-31 | 2023-03-09 | 株式会社レゾナック | Polishing liquid, polishing method, component manufacturing method, and semiconductor component manufacturing method |
| JPWO2023032930A1 (en) * | 2021-08-31 | 2023-03-09 | ||
| WO2023032028A1 (en) * | 2021-08-31 | 2023-03-09 | 株式会社レゾナック | Polishing solution, polishing method, method for producing semiconductor component, and method for producing joined body |
| EP4339254A4 (en) * | 2021-08-31 | 2024-11-20 | Resonac Corporation | POLISHING LIQUID, POLISHING METHOD, COMPONENT MANUFACTURING METHOD, AND SEMICONDUCTOR COMPONENT MANUFACTURING METHOD |
| EP4379780A4 (en) * | 2021-08-31 | 2024-12-25 | Resonac Corporation | POLISHING LIQUID, POLISHING METHOD, COMPONENT MANUFACTURING METHOD, AND SEMICONDUCTOR COMPONENT MANUFACTURING METHOD |
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