WO2019124442A1 - レーザーマーク周辺の隆起を解消するための研磨用組成物 - Google Patents
レーザーマーク周辺の隆起を解消するための研磨用組成物 Download PDFInfo
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- WO2019124442A1 WO2019124442A1 PCT/JP2018/046797 JP2018046797W WO2019124442A1 WO 2019124442 A1 WO2019124442 A1 WO 2019124442A1 JP 2018046797 W JP2018046797 W JP 2018046797W WO 2019124442 A1 WO2019124442 A1 WO 2019124442A1
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- Prior art keywords
- polishing
- group
- acid
- wafer
- laser mark
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002738 chelating agent Substances 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007517 polishing process Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 25
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 239000000908 ammonium hydroxide Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
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- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
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- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 claims description 4
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- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical group OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 3
- DIWZKTYQKVKILN-VKHMYHEASA-N (2s)-2-(dicarboxymethylamino)pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)NC(C(O)=O)C(O)=O DIWZKTYQKVKILN-VKHMYHEASA-N 0.000 claims description 3
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- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 3
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims description 3
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- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
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- GOGOEWCHHXLXRR-UHFFFAOYSA-N acetic acid propane Chemical compound CCC.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O GOGOEWCHHXLXRR-UHFFFAOYSA-N 0.000 claims 1
- -1 hydroxyethyl group Chemical group 0.000 abstract description 20
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
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Classifications
-
- 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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
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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
- 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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
- H01L21/67294—Apparatus for monitoring, sorting or marking using identification means, e.g. labels on substrates or labels on containers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
Definitions
- the present invention relates to a polishing composition used for polishing the surface of a wafer, and in particular, for polishing to obtain a flat polishing surface without height difference of the wafer peripheral portion (for example, also referred to as laser mark portion) in the polishing process of the wafer. It relates to a composition.
- a silicon wafer used for semiconductor products is mirror finished through a lapping process (rough polishing process) and a polishing process (precision polishing process).
- the polishing process includes a preliminary polishing process (pre-polishing process) and a finish polishing process (finish polishing process).
- a mark such as a bar code, a numeral, or a symbol may be attached to the silicon wafer by irradiating the surface of the silicon wafer with laser light for the purpose of identification and the like.
- the application of the laser marks is generally performed after finishing the lapping process of the silicon substrate and before starting the polishing process.
- irradiation of a laser beam for attaching a laser mark produces a bump on the silicon wafer surface around the laser mark.
- the yield may be lowered more than necessary if the above-mentioned ridges are not properly eliminated in the polishing step after the laser mark application.
- To eliminate the ridges of the laser marks is to reduce the height from the reference plane (horizontal surface) around the laser marks on the wafer to the highest point of the ridges.
- An object of the present invention is to provide a polishing composition which provides a flat polishing surface for the purpose of eliminating the bumps on the periphery of a laser mark in a wafer polishing process, and a wafer polishing method using the same.
- a polishing composition for eliminating the bumps on the periphery of a laser mark on a wafer having a laser mark, wherein the polishing composition comprises a water soluble compound, a chelating agent and metal oxidation.
- Water soluble compound having a hydrophobic portion and a hydrophilic portion, the hydrophilic portion having a hydroxyl group at its terminal or side chain The above polishing composition having an alkyl group, an acyloxy group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, or a sulfonic acid group, and the water-soluble compound having a content of 5 to 700 ppm in the polishing composition object,
- the polishing composition according to the first aspect wherein the metal oxide particles are silica particles, zirconia particles, or ceria particles having an average primary particle diameter of 5 to 100 nm
- the hydrophobic portion of the water-soluble compound has a glucose structure, an alkylene group, an alkylene oxide group, or a repeating unit thereof
- the water-soluble compound is represented by the following formula (1), formula (2), or formula (3): (Where
- the polishing composition according to any one of the first to third aspects which is a compound having a unit structure of As a fifth aspect, the polishing composition according to any one of the first to fourth aspects, wherein the chelating agent is an aminocarboxylic acid chelating agent or a phosphonic acid chelating agent,
- the aminocarboxylic acid chelating agent is ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-propanediamine tetraacetic acid Diamine 2-hydroxypropane tetraacetic acid, hydroxyethyl iminodiacetic acid, dihydroxyethyl glycine, glycol ether diamine tetraacetic acid, dicarboxymethyl glutamic acid, or ethylenediamine
- a method of polishing a wafer comprising the step of polishing the ridge of the peripheral portion, and as the eleventh aspect, the step of polishing the ridge comprises a laser having a height of 50 nm to 500 nm with respect to the horizontal surface of the wafer surface on which the laser mark is provided.
- the method for polishing a wafer according to the ninth aspect or tenth aspect which is a step of polishing the bumps on the periphery of the mark to a height of 30 nm to minus 10 nm with respect to the horizontal surface.
- the polishing composition of the present invention aims to eliminate the bumps on the periphery of the laser marks applied to the periphery of the wafer in the wafer polishing process.
- the roles of silica particles and components other than water in the composition are significant.
- the raised portion at the periphery of the laser mark is more wettable than the other portions, so that the abrasive composition is in contact with the abrasive composition efficiently, so that the balance of hydrophilicity and hydrophobicity is appropriate as an additive in the abrasive composition.
- Compounds are sought. Water soluble compounds include, for example, compounds, oligomers and polymers having hydrophobic and hydrophilic moieties.
- a substance having a hydrophobic core in the center of the polymer and having a hydrophilic periphery can efficiently contact the polishing component (eg, silica particles, zirconia particles, ceria particles, etc.) with the ridge of the laser mark peripheral portion.
- the polishing component eg, silica particles, zirconia particles, ceria particles, etc.
- the polishing component for example, silica particles, zirconia particles and ceria efficiently
- water-soluble compounds such as polymers having such a hydrophilic portion and a hydrophobic portion
- one of the hydrophilic portions is a hydroxyl group
- the others are a hydroxyalkyl group, an acyloxy group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid And sulfonate groups.
- the combination of these functional groups is to modify the polymer, but the modification is to substitute part of the hydrogen atoms of the hydroxyl methyl group with the above-mentioned hydroxyethyl group or polyhydroxy alkyl group, or to substitute the hydrogen atoms of the hydroxyl group with acyl. It can be achieved by conversion to a group (resulting in the provision of an acyloxy group).
- a combination of the above functional groups can be achieved by modifying a part of hydroxy groups such as cellulose, polyvinyl alcohol and polyglycerin to the above other hydrophilic groups.
- carboxylic acid groups and sulfonic acid groups can be converted to carboxylic acid groups and sulfonic acid groups by neutralization with aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, and aqueous ammonia solution.
- the ratio of hydroxyl group to hydroxyalkyl group, acyloxy group, carboxylic acid group, carboxylic acid group, sulfonic acid group or sulfonic acid group increases the latter ratio as the molar ratio of the former to the latter To improve.
- the polishing composition of the present invention can be used as a polishing component or an additive because the polishing component (for example, silica particles, zirconia particles, ceria particles, etc.) can efficiently contact the bumps of the peripheral portion of the laser mark. Even if the content of is lower than that of the conventional abrasive, good polishing performance can be exhibited. Further, since the polishing composition of the present invention contains the polishing component at a low concentration, the polishing resistance is relatively small, and the generation of flaws on the polishing surface can be suppressed.
- the present invention is a polishing composition for eliminating the bumps on the periphery of a laser mark of a wafer having a laser mark, wherein the polishing composition comprises a water-soluble compound, a chelating agent and metal oxide particles. And a pH of 7 to 12, the water-soluble compound has a hydrophobic moiety and a hydrophilic moiety, and the hydrophilic moiety comprises a hydroxyl group at its terminal or side chain, a hydroxyethyl group, an acyloxy group
- the polishing composition having a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, or a sulfonic acid group, wherein the water-soluble compound has a content of 5 to 700 ppm or 10 to 500 ppm in the polishing composition It is a thing.
- the above-mentioned hydrophilic moiety has a hydroxyl group and a hydroxyalkyl group, an acyloxy group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, or a sulfonic acid group at its terminal or side chain; It means that a hydroxyalkyl group, an acyloxy group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, or a sulfonic acid group is present at the terminal or side chain part of the water-soluble compound to be a hydrophilic group. .
- hydroxyalkyl group examples include hydroxyalkyl groups having 2 to 10 carbon atoms, such as hydroxyethyl and hydroxypropyl.
- the polishing composition can contain water and be diluted to a desired concentration. Moreover, surfactant can be contained as needed.
- the metal oxide particles may be added to the polishing composition as it is, or may be added in the form of a colloidal sol of an aqueous medium, more preferably a colloidal sol of water.
- other components may be added to the colloidal sol of metal oxide fine particles to obtain a polishing composition.
- coarse particles for example, 0.5 ⁇ m or more
- the metal oxide particles are abrasive particles, and are silica particles having an average primary particle size of 5 to 100 nm in a colloidal sol, zirconia particles, or ceria particles, and metal oxide particles based on these metal oxide sols.
- the polishing composition has a solid content of 0.1 to 15% by mass.
- the solid content is the remaining component of the polishing composition from which the aqueous medium is removed.
- the aqueous medium is a liquid containing water as a main component, and may contain a hydrophilic organic solvent.
- the metal oxide particles can be contained in the range of 0.1 to 10% by mass, 0.1 to 5% by mass, or 0.1 to 1% by mass in the polishing composition. Especially as a metal oxide particle, a silica particle is preferable.
- the metal oxide particles to be used commercially available products or those manufactured by known methods can be used, and although not particularly limited, for example, those having an average primary particle diameter of 5 to 100 nm can be used.
- silica particles used silica particles with an aqueous dispersion of silica particles having an average primary particle diameter of 5 to 100 nm can be used.
- These aqueous dispersions are silica sols, silica in the silica sol is silica particles in the polishing composition of the present invention, and the aqueous medium in the silica sol can replace water in the polishing composition.
- the water in the polishing composition is attributable to the water in the silica sol, but other water to be added as dilution water can be added.
- the silica particles used in the present invention are preferably colloidal silica particles having an average primary particle diameter of 5 to 100 nm as determined by a nitrogen adsorption method. If the average primary particle size is less than 5 nm, the polishing rate may be low, and the aggregation of the silica particles is likely to occur, resulting in a decrease in the stability of the polishing composition. If the average primary particle size is larger than 100 nm, scratches may easily occur on the wafer surface, and the flatness of the polished surface may be deteriorated. The same applies to other metal oxide particles such as zirconia particles and ceria particles.
- the silica sol in which silica particles are dispersed in an aqueous medium contains coarse particles of 0.5 ⁇ m or more, it is preferable to remove the coarse particles.
- metal oxide particle sols in which other metal oxide particles such as zirconia particles and ceria particles are dispersed Removal of coarse particles includes forced sedimentation and precision filtration.
- filters used for microfiltration there are depth filters, pleated filters, membrane filters, hollow fiber filters, etc. Any of them can be used.
- the material of the filter includes cotton, polypropylene, polystyrene, polysulfone, polyether sulfone, nylon, cellulose, glass and the like, any of which can be used.
- the filtration accuracy of the filter is expressed by the absolute filtration accuracy (the size of the particle to be captured 99.9% or more), but in the case of metal oxide particles such as silica particles, the production efficiency (treatment time, clogging of the filter It is preferable to treat with a filter with an absolute filtration accuracy of 0.5 ⁇ m to 1.0 ⁇ m from the viewpoint of
- the pH of the metal oxide aqueous sol such as silica sol, zirconia sol, ceria sol, etc. is adjusted with ammonia or the like, and a polymer, a chelating agent or the like can be added to the aqueous sol.
- the pH adjustment of the metal oxide sol can be performed before, after, or both of the addition of the compound (polymer) and the chelating agent.
- the pH of the polishing composition of the present invention can be set in the range of 7 to 12, 9 to 12, or 9.5 to 11, or 10 to 11.
- an alkali component for setting to these pHs sodium hydroxide, potassium hydroxide, ammonia, primary ammonium hydroxide, secondary ammonium hydroxide, tertiary ammonium hydroxide, quaternary ammonium hydroxide,
- An aqueous solution of an organic amine, an alkali metal carbonate or the like can be used.
- ammonium salts based on ammonia examples include ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate and the like. Among them, ammonium hydroxide is preferred.
- quaternary ammonium salts may be mentioned as ammonium salts based on ammonia, such as tetramethyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, diethyl dimethyl ammonium hydroxide, triethyl methyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetramethyl chloride. Ammonium, tetraethylammonium chloride and the like can be mentioned.
- organic amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N, N-diethanolamine, N, N-dimethylamine Ethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, ethylenediamine, hexaethylenediamine, ethylethylenediaminepiperazine hexahydrate, anhydrous piperazine, N-methylpiperazine, hydroxyethylpiperazine, N-aminoethylpiperazine 1,3-propanediamine N, N-dimethylethylenediamine, diethyleneamine, monoisopropanolamine, diisopropanolamine Li iso Buropa alkanolamines and the like, among which even monoethanolamine, ethylenediamine, or piperazine is preferred.
- alkali metal carbonate examples include lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.
- sodium carbonate or potassium carbonate is preferred.
- polishing composition 5 to 1000 ppm, or 10 to 500 ppm of an alkali component can be contained in the polishing composition by pH adjustment
- the average primary particle size of the metal oxide particles can also be measured by observation with a transmission electron microscope.
- the range of the average primary particle size can be in the range of 5 to 100 nm, or 5 to 80 nm.
- the water-soluble compound used in the present invention has a hydrophobic moiety and a hydrophilic moiety, and the hydrophilic moiety is a hydroxyl group and a hydroxyethyl group, an acyloxy group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group or a sulfone
- the acid group and the acid group constitute the hydrophilic end or side chain of the compound.
- the hydrophobic portion of the water-soluble compound is not particularly limited, but preferably has a glucose structure, an alkylene group, an alkylene oxide group, or a repeating unit thereof.
- the water-soluble compound having a repeating unit (unit structure) of the formula (1) is a polymer and is hydroxyethyl cellulose.
- the hydrogen atom of the hydroxyl group of the hydroxymethyl group extending from the glucose skeleton can be rendered hydrophilic by substituting it with a hydroxyethyl group via an oxyethylene group.
- the hydrogen atoms of the hydroxyl group of the hydroxymethyl group extending from the glucose skeleton can be substituted in part or in whole, but it is preferable to substitute 50 mol% or more of the total.
- the above hydroxyethyl cellulose can be used in an average molecular weight of 100,000 to 1,500,000, or 500,000 to 1,300,000, or 600,000 to 1,200,000.
- trade name SE-400 average molecular weight 600,000
- trade name CF-X average molecular weight 1.2 million manufactured by Sumitomo Seika Chemicals Co., Ltd.
- the water-soluble compound having a repeating unit (unit structure) of the formula (2) is glycerin or polyglycerin.
- n3 is an integer of 1 to 30.
- Glycerin or polyglycerin is one having a hydroxyl group and a hydroxyethyl or hydroxypropyl group in the structure. For example, those having a hydroxyl group and a hydroxypropyl group in the structure can be exemplified.
- the hydrogen atom of the hydroxyl group at the terminal or side chain of the polyoxyalkylene skeleton can be rendered hydrophilic by substitution with a hydroxyethyl group or a hydroxypropyl group via an oxyalkylene group, and a part or all of them can be substituted Although it is possible, it is preferable to replace 50 mol% or more of the whole.
- the polyglycerin include (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name: polyglycerin # 750, average molecular weight 750). They exhibit good laser mark removability at a content of 10 to 500 ppm, or 10 to 100 ppm in the polishing composition.
- a water-soluble compound having a unit structure of Formula (3) that is, a water-soluble compound having a repeating unit (unit structure) of Formula (3-1) and Formula (3-2) is a polymer and is a modified polyvinyl alcohol .
- R 1 represents an acetoxy group, a carboxylic acid group (carboxyl group), a carboxylic acid group, a sulfonic acid group or a sulfonic acid group.
- the carboxylic acid and the sulfonic acid can be introduced with counter ions such as Na + , K + , NH 4 + and the like by neutralizing them with an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia and the like.
- the acetoxy group can be introduced into the alkylene skeleton by reacting polyvinyl acetate with acetic acid and replacing the hydrogen atom of the hydroxyl group with an acetyl group.
- the carboxylic acid group and the sulfonic acid group can be introduced by copolymerizing acrylic acid, methacrylic acid, vinyl sulfonic acid and vinyl alcohol.
- Acrylic acid, methacrylic acid, vinyl sulfonic acid and vinyl alcohol can be block copolymerized or random copolymerized.
- the sum n4 + n5 of the number n4 of the unit structures of the formula (3-1) and the number n5 of the unit structures of the formula (3-2) represents an integer of 100 to 10,000. it can.
- the hydroxyl group of the side chain of the polyalkylene skeleton can be rendered hydrophilic by conversion with an acetoxy group of R 1 , a carboxylic acid group (carboxyl group), a carboxylic acid group, a sulfonic acid group, or a sulfonic acid group. Although it is possible to convert all or part, it is preferable to convert 50 mol% or more of the whole.
- water-soluble compounds are acetoxy group-introduced polyvinyl alcohol (Nippon Acetate Bipobar Co., Ltd., trade name JP-03, average molecular weight 15,000), sulfonic acid group-introduced polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. , Trade name L-3266, average molecular weight 20,000), carboxylic acid base-introduced polyvinyl alcohol (Nippon Synthetic Chemical Industry Co., Ltd. trade name T-330, average molecular weight 140,000).
- sulfonic acid group-introduced polyvinyl alcohol and carboxylic acid group-introduced polyvinyl alcohol are preferred. They exhibit good laser mark removability at a content of 10 to 500 ppm, or 10 to 100 ppm in the polishing composition.
- a chelating agent can be added.
- chelating agents aminocarboxylic acid type chelating agents and phosphonic acid type chelating agents can be mentioned.
- aminocarboxylic acid chelating agent ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, 1,3-propanediaminetetraacetic acid, 1,3-diamine-2-hydroxypropane Examples include tetraacetic acid, hydroxyethyl iminodiacetic acid, dihydroxyethyl glycine, glycol ether diamine tetraacetic acid, dicarboxymethyl glutamic acid, and ethylenediamine-N, N'-disuccinic acid.
- phosphonic acid chelating agents examples include hydroxyethylidene diphosphonic acid, nitrilotris (methylene phosphonic acid), phosphonobutane tricarboxylic acid, and ethylene diamine tetra (methylene phosphonic acid).
- the chelating agent can be contained in a proportion of 0.005 to 1.0% by mass with respect to the total mass of the polishing composition of the present invention.
- the wafer to which the composition for polishing a wafer of the present invention can be applied is a silicon wafer, a SiC wafer, a GaN wafer, a GaAs wafer, a GaP wafer, a glass wafer, an aluminum wafer, a sapphire wafer and the like.
- the polishing apparatus for polishing a wafer includes a single-side polishing method and a double-side polishing method, and the polishing composition for a wafer of the present invention can be used in any of the devices.
- the polishing composition of the present invention By performing polishing using the polishing composition of the present invention, it is possible to produce a wafer giving a flat polishing surface having a small difference in height between the central portion and the peripheral portion (laser mark portion) of the wafer in the wafer polishing step. .
- the polishing composition of the present invention can be used to polish the ridges on the periphery of the laser mark of a wafer having a laser mark.
- the step of polishing the ridge on the periphery of the laser mark of the wafer having the laser mark may be performed using the polishing composition of the present invention. it can.
- the ridge of the laser mark peripheral portion with a height of 50 to 500 nm or 50 to 200 nm with respect to the horizontal surface of the wafer surface on which the laser mark is applied, and a height of 30 nm to ⁇ 10 nm, preferably 25 to 0 nm with respect to the horizontal surface. More preferably, polishing can be performed to 0 nm.
- the reason why the peripheral portion of the laser mark after polishing becomes about -10 nm is that the peripheral portion of the laser mark may be lowered to about -10 nm toward the depression of the laser mark portion due to the polishing. They are those in which the edge of the depression is polished and show a negative value, and it is preferable that it is ideally 0 nm.
- a commercially available silicon wafer was polished by the following method. 1) Preparation of a composition containing a chelating agent and metal oxide particles 0.33% by mass of colloidal silica (silica particles based on silica sol) having an average primary particle diameter of 40 nm determined from a nitrogen adsorption method, and a basic compound (alkali component And 25 ppm of ammonium hydroxide, 110 ppm of sodium ethylenediaminetetraacetate (reagent) as a chelating agent, and various additives as shown in Table 1 below, and the balance is water, and the chelating agent and metal oxide particles
- the composition (A) was produced. Each component was added in the same manner as the composition (A) to prepare each composition.
- composition (A) the content (% by mass) of colloidal silica (silica particles based on silica sol) having an average primary particle diameter of 40 nm, the type and content (ppm) of basic substances, the type and content of chelating agents Compositions (B) to (J) were similarly prepared by changing the amount (ppm) to the ratio shown in Table 1 below.
- sodium ethylenediaminetetraacetate is represented by EDTA
- ammonium hydroxide is represented by NH 4 OH
- potassium hydroxide is represented by KOH
- ethyltrimethylammonium hydroxide is represented by ETMAH.
- Example 1 In the composition (A) prepared in the preparation of the above composition, hydroxyethyl cellulose (average molecular weight 600,000, Daicel Finechem Co., Ltd., trade name SE-400) as a water-soluble compound is added in the polishing composition
- the polishing composition of Example 1 was manufactured to 100 ppm.
- the silicon wafer was polished for 5 minutes using the polishing composition. Subsequently, the silicon wafer was washed and the laser mark height was measured. Although the height of the peripheral portion of the laser mark before polishing was 151 nm, the height of the laser mark after polishing was 0 nm, and good results were obtained.
- the polishing rate was 0.06 ⁇ m / min.
- Examples 2 to 20, Comparative Examples 1 to 5 As shown in Table 2 below, a water-soluble compound was added to each composition in the same manner as in Example 1 to prepare polishing compositions of Examples 2 to 20 and Comparative Examples 1 to 5. The type of the composition used in each example and the type and concentration (ppm) of the water-soluble compound in the polishing composition are shown in Table 2 below. The pHs of the polishing compositions of Examples 1 to 20 and Comparative Examples 1 to 5 were the same as the pHs of the compositions (A) to (J) used.
- hydroxyethyl cellulose (average molecular weight 600,000, manufactured by Daicel Finechem Co., Ltd., trade name SE-400) is a water soluble compound (a), Hydroxyethylcellulose (average molecular weight: 1.2 million, manufactured by Sumitomo Seika Chemicals Co., Ltd., trade name CF-X) as a water-soluble compound (b), Water-soluble compound (c), glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name: purified glycerin); Water-soluble compound (d) polyglycerin (average molecular weight 750, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., trade name polyglycerin # 750), A sulfonic acid group-modified polyvinyl alcohol (average molecular weight: 20,000, manufactured by Japan Synthetic Chemical Industry Co., Ltd., trade name L-3266) as a water-soluble compound (e
- Water-soluble compound modified polyglycerin manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., polyoxypropylene polyglyceryl ether, trade name SC-E1600, hydrogen atom of hydroxyl group of polyglycerin was converted to 1-methylhydroxyethyl group).
- Polyvinyl alcohol average molecular weight 3500, reagent was used as the water soluble compound (j).
- the value of the polishing rate is a value obtained by determining the polishing rate of the silicon wafer, but the magnitude of the polishing rate on the silicon wafer is not necessarily related to the elimination (polishing) of the ridge around the laser mark. It is considered that the raised portion at the periphery of the laser mark can be efficiently contacted with the polishing component by the contact with the hydrophilic portion of the water-soluble compound, and the raised portion is polished. This shows from the known polishing compositions for silicon wafers that one can not expect a polishing composition which eliminates the bumps on the periphery of the laser mark.
- polishing composition of the present invention it is possible to eliminate the bumps on the periphery of the laser mark in the wafer polishing process and to provide a flat polishing surface.
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Abstract
Description
レーザーマークの隆起を解消することとは、ウェハーのレーザーマーク周辺の基準平面(水平面)から隆起の最高点までの高さを小さくすることである。
第2観点として、前記金属酸化物粒子が、5~100nmの平均一次粒子径を有するシリカ粒子、ジルコニア粒子、又はセリア粒子である第1観点に記載の研磨用組成物、
第3観点として、前記水溶性化合物の疎水性部分は、グルコース構造、アルキレン基、アルキレンオキシド基、又はその繰り返し単位を有するものである第1観点に記載の研磨用組成物、
第4観点として、前記水溶性化合物が、下記式(1)、式(2)、又は式(3):
第5観点として、前記キレート剤が、アミノカルボン酸系キレート剤又はホスホン酸系キレート剤である第1観点乃至第4観点の何れか一つに記載の研磨用組成物、
第6観点として、前記アミノカルボン酸系キレート剤が、エチレンジアミンテトラ酢酸、ニトリロトリ酢酸、ジエチレントリアミンペンタ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、トリエチレンテトラミンヘキサ酢酸、1,3-プロパンジアミンテトラ酢酸、1,3-ジアミン-2-ヒドロキシプロパンテトラ酢酸、ヒドロキシエチルイミノジ酢酸、ジヒドロキシエチルグリシン、グリコールエーテルジアミンテトラ酢酸、ジカルボキシメチルグルタミン酸、又はエチレンジアミン-N,N’-ジコハク酸である第1観点乃至第5観点の何れか一つに記載の研磨用組成物、
第7観点として、前記ホスホン酸系キレート剤が、ヒドロキシエチリデンジホスホン酸、ニトリロトリス(メチレンホスホン酸)、ホスホノブタントリカルボン酸、又はエチレンジアミンテトラ(メチレンホスホン酸)である第1観点乃至第5観点の何れか一つに記載の研磨用組成物、
第8観点として、更にアルカリ成分として、水酸化アンモニウム、水酸化第1級アンモニウム、水酸化第2級アンモニウム、水酸化第3級アンモニウム、水酸化第4級アンモニウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、水酸化ナトリウム、又は水酸化カリウムを含む、第1観点乃至第7観点の何れか一つに記載の研磨用組成物、
第9観点として、第1観点乃至第8観点の何れか一つに記載の研磨用組成物を用いてレーザーマークが付されたウェハーのレーザーマーク周辺部の隆起を研磨する工程を含むウェハーの研磨方法、
第10観点として、レーザーマークが付されたウェハーを予備研磨する工程、第1観点乃至第8観点の何れか一つに記載の研磨用組成物を用いてレーザーマークが付されたウェハーのレーザーマーク周辺部の隆起を研磨する工程を含むウェハーの研磨方法、及び
第11観点として、前記隆起を研磨する工程が、前記レーザーマークが賦されたウェハー表面の水平面に対して高さ50nmから500nmのレーザーマーク周辺部の隆起を、該水平面に対して高さ30nmからマイナス10nmになるまで研磨する工程である、第9観点又は第10観点に記載のウェハーの研磨方法である。
研磨用組成物の研磨性能は、組成物中のシリカ粒子と水以外の成分の役割が大きい。
レーザーマーク周辺部の隆起部分は他の部分よりヌレ性が高いため、研磨成分が効率よく接触するために、研磨剤組成物には添加剤として親水性と疎水性のバランスが適切である水溶性化合物が求められる。水溶性化合物として、たとえば疎水性部分及び親水性部分を有する化合物、オリゴマー及びポリマーが挙げられる。
たとえばポリマーの中心部が疎水性であり、周囲が親水性の物質は効率的に研磨成分(例えば、シリカ粒子、ジルコニア粒子及びセリア粒子等)とレーザーマーク周辺部の隆起とを接触させることが可能であることを見出した。
たとえば、ポリマーの疎水性主鎖と、親水性の末端及び/又は側鎖を含む構造の物質を研磨用組成物中に介在する事で効率的に研磨成分(例えば、シリカ粒子、ジルコニア粒子及びセリア粒子等)と、レーザーマークの周辺部の隆起とを接触させる事が可能である。
例えば、セルロース、ポリビニルアルコール、ポリグリセリン等のヒドロキシ基の一部を上記その他の親水性基に変性することにより、上記官能基の組み合せを達成することができる。
また、研磨成分(例えば、シリカ粒子、ジルコニア粒子及びセリア粒子等)と、レーザーマークの周辺部の隆起が効率的に接触可能であるため、本発明の研磨用組成物は、研磨成分や添加剤の含有量が従来の研磨剤よりも低濃度でも良好な研磨性能を発揮することができる。また本発明の研磨用組成物は、研磨成分を低濃度で含有するため研磨抵抗が比較的小さく、研磨面のキズの発生を抑制することができる。
金属酸化物粒子は研磨粒子であって、コロイドゾル中の5~100nmの平均一次粒子径を有するシリカ粒子、ジルコニア粒子、又はセリア粒子であり、これら金属酸化物ゾルに基づく金属酸化物粒子である。
ジルコニア粒子及びセリア粒子等のその他の金属酸化物粒子も同様である。
これらのpHに設定するためのアルカリ成分として、水酸化ナトリウム、水酸化カリウム、アンモニア、水酸化第1級アンモニウム、水酸化第2級アンモニウム、水酸化第3級アンモニウム、水酸化第4級アンモニウム、有機アミン、アルカリ金属炭酸塩等の水溶液を用いることができる。特にアンモニア水溶液、水酸化カリウム水溶液を用いることが好ましい。
また、アンモニアに基づくアンモニウム塩として第4級アンモニウム塩が挙げられ、例えば水酸化テトラメチルアンモニウム、水酸化エチルトリメチルアンモニウム、水酸化ジエチルジメチルアンモニウム、水酸化トリエチルメチルアンモニウム、水酸化テトラエチルアンモニウム、塩化テトラメチルアンモニウム、塩化テトラエチルアンモニウム等が挙げられる。
水溶性化合物の疎水性部分は特に限定されるものではないが、好ましくはグルコース構造、アルキレン基、アルキレンオキシド基、又はその繰り返し単位を有するものである。
グリセリン又はポリグリセリンはヒドロキシル基と、ヒドロキシエチル基又はヒドロキシプロピル基とを構造に含むものである。例えば、ヒドロキシル基と、ヒドロキシプロピル基とを構造に含むものを例示することができる。
上記ポリグリセリンは(阪本薬品工業(株)社製、商品名ポリグリセリン♯750、平均分子量750)が挙げられる。
これらは研磨用組成物中で10~500ppm、又は10~100ppmの含有量で良好なレーザーマーク解消性を示す。
これらは研磨用組成物中で10~500ppm、又は10~100ppmの含有量で良好なレーザーマーク解消性を示す。
アミノカルボン酸系キレート剤として、エチレンジアミンテトラ酢酸、ニトリロトリ酢酸、ジエチレントリアミンペンタ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、トリエチレンテトラミンヘキサ酢酸、1,3-プロパンジアミンテトラ酢酸、1,3-ジアミン-2-ヒドロキシプロパンテトラ酢酸、ヒドロキシエチルイミノジ酢酸、ジヒドロキシエチルグリシン、グリコールエーテルジアミンテトラ酢酸、ジカルボキシメチルグルタミン酸、及びエチレンジアミン-N,N’-ジコハク酸が挙げられる。
本発明の研磨用組成物を用いて研磨を行うことにより、ウェハーの研磨工程でウェハーの中心部と周辺部(レーザーマーク部分)の高低差が小さいフラット研磨面を与えるウェハーを製造することができる。
本発明ではレーザーマークが付されたウェハーを予備研磨する工程を経て、本願発明の研磨用組成物を用いてレーザーマークが付されたウェハーのレーザーマーク周辺部の隆起を研磨する工程を行う事ができる。
1)キレート剤と金属酸化物粒子とを含む組成物の調製
窒素吸着法から求められる平均一次粒子径40nmのコロイダルシリカ(シリカゾルに基づくシリカ粒子)0.33質量%と、塩基性化合物(アルカリ成分)として、水酸化アンモニウム25ppm、キレート剤として、エチレンジアミンテトラ酢酸ナトリウム(試薬)110ppm、各種添加剤を下記表1に示す割合で添加し、残部は水となるようなキレート剤と金属酸化物粒子とを含む組成物(A)を製造した。
組成物(A)と同様に各成分の添加を行い、各組成物を作成した。上記組成物(A)中において、平均一次粒子径40nmのコロイダルシリカ(シリカゾルに基づくシリカ粒子)の含有量(質量%)、塩基性物質の種類と含有量(ppm)、キレート剤の種類と含有量(ppm)を以下表1に示す割合に変更して同様に組成物(B)~(J)を作成した。
表中、エチレンジアミンテトラ酢酸ナトリウムはEDTA、水酸化アンモニウムはNH4OH、水酸化カリウムはKOH、水酸化エチルトリメチルアンモニウムはETMAHで示す。
研磨機:浜井産業社製両面研磨機13BF
荷重:150g/cm2
上定盤回転数:7rpm
下定盤回転数:20rpm
研磨パッド:発泡ポリウレタン製研磨パッド
研磨希釈液の供給量:6.0L/分
研磨時間:5分
シリコンウェハー:直径200mm、伝導型P型、結晶方位が<100>、抗率が100Ω・cm未満
3)洗浄条件
水洗浄を行った後、40℃に加温したSC1洗浄液(29%アンモニア水:30%過酸化水素水:水の重量比=1:1:28の洗浄液)で洗浄し、ウェハー表面の不純物を除去した。
4)レーザーマーク高さの測定方法
(株)ニコンインステック社製光干渉顕微鏡システムBW-M7000を用い、一定幅(500μm)をスキャンして得られる粗さ曲線に対し、ウェハー表面の最も高い部分と最も低い部分の高さの差分を測定した。
上記組成物の調製で調製した組成物(A)に、水溶性化合物としてヒドロキシエチルセルロース(平均分子量60万、ダイセルファインケム(株)社製、商品名SE-400)を添加量が研磨用組成物中に100ppmとなるように加え、実施例1の研磨用組成物を製造した。該研摩用組成物を用いてシリコンウェハーを5分間研磨した。引き続きシリコンウェハーを洗浄し、レーザーマーク高さの測定を行った。研磨前のレーザーマーク周辺部の高さが151nmであったものが、研磨後にレーザーマーク高さは0nmとなり、良好な結果を得た。研磨速度は0.06μm/分であった。
下記表2に示す様に、実施例1と同様に各組成物に水溶性化合物の添加を行い各実施例2~20及び各比較例1~5の研磨用組成物を作成した。各実施例において使用した上記組成物の種類と、研磨用組成物中での水溶性化合物の種類と濃度(ppm)を下表2に示した。実施例1~実施例20、比較例1~5の研磨用組成物のpHは、使用した組成物(A)~(J)のpHと同じであった。
下表2では、ヒドロキシエチルセルロース(平均分子量60万、ダイセルファインケム(株)社製、商品名SE-400)を水溶性化合物(a)、
ヒドロキシエチルセルロース(平均分子量120万、住友精化(株)製、商品名CF-X)を水溶性化合物(b)、
グリセリン(阪本薬品工業(株)社製、商品名精製グリセリン)を水溶性化合物(c)、
ポリグリセリン(平均分子量750、阪本薬品工業(株)社製、商品名ポリグリセリン♯750)を水溶性化合物(d)、
スルホン酸基変性ポリビニルアルコール(平均分子量2万、日本合成化学工業(株)社製、商品名L-3266)を水溶性化合物(e)、
カルボキシル基変性ポリビニルアルコール(平均分子量14万、日本合成化学工業(株)社製、商品名T-330)を水溶性化合物(f)、
変性ポリグリセリン(阪本薬品工業(株)社製、ポリオキシエチレンポリグリセリルエーテル、商品名SC-E1500、ポリグリセリンのヒドロキシル基の水素原子を、ヒドロキシエチル基に変換した。)を水溶性化合物(g)、
変性ポリグリセリン(阪本薬品工業(株)社製、カプリル酸エステル、商品名MCA750、ポリグリセリンのヒドロキシル基とカプリル酸とを反応させた。)を水溶性化合物(h)、
変性ポリグリセリン(阪本薬品工業(株)社製、ポリオキシプロピレンポリグリセリルエーテル、商品名SC-E1600、ポリグリセリンのヒドロキシル基の水素原子を、1-メチルヒドロキシエチル基に変換した。)を水溶性化合物(i)、
ポリビニルアルコール(平均分子量3500、試薬)を水溶性化合物(j)とした。
Claims (11)
- レーザーマークが付されたウェハーのレーザーマーク周辺部の隆起を解消するための研磨用組成物であって、該研磨用組成物は水溶性化合物とキレート剤と金属酸化物粒子とを含み、且つ7~12のpHを有し、該水溶性化合物は疎水性部分と親水性部分とを有し、該親水性部分は、その末端もしくは側鎖にヒドロキシル基と、ヒドロキシアルキル基、アシルオキシ基、カルボン酸基、カルボン酸塩基、スルホン酸基、又はスルホン酸塩基とを有し、該水溶性化合物は研磨用組成物中で5~700ppmの含有量となる上記研磨用組成物。
- 前記金属酸化物粒子が、5~100nmの平均一次粒子径を有するシリカ粒子、ジルコニア粒子、又はセリア粒子である請求項1に記載の研磨用組成物。
- 前記水溶性化合物の疎水性部分は、グルコース構造、アルキレン基、アルキレンオキシド基、又はその繰り返し単位を有するものである請求項1に記載の研磨用組成物。
- 前記キレート剤が、アミノカルボン酸系キレート剤又はホスホン酸系キレート剤である請求項1乃至請求項4の何れか1項に記載の研磨用組成物。
- 前記アミノカルボン酸系キレート剤が、エチレンジアミンテトラ酢酸、ニトリロトリ酢酸、ジエチレントリアミンペンタ酢酸、ヒドロキシエチルエチレンジアミントリ酢酸、トリエチレンテトラミンヘキサ酢酸、1,3-プロパンジアミンテトラ酢酸、1,3-ジアミン-2-ヒドロキシプロパンテトラ酢酸、ヒドロキシエチルイミノジ酢酸、ジヒドロキシエチルグリシン、グリコールエーテルジアミンテトラ酢酸、ジカルボキシメチルグルタミン酸、又はエチレンジアミン-N,N’-ジコハク酸である請求項1乃至請求項5の何れか1項に記載の研磨用組成物。
- 前記ホスホン酸系キレート剤が、ヒドロキシエチリデンジホスホン酸、ニトリロトリス(メチレンホスホン酸)、ホスホノブタントリカルボン酸、又はエチレンジアミンテトラ(メチレンホスホン酸)である請求項1乃至請求項5の何れか1項に記載の研磨用組成物。
- 更にアルカリ成分として、水酸化アンモニウム、水酸化第1級アンモニウム、水酸化第2級アンモニウム、水酸化第3級アンモニウム、水酸化第4級アンモニウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素カリウム、水酸化ナトリウム、又は水酸化カリウムを含む、請求項1乃至請求項7の何れか1項に記載の研磨用組成物。
- 請求項1乃至請求項8の何れか1項に記載の研磨用組成物を用いてレーザーマークが付されたウェハーのレーザーマーク周辺部の隆起を研磨する工程を含むウェハーの研磨方法。
- レーザーマークが付されたウェハーを予備研磨する工程、請求項1乃至請求項8の何れか1項に記載の研磨用組成物を用いてレーザーマークが付されたウェハーのレーザーマーク周辺部の隆起を研磨する工程を含むウェハーの研磨方法。
- 前記隆起を研磨する工程が、前記レーザーマークが付されたウェハー表面の水平面に対して高さ50nmから500nmのレーザーマーク周辺部の隆起を、該水平面に対して高さ30nmからマイナス10nmになるまで研磨する工程である、請求項9又は請求項10に記載のウェハーの研磨方法。
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SG11202005839VA SG11202005839VA (en) | 2017-12-22 | 2018-12-19 | Composition for polishing for use in eliminating protrusion in periphery of laser mark |
US16/956,753 US20200317955A1 (en) | 2017-12-22 | 2018-12-19 | Composition for polishing for use in eliminating protrusion in periphery of laser mark |
CN201880089885.3A CN111758151A (zh) | 2017-12-22 | 2018-12-19 | 用于消除激光标记周边的隆起的研磨用组合物 |
EP18892121.7A EP3731261A4 (en) | 2017-12-22 | 2018-12-19 | POLISHING COMPOSITION INTENDED FOR USE IN THE REMOVAL OF SURFACE IN THE PERIPHERY OF A LASER BRAND |
KR1020207019431A KR20200098573A (ko) | 2017-12-22 | 2018-12-19 | 레이저마크 주변의 융기를 해소하기 위한 연마용 조성물 |
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US20200317955A1 (en) | 2020-10-08 |
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JPWO2019124442A1 (ja) | 2021-01-14 |
KR20200098573A (ko) | 2020-08-20 |
TW201936880A (zh) | 2019-09-16 |
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