TWI664277B - Abrasive composition for sapphire substrate - Google Patents
Abrasive composition for sapphire substrate Download PDFInfo
- Publication number
- TWI664277B TWI664277B TW104130330A TW104130330A TWI664277B TW I664277 B TWI664277 B TW I664277B TW 104130330 A TW104130330 A TW 104130330A TW 104130330 A TW104130330 A TW 104130330A TW I664277 B TWI664277 B TW I664277B
- Authority
- TW
- Taiwan
- Prior art keywords
- sapphire substrate
- abrasive composition
- acid
- polishing
- substrate according
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 159
- 239000000758 substrate Substances 0.000 title claims abstract description 116
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 110
- 239000010980 sapphire Substances 0.000 title claims abstract description 110
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000002245 particle Substances 0.000 claims abstract description 109
- 238000005498 polishing Methods 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000013522 chelant Substances 0.000 claims abstract description 19
- -1 amine salts Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002270 dispersing agent Substances 0.000 claims description 21
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 229910001593 boehmite Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000002738 chelating agent Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 12
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 4
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 4
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 229960003330 pentetic acid Drugs 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- DIWZKTYQKVKILN-VKHMYHEASA-N (2s)-2-(dicarboxymethylamino)pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)NC(C(O)=O)C(O)=O DIWZKTYQKVKILN-VKHMYHEASA-N 0.000 claims description 3
- XNSPQPOQXWCGKC-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] XNSPQPOQXWCGKC-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 claims description 2
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 claims 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 239000003082 abrasive agent Substances 0.000 abstract description 21
- 230000007547 defect Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000000227 grinding Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 11
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 9
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- 239000006061 abrasive grain Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 235000010980 cellulose Nutrition 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910001679 gibbsite Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 4
- QOPUBSBYMCLLKW-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-4-hydroxybutanoic acid Chemical compound OCCC(C(O)=O)N(CC(O)=O)CCN(CC(O)=O)CC(O)=O QOPUBSBYMCLLKW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 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
- 239000006059 cover glass Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001680 bayerite Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DPRXWSVZQIHSJQ-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)-4-hydroxybutyl]amino] acetate Chemical compound CC(=O)ON(OC(C)=O)CC(CCO)N(OC(C)=O)OC(C)=O DPRXWSVZQIHSJQ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910001586 aluminite Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229940074355 nitric acid Drugs 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940098424 potassium pyrophosphate Drugs 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- WSHUUEZZULHHSX-UHFFFAOYSA-K trisodium 2-[2-[(1-carboxy-3-hydroxypropyl)-(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].OCCC(C(=O)O)N(CCN(CC(=O)[O-])CC(=O)[O-])CC(=O)[O-] WSHUUEZZULHHSX-UHFFFAOYSA-K 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
本發明提供一種獲得無刮痕等表面缺陷，較高之研磨速度且高精度之研磨面的藍寶石基板用研磨劑組合物。 The present invention provides an abrasive composition for a sapphire substrate that obtains a polishing surface with high polishing speed and high accuracy without surface defects such as scratches.
該組合物含有無機研磨材粒子、研磨促進劑、及水作為成分。無機研磨材粒子為氧化鋁粒子，研磨促進劑為有機羧酸系螯合性化合物，pH值為9.0~13.0。 This composition contains inorganic abrasive material particles, a polishing accelerator, and water as components. The inorganic abrasive material particles are alumina particles, the polishing accelerator is an organic carboxylic acid-based chelate compound, and the pH is 9.0 to 13.0.
Description
本發明係關於一種研磨劑組合物，尤其是藍寶石用之研磨劑組合物。 The present invention relates to an abrasive composition, especially an abrasive composition for sapphire.
一般而言，稱為硬脆材料者包括玻璃、陶瓷、石材、半導體結晶材料等。此種稱為硬脆材料者係難以加工，研磨速度亦較慢，需要較長加工時間的被研磨材料，且需要刮痕或缺陷等極少之平坦性較高之高品質研磨面。作為此種被研磨材料，典型而言可列舉藍寶石基板。 Generally speaking, those referred to as hard and brittle materials include glass, ceramics, stone, semiconductor crystal materials, and the like. This kind of hard and brittle material is difficult to process, the grinding speed is slow, the material to be ground that requires longer processing time, and requires high quality polished surfaces with few flatness such as scratches or defects. A typical example of such a material to be polished is a sapphire substrate.
藍寶石基板多用於LED元件基板等用途，近年來其生產量亦增加。例如，LED係於藍寶石基板上CVD(chemical vapor deposition，化學氣相沈積)塗佈GaN膜，使之沈積而成者。對於智慧型手機或平板電腦之覆蓋玻璃亦使用藍寶石。 Sapphire substrates are mostly used for applications such as LED element substrates, and their production has increased in recent years. For example, LEDs are formed by coating a GaN film by CVD (chemical vapor deposition) on a sapphire substrate and depositing it. Sapphire is also used for the cover glass of a smartphone or tablet.
關於藍寶石基板之製造，隨著需求增大、市場擴大，廉價化或高品質化之需求亦日益增強，全行業之競爭日益激化。藍寶石由於係化學穩定且莫氏硬度為9之極硬之材料，故而切斷、研削、研磨等加工極難進行，加工需要極長時間。為了儘量縮短加工時間而實現成本降低，業界進行有各種嘗試。先前，對於自藍寶石錠切斷之藍寶石晶圓，於經過將較藍寶石更硬之金剛石研磨粒自較大研磨粒多級地機械研磨成較小研磨粒之研削步驟後，於使用有二氧化矽系研磨劑、尤其是膠體二氧化矽系研磨劑之拋光步驟中進行最終研磨，而生產藍寶石基板。 Regarding the manufacture of sapphire substrates, with the increase in demand and the expansion of the market, the demand for cheaper or higher quality has also increased, and competition in the industry has intensified. Sapphire is a very hard material that is chemically stable and has a Mohs hardness of 9, so cutting, grinding, and grinding are extremely difficult to perform, and processing takes an extremely long time. Various attempts have been made in the industry to reduce processing time and minimize costs. Previously, for sapphire wafers cut from sapphire ingots, after the grinding step of mechanically grinding diamond abrasive grains that are harder than sapphire from larger abrasive grains into smaller abrasive grains, silicon dioxide was used. In the polishing step of a polishing agent based on a colloidal silica, particularly a colloidal silicon dioxide based polishing agent, final polishing is performed to produce a sapphire substrate.
然而，於該等步驟中，由於使用金剛石之昂貴研磨材、或因複數 個加工步驟導致加工時間延長，故而存在生產成本增大之問題。進而，由於係使用高硬度金剛石研磨材之加工，故而加工基板表面容易產生刮痕，並且基板內部容易產生藉由目測無法確認到之「潛傷」，因此存在變得難以進行對LED基板等所要求之高品質加工之問題。因此，現狀為達成市場所要求之廉價基板或成本降低、進而高品質加工等相當困難。 However, in these steps, due to the use of expensive diamond abrasives, Each processing step leads to prolonged processing time, so there is a problem that production costs increase. Furthermore, since the processing is performed using a high-hardness diamond abrasive, the surface of the processed substrate is prone to scratches, and the inside of the substrate is prone to "latent damage" that cannot be confirmed by visual inspection. Therefore, it is difficult to perform LED substrates and the like. The problem of high quality processing required. Therefore, it is quite difficult to achieve the low-cost substrate required by the market, the cost reduction, and the high-quality processing.
揭示有於藍寶石基板之研磨中用以同時實現較高之研磨速度與刮痕或缺陷之降低或平坦性之提昇的研磨劑組合物。 Disclosed is an abrasive composition used in the polishing of a sapphire substrate to achieve both a higher polishing speed and a reduction in scratches or defects or an improvement in flatness.
於專利文獻1中，揭示有於懸浮有氧化鋁粒子、膠體二氧化矽等之水性介質中包含氯化合物之具有鹼性pH值之藍寶石用研磨劑。有如下記載：所謂氯化合物係指酸之鹼金屬或鹼土金屬鹽，此處所謂酸係指氫氯酸、氫溴酸、氫碘酸、硫酸、硝酸、抗壞血酸、草酸或吡啶甲酸。然而，專利文獻1中關於有機羧酸系螯合性化合物之使用完全未揭示。 Patent Document 1 discloses an abrasive for sapphire having an alkaline pH value containing a chlorine compound in an aqueous medium in which alumina particles, colloidal silica and the like are suspended. It is described as follows: The so-called chlorine compound refers to an alkali metal or alkaline earth metal salt of an acid, and the so-called acid refers to hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, ascorbic acid, oxalic acid, or picolinic acid. However, the use of an organic carboxylic acid chelate compound in Patent Document 1 is not disclosed at all.
於專利文獻2中，揭示有包含膠體二氧化矽與氧化鋁等之複合研磨粒，且用於氧化鋁基板等之研磨的研磨劑組合物。然而，專利文獻2中關於有機羧酸系螯合性化合物之使用完全未揭示。 Patent Document 2 discloses an abrasive composition containing a composite abrasive particle of colloidal silica and alumina, and used for polishing an alumina substrate or the like. However, the use of an organic carboxylic acid chelate compound in Patent Document 2 is not disclosed at all.
於專利文獻3中，揭示有含有包含氧化鋁粒子之研磨劑與包含磷化合物之添加劑，且具有約8以上之pH值的用於含鋁陶瓷基板之研磨的研磨劑組合物。然而，專利文獻3中關於有機羧酸系螯合性化合物之使用完全未揭示。 Patent Document 3 discloses an abrasive composition for polishing an aluminum-containing ceramic substrate containing a polishing agent containing alumina particles and an additive containing a phosphorus compound and having a pH value of about 8 or more. However, the use of an organic carboxylic acid chelate compound in Patent Document 3 is not disclosed at all.
於專利文獻4中，揭示有以pH值為10.0~14.0之範圍為特徵之含氧化鋁研磨粒之藍寶石研磨用漿料。然而，專利文獻4中關於有機羧酸系螯合性化合物之使用完全未揭示。 Patent Document 4 discloses a slurry for polishing sapphire containing alumina-containing abrasive particles having a pH range of 10.0 to 14.0. However, Patent Document 4 does not disclose the use of an organic carboxylic acid chelate compound at all.
於專利文獻5中，作為維氏硬度為1500Hv以上之硬脆材料用研磨劑組合物，揭示有含有具有8.5以上之pH值且具有20m2/g以下之表面 積之氧化鋁研磨粒的研磨劑組合物。然而，專利文獻5中關於有機羧酸系螯合性化合物之使用完全未揭示。 In Patent Document 5, as an abrasive composition for hard and brittle materials having a Vickers hardness of 1500 Hv or more, an abrasive composition containing alumina abrasive particles having a pH value of 8.5 or more and a surface area of 20 m 2 / g or less is disclosed. Thing. However, Patent Document 5 does not disclose the use of an organic carboxylic acid chelate compound at all.
[專利文獻1]日本專利特表2008-531319號公報 [Patent Document 1] Japanese Patent Publication No. 2008-531319
[專利文獻2]日本專利特開平5-156238號公報 [Patent Document 2] Japanese Patent Laid-Open No. 5-156238
[專利文獻3]日本專利特開2011-62815號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2011-62815
[專利文獻4]國際公開第2011/136387號 [Patent Document 4] International Publication No. 2011/136387
[專利文獻5]國際公開第2012/115020號 [Patent Document 5] International Publication No. 2012/115020
然而，於將膠體二氧化矽用於研磨粒之專利文獻1中，雖然獲得良好之研磨面，但未獲得充分之研磨速度。 However, in Patent Document 1 in which colloidal silica is used for abrasive grains, although a good abrasive surface is obtained, a sufficient polishing rate is not obtained.
於專利文獻2~5中，由於將相對較硬之粒子即氧化鋁用於研磨粒，故而雖然研磨速度提昇，但難言獲得了充分之研磨速度。又，於研磨後未獲得高精度之研磨表面。 In Patent Documents 2 to 5, since alumina, which is a relatively hard particle, is used for the abrasive grains, although the polishing rate is increased, it is difficult to say that a sufficient polishing rate is obtained. Moreover, a highly accurate polished surface was not obtained after polishing.
本發明係鑒於此種課題反覆進行努力研究而成者，提供一種以較高之研磨速度獲得刮痕較少，表面粗糙度較低，高精度之研磨表面的藍寶石基板用研磨劑組合物。 The present invention has been made through intensive research in view of such a problem, and provides a polishing composition for a sapphire substrate which can obtain a high-precision polished surface with fewer scratches, a lower surface roughness, and a higher polishing rate.
又，提供一種不僅對藍寶石基板可使用，而且對具有與上述相同之課題之硬質玻璃基板、水晶基板、矽或半導體基板等之硬脆材料亦可使用之研磨劑組合物。 In addition, it is possible to provide an abrasive composition which can be used not only for sapphire substrates, but also for hard and brittle materials such as hard glass substrates, crystal substrates, silicon or semiconductor substrates having the same problems as described above.
本發明者發現，藉由如下藍寶石基板用研磨劑組合物，可解決上述課題，該藍寶石基板用研磨劑組合物係含有無機研磨材粒子、研磨促進劑、及水者，並且無機研磨材粒子為氧化鋁粒子，研磨促進劑為 有機羧酸系螯合性化合物，pH值為9.0~13.0。即，本發明係關於下述[1]至[18]。 The present inventors have found that the above-mentioned problems can be solved by an abrasive composition for a sapphire substrate. The abrasive composition for an sapphire substrate contains inorganic abrasive particles, a polishing accelerator, and water, and the inorganic abrasive particles are Alumina particles, grinding accelerator is Organic carboxylic acid chelating compound, pH value is 9.0 ~ 13.0. That is, the present invention relates to the following [1] to [18].
[1]一種藍寶石基板用研磨劑組合物，其特徵在於：其係含有無機研磨材粒子、研磨促進劑、及水者，並且上述無機研磨材粒子為氧化鋁粒子，上述研磨促進劑為有機羧酸系螯合性化合物，pH值為9.0~13.0。 [1] An abrasive composition for a sapphire substrate, characterized in that it contains inorganic abrasive material particles, a polishing accelerator, and water, and the inorganic abrasive material particles are alumina particles, and the polishing accelerator is an organic carboxylic acid. Acidic chelating compound, pH value is 9.0 ~ 13.0.
[2]如上述[1]之藍寶石基板用研磨劑組合物，其中上述有機羧酸系螯合性化合物為選自由乙二胺四乙酸、氮基三乙酸、二乙三胺五乙酸、羥基乙基乙二胺四乙酸、三乙四胺六乙酸、羥基乙基亞胺基二乙酸、二羥基乙基甘胺酸、二羧甲基麩胺酸及乙二胺-N,N"-二琥珀酸以及該等之鈉鹽、鉀鹽、銨鹽及胺鹽所組成之群中之一種以上。 [2] The abrasive composition for a sapphire substrate according to the above [1], wherein the organic carboxylic acid-based chelating compound is selected from the group consisting of ethylenediaminetetraacetic acid, nitrogen triacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyl Ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, dicarboxymethylglutamic acid and ethylenediamine-N, N "-bisamber Acid and one or more of these groups consisting of sodium, potassium, ammonium and amine salts.
[3]如上述[2]之藍寶石基板用研磨劑組合物，其中上述有機羧酸系螯合性化合物為乙二胺四乙酸四鉀鹽或羥基乙基乙二胺四乙酸三鈉鹽。 [3] The abrasive composition for a sapphire substrate according to the above [2], wherein the organic carboxylic acid-based chelating compound is an ethylenediaminetetraacetic acid tetrapotassium salt or a hydroxyethylethylenediaminetetraacetic acid trisodium salt.
[4]如上述[1]至[3]中任一項之藍寶石基板用研磨劑組合物，其中上述有機羧酸系螯合性化合物之含量相對於上述藍寶石基板用研磨劑組合物之質量為0.01~5質量%。 [4] The abrasive composition for a sapphire substrate according to any one of the above [1] to [3], wherein the content of the organic carboxylic acid-based chelating compound relative to the mass of the abrasive composition for a sapphire substrate is 0.01 to 5 mass%.
[5]如上述[4]之藍寶石基板用研磨劑組合物，其中上述有機羧酸系螯合性化合物之含量相對於上述藍寶石基板用研磨劑組合物之質量為0.01~2質量%。 [5] The abrasive composition for a sapphire substrate according to the above [4], wherein the content of the organic carboxylic acid-based chelate compound is 0.01 to 2% by mass based on the mass of the abrasive composition for a sapphire substrate.
[6]如上述[1]至[5]中任一項之藍寶石基板用研磨劑組合物，其中上述氧化鋁粒子之比表面積為0.1~15m2/g。 [6] The abrasive composition for a sapphire substrate according to any one of the above [1] to [5], wherein the specific surface area of the alumina particles is 0.1 to 15 m 2 / g.
[7]如上述[1]至[6]中任一項之藍寶石基板用研磨劑組合物，其中上述氧化鋁粒子為α氧化鋁粒子。 [7] The abrasive composition for a sapphire substrate according to any one of the above [1] to [6], wherein the alumina particles are α alumina particles.
[8]如上述[1]至[7]中任一項之藍寶石基板用研磨劑組合物，其中 上述氧化鋁粒子之D50值為0.01~1.0μm。 [8] The abrasive composition for a sapphire substrate according to any one of the above [1] to [7], wherein The D50 value of the alumina particles is 0.01 to 1.0 μm.
[9]如上述[1]至[8]中任一項之藍寶石基板用研磨劑組合物，其中上述氧化鋁粒子係以軟水鋁石Al2O3．H2O及/或假軟水鋁石Al2O3nH2O(n=1~2)作為原料之氧化鋁。 [9] The abrasive composition for a sapphire substrate according to any one of the above [1] to [8], wherein the alumina particles are boehmite Al 2 O 3 . Alumina with H 2 O and / or pseudo-boehmite Al 2 O 3 nH 2 O (n = 1 ~ 2) as raw materials.
[10]如上述[1]至[9]中任一項之藍寶石基板用研磨劑組合物，其中上述氧化鋁粒子之含量相對於上述藍寶石基板用研磨劑組合物之質量為5~50質量%。 [10] The abrasive composition for a sapphire substrate according to any one of the above [1] to [9], wherein the content of the alumina particles is 5 to 50% by mass relative to the mass of the abrasive composition for a sapphire substrate. .
[11]如上述[1]至[10]中任一項之藍寶石基板用研磨劑組合物，其進而含有分散劑。 [11] The abrasive composition for a sapphire substrate according to any one of the above [1] to [10], which further contains a dispersant.
[12]如上述[11]之藍寶石基板用研磨劑組合物，其中上述分散劑為選自由聚羧酸(鹽)、包含聚羧酸(鹽)之重複單元的共聚物及縮合磷酸鹽所組成之群中之一種以上。 [12] The abrasive composition for a sapphire substrate according to the above [11], wherein the dispersant is selected from the group consisting of a polycarboxylic acid (salt), a copolymer containing a repeating unit of a polycarboxylic acid (salt), and a condensed phosphate More than one of the group.
[13]如上述[11]或[12]之藍寶石基板用研磨劑組合物，其中上述分散劑之含量相對於上述藍寶石基板用研磨劑組合物之質量為0.005~0.5質量%。 [13] The abrasive composition for a sapphire substrate according to the above [11] or [12], wherein the content of the dispersant is 0.005 to 0.5% by mass relative to the mass of the abrasive composition for a sapphire substrate.
[14]如上述[1]至[13]中任一項之藍寶石基板用研磨劑組合物，其進而含有分散助劑，上述分散助劑為選自由氧化鋁溶膠及纖維素類所組成之群中之至少一種化合物。 [14] The abrasive composition for a sapphire substrate according to any one of the above [1] to [13], further comprising a dispersing aid, the dispersing aid being selected from the group consisting of alumina sol and cellulose At least one of the compounds.
[15]如上述[14]之藍寶石基板用研磨劑組合物，其中上述氧化鋁溶膠為選自由鋁鹽之溶膠化組合物及軟水鋁石溶膠所組成之群中之一種以上。 [15] The abrasive composition for a sapphire substrate according to the above [14], wherein the alumina sol is one or more selected from the group consisting of a sol-forming composition of an aluminum salt and a boehmite sol.
[16]如上述[14]或[15]之藍寶石基板用研磨劑組合物，其中上述分散助劑之含量相對於上述藍寶石基板用研磨劑組合物之質量為0.01~5質量%。 [16] The abrasive composition for a sapphire substrate according to the above [14] or [15], wherein the content of the dispersion aid is 0.01 to 5% by mass relative to the mass of the abrasive composition for a sapphire substrate.
[17]一種藍寶石基板之研磨方法，其特徵在於：使用如上述[1]至[16]中任一項之藍寶石基板用研磨劑組合物進行研磨。 [17] A method for polishing a sapphire substrate, characterized in that the sapphire substrate is polished using the abrasive composition for a sapphire substrate according to any one of [1] to [16].
[18]一種藍寶石基板之製造方法，其包括使用如上述[1]至[16]中任一項之藍寶石基板用研磨劑組合物進行研磨之步驟。 [18] A method for producing a sapphire substrate, comprising the step of polishing using the abrasive composition for a sapphire substrate according to any one of the above [1] to [16].
本發明之研磨劑組合物可將藍寶石基板等硬脆材料高速地進行研磨，且將研磨加工表面最後加工為高平坦度且刮痕或缺陷等較少之高品質研磨表面狀態。本發明之研磨劑組合物尤其適合於藍寶石基板之研磨。 The abrasive composition of the present invention can grind hard and brittle materials such as sapphire substrates at high speed, and finally process the polished surface into a high-quality polished surface state with high flatness and few scratches or defects. The abrasive composition of the present invention is particularly suitable for polishing a sapphire substrate.
又，本發明之研磨劑組合物可縮短研磨時間，而以低成本研磨藍寶石基板等。 In addition, the abrasive composition of the present invention can shorten the polishing time, and can polish a sapphire substrate or the like at a low cost.
以下，對本發明之實施形態進行說明。本發明並非限定於以下之實施形態者，只要不脫離發明之範圍，則亦可進行變更、修正、改良。 Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be made without departing from the scope of the invention.
本發明之藍寶石基板用研磨劑組合物含有無機研磨材粒子、研磨促進劑、及水，無機研磨材粒子為氧化鋁粒子，研磨促進劑為有機羧酸系螯合性化合物，藍寶石基板用研磨劑組合物之pH值為9.0~13.0。 The abrasive composition for a sapphire substrate of the present invention contains inorganic abrasive material particles, a polishing accelerator, and water. The inorganic abrasive material particles are alumina particles, the polishing accelerator is an organic carboxylic acid chelating compound, and the abrasive for a sapphire substrate. The pH of the composition is 9.0 ~ 13.0.
本發明之研磨劑組合物包含無機研磨材粒子，無機研磨材粒子為氧化鋁粒子。無機研磨材粒子中視需要亦可添加氧化矽、鋯英石、氧化鋯、氧化鈰、氮化矽、碳化矽等。 The abrasive composition of the present invention includes inorganic abrasive particles, and the inorganic abrasive particles are alumina particles. To the inorganic abrasive material particles, silicon oxide, zircon, zirconia, cerium oxide, silicon nitride, silicon carbide, etc. may be added as necessary.
一般而言，作為氧化鋁粒子之原料，可列舉：三水鋁石Al2O3．3H2O、軟水鋁石Al2O3．H2O、假軟水鋁石Al2O3．nH2O(n=1~2)、銨礬AlNH4(SO4)2．12H2O或碳鈉鋁銨石NH4AlCO3(OH)2之鋁鹽等。該等氧化鋁原料係藉由例如以下方法而製備。 In general, as a raw material of alumina particles, gibbsite Al 2 O 3 can be cited. 3H 2 O, boehmite Al 2 O 3 . H 2 O, pseudo-boehmite Al 2 O 3 . nH 2 O (n = 1 ~ 2), ammonium alumium (NH 4 (SO 4 ) 2 ) 2 . 12H 2 O or alumite of NH 4 AlCO 3 (OH) 2 and so on. These alumina raw materials are prepared by the following method, for example.
藉由將鋁礬土溶解於氫氧化鈉之熱溶液中，將藉由過濾去除雜質成分而獲得之溶液進行冷卻，將所產生之沈澱物加以乾燥而獲得。該方法通常稱為拜耳法。 It is obtained by dissolving bauxite in a hot solution of sodium hydroxide, cooling the solution obtained by removing the impurity components by filtration, and drying the resulting precipitate. This method is commonly referred to as the Bayer method.
藉由將利用金屬鋁與醇之反應所獲得之烷醇鋁Al(OR)3進行水解而獲得。該方法通常稱為烷醇鋁法。 Obtained by hydrolyzing aluminum alkoxide Al (OR) 3 obtained by the reaction of metal aluminum with alcohol. This method is commonly referred to as the aluminum alkoxide method.
將三水鋁石或三羥鋁石於鹼性環境下利用水蒸汽進行處理而獲得。 Obtained by treating gibbsite or bayerite with water vapor in an alkaline environment.
例如，銨礬係藉由將硫酸銨與硫酸鋁之水溶液進行冷卻，使之自溶液中析出而獲得。碳鈉鋁銨石係藉由使銨礬與碳酸銨進行反應而獲得。 For example, ammonium alum is obtained by cooling an aqueous solution of ammonium sulfate and aluminum sulfate and precipitating it from the solution. Sodium aluminite is obtained by reacting ammonium alum and ammonium carbonate.
藉由將該等氧化鋁原料進行煅燒或熱分解等方式，而獲得氧化鋁。藉由將所獲得之氧化鋁進行粉碎或分級，而獲得氧化鋁粒子。氧化鋁粒子存在α氧化鋁、γ氧化鋁、δ氧化鋁、θ氧化鋁等多種晶形，任一晶形均可使用。 Alumina is obtained by calcining or thermally decomposing these alumina raw materials. Alumina particles are obtained by pulverizing or classifying the obtained alumina. The alumina particles have various crystal forms such as α alumina, γ alumina, δ alumina, and θ alumina, and any crystal form can be used.
本發明中所使用之氧化鋁粒子之原料並無特別限定，尤佳為以軟水鋁石Al2O3．H2O及/或假軟水鋁石Al2O3．nH2O(n=1~2)作為原料之氧化鋁。 The raw material of the alumina particles used in the present invention is not particularly limited, and the boehmite Al 2 O 3 is particularly preferred. H 2 O and / or pseudo-boehmite Al 2 O 3 . nH 2 O (n = 1 ~ 2) as the raw material of alumina.
以軟水鋁石或假軟水鋁石作為原料之氧化鋁粒子與由其他原料所製備之氧化鋁粒子相比，獲得球形且多晶狀之氧化鋁粒子，容易獲得相對高純度之氧化鋁粒子。又，於粒度製備時，容易獲得粗粒較少、粒度分佈較窄、角較少之微粒子。 Compared with alumina particles prepared from other raw materials, alumina particles using boehmite or pseudo-boehmite as raw materials can obtain spherical and polycrystalline alumina particles, and relatively easy to obtain alumina particles of relatively high purity. In addition, during particle size preparation, it is easy to obtain fine particles with fewer coarse particles, narrow particle size distribution, and fewer angles.
由於成為具有此種特徵之氧化鋁粒子，故而若將以軟水鋁石或假軟水鋁石作為原料之氧化鋁粒子用於本發明之藍寶石基板用研磨劑組 合物，則基板之刮痕變少，可獲得較高之研磨速度。 As alumina particles having such characteristics, if alumina particles using boehmite or pseudo-boehmite as raw materials are used in the abrasive set for a sapphire substrate of the present invention, Composition, the number of scratches on the substrate is reduced, and a higher polishing speed can be obtained.
較佳為本發明之無機研磨材粒子之D50值(中值粒徑)為0.01~1.00μm。若D50小於0.01μm，則變得難以獲得充分之研磨速度，若大於1.00μm，則有導致產生刮痕或潛傷、表面粗糙度之惡化、平坦度之降低等研磨表面之面質惡化的情況。又，若D50大於1.00μm，則亦有導致分散穩定性(可將水性介質中粒子不沈澱而以分散之狀態保持多長時間)惡化之情況。D50更佳為0.10~0.90μm，進而較佳為0.20~0.70μm。 The D50 value (median diameter) of the inorganic abrasive material particles of the present invention is preferably 0.01 to 1.00 μm. If D50 is less than 0.01 μm, it becomes difficult to obtain a sufficient polishing rate. If it is more than 1.00 μm, scratches or latent injuries, deterioration of surface roughness, and reduction in flatness may deteriorate surface quality of the polished surface. . When D50 is larger than 1.00 μm, the dispersion stability (how long the particles in the aqueous medium can be kept in a dispersed state without being precipitated) may be deteriorated. D50 is more preferably 0.10 to 0.90 μm, and still more preferably 0.20 to 0.70 μm.
D50可使用雷射繞射式粒度分佈測定裝置(例如島津製作所公司製造、SALD2200)進行測定。D50係指於以雷射繞射法作為測定原理之以體積基準所測得之粒度分佈中，將所測得之粒徑以最小粒徑為起點以粒徑遞增之順序加以累計時占全部粒子之體積之50%的粒徑。例如，所謂D50為0.45μm意指粒徑0.45μm以下之粒子之體積之合計占成為對象之全部粒子之體積之合計之50%。 D50 can be measured using a laser diffraction type particle size distribution measuring device (for example, Shimadzu Corporation, SALD2200). D50 refers to the particle size distribution measured on a volume basis using the laser diffraction method as the measuring principle. The measured particle size is the smallest particle size as the starting point and the particle size increases in the order of cumulative particle size. The particle size is 50% of the volume. For example, the D50 of 0.45 μm means that the total volume of particles having a particle diameter of 0.45 μm or less accounts for 50% of the total volume of all the particles to be targeted.
較佳為本發明之無機研磨材粒子之比表面積為0.1~15m2/g。氧化鋁研磨粒之比表面積成為因氧化鋁原料之煅燒或熱分解而緩慢減小之值，可根據煅燒或熱分解之條件進行調整。 The specific surface area of the inorganic abrasive material particles of the present invention is preferably 0.1 to 15 m 2 / g. The specific surface area of the alumina abrasive particles gradually decreases due to the calcination or thermal decomposition of the alumina raw material, and can be adjusted according to the conditions of the calcination or thermal decomposition.
若比表面積小於0.1m2/g，則有表面粗糙度增大，刮痕變多之情況，若大於15m2/g，則變得難以充分地獲得研磨速度。比表面積更佳為1~14m2/g。 If the specific surface area is less than 0.1 m 2 / g, the surface roughness may increase and the number of scratches may increase. If it is more than 15 m 2 / g, it may become difficult to obtain a sufficient polishing rate. The specific surface area is more preferably 1 to 14 m 2 / g.
比表面積可使用流動式比表面積自動測定裝置(例如，島津製作所公司製造、Flowsorb II)作為BET值而測定。所謂BET值係指藉由BET法(氣體吸附法)所求出之比表面積。 The specific surface area can be measured as a BET value using an automatic flow-type specific surface area measurement device (for example, Shimadzu Corporation, Flowsorb II). The BET value refers to a specific surface area obtained by a BET method (gas adsorption method).
較佳為本發明之氧化鋁粒子之晶形為α氧化鋁。若將氧化鋁原料進行煅燒或熱分解，則會經過γ晶、δ晶、θ晶等結晶相，而結晶相轉移為高溫穩定相之α晶。隨著煅燒或熱分解，結晶相之硬度隨之增大，又，結晶粒子之尺寸亦成長，因此結晶相可根據煅燒或熱分解之條件進行 調整。例如，如日本專利第4290799號公報之段落0021所記述，可藉由將氧化鋁原料於1000℃以上之溫度下供於煅燒或熱分解，而使氧化鋁原料結晶相轉移為α晶。 The crystal form of the alumina particles of the present invention is preferably alumina. If the alumina raw material is calcined or thermally decomposed, it will pass through crystalline phases such as γ crystals, δ crystals, and θ crystals, and the crystalline phases will be transferred into α crystals of high temperature stable phases. With the calcination or thermal decomposition, the hardness of the crystalline phase increases, and the size of the crystalline particles also grows, so the crystalline phase can be carried out according to the conditions of the calcination or thermal decomposition. Adjustment. For example, as described in paragraph 0021 of Japanese Patent No. 4290799, the alumina raw material crystal phase can be transferred to α crystals by supplying the alumina raw material to calcination or thermal decomposition at a temperature of 1000 ° C. or higher.
α氧化鋁由於係具有充分硬度之晶形，故而於本發明之研磨劑組合物中若使用α氧化鋁粒子，則會獲得較高之研磨速度。 Since α alumina has a crystalline form with sufficient hardness, if α alumina particles are used in the abrasive composition of the present invention, a higher polishing rate will be obtained.
較佳為本發明之無機研磨材粒子之含量相對於藍寶石基板用研磨劑組合物之質量為5~50質量%。若含量小於5質量%，則變得難以獲得充分之研磨速度，即使高於50質量%，亦不見研磨速度之進一步提昇，非但不經濟，而且無機研磨材粒子之分散性惡化，研磨劑組合物之黏度上升，因而有研磨速度反而降低之情況，又，有於循環使用研磨劑組合物時送液阻力變高而產生不良情況之情形。無機研磨材粒子之含量相對於藍寶石基板用研磨劑組合物之質量更佳為5~20質量%，進而較佳為8~15質量%。 The content of the inorganic abrasive particles in the present invention is preferably 5 to 50% by mass based on the mass of the abrasive composition for a sapphire substrate. If the content is less than 5% by mass, it becomes difficult to obtain a sufficient polishing rate. Even if it is higher than 50% by mass, no further increase in the polishing rate is observed. This is not only uneconomical, but also the dispersion of the inorganic abrasive material particles deteriorates, and the abrasive composition Since the viscosity increases, the polishing rate may decrease, and the liquid-feeding resistance may increase when the abrasive composition is circulated, which may cause a problem. The content of the inorganic abrasive material particles is more preferably 5 to 20% by mass, and more preferably 8 to 15% by mass, relative to the mass of the abrasive composition for a sapphire substrate.
本發明之研磨劑組合物之pH值為9.0~13.0。於藍寶石基板之研磨中上述pH值適合之理由認為如下。 The pH value of the abrasive composition of the present invention is 9.0 to 13.0. The reason why the above-mentioned pH value is suitable for polishing the sapphire substrate is considered as follows.
所謂藍寶石係指單晶之氧化鋁，已知於水中藍寶石之表面作為固體酸而發揮作用。因此，認為於研磨時局部產生摩擦熱之情形時，藍寶石容易因摩擦熱而以鹼性之液性引起表面之溶解反應。認為藉由該溶解反應，而開始研磨。若pH值未達9，則溶解反應不開始，研磨速度之降低明顯。即使成為大於13.0之值，亦不見研磨速度之進一步提昇，又，使用時有危險。 The sapphire refers to single crystal alumina, and it is known that the surface of sapphire in water functions as a solid acid. Therefore, it is considered that when frictional heat is locally generated during polishing, sapphire is likely to cause a surface dissolution reaction with alkaline liquidity due to the frictional heat. It is considered that grinding is started by the dissolution reaction. If the pH value does not reach 9, the dissolution reaction does not start, and the reduction in the grinding speed is significant. Even if the value is greater than 13.0, no further increase in the grinding speed is seen, and it is dangerous during use.
pH值更佳為10.0~13.0。 The pH is more preferably 10.0 ~ 13.0.
研磨促進劑係於研磨組合物之pH值9.0~13.0下促進藍寶石基板之表面上之反應，而提供較高之研磨速度者。 The polishing accelerator promotes the reaction on the surface of the sapphire substrate at a pH value of 9.0 to 13.0 of the polishing composition, and provides a higher polishing speed.
作為研磨促進劑，於本發明中使用有機羧酸系螯合性化合物。本發明之研磨劑組合物亦可任意地併用氧酸鹽研磨促進劑。 As the polishing accelerator, an organic carboxylic acid-based chelating compound is used in the present invention. The abrasive composition of the present invention may be optionally combined with an oxo acid salt polishing accelerator.
認為本發明所謂研磨促進劑具有促進由pH值為9.0~13.0之研磨劑組合物於藍寶石基板表面所產生之因溶解形成之變質層之去除的作用，認為其結果為，於已去除變質層之藍寶石基板表面再次由pH值為9.0~13.0之研磨劑組合物而產生因溶解形成之變質層，利用研磨促進劑而去除該變質層，藉此研磨進行，而提昇研磨速度。 It is considered that the so-called polishing accelerator of the present invention has the effect of promoting the removal of the deteriorated layer formed by the dissolution caused by the abrasive composition having a pH value of 9.0 to 13.0 on the surface of the sapphire substrate. The surface of the sapphire substrate is changed from the abrasive composition having a pH value of 9.0 to 13.0 to generate a deteriorated layer formed by dissolution. The deteriorated layer is removed by using a polishing accelerator, thereby polishing is performed and the polishing speed is increased.
有機羧酸系螯合性化合物係與金屬離子形成螯合化合物之具有多牙配位基之化合物即螯合性化合物中，包含羧酸或羧酸之鹽作為配位基之螯合性化合物。 The organic carboxylic acid chelate compound is a chelate compound that is a compound having a multidentate ligand that forms a chelate compound with a metal ion. The chelate compound contains a carboxylic acid or a salt of a carboxylic acid as a ligand.
就將研磨劑組合物之pH值設為9.0~13.0之觀點而言，較佳為有機羧酸系螯合性化合物係與鹼金屬、氨、胺等形成鹽。該等鹽亦可藉由向研磨劑組合物中分別添加有機羧酸系螯合化合物、與鹼金屬氫氧化物、氨或胺，而於研磨劑組合物中生成。 From the viewpoint of setting the pH of the abrasive composition to 9.0 to 13.0, it is preferred that the organic carboxylic acid-based chelate compound forms a salt with an alkali metal, ammonia, amine, or the like. These salts can also be produced in the abrasive composition by adding an organic carboxylic acid-based chelate compound and an alkali metal hydroxide, ammonia or amine to the abrasive composition, respectively.
作為有機羧酸系螯合性化合物，可列舉：乙二胺四乙酸(EDTA)、氮基三乙酸(NTA)、二乙三胺五乙酸(DTPA)、羥基乙基乙二胺四乙酸(HEDTA)、三乙四胺六乙酸(TTHA)、羥基乙基亞胺基二乙酸(HIDA)、二羥基乙基甘胺酸(DHEG)、二羧甲基麩胺酸(GMGA)、乙二胺-N,N"-二琥珀酸(EDDS)及該等之鈉鹽、鉀鹽、銨鹽、胺鹽等。上述化合物可單獨使用，亦可組合2種以上而使用。作為較佳之有機羧酸螯合性化合物，可列舉：乙二胺四乙酸四鉀鹽、羥基乙基乙二胺四乙酸三鈉鹽等。 Examples of the organic carboxylic acid chelating compound include ethylenediaminetetraacetic acid (EDTA), nitrogen triacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), and hydroxyethylethylenediaminetetraacetic acid (HEDTA). ), Triethylenetetraaminehexaacetic acid (TTHA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), dicarboxymethylglutamic acid (GMGA), ethylenediamine- N, N "-disuccinic acid (EDDS) and the sodium, potassium, ammonium, amine salts, etc. of the above compounds can be used alone or in combination of two or more. As a preferred organic carboxylic acid chelate Synthetic compounds include tetrapotassium salt of ethylenediamine tetraacetate, and trisodium salt of hydroxyethylethylenediamine tetraacetate.
有機羧酸系螯合性化合物為公知，可於市場上容易地取得，或進行製備。 Organic carboxylic acid-based chelating compounds are well known and can be easily obtained on the market or prepared.
較佳為有機羧酸系螯合性化合物之含量相對於藍寶石基板用研磨劑組合物之質量為0.01~5質量%之範圍。若少於0.01質量%，則促 進研磨速度之效果不充分，即使超過5質量%，亦不見研磨速度之進一步提昇，非但不經濟，而且有分散性開始惡化之情況。有機羧酸系螯合性化合物之含量相對於藍寶石基板用研磨劑組合物之質量更佳為0.01~2質量%，進而較佳為0.1~1質量%之範圍。 The content of the organic carboxylic acid-based chelating compound is preferably in a range of 0.01 to 5% by mass based on the mass of the abrasive composition for a sapphire substrate. If less than 0.01% by mass, The effect of the grinding speed is not sufficient. Even if it exceeds 5% by mass, there is no further improvement in the grinding speed. It is not only uneconomical, but the dispersion may start to deteriorate. The content of the organic carboxylic acid-based chelating compound is more preferably 0.01 to 2% by mass, and more preferably 0.1 to 1% by mass relative to the mass of the abrasive composition for a sapphire substrate.
對於本發明之研磨劑組合物亦可任意地併用氧酸鹽研磨促進劑。 The abrasive composition of the present invention may be optionally combined with an oxo acid salt polishing accelerator.
較佳為於本發明中任意地使用之氧酸鹽之氧酸係選自由鋁、矽及硼所組成之群中之一種以上之元素之氧酸。作為該等氧酸鹽，可列舉：鋁酸鹽、矽酸鹽、鋁矽酸鹽及硼酸鹽。該等中，較佳為使用鋁酸鹽。 It is preferable that the oxo acid of the oxo acid used arbitrarily in the present invention is an oxo acid of one or more elements selected from the group consisting of aluminum, silicon, and boron. Examples of the oxo acid salt include aluminate, silicate, aluminosilicate, and borate. Among these, aluminate is preferably used.
較佳為本發明中所使用之氧酸鹽之鹽係選自由鹼金屬鹽、鹼土金屬鹽所組成之群中之一種以上之鹽。作為該等氧酸鹽，可列舉：鈉鹽、鉀鹽、鋰鹽、鈣鹽等。該等中，較佳為使用鈉鹽或鉀鹽。 Preferably, the salt of the oxo acid salt used in the present invention is one or more salts selected from the group consisting of alkali metal salts and alkaline earth metal salts. Examples of the oxo acid salt include sodium salt, potassium salt, lithium salt, and calcium salt. Among these, a sodium salt or a potassium salt is preferably used.
更佳為本發明中所使用之氧酸鹽包含鋁酸鈉或鋁酸鉀，最佳為包含鋁酸鈉。 More preferably, the oxo acid salt used in the present invention contains sodium aluminate or potassium aluminate, and most preferably contains sodium aluminate.
氧酸鹽為公知，可於市場上容易地取得，或進行製備。 Oxyacids are well known and can be easily obtained on the market or prepared.
較佳為於併用氧酸鹽作為研磨促進劑之情形時之氧酸鹽之含量相對於藍寶石基板用研磨劑組合物之質量為0.01~5質量%之範圍。若少於0.01質量%，則促進研磨速度之效果更不充分，若超過5質量%，則有分散性開始惡化之情況。氧酸鹽之含量相對於藍寶石基板用研磨劑組合物之質量更佳為0.01~2質量%，進而較佳為0.01~0.5質量%，最佳為0.1~0.4質量%之範圍。 When the oxo acid salt is used as a polishing accelerator in combination, the content of the oxo acid salt is preferably in a range of 0.01 to 5% by mass based on the mass of the sapphire substrate abrasive composition. If it is less than 0.01% by mass, the effect of promoting the polishing rate is insufficient, and if it exceeds 5% by mass, the dispersibility may start to deteriorate. The content of the oxo acid salt is more preferably 0.01 to 2% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.1 to 0.4% by mass relative to the mass of the abrasive composition for a sapphire substrate.
藉由使研磨劑組合物中發生無機研磨材粒子之凝集，有引起產生損傷或表面粗糙度惡化之研磨面質降低或研磨速度降低之情況。 Aggregation of the inorganic abrasive material particles in the abrasive composition may cause deterioration of the polishing surface or deterioration of the polishing speed, which may cause damage or deterioration of the surface roughness.
為了改善無機研磨材粒子之分散狀態，而改善如上所述之問題，於本發明之研磨劑組合物中亦可併用分散劑。 In order to improve the dispersion state of the inorganic abrasive material particles and to solve the problems described above, a dispersant may be used in combination in the abrasive composition of the present invention.
作為分散劑，可列舉：高分子型分散劑、界面活性劑型分散劑、無機型分散劑等。於本發明之研磨劑組合物中，較佳為使用高分子型分散劑及無機型分散劑。 Examples of the dispersant include a polymer-type dispersant, a surfactant-type dispersant, and an inorganic-type dispersant. In the abrasive composition of the present invention, a polymer dispersant and an inorganic dispersant are preferably used.
作為高分子型分散劑，可列舉聚羧酸(鹽)、包含聚羧酸(鹽)之重複單元的共聚物等，作為無機型分散劑，可列舉縮合磷酸鹽等。 Examples of the polymer-type dispersant include polycarboxylic acid (salt), a copolymer containing a repeating unit of the polycarboxylic acid (salt), and the like, and examples of the inorganic-type dispersant include condensed phosphate.
作為聚羧酸(鹽)，可列舉：聚丙烯酸、聚甲基丙烯酸、聚丙烯酸鹼金屬鹽、聚甲基丙烯酸鹼金屬鹽、聚丙烯酸銨鹽、聚甲基丙烯酸銨鹽、聚丙烯酸胺鹽、聚甲基丙烯酸胺鹽等。 Examples of the polycarboxylic acid (salt) include polyacrylic acid, polymethacrylic acid, polyacrylic acid alkali metal salt, polymethacrylic acid alkali metal salt, polyacrylic acid ammonium salt, polymethacrylic acid ammonium salt, polyacrylic acid amine salt, Polyamine methacrylate and the like.
作為包含聚羧酸(鹽)之重複單元的共聚物，可列舉：聚丙烯酸與包含磺酸基之構成單位之共聚物、聚丙烯酸與聚丙烯酸酯之共聚物等。 Examples of the copolymer containing a repeating unit of a polycarboxylic acid (salt) include a copolymer of polyacrylic acid and a structural unit containing a sulfonic acid group, and a copolymer of polyacrylic acid and polyacrylate.
作為縮合磷酸鹽，可列舉：六偏磷酸鈉、焦磷酸鈉、焦磷酸鉀、三聚磷酸鈉、酸性偏磷酸鈉、酸性焦磷酸鈉等。 Examples of the condensed phosphate include sodium hexametaphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, acidic sodium metaphosphate, and acidic sodium pyrophosphate.
較佳為分散劑之含量相對於藍寶石基板用研磨劑組合物之質量為0.005~0.5質量%之範圍。於未達0.005質量%時，改善無機研磨材粒子之分散狀態的效果不充分，即使超過0.5質量%，改善無機研磨材粒子之分散狀態的效果亦達到極限，且不經濟。分散劑之含量相對於藍寶石基板用研磨劑組合物之質量更佳為0.01~0.5質量%，進而較佳為0.02~0.3質量%，最佳為0.05~0.2質量%。 The content of the dispersant is preferably in a range of 0.005 to 0.5% by mass based on the mass of the abrasive composition for a sapphire substrate. When it is less than 0.005 mass%, the effect of improving the dispersion state of the inorganic abrasive material particles is insufficient. Even if it exceeds 0.5 mass%, the effect of improving the dispersion state of the inorganic abrasive material particles reaches a limit, and it is not economical. The content of the dispersant is more preferably 0.01 to 0.5% by mass, more preferably 0.02 to 0.3% by mass, and most preferably 0.05 to 0.2% by mass relative to the mass of the abrasive composition for a sapphire substrate.
若於將研磨劑組合物收納至瓶中之狀態下進行靜置，則引起氧化鋁研磨粒之沈澱，再次使用研磨劑組合物時，有再次製成均勻之分散狀態需要時間之情況。又，於藍寶石基板等之研磨中，一般於對研磨機供給研磨劑組合物時，以循環方式供給研磨劑組合物。於該情形時，有於研磨劑組合物之流路、研磨劑組合物之儲罐或輸送管道內引起氧化鋁研磨粒之沈澱之情況，亦有引起研磨速度降低等之可能性。 If the abrasive composition is left to stand in a state where the abrasive composition is stored in a bottle, precipitation of alumina abrasive particles may be caused. When the abrasive composition is used again, it may take time to make the dispersion state uniform again. In addition, in the polishing of a sapphire substrate or the like, the abrasive composition is generally supplied in a circulating manner when the abrasive composition is supplied to a polishing machine. In this case, precipitation of alumina abrasive grains may occur in the flow path of the abrasive composition, the storage tank of the abrasive composition, or the conveying pipe, and there may be a possibility that the polishing speed may decrease.
為了解決如上所述之沈澱或再分散之問題，於本發明之研磨劑組 合物中亦可併用分散助劑。作為分散助劑，可列舉：氧化鋁溶膠、纖維素類等。藉由添加分散助劑而使無機研磨材粒子之分散性提昇之原因推測為研磨材粒子處於被氧化鋁溶膠或纖維素類等之化學相互作用網狀結構所捕捉之狀態。 In order to solve the problem of precipitation or redispersion as described above, the abrasive agent set of the present invention A dispersing aid may also be used in combination. Examples of the dispersing aid include alumina sol and cellulose. The reason why the dispersibility of the inorganic abrasive material particles is improved by adding a dispersion aid is presumed to be that the abrasive material particles are captured by a chemically-interactive network structure such as alumina sol or cellulose.
又，藉由添加分散助劑，亦可見到研磨速度提昇之效果。 In addition, the effect of increasing the polishing speed can be seen by adding a dispersing aid.
所謂氧化鋁溶膠係指將氫氧化鋁或水合氧化鋁於水系分散介質中分散為膠體狀而成者。關於水合氧化鋁，可列舉：軟水鋁石、假軟水鋁石、水鋁石、三水鋁石、三羥鋁石等。 The alumina sol refers to a product obtained by dispersing aluminum hydroxide or hydrated aluminum oxide in a colloidal state in an aqueous dispersion medium. Examples of the hydrated alumina include boehmite, pseudo-boehmite, gibbsite, gibbsite, and bayerite.
作為將氫氧化鋁於水系分散介質中分散為膠體狀而成之氧化鋁溶膠，可列舉鋁鹽之溶膠化生成物。 Examples of the alumina sol obtained by dispersing aluminum hydroxide in a colloidal state in an aqueous dispersion medium include a solization product of an aluminum salt.
鋁鹽之溶膠化生成物係藉由鋁鹽、與容易與水反應而生成羥基之物質或含有羥基之化合物之反應而獲得。 The solization product of an aluminum salt is obtained by reacting an aluminum salt with a substance that easily reacts with water to form a hydroxyl group or a compound containing a hydroxyl group.
作為所使用之鋁鹽，可列舉：硫酸鋁、氯化鋁、硝酸鋁等。作為容易與所使用之水反應而生成羥基之物質，可列舉：氨或烷基胺、胺系螯合化合物、胺基羧酸、胺基羧酸系螯合化合物、胺基膦酸系螯合化合物等。作為所使用之含有羥基之化合物，可列舉氫氧化鈉或氫氧化鉀等。 Examples of the aluminum salt used include aluminum sulfate, aluminum chloride, and aluminum nitrate. Examples of substances that easily react with the water used to form a hydroxyl group include ammonia or alkylamines, amine-based chelate compounds, aminocarboxylic acids, aminocarboxylic acid-based chelate compounds, and aminophosphonic acid-based chelate. Compounds etc. Examples of the compound containing a hydroxyl group include sodium hydroxide and potassium hydroxide.
作為將水合氧化鋁於水系分散介質中分散為膠體狀而成之氧化鋁溶膠，可列舉軟水鋁石溶膠。 Examples of the alumina sol obtained by dispersing hydrated alumina in a colloidal state in an aqueous dispersion medium include a boehmite sol.
軟水鋁石溶膠係藉由利用鋁鹽、無機酸或有機酸將軟水鋁石及/或假軟水鋁石進行溶膠化而獲得。 The boehmite sol is obtained by sol-gelating boehmite and / or pseudo-boehmite with an aluminum salt, an inorganic acid or an organic acid.
作為所使用之鋁鹽，可列舉：硫酸鋁、氯化鋁、硝酸鋁等。作為所使用之無機酸，可列舉：硝酸、鹽酸等。作為所使用之有機酸，可列舉：乙酸、葡萄糖酸等。 Examples of the aluminum salt used include aluminum sulfate, aluminum chloride, and aluminum nitrate. Examples of the inorganic acid used include nitric acid and hydrochloric acid. Examples of the organic acid used include acetic acid and gluconic acid.
軟水鋁石溶膠可使用藉由上述方法所製備者，亦可將使市售之軟水鋁石溶膠固化而成者於使用時溶解至水中生成軟水鋁石溶膠而使 用。 The boehmite sol can be prepared by the above method, or a commercially available boehmite sol can be cured and dissolved in water to generate a boehmite sol during use. use.
作為纖維素類，可列舉：纖維素、結晶性纖維素、羧甲基纖維素、羥丙基甲基纖維素等。 Examples of celluloses include cellulose, crystalline cellulose, carboxymethyl cellulose, and hydroxypropyl methyl cellulose.
作為本發明中所使用之分散助劑，較佳為氧化鋁溶膠，更佳為鋁鹽之溶膠化生成物及軟水鋁石溶膠。 As the dispersing aid used in the present invention, an alumina sol is preferable, and a solization product of an aluminum salt and a boehmite sol are more preferable.
較佳為分散助劑之含量相對於藍寶石基板用研磨劑組合物之質量為0.01~5質量%。若少於0.01質量%，則無法充分地獲得無機研磨材粒子之分散效果。若多於5質量%，則可見研磨劑組合物之黏度上升，變得對循環使用帶來障礙。又，若分散助劑之含量多於5質量%，則亦有研磨速度降低之情況。更佳為分散助劑之含量相對於藍寶石基板用研磨劑組合物之質量為0.01~2質量%。 The content of the dispersing assistant is preferably 0.01 to 5% by mass based on the mass of the abrasive composition for a sapphire substrate. If it is less than 0.01% by mass, the dispersion effect of the inorganic abrasive material particles cannot be sufficiently obtained. If it is more than 5% by mass, the viscosity of the abrasive composition may increase, which may cause an obstacle to recycling. In addition, if the content of the dispersing assistant is more than 5% by mass, the polishing rate may be reduced. More preferably, the content of the dispersion aid is 0.01 to 2% by mass based on the mass of the abrasive composition for a sapphire substrate.
本發明之研磨劑組合物中，為了設為特定之pH值，可包含pH值調整劑。作為pH值調整劑，可列舉：無機鹼、有機鹼、無機酸、有機酸等。作為無機鹼，可列舉：氫氧化鈉、氫氧化鉀、氨等。作為有機鹼，可列舉：氫氧化四甲基銨、烷醇胺等。作為無機酸，可列舉：硫酸、硝酸、磷酸、鹽酸等。作為有機酸，可列舉：檸檬酸、蘋果酸等。 The abrasive composition of the present invention may contain a pH adjuster in order to set a specific pH value. Examples of the pH adjusting agent include inorganic bases, organic bases, inorganic acids, and organic acids. Examples of the inorganic base include sodium hydroxide, potassium hydroxide, and ammonia. Examples of the organic base include tetramethylammonium hydroxide and alkanolamine. Examples of the inorganic acid include sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid. Examples of the organic acid include citric acid and malic acid.
本發明之研磨劑組合物中，視需要亦可併用防銹劑、防菌劑、洗淨劑、表面改質劑、刮痕降低劑、黏度調整劑、消泡劑、抗氧化劑、其他目的之界面活性劑等。 In the abrasive composition of the present invention, if necessary, rust inhibitors, bactericides, detergents, surface modifiers, scratch reduction agents, viscosity modifiers, defoamers, antioxidants, and other purposes may be used in combination. Surfactants and so on.
本發明之研磨劑組合物可藉由將各成分加以混合而製備。 The abrasive composition of the present invention can be prepared by mixing the ingredients.
本發明之研磨劑組合物可為了研磨用作LED元件等電子零件材料、光學濾光器等光學零件、電氣絕緣性材料、鐘錶外罩或窗材、耐摩耗性材料等的藍寶石基板、玻璃基板、水晶基板、矽或半導體基板等而使用。 The abrasive composition of the present invention can be used for polishing sapphire substrates, glass substrates, such as electronic component materials such as LED elements, optical components such as optical filters, electrical insulating materials, timepiece covers or window materials, wear-resistant materials, Used for crystal substrates, silicon or semiconductor substrates.
以下，對實施例及比較例進行詳細說明，但本發明並非限定於該等實施例者。 Hereinafter, examples and comparative examples will be described in detail, but the present invention is not limited to those examples.
實施例及比較例中所使用之氧化鋁粒子係藉由以下方法而製備。 The alumina particles used in the examples and comparative examples were prepared by the following methods.
將市售之軟水鋁石氧化鋁(Sasol公司製造CA氧化鋁)以成為比表面積BET 4m2/g之方式於1160℃下煅燒9小時。煅燒後之氧化鋁之晶形為α氧化鋁。將煅燒品進行濕式微粉碎，而調整為0.35μm、0.45μm、0.70μm之各D50。所製備之氧化鋁粒子之比表面積如表中所示。 Commercially available boehmite alumina (CA alumina manufactured by Sasol) was calcined at 1160 ° C. for 9 hours so as to have a specific surface area of BET 4 m 2 / g. The crystal form of the alumina after calcination is alpha alumina. The calcined product was subjected to wet fine pulverization, and adjusted to each D50 of 0.35 μm, 0.45 μm, and 0.70 μm. The specific surface area of the prepared alumina particles is shown in the table.
將以軟水鋁石氧化鋁作為原料之晶形為α氧化鋁的市售之氧化鋁(Sasol公司製造APA-0.4AF)進行濕式粉碎，而將D50調整為0.35μm。所製備之氧化鋁粒子之比表面積為BET 11m2/g。 The commercially available alumina (APA-0.4AF manufactured by Sasol Corporation) having a crystalline form of alumina using boehmite alumina as a raw material was wet-pulverized, and D50 was adjusted to 0.35 μm. The specific surface area of the prepared alumina particles was BET 11 m 2 / g.
氧化鋁粒子之D50係使用雷射繞射式粒度分佈測定機(島津製作所公司製造、SALD2200)而測定。氧化鋁粒子之粒度分佈係設為體積基準者。 The D50 of the alumina particles was measured using a laser diffraction particle size distribution measuring machine (manufactured by Shimadzu Corporation, SALD2200). The particle size distribution of the alumina particles is a volume basis.
氧化鋁粒子之比表面積係使用流動式比表面積自動測定裝置(島津製作所公司製造、Flowsorb II)而測定。 The specific surface area of the alumina particles was measured using a flow-type specific surface area automatic measuring device (manufactured by Shimadzu Corporation, Flowsorb II).
實施例及比較例中所使用之作為分散助劑之氧化鋁溶膠係藉由以下方法而製備。 The alumina sols used as dispersion aids in the examples and comparative examples were prepared by the following methods.
藉由將市售之軟水鋁石氧化鋁(Sasol公司製造CA氧化鋁)77g與氯化鋁44g及水879g利用均質混合機進行混合攪拌使之溶膠化而製備。 77 g of commercially available boehmite alumina (CA alumina manufactured by Sasol Corporation), 44 g of aluminum chloride, and 879 g of water were mixed and stirred with a homomixer to prepare a sol.
藉由向將硫酸鋁179g溶解至714g之水中而成之硫酸鋁水溶液中 添加25%氨水107g，利用均質混合機進行混合攪拌使之溶膠化而製備。 An aqueous solution of aluminum sulfate prepared by dissolving 179 g of aluminum sulfate in 714 g of water 107 g of 25% ammonia water was added, and the mixture was stirred with a homomixer to prepare a sol.
藉由將市售之軟水鋁石溶膠(Sasol公司製造Dispal23N4-80)100g添加至水888g中，進行充分混合攪拌使之溶膠化而製備。 It was prepared by adding 100 g of a commercially available boehmite sol (Dispal23N4-80 manufactured by Sasol Corporation) to 888 g of water and thoroughly mixing and stirring to make it sol.
使用作為氧化鋁研磨粒之藉由上述方法所製備之氧化鋁粒子、作為研磨促進劑之乙二胺四乙酸之四鉀鹽(EDTA-4K)、羥基乙基乙二胺四乙酸之三鈉鹽(HEDTA-3Na)及鋁酸鈉、作為分散劑之六偏磷酸鈉、作為分散助劑之藉由上述方法所製備之氧化鋁溶膠，藉由以下方法而製備研磨劑組合物。 Alumina particles prepared by the above method as alumina abrasive particles, tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), and trisodium salt of hydroxyethylethylenediaminetetraacetic acid as grinding accelerator (HEDTA-3Na), sodium aluminate, sodium hexametaphosphate as a dispersant, and an alumina sol prepared by the above method as a dispersing aid, and an abrasive composition was prepared by the following method.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、乙二胺四乙酸之四鉀鹽(EDTA-4K)及水以成為表1中之比率之方式進行攪拌混合而製備研磨劑組合物。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), and water were mixed so as to have the ratios shown in Table 1 to prepare an abrasive. combination. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、乙二胺四乙酸之四鉀鹽(EDTA-4K)、六偏磷酸鈉(Hexameta)、氧化鋁溶膠1及水以成為表1中之比率之方式進行攪拌混合而製備研磨劑組合物。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), sodium hexametaphosphate (Hexameta), alumina sol 1 and water were used to form a table. The ratio in 1 was stirred and mixed to prepare an abrasive composition. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、乙二胺四乙酸之四鉀鹽(EDTA-4K)、六偏磷酸鈉(Hexameta)及水以成為表1中之比率之方式進行攪拌混合而製備研磨劑組合物。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), sodium hexametaphosphate (Hexameta), and water were used as the ratios in Table 1. The mixture was stirred and mixed to prepare an abrasive composition. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、乙二胺四乙酸之四鉀鹽(EDTA-4K)、氧化鋁溶膠1及水以成為表1中之比率之方式進行攪拌混合而製備研磨劑組合物。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), alumina sol 1 and water were stirred so as to have the ratios shown in Table 1. Mix to prepare an abrasive composition. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、乙二胺四乙酸之四鉀鹽(EDTA-4K)、鋁酸鈉、六偏磷酸鈉(Hexameta)、氧化鋁溶膠1及水以成為表1中之比率之方式進行攪拌混合而製備研磨劑組合物。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), sodium aluminate, sodium hexametaphosphate (Hexameta), alumina sol 1 and Water was stirred and mixed so that it might become the ratio in Table 1, and the abrasive composition was prepared. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、羥基乙基乙二胺四乙酸之三鈉鹽(HEDTA-3Na)、六偏磷酸鈉(Hexameta)、氧化鋁溶膠2及水以成為表中之比率之方式進行攪拌混合，製備研磨劑組合物，進而添加氫氧化四甲基銨(TMAH)而調整為表1中之pH值。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), hydroxyethyl ethylenediamine tetraacetic acid trisodium salt (HEDTA-3Na), sodium hexametaphosphate (Hexameta), alumina sol 2 and water The mixture was stirred and mixed so as to have the ratio shown in the table to prepare an abrasive composition, and further tetramethylammonium hydroxide (TMAH) was added to adjust the pH value in Table 1. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
使用作為氧化鋁研磨粒之氧化鋁粒子1(D50：0.35μm、BET 13m2/g)，將EDTA-4K之濃度設為0.6質量%，除此以外，藉由與實施例2相同之方法而製備研磨劑組合物。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.35 μm, BET 13 m 2 / g) were used as alumina abrasive particles, and the concentration of EDTA-4K was set to 0.6% by mass, except that the same method as in Example 2 was used. An abrasive composition is prepared. A polishing test was performed using the obtained abrasive composition.
使用作為氧化鋁研磨粒之氧化鋁粒子1(D50：0.70μm、BET 8 m2/g)，將EDTA-4K之濃度設為0.6質量%，除此以外，藉由與實施例2相同之方法而製備研磨劑組合物。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.70 μm, BET 8 m 2 / g) were used as alumina abrasive particles, and the concentration of EDTA-4K was set to 0.6% by mass, except that the same method as in Example 2 was used. Instead, an abrasive composition is prepared. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子2(D50：0.35μm、BET 11m2/g)、乙二胺四乙酸之四鉀鹽(EDTA-4K)、鋁酸鈉、氧化鋁溶膠3及水以成為表1中之比率之方式進行攪拌混合而製備研磨劑組合物。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 2 (D50: 0.35 μm, BET 11 m 2 / g), tetrapotassium salt of ethylenediaminetetraacetic acid (EDTA-4K), sodium aluminate, alumina sol 3, and water were used to make the ratios in Table 1. An abrasive composition is prepared by stirring in this manner. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)及水以成為表中之比率之方式進行攪拌混合，製備研磨劑組合物，進而添加氫氧化鈉而調整為表1中之pH值。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g) and water were stirred and mixed so as to have the ratios in the table to prepare an abrasive composition, and sodium hydroxide was added to adjust the pH in Table 1 value. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、六偏磷酸鈉(Hexameta)、氧化鋁溶膠1及水以成為表中之比率之方式進行攪拌混合，製備研磨劑組合物，進而添加氫氧化鈉而調整為表1中之pH值。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10m 2 / g), sodium hexametaphosphate (Hexameta), alumina sol 1 and water are stirred and mixed so as to have the ratios in the table to prepare an abrasive composition, Further, sodium hydroxide was added to adjust the pH value in Table 1. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子1(D50：0.45μm、BET 10m2/g)、作為有機磺酸系螯合性化合物之羥基亞乙基二膦酸(HEDP)、六偏磷酸鈉(Hexameta)、氧化鋁溶膠1及水以成為表中之比率之方式進行攪拌混合，製備研磨劑組合物，進而添加氫氧化鈉而調整為表1中之pH值。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑 組合物而進行研磨試驗。 Alumina particles 1 (D50: 0.45 μm, BET 10 m 2 / g), hydroxyethylene diphosphonic acid (HEDP), an organic sulfonic acid chelating compound, sodium hexametaphosphate (Hexameta), and alumina sol 1 and water were stirred and mixed so as to have the ratios in the table to prepare an abrasive composition, and sodium hydroxide was further added to adjust the pH in Table 1. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
使用作為氧化鋁研磨粒之氧化鋁粒子1(D50：0.35μm、BET 13m2/g)，除此以外，藉由與比較例2相同之方法而製備研磨劑組合物。使用所獲得之研磨劑組合物而進行研磨試驗。 A polishing composition was prepared by the same method as Comparative Example 2 except that alumina particles 1 (D50: 0.35 μm, BET 13 m 2 / g) were used as alumina abrasive particles. A polishing test was performed using the obtained abrasive composition.
使用作為氧化鋁研磨粒之氧化鋁粒子1(D50：0.70μm、BET 8m2/g)，除此以外，藉由與比較例2相同之方法而製備研磨劑組合物。使用所獲得之研磨劑組合物而進行研磨試驗。 A polishing composition was prepared by the same method as Comparative Example 2 except that alumina particles 1 (D50: 0.70 μm, BET 8 m 2 / g) were used as alumina abrasive particles. A polishing test was performed using the obtained abrasive composition.
將氧化鋁粒子2(D50：0.35μm、BET 11m2/g)、氧化鋁溶膠3及水以成為表中之比率之方式進行攪拌混合，製備研磨劑組合物，進而添加氫氧化鈉而調整為表1中之pH值。再者，水係以成為自組合物去除其他成分之剩餘量之方式添加。使用所獲得之研磨劑組合物而進行研磨試驗。 Alumina particles 2 (D50: 0.35 μm, BET 11 m 2 / g), alumina sol 3, and water were stirred and mixed so as to have the ratios in the table to prepare an abrasive composition, and sodium hydroxide was added to adjust the content to The pH values in Table 1. In addition, the water system is added so that the remaining amount of other components may be removed from the composition. A polishing test was performed using the obtained abrasive composition.
表中之螯合性化合物之記載係指如下內容。 The description of the chelate compound in the table means the following.
EDTA-4K：乙二胺四乙酸四鉀鹽 EDTA-4K: Tetrapotassium salt of ethylenediamine tetraacetate
HEDTA-3Na：羥基乙基乙二胺四乙酸三鈉鹽 HEDTA-3Na: hydroxyethyl ethylenediamine tetraacetic acid trisodium salt
HEDP：羥基亞乙基二膦酸 HEDP: hydroxyethylene diphosphonic acid
表中之氧酸鹽之記載係指如下內容。 The description of the oxo acid salt in the table means the following.
鋁酸Na：鋁酸鈉 Na aluminate: sodium aluminate
表中之分散劑之記載係指如下內容。 The description of the dispersant in the table means the following.
Hexameta：六偏磷酸鈉 Hexameta: sodium hexametaphosphate
表中之pH值調整劑之記載係指如下內容。 The description of the pH adjuster in the table means the following.
TMAH：氫氧化四甲基銨 TMAH: Tetramethylammonium hydroxide
NaOH：氫氧化鈉 NaOH: sodium hydroxide
使用所獲得之研磨劑組合物，於以下之研磨條件下對藍寶石基板進行研磨。 Using the obtained abrasive composition, the sapphire substrate was polished under the following polishing conditions.
研磨機：SpeedFam製造之空氣加壓式6B兩面研磨機 Grinder: Air-pressurized 6B double-sided grinder manufactured by SpeedFam
研磨墊：SUBA-800(Nitta Haas製造) Polishing pad: SUBA-800 (made by Nitta Haas)
定盤旋轉數：下60rpm、上20rpm Fixed plate rotation: 60rpm lower, 20rpm upper
荷重：120g/cm2 Load: 120g / cm 2
研磨時間：420分鐘(7小時) Grinding time: 420 minutes (7 hours)
研磨劑組合物供給量：120ml/分鐘循環 Supply of abrasive composition: 120ml / min cycle
研磨工件：7.62cm(3英吋)藍寶石晶圓×3P Grinding workpiece: 7.62cm (3 inches) sapphire wafer × 3P
經研磨之基板之評價係將藉由上述方法進行研磨之藍寶石基板進行洗淨、乾燥後，使用下述之測定法、測定機進行評價。 The evaluation of the polished substrate was performed by washing and drying the sapphire substrate polished by the method described above, and then using the following measuring method and measuring machine for evaluation.
根據研磨速度[μm/hr]=(藍寶石基板之研磨前質量-藍寶石基板 之研磨後質量)[g]÷藍寶石基板之研磨面積[45cm2]÷藍寶石基板之密度[3.98g/cm3]÷研磨時間[420分鐘]×10000[μm/cm]×60[分鐘/hr]而算出，並示於表中。 According to the grinding speed [μm / hr] = (the mass before grinding of the sapphire substrate-the mass after grinding of the sapphire substrate) [g] ÷ the grinding area of the sapphire substrate [45cm 2 ] ÷ the density of the sapphire substrate [3.98g / cm 3 ] ÷ The polishing time [420 minutes] × 10000 [μm / cm] × 60 [minutes / hr] was calculated and shown in the table.
利用原子力顯微鏡AFM(SII Technology製造之SPA-500型)，於非接觸模式、掃描速率1.0Hz、視野10μm2下測定藍寶石基板之表面粗度Ra。 The surface roughness Ra of the sapphire substrate was measured using an atomic force microscope AFM (SPA-500 type manufactured by SII Technology) in a non-contact mode, a scanning rate of 1.0 Hz, and a field of view of 10 μm 2 .
利用田中機販製造之MICRO-MAX(VMX-2200Z-PL)觀察藍寶石基板，並計數刮痕數量。 Observe the sapphire substrate with MICRO-MAX (VMX-2200Z-PL) manufactured by Tanaka Machine Sales and count the number of scratches.
將兩面之刮痕數量之合計為2以下者設為評價1，將該合計為3者設為評價2，將該合計為4者設為評價3，將該合計為5~8者設為評價4，將該合計為9以上者設為評價5。 The total number of scratches on both sides was 2 or less as Evaluation 1, the total was 3 as Evaluation 2, the total was 4 as Evaluation 3, and the total was 5 to 8 as Evaluation. 4. The sum of 9 or more is evaluated as 5.
針對漿料之再分散性，藉由下述方法評價所製備之研磨劑組合物。 Regarding the redispersibility of the slurry, the prepared abrasive composition was evaluated by the following method.
將研磨劑組合物1kg置於1L之容器中，進行晝夜靜置，將容器上下翻轉手動振搖20次，將漿料中之沈澱固形分不殘留於底面者設為沈澱殘留「無」，只要稍有殘留則設為沈澱殘留「有」。 Put 1kg of the abrasive composition in a 1L container, and let it stand still day and night. Turn the container upside down and shake it manually for 20 times. If the precipitated solid content in the slurry does not remain on the bottom surface, set it as Shendian residue. If there is a slight residue, it will be set as Shendian residue.
若將實施例1與比較例1、實施例2及6與比較例2、實施例7與比較例4、實施例8與比較例5加以比較，則可知藉由添加有機羧酸系螯合性化合物作為研磨促進劑，而獲得較高之研磨速度。 If Example 1 and Comparative Example 1, Examples 2 and 6 and Comparative Example 2, Example 7 and Comparative Example 4, Example 8 and Comparative Example 5 are compared, it can be seen that by adding an organic carboxylic acid chelating property The compound acts as a grinding accelerator to obtain a higher grinding speed.
若將實施例2、3、4與實施例1加以比較，則可知若包含分散劑與分散助劑中之至少一種，則漿料之再分散性提昇。 Comparing Examples 2, 3, and 4 with Example 1, it can be seen that if at least one of a dispersant and a dispersing aid is included, the re-dispersibility of the slurry is improved.
本發明係關於為了研磨用作LED元件等電子零件材料、光學濾光 器等光學零件、電氣絕緣性材料、鐘錶外罩或窗材、耐摩耗性材料等的藍寶石基板、玻璃基板、水晶基板、矽或半導體基板等而使用之研磨劑組合物者。本發明並不限定於該等用途，可用作其他硬脆材料等之研磨劑組合物。 The present invention relates to an optical filter used for polishing electronic component materials such as LED elements and the like. Abrasive compositions used for optical parts such as electrical appliances, electrical insulating materials, watch covers or windows, sapphire substrates such as abrasion-resistant materials, glass substrates, crystal substrates, silicon or semiconductor substrates. The present invention is not limited to these applications, and can be used as an abrasive composition for other hard and brittle materials.
尤其是本發明之研磨劑組合物適合用於雷射發光用耐熱晶片、LED照明之基板、用作藍寶石基板生長氮化鎵(GaN on Sapphire)之高頻功率裝置用基板等電子零件材料、液晶投影儀用偏光元件保持板、相機等所使用之透光性之光學零件構件、電氣絕緣材料、耐熱爐之窗材、藍寶石管(熱電偶之保護管)、作為藍寶石玻璃之高級智慧型手機(多功能行動電話)之覆蓋玻璃、相機之保護鏡、Touch ID感應器、平板電腦(小型板狀攜帶型資訊通訊機器)、汽車導航系統等之覆蓋玻璃(屏幕)、Touch ID感應器等所使用、研究之藍寶石基板之研磨。 In particular, the abrasive composition of the present invention is suitable for use in electronic component materials such as heat-resistant wafers for laser light emission, substrates for LED lighting, substrates for high-frequency power devices such as GaN on sapphire substrates, and liquid crystals. Polarizing element holding plates for projectors, light-transmitting optical parts and components used in cameras, electrical insulation materials, window materials for heat-resistant furnaces, sapphire tubes (protective tubes for thermocouples), and advanced smart phones as sapphire glass ( Multi-functional mobile phone) Cover glass, Camera protective lens, Touch ID sensor, Tablet PC (small plate-shaped portable information communication device), Cover glass (screen) of car navigation system, Touch ID sensor, etc. 2. Grinding of the sapphire substrate.
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| JP6096969B1 (en) | 2016-04-26 | 2017-03-15 | 株式会社フジミインコーポレーテッド | Abrasive material, polishing composition, and polishing method |
| CN106700944B (en) * | 2016-12-09 | 2018-08-21 | 北京国瑞升科技股份有限公司 | A kind of synthetic alkali, A are to sapphire polishing liquid and preparation method thereof |
| CN110744362A (en) * | 2019-10-17 | 2020-02-04 | 江苏吉星新材料有限公司 | Sapphire wafer grinding and polishing method |
| JP7457586B2 (en) * | 2020-06-18 | 2024-03-28 | 株式会社フジミインコーポレーテッド | Concentrated solution of polishing composition and polishing method using the same |
| CN115216224A (en) * | 2022-07-20 | 2022-10-21 | 苏州博来纳润电子材料有限公司 | Sapphire polishing solution and preparation method and application thereof |
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| JPH0770553A (en) * | 1993-09-01 | 1995-03-14 | Asahi Glass Co Ltd | Abrasive fluid and grinding of substrate therewith |
| JP2000135673A (en) * | 1998-10-30 | 2000-05-16 | Okamoto Machine Tool Works Ltd | Polishing end point detecting method and polishing end point detecting device of wafer |
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| JP2014024157A (en) * | 2012-07-26 | 2014-02-06 | Fujimi Inc | Abrasive composition, polishing method of crustaceous material, and manufacturing method of crustaceous material substrate |
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