US20040092103A1 - Polishing fluid composition - Google Patents
Polishing fluid composition Download PDFInfo
- Publication number
- US20040092103A1 US20040092103A1 US10/333,028 US33302803A US2004092103A1 US 20040092103 A1 US20040092103 A1 US 20040092103A1 US 33302803 A US33302803 A US 33302803A US 2004092103 A1 US2004092103 A1 US 2004092103A1
- Authority
- US
- United States
- Prior art keywords
- polishing
- acid
- weight
- polished
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000005498 polishing Methods 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 239000012530 fluid Substances 0.000 title 1
- 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 57
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 238000007517 polishing process Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 51
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 abstract description 23
- 230000007547 defect Effects 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- 239000004065 semiconductor Substances 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011976 maleic acid Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 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 description 4
- 229910018104 Ni-P Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910018536 Ni—P Inorganic materials 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 3
- 229940018557 citraconic acid Drugs 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
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 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
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
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- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- -1 inorganic acid salt Chemical class 0.000 description 2
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
-
- 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
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
Definitions
- the present invention relates to a polishing composition and a polishing process of a substrate to be polished.
- An object of the present invention is to provide a polishing composition capable of increasing the polishing rate and reducing the surface roughness, without causing surface defects on a surface of an object to be polished; and a polishing process for a substrate to be polished.
- the present invention relates to:
- a polishing composition comprising water, an abrasive, an intermediate alumina, and a polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof, wherein a content of the intermediate alumina is from 1 to 90 parts by weight, based on 100 parts by weight of the abrasive; and
- a polishing process for a substrate to be polished comprising polishing a substrate to be polished under conditions that a composition of a polishing liquid during polishing is the composition as defined in item [1] above.
- any abrasives generally employed for polishing can be used.
- the abrasive include metals; carbides, nitrides, oxides, or borides of metals or metalloids; diamond, and the like.
- the metal elements or metalloid elements include those elements belonging to the Groups 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A or 8 of the Periodic Table (long period form).
- Concrete examples of the abrasive include ⁇ -alumina particles, silicon carbide particles, diamond particles, magnesium oxide particles, zinc oxide particles, cerium oxide particles, zirconium oxide particles, colloidal silica particles, fumed silica particles, and the like.
- ⁇ -alumina particles, cerium oxide particles, zirconium oxide particles, colloidal silica particles, and fumed silica particles are suitable for polishing semiconductor wafers and semiconductor elements and substrates for precision parts such as substrates for magnetic recording media.
- the ⁇ -alumina particles are suitable for polishing a substrate for magnetic recording medium.
- the average particle size of the primary particles of the abrasive is preferably from 0.01 to 3 ⁇ m, more preferably from 0.02 to 0.8 ⁇ m, especially preferably from 0.05 to 0.5 ⁇ m, from the viewpoint of increasing the polishing rate.
- the average particle size of the secondary particles thereof is preferably from 0.05 to 2 ⁇ m, more preferably from 0.1 to 1.5 ⁇ m, especially preferably from 0.2 to 1.2 ⁇ m, similarly from the viewpoint of increasing the polishing rate and from the viewpoint of reducing the surface roughness of the object to be polished.
- the average particle size of the primary particles of the abrasive can be determined by carrying out image analysis by observation with a scanning electron microscope (magnification: preferably from 3000 to 30000 times) to determine an average particle size.
- the average particle size of the secondary particles can be determined as a volume-average particle size by using a laser beam diffraction method.
- the specific gravity of the abrasive is preferably from 2 to 6, more preferably from 2 to 5, from the viewpoints of dispersibility, feeding ability and collecting and reusability for a polishing device.
- the content of the abrasive is preferably from 1 to 40% by weight, more preferably from 2 to 30% by weight, more preferably from 3 to 15% by weight, of the polishing composition, from the viewpoints of economic advantages and reduction in the surface roughness, thereby making it possible to efficiently polish the object.
- intermediate alumina particles is a generic term referring to alumina particles other than the ⁇ -alumina particles. Concrete examples thereof include ⁇ -alumina particles, ⁇ -alumina particles, ⁇ -alumina particles, ⁇ -alumina particles, ⁇ -alumina particles, mixtures thereof, and the like. Among them, the following intermediate aluminas are preferable, from the viewpoints of the effects of increasing the polishing rate and reducing the surface roughness.
- Their crystal forms are preferably ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, mixtures thereof, and the like, more preferably ⁇ -alumina, ⁇ -alumina, mixtures thereof, especially preferably ⁇ -alumina.
- their specific surface area is preferably from 30 to 300 m 2 /g, more preferably from 50 to 200 m 2 /g.
- Their average particle size is preferably from 0.01 to 5 ⁇ m, more preferably from 0.05 to 5 ⁇ m, still more preferably from 0.1 to 3 ⁇ m, especially preferably from 0.1 to 1.5 ⁇ m.
- This average particle size can be determined as a volume-average particle size by using a laser beam diffraction method (for instance, a method using LA-920 manufactured by Horiba, LTD. as a measurement device).
- the content of the alkali metal and the alkaline earth metal is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, especially preferably 0.01% by weight or less, of the intermediate alumina particles.
- the fusion of the prepared intermediate alumina is small and the particle strength is small, so that there are no surface defects in the substrate to be polished, and thereby are especially effective for reducing the surface roughness.
- the aluminum hydroxide used as a raw material for this purpose has a specific surface area of preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more, especially preferably 50 m 2 /g or more.
- the aluminum hydroxide has a content of the alkali metal and the alkaline earth metal of preferably 0.1% by weight or less, more preferably 0.05% by weight or less, still more preferably 0.03% by weight or less, especially preferably 0.01% by weight or less.
- thermal dehydration treatment can be carried out by an ordinary process.
- These intermediate aluminas are adjusted to a given particle size by wet pulverization or dry pulverization by using a pulverizer such as a ball-mill, a beads-mill, a high-pressure homogenizer or a jet mill as occasion demands.
- a pulverizer such as a ball-mill, a beads-mill, a high-pressure homogenizer or a jet mill as occasion demands.
- the aluminum hydroxide is represented by the formula Al(OH)3, AlOOH, AlOOH.nH2O, or Al 2 O 3 .nH 2 O, wherein n is 1 to 3, and is not particularly limited, as long as the aluminum hydroxide can prepare an intermediate alumina by thermal dehydration. Concrete examples thereof include gibbsite, bayerite, nordstrandite, diaspore, boehmite, pseudo-boehmite, alumino-gel, and the like.
- the intermediate alumina has an accelerated effect of polishing and an effect of reducing the surface roughness, and also further improves the accelerated effect of polishing together with preventing surface defects such as pits, which are thought to be caused by a strong chemical action of the polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof, which is one component of the polishing composition of the present invention, to the polished surface, whereby the surface roughness can be reduced.
- the intermediate alumina particles used in the present invention are formulated as an additive in the polishing composition.
- the intermediate alumina particles together with the ⁇ -alumina particles used as the above-mentioned abrasive there are exhibited excellent effects such as the accelerated polishing and the reduction in the surface roughness.
- the content of the intermediate alumina in the polishing composition is from 1 to 90 parts by weight, preferably from 1 to 50 parts by weight, more preferably from 2 to 40 parts by weight, especially preferably from 4 to 30 parts by weight, based on 100 parts by weight of the abrasive, from the viewpoints of obtaining economic advantages, the accelerated effect of polishing, the effect of reducing the surface roughness, and the ability for preventing surface defects such as scratches and pits.
- the lower limit of the content of the intermediate alumina in the polishing composition is 1 part by weight or more, based on 100 parts by weight of the abrasive, from the viewpoints of the accelerated effect of polishing, the effect of reducing the surface roughness, and the ability for preventing surface defects such as scratches and pits, and its upper limit is 90 parts by weight or less, based on 100 parts by weight of the abrasive, from the viewpoint of the accelerated effect of polishing.
- polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof used in the present invention (hereinafter referred to as the “polycarboxylic acid having no OH groups”)
- those polycarboxylic acids having 4 to 20 carbon atoms are preferable, more preferably 4 to 10 carbon atoms, especially preferably 4 to 6 carbon atoms, from the viewpoint of increasing the polishing rate.
- the number of carboxyl groups is preferably from 2 to 10, more preferably from 2 to 6, especially preferably from 2 to 4, from the viewpoint of increasing the polishing rate.
- Concrete examples thereof include succinic acid, maleic acid, fumaric acid, glutaric acid, citraconic acid, itaconic acid, tricarballylic acid, adipic acid, and diglycolic acid; (meth)acrylic acid polymers; copolymers of (meth)acrylic acid with other monomers; and the like.
- succinic acid, maleic acid, fumaric acid, glutaric acid, citraconic acid, itaconic acid, tricarballylic acid, adipic acid, and diglycolic acid are preferable, and succinic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, tricarballylic acid, and diglycolic acid are especially preferable.
- the salt of these polycarboxylic acids having no OH groups is not particularly limited, as long as it is a salt capable of forming a salt with the polycarboxylic acid having no OH groups.
- the metals include metals belonging to the Groups 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A and 8 of the Periodic Table (long period form).
- those belonging to the Groups 1A, 3A, 3B, 7A and 8 are preferable, from the viewpoint of increasing the polishing rate, and sodium and potassium belonging to the Group 1A, cerium belonging to the Group 3A, aluminum belonging to the Group 3B, manganese belonging to the Group 7A, and iron and cobalt belonging to the Group 8 are especially preferable, and aluminum belonging to the Group 3B, and iron and cobalt belonging to the Group 8 are most preferable.
- a salt with a required metal may be previously formed, or a desired salt may be obtained by mixing an inorganic acid salt such as nitrate, sulfate or phosphate, or an organic acid salt such as acetate containing these metals with a polycarboxylic acid having no OH groups to carry out chelation exchange in the polishing composition.
- alkylammoniums include tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like.
- organic amines examples include dimethylamine, trimethylamine, alkanolamines, and the like.
- the salt of the polycarboxylic acid having no OH groups is ammonium salts, sodium salts, potassium salts and aluminum salts of the polycarboxylic acid having no OH groups, from the viewpoint of increasing the polishing rate.
- the ammonium salts of the polycarboxylic acid having no OH groups are most preferable.
- polycarboxylic acids having no OH groups or salts thereof may be used alone, or in admixture of two or more kinds.
- the content of the polycarboxylic acid having no OH groups or a salt thereof is preferably from 0.05 to 20% by weight, more preferably from 0.05 to 15% by weight, still more preferably from 0.1 to 15% by weight, especially preferably from 0.1 to 10% by weight, most preferably from 0.5 to 10% by weight, of the polishing composition, from the viewpoint of increasing the polishing rate.
- the content of the polycarboxylic acid having no OH groups or a salt thereof is preferably from 10 to 1000 parts by weight, more preferably 20 to 300 parts by weight, especially preferably from 30 to 100 parts by weight, based on 100 parts by weight of the intermediate alumna simultaneously formulated therewith, from the viewpoints of obtaining an effect of reducing the surface roughness and an ability of preventing surface defects such as pits.
- Water in the polishing composition of the present invention is used as a medium.
- the water content is from 40 to 98.94% by weight, preferably from 40 to 98% by weight, more preferably 50 to 97% by weight, especially preferably from 60 to 95% by weight or more, of the polishing composition, from the viewpoint that the substrate to be polished can be efficiently polished.
- the polishing composition of the present invention can be formulated with other optional components as occasion demands.
- Other components are metal salts and ammonium salts of monomeric acid compounds; peroxides; thickening agents; dispersants; anticorrosive agents; basic substances; surfactants; chelating compounds; and the like.
- Concrete examples of the metal salts and ammonium salts of monomeric acid compounds, peroxides, thickening agents, and dispersants include those listed in Japanese Patent Laid-Open No. Sho 62-25187, page 2, upper right column, line 3 to upper right column, line 11; Japanese Patent Laid-Open No. Hei 1-205973, page 3, upper left column, line 11 to upper right column, line 2; Japanese Patent Laid-Open No. Hei 4-275387, page 2, right column, line 27 to page 3, left column, line 12; Japanese Patent Laid-Open No. Hei 5-59351, page 2, right column, line 23 to page 3, left column, line 37.
- the chelating compound includes, for instance, hydroxycarboxylic acids, aminopolycarboxylic acids, amino acids and salts thereof.
- the chelating compound is a compound having a multidentate ligand, capable of forming a complex by binding with a metal ion.
- chelating compounds those having two or more carboxyl groups are preferable, from the viewpoint of increasing the polishing rate, and further aminopolycarboxylic acids are especially preferable.
- the number of carbon atoms of the hydroxycarboxylic acid is from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8, still more preferably from 2 to 6, from the viewpoint of the solubility in water.
- Concrete examples thereof include glycolic acid, lactic acid, citric acid, gluconic acid, glyoxylic acid, tartaric acid, malic acid, and the like
- the number of amino groups in one molecule is preferably from 1 to 6, more preferably from 1 to 4, from the viewpoint of increasing the polishing rate.
- the number of carboxylic acids is preferably from 1 to 12, more preferably from 2 to 8.
- the number of carbon atoms is preferably from 1 to 30, more preferably from 1 to 20. Concrete examples thereof include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetetraacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), dicarboxymethylglutamic acid (GLDA), and the like.
- the amino acid has the number of carbon atoms of preferably from 2 to 20, more preferably the number of carbon atoms of more preferably from 2 to 10, from the viewpoint of increasing the polishing rate.
- Concrete examples thereof include glycine, alanine and the like.
- malic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and glycine are preferable, and nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are more preferable, and ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are especially preferable.
- the salt of these chelating compounds are the same as the above-mentioned salt of the polycarboxylic acid having no OH groups.
- salts formed between the aminopolycarboxylic acid and sodium and potassium belonging to Group 1A, cerium belonging to Group 3A, aluminum belonging to Group 3B, manganese belonging to Group 7A, and iron and cobalt belonging to Group 8, and an ammonium salt of the aminopolycarboxylic acid are preferable, from the viewpoint of increasing the polishing rate.
- salts formed between the aminopolycarboxylic acid and aluminum belonging to Group 3B and iron and cobalt belonging to Group 8 are most preferable.
- these optional components can be used alone or in admixture of two or more kinds.
- the content of the optional components is preferably from 0.05 to 20% by weight, more preferably from 0.05 to 10% by weight, still more preferably from 0.05 to 5% by weight, of the polishing composition, from the viewpoint of increasing the polishing rate, from the viewpoint of exhibiting each of the functions, and from the viewpoint of economic advantages.
- the concentration of each component of the above-mentioned polishing composition is a preferable concentration during polishing, and the concentration may be the concentration during the preparation of the composition.
- the composition is usually prepared as a concentrate, which is diluted upon use.
- the pH of the polishing composition of the present invention is properly determined depending upon the kinds of the object to be polished, the required qualities and the like.
- the pH of the polishing composition of the present invention is preferably from 2 to 12, from the viewpoints of cleanability of the substrate to be polished and preventiveness of the corrosion of working machines.
- the pH of the polishing composition is preferably from 2 to 9, more preferably from 2 to 8, still more preferably from 3 to 8, especially preferably from 3 to 7, from the viewpoints of increasing the polishing rate and improving the surface qualities.
- the pH of the polishing composition is preferably from 7 to 12, more preferably from 8 to 12, especially preferably from 9 to 11, from the viewpoints of increasing the polishing rate and improving the surface qualities.
- the pH can be adjusted by properly adding an inorganic acid such as nitric acid or sulfuric acid, a metal salt or ammonium salt of a monomeric acid compound mentioned above, or a basic substance such as ammonia, an alkylamine, sodium hydroxide, or potassium hydroxide, in a desired amount as occasion demands.
- the polishing process of a substrate to be polished of the present invention comprises polishing a substrate to be polished by using the polishing composition of the present invention, or preparing a polishing liquid by mixing each component so as to give the composition of the polishing composition of the present invention, and especially the substrate for precision parts can be favorably produced.
- the material for the object to be polished includes, for instance, metals or metalloids such as silicon, aluminum, nickel, tungsten, copper tantalum, and titanium; alloys made of these metals as the main components; glassy substances such as glass, glassy carbon and amorphous carbons; ceramic materials such as alumina, titanium carbide, silicon dioxide, silicon nitride, tantalum nitride, and titanium nitride; resins such as polyimide resins; and the like.
- metals or metalloids such as silicon, aluminum, nickel, tungsten, copper tantalum, and titanium
- alloys made of these metals as the main components
- glassy substances such as glass, glassy carbon and amorphous carbons
- ceramic materials such as alumina, titanium carbide, silicon dioxide, silicon nitride, tantalum nitride, and titanium nitride
- resins such as polyimide resins; and the like.
- metals such as aluminum, nickel, tungsten and copper, and alloys made of these metals as the main components are the materials for the object to be polished, or semiconductor substrates such as semiconductor elements containing these metals are the materials for the object to be polished.
- the polishing composition of the present invention is used during the polishing of a substrate to be polished made of an Ni—P plated aluminum alloy, it is preferable, because the generation of surface defects such as scratches and pits is suppressed, so that the polishing can be carried out a fast rate with reducing the surface roughness as compared to that of the prior art.
- the shapes for the objects to be polished are not particularly limited. For instance, those having shapes containing planar portions such as those in the forms of disks, plates, slabs and prisms, or shapes containing curved portions such as lenses can be subjects for polishing with the polishing composition of the present invention. Among them, the disc-shaped objects to be polished are especially excellent in polishing.
- the polishing composition of the present invention can be favorably used especially in polishing the substrate for precision parts.
- the polishing composition is suitable for polishing substrates for magnetic recording media such as hard disks, optical disks, opto-magnetic disks, and the like; semiconductor substrates such as semiconductor wafers and semiconductor elements; photomask substrates; optical lenses, optical mirrors, half mirrors and optical prisms; and the like.
- the polishing composition is suitable for polishing the substrates for magnetic recording media and the semiconductor substrates, especially for polishing the hard disk substrates.
- the polishing of the semiconductor elements is carried out in, for instance, the step of polishing a silicon wafer (bare wafer), the step of flattening an interlayer insulating film, the step of forming an embedded metal line, the step of forming separation membrane for an embedded element, the step of forming an embedded capacitor, and the like.
- the polishing composition of the present invention especially has an effect in the polishing process, and the polishing composition can be similarly applied to the other polishing process, for instance, a lapping process or the like.
- An alumina vessel (200 mm in length ⁇ 100 mm in width ⁇ 100 mm in height) was charged with 200 g of pseudo-boehmite particles having an average particle size of 20 ⁇ m, a specific surface area of 250 m 2 /g, an alkali metal content of 0.005% by weight, and an alkaline earth metal content of 0.001% by weight.
- the pseudo-boehmite particles were baked in a muffle furnace at a baking rate of 50° C./minute, and a baking temperature of 600° C. for 4 hours with nitrogen gas stream at a flow rate of 5 L/minute, to give 140 g of an intermediate alumina.
- the intermediate alumina was transferred to a 2-L alumina ball-mill, and 327 g of ion-exchanged water was added thereto to prepare a 30% by weight slurry. Thereafter, 1000 g of alumina balls of 5 mm in diameters were introduced into the ball-mill to disrupt the slurry, and the disrupted slurry was then sieved to remove the alumina balls, to prepare 130 g of intermediate alumina particles.
- the prepared intermediate alumina particles were found to be ⁇ -alumina having an average particle size of 0.7 ⁇ m, a specific surface area of 130 m 2 /g, an alkali metal content of 0.0055% by weight, and an alkaline earth metal content of 0.0013% by weight.
- the average particle size of the intermediate alumina particles described in Preparation Example 1 mentioned above was determined as a volume-average particle size which was found on the basis of laser beam diffraction method using an analyzer LA-920 manufactured by Horiba LTD.
- the specific surface area was determined on the basis of BET method.
- the contents of an alkali metal and an alkaline earth metal in the intermediate alumina particles were determined on the basis of atomic absorption analysis and ICP emission analysis.
- An abrasive ( ⁇ -alumina having a primary average particle size of 0.25 ⁇ m, and a secondary average particle size of 0.7 ⁇ m (purity: about 99.9%), specific gravity: 4.0), an intermediate alumina, a salt of a polycarboxylic acid having 4 or more carbon atoms and having no OH groups, a pH adjusting agent (an aqueous ammonia or methanesulfonic acid), and ion-exchanged water were mixed and stirred, to prepare a polishing composition having the composition as shown in Table 1.
- a substrate surface made of an Ni—P plated aluminum alloy, the substrate surface having an average surface roughness Ra of 0.1 ⁇ m, as determined by the following method a thickness of 0.8 mm and a diameter of 3.5 inches was polished with a double-sided processing machine under the set conditions for double-sided processing machine given below, to give a polished object, which is an Ni—P plated, aluminum alloy substrate usable as a substrate for magnetic recording media.
- Double-sided processing machine used double-sided processing machine, Model 9B, manufactured by SPEEDFAM CO., LTD.
- Polishing Pad POLYTEX DG (manufactured by Rodel Nitta K.K.).
- Feeding flow rate for a polishing composition 100 mL/min
- Polishing time period 5 minutes
- the average surface roughness was determined under the following conditions by using Talystep commercially available from Rank Taylor-Hobson Limited.
- Each of the substrate surfaces was observed with an optical microscope (differential interference microscope) with a magnification of 50 times at 6 locations at 60-degree intervals.
- the depth of the scratches was determined by Zygo (commercially available from Zygo). The evaluation criteria are as follows.
- B Scratches with a depth exceeding 50 nm are 0.5 or more and less than 1/field on average.
- C Scratches with a depth exceeding 50 nm is 1 or more/field on average.
- Each of the substrate surface was observed with an optical microscope (differential interference microscope) at a magnification of 200 times at an interval of 30( for 12 locations, and the number of pits for the 12 fields was counted.
- optical microscope differential interference microscope
- any of the polishing compositions obtained in Examples 1 to 3 has a higher polishing rate, and provides a substrate to be polished with a reduced surface roughness and with reduced surface defects such as scratches and pits, as compared to each of the polishing compositions obtained in Comparative Examples 1 to 5.
- each of the polishing compositions (Examples 1 to 3) in which the content of the intermediate alumina in the polishing composition is from 1 to 90 parts by weight, based on 100 parts by weight of the abrasive has a higher polishing rate, and provides a substrate to be polished with a reduced surface roughness, as compared to the polishing composition (Comparative Example 4) in which the content of the intermediate alumina exceeds 90 parts by weight.
- the polishing rate can be improved and the surface roughness can be reduced, without causing surface defects on the surface of an object to be polished. Therefore, a substrate for precision parts or the like can be produced.
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Abstract
To provide a polishing composition capable of increasing polishing rate and reducing surface roughness, without causing surface defects on a surface of an object to be polished; and a polishing process for a substrate to be polished. [1] a polishing composition comprising water, an abrasive, an intermediate alumina, and a polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof, wherein a content of the intermediate alumina is from 1 to 90 parts by weight, based on 100 parts by weight of the abrasive; and [2] a polishing process for a substrate to be polished, comprising polishing a substrate to be polished under conditions that a composition of a polishing liquid during polishing is the composition as defined in item [1] above.
Description
- The present invention relates to a polishing composition and a polishing process of a substrate to be polished.
- With advancement of densification of hard disks, the floating amount of the magnetic head has become increasingly smaller. As a result, in the polishing step in hard disk substrates, there have been desired increase in the polishing rate and reduction in the surface roughness. Therefore, a polishing composition using water, alumina, boehmite, and a chelating compound, and a polishing process have been studied (Japanese Patent Laid-Open No. Hei 11-92749). However, this polishing composition has some but insufficient effects for increasing the polishing rate and for reducing surface defects such as scratches and pits. Also, its effects cannot also be said to be satisfactory for reduction in the surface roughness and for the planarization.
- Also, even in the field of semiconductors, the finely sizing of a design room for a semiconductor device has been progressed with the advancements in high integration and high speeds, so that a focal depth becomes shallow during the process for manufacturing the device, whereby further demanding planarization of the pattern-forming surface.
- An object of the present invention is to provide a polishing composition capable of increasing the polishing rate and reducing the surface roughness, without causing surface defects on a surface of an object to be polished; and a polishing process for a substrate to be polished.
- Specifically, the present invention relates to:
- [1] a polishing composition comprising water, an abrasive, an intermediate alumina, and a polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof, wherein a content of the intermediate alumina is from 1 to 90 parts by weight, based on 100 parts by weight of the abrasive; and
- [2] a polishing process for a substrate to be polished, comprising polishing a substrate to be polished under conditions that a composition of a polishing liquid during polishing is the composition as defined in item [1] above.
- As the abrasive used in the present invention, any abrasives generally employed for polishing can be used. Examples of the abrasive include metals; carbides, nitrides, oxides, or borides of metals or metalloids; diamond, and the like. The metal elements or metalloid elements include those elements belonging to the Groups 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A or 8 of the Periodic Table (long period form). Concrete examples of the abrasive include α-alumina particles, silicon carbide particles, diamond particles, magnesium oxide particles, zinc oxide particles, cerium oxide particles, zirconium oxide particles, colloidal silica particles, fumed silica particles, and the like. It is preferable to use one or more kinds of these abrasives, from the viewpoint of increasing the polishing rate. Among them, α-alumina particles, cerium oxide particles, zirconium oxide particles, colloidal silica particles, and fumed silica particles are suitable for polishing semiconductor wafers and semiconductor elements and substrates for precision parts such as substrates for magnetic recording media. Especially, the α-alumina particles are suitable for polishing a substrate for magnetic recording medium.
- The average particle size of the primary particles of the abrasive is preferably from 0.01 to 3 μm, more preferably from 0.02 to 0.8 μm, especially preferably from 0.05 to 0.5 μm, from the viewpoint of increasing the polishing rate. Further, in the case where the primary particles are aggregated to form secondary particles, the average particle size of the secondary particles thereof is preferably from 0.05 to 2 μm, more preferably from 0.1 to 1.5 μm, especially preferably from 0.2 to 1.2 μm, similarly from the viewpoint of increasing the polishing rate and from the viewpoint of reducing the surface roughness of the object to be polished. The average particle size of the primary particles of the abrasive can be determined by carrying out image analysis by observation with a scanning electron microscope (magnification: preferably from 3000 to 30000 times) to determine an average particle size. In addition, the average particle size of the secondary particles can be determined as a volume-average particle size by using a laser beam diffraction method.
- The specific gravity of the abrasive is preferably from 2 to 6, more preferably from 2 to 5, from the viewpoints of dispersibility, feeding ability and collecting and reusability for a polishing device.
- The content of the abrasive is preferably from 1 to 40% by weight, more preferably from 2 to 30% by weight, more preferably from 3 to 15% by weight, of the polishing composition, from the viewpoints of economic advantages and reduction in the surface roughness, thereby making it possible to efficiently polish the object.
- The term “intermediate alumina particles” as referred to in the present invention is a generic term referring to alumina particles other than the α-alumina particles. Concrete examples thereof include γ-alumina particles, δ-alumina particles, θ-alumina particles, η-alumina particles, κ-alumina particles, mixtures thereof, and the like. Among them, the following intermediate aluminas are preferable, from the viewpoints of the effects of increasing the polishing rate and reducing the surface roughness. Their crystal forms are preferably γ-alumina, δ-alumina, θ-alumina, mixtures thereof, and the like, more preferably γ-alumina, δ-alumina, mixtures thereof, especially preferably γ-alumina. In addition, their specific surface area (as determined by BET method) is preferably from 30 to 300 m 2/g, more preferably from 50 to 200 m2/g. Their average particle size is preferably from 0.01 to 5 μm, more preferably from 0.05 to 5 μm, still more preferably from 0.1 to 3 μm, especially preferably from 0.1 to 1.5 μm. This average particle size can be determined as a volume-average particle size by using a laser beam diffraction method (for instance, a method using LA-920 manufactured by Horiba, LTD. as a measurement device). In addition, the content of the alkali metal and the alkaline earth metal is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, especially preferably 0.01% by weight or less, of the intermediate alumina particles.
- For instance, in a case where aluminum hydroxide, which has a relatively large specific surface area and a low content of the alkali metal and the alkaline earth metal, is used as a raw material, the fusion of the prepared intermediate alumina is small and the particle strength is small, so that there are no surface defects in the substrate to be polished, and thereby are especially effective for reducing the surface roughness.
- The aluminum hydroxide used as a raw material for this purpose has a specific surface area of preferably 10 m 2/g or more, more preferably 30 m2/g or more, especially preferably 50 m2/g or more. In addition, the aluminum hydroxide has a content of the alkali metal and the alkaline earth metal of preferably 0.1% by weight or less, more preferably 0.05% by weight or less, still more preferably 0.03% by weight or less, especially preferably 0.01% by weight or less. Furthermore, in the case where an intermediate alumina is prepared by subjecting aluminum hydroxide to thermal dehydration, forcible introduction of dry air or nitrogen gas during calcination is further effective in the reduction of the surface defects and the surface roughness of the substrate to be polished. Here, the above-mentioned thermal dehydration treatment can be carried out by an ordinary process.
- These intermediate aluminas are adjusted to a given particle size by wet pulverization or dry pulverization by using a pulverizer such as a ball-mill, a beads-mill, a high-pressure homogenizer or a jet mill as occasion demands.
- The aluminum hydroxide is represented by the formula Al(OH)3, AlOOH, AlOOH.nH2O, or Al 2O3.nH2O, wherein n is 1 to 3, and is not particularly limited, as long as the aluminum hydroxide can prepare an intermediate alumina by thermal dehydration. Concrete examples thereof include gibbsite, bayerite, nordstrandite, diaspore, boehmite, pseudo-boehmite, alumino-gel, and the like.
- Although the details of the function mechanism during the polishing of this intermediate alumina are unknown, the intermediate alumina has an accelerated effect of polishing and an effect of reducing the surface roughness, and also further improves the accelerated effect of polishing together with preventing surface defects such as pits, which are thought to be caused by a strong chemical action of the polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof, which is one component of the polishing composition of the present invention, to the polished surface, whereby the surface roughness can be reduced.
- Especially, the intermediate alumina particles used in the present invention are formulated as an additive in the polishing composition. By using the intermediate alumina particles together with the α-alumina particles used as the above-mentioned abrasive, there are exhibited excellent effects such as the accelerated polishing and the reduction in the surface roughness.
- The content of the intermediate alumina in the polishing composition is from 1 to 90 parts by weight, preferably from 1 to 50 parts by weight, more preferably from 2 to 40 parts by weight, especially preferably from 4 to 30 parts by weight, based on 100 parts by weight of the abrasive, from the viewpoints of obtaining economic advantages, the accelerated effect of polishing, the effect of reducing the surface roughness, and the ability for preventing surface defects such as scratches and pits.
- The lower limit of the content of the intermediate alumina in the polishing composition is 1 part by weight or more, based on 100 parts by weight of the abrasive, from the viewpoints of the accelerated effect of polishing, the effect of reducing the surface roughness, and the ability for preventing surface defects such as scratches and pits, and its upper limit is 90 parts by weight or less, based on 100 parts by weight of the abrasive, from the viewpoint of the accelerated effect of polishing.
- As the polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof used in the present invention (hereinafter referred to as the “polycarboxylic acid having no OH groups”), those polycarboxylic acids having 4 to 20 carbon atoms are preferable, more preferably 4 to 10 carbon atoms, especially preferably 4 to 6 carbon atoms, from the viewpoint of increasing the polishing rate. Also, the number of carboxyl groups is preferably from 2 to 10, more preferably from 2 to 6, especially preferably from 2 to 4, from the viewpoint of increasing the polishing rate. Concrete examples thereof include succinic acid, maleic acid, fumaric acid, glutaric acid, citraconic acid, itaconic acid, tricarballylic acid, adipic acid, and diglycolic acid; (meth)acrylic acid polymers; copolymers of (meth)acrylic acid with other monomers; and the like.
- Among them, succinic acid, maleic acid, fumaric acid, glutaric acid, citraconic acid, itaconic acid, tricarballylic acid, adipic acid, and diglycolic acid are preferable, and succinic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, tricarballylic acid, and diglycolic acid are especially preferable.
- The salt of these polycarboxylic acids having no OH groups is not particularly limited, as long as it is a salt capable of forming a salt with the polycarboxylic acid having no OH groups. Concretely, there are included salts with metals, ammonium, alkylammoniums, organic amines, and the like. Concrete examples of the metals include metals belonging to the Groups 1A, 1B, 2A, 2B, 3A, 3B, 4A, 6A, 7A and 8 of the Periodic Table (long period form). Among these metals, those belonging to the Groups 1A, 3A, 3B, 7A and 8 are preferable, from the viewpoint of increasing the polishing rate, and sodium and potassium belonging to the Group 1A, cerium belonging to the Group 3A, aluminum belonging to the Group 3B, manganese belonging to the Group 7A, and iron and cobalt belonging to the Group 8 are especially preferable, and aluminum belonging to the Group 3B, and iron and cobalt belonging to the Group 8 are most preferable. As to the salt of these polycarboxylic acids having no OH groups, a salt with a required metal may be previously formed, or a desired salt may be obtained by mixing an inorganic acid salt such as nitrate, sulfate or phosphate, or an organic acid salt such as acetate containing these metals with a polycarboxylic acid having no OH groups to carry out chelation exchange in the polishing composition.
- Concrete examples of the alkylammoniums include tetramethylammonium, tetraethylammonium, tetrabutylammonium, and the like.
- Concrete examples of the organic amines include dimethylamine, trimethylamine, alkanolamines, and the like.
- It is preferable that the salt of the polycarboxylic acid having no OH groups is ammonium salts, sodium salts, potassium salts and aluminum salts of the polycarboxylic acid having no OH groups, from the viewpoint of increasing the polishing rate. Among them, the ammonium salts of the polycarboxylic acid having no OH groups are most preferable.
- These polycarboxylic acids having no OH groups or salts thereof may be used alone, or in admixture of two or more kinds.
- The content of the polycarboxylic acid having no OH groups or a salt thereof is preferably from 0.05 to 20% by weight, more preferably from 0.05 to 15% by weight, still more preferably from 0.1 to 15% by weight, especially preferably from 0.1 to 10% by weight, most preferably from 0.5 to 10% by weight, of the polishing composition, from the viewpoint of increasing the polishing rate. Also, the content of the polycarboxylic acid having no OH groups or a salt thereof is preferably from 10 to 1000 parts by weight, more preferably 20 to 300 parts by weight, especially preferably from 30 to 100 parts by weight, based on 100 parts by weight of the intermediate alumna simultaneously formulated therewith, from the viewpoints of obtaining an effect of reducing the surface roughness and an ability of preventing surface defects such as pits.
- Water in the polishing composition of the present invention is used as a medium. The water content is from 40 to 98.94% by weight, preferably from 40 to 98% by weight, more preferably 50 to 97% by weight, especially preferably from 60 to 95% by weight or more, of the polishing composition, from the viewpoint that the substrate to be polished can be efficiently polished.
- In addition, the polishing composition of the present invention can be formulated with other optional components as occasion demands. Other components are metal salts and ammonium salts of monomeric acid compounds; peroxides; thickening agents; dispersants; anticorrosive agents; basic substances; surfactants; chelating compounds; and the like. Concrete examples of the metal salts and ammonium salts of monomeric acid compounds, peroxides, thickening agents, and dispersants include those listed in Japanese Patent Laid-Open No. Sho 62-25187, page 2, upper right column, line 3 to upper right column, line 11; Japanese Patent Laid-Open No. Hei 1-205973, page 3, upper left column, line 11 to upper right column, line 2; Japanese Patent Laid-Open No. Hei 4-275387, page 2, right column, line 27 to page 3, left column, line 12; Japanese Patent Laid-Open No. Hei 5-59351, page 2, right column, line 23 to page 3, left column, line 37.
- The chelating compound includes, for instance, hydroxycarboxylic acids, aminopolycarboxylic acids, amino acids and salts thereof. Here, the chelating compound is a compound having a multidentate ligand, capable of forming a complex by binding with a metal ion.
- Among these chelating compounds, those having two or more carboxyl groups are preferable, from the viewpoint of increasing the polishing rate, and further aminopolycarboxylic acids are especially preferable.
- It is desired that the number of carbon atoms of the hydroxycarboxylic acid is from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8, still more preferably from 2 to 6, from the viewpoint of the solubility in water. Concrete examples thereof include glycolic acid, lactic acid, citric acid, gluconic acid, glyoxylic acid, tartaric acid, malic acid, and the like
- Regarding the aminopolycarboxylic acids, the number of amino groups in one molecule is preferably from 1 to 6, more preferably from 1 to 4, from the viewpoint of increasing the polishing rate. Also, the number of carboxylic acids is preferably from 1 to 12, more preferably from 2 to 8. In addition, the number of carbon atoms is preferably from 1 to 30, more preferably from 1 to 20. Concrete examples thereof include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetetraacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), dicarboxymethylglutamic acid (GLDA), and the like.
- The amino acid has the number of carbon atoms of preferably from 2 to 20, more preferably the number of carbon atoms of more preferably from 2 to 10, from the viewpoint of increasing the polishing rate. Concrete examples thereof include glycine, alanine and the like.
- Among them, malic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and glycine are preferable, and nitrilotriacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are more preferable, and ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are especially preferable.
- In addition, the salt of these chelating compounds are the same as the above-mentioned salt of the polycarboxylic acid having no OH groups. Among them, salts formed between the aminopolycarboxylic acid and sodium and potassium belonging to Group 1A, cerium belonging to Group 3A, aluminum belonging to Group 3B, manganese belonging to Group 7A, and iron and cobalt belonging to Group 8, and an ammonium salt of the aminopolycarboxylic acid are preferable, from the viewpoint of increasing the polishing rate. Among them, salts formed between the aminopolycarboxylic acid and aluminum belonging to Group 3B and iron and cobalt belonging to Group 8 are most preferable.
- These optional components can be used alone or in admixture of two or more kinds. In addition, the content of the optional components is preferably from 0.05 to 20% by weight, more preferably from 0.05 to 10% by weight, still more preferably from 0.05 to 5% by weight, of the polishing composition, from the viewpoint of increasing the polishing rate, from the viewpoint of exhibiting each of the functions, and from the viewpoint of economic advantages.
- The concentration of each component of the above-mentioned polishing composition is a preferable concentration during polishing, and the concentration may be the concentration during the preparation of the composition. Usually, the composition is usually prepared as a concentrate, which is diluted upon use.
- It is preferable that the pH of the polishing composition of the present invention is properly determined depending upon the kinds of the object to be polished, the required qualities and the like. For instance, the pH of the polishing composition of the present invention is preferably from 2 to 12, from the viewpoints of cleanability of the substrate to be polished and preventiveness of the corrosion of working machines. In addition, in the case where the object to be polished is a substrate for precision parts mainly made of a metal, such as an aluminum substrate produced by Ni—P plating, the pH of the polishing composition is preferably from 2 to 9, more preferably from 2 to 8, still more preferably from 3 to 8, especially preferably from 3 to 7, from the viewpoints of increasing the polishing rate and improving the surface qualities. Further, in a case where the polishing composition of the present invention is used for polishing semiconductor wafers and semiconductor elements, especially for polishing silicon wafers, poly-silicon layers, and SiO 2 layers, the pH of the polishing composition is preferably from 7 to 12, more preferably from 8 to 12, especially preferably from 9 to 11, from the viewpoints of increasing the polishing rate and improving the surface qualities. The pH can be adjusted by properly adding an inorganic acid such as nitric acid or sulfuric acid, a metal salt or ammonium salt of a monomeric acid compound mentioned above, or a basic substance such as ammonia, an alkylamine, sodium hydroxide, or potassium hydroxide, in a desired amount as occasion demands.
- The polishing process of a substrate to be polished of the present invention comprises polishing a substrate to be polished by using the polishing composition of the present invention, or preparing a polishing liquid by mixing each component so as to give the composition of the polishing composition of the present invention, and especially the substrate for precision parts can be favorably produced.
- The material for the object to be polished includes, for instance, metals or metalloids such as silicon, aluminum, nickel, tungsten, copper tantalum, and titanium; alloys made of these metals as the main components; glassy substances such as glass, glassy carbon and amorphous carbons; ceramic materials such as alumina, titanium carbide, silicon dioxide, silicon nitride, tantalum nitride, and titanium nitride; resins such as polyimide resins; and the like. Among them, it is preferable that metals such as aluminum, nickel, tungsten and copper, and alloys made of these metals as the main components are the materials for the object to be polished, or semiconductor substrates such as semiconductor elements containing these metals are the materials for the object to be polished. Especially when the polishing composition of the present invention is used during the polishing of a substrate to be polished made of an Ni—P plated aluminum alloy, it is preferable, because the generation of surface defects such as scratches and pits is suppressed, so that the polishing can be carried out a fast rate with reducing the surface roughness as compared to that of the prior art.
- The shapes for the objects to be polished are not particularly limited. For instance, those having shapes containing planar portions such as those in the forms of disks, plates, slabs and prisms, or shapes containing curved portions such as lenses can be subjects for polishing with the polishing composition of the present invention. Among them, the disc-shaped objects to be polished are especially excellent in polishing.
- The polishing composition of the present invention can be favorably used especially in polishing the substrate for precision parts. For instance, the polishing composition is suitable for polishing substrates for magnetic recording media such as hard disks, optical disks, opto-magnetic disks, and the like; semiconductor substrates such as semiconductor wafers and semiconductor elements; photomask substrates; optical lenses, optical mirrors, half mirrors and optical prisms; and the like. Among them, the polishing composition is suitable for polishing the substrates for magnetic recording media and the semiconductor substrates, especially for polishing the hard disk substrates. The polishing of the semiconductor elements is carried out in, for instance, the step of polishing a silicon wafer (bare wafer), the step of flattening an interlayer insulating film, the step of forming an embedded metal line, the step of forming separation membrane for an embedded element, the step of forming an embedded capacitor, and the like.
- By polishing the substrate to be polished in the manner described above, a substrate for precision parts or the like can be produced.
- The polishing composition of the present invention especially has an effect in the polishing process, and the polishing composition can be similarly applied to the other polishing process, for instance, a lapping process or the like.
- The present invention will be described in detail hereinbelow by means of Examples, without intending to limit the scope of the present invention thereto.
- An alumina vessel (200 mm in length×100 mm in width×100 mm in height) was charged with 200 g of pseudo-boehmite particles having an average particle size of 20 μm, a specific surface area of 250 m 2/g, an alkali metal content of 0.005% by weight, and an alkaline earth metal content of 0.001% by weight. The pseudo-boehmite particles were baked in a muffle furnace at a baking rate of 50° C./minute, and a baking temperature of 600° C. for 4 hours with nitrogen gas stream at a flow rate of 5 L/minute, to give 140 g of an intermediate alumina. The intermediate alumina was transferred to a 2-L alumina ball-mill, and 327 g of ion-exchanged water was added thereto to prepare a 30% by weight slurry. Thereafter, 1000 g of alumina balls of 5 mm in diameters were introduced into the ball-mill to disrupt the slurry, and the disrupted slurry was then sieved to remove the alumina balls, to prepare 130 g of intermediate alumina particles. The prepared intermediate alumina particles were found to be γ-alumina having an average particle size of 0.7 μm, a specific surface area of 130 m2/g, an alkali metal content of 0.0055% by weight, and an alkaline earth metal content of 0.0013% by weight.
- Here, the average particle size of the intermediate alumina particles described in Preparation Example 1 mentioned above was determined as a volume-average particle size which was found on the basis of laser beam diffraction method using an analyzer LA-920 manufactured by Horiba LTD. The specific surface area was determined on the basis of BET method. The contents of an alkali metal and an alkaline earth metal in the intermediate alumina particles were determined on the basis of atomic absorption analysis and ICP emission analysis.
- An abrasive (α-alumina having a primary average particle size of 0.25 μm, and a secondary average particle size of 0.7 μm (purity: about 99.9%), specific gravity: 4.0), an intermediate alumina, a salt of a polycarboxylic acid having 4 or more carbon atoms and having no OH groups, a pH adjusting agent (an aqueous ammonia or methanesulfonic acid), and ion-exchanged water were mixed and stirred, to prepare a polishing composition having the composition as shown in Table 1.
TABLE 1 Polycarboxylic Acid Having 4 or More Carbon Atoms and Having No OH Groups Ion-Exchanged α-Alumina Intermediate Alumina or Chelating Compound Water and Content Content Content pH Adjusting (parts by (parts by (parts by Agent weight) weight) weight) (parts by weight) pH Ex. 1 8 Prep. Ex. 1 1.5 Maleic Acid 1 89.5 6.5 Ex. 2 8 Prep. Ex. 1 1.5 Itaconic Acid 1 89.5 6.5 Ex. 3 8 Prep. Ex. 1 6 Maleic Acid 1 85 6.5 Comp. 8 None — None — 92 7.0 Ex. 1 Comp. 8 Prep. Ex. 1 1 None — 91 4.5 Ex. 2 Comp. 8 None — Maleic Acid 1 91 6.5 Ex. 3 Comp. 8 Prep. Ex. 1 10 Maleic Acid 1 81 6.5 Ex. 4 Comp. 8 Boehmite* 1.5 Maleic Acid 1 89.5 6.5 Ex. 5 - Using each of the resulting polishing compositions, a substrate surface made of an Ni—P plated aluminum alloy, the substrate surface having an average surface roughness Ra of 0.1 μm, as determined by the following method, a thickness of 0.8 mm and a diameter of 3.5 inches was polished with a double-sided processing machine under the set conditions for double-sided processing machine given below, to give a polished object, which is an Ni—P plated, aluminum alloy substrate usable as a substrate for magnetic recording media.
- The set conditions for double-sided processing machine are shown below.
- Double-sided processing machine used: double-sided processing machine, Model 9B, manufactured by SPEEDFAM CO., LTD.
- Processing pressure: 9.8 kPa
- Polishing Pad: POLYTEX DG (manufactured by Rodel Nitta K.K.).
- Disc rotational speed: 50 r/min
- Feeding flow rate for a polishing composition: 100 mL/min
- Polishing time period: 5 minutes
- Number of substrate introduced: 10
- After polishing, the thickness of an aluminum alloy substrate was determined, and a rate of decrease in the thickness was determined from the changes in the thickness of the aluminum alloy substrate before and after polishing. A relative value (relative rate) was determined on the basis of that of Comparative Example 1. The results are shown in Table 2.
- In addition, average surface roughness Ra and scratches of each of the substrate surfaces after polishing were determined in the same manner as above, and pits were determined in accordance with the following methods. Incidentally, in Examples 1 to 3 and Comparative Examples 2 to 5, the relative value (relative roughness) was determined on the basis of that of Comparative Example 1. The results are shown in Table 2.
- The average surface roughness was determined under the following conditions by using Talystep commercially available from Rank Taylor-Hobson Limited.
- Size of tip end of profilometer: 25 μm×25 μm
- By-pass filter: 80 μm
- Measurement length: 0.64 mm
- Each of the substrate surfaces was observed with an optical microscope (differential interference microscope) with a magnification of 50 times at 6 locations at 60-degree intervals. The depth of the scratches was determined by Zygo (commercially available from Zygo). The evaluation criteria are as follows.
- S: Scratches with a depth exceeding 50 nm are zero (0)/field.
- A: Scratches with a depth exceeding 50 nm are less than 0.5/field on average.
- B: Scratches with a depth exceeding 50 nm are 0.5 or more and less than 1/field on average.
- C: Scratches with a depth exceeding 50 nm is 1 or more/field on average.
- Each of the substrate surface was observed with an optical microscope (differential interference microscope) at a magnification of 200 times at an interval of 30( for 12 locations, and the number of pits for the 12 fields was counted. The evaluation criteria are as follows.
- S: 0
- A: 1 to3
- B: 4to 10
- C: 10 or more
TABLE 2 Evaluation of Properties Surface Surface Relative Relative Defects Defects Rate Roughness (Scratches) (Pits) Ex. 1 2.8 0.73 S S Ex. 2 2.8 0.67 S S Ex. 3 2.2 0.61 S S Comp. 1 1 C B Ex. 1 Comp. 1.3 0.96 B S Ex. 2 Comp. 2.0 2.2 C B Ex. 3 Comp. 1.4 1.0 A S Ex. 4 Comp. 1.5 1.7 A B Ex. 5 - It is seen from the results in Table 2 that any of the polishing compositions obtained in Examples 1 to 3 has a higher polishing rate, and provides a substrate to be polished with a reduced surface roughness and with reduced surface defects such as scratches and pits, as compared to each of the polishing compositions obtained in Comparative Examples 1 to 5.
- Also, it is seen from the results of Examples 1 to 3 and Comparative Example 4 that each of the polishing compositions (Examples 1 to 3) in which the content of the intermediate alumina in the polishing composition is from 1 to 90 parts by weight, based on 100 parts by weight of the abrasive has a higher polishing rate, and provides a substrate to be polished with a reduced surface roughness, as compared to the polishing composition (Comparative Example 4) in which the content of the intermediate alumina exceeds 90 parts by weight.
- By using the polishing composition of the present invention, the polishing rate can be improved and the surface roughness can be reduced, without causing surface defects on the surface of an object to be polished. Therefore, a substrate for precision parts or the like can be produced.
Claims (5)
1. A polishing composition comprising water, an abrasive, an intermediate alumina, and a polycarboxylic acid having 4 or more carbon atoms with no OH groups or a salt thereof, wherein a content of the intermediate alumina is from 1 to 90 parts by weight, based on 100 parts by weight of the abrasive.
2. The polishing composition according to claim 1 , wherein the intermediate alumina has a specific surface area of from 30 to 300 m2/g and an average particle size of from 0.01 to 5 μm.
3. The polishing composition according to claim 1 or 2, wherein the intermediate alumina is prepared from aluminum hydroxide having a specific surface area of 10 m /g or more and a content of an alkali metal and an alkaline earth metal of 0.1% by weight or less.
4. The polishing composition according to any one of claims 1 to 3 , wherein a content of the polycarboxylic acid having 4 or more carbon atoms with no OH groups is from 0.05 to 20% by weight of the polishing composition.
5. A polishing process for a substrate to be polished, comprising polishing a substrate to be polished under conditions that a composition of a polishing liquid during polishing is the composition as defined in any one of claims 1 to 4 .
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| PCT/JP2001/004728 WO2002006418A1 (en) | 2000-07-19 | 2001-06-05 | Polishing fluid composition |
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| CN110039381B (en) * | 2019-04-23 | 2020-04-07 | 新昌浙江工业大学科学技术研究院 | Ultra-precision polishing method for cylindrical roller |
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| US20040123527A1 (en) * | 2002-12-26 | 2004-07-01 | Hiroaki Kitayama | Polishing composition |
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| US10570314B2 (en) | 2016-09-13 | 2020-02-25 | AGC Inc. | Polishing agent, polishing method, and liquid additive for polishing |
| US11335367B2 (en) * | 2018-03-23 | 2022-05-17 | Furukawa Electric Co., Ltd. | Aluminum alloy substrate for magnetic disk, disk drive device, method for manufacturing aluminum alloy substrate for magnetic disk, and method for measuring aluminum alloy substrate for magnetic disk |
| CN115247026A (en) * | 2021-04-26 | 2022-10-28 | 福建晶安光电有限公司 | Sapphire polishing solution and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US7955517B2 (en) | 2011-06-07 |
| CN1443231A (en) | 2003-09-17 |
| US20090197415A1 (en) | 2009-08-06 |
| CN1197930C (en) | 2005-04-20 |
| WO2002006418A1 (en) | 2002-01-24 |
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Legal Events
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| AS | Assignment |
Owner name: KAO CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUJII, SHIGEO;OSHIMA, YOSHIAKI;NAITO, KOICHI;REEL/FRAME:014306/0500;SIGNING DATES FROM 20021217 TO 20021218 Owner name: KAO CORPORATION, JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FUJII, SHIGEO;OSHIMA, YOSHIAKI;NAITO, KOICHI;REEL/FRAME:014330/0389;SIGNING DATES FROM 20021217 TO 20021218 |
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