WO2018150856A1 - 研磨用組成物、その製造方法および研磨用組成物を用いた研磨方法 - Google Patents
研磨用組成物、その製造方法および研磨用組成物を用いた研磨方法 Download PDFInfo
- Publication number
- WO2018150856A1 WO2018150856A1 PCT/JP2018/002697 JP2018002697W WO2018150856A1 WO 2018150856 A1 WO2018150856 A1 WO 2018150856A1 JP 2018002697 W JP2018002697 W JP 2018002697W WO 2018150856 A1 WO2018150856 A1 WO 2018150856A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- polishing composition
- water
- soluble polymer
- styrene
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims description 17
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- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 50
- 239000006061 abrasive grain Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000007514 bases Chemical class 0.000 claims abstract description 24
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- 239000000178 monomer Substances 0.000 claims abstract description 10
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
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- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 229960003506 piperazine hexahydrate Drugs 0.000 description 1
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- USIPWJRLUGPSJM-UHFFFAOYSA-K trisodium 2-(2-aminoethylamino)ethanol triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCO USIPWJRLUGPSJM-UHFFFAOYSA-K 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
-
- 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
Definitions
- the present invention relates to a polishing composition, a method for producing a polishing composition, and a polishing method using the polishing composition.
- polishing process typically includes a preliminary polishing process (preliminary polishing process) and a final polishing process (final polishing process).
- a silicon wafer may be marked with a mark (hard laser mark) such as a bar code, a number, or a symbol by irradiating the front or back surface of the silicon wafer with laser light for the purpose of identification or the like.
- a mark such as a bar code, a number, or a symbol by irradiating the front or back surface of the silicon wafer with laser light for the purpose of identification or the like.
- Such a hard laser mark is generally applied after the lapping process of the silicon wafer is finished and before the polishing process is started.
- Patent Document 1 discloses a polishing composition containing abrasive grains, a weak acid salt, and a quaternary ammonium compound, and the polishing composition suppresses pH fluctuations and maintains polishing efficiency. It is described that the bulge at the periphery of the hard laser mark can be eliminated.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a polishing composition excellent in performance for eliminating the bulge at the periphery of the hard laser mark.
- an object of the present invention is to provide a method for producing the polishing composition.
- an object of the present invention is to provide a method for polishing an object to be polished with a hard laser mark using the polishing composition.
- the present inventors have found that the above problem can be solved by including a water-soluble polymer containing a structural unit derived from styrene or a derivative thereof in a polishing composition, and have completed the present invention.
- the present invention includes abrasive grains, a water-soluble polymer, a basic compound, and water, and the water-soluble polymer includes a structural unit derived from styrene or a derivative thereof.
- the present invention relates to a composition for use.
- the present invention also relates to a method for producing the polishing composition and a method for polishing an object to be polished with a hard laser mark using the polishing composition.
- a polishing composition excellent in performance for eliminating the bulge at the periphery of the hard laser mark.
- the polishing composition of the present invention contains abrasive grains, a water-soluble polymer, a basic compound, and water, and the water-soluble polymer contains a structural unit derived from styrene or a derivative thereof.
- polishing composition of the present invention it is possible to effectively eliminate the bulge at the periphery of the hard laser mark.
- to eliminate the protrusion of the peripheral edge of the hard laser mark means to reduce the height of the protrusion on the peripheral edge of the hard laser mark of the silicon wafer.
- the height of the protrusion on the periphery of the hard laser mark of the silicon wafer can be measured, for example, by the method described in Examples described later.
- the water-soluble polymer when a water-soluble polymer containing a structural unit derived from styrene or a derivative thereof described in the present invention is added, the water-soluble polymer suitably acts on the surface of the silicon wafer other than the raised portion, The etching rate of the silicon wafer or the mechanical polishing rate by the abrasive grains can be suppressed as compared with the case where the water-soluble polymer is not included. Thereby, it is considered that the difference in the polishing rate between the altered portion and the other wafer portions is reduced.
- the altered portion of the periphery of the hard laser mark and the other portions are polished at a polishing rate close to that, and the partial bulge can be eliminated.
- the polishing composition of the present invention contains abrasive grains, a water-soluble polymer, a basic compound, and water, and the water-soluble polymer contains a structural unit derived from styrene or a derivative thereof.
- the water-soluble polymer contains a structural unit derived from styrene or a derivative thereof.
- the polishing composition of the present invention contains abrasive grains.
- the abrasive grains contained in the polishing composition have an action of mechanically polishing the object to be polished.
- the abrasive used may be any of inorganic particles, organic particles, and organic-inorganic composite particles.
- the inorganic particles include particles made of metal oxides such as silica, alumina, ceria, titania, silicon nitride particles, silicon carbide particles, and boron nitride particles.
- Specific examples of the organic particles include polymethyl methacrylate (PMMA) particles.
- PMMA polymethyl methacrylate
- silica is preferable, and colloidal silica is particularly preferable.
- the lower limit of the average primary particle diameter of the abrasive grains is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more, and particularly preferably 30 nm or more.
- the upper limit of the average primary particle diameter of the abrasive grains is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.
- the polishing rate of the object to be polished by the polishing composition is further improved, and the occurrence of defects on the surface of the object to be polished after polishing with the polishing composition is further suppressed. be able to.
- the average primary particle diameter of an abrasive grain is calculated based on the specific surface area of the abrasive grain measured by BET method, for example.
- the lower limit of the average secondary particle diameter of the abrasive grains is preferably 15 nm or more, more preferably 30 nm or more, further preferably 50 nm or more, and particularly preferably 70 nm or more.
- the upper limit of the average secondary particle diameter of the abrasive grains is preferably 300 nm or less, more preferably 260 nm or less, and further preferably 220 nm or less. Within such a range, the polishing rate of the object to be polished by the polishing composition is further improved, and the occurrence of defects on the surface of the object to be polished after polishing with the polishing composition is further suppressed. be able to.
- the average secondary particle diameter of the secondary particles can be measured, for example, by a dynamic light scattering method.
- the content of abrasive grains in the polishing composition according to the present invention is not particularly limited. As will be described later, in the case of a polishing composition (typically a slurry-like polishing liquid, sometimes referred to as a working slurry or a polishing slurry) used for polishing a polishing object as it is as a polishing liquid.
- the content of the abrasive grains with respect to the polishing composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0.5% by mass or more. Is more preferable. By increasing the content of the abrasive grains, there is a tendency that higher bulge resolution is obtained.
- the content of abrasive grains is usually suitably 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less. Reducing the content of abrasive grains is also preferable from the viewpoint of economy.
- the polishing composition according to the present invention can exhibit practically sufficient uplifting properties even at such a low abrasive content.
- the content of abrasive grains is usually 30% by mass or less from the viewpoint of storage stability, filterability, and the like. It is suitable and it is more preferable that it is 15 mass% or less.
- the content of the abrasive is preferably 1% by mass or more, more preferably 5% by mass or more.
- the polishing composition according to the present invention contains water as a dispersion medium in order to disperse or dissolve each component. It is preferable that water does not contain impurities as much as possible from the viewpoint of inhibiting the contamination of the object to be cleaned and the action of other components.
- water for example, water having a total content of transition metal ions of 100 ppb or less is preferable.
- the purity of water can be increased by operations such as removal of impurity ions using an ion exchange resin, removal of foreign matters by a filter, distillation, and the like.
- the water for example, deionized water (ion exchange water), pure water, ultrapure water, distilled water, or the like is preferably used.
- the dispersion medium may be a mixed solvent of water and an organic solvent for dispersing or dissolving each component.
- organic solvent examples include acetone, acetonitrile, ethanol, methanol, isopropanol, glycerin, ethylene glycol, propylene glycol and the like, which are organic solvents miscible with water.
- these organic solvents may be used without being mixed with water, and each component may be dispersed or dissolved and then mixed with water. These organic solvents can be used alone or in combination of two or more.
- the polishing composition according to the present invention includes a water-soluble polymer, and the water-soluble polymer includes a structural unit derived from styrene or a derivative thereof.
- the water-soluble polymer that can be used in the present invention includes a structural unit derived from styrene or a derivative thereof, and thus is considered to act suitably on the surface of a silicon wafer. Accordingly, it is considered that the polishing rate of the silicon wafer can be reduced, the difference in the polishing rate with the altered portion around the periphery of the hard laser mark can be reduced, and the bulge can be eliminated.
- the water-soluble polymer that can be used in the present invention may be a polymer containing only a structural unit derived from styrene or a derivative thereof, a structural unit derived from styrene or a derivative thereof, and a structural unit derived from another monomer.
- the copolymer containing these may be sufficient.
- a copolymer containing a structural unit derived from the styrene or a derivative thereof and a structural unit derived from another monomer it is preferable because better uplifting properties can be obtained.
- water-soluble polymer containing only a structural unit derived from styrene or a derivative thereof examples include polystyrene sulfonic acid or a salt thereof, polyvinyl benzoic acid or a salt thereof, and a styrene-styrene sulfonic acid copolymer.
- a water-soluble polymer of a copolymer containing a structural unit derived from styrene or a derivative thereof and a structural unit derived from another monomer for example, a structural unit derived from styrene or a derivative thereof and a hydrophilic group
- a copolymer containing a structural unit derived from a monomer having a carboxy group or an acid anhydride group can be used.
- styrene-maleic acid copolymers examples include styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, styrene sulfonic acid-maleic acid copolymers, copolymers of styrene sulfonate and maleic acid, styrene- (meth)
- acrylic acid copolymers examples include acrylic acid copolymers, styrene sulfonic acid- (meth) acrylic acid copolymers, and copolymers of styrene sulfonate and (meth) acrylic acid.
- a styrene-maleic acid copolymer or a styrene-maleic anhydride copolymer can be preferably used, and a styrene-maleic anhydride copolymer can be more preferably used.
- the water-soluble polymer of the copolymer is suitable because it is easy to act on a silicon wafer because the hydrophobic group and the hydrophilic group are independent.
- the water-soluble polymer of the copolymer can be produced, for example, by radical copolymerization of styrene or a derivative thereof and other monomers.
- the copolymerization ratio of the structural unit derived from styrene or its derivative in the copolymer and the structural unit derived from the other monomer is not particularly limited, but from the viewpoint of hydrophilicity. Is preferably 1:10 or more, more preferably 1: 5 or more, and particularly preferably 1: 1 or more. Further, the copolymerization ratio is not particularly limited, but is preferably 10: 1 or less, more preferably 5: 1 or less, and particularly preferably 3: 1 or less, from the viewpoint of bulge resolution. preferable.
- the weight average molecular weight of the water-soluble polymer that can be used in the present invention is not particularly limited, but is preferably 3,000 or more, more preferably 4,000 or more, and particularly preferably 5,000 or more. preferable.
- the weight average molecular weight of the water-soluble polymer is not particularly limited, but is preferably 300,000 or less, more preferably 100,000 or less, and particularly preferably 30,000 or less.
- the weight average molecular weight of the water-soluble polymer increases, the coverage of the silicon wafer increases, and it is considered that the bulge elimination can be improved.
- the weight average molecular weight of the water-soluble polymer decreases, the number of water-soluble polymer chains that can act on the wafer increases and a denser protective film can be formed.
- the value measured by GPC method aqueous type, polyethylene oxide conversion
- the content of the water-soluble polymer is preferably 0.0001% by mass or more with respect to the polishing composition. More preferably, it is 001% by mass or more. By increasing the content of the water-soluble polymer, there is a tendency that higher bulge resolution can be obtained. Further, the content of the water-soluble polymer is usually suitably 0.1% by mass or less, more preferably 0.05% by mass or less. As the content of the water-soluble polymer in the polishing composition decreases, the decrease in the polishing rate is suppressed.
- the content of the water-soluble polymer is usually 1% by mass or less from the viewpoint of storage stability, filterability, and the like. It is suitable and it is more preferable that it is 0.5 mass% or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the water-soluble polymer is preferably 0.001% by mass or more, more preferably 0.01% by mass or more.
- the water-soluble polymer may be synthesized by a known method, or a commercially available product may be used.
- the polishing composition according to the present invention contains a basic compound.
- the basic compound refers to a compound having a function of increasing the pH of the composition when added to the polishing composition.
- the basic compound serves to chemically polish the surface to be polished, and can contribute to an improvement in the polishing rate.
- the basic compound can be useful for improving the dispersion stability of the polishing composition.
- an organic or inorganic basic compound containing nitrogen, an alkali metal or alkaline earth metal hydroxide, various carbonates or hydrogencarbonates, and the like can be used.
- alkali metal hydroxide, quaternary ammonium hydroxide or a salt thereof, ammonia, amine and the like can be mentioned.
- Specific examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide.
- Specific examples of the carbonate or bicarbonate include ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate and the like.
- quaternary ammonium hydroxide or a salt thereof examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like.
- amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- ( ⁇ -aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine , Piperazine hexahydrate, 1- (2-aminoethyl) piperazine, N-methylpiperazine, guanidine, azoles such as imidazole and triazole, and the like.
- Preferred basic compounds from the viewpoint of improving the polishing rate include ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogen carbonate, ammonium carbonate, potassium hydrogen carbonate, potassium carbonate, hydrogen carbonate.
- Sodium and sodium carbonate are mentioned. Of these, preferred are ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide and tetraethylammonium hydroxide. More preferred are potassium carbonate and tetramethylammonium hydroxide.
- Such basic compounds can be used singly or in combination of two or more. When using 2 or more types in combination, for example, a combination of potassium carbonate and tetramethylammonium hydroxide is preferable.
- the content of the basic compound with respect to the polishing composition is preferably 0.01% by mass from the viewpoint of promoting the polishing rate. As mentioned above, More preferably, it is 0.05 mass% or more, More preferably, it is 0.09 mass% or more. Stability can also be improved by increasing the content of the basic compound.
- the upper limit of the content of the basic compound is suitably 1% by mass or less, and preferably 0.5% by weight or less from the viewpoint of surface quality and the like.
- the said content refers to the total content of 2 or more types of basic compounds.
- the content of the basic compound is usually 10% by mass or less from the viewpoint of storage stability, filterability, and the like. Is suitable, and it is more preferable that it is 5 mass% or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the basic compound is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.9% by mass or more. It is.
- the polishing composition according to the present invention is a polishing composition (typically a silicon wafer) such as a chelating agent, a surfactant, an antiseptic and an antifungal agent, as long as the effects of the present invention are not significantly hindered.
- a known additive that can be used in the polishing composition used in the polishing step) may be further contained as necessary.
- Examples of chelating agents that may be included in the polishing composition include aminocarboxylic acid chelating agents and organic phosphonic acid chelating agents.
- Examples of aminocarboxylic acid chelating agents include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid sodium, nitrilotriacetic acid, nitrilotriacetic acid sodium, nitrilotriacetic acid ammonium, hydroxyethylethylenediaminetriacetic acid, hydroxyethylethylenediamine sodium triacetate, diethylenetriaminepentaacetic acid Diethylenetriamine sodium pentaacetate, triethylenetetramine hexaacetic acid and sodium triethylenetetramine hexaacetate.
- organic phosphonic acid chelating agents examples include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic).
- ethylenediaminetetrakis methylenephosphonic acid
- diethylenetriaminepenta methylenephosphonic acid
- diethylenetriaminepentaacetic acid are preferable.
- Particularly preferred chelating agents include ethylenediaminetetrakis (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid).
- a chelating agent can be used individually by 1 type or in combination of 2 or more types.
- the content of the chelating agent is preferably 0.0001% by mass or more, more preferably 0.001% by mass with respect to the polishing composition. % Or more, more preferably 0.005 mass% or more.
- the upper limit of the content of the chelating agent is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, and 0.15% by mass. % Or less is particularly preferable.
- the content of the chelating agent is usually 5% by mass or less from the viewpoint of storage stability, filterability, and the like. It is suitable, it is more preferable that it is 3 mass% or less, and it is especially preferable that it is 1.5 mass% or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the chelating agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more. is there.
- preservatives and fungicides examples include 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one. And the like, isothiazoline-based preservatives such as paraoxybenzoates, and phenoxyethanol. These antiseptics and fungicides may be used alone or in combination of two or more.
- the polishing composition according to the present invention is typically supplied to a polishing object in the form of a polishing liquid containing the polishing composition, and used for polishing the polishing object.
- the polishing composition according to the present invention may be used, for example, as a polishing liquid after being diluted (typically diluted with water), or may be used as a polishing liquid as it is. Good. That is, the concept of the polishing composition in the technology according to the present invention is used for polishing by diluting with a polishing composition (working slurry) that is supplied to a polishing object and used for polishing the polishing object. Both concentrates (working slurry stock solutions) are included.
- the concentration ratio of the concentrated liquid can be, for example, about 2 to 100 times on a volume basis, and usually about 5 to 50 times is appropriate.
- the pH of the polishing composition is typically 9.0 or higher, preferably 9.5 or higher, more preferably 10. It is 0 or more, more preferably 10.2 or more, for example 10.5 or more.
- the pH of the polishing liquid is suitably 12.0 or less and 11.8 or less from the viewpoint of preventing dissolution of the abrasive grains and suppressing a decrease in the mechanical polishing action by the abrasive grains. Preferably, it is 11.5 or less.
- the pH of the polishing composition is typically 9.5 or higher, preferably 10.0 or higher, more preferably 10.2 or more.
- the pH of the polishing composition is suitably 12.0 or less, and preferably 11.5 or less.
- the pH of the polishing composition was measured using a pH meter (for example, a glass electrode type hydrogen ion concentration indicator (Model No. F-23) manufactured by Horiba, Ltd.) and a standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C)) It can be grasped by putting the glass electrode into the polishing composition and measuring the value after 2 minutes or more has been stabilized.
- a pH meter for example, a glass electrode type hydrogen ion concentration indicator (Model No. F-23) manufactured by Horiba, Ltd.
- a standard buffer solution phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C)
- the present invention further provides a production method for producing the polishing composition.
- the manufacturing method of the polishing composition which concerns on this invention is not specifically limited. For example, it can be obtained by stirring and mixing abrasive grains, water-soluble polymer, basic compound and other additives as required. That is, one method for producing a polishing composition according to the present invention includes a step of stirring and mixing abrasive grains, a water-soluble polymer, and a basic compound in water, wherein the water-soluble polymer is styrene or It is a manufacturing method of polishing composition containing the structural unit derived from the derivative
- the temperature at the time of mixing is not particularly limited, but is preferably 10 to 40 ° C., and may be heated to increase the dissolution rate. Further, the mixing time is not particularly limited as long as uniform mixing can be performed.
- a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer is used.
- the aspect which mixes these components is not specifically limited, For example, all the components may be mixed at once and may be mixed in the order set suitably.
- the polishing composition according to the present invention can be used for polishing a polishing object, for example, in an embodiment including the following operations.
- a working slurry containing the polishing composition according to the present invention is prepared.
- the polishing composition is supplied to the object to be polished and polished by a conventional method.
- a polishing object is set in a general polishing apparatus, and the polishing composition is supplied to the surface (polishing object surface) of the polishing object through a polishing pad of the polishing apparatus.
- the polishing pad is pressed against the surface of the object to be polished, and both are relatively moved (for example, rotated). The polishing of the object to be polished is completed through this polishing step.
- the polishing pad used in the above polishing process is not particularly limited.
- any of polyurethane foam type, non-woven fabric type, suede type, those containing abrasive grains, and those not containing abrasive grains may be used.
- the polishing apparatus a double-side polishing apparatus that simultaneously polishes both surfaces of an object to be polished, or a single-side polishing apparatus that polishes only one surface of the object to be polished may be used.
- the above polishing composition may be used in a disposable form (so-called “flowing”) once used for polishing, or may be repeatedly used after circulation.
- a method of circulating and using the polishing composition there is a method of collecting a used polishing composition discharged from the polishing apparatus in a tank and supplying the recovered polishing composition to the polishing apparatus again. .
- the environmental load can be reduced by reducing the amount of the used polishing composition to be treated as a waste liquid, compared with the case of using the polishing composition by pouring.
- cost can be suppressed by reducing the usage-amount of polishing composition.
- the polishing composition according to the present invention is excellent in the performance (uplift-removing property) for eliminating the uplift of the peripheral edge of the hard laser mark. Taking advantage of such features, the polishing composition can be preferably applied to polishing a polishing object including a surface with a hard laser mark. That is, in one embodiment of the present invention, a method for polishing an object to be polished with a hard laser mark using the polishing composition according to the present invention is provided.
- the polishing object include a substrate on which an inorganic insulating film such as a silicon oxide film and a silicon nitride film is formed, a substrate on which a polycrystalline silicon film is formed, a silicon single crystal substrate (silicon wafer), and the like. .
- the polishing composition according to the present invention is suitable as a polishing composition for polishing a silicon wafer with a hard laser mark. Further, the polishing composition according to the present invention is suitable as a polishing composition used in a polishing process of a silicon wafer having a hard laser mark. It is desirable to eliminate the bulge around the hard laser mark at the beginning of the polishing process. For this reason, the polishing composition according to the present invention can be particularly preferably used in the first polishing step (primary polishing step) after applying the hard laser mark.
- the first polishing step is typically performed as a double-side polishing step in which both sides of a silicon wafer are simultaneously polished.
- the polishing composition according to the present invention can be preferably used in such a double-side polishing step.
- the present invention also improves the flatness of a silicon wafer with a hard laser mark using a polishing composition containing abrasive grains, a water-soluble polymer, a basic compound, and water.
- a polishing composition containing abrasive grains, a water-soluble polymer, a basic compound, and water.
- the water-soluble polymer includes a structural unit derived from styrene or a derivative thereof.
- the polishing composition according to the present invention can also be used for polishing a surface to be polished that does not have a hard laser mark.
- the present invention can be preferably applied to preliminary polishing of a lapped silicon wafer regardless of the presence or absence of a hard laser mark.
- polishing composition A1 The content of colloidal silica (average primary particle size 55 nm) is 9% by mass, the content of potassium carbonate (K 2 CO 3 ) is 1.7% by mass, and the content of tetramethylammonium hydroxide (TMAH) is 2.5%.
- % By mass, ethylenediaminetetrakis (methylenephosphonic acid) (EDTPO) content of 0.1% by mass, styrene-maleic anhydride copolymer (weight average molecular weight: 9,500, styrene / maleic anhydride (S / M)) 3/1)
- EDTPO ethylenediaminetetrakis
- S / M maleic anhydride
- the polishing composition A1 was prepared by stirring and mixing the above components and ion-exchanged water at a room temperature of about 25 ° C. for about 30 minutes so that the content was 0.01% by mass. .
- Polishing compositions A2 to A4, Polishing compositions C1 to C4 were the same as the polishing composition A1, except that the type or content of the water-soluble polymer was changed as shown in Table 1.
- ⁇ C4 was prepared.
- Each polishing composition was diluted 10 times with water, and the diluted liquid was used as a polishing
- Examples 1-4 and Comparative Examples 1 to 4 were used.
- a commercially available silicon etched wafer (Bare Si P- ⁇ 100>, thickness: 545 ⁇ m) having a diameter of 4 inches (100 mm) after lapping was used.
- a hard laser mark based on the SEMI M1 (T7) standard is imprinted on the polished surface.
- Polishing machine Nippon Engis Co., Ltd. single-side polishing machine, model “EJ-380IN” Polishing pressure: 12.0kPa Slurry flow rate: 100 ml / min Plate rotation speed: 50 rpm Head rotation speed: 40rpm Polishing amount: 3.5 ⁇ m Polishing pad: Nitta Haas Co., Ltd., trade name “MH-S15A” Polishing environment temperature: 20 ° C Polishing time: 20 minutes ⁇ Uplift elimination evaluation> About the silicon wafer after grinding
- the results obtained by the above measurement are shown in Table 1.
- polishing compositions of the present invention in Examples 1 to 4 all showed good bulge resolution.
- polishing compositions containing a water-soluble polymer having a structural unit derived from styrene or a derivative thereof according to an example using a styrene-maleic anhydride copolymer, higher bulge resolving properties were obtained.
- Comparative Example 1 in which a water-soluble polymer having a structural unit derived from styrene or a derivative thereof was not added was inferior to the bulge-removing property as compared with Examples.
- Comparative Examples 2 to 4 another water-soluble polymer was added in place of the water-soluble polymer having a structural unit derived from styrene or a derivative thereof, but the bulge-removability was lower than that of the example. This is because when the copolymer having a structural unit derived from styrene is not included, the polishing rate of the silicon wafer is higher than the polishing rate of the denatured portion at the periphery of the hard laser mark, both compared with the polishing composition of the example. This is thought to be due to the widening of the height difference.
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Abstract
Description
本発明の研磨用組成物は、砥粒を含む。研磨用組成物中に含まれる砥粒は、研磨対象物を機械的に研磨する作用を有する。
本発明に係る研磨用組成物は、各成分を分散または溶解するために分散媒として水を含む。水は、洗浄対象物の汚染や他の成分の作用を阻害するという観点から、不純物をできる限り含有しないことが好ましい。このような水としては、例えば、遷移金属イオンの合計含有量が100ppb以下である水が好ましい。ここで、水の純度は、例えば、イオン交換樹脂を用いる不純物イオンの除去、フィルタによる異物の除去、蒸留等の操作によって高めることができる。具体的には、水としては、例えば、脱イオン水(イオン交換水)、純水、超純水、蒸留水などを用いることが好ましい。
本発明に係る研磨用組成物は、水溶性高分子を含み、前記水溶性高分子は、スチレンまたはその誘導体由来の構造単位を含む。本発明に使用できる水溶性高分子は、スチレンまたはその誘導体由来の構造単位を含むため、シリコンウェーハ表面に好適に作用すると考えられる。これにより、シリコンウェーハの研磨速度を低下させ、ハードレーザーマーク周縁の変質部分との研磨速度の差を減少し隆起を解消できると考えられる。
本発明に係る研磨用組成物は、塩基性化合物を含む。ここで塩基性化合物とは、研磨用組成物に添加されることによって該組成物のpHを上昇させる機能を有する化合物を指す。塩基性化合物は、研磨対象となる面を化学的に研磨する働きをし、研磨速度の向上に寄与し得る。また、塩基性化合物は、研磨用組成物の分散安定性の向上に役立ち得る。
本発明に係る研磨用組成物は、本発明の効果が著しく妨げられない範囲で、キレート剤、界面活性剤、防腐剤、防カビ剤等の、研磨用組成物(典型的には、シリコンウェーハのポリシング工程に用いられる研磨用組成物)に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。
本発明に係る研磨用組成物は、典型的には該研磨用組成物を含む研磨液の形態で研磨対象物に供給されて、その研磨対象物の研磨に用いられる。本発明に係る研磨用組成物は、例えば、希釈(典型的には、水により希釈)して研磨液として使用されるものであってもよく、そのまま研磨液として使用されるものであってもよい。すなわち、本発明に係る技術における研磨用組成物の概念には、研磨対象物に供給されて該研磨対象物の研磨に用いられる研磨用組成物(ワーキングスラリー)と、希釈して研磨に用いられる濃縮液(ワーキングスラリーの原液)との双方が包含される。上記濃縮液の濃縮倍率は、例えば、体積基準で2倍~100倍程度とすることができ、通常は5倍~50倍程度が適当である。
本発明において、さらに、前記研磨用組成物を製造する、製造方法を提供する。本発明に係る研磨用組成物の製造方法は特に限定されない。例えば、砥粒、水溶性高分子、塩基性化合物および必要に応じて他の添加剤を、水中で攪拌混合することにより得ることができる。すなわち、本発明に係る研磨用組成物の一製造方法は、砥粒と、水溶性高分子と、塩基性化合物とを、水中で攪拌混合する工程を含み、前記水溶性高分子は、スチレンまたはその誘導体由来の構造単位を含む、研磨用組成物の製造方法である。混合する際の温度は特に制限されないが、10~40℃が好ましく、溶解速度を上げるために加熱してもよい。また、混合時間も、均一混合できれば特に制限されない。撹拌装置としては、例えば、翼式攪拌機、超音波分散機、ホモミキサー等の周知の混合装置が用いられる。これらの成分を混合する態様は特に限定されず、例えば全成分を一度に混合してもよく、適宜設定した順序で混合してもよい。
本発明に係る研磨用組成物は、例えば以下の操作を含む態様で、研磨対象物の研磨に使用することができる。
本発明に係る研磨用組成物は、ハードレーザーマーク周縁の隆起を解消する性能(隆起解消性)に優れる。かかる特長を活かして、上記研磨用組成物は、ハードレーザーマークの付された表面を含む研磨対象物の研磨に好ましく適用することができる。すなわち、本発明の一実施形態においては、本発明に係る研磨用組成物を使用してハードレーザーマークの付された研磨対象物を研磨する方法が提供される。また、前記研磨対象物としては、酸化ケイ素膜、窒化ケイ素膜等の無機絶縁膜が形成された基板、多結晶シリコン膜が形成された基板、およびシリコン単結晶基板(シリコンウェーハ)等が挙げられる。これらのうち、シリコンウェーハであることが好ましい。すなわち、本発明に係る研磨用組成物は、ハードレーザーマークの付されたシリコンウェーハを研磨する研磨用組成物として好適である。また、本発明に係る研磨用組成物は、ハードレーザーマークの付されたシリコンウェーハのポリシング工程において用いられる研磨用組成物として好適である。ハードレーザーマーク周縁の隆起は、ポリシング工程の初期に解消しておくことが望ましい。このため、本発明に係る研磨用組成物は、ハードレーザーマーク付与後の最初のポリシング工程(1次研磨工程)において特に好ましく使用され得る。上記最初のポリシング工程は、典型的には、シリコンウェーハの両面を同時に研磨する両面研磨工程として実施される。本発明に係る研磨用組成物は、このような両面研磨工程において好ましく使用され得る。
(研磨用組成物A1)
コロイダルシリカ(平均一次粒子径55nm)の含有量が9質量%、炭酸カリウム(K2CO3)の含有量が1.7質量%、水酸化テトラメチルアンモニウム(TMAH)の含有量が2.5質量%、エチレンジアミンテトラキス(メチレンホスホン酸)(EDTPO)の含有量が0.1質量%、スチレン-無水マレイン酸共重合体(重量平均分子量:9,500、スチレン/無水マレイン酸(S/M)=3/1)の含有量が0.01質量%になるように、前記各成分およびイオン交換水を、室温25℃程度で約30分間攪拌混合することにより、研磨用組成物A1を調製した。
水溶性高分子の種類または含有量を表1の記載になるように変えたこと以外は、前記研磨用組成物A1と同様な方法で、研磨用組成物A2~A4、および研磨用組成物C1~C4を調製した。
・スチレン-無水マレイン酸共重合体(Mw=9,500 S/M=3/1)
・スチレン-無水マレイン酸共重合体(Mw=9,500 S/M=3/1)
・スチレン-無水マレイン酸共重合体(Mw=5,500 S/M=1/1)
・ポリスチレンスルホン酸ナトリウム(Mw=20,000)
・ポリメチルビニルエーテル-無水マレイン酸共重合体(Mw=200,000 Me/M=1/1)
・ヒドロキシエチルセルロース(Mw=250,000)
・ポリビニルアルコール(Mw=10,000)
<シリコンウェーハの研磨>
各研磨用組成物を水で10倍希釈し、希釈液を研磨液(ワーキングスラリー)として使用して、研磨対象物(試験片)の表面を下記の条件で研磨し、実施例1~4および比較例1~4とした。試験片としては、ラッピングを終えた直径4インチ(100mm)の市販シリコンエッチドウェーハ(Bare Si P-<100>、厚み:545μm)を使用した。本ウェーハには、SEMI M1(T7)規格に基づくハードレーザーマークが研磨面に刻印されている。
研磨装置:日本エンギス株式会社製 片面研磨機、型式「EJ-380IN」
研磨圧力:12.0kPa
スラリー流量:100ml/min
定盤回転数:50rpm
ヘッド回転数:40rpm
研磨量:3.5μm
研磨パッド:ニッタ・ハース株式会社製、商品名「MH-S15A」
研磨環境の温度:20℃
研磨時間:20分
<隆起解消性評価>
研磨後のシリコンウェーハについて、SURFCOM 1500DX(株式会社東京精密製)を用いて隆起の高さを測定し、隆起解消性を評価した。具体的には、シリコンウェーハの周縁部に直接針を走らせて突起高さを確認し、隆起がない部分との段差(=突起高さ)を算出した。突起高さが大きいほど、隆起解消性が悪いとの評価結果になる。以上の測定により得られた結果を表1に示した。
Claims (7)
- 砥粒と、水溶性高分子と、塩基性化合物と、水と、を含み、前記水溶性高分子は、スチレンまたはその誘導体由来の構造単位を含む、研磨用組成物。
- 前記水溶性高分子は、前記スチレンまたはその誘導体由来の構造単位と、それ以外の単量体由来の構造単位とを含む共重合体である、請求項1に記載の研磨用組成物。
- 前記それ以外の単量体は、カルボキシ基または酸無水物基を有する単量体である、請求項2に記載の研磨用組成物。
- 前記水溶性高分子は、スチレン-無水マレイン酸共重合体またはスチレン-マレイン酸共重合体である、請求項1~3のいずれか1項に記載の研磨用組成物。
- 砥粒と、水溶性高分子と、塩基性化合物とを、水中で攪拌混合する工程を含み、前記水溶性高分子は、スチレンまたはその誘導体由来の構造単位を含む、研磨用組成物の製造方法。
- ハードレーザーマークの付された研磨対象物の研磨に用いられる、請求項1~4のいずれか1項に記載の研磨用組成物。
- 請求項1~4のいずれか1項に記載の研磨用組成物を用いて、ハードレーザーマークの付された研磨対象物を研磨する方法。
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JPWO2020196370A1 (ja) * | 2019-03-26 | 2020-10-01 | ||
WO2021061510A1 (en) * | 2019-09-24 | 2021-04-01 | Fujifilm Electronic Materials U.S.A., Inc. | Polishing compositions and methods of use thereof |
JP2022040139A (ja) * | 2017-09-29 | 2022-03-10 | 昭和電工マテリアルズ株式会社 | 研磨液、研磨液セット及び研磨方法 |
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KR20190120192A (ko) | 2019-10-23 |
CN110312776A (zh) | 2019-10-08 |
KR102575250B1 (ko) | 2023-09-06 |
EP3584298A4 (en) | 2020-07-08 |
TW201835285A (zh) | 2018-10-01 |
EP3584298A1 (en) | 2019-12-25 |
TWI767993B (zh) | 2022-06-21 |
EP3584298B1 (en) | 2022-12-28 |
CN110312776B (zh) | 2021-11-30 |
JPWO2018150856A1 (ja) | 2019-12-26 |
JP7208019B2 (ja) | 2023-01-18 |
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