TWI537368B - Abrasive composition - Google Patents
Abrasive composition Download PDFInfo
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- TWI537368B TWI537368B TW100104043A TW100104043A TWI537368B TW I537368 B TWI537368 B TW I537368B TW 100104043 A TW100104043 A TW 100104043A TW 100104043 A TW100104043 A TW 100104043A TW I537368 B TWI537368 B TW I537368B
- Authority
- TW
- Taiwan
- Prior art keywords
- polishing composition
- concentration
- electrolyte
- polishing
- acid
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 259
- 238000005498 polishing Methods 0.000 claims description 395
- 239000003792 electrolyte Substances 0.000 claims description 144
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 92
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 92
- 239000000654 additive Substances 0.000 claims description 74
- 230000000996 additive effect Effects 0.000 claims description 74
- 150000003839 salts Chemical class 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- 150000001413 amino acids Chemical class 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- -1 hydrogen ions Chemical class 0.000 claims description 22
- 230000007935 neutral effect Effects 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 8
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 8
- 150000004715 keto acids Chemical class 0.000 claims description 7
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 40
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 40
- 239000002245 particle Substances 0.000 description 36
- 235000001014 amino acid Nutrition 0.000 description 30
- 229940024606 amino acid Drugs 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 13
- 235000011130 ammonium sulphate Nutrition 0.000 description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 10
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 235000003704 aspartic acid Nutrition 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 235000004279 alanine Nutrition 0.000 description 7
- 229960003767 alanine Drugs 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 150000001412 amines Chemical class 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 229920000137 polyphosphoric acid Polymers 0.000 description 5
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- 235000011151 potassium sulphates Nutrition 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- 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 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000011975 tartaric acid Substances 0.000 description 4
- 235000002906 tartaric acid Nutrition 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000004475 Arginine Substances 0.000 description 3
- 108010011485 Aspartame Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 3
- IAOZJIPTCAWIRG-QWRGUYRKSA-N aspartame Chemical compound OC(=O)C[C@H](N)C(=O)N[C@H](C(=O)OC)CC1=CC=CC=C1 IAOZJIPTCAWIRG-QWRGUYRKSA-N 0.000 description 3
- 235000010357 aspartame Nutrition 0.000 description 3
- 239000000605 aspartame Substances 0.000 description 3
- 229960003438 aspartame Drugs 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 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 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 229940009098 aspartate Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係關於一種用於研磨氧化矽(SiOx(0<x≦2))之研磨用組合物。The present invention relates to a polishing composition for polishing cerium oxide (SiO x (0 < x 2)).
先前，於研磨玻璃等SiO2時，由於採用二氧化鈰漿料可獲得高研磨速率，故而一直使用至今。Previously, when SiO 2 such as glass was ground, since a high polishing rate was obtained by using a cerium oxide slurry, it has been used until now.
但是，隨著技術進步，若使用二氧化鈰漿料進行研磨，則變得無法容許產生於表面之傷痕等缺陷，而於拋光研磨時須使用低缺陷之二氧化矽漿料。現尤其通用的是可耐受循環使用之膠體二氧化矽。However, as technology advances, if the cerium oxide slurry is used for polishing, defects such as scratches on the surface cannot be tolerated, and a low-defect cerium oxide slurry must be used during polishing. It is now especially versatile to be able to withstand the recycling of colloidal cerium oxide.
並且，作為含有膠體二氧化矽之研磨用組合物，已知有含有12.5(質量%)之膠體二氧化矽、0.49(質量%)之氫氧化鉀、及0.25(質量%)之側鏈型聚氧乙烯改性聚矽氧油(HLB值=12)的研磨用組合物(專利文獻1)。此處，側鏈型聚氧乙烯改性聚矽氧油之HLB(Hydrophile-Lipophile Balance：親水親油平衡)值為12。Further, as a polishing composition containing colloidal cerium oxide, a side chain type polymerization containing 12.5 (% by mass) of colloidal cerium oxide, 0.49 (% by mass) of potassium hydroxide, and 0.25 (% by mass) is known. A polishing composition of oxyethylene modified polyoxyxide oil (HLB value = 12) (Patent Document 1). Here, the HLB (Hydrophile-Lipophile Balance) value of the side chain type polyoxyethylene modified polyoxygenated oil is 12.
專利文獻1：日本專利特開2008-130988號公報Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-130988
但是，於使用專利文獻1中所揭示之含有膠體二氧化矽之研磨用組合物研磨SiO2之情形時，研磨速率為1003(/min)，存在研磨速率較低之問題。However, in the case of polishing SiO 2 using the polishing composition containing colloidal ceria disclosed in Patent Document 1, the polishing rate is 1003 ( /min), there is a problem that the polishing rate is low.
因此，本發明係為了解決上述問題研究而成者，其目的在於提供一種可提高SiOx(0<x≦2)之研磨速率之研磨用組合物。Accordingly, the present invention has been made in order to solve the above problems, and an object thereof is to provide a polishing composition which can increase the polishing rate of SiO x (0 < x 2).
根據本發明，研磨用組合物含有膠體二氧化矽與添加劑。該添加劑包含在水溶液中釋放氫離子之電解質或電解質之鹽。According to the invention, the polishing composition contains colloidal cerium oxide and an additive. The additive comprises a salt of an electrolyte or electrolyte that releases hydrogen ions in an aqueous solution.
較佳為該添加劑包含含氧酸、含氧酸鹽、鹽酸、鹽酸鹽、酸性或中性之胺基酸、及酸性或中性之胺基酸之鹽中之任一者。Preferably, the additive comprises any one of an oxoacid, an oxoacid salt, a hydrochloric acid, a hydrochloride, an acidic or neutral amino acid, and a salt of an acidic or neutral amino acid.
較佳為該添加劑包含硫酸、焦硫酸、磷酸、焦磷酸、或該等之鹽，添加劑之濃度相對於該研磨用組合物整體而為2重量%以下。Preferably, the additive contains sulfuric acid, pyrosulfuric acid, phosphoric acid, pyrophosphoric acid, or the like, and the concentration of the additive is 2% by weight or less based on the entire polishing composition.
較佳為該添加劑之濃度相對於該研磨用組合物整體而為1重量%以下。The concentration of the additive is preferably 1% by weight or less based on the entire polishing composition.
本發明之實施形態之研磨用組合物含有膠體二氧化矽、與包含在水溶液中釋放氫離子之電解質或電解質之鹽的添加劑。其結果為，可於實質上不提高膠體二氧化矽之濃度的狀態下研磨SiOx。The polishing composition according to the embodiment of the present invention contains colloidal cerium oxide and an additive containing a salt of an electrolyte or an electrolyte which releases hydrogen ions in an aqueous solution. As a result, SiO x can be polished without substantially increasing the concentration of colloidal cerium oxide.
因此，可提高SiOx之研磨速率。Therefore, the polishing rate of SiO x can be increased.
一邊參照圖式，一邊詳細說明本發明之實施形態。再者，圖中相同或相當部分採用相同符號，不再重複說明。Embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference numerals and the description will not be repeated.
本發明之實施形態之研磨用組合物COMP含有膠體二氧化矽、與包含在水溶液中釋放氫離子之電解質或電解質之鹽的添加劑。The polishing composition COMP of the embodiment of the present invention contains an additive of colloidal cerium oxide and a salt containing an electrolyte or an electrolyte which releases hydrogen ions in an aqueous solution.
並且，該研磨用組合物COMP係以如下者作為研磨對象：LSI(Large Scale Integrated circuit，大型積體電路)所使用之作為層間絕緣膜之SiO2、硬碟所使用之SiO2、及作為石英、玻璃之SiO2等SiOx(0<x≦2)。又，研磨用組合物COMP尤其是用於拋光研磨。Further, the polishing composition COMP-based as in the following by polishing an object: between LSI (Large Scale Integrated circuit, large-scale integrated circuits) to be used as the layer insulating film of SiO 2, SiO 2 used in the hard disk, and a quartz SiO x such as SiO 2 of glass (0<x≦2). Further, the polishing composition COMP is especially used for polishing.
添加劑包含含氧酸、含氧酸鹽、鹽酸、鹽酸鹽、胺基酸、胺基酸鹽、及醇中之任一者。The additive comprises any one of an oxo acid, an oxoacid salt, hydrochloric acid, a hydrochloride, an amino acid, an amine acid salt, and an alcohol.
含氧酸包含無機含氧酸或有機含氧酸。The oxyacid comprises an inorganic oxyacid or an organic oxyacid.
無機含氧酸包含硫酸、磷酸、硫代硫酸、硝酸、焦磷酸、碳酸、過硫酸、多元磷酸、及焦硫酸中之任一者。The inorganic oxyacid includes any one of sulfuric acid, phosphoric acid, thiosulfuric acid, nitric acid, pyrophosphoric acid, carbonic acid, persulfuric acid, polyphosphoric acid, and pyrosulfuric acid.
有機含氧酸包含草酸、鄰苯二甲酸、苯甲酸、丙二酸、甲磺酸、乳酸、順丁烯二酸、酒石酸、檸檬酸、羥乙酸、聚丙烯酸(PAA)及苯磺酸中之任一者。The organic oxyacid comprises oxalic acid, phthalic acid, benzoic acid, malonic acid, methanesulfonic acid, lactic acid, maleic acid, tartaric acid, citric acid, glycolic acid, polyacrylic acid (PAA) and benzenesulfonic acid. Either.
含氧酸鹽包含上述無機含氧酸與鹼金屬、鹼土金屬及氨中之任一者的鹽，或上述有機含氧酸與鹼金屬、鹼土金屬及氨中之任一者的鹽。鹼金屬包含鉀及鈉等。鹼土金屬包含鈣、鎂及鋇等。The oxyacid salt includes a salt of any one of the above inorganic oxo acid and an alkali metal, an alkaline earth metal, and ammonia, or a salt of the above organic oxyacid with any of an alkali metal, an alkaline earth metal, and ammonia. The alkali metal contains potassium, sodium, and the like. Alkaline earth metals include calcium, magnesium and barium.
無機含氧酸之鹽例如包含硫酸銨、硫酸鉀、焦硫酸鉀、碳酸氫銨、碳酸鉀、過硫酸銨、磷酸氫二鉀、及硫代硫酸銨中之任一者。The inorganic oxyacid salt includes, for example, any of ammonium sulfate, potassium sulfate, potassium pyrosulfate, ammonium hydrogencarbonate, potassium carbonate, ammonium persulfate, dipotassium hydrogen phosphate, and ammonium thiosulfate.
胺基酸包含天冬醯胺酸、天冬醯胺、及丙胺酸中之任一者。天冬醯胺酸為酸性胺基酸，天冬醯胺及丙胺酸為中性胺基酸。The amino acid includes any one of aspartic acid, aspartame, and alanine. Aspartic acid is an acidic amino acid, and asparagine and alanine are neutral amino acids.
胺基酸鹽包含上述胺基酸與鹼金屬、鹼土金屬及氨中之任一者的鹽。於該情形時，鹼金屬及鹼土金屬之具體例與上述具體例相同。The amino acid salt comprises a salt of any of the above amino acids and an alkali metal, an alkaline earth metal, and ammonia. In this case, specific examples of the alkali metal and the alkaline earth metal are the same as the above specific examples.
醇包含丁醇、甘油、丙醇及乙醇中之任一者。The alcohol contains any one of butanol, glycerin, propanol and ethanol.
鹽酸鹽包含鹽酸與鹼金屬、鹼土金屬及氨中之任一者的鹽。於該情形時，鹼金屬及鹼土金屬之具體例亦與上述具體例相同。The hydrochloride salt contains a salt of hydrochloric acid with any of an alkali metal, an alkaline earth metal, and ammonia. In this case, specific examples of the alkali metal and the alkaline earth metal are also the same as the above specific examples.
再者，研磨用組合物COMP亦可含有pH值調節劑。pH值調節劑包含氨、氫氧化鉀及氫氧化鈉等通常用於調節pH值者。Further, the polishing composition COMP may also contain a pH adjuster. The pH adjuster contains ammonia, potassium hydroxide and sodium hydroxide, which are usually used to adjust the pH.
研磨用組合物COMP可藉由將膠體二氧化矽、與包含在水溶液中釋放氫離子之電解質或電解質之鹽的添加劑適宜混合並添加水而製作。又，研磨用組合物COMP可藉由將膠體二氧化矽、與包含在水溶液中釋放氫離子之電解質或電解質之鹽的添加劑依次混合至水中而製作。並且，作為混合該等成分之手段，可採用均質機、及超音波等研磨用組合物之技術領域中常用之手段。The polishing composition COMP can be produced by suitably mixing colloidal cerium oxide, an additive containing a salt of an electrolyte or an electrolyte which releases hydrogen ions in an aqueous solution, and adding water. Further, the polishing composition COMP can be produced by sequentially mixing colloidal cerium oxide and an additive containing a salt of an electrolyte or an electrolyte which releases hydrogen ions in an aqueous solution into water. Further, as means for mixing the components, a means commonly used in the technical field of a polishing composition such as a homogenizer or an ultrasonic wave can be employed.
再者，於研磨用組合物COMP含有pH值調節劑之情形時，研磨用組合物COMP可藉由上述方法進而混合pH值調節劑而製作。Further, when the polishing composition COMP contains a pH adjuster, the polishing composition COMP can be produced by further mixing a pH adjuster by the above method.
並且，使用研磨用組合物COMP之SiOx之研磨條件及研磨速率之評價方法如下。Further, the polishing conditions of the SiO x using the polishing composition COMP and the polishing rate were evaluated as follows.
使用研磨裝置(裝置名：ECOMET3、BUEHLER公司製造)，以16 ml/分之速度向研磨墊(商品名：Supreme RN-H、NITTA HAAS股份有限公司製造)供給研磨用組合物COMP，且一邊對2.5×3.0 cm之TEOS晶圓晶片施加3.5(psi)之壓力，一邊以250 rpm之旋轉速度旋轉研磨定盤，並且一邊以60 rpm之旋轉速度旋轉載具，一邊研磨60秒鐘。The polishing composition COMP was supplied to the polishing pad (trade name: Supreme RN-H, manufactured by NITTA HAAS Co., Ltd.) at a rate of 16 ml/min, using a polishing apparatus (device name: ECOMET3, manufactured by BUEHLER Co., Ltd.) A 2.5 x 3.0 cm TEOS wafer wafer was subjected to a pressure of 3.5 (psi), and the polishing plate was rotated at a rotation speed of 250 rpm, and the carrier was rotated at a rotation speed of 60 rpm while being ground for 60 seconds.
研磨速率表示每單位時間內藉由研磨而除去之各膜之厚度(/min)。藉由研磨而除去之膜之厚度係藉由自研磨前之膜之厚度減去研磨後之膜之厚度而算出。又，膜之厚度係使用NANOMETRICS公司製造之Nanospec/AFT5100而測定。The polishing rate means the thickness of each film removed by grinding per unit time ( /min). The thickness of the film removed by the polishing was calculated by subtracting the thickness of the film after polishing from the thickness of the film before polishing. Further, the thickness of the film was measured using a Nanospec/AFT 5100 manufactured by NANOMETRICS.
圖1係表示研磨速率與膠體二氧化矽之平均粒徑之關係的圖。圖1中，縱軸表示研磨速率，橫軸表示膠體二氧化矽之平均粒徑。又，圖1所示之研磨速率與膠體二氧化矽之平均粒徑之關係係膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為22(重量%)，添加劑為硫酸銨，且硫酸銨之濃度相對於研磨用組合物COMP整體而為0.5(重量%)時之研磨速率與膠體二氧化矽之平均粒徑之關係。進而，研磨之對象物係使用TEOS(四乙氧基矽烷)作為原料氣體並藉由電漿CVD(Chemical Vapour Deposition，化學氣相沈積)法而製作之TEOS膜(SiO2膜)(以下相同)。Fig. 1 is a graph showing the relationship between the polishing rate and the average particle diameter of colloidal cerium oxide. In Fig. 1, the vertical axis represents the polishing rate, and the horizontal axis represents the average particle diameter of the colloidal cerium oxide. Further, the relationship between the polishing rate shown in Fig. 1 and the average particle diameter of the colloidal ceria is that the concentration of the colloidal ceria is 22 (% by weight) based on the entire composition for polishing COMP, and the additive is ammonium sulfate, and sulfuric acid The relationship between the polishing rate and the average particle diameter of the colloidal cerium oxide when the concentration of ammonium is 0.5% by weight based on the entire polishing composition COMP. Further, the object to be polished is a TEOS film (SiO 2 film) produced by a plasma CVD (Chemical Vapor Deposition) method using TEOS (tetraethoxy decane) as a material gas (the same applies hereinafter) .
再者，所謂平均粒徑為X(nm)，係指膠體二氧化矽之粒徑主要分佈於X(nm)。Further, the average particle diameter is X (nm), which means that the particle diameter of the colloidal ceria is mainly distributed in X (nm).
參照圖1，於膠體二氧化矽之平均粒徑為25.3(nm)時，研磨速率約為1800(/min)，於膠體二氧化矽之平均粒徑為32.8(nm)時，研磨速率約為1577(/min)。Referring to Fig. 1, when the average particle diameter of the colloidal ceria is 25.3 (nm), the polishing rate is about 1800 ( /min), when the average particle size of the colloidal cerium oxide is 32.8 (nm), the polishing rate is about 1577 ( /min).
並且，若膠體二氧化矽之平均粒徑大於55(nm)，則研磨速率會激增至約2400(/min)，但即使膠體二氧化矽之平均粒徑增加至80(nm)及90(nm)，研磨速率亦大致保持固定。Moreover, if the average particle size of the colloidal cerium oxide is greater than 55 (nm), the polishing rate will surge to about 2,400 ( /min), but even if the average particle size of the colloidal cerium oxide is increased to 80 (nm) and 90 (nm), the polishing rate remains substantially constant.
因此，本發明之實施形態中，膠體二氧化矽之平均粒徑較佳為55(nm)以上。Therefore, in the embodiment of the present invention, the average particle diameter of the colloidal cerium oxide is preferably 55 (nm) or more.
圖2係表示膠體二氧化矽之平均粒徑及研磨速率與電解質濃度之關係的圖。圖2中，縱軸表示膠體二氧化矽之平均粒徑及研磨速率，橫軸表示相對於研磨用組合物COMP整體之電解質濃度。又，圖2所示之膠體二氧化矽之平均粒徑及研磨速率與電解質濃度之關係係膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為5(重量%)，膠體二氧化矽之平均粒徑為80(nm)，且添加劑為硫酸銨時之膠體二氧化矽之平均粒徑及研磨速率與電解質濃度之關係。並且，曲線k1表示研磨速率與電解質濃度之關係，曲線k2表示膠體二氧化矽之平均粒徑與電解質濃度之關係。Fig. 2 is a graph showing the relationship between the average particle diameter of the colloidal cerium oxide and the polishing rate and the electrolyte concentration. In FIG. 2, the vertical axis represents the average particle diameter and the polishing rate of the colloidal cerium oxide, and the horizontal axis represents the electrolyte concentration with respect to the entire polishing composition COMP. Further, the relationship between the average particle diameter of the colloidal cerium oxide and the polishing rate and the electrolyte concentration shown in Fig. 2 is that the concentration of the colloidal cerium oxide is 5 (% by weight) based on the entire polishing composition COMP, and colloidal cerium oxide. The average particle diameter is 80 (nm), and the average particle diameter of the colloidal ceria and the relationship between the polishing rate and the electrolyte concentration when the additive is ammonium sulfate. Further, the curve k1 represents the relationship between the polishing rate and the electrolyte concentration, and the curve k2 represents the relationship between the average particle diameter of the colloidal ceria and the electrolyte concentration.
參照圖2，至電解質濃度達到2(重量%)為止，研磨速率隨著電解質濃度之增加而提高，若電解質濃度達到3(重量%)，則研磨速率降低(參照曲線k1)。Referring to Fig. 2, until the electrolyte concentration reaches 2 (% by weight), the polishing rate increases as the electrolyte concentration increases, and if the electrolyte concentration reaches 3 (% by weight), the polishing rate decreases (refer to the curve k1).
另一方面，膠體二氧化矽之平均粒徑於電解質濃度達到1(重量%)為止之範圍內保持在約80(nm)之固定值，若電解質濃度增加至2(重量%)及3(重量%)，則電解質濃度大幅度提高(參照曲線k2)。因此認為，於2(重量%)及3(重量%)之電解質濃度下，膠體二氧化矽發生凝集。On the other hand, the average particle diameter of the colloidal cerium oxide is maintained at a fixed value of about 80 (nm) in the range of the electrolyte concentration of 1 (% by weight), and if the electrolyte concentration is increased to 2 (% by weight) and 3 (weight) %), the electrolyte concentration is greatly increased (refer to curve k2). Therefore, it is considered that the colloidal ceria is agglomerated at an electrolyte concentration of 2 (% by weight) and 3 (% by weight).
根據圖2所示之結果，電解質濃度較佳為相對於研磨用組合物COMP整體而為2(重量%)以下。其原因在於：於2(重量%)以下之電解質濃度下，研磨速率隨著電解質濃度之增加而提高。According to the results shown in FIG. 2, the electrolyte concentration is preferably 2% by weight or less based on the entire polishing composition COMP. The reason for this is that at an electrolyte concentration of 2% by weight or less, the polishing rate increases as the electrolyte concentration increases.
又，電解質濃度更佳為相對於研磨用組合物COMP整體而為1(重量%)以下。其原因在於：於1(重量%)以下之電解質濃度下，研磨速率隨著電解質濃度之增加而提高，且膠體二氧化矽不發生凝集。Further, the electrolyte concentration is preferably 1% by weight or less based on the entire polishing composition COMP. The reason for this is that at an electrolyte concentration of 1% by weight or less, the polishing rate increases as the electrolyte concentration increases, and the colloidal cerium oxide does not agglomerate.
圖3係表示改變膠體二氧化矽之濃度時之研磨速率與電解質濃度之關係的圖。圖3中，縱軸表示研磨速率，橫軸表示相對於研磨用組合物COMP整體之電解質濃度。又，曲線k3表示膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為5(重量%)，膠體二氧化矽之平均粒徑為80(nm)，且添加劑為硫酸銨時之研磨速率與電解質濃度之關係。進而，曲線k4表示膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為12.5(重量%)，膠體二氧化矽之平均粒徑為80(nm)，且添加劑為硫酸銨時之研磨速率與電解質濃度之關係。進而，曲線k5表示膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為22(重量%)，膠體二氧化矽之平均粒徑為80(nm)，且添加劑為硫酸銨時之研磨速率與電解質濃度之關係。Fig. 3 is a graph showing the relationship between the polishing rate and the electrolyte concentration when the concentration of colloidal cerium oxide is changed. In Fig. 3, the vertical axis represents the polishing rate, and the horizontal axis represents the electrolyte concentration with respect to the entire polishing composition COMP. Further, the curve k3 indicates that the concentration of the colloidal cerium oxide is 5 (% by weight) based on the entire polishing composition COMP, the average particle diameter of the colloidal cerium oxide is 80 (nm), and the polishing rate when the additive is ammonium sulfate. Relationship with electrolyte concentration. Further, the curve k4 indicates that the concentration of the colloidal cerium oxide is 12.5 % by weight based on the entire composition for polishing COMP, the average particle diameter of the colloidal cerium oxide is 80 (nm), and the polishing rate when the additive is ammonium sulfate. Relationship with electrolyte concentration. Further, the curve k5 indicates that the concentration of the colloidal cerium oxide is 22 (% by weight) based on the entire polishing composition COMP, the average particle diameter of the colloidal cerium oxide is 80 (nm), and the polishing rate when the additive is ammonium sulfate. Relationship with electrolyte concentration.
再者，電解質濃度於圖2中係於表示為更佳的濃度之1(重量%)以下之範圍內變化。Further, the electrolyte concentration is changed within a range of 1 (% by weight) or less which is expressed as a more preferable concentration in Fig. 2 .
參照圖3，研磨速率於膠體二氧化矽之各濃度下隨著電解質濃度之增加而提高。又，研磨速率於電解質濃度之各濃度下隨著膠體二氧化矽濃度之增加而提高。並且，於1(重量%)之電解質濃度及22(重量%)之膠體二氧化矽之濃度下，獲得2500(/min)以上之研磨速率(參照曲線k3~k5)。Referring to Figure 3, the polishing rate increases with increasing electrolyte concentration at each concentration of colloidal cerium oxide. Further, the polishing rate increases as the concentration of the colloidal cerium oxide increases at each concentration of the electrolyte concentration. And, at a concentration of 1 (% by weight) of the electrolyte and 22% by weight of the colloidal cerium oxide, 2,500 ( /min) The above polishing rate (refer to the curve k3~k5).
已知，於如此使用研磨用組合物COMP研磨SiO2之情形時，研磨速率隨著電解質濃度及/或膠體二氧化矽之濃度之增加而提高。It is known that in the case where SiO 2 is polished by using the polishing composition COMP, the polishing rate increases as the electrolyte concentration and/or the concentration of colloidal cerium oxide increases.
圖4係表示改變電解質時之研磨速率與電解質濃度之關係的圖。圖4中，縱軸表示研磨速率，橫軸表示相對於研磨用組合物COMP整體之電解質濃度。又，曲線k6表示使用鹽酸(HCl)作為電解質時之研磨速率與電解質濃度之關係。進而，曲線k7表示使用硝酸(HNO3)作為電解質時之研磨速率與電解質濃度之關係。進而，曲線k8表示使用磷酸(H3PO4)作為電解質時之研磨速率與電解質濃度之關係。進而，曲線k9表示使用硫酸(H2SO4)作為電解質時之研磨速率與電解質濃度之關係。Fig. 4 is a graph showing the relationship between the polishing rate and the electrolyte concentration when the electrolyte is changed. In Fig. 4, the vertical axis represents the polishing rate, and the horizontal axis represents the electrolyte concentration with respect to the entire polishing composition COMP. Further, the curve k6 indicates the relationship between the polishing rate and the electrolyte concentration when hydrochloric acid (HCl) is used as the electrolyte. Further, a curve k7 indicates the relationship between the polishing rate and the electrolyte concentration when nitric acid (HNO 3 ) is used as the electrolyte. Further, a curve k8 indicates the relationship between the polishing rate and the electrolyte concentration when phosphoric acid (H 3 PO 4 ) is used as the electrolyte. Further, a curve k9 indicates the relationship between the polishing rate and the electrolyte concentration when sulfuric acid (H 2 SO 4 ) is used as the electrolyte.
再者，曲線k6~k9所示之實驗結果係於1(重量%)以下之範圍內改變HCl、HNO3、H3PO4、及H2SO4之各濃度時所獲得之實驗結果。於該情形時，HCl及H2SO4係將濃度改變為0.0、0.25、0.5，HNO3及H3PO4係將濃度改變為0.0、0.25、0.5、1.0。又，膠體二氧化矽之平均粒徑為80 nm。Further, the experimental results shown by the curves k6 to k9 are experimental results obtained by changing the respective concentrations of HCl, HNO 3 , H 3 PO 4 , and H 2 SO 4 in the range of 1 (% by weight or less). In this case, the concentrations of HCl and H 2 SO 4 were changed to 0.0, 0.25, and 0.5, and the concentrations of HNO 3 and H 3 PO 4 were changed to 0.0, 0.25, 0.5, and 1.0. Further, the colloidal ceria has an average particle diameter of 80 nm.
參照圖4，於使用HCl、HNO3、H3PO4、及H2SO4作為電解質之情形時，研磨速率隨著電解質之濃度之增加而提高(參照曲線k6~k9)。Referring to Fig. 4, in the case where HCl, HNO 3 , H 3 PO 4 , and H 2 SO 4 are used as the electrolyte, the polishing rate increases as the concentration of the electrolyte increases (refer to the curves k6 to k9).
並且，於使用HCl及H2SO4作為電解質之情形時，於0.5(重量%)之濃度下，研磨速率分別為1968 /min或1916 /min(參照曲線k6、k9)。又，於使用HNO3及H3PO4作為電解質之情形時，於1.0(重量%)之濃度下，研磨速率分別為2036 /min及1925 /min(參照曲線k7、k8)。因此，於使用HCl及H2SO4作為電解質之情形時，即使將電解質之濃度自1.0(重量%)減少至0.5(重量%)，亦可獲得與使用1.0(重量%)之HNO3及H3PO4作為電解質之情形同等之研磨速率。Moreover, in the case of using HCl and H 2 SO 4 as the electrolyte, the polishing rate was 1968 at a concentration of 0.5 (% by weight), respectively. /min or 1916 /min (refer to curves k6, k9). Further, in the case of using HNO 3 and H 3 PO 4 as the electrolyte, the polishing rate was 2036 at a concentration of 1.0 (% by weight), respectively. /min and 1925 /min (refer to curves k7, k8). Therefore, when HCl and H 2 SO 4 are used as the electrolyte, even if the concentration of the electrolyte is reduced from 1.0 (% by weight) to 0.5 (% by weight), 1.0 (% by weight) of HNO 3 and H can be obtained and used. 3 PO 4 as the electrolyte in the case of the same grinding rate.
圖5係表示改變電解質鹽時之研磨速率與電解質濃度之關係的圖。圖5中，縱軸表示研磨速率，橫軸表示相對於研磨用組合物COMP整體之電解質濃度。又，曲線k10表示使用硫酸鉀(K2SO4)作為電解質鹽時之研磨速率與電解質濃度之關係。進而，曲線k11表示使用磷酸氫二鉀(K2HPO4)作為電解質鹽時之研磨速率與電解質濃度之關係。進而，曲線k12表示使用碳酸鉀(K2CO3)作為電解質鹽時之研磨速率與電解質濃度之關係。Fig. 5 is a graph showing the relationship between the polishing rate and the electrolyte concentration when the electrolyte salt is changed. In Fig. 5, the vertical axis represents the polishing rate, and the horizontal axis represents the electrolyte concentration with respect to the entire polishing composition COMP. Further, the curve k10 indicates the relationship between the polishing rate and the electrolyte concentration when potassium sulfate (K 2 SO 4 ) is used as the electrolyte salt. Further, the curve k11 represents the relationship between the polishing rate and the electrolyte concentration when dipotassium hydrogen phosphate (K 2 HPO 4 ) is used as the electrolyte salt. Further, a curve k12 indicates the relationship between the polishing rate and the electrolyte concentration when potassium carbonate (K 2 CO 3 ) is used as the electrolyte salt.
再者，曲線k10~k12所示之實驗結果係於1(重量%)以下之範圍內改變K2SO4、K2HPO4、及K2CO3之各濃度時所獲得之實驗結果。於該情形時，K2SO4係將濃度改變為0.00、0.25、0.50、0.75、1.00，K2HPO4係將濃度改變為0.00、0.25、0.50、0.72、1.00，K2CO3係將濃度改變為0.00、0.25、0.50、0.75、1.00。又，膠體二氧化矽之平均粒徑為80 nm。Further, the experimental results shown by the curves k10 to k12 are experimental results obtained by changing the respective concentrations of K 2 SO 4 , K 2 HPO 4 , and K 2 CO 3 in the range of 1 (% by weight or less). In this case, the K 2 SO 4 system changes the concentration to 0.00, 0.25, 0.50, 0.75, 1.00, and the K 2 HPO 4 system changes the concentration to 0.00, 0.25, 0.50, 0.72, 1.00, and the concentration of the K 2 CO 3 system. Change to 0.00, 0.25, 0.50, 0.75, 1.00. Further, the colloidal ceria has an average particle diameter of 80 nm.
參照圖5，於使用K2SO4、K2HPO4、及K2CO3作為電解質鹽之情形時，研磨速率隨著電解質鹽之濃度之增加而提高(參照曲線k10~k12)。Referring to Fig. 5, in the case where K 2 SO 4 , K 2 HPO 4 , and K 2 CO 3 are used as the electrolyte salt, the polishing rate increases as the concentration of the electrolyte salt increases (refer to the curve k10 to k12).
並且，於使用K2SO4作為電解質鹽之情形時，於1.0(重量%)之濃度下，獲得2170 /min之研磨速率(參照曲線k10)，於使用K2HPO4作為電解質鹽之情形時，於1.0(重量%)之濃度下，獲得1982 /min之研磨速率(參照曲線k11)，於使用K2CO3作為電解質鹽之情形時，於1.0(重量%)之濃度下，獲得1864 /min之研磨速率(參照曲線k12)。And, in the case of using K 2 SO 4 as an electrolyte salt, at a concentration of 1.0 (% by weight), 2170 is obtained. /min grinding rate (refer to curve k10), in the case of using K 2 HPO 4 as the electrolyte salt, at a concentration of 1.0 (% by weight), obtained 1982 /min grinding rate (refer to curve k11), when using K 2 CO 3 as the electrolyte salt, at a concentration of 1.0 (% by weight), 1864 /min grinding rate (refer to curve k12).
已知，於如此使用含有電解質或電解質鹽之研磨用組合物COMP研磨SiO2之情形時，研磨速率隨著電解質或電解質鹽之濃度於1.0(重量%)以下之範圍內增加而提高。It is known that in the case where SiO 2 is polished by using the polishing composition COMP containing an electrolyte or an electrolyte salt, the polishing rate is increased as the concentration of the electrolyte or the electrolyte salt is increased in the range of 1.0 (% by weight or less) or less.
圖6係表示研磨速率與電解質之種類之關係的圖。圖6中，縱軸表示研磨速率，橫軸表示電解質之種類。又，圖6所示之研磨速率與電解質之種類之關係係電解質之濃度相對於研磨用組合物COMP整體而為0.5(重量%)，膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為20(重量%)，且膠體二氧化矽之平均粒徑為80(nm)時之研磨速率與電解質之種類之關係。進而，電解質係使用磷酸、焦磷酸、多元磷酸、硫代硫酸銨、過硫酸銨、碳酸氫銨、硫酸、鹽酸、硝酸及硫酸銨。進而，為了進行比較，亦揭示未添加添加劑(=電解質)之情形。Fig. 6 is a graph showing the relationship between the polishing rate and the kind of electrolyte. In Fig. 6, the vertical axis represents the polishing rate, and the horizontal axis represents the type of the electrolyte. Further, the relationship between the polishing rate and the type of the electrolyte shown in FIG. 6 is that the concentration of the electrolyte is 0.5% by weight based on the entire polishing composition COMP, and the concentration of the colloidal cerium oxide is relative to the entire polishing composition COMP. It is 20 (% by weight), and the relationship between the polishing rate and the kind of the electrolyte when the average particle diameter of the colloidal cerium oxide is 80 (nm). Further, as the electrolyte, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, ammonium thiosulfate, ammonium persulfate, ammonium hydrogencarbonate, sulfuric acid, hydrochloric acid, nitric acid, and ammonium sulfate are used. Further, for comparison, it was also revealed that no additive (=electrolyte) was added.
參照圖6，研磨速率藉由添加電解質而大幅度提高。又，已知於使用磷酸、焦磷酸、硫酸、鹽酸及硫酸銨中之任一者作為電解質之情形時，與未添加電解質之情形相比，研磨速率提高約2倍。並且，於使用硫酸銨作為電解質之情形時，獲得1993(/min)之研磨速率。Referring to Fig. 6, the polishing rate is greatly improved by the addition of an electrolyte. Further, it is known that when any one of phosphoric acid, pyrophosphoric acid, sulfuric acid, hydrochloric acid, and ammonium sulfate is used as the electrolyte, the polishing rate is increased by about 2 times as compared with the case where no electrolyte is added. Also, when using ammonium sulfate as the electrolyte, it was obtained in 1993 ( /min) grinding rate.
如此證實，藉由添加電解質，研磨速率會大幅度提高。It was thus confirmed that the polishing rate was greatly increased by the addition of the electrolyte.
圖7係表示研磨速率與鹽之種類之關係的圖。圖7中，縱軸表示研磨速率，橫軸表示鹽之種類。又，圖7所示之研磨速率與鹽之種類之關係係電解質之濃度相對於研磨用組合物COMP整體而為0.5(重量%)，膠體二氧化矽之濃度相對於研磨用組合物COMP整體而為22(重量%)，pH值為9.5，且膠體二氧化矽之平均粒徑為80(nm)時之研磨速率與鹽之種類之關係。並且，pH值之調節係藉由添加氨而進行。Fig. 7 is a graph showing the relationship between the polishing rate and the type of salt. In Fig. 7, the vertical axis represents the polishing rate, and the horizontal axis represents the type of salt. Further, the relationship between the polishing rate and the type of the salt shown in Fig. 7 is that the concentration of the electrolyte is 0.5% by weight based on the entire polishing composition COMP, and the concentration of the colloidal cerium oxide is relative to the entire polishing composition COMP. It is 22 (% by weight), the pH is 9.5, and the relationship between the polishing rate and the kind of the salt when the average particle diameter of the colloidal cerium oxide is 80 (nm). Further, the adjustment of the pH is carried out by adding ammonia.
進而，銨鹽表示硫酸銨，鉀鹽表示硫酸鉀，鈉鹽表示硫酸鈉。Further, the ammonium salt means ammonium sulfate, the potassium salt means potassium sulfate, and the sodium salt means sodium sulfate.
參照圖7，研磨速率藉由添加銨鹽、鉀鹽及鈉鹽中之任一者而提高。並且，於添加有銨鹽及鉀鹽中之任一者之情形時，研磨速率提高至約2000(/min)。Referring to Fig. 7, the polishing rate is increased by adding any one of an ammonium salt, a potassium salt, and a sodium salt. Also, in the case where any of an ammonium salt and a potassium salt is added, the polishing rate is increased to about 2,000 ( /min).
因此證實，藉由添加鹼性電解質，會提高研磨速率。Therefore, it was confirmed that the polishing rate was increased by adding an alkaline electrolyte.
圖8係表示研磨速率及膠體二氧化矽之平均粒徑與pH值之關係的圖。圖8中，縱軸表示研磨速率及膠體二氧化矽之平均粒徑，橫軸表示pH值。又，圖8所示之研磨速率及膠體二氧化矽之平均粒徑與pH值之關係係電解質為硫酸，電解質之濃度相對於研磨用組合物COMP整體為0.5(重量%)，膠體二氧化矽之濃度相對於研磨用組合物COMP整體為22(重量%)，且膠體二氧化矽之平均粒徑為80(nm)時之研磨速率及膠體二氧化矽之平均粒徑與pH值之關係。並且，曲線k13表示研磨速率與pH值之關係，曲線k14表示膠體二氧化矽之平均粒徑與pH值之關係。Fig. 8 is a graph showing the relationship between the polishing rate and the average particle diameter of colloidal cerium oxide and pH. In Fig. 8, the vertical axis represents the polishing rate and the average particle diameter of the colloidal ceria, and the horizontal axis represents the pH. Further, the relationship between the polishing rate and the average particle diameter of the colloidal cerium oxide and the pH value shown in Fig. 8 is that the electrolyte is sulfuric acid, and the concentration of the electrolyte is 0.5 (% by weight) based on the entire composition for polishing COMP, colloidal cerium oxide. The concentration is 22 (% by weight) based on the entire composition for polishing COMP, and the polishing rate of the colloidal cerium oxide is 80 (nm) and the relationship between the average particle diameter of the colloidal cerium oxide and the pH. Further, the curve k13 represents the relationship between the polishing rate and the pH value, and the curve k14 represents the relationship between the average particle diameter of the colloidal ceria and the pH.
再者，藉由添加硫酸，pH值達到1.3左右，為了將pH值調節為大於1.3之值而使用氨。Further, by adding sulfuric acid, the pH was about 1.3, and ammonia was used in order to adjust the pH to a value larger than 1.3.
參照圖8，於0~12之pH值之範圍內，研磨速率大於1500(/min)。並且，於2以下之pH值及8以上之pH值下，研磨速率大於2000(/min)(參照曲線k13)。Referring to Figure 8, the polishing rate is greater than 1500 in the range of pH values from 0 to 12 ( /min). Moreover, at a pH of 2 or less and a pH of 8 or more, the polishing rate is greater than 2000 ( /min) (refer to curve k13).
另一方面，於2以下之pH值及8以上之pH值下，膠體二氧化矽之平均粒徑為約80(nm)，於2~8之pH值下，膠體二氧化矽之平均粒徑大於80(nm)(參照曲線k14)。因此認為，於2~8之pH值下，膠體二氧化矽發生凝集。On the other hand, at a pH value of 2 or less and a pH value of 8 or more, the average particle diameter of the colloidal cerium oxide is about 80 (nm), and the average particle diameter of the colloidal cerium oxide at a pH of 2 to 8 More than 80 (nm) (refer to curve k14). Therefore, it is considered that the colloidal ceria is agglomerated at a pH of 2-8.
根據圖8所示之結果，於2~8之pH值下，膠體二氧化矽發生凝集，研磨速率大幅超出1500(/min)。因此證實，研磨用組合物COMP於不循環使用之情形時，無論pH值如何均適合研磨SiO2。According to the results shown in Fig. 8, the colloidal cerium oxide agglomerates at a pH of 2-8, and the polishing rate greatly exceeds 1500 ( /min). Therefore, it was confirmed that the polishing composition COMP is suitable for grinding SiO 2 regardless of the pH value when it is not recycled.
並且，於欲防止膠體二氧化矽發生凝集之情形時，即循環使用研磨用組合物COMP之情形時，對於研磨用組合物COMP，較佳為調節至2以下之pH值、或8以上之pH值。Further, when it is desired to prevent the colloidal cerium from agglomerating, that is, when the polishing composition COMP is recycled, the polishing composition COMP is preferably adjusted to a pH of 2 or less, or a pH of 8 or more. value.
圖9係表示改變電解質之濃度時之研磨速率與膠體二氧化矽之濃度之關係的圖。圖9中，縱軸表示研磨速率，橫軸表示膠體二氧化矽之濃度。又，圖9所示之研磨速率與膠體二氧化矽之濃度之關係係電解質為硫酸銨，膠體二氧化矽之平均粒徑為80(nm)時之研磨速率與膠體二氧化矽之濃度之關係。並且，×表示未添加電解質時之研磨速率與膠體二氧化矽之濃度之關係，黑圓點表示電解質之濃度相對於研磨用組合物COMP整體為0.25(重量%)時之研磨速率與膠體二氧化矽之濃度之關係，黑三角表示電解質之濃度相對於研磨用組合物COMP整體為0.50(重量%)時之研磨速率與膠體二氧化矽之濃度之關係，黑四方形表示電解質之濃度相對於研磨用組合物COMP整體為1.00(重量%)時之研磨速率與膠體二氧化矽之濃度之關係。Fig. 9 is a graph showing the relationship between the polishing rate and the concentration of colloidal cerium oxide when the concentration of the electrolyte is changed. In Fig. 9, the vertical axis represents the polishing rate, and the horizontal axis represents the concentration of colloidal cerium oxide. Moreover, the relationship between the polishing rate and the concentration of the colloidal cerium oxide shown in FIG. 9 is the relationship between the polishing rate and the concentration of the colloidal cerium oxide when the electrolyte is ammonium sulfate and the average particle diameter of the colloidal cerium oxide is 80 (nm). . Further, x represents the relationship between the polishing rate when no electrolyte is added and the concentration of colloidal cerium oxide, and the black dot indicates the polishing rate and colloidal oxidation when the concentration of the electrolyte is 0.25 (% by weight) as a whole with respect to the polishing composition COMP. The relationship between the concentration of cerium and the black triangle indicates the relationship between the polishing rate and the concentration of colloidal cerium oxide when the concentration of the electrolyte is 0.50 (% by weight) as a whole of the polishing composition COMP, and the black square indicates the concentration of the electrolyte relative to the polishing. The relationship between the polishing rate and the concentration of colloidal cerium oxide when the composition COMP was 1.00 (% by weight) as a whole.
參照圖9，於未添加電解質之情形時，研磨速率隨著膠體二氧化矽之濃度增加至40(重量%)為止而大致呈直線性提高，於40(重量%)以上之膠體二氧化矽之濃度下，大致達到固定值(參照×)。Referring to Fig. 9, in the case where no electrolyte is added, the polishing rate is substantially linearly increased as the concentration of colloidal cerium oxide is increased to 40% by weight, and 40% by weight or more of colloidal cerium oxide is used. At the concentration, it is approximately fixed (see ×).
另一方面，於添加電解質之情形時，研磨速率隨著膠體二氧化矽之濃度增加至約20(重量%)為止而大致呈直線性提高，於20(重量%)以上之膠體二氧化矽之濃度下，大致達到固定值(參照黑圓點、黑三角及黑四方形)。On the other hand, in the case of adding an electrolyte, the polishing rate is substantially linearly increased as the concentration of the colloidal ceria is increased to about 20% by weight, and the colloidal ceria is more than 20% by weight. At a concentration, it is approximately fixed (see black circles, black triangles, and black squares).
並且，隨著膠體二氧化矽之濃度接近20(重量%)，研磨速率激增。Also, as the concentration of colloidal cerium oxide approaches 20 (% by weight), the polishing rate surges.
又，添加電解質之情形時之研磨速率，於20(重量%)以上之膠體二氧化矽之濃度下，與未添加電解質且於40(重量%)以上之膠體二氧化矽之濃度下之研磨速率大致相同。Further, the polishing rate in the case of adding an electrolyte, the polishing rate at a concentration of colloidal cerium oxide of 20% by weight or more, and the concentration of colloidal cerium oxide having no electrolyte added at 40% by weight or more Roughly the same.
即，藉由添加電解質，即使將膠體二氧化矽之濃度自40(重量%)減半而達到20(重量%)，研磨速率亦保持未添加電解質且於40(重量%)以上之膠體二氧化矽之濃度下之研磨速率。That is, by adding an electrolyte, even if the concentration of the colloidal cerium oxide is halved from 40 (% by weight) to 20% by weight, the polishing rate is maintained as a colloidal dioxide which is not added with an electrolyte and is more than 40% by weight. The polishing rate at the concentration of bismuth.
此情況表明，藉由添加電解質，會實質上提高研磨用組合物中之膠體二氧化矽之濃度。This situation indicates that the concentration of the colloidal cerium oxide in the polishing composition is substantially increased by the addition of the electrolyte.
因此，藉由使用研磨用組合物COMP研磨SiO2，可於研磨用組合物中之膠體二氧化矽之濃度實質上提高之狀態下研磨SiO2。Thus the polishing state SiO 2, by the polishing using the polishing composition COMP SiO 2, concentration of the colloidal silicon dioxide can be in the polishing composition of the substantially improved.
因此，可提高SiO2之研磨速率。Therefore, the polishing rate of SiO 2 can be increased.
又，由於即使將膠體二氧化矽之濃度減半，亦可獲得大致相同之研磨速率，故而可減低研磨用組合物COMP中之膠體二氧化矽之濃度。其結果為，即使最終將研磨用組合物COMP廢棄，環境負擔亦較小。Further, even if the concentration of the colloidal cerium oxide is halved, substantially the same polishing rate can be obtained, so that the concentration of the colloidal cerium oxide in the polishing composition COMP can be reduced. As a result, even if the polishing composition COMP is finally discarded, the environmental burden is small.
以下，列舉實施例，具體地說明本發明。Hereinafter, the present invention will be specifically described by way of examples.
將實施例1~實施例31中之研磨用組合物之成分、與評價結果示於表1~表7。又，將比較例1~比較例13中之研磨用組合物之成分、與評價結果示於表8~表10。The components of the polishing composition of Examples 1 to 31 and the evaluation results are shown in Tables 1 to 7. Moreover, the components of the polishing composition of Comparative Examples 1 to 13 and the evaluation results are shown in Tables 8 to 10.
(實施例1)(Example 1)
實施例1中之研磨用組合物COMP1含有濃度相對於研磨用組合物COMP1整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP1整體而為0.5(重量%)之硫酸銨。The polishing composition COMP1 of Example 1 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP1, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP1. Ammonium sulfate.
(實施例2)(Example 2)
實施例2中之研磨用組合物COMP2含有濃度相對於研磨用組合物COMP2整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP2整體而為0.5(重量%)之硫酸鉀。The polishing composition COMP2 of Example 2 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP2, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP2. Potassium sulfate.
(實施例3)(Example 3)
實施例3中之研磨用組合物COMP3含有濃度相對於研磨用組合物COMP3整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP3整體而為0.5(重量%)之鹽酸。The polishing composition COMP3 of Example 3 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP3, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP3. Hydrochloric acid.
(實施例4)(Example 4)
實施例4中之研磨用組合物COMP4含有濃度相對於研磨用組合物COMP4整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP4整體而為0.5(重量%)之羥乙酸。The polishing composition COMP4 of Example 4 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP4, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP4. Glycolic acid.
(實施例5)(Example 5)
實施例5中之研磨用組合物COMP5含有濃度相對於研磨用組合物COMP5整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP5整體而為0.5(重量%)之焦硫酸鉀。The polishing composition COMP5 of Example 5 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP5, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP5. Potassium pyrosulfate.
(實施例6)(Example 6)
實施例6中之研磨用組合物COMP6含有濃度相對於研磨用組合物COMP6整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP6整體而為0.5(重量%)之天冬醯胺酸。The polishing composition COMP6 of Example 6 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP6, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP6. Aspartic acid.
(實施例7)(Example 7)
實施例7中之研磨用組合物COMP7含有濃度相對於研磨用組合物COMP7整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP7整體而為0.5(重量%)之硫酸。The polishing composition COMP7 of Example 7 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP7, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP7. Sulfuric acid.
(實施例8)(Example 8)
實施例8中之研磨用組合物COMP8含有濃度相對於研磨用組合物COMP8整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP8整體而為0.5(重量%)之焦磷酸。The polishing composition COMP8 of Example 8 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP8, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP8. Pyrophosphoric acid.
(實施例9)(Example 9)
實施例9中之研磨用組合物COMP9含有濃度相對於研磨用組合物COMP9整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP9整體而為0.5(重量%)之磷酸。The polishing composition COMP9 of Example 9 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP9, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP9. Phosphoric acid.
(實施例10)(Embodiment 10)
實施例10中之研磨用組合物COMP10含有濃度相對於研磨用組合物COMP10整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP10整體而為0.5(重量%)之硝酸。The polishing composition COMP10 of Example 10 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP10, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP10. Nitric acid.
(實施例11)(Example 11)
實施例11中之研磨用組合物COMP11含有濃度相對於研磨用組合物COMP11整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP11整體而為0.5(重量%)之草酸。The polishing composition COMP11 of Example 11 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP11, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP11. Oxalic acid.
(實施例12)(Embodiment 12)
實施例12中之研磨用組合物COMP12含有濃度相對於研磨用組合物COMP12整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP12整體而為0.5(重量%)之PAA(聚丙烯酸)。The polishing composition COMP12 of Example 12 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP12, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP12. PAA (polyacrylic acid).
(實施例13)(Example 13)
實施例13中之研磨用組合物COMP13含有濃度相對於研磨用組合物COMP13整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP13整體而為0.5(重量%)之天冬醯胺。The polishing composition COMP13 of Example 13 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP13, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP13. Aspartate.
(實施例14)(Example 14)
實施例14中之研磨用組合物COMP14含有濃度相對於研磨用組合物COMP14整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP14整體而為0.5(重量%)之鄰苯二甲酸。The polishing composition COMP14 of Example 14 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP14, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP14. Phthalic acid.
(實施例15)(Example 15)
實施例15中之研磨用組合物COMP15含有濃度相對於研磨用組合物COMP15整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP15整體而為0.5(重量%)之苯甲酸。The polishing composition COMP15 of Example 15 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP15, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP15. Benzoic acid.
(實施例16)(Embodiment 16)
實施例16中之研磨用組合物COMP16含有濃度相對於研磨用組合物COMP16整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP16整體而為0.5(重量%)之丙二酸。The polishing composition COMP16 of Example 16 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP16, and the concentration was 0.5% by weight based on the entire polishing composition COMP16. Malonic acid.
(實施例17)(Example 17)
實施例17中之研磨用組合物COMP17含有濃度相對於研磨用組合物COMP17整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP17整體而為0.5(重量%)之碳酸氫銨。The polishing composition COMP17 of Example 17 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP17, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP17. Ammonium bicarbonate.
(實施例18)(Embodiment 18)
實施例18中之研磨用組合物COMP18含有濃度相對於研磨用組合物COMP18整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP18整體而為0.5(重量%)之過硫酸銨。The polishing composition COMP18 of Example 18 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP18, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP18. Ammonium persulfate.
(實施例19)(Embodiment 19)
實施例19中之研磨用組合物COMP19含有濃度相對於研磨用組合物COMP19整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP19整體而為0.5(重量%)之硫代硫酸銨。The polishing composition COMP19 of Example 19 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP19, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP19. Ammonium thiosulfate.
(實施例20)(Embodiment 20)
實施例20中之研磨用組合物COMP20含有濃度相對於研磨用組合物COMP20整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP20整體而為0.5(重量%)之甲磺酸。The polishing composition COMP20 of Example 20 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP20, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP20. Methanesulfonic acid.
(實施例21)(Example 21)
實施例21中之研磨用組合物COMP21含有濃度相對於研磨用組合物COMP21整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP21整體而為0.5(重量%)之多元磷酸。The polishing composition COMP21 of Example 21 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP21, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP21. Polyphosphoric acid.
(實施例22)(Example 22)
實施例22中之研磨用組合物COMP22含有濃度相對於研磨用組合物COMP22整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP22整體而為0.5(重量%)之乳酸。The polishing composition COMP22 of Example 22 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP22, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP22. Lactic acid.
(實施例23)(Example 23)
實施例23中之研磨用組合物COMP23含有濃度相對於研磨用組合物COMP23整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP23整體而為0.5(重量%)之丙胺酸。The polishing composition COMP23 of Example 23 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP23, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP23. Alanine.
(實施例24)(Example 24)
實施例24中之研磨用組合物COMP24含有濃度相對於研磨用組合物COMP24整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP24整體而為0.5(重量%)之順丁烯二酸。The polishing composition COMP24 of Example 24 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP24, and the concentration was 0.5 (% by weight) based on the entire composition COMP24 for polishing. Maleic acid.
(實施例25)(Embodiment 25)
實施例25中之研磨用組合物COMP25含有濃度相對於研磨用組合物COMP25整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP25整體而為0.5(重量%)之酒石酸。The polishing composition COMP25 of Example 25 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP25, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP25. Tartaric acid.
(實施例26)(Example 26)
實施例26中之研磨用組合物COMP26含有濃度相對於研磨用組合物COMP26整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP26整體而為0.5(重量%)之檸檬酸。The polishing composition COMP26 of Example 26 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP26, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP26. Citric acid.
(實施例27)(Example 27)
實施例27中之研磨用組合物COMP27含有濃度相對於研磨用組合物COMP27整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP27整體而為0.5(重量%)之苯磺酸。The polishing composition COMP27 of Example 27 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP27, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP27. Benzenesulfonic acid.
(實施例28)(Embodiment 28)
實施例28中之研磨用組合物COMP28含有濃度相對於研磨用組合物COMP28整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP28整體而為0.5(重量%)之丁醇。The polishing composition COMP28 of Example 28 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP28, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP28. Butanol.
(實施例29)(Example 29)
實施例29中之研磨用組合物COMP29含有濃度相對於研磨用組合物COMP29整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP29整體而為0.5(重量%)之甘油。The polishing composition COMP29 of Example 29 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP29, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP29. Glycerin.
(實施例30)(Embodiment 30)
實施例30中之研磨用組合物COMP30含有濃度相對於研磨用組合物COMP30整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP30整體而為0.5(重量%)之丙醇。The polishing composition COMP30 of Example 30 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP30, and the concentration was 0.5 (% by weight) based on the entire composition for polishing COMP30. Propanol.
(實施例31)(Example 31)
實施例31中之研磨用組合物COMP31含有濃度相對於研磨用組合物COMP31整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP31整體而為0.5(重量%)之乙醇。The polishing composition COMP31 of Example 31 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP31, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP31. Ethanol.
(比較例1)(Comparative Example 1)
比較例1中之研磨用組合物COMP_CP1含有濃度相對於研磨用組合物COMP_CP1整體而為20(重量%)之膠體二氧化矽。即，研磨用組合物COMP_CP1不含有電解質或電解質之鹽作為添加劑。The polishing composition COMP_CP1 in Comparative Example 1 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP_CP1. That is, the polishing composition COMP_CP1 does not contain an electrolyte or a salt of an electrolyte as an additive.
(比較例2)(Comparative Example 2)
比較例2中之研磨用組合物COMP_CP2含有濃度相對於研磨用組合物COMP_CP2整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP2整體而為0.5(重量%)之葡萄糖。The polishing composition COMP_CP2 of Comparative Example 2 contained colloidal cerium oxide having a concentration of 20% by weight based on the entire polishing composition COMP_CP2, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP2. Glucose.
(比較例3)(Comparative Example 3)
比較例3中之研磨用組合物COMP_CP3含有濃度相對於研磨用組合物COMP_CP3整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP3整體而為0.5(重量%)之吡啶。The polishing composition COMP_CP3 of Comparative Example 3 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP3, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP3. Pyridine.
(比較例4)(Comparative Example 4)
比較例4中之研磨用組合物COMP_CP4含有濃度相對於研磨用組合物COMP_CP4整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP4整體而為0.5(重量%)之糊精。The polishing composition COMP_CP4 of Comparative Example 4 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP4, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP4. Dextrin.
(比較例5)(Comparative Example 5)
比較例5中之研磨用組合物COMP_CP5含有濃度相對於研磨用組合物COMP_CP5整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP5整體而為0.5(重量%)之PEG(聚乙二醇)。The polishing composition COMP_CP5 of Comparative Example 5 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP5, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP5. PEG (polyethylene glycol).
(比較例6)(Comparative Example 6)
比較例6中之研磨用組合物COMP_CP6含有濃度相對於研磨用組合物COMP_CP6整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP6整體而為0.5(重量%)之可溶性澱粉。The polishing composition COMP_CP6 of Comparative Example 6 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP6, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP6. Soluble starch.
(比較例7)(Comparative Example 7)
比較例7中之研磨用組合物COMP_CP7含有濃度相對於研磨用組合物COMP_CP7整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP7整體而為0.5(重量%)之三乙醇胺。The polishing composition COMP_CP7 in Comparative Example 7 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP7, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP7. Triethanolamine.
(比較例8)(Comparative Example 8)
比較例8中之研磨用組合物COMP_CP8含有濃度相對於研磨用組合物COMP_CP8整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP8整體而為0.5(重量%)之PVP(聚(N-乙烯基吡咯啶酮))。The polishing composition COMP_CP8 of Comparative Example 8 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP8, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP8. PVP (poly(N-vinylpyrrolidone)).
(比較例9)(Comparative Example 9)
比較例9中之研磨用組合物COMP_CP9含有濃度相對於研磨用組合物COMP_CP9整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP9整體而為0.5(重量%)之TMAH(氫氧化四甲基銨)。The polishing composition COMP_CP9 of Comparative Example 9 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP9, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP9. TMAH (tetramethylammonium hydroxide).
(比較例10)(Comparative Example 10)
比較例10中之研磨用組合物COMP_CP10含有濃度相對於研磨用組合物COMP_CP10整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP10整體而為0.5(重量%)之乙胺。The polishing composition COMP_CP10 in Comparative Example 10 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP10, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP10. Ethylamine.
(比較例11)(Comparative Example 11)
比較例11中之研磨用組合物COMP_CP11含有濃度相對於研磨用組合物COMP_CP11整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP11整體而為0.5(重量%)之DABCO(1,4-二氮雜雙環[2.2.2]辛烷)。The polishing composition COMP_CP11 of Comparative Example 11 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP11, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP11. DABCO (1,4-diazabicyclo[2.2.2]octane).
(比較例12)(Comparative Example 12)
比較例12中之研磨用組合物COMP_CP12含有濃度相對於研磨用組合物COMP_CP12整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP12整體而為0.5(重量%)之精胺酸。The polishing composition COMP_CP12 of Comparative Example 12 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP12, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP12. The arginine.
(比較例13)(Comparative Example 13)
比較例13中之研磨用組合物COMP_CP13含有濃度相對於研磨用組合物COMP_CP13整體而為20(重量%)之膠體二氧化矽、與濃度相對於研磨用組合物COMP_CP13整體而為0.5(重量%)之哌啶。The polishing composition COMP_CP13 of Comparative Example 13 contained colloidal ceria having a concentration of 20% by weight based on the entire polishing composition COMP_CP13, and the concentration was 0.5 (% by weight) based on the entire polishing composition COMP_CP13. Piperidine.
實施例1~31及比較例1~11、13中之研磨用組合物COMP1~COMP31、COMP_CP1~COMP_CP11、COMP_CP13係使用氨調節為9.5之pH值，比較例12中之研磨用組合物COMP_CP12係使用氨調節為10.1之pH值。The polishing compositions COMP1 to COMP31, COMP_CP1 to COMP_CP11, and COMP_CP13 of Examples 1 to 31 and Comparative Examples 1 to 11 and 13 were adjusted to a pH of 9.5 using ammonia, and the polishing composition COMP_CP12 of Comparative Example 12 was used. The ammonia was adjusted to a pH of 10.1.
因此，研磨用組合物COMP1~COMP31、COMP_CP1~COMP_CP13除表1~表10所示之成分以外，亦含有氨。Therefore, the polishing compositions COMP1 to COMP31 and COMP_CP1 to COMP_CP13 contain ammonia in addition to the components shown in Tables 1 to 10.
又，研磨用組合物COMP6中所含之天冬醯胺酸為酸性胺基酸，研磨用組合物COMP13中所含之天冬醯胺及研磨用組合物COMP23中所含之丙胺酸為中性胺基酸，研磨用組合物COMP_CP12中所含之精胺酸為鹼性胺基酸。並且，該等胺基酸具有胺及酸兩者。Further, the aspartic acid contained in the polishing composition COMP6 is an acidic amino acid, and the alanine contained in the polishing composition COMP13 and the alanine contained in the polishing composition COMP23 are neutral. The amino acid, the arginine acid contained in the polishing composition COMP_CP12 is a basic amino acid. Also, the amino acids have both an amine and an acid.
(結果)(result)
使用研磨用組合物COMP1~COMP31研磨SiO2時之研磨速率高於使用研磨用組合物COMP_CP1~COMP_CP13研磨SiO2時之研磨速率。Polishing using the polishing composition COMP1 ~ COMP31 of SiO 2 is higher than the polishing rate of polishing using the polishing composition COMP_CP1 ~ COMP_CP13 SiO 2 of the polishing rate.
並且，使用研磨用組合物COMP1~COMP9研磨SiO2時之研磨速率較使用研磨用組合物COMP_CP1~COMP_CP13研磨SiO2時之研磨速率高約2倍。Further, the polishing rate when the SiO 2 was polished using the polishing compositions COMP1 to COMP9 was about twice as high as the polishing rate when the SiO 2 was polished using the polishing compositions COMP_CP1 to COMP_CP13.
尤其是使用研磨用組合物COMP1之情形時，獲得2098(/min)之研磨速率。In particular, when using the polishing composition COMP1, 2098 (obtained) /min) grinding rate.
又，使用含有包含作為酸性胺基酸之天冬醯胺酸的電解質作為添加劑的研磨用組合物COMP6時之研磨速率高於使用研磨用組合物COMP_CP1時之研磨速率。使用含有包含作為中性胺基酸之天冬醯胺的電解質作為添加劑的研磨用組合物COMP13時之研磨速率高於使用研磨用組合物COMP_CP1時之研磨速率。使用含有包含作為中性胺基酸之丙胺酸的電解質作為添加劑的研磨用組合物COMP23時之研磨速率高於使用研磨用組合物COMP_CP1時之研磨速率。使用含有包含作為鹼性胺基酸之精胺酸的電解質作為添加劑的研磨用組合物COMP_CP12時之研磨速率低於使用研磨用組合物COMP_CP1時之研磨速率。Further, the polishing rate when using the polishing composition COMP6 containing an electrolyte containing aspartic acid as the acidic amino acid as an additive is higher than the polishing rate when the polishing composition COMP_CP1 is used. The polishing rate when using the polishing composition COMP13 containing an electrolyte containing aspartic acid as a neutral amino acid as an additive is higher than the polishing rate when the polishing composition COMP_CP1 is used. The polishing rate when using the polishing composition COMP23 containing an electrolyte containing an amino acid as a neutral amino acid as an additive is higher than the polishing rate when the polishing composition COMP_CP1 is used. The polishing rate when using the polishing composition COMP_CP12 containing an electrolyte containing arginine as a basic amino acid as an additive is lower than the polishing rate when the polishing composition COMP_CP1 is used.
因此，藉由添加包含酸性或中性之胺基酸之電解質，會提高研磨速率，而藉由添加包含鹼性胺基酸之電解質，會降低研磨速率。Therefore, by adding an electrolyte containing an acidic or neutral amino acid, the polishing rate is increased, and by adding an electrolyte containing a basic amino acid, the polishing rate is lowered.
因此，本發明之實施形態中，係添加包含酸性或中性之胺基酸之電解質作為添加劑。Therefore, in the embodiment of the present invention, an electrolyte containing an acidic or neutral amino acid is added as an additive.
進而，使用含有包含醇之電解質作為添加劑的研磨用組合物COMP28~COMP31時之研磨速率高於使用研磨用組合物COMP_CP1時之研磨速率。Further, the polishing rate when using the polishing compositions COMP28 to COMP31 containing an electrolyte containing an alcohol as an additive is higher than the polishing rate when the polishing composition COMP_CP1 is used.
因此，本發明之實施形態中，係添加包含醇之電解質作為添加劑。Therefore, in the embodiment of the present invention, an electrolyte containing an alcohol is added as an additive.
進而，使用含有包含胺之電解質作為添加劑的研磨用組合物COMP_CP7、COMP_CP10時之研磨速率低於使用研磨用組合物COMP_CP1時之研磨速率。Further, the polishing rate when using the polishing compositions COMP_CP7 and COMP_CP10 containing an electrolyte containing an amine as an additive is lower than the polishing rate when the polishing composition COMP_CP1 is used.
因此，藉由添加包含胺之電解質，會降低研磨速率。Therefore, by adding an electrolyte containing an amine, the polishing rate is lowered.
因此，本發明之實施形態中，係自添加劑中排除包含胺之電解質。Therefore, in the embodiment of the present invention, the electrolyte containing an amine is excluded from the additive.
研磨用組合物COMP1含有作為硫酸鹽之硫酸銨作為添加劑。研磨用組合物COMP2含有作為硫酸鹽之硫酸鉀作為添加劑。研磨用組合物COMP4含有羥乙酸作為添加劑。研磨用組合物COMP5含有作為焦硫酸鹽之焦硫酸鉀作為添加劑。研磨用組合物COMP7含有硫酸作為添加劑。研磨用組合物COMP8含有焦磷酸作為添加劑。研磨用組合物COMP9含有磷酸作為添加劑。研磨用組合物COMP10含有硝酸作為添加劑。研磨用組合物COMP17含有作為碳酸鹽之碳酸氫銨作為添加劑。研磨用組合物COMP18含有作為過硫酸鹽之過硫酸銨作為添加劑。研磨用組合物COMP19含有作為硫代硫酸鹽之硫代硫酸銨作為添加劑。研磨用組合物COMP21含有多元磷酸作為添加劑。The polishing composition COMP1 contains ammonium sulfate as a sulfate as an additive . The polishing composition COMP2 contains potassium sulfate as a sulfate as an additive. The polishing composition COMP4 contains glycolic acid as an additive. The polishing composition COMP5 contains potassium pyrosulfate as a pyrosulfate as an additive. The polishing composition COMP7 contains sulfuric acid as an additive. The polishing composition COMP8 contains pyrophosphoric acid as an additive. The polishing composition COMP9 contains phosphoric acid as an additive. The polishing composition COMP10 contains nitric acid as an additive. The polishing composition COMP17 contains ammonium hydrogencarbonate as a carbonate as an additive. The polishing composition COMP18 contains ammonium persulfate as a persulfate as an additive. The polishing composition COMP19 contains ammonium thiosulfate as a thiosulfate as an additive. The polishing composition COMP21 contains a polyphosphoric acid as an additive.
並且，硫酸、羥乙酸、焦硫酸、焦磷酸、磷酸、硝酸、碳酸、過硫酸、硫代硫酸及多元磷酸為無機含氧酸。Further, sulfuric acid, glycolic acid, pyrosulfuric acid, pyrophosphoric acid, phosphoric acid, nitric acid, carbonic acid, persulfuric acid, thiosulfuric acid, and polyphosphoric acid are inorganic oxo acids.
因此，研磨用組合物COMP1、COMP2、COMP4、COMP5、COMP7~COMP10、COMP17~COMP19、COMP21含有包含無機含氧酸、或無機含氧酸之鹽的電解質作為添加劑。Therefore, the polishing compositions COMP1, COMP2, COMP4, COMP5, COMP7 to COMP10, COMP17 to COMP19, and COMP21 contain an electrolyte containing an inorganic oxyacid or a salt of an inorganic oxyacid as an additive.
又，研磨用組合物COMP11含有草酸作為添加劑。研磨用組合物COMP12含有包含PAA(聚丙烯酸)之電解質作為添加劑。研磨用組合物COMP14含有鄰苯二甲酸作為添加劑。研磨用組合物COMP15含有苯甲酸作為添加劑。研磨用組合物COMP16含有丙二酸作為添加劑。研磨用組合物COMP20含有甲磺酸作為添加劑。研磨用組合物COMP22含有乳酸作為添加劑。研磨用組合物COMP24含有順丁烯二酸作為添加劑。研磨用組合物COMP25含有酒石酸作為添加劑。研磨用組合物COMP26含有檸檬酸作為添加劑。研磨用組合物COMP27含有苯磺酸作為添加劑。Further, the polishing composition COMP11 contains oxalic acid as an additive. The polishing composition COMP12 contains an electrolyte containing PAA (polyacrylic acid) as an additive. The polishing composition COMP14 contains phthalic acid as an additive. The polishing composition COMP15 contains benzoic acid as an additive. The polishing composition COMP16 contains malonic acid as an additive. The polishing composition COMP20 contains methanesulfonic acid as an additive. The polishing composition COMP22 contains lactic acid as an additive. The polishing composition COMP24 contains maleic acid as an additive. The polishing composition COMP25 contains tartaric acid as an additive. The polishing composition COMP26 contains citric acid as an additive. The polishing composition COMP27 contains benzenesulfonic acid as an additive.
並且，草酸、鄰苯二甲酸、苯甲酸、丙二酸、甲磺酸、乳酸、順丁烯二酸、酒石酸、檸檬酸、聚丙烯酸及苯磺酸為有機含氧酸。Further, oxalic acid, phthalic acid, benzoic acid, malonic acid, methanesulfonic acid, lactic acid, maleic acid, tartaric acid, citric acid, polyacrylic acid, and benzenesulfonic acid are organic oxyacids.
因此，研磨用組合物COMP11、COMP12、COMP14~COMP16、COMP20、COMP22、COMP24~COMP27含有包含有機含氧酸之電解質作為添加劑。Therefore, the polishing compositions COMP11, COMP12, COMP14 to COMP16, COMP20, COMP22, and COMP24 to COMP27 contain an electrolyte containing an organic oxyacid as an additive.
進而，研磨用組合物COMP3含有包含鹽酸之電解質作為添加劑。Further, the polishing composition COMP3 contains an electrolyte containing hydrochloric acid as an additive.
進而，研磨用組合物COMP6含有天冬醯胺酸作為添加劑。研磨用組合物COMP13含有天冬醯胺作為添加劑。研磨用組合物COMP23含有丙胺酸作為添加劑。Further, the polishing composition COMP6 contains aspartic acid as an additive. The polishing composition COMP13 contains aspartame as an additive. The polishing composition COMP23 contains alanine as an additive.
並且，天冬醯胺酸、天冬醯胺及丙胺酸為酸性或中性之胺基酸。Further, aspartic acid, aspartame and alanine are acidic or neutral amino acids.
因此，研磨用組合物COMP6、COMP13、COMP23含有包含酸性或中性之胺基酸之電解質作為添加劑。Therefore, the polishing compositions COMP6, COMP13, and COMP23 contain an electrolyte containing an acidic or neutral amino acid as an additive.
進而，研磨用組合物COMP28含有丁醇作為添加劑。研磨用組合物COMP29含有甘油作為添加劑。研磨用組合物COMP30含有丙醇作為添加劑。研磨用組合物COMP31含有乙醇作為添加劑。Further, the polishing composition COMP28 contains butanol as an additive. The polishing composition COMP29 contains glycerin as an additive. The polishing composition COMP30 contains propanol as an additive. The polishing composition COMP31 contains ethanol as an additive.
並且，丁醇、甘油、丙醇及乙醇為醇。Further, butanol, glycerin, propanol and ethanol are alcohols.
因此，研磨用組合物COMP28~COMP31含有包含醇之電解質作為添加劑。Therefore, the polishing compositions COMP28 to COMP31 contain an electrolyte containing an alcohol as an additive.
其結果為，研磨用組合物COMP1~COMP31含有包含無機含氧酸、無機含氧酸之鹽、有機含氧酸、鹽酸、酸性或中性之胺基酸、及醇中之任一者的電解質作為添加劑。As a result, the polishing compositions COMP1 to COMP31 contain an electrolyte containing an inorganic oxyacid, an inorganic oxyacid salt, an organic oxyacid, hydrochloric acid, an acidic or neutral amino acid, and an alcohol. As an additive.
於該情形時，無機含氧酸、無機含氧酸之鹽、有機含氧酸、鹽酸、酸性或中性之胺基酸、及醇會在水溶液中釋放氫離子。In this case, the inorganic oxyacid, the inorganic oxyacid salt, the organic oxyacid, hydrochloric acid, the acidic or neutral amino acid, and the alcohol release hydrogen ions in the aqueous solution.
因此，研磨用組合物COMP1~COMP31含有在水溶液中釋放氫離子之電解質或電解質之鹽作為添加劑。Therefore, the polishing compositions COMP1 to COMP31 contain an electrolyte or a salt of an electrolyte which releases hydrogen ions in an aqueous solution as an additive.
結果證實，藉由添加包含在水溶液中釋放氫離子之電解質或電解質之鹽的添加劑，可提高SiO2之研磨速率。As a result, it was confirmed that the polishing rate of SiO 2 can be increased by adding an additive containing a salt of an electrolyte or an electrolyte which releases hydrogen ions in an aqueous solution.
有機含氧酸之鹽、鹽酸鹽、及胺基酸鹽亦可在水溶液中釋放氫離子。Organic oxoacid salts, hydrochlorides, and amine acid salts can also release hydrogen ions in aqueous solutions.
因此，本發明之實施形態中之研磨用組合物COMP含有包含無機含氧酸、無機含氧酸之鹽、有機含氧酸、有機含氧酸之鹽、鹽酸、鹽酸鹽、酸性或中性之胺基酸、酸性或中性之胺基酸之鹽及醇中之任一者的電解質作為添加劑即可。即，研磨用組合物COMP含有包含含氧酸、含氧酸鹽、鹽酸、鹽酸鹽、酸性或中性之胺基酸、酸性或中性之胺基酸之鹽及醇中之任一者的電解質作為添加劑即可。並且，研磨用組合物COMP通常含有包含在水溶液中釋放氫離子之電解質或電解質之鹽的添加劑即可。Therefore, the polishing composition COMP in the embodiment of the present invention contains a salt containing an inorganic oxyacid, an inorganic oxyacid, an organic oxyacid, a salt of an organic oxyacid, hydrochloric acid, a hydrochloride, an acid or a neutral An electrolyte of any of an amino acid, an acid or a neutral amino acid salt, and an alcohol may be used as an additive. That is, the polishing composition COMP contains any one of an acid containing an oxo acid, an oxoacid salt, a hydrochloric acid, a hydrochloride, an acidic or neutral amino acid, an acidic or neutral amino acid, and an alcohol. The electrolyte can be used as an additive. Further, the polishing composition COMP usually contains an additive containing a salt of an electrolyte or an electrolyte which releases hydrogen ions in an aqueous solution.
研磨用組合物COMP較佳為含有包含含氧酸、含氧酸鹽、鹽酸、鹽酸鹽、酸性或中性之胺基酸、及酸性或中性之胺基酸之鹽中之任一者的電解質作為添加劑。The polishing composition COMP preferably contains any one of a salt containing an oxo acid, an oxoacid salt, a hydrochloric acid, a hydrochloride, an acidic or neutral amino acid, and an acidic or neutral amino acid. The electrolyte acts as an additive.
又，研磨用組合物COMP之研磨對象並不限定於SiO2，通常可為SiOx(0<x≦2)。Moreover, the polishing target of the polishing composition COMP is not limited to SiO 2 , and may be usually SiO x (0<x≦2).
此次揭示之實施形態在所有方面均為例示，並非具有制限性之內容。本發明之範圍係由專利申請範圍揭示，而非上述實施形態之說明，該範圍意在包括與專利申請範圍等同之含義及在範圍內之全部變更。The embodiments disclosed herein are illustrative in all aspects and are not intended to be limiting. The scope of the present invention is defined by the scope of the patent application, and is not intended to
本發明可應用於研磨SiOx(0<x≦2)之研磨用組合物。The present invention can be applied to a polishing composition for polishing SiO x (0 < x 2).
圖1係表示研磨速率與膠體二氧化矽之平均粒徑之關係的圖。Fig. 1 is a graph showing the relationship between the polishing rate and the average particle diameter of colloidal cerium oxide.
圖2係表示膠體二氧化矽之平均粒徑及研磨速率、與電解質濃度之關係的圖。Fig. 2 is a graph showing the relationship between the average particle diameter of the colloidal cerium oxide and the polishing rate, and the concentration of the electrolyte.
圖3係表示改變膠體二氧化矽之濃度時之研磨速率與電解質濃度之關係的圖。Fig. 3 is a graph showing the relationship between the polishing rate and the electrolyte concentration when the concentration of colloidal cerium oxide is changed.
圖4係表示改變電解質時之研磨速率與電解質濃度之關係的圖。Fig. 4 is a graph showing the relationship between the polishing rate and the electrolyte concentration when the electrolyte is changed.
圖5係表示改變電解質鹽時之研磨速率與電解質濃度之關係的圖。Fig. 5 is a graph showing the relationship between the polishing rate and the electrolyte concentration when the electrolyte salt is changed.
圖6係表示研磨速率與電解質之種類之關係的圖。Fig. 6 is a graph showing the relationship between the polishing rate and the kind of electrolyte.
圖7係表示研磨速率與鹽之種類之關係的圖。Fig. 7 is a graph showing the relationship between the polishing rate and the type of salt.
圖8係表示研磨速率及膠體二氧化矽之平均粒徑、與pH值之關係的圖。Fig. 8 is a graph showing the relationship between the polishing rate and the average particle diameter of the colloidal cerium oxide and the pH.
圖9係表示改變電解質之濃度時之研磨速率與膠體二氧化矽之濃度之關係的圖。Fig. 9 is a graph showing the relationship between the polishing rate and the concentration of colloidal cerium oxide when the concentration of the electrolyte is changed.
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| JP6373029B2 (en) * | 2014-03-27 | 2018-08-15 | 株式会社フジミインコーポレーテッド | Polishing composition |
| JP7330668B2 (en) * | 2018-03-08 | 2023-08-22 | 株式会社フジミインコーポレーテッド | Surface treatment composition, method for producing surface treatment composition, method for surface treatment, and method for production of semiconductor substrate |
| JP7409918B2 (en) * | 2020-03-13 | 2024-01-09 | 株式会社フジミインコーポレーテッド | Polishing composition, method for producing polishing composition, polishing method, and method for producing semiconductor substrate |
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| JP2008124377A (en) * | 2006-11-15 | 2008-05-29 | Jsr Corp | Aqueous dispersant for chemical-mechanical polishing, chemical-mechanical polishing method, and kit for preparing aqueous dispersant for chemical-mechanical polishing |
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