WO2022074835A1 - Polishing of silicon substrate - Google Patents

Polishing of silicon substrate Download PDF

Info

Publication number
WO2022074835A1
WO2022074835A1 PCT/JP2020/038345 JP2020038345W WO2022074835A1 WO 2022074835 A1 WO2022074835 A1 WO 2022074835A1 JP 2020038345 W JP2020038345 W JP 2020038345W WO 2022074835 A1 WO2022074835 A1 WO 2022074835A1
Authority
WO
WIPO (PCT)
Prior art keywords
polishing
component
less
liquid composition
finish
Prior art date
Application number
PCT/JP2020/038345
Other languages
French (fr)
Japanese (ja)
Inventor
三浦穣史
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN202080104227.4A priority Critical patent/CN116034149A/en
Priority to PCT/JP2020/038345 priority patent/WO2022074835A1/en
Priority to JP2022555239A priority patent/JPWO2022074835A1/ja
Priority to KR1020237005732A priority patent/KR20230082605A/en
Priority to TW110137561A priority patent/TW202221099A/en
Publication of WO2022074835A1 publication Critical patent/WO2022074835A1/en

Links

Classifications

    • 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
    • C09G1/06—Other polishing compositions
    • C09G1/14—Other polishing compositions based on non-waxy substances
    • C09G1/16—Other polishing compositions based on non-waxy substances on natural or synthetic resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02013—Grinding, lapping
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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

  • This disclosure relates to the polishing of a silicon substrate, the polishing speed of the silicon substrate, and the method of adjusting the surface quality of the substrate after polishing.
  • the silicon substrate is polished in multiple stages.
  • finish polishing which is performed at the final stage of polishing, suppresses surface roughness (haze) and improves the wettability (hydrophilization) of the silicon substrate surface after polishing, resulting in surface defects (LPD: Light point) such as particles, scratches, and pits. It is done for the purpose of suppressing defects).
  • LPD Light point
  • the size of surface defects allowed on the surface of a silicon substrate is decreasing year by year, and these defects are usually measured by irradiating the surface of the substrate with laser light and detecting the scattered light at that time. Therefore, in order to measure finer defects, it is necessary to reduce the surface roughness (haze) of the silicon substrate and improve the S / N ratio at the time of defect measurement.
  • a polishing liquid composition used for finish polishing a polishing liquid composition for chemical mechanical polishing using colloidal silica and an alkaline compound is known.
  • Japanese Patent Application Laid-Open No. 2004-128089 reports a polishing liquid composition containing a water-soluble polymer compound such as hydroxyethyl cellulose or polyethylene oxide as a polishing liquid composition for the purpose of improving the haze level.
  • Japanese Patent Application Laid-Open No. 2008-53415 describes a water-soluble polymer having a nitrogen-containing group such as polyvinylpyrrolidone and polyN-vinylformamide as a polishing liquid composition for the purpose of reducing the number of surface defects (LPD). Abrasive liquid compositions containing compounds have been reported.
  • Japanese Patent Application Laid-Open No. 2015-185672 proposes a method for polishing a silicon substrate, which defines the relationship between the product concentration of the water-soluble polymer concentration and the weight average molecular weight of each polishing slurry used in a multi-step polishing step. ing.
  • Japanese Unexamined Patent Publication No. 2015-185674 proposes a method for polishing a silicon substrate, which defines the relationship between the concentration of the abrasive grains of each polishing slurry used in the multi-step polishing step and the value of the volume average particle diameter.
  • 2016-4953 proposes a method for polishing a silicon substrate, which defines the relationship of relative haze of each polishing slurry used in a two-step polishing step.
  • Japanese Patent Application Laid-Open No. 2017-183478 describes the hydrophilicity parameters of the polishing liquid composition used in the pre-polishing step and the rinsing agent used in the rinsing step in the polishing method performed in the order of the pre-polishing step, the rinsing step, and the finish polishing step.
  • a method for polishing a silicon substrate that defines the relationship between hydrophilicity parameters has been proposed.
  • 2017/161954 defines the values of the hydrophilicity parameter and the finish accuracy parameter of the polishing liquid composition used in the pre-polishing process, and the value of the polishing processability parameter of the polishing liquid composition used in the finish polishing process for polishing.
  • a composition set has been proposed. Hydroxyethyl cellulose and polyvinylpyrrolidone are used as the water-soluble polymers of the polishing liquid compositions described in the above five documents.
  • the present disclosure is at least one selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less in one embodiment.
  • a method for adjusting the polishing speed of a silicon substrate and the surface quality of the polished substrate by changing the content ratio of the component A and the component B using the polishing liquid composition containing the above-mentioned components hereinafter, “the present disclosure”). Also referred to as “adjustment method”).
  • the present disclosure comprises, in one embodiment, a finish polishing step 2 for performing a finish polishing of a silicon substrate, and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2, the finish polishing step 1 and the finishing.
  • the polishing step 2 is a method for polishing a silicon substrate in this order, and the polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble substance having a pKa of 5 or more and 8.5 or less. It contains at least one component selected from the group consisting of a polymer compound (component A) and a nonionic water-soluble polymer compound (component B), and in the finish polishing step 1, the polishing liquid composition contains silica particles (components).
  • the present invention relates to a method for polishing a silicon substrate (hereinafter, also referred to as “the polishing method of the present disclosure”) for polishing with a polishing liquid composition in which the ratio of the content of component B to the total content is 50% by mass or more.
  • the present disclosure relates to, in one aspect, a method for manufacturing a semiconductor substrate, which comprises performing the adjusting method of the present disclosure or the polishing method of the present disclosure.
  • colloidal silica having a smaller particle size is used as the polishing liquid used for finish polishing, and the polishing speed tends to be slow, and there is a problem in improving the polishing speed.
  • the polishing speed is sufficient in the polishing using the polishing liquid compositions of JP-A-2004-128089 and JP-A-2008-53415.
  • the silicon substrates of JP-A-2015-185672, JP-A-2015-185674, JP-A-2016-4953, JP-A-2017-183478, and International Publication No. 2017/169154 are used in multiple stages. All of the polishing methods to be performed are aimed at achieving a high-quality polished surface such as improvement of surface smoothness and suppression of generation of minute defects, and there is no mention of polishing speed.
  • the present disclosure provides a method capable of adjusting the polishing speed of a silicon substrate and the surface quality of the substrate after polishing.
  • the polishing speed and the surface quality of the substrate after polishing (for example, the surface roughness (haze) of the substrate) can be improved.
  • the details of the effect manifestation mechanism of the present disclosure are not clear, but it is inferred as follows.
  • the amino group-containing water-soluble polymer (component A) having a pKa of 5 or more and 8.5 or less has low cationicity, and has an electrostatic interaction with the amino group on the silica particles (component C) and the silicon substrate to be polished. Rather, it suppresses the electrostatic repulsive force between the silica abrasive grains and the silicon substrate by adsorbing with the van der Waals force of the whole molecule as the main factor.
  • the nonionic water-soluble polymer (component B) is adsorbed on the surface of the silicon substrate, and hydrophilic groups such as alkylene oxides and hydroxyl groups overhang on the surface of the silicon substrate, thereby suppressing excessive corrosion by alkali and approaching silica abrasive grains. That is, it has the effect of improving the surface quality of the substrate after polishing (for example, reducing haze).
  • both components are adsorbed by van der Waals force as the main factor, and since the adsorption force is considered to be about the same, it does not interfere with the adsorption of each other and depends on the ratio of component A and component B in the polishing liquid. Then, it is adsorbed on the silica particles (component C) and the silicon substrate to be polished.
  • the effect of the component A depends on the ratio of the adsorption amount, that is, the ratio of the component A and the component B, without impairing the effect of improving the polishing rate of the component A and the effect of improving the surface quality of the component B. It is considered that the effect of component B can be exhibited and the polishing speed and surface quality of the substrate can be freely adjusted.
  • the present disclosure may not be construed as being limited to these mechanisms.
  • the polishing in the adjusting method or polishing method of the present disclosure is, in one or more embodiments, polishing of a silicon substrate, and in one or more embodiments, polishing of a silicon substrate to be polished in a method of manufacturing a semiconductor substrate.
  • Examples of the silicon substrate to be polished in the adjusting method or polishing method of the present disclosure include a silicon substrate and the like in one or more embodiments, and a single crystal silicon substrate in one or more embodiments.
  • the polishing liquid composition in the adjusting method or polishing method of the present disclosure (hereinafter, also referred to as “polishing liquid composition of the present disclosure”) is an amino group-containing water-soluble polymer compound having a pKa of 5 or more and 8.5 or less (hereinafter, also referred to as “polishing liquid composition of the present disclosure”). It contains at least one component selected from the group consisting of component A) and a nonionic water-soluble polymer compound (component B).
  • the polishing liquid composition of the present disclosure may contain polishing abrasive grains, if necessary.
  • the abrasive grains include, in one or more embodiments, silica particles.
  • the polishing liquid composition of the "finish polishing step 1" in the polishing method of the present disclosure preferably contains polishing abrasive grains from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing.
  • the polishing liquid composition of the "finish polishing step 2" in the polishing method of the present disclosure may or may not contain polishing abrasive grains.
  • the improvement of the surface quality of the polished substrate is the reduction of the surface roughness (haze) of the polished substrate in one or more embodiments.
  • the polishing liquid composition of the present disclosure may contain an amino group-containing water-soluble polymer (hereinafter, also referred to as “component A”) having a pKa of 5 or more and 8.5 or less.
  • component A an amino group-containing water-soluble polymer having a pKa of 5 or more and 8.5 or less.
  • the component A can exert the effect of suppressing the aggregation of the abrasive grains and improving the polishing rate.
  • water-soluble means having a solubility of 0.5 g / 100 mL or more, preferably 2 g / 100 mL or more, in water (20 ° C.).
  • the pKa of the component A is 5 or more, preferably 5.5 or more, more preferably 5.9 or more, further preferably 6.3 or more, still more preferably 6.8 or more, from the viewpoint of improving the polishing rate. , 7.3 or more is more preferable, 7.5 or more is further preferable, 7.7 or more is further preferable, and from the viewpoint of improving the surface quality, 8.5 or less and 8.3 or less are preferable. 8.1 or less is more preferable, and 8 or less is further preferable.
  • the pKa of the component A is preferably in the above range.
  • the pKa of the component A is more preferably 6.6 or more, further preferably 6.9 or more, still more preferably 7.1 or more, from the viewpoint of improving the polishing speed. From the viewpoint of improving the surface quality, 7.8 or less is further preferable, 7.6 or less is further preferable, and 7.4 or less is further preferable.
  • the component A preferably contains a structural unit derived from one or more monomers selected from allylamine and diallylamine from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • the component A is preferably an amino group-containing water-soluble polymer (hereinafter, also referred to as “component A1”) containing a structural unit derived from allylamine in one or more embodiments.
  • component A1 amino group-containing water-soluble polymer
  • the amino group containing a structural unit derived from diallylamine is a water-soluble polymer (hereinafter, also referred to as “component A2”).
  • Component A1 Amino group-containing water-soluble polymer containing a structural unit derived from allylamine
  • At least a part of the amino groups in the allylamine-derived structural unit has a steric shielding group in one or more embodiments from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing, and from the viewpoint of availability. Is preferable.
  • the steric shielding group refers to a steric (bulky) substituent capable of shielding the nitrogen atom of the amino group of the component A to suppress cationization, that is, lowering pKa.
  • the amino group having a steric shielding group is preferably a secondary amino group or a tertiary amino group containing a hydrocarbon group having a hydroxyl group and having 3 or more carbon atoms and 11 or less carbon atoms.
  • the number of carbon atoms of the hydrocarbon group is 3 from the viewpoint of improving the shielding property of the amino group (suppressing the cationization of the nitrogen atom of the amino group) and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • the above is preferable, and from the viewpoint of improving water solubility and availability, 11 or less is preferable, 7 or less is more preferable, 5 or less is further preferable, and 4 or less is further preferable.
  • the amino group having a steric shielding group is, in one or more embodiments, a modifying group with a glycidole derivative to the amino group, and in one or more embodiments, the amino group and the glycidol derivative in the allylamine-derived structural unit. Is a group formed by the reaction. At least a part of the amino groups of the total amino group of the component A1 is modified by the glycidol derivative to become an amino group having a steric shielding group.
  • the equivalent of the glycidol derivative to the number of amino groups (1 equivalent) in the allylamine-derived structural unit (hereinafter, also referred to as "glycidol modification rate”) is 0.3 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • 0.5 or more is more preferable, 0.8 or more is further preferable, 1 or more is further preferable, 1.3 or more is further preferable, 1.5 or more is further preferable, 1.7 or more is further preferable, and From the viewpoint of improving the polishing speed, 4 or less is preferable, 3 or less is more preferable, 2.5 or less is further preferable, and 2 or less is further preferable.
  • the glycidol modification rate is a value measured by the method described in Examples using 13 C-NMR.
  • the glycidol modification rate can also be measured by the following method (1) or (2).
  • (1) It can be obtained from the amino group equivalent of the allylamine polymer used as the reaction raw material and the number of moles of the glycidol derivative.
  • (2) The nitrogen content N (mass%) of the reaction product of the glycidol derivative and the allylamine polymer can be measured and calculated from the following formula.
  • Glycidol denaturation rate A / B
  • A (100-N ⁇ molecular weight of allylamine polymer / 14) / glycidol derivative molecular weight
  • B N / 14.
  • Examples of the glycidol derivative include glycidol, alkylglycidyl ether, and the like, and glycidol is preferable from the viewpoint of availability and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • the alkyl group of the alkylglycidyl ether is preferably an alkyl group having 1 to 8 carbon atoms from the viewpoint of availability, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a 2-ethylhexyl group.
  • Examples of the alkyl glycidyl ether include methyl glycidyl ether and 2-ethylhexyl glycidyl ether.
  • the component A1 includes polyallylamine in which at least a part of the amino groups has a steric shielding group in one or more embodiments, and a reaction product of polyallylamine and a glycidol derivative in one or more embodiments. Be done.
  • component A1 examples include a compound (glycidol-modified polyallylamine) containing the structural unit of the following formula (I) in one or more embodiments.
  • R 1 and R 2 are hydrogen atoms or steric shielding groups, respectively.
  • the steric shielding group include a modifying group derived from a glycidol derivative, and in one or more embodiments, a 1-molar adduct or a 2-molar adduct of glycidol can be mentioned, and in one or more embodiments, -CH 2 CH (OH) CH 2 (OH), ⁇ CH 2 CH (OH) CH 2 O—CH 2 CH (OH) CH 2 (OH) and the like can be mentioned.
  • Component A2 Amino group-containing water-soluble polymer containing a structural unit derived from diallylamine
  • At least a part of the amino group in the constituent unit derived from diallylamine is an electron-withdrawing group at the ⁇ -position or the ⁇ -position of the amino group from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing in one or more embodiments. It is preferable to have.
  • the electron-withdrawing group include a group represented by the following formula (II).
  • Examples of the component A2 include compounds containing a structural unit derived from diallylamine and a structural unit derived from sulfur dioxide in one or more embodiments, and examples thereof include a compound containing a structural unit represented by the following formula (III). Be done.
  • Examples of the component A2 include compounds containing a structural unit represented by the following formula (IV) in one or more embodiments, and examples thereof include a methyldiallylamine / sulfur dioxide copolymer.
  • the weight average molecular weight of the component A is preferably 800 or more, more preferably 1,000 or more, further preferably 1,500 or more, further preferably 2,000 or more, and the polishing rate. From the viewpoint of adjusting the surface quality of the substrate after polishing, 100,000 or less is preferable, 50,000 or less is more preferable, 30,000 or less is further preferable, 20,000 or less is further preferable, and 15,000 or less is further preferable. , 12,000 or less is more preferable.
  • the weight average molecular weight of component A in the present disclosure can be measured, for example, by the method described in Examples.
  • the weight average molecular weight of the component A is preferably 800 or more, more preferably 1,000 or more, further preferably 1,500 or more, and further preferably 2,000 or more from the viewpoint of improving the polishing rate.
  • 3,000 or more is preferable
  • 5,000 or more is more preferable
  • 6,000 or more is further preferable
  • 100,000 or less is preferable from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing.
  • 50,000 or less is more preferable, 30,000 or less is further preferable, 20,000 or less is further preferable, 15,000 or less is further preferable, and 12,000 or less is further preferable.
  • the weight average molecular weight of the component A is preferably 800 or more, more preferably 1,000 or more, further preferably 1,500 or more, and further preferably 2,000 or more from the viewpoint of improving the polishing rate.
  • 100,000 or less is preferable, 50,000 or less is more preferable, 30,000 or less is further preferable, and 20,000 or less is further preferable.
  • 15,000 or less is further preferable, 12,000 or less is further preferable, 10,000 or less is further preferable, 7,000 or less is further preferable, 5,000 or less is further preferable, and 4,000 or less is further preferable.
  • the content of component A in the polishing liquid composition of the present disclosure is 10% by mass or more, 20% by mass or more, or 20% by mass or more in one or more embodiments from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. 30 mass ppm or more, and from the same viewpoint, in one or more embodiments, 200 mass ppm or less, 150 mass ppm or less, or 120 mass ppm or less. In the present disclosure, 1% by mass is 10,000% by mass (the same applies hereinafter).
  • the polishing liquid composition of the present disclosure may contain a nonionic water-soluble polymer (hereinafter, also referred to as “component B”) from the viewpoint of improving the surface quality of the substrate after polishing. ..
  • component B is preferably a nonionic water-soluble polymer having an alkylene oxide group, a hydroxyl group, or an amide group in the molecule. Examples of the alkylene oxide group include an ethylene oxide group and a propylene oxide group.
  • the component B may be one kind or a combination of two or more kinds.
  • the component B includes polyglycerin, polyglycerin alkyl ether, polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethyl acrylamide, and polyhydroxyethyl acrylamide from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. At least one selected from polyethylene glycols having a weight average molecular weight of 300 or more and 1,000 or less can be mentioned.
  • the alkyl group of the polyglycerin alkyl ether is preferably an alkyl group having 3 or more and 22 or less carbon atoms, preferably 5 carbon atoms, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing and suppressing foaming of the polishing liquid.
  • Alkyl groups having 16 or more carbon atoms are more preferable, and alkyl groups having 7 or more carbon atoms and 12 or less carbon atoms are further preferable.
  • the alkyl group may be a linear alkyl group or a branched chain alkyl group.
  • the average degree of polymerization of the polyglycerin alkyl ether in units of glycerin is 5 or more, preferably 10 or more, more preferably 15 or more, further preferably 18 or more, and the polishing rate and after polishing. From the viewpoint of adjusting the surface quality of the substrate, it is 100 or less, preferably 60 or less, more preferably 45 or less, still more preferably 25 or less.
  • the polyglycerin alkyl ether include polyglycerin lauryl ether, polyglycerin decyl ether, and polyglycerin myristyl ether.
  • the alkyl group of the polyglycerin alkyl ester is preferably an alkyl group having 3 or more and 22 or less carbon atoms, preferably 5 carbon atoms, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing and suppressing foaming of the polishing liquid.
  • Alkyl groups having 16 or more carbon atoms are more preferable, and alkyl groups having 7 or more carbon atoms and 12 or less carbon atoms are further preferable.
  • the alkyl group may be a linear alkyl group or a branched chain alkyl group.
  • the average degree of polymerization of the polyglycerin alkyl ester in units of glycerin is 5 or more, preferably 10 or more, more preferably 15 or more, further preferably 18 or more, and the polishing rate and after polishing. From the viewpoint of adjusting the surface quality of the substrate, it is 100 or less, preferably 60 or less, more preferably 45 or less, still more preferably 25 or less.
  • the polyglycerin alkyl ester include polyglycerin lauryl ester, polyglycerin decyl ester, and polyglycerin myristyl ester.
  • the hydroxyalkyl cellulose is preferably at least one selected from hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, and hydroxybutyl cellulose from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing, and hydroxyethyl cellulose (HEC) is preferable. More preferred.
  • component B is polyglycerin, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hydroxyethyl cellulose (HEC), and has a weight average molecular weight of 300 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. At least one selected from 1,000 or less polyethylene glycol (PEG) is preferable, and polyglycerin is more preferable.
  • the weight average molecular weight of the component B is preferably 300 or more, more preferably 500 or more, further preferably 1,000 or more, still more preferably 1,500 or more, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. More than 2,000 is more preferable, and from the same viewpoint and the filterability of the polishing liquid, less than 500,000 is preferable, 400,000 or less is more preferable, 300,000 or less is further preferable, and 150,000 or less is further preferable. 100,000 or less is further preferable, 50,000 or less is further preferable, 20,000 or less is further preferable, and 10,000 or less is further preferable.
  • the weight average molecular weight of the component B is preferably 1,000 or more, more preferably 1,500 or more, further preferably 2,000 or more, and 10,000 or less from the same viewpoint. It is preferable, 8000 or less is more preferable, and 6000 or less is further preferable.
  • the weight average molecular weight of the component B is preferably 5,000 or more, more preferably 10,000 or more, further preferably 20,000 or more, and more preferably 20,000 or more, from the same viewpoint. It is preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less.
  • the weight average molecular weight of the component B is preferably 5,000 or more, more preferably 10,000 or more, further preferably 20,000 or more, and preferably 150,000 or less, from the same viewpoint. 120,000 or less is more preferable, and 100,000 or less is further preferable.
  • the component B is hydroxyethyl cellulose (HEC)
  • the weight average molecular weight of the component B is preferably 50,000 or more, more preferably 100,000 or more, further preferably 150,000 or more, and 500,000 or less from the same viewpoint. Is preferable, 400,000 or less is more preferable, and 300,000 or less is further preferable.
  • the weight average molecular weight of the component B is preferably 500 or more, preferably 900 or less, and 800 or less from the same viewpoint. Is more preferable.
  • the weight average molecular weight of component B can be measured by the method described in a later example.
  • the content of component B in the polishing liquid composition of the present disclosure is 0% by mass or more, 2% by mass or more, and 10 in one or more embodiments from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • Mass ppm or more 20 mass ppm or more, 30 mass ppm or more, 50 mass ppm or more, or 100 mass ppm or more, and 1,000 mass ppm or less, 500 mass ppm or less, 300 mass ppm or less, or 200 mass ppm or more.
  • the content of the component B means the total content thereof.
  • the total content of the component A and the component B in the polishing liquid composition of the present disclosure is preferably 20% by mass or more, more preferably 40% by mass or more, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • 60% by mass or more is further preferable, 80% by mass or more is further preferable, and 90% by mass or more is further preferable.
  • 400 mass ppm or less is preferable, 350 mass ppm or less is more preferable, 300 mass ppm or less is further preferable, 260 mass ppm or less is further preferable, 240 mass ppm or less is further preferable, and 220 mass ppm or less. Is more preferable.
  • the total content of the component A and the component B in the polishing liquid composition of the present disclosure is preferably 20% by mass or more and 400% by mass or less, more preferably 40% by mass or more and 350ppm by mass or less, and more preferably 60% by mass. It is more preferably ppm or more and 300 mass ppm or less, further preferably 80 mass ppm or more and 260 mass ppm or less, further preferably 90 mass ppm or more and 240 mass ppm or less, and further preferably 90 mass ppm or more and 220 mass ppm or less.
  • the polishing abrasive grains that can be contained in the polishing liquid composition of the present disclosure are silica particles (hereinafter, also referred to as “component C”) in one or more embodiments.
  • component C include colloidal silica, fumed silica, pulverized silica, and silica whose surface is modified thereof, from the viewpoint of achieving both improvement in polishing speed and storage stability, and surface roughness (haze).
  • Colloidal silica is preferable from the viewpoint of improving surface quality such as reduction of surface defects and scratches.
  • the component C may be one kind or a combination of two or more kinds.
  • a slurry is preferable from the viewpoint of operability.
  • colloidal silica colloidal silica is obtained from a hydrolyzate of alkoxysilane from the viewpoint of preventing contamination of the silicon substrate with an alkali metal, an alkaline earth metal, or the like. It is preferable that the material is silica. Silica particles obtained from a hydrolyzate of alkoxysilane can be produced by a conventionally known method.
  • the average primary particle size of the component C is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more from the viewpoint of maintaining the polishing rate, and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. , 50 nm or less is preferable, 45 nm or less is more preferable, and 40 nm or less is further preferable. From the same viewpoint, the average primary particle size of the component C is preferably 10 nm or more and 50 nm or less, more preferably 15 nm or more and 45 nm or less, and further preferably 20 nm or more and 40 nm or less.
  • the average primary particle size of the component C is calculated using the specific surface area S (m 2 / g) calculated by the nitrogen adsorption method (BET method).
  • the value of the average primary particle size is a value measured by the method described in Examples.
  • the average secondary particle diameter of the component C is preferably 20 nm or more, more preferably 30 nm or more, further preferably 40 nm or more from the viewpoint of maintaining the polishing rate, and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. It is preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less. From the same viewpoint, the average secondary particle diameter of the component C is preferably 20 nm or more and 100 nm or less, more preferably 30 nm or more and 90 nm or less, and further preferably 40 nm or more and 80 nm or less. In the present disclosure, the average secondary particle size is a value measured by a dynamic light scattering (DLS) method and is a value measured by the method described in Examples.
  • DLS dynamic light scattering
  • the degree of association of the component C is preferably 3 or less, more preferably 2.5 or less, further preferably 2.3 or less, and from the same viewpoint, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. 1.1 or more is preferable, 1.5 or more is more preferable, and 1.8 or more is further preferable.
  • the degree of association of component C is a coefficient representing the shape of silica particles, and is calculated by the following formula.
  • Association average secondary particle size / average primary particle size
  • Examples of the method for adjusting the degree of association of the component C include JP-A-6-254383, JP-A-11-214338, JP-A-11-60232, JP-A-2005-060217, and JP-A-2005-060219.
  • the method described in the publication can be adopted.
  • the shape of the component C is preferably a so-called spherical shape and / or a so-called eyebrows shape from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing.
  • the content of component C in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, preferably 0.05% by mass, in terms of SiO 2 from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • the above is more preferable, 0.07% by mass or more is further preferable, and from the same viewpoint, 2.5% by mass or less is preferable, 1% by mass or less is more preferable, 0.8% by mass or less is further preferable, and 0. It is even more preferably 5.5% by mass or less, and even more preferably 0.3% by mass or less.
  • the content of component C in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more and 2.5% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less, and more preferably 0.05% by mass. More than 0.8% by mass is more preferable, 0.05% by mass or more and 0.5% by mass or less is more preferable, and 0.07% by mass or more and 0.3% by mass or less is even more preferable.
  • the content of the component C means the total content thereof.
  • the ratio of the content of component A to the content of component C in the polishing liquid composition of the present disclosure is 0.001 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. Is preferable, 0.005 or more is more preferable, 0.008 or more is further preferable, and from the same viewpoint, 0.2 or less is preferable, 0.18 or less is more preferable, and 0.16 or less is further preferable.
  • the ratio of the content of component B to the content of component C in the polishing liquid composition of the present disclosure is 0.0005 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. Is more preferable, 0.001 or more is more preferable, 0.0012 or more is further preferable, 0.4 or less is more preferable, 0.2 or less is more preferable, 0.18 or less is further preferable, and 0.17 or less is further preferable. preferable.
  • the polishing liquid composition of the present disclosure may contain water in one or more embodiments.
  • water include water such as ion-exchanged water and ultrapure water.
  • the content of water in the polishing liquid composition of the present disclosure can be, for example, the residue of component A, component B, component C and any component described later.
  • the polishing liquid composition of the present disclosure preferably further contains a nitrogen-containing basic compound (hereinafter, also referred to as “component D”) from the viewpoint of adjusting the pH.
  • the component D is preferably a water-soluble nitrogen-containing basic compound from the viewpoint of achieving both improvement in polishing speed and storage stability and improvement in surface quality.
  • water-soluble nitrogen-containing basic means a nitrogen-containing compound that exhibits basicity when dissolved in water.
  • Component D does not include the amino group-containing water-soluble polymer (component A) having a pKa of 5 or more and 8.5 or less in one or more embodiments.
  • the component D may be one kind or a combination of two or more kinds.
  • the component D includes at least one selected from an amine compound and an ammonium compound in one or more embodiments.
  • Examples of component D include ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogencarbonate, dimethylamine, trimethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, and N-methyl-N.
  • N-dietanolamine N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- ( ⁇ -aminoethyl) ethanolamine, monoisopropanolamine, diisopropanolamine , Triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine / hexahydrate, anhydrous piperazine, 1- (2-aminoethyl) piperazine, N-methylpiperazin, diethylenetriamine, tetramethylammonium hydroxide, and hydroxyamine.
  • the component D ammonia or a mixture of ammonia and hydroxyamine is preferable, and ammonia is more preferable, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • the content of the component D in the polishing liquid composition of the present disclosure is preferably 5% by mass or more, preferably 10% by mass or more, from the viewpoint of improving the polishing rate. More preferably, 20 mass ppm or more is further preferable, and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing, 500 mass ppm or less is more preferable, 300 mass ppm or less is more preferable, 150 mass ppm or less is further preferable, and 100 by mass is 100. More preferably, the mass is ppm or less.
  • the content of the component D is preferably 5 mass ppm or more and 500 mass ppm or less, more preferably 10 mass ppm or more and 300 mass ppm or less, further preferably 20 mass ppm or more and 150 mass ppm or less, and further preferably 20 mass ppm or more. It is more preferably 100 mass ppm or less.
  • the content of the component D means the total content thereof.
  • the ratio D / C (mass ratio D / C) of the content of the component D to the content of the component C in the polishing liquid composition of the present disclosure is the polishing rate.
  • 0.002 or more is preferable, 0.01 or more is more preferable, 0.015 or more is further preferable, and 1 or less is preferable from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • 0.5 or less is more preferable, 0.1 or less is further preferable, and 0.08 or less is further preferable.
  • the mass ratio D / C is preferably 0.002 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, further preferably 0.015 or more and 0.1 or less, and 0.015 or more and 0. It is more preferably .08 or less.
  • the polishing liquid composition of the present disclosure may further contain other components as long as the effects of the present disclosure are not impaired.
  • other components include, in one or more embodiments, water-soluble polymers other than components A and B, pH adjusters other than component D, preservatives, alcohols, chelating agents, oxidizing agents and the like.
  • the pH of the polishing liquid composition of the present disclosure is more than 8.5, preferably 9 or more, more preferably 9.5 or more, still more preferably 10 or more, from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing. It is preferable, and from the same viewpoint, it is 14 or less, preferably 13 or less, more preferably 12.5 or less, further preferably 12 or less, further preferably 11.5 or less, still more preferably 11 or less. From the same viewpoint, the pH of the polishing liquid composition of the present disclosure is more than 8.5 and 14 or less, preferably 9 or more and 13 or less, more preferably 9.5 or more and 12.5 or less, and 9.5 or more and 12 or less.
  • the pH of the polishing liquid composition of the present disclosure can be adjusted by using component D or a known pH adjuster.
  • the pH is a value measured by the method described in Examples.
  • the pH of the polishing liquid composition of the present disclosure is preferably larger than the pKa of the component A from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
  • the difference between pH and pKa (pH-pKa) is preferably more than 0, more preferably 0.5 or more, further preferably 1 or more, further preferably 1.5 or more, still more preferably 2 or more.
  • 7 or less is preferable, 6 or less is more preferable, 5.5 or less is further preferable, 5 or less is further preferable, and 4.5 or less is further preferable.
  • the polishing liquid composition of the present disclosure can be produced, for example, by blending component A and component B, and if desired, water, component C and component D, and other components by a known method. That is, the polishing liquid composition of the present disclosure can be produced, for example, by blending at least component A and component B. Therefore, the present disclosure relates to a method for producing an abrasive liquid composition, which comprises, in other embodiments, at least a step of blending component A and component B.
  • "blending" includes mixing component A, component B, and optionally water, component C and other components simultaneously or in any order.
  • the compounding can be carried out using, for example, a stirrer such as a homomixer, a homogenizer, an ultrasonic disperser, a wet ball mill, or a bead mill.
  • a stirrer such as a homomixer, a homogenizer, an ultrasonic disperser, a wet ball mill, or a bead mill.
  • the preferable blending amount of each component in the method for producing the polishing liquid composition of the present disclosure can be the same as the preferable content of each component in the polishing liquid composition of the present disclosure described above.
  • content of each component in the polishing liquid composition means the content of each component at the time of use, that is, at the time when the polishing liquid composition is started to be used for polishing.
  • the polishing liquid composition of the present disclosure may be produced as a concentrate from the viewpoint of storage and transportation, and may be diluted at the time of use.
  • the dilution ratio is preferably 2 times or more, more preferably 10 times or more, still more preferably 30 times or more, still more preferably 50 times or more, from the viewpoint of manufacturing and transportation costs, and from the viewpoint of storage stability. It is preferably 180 times or less, more preferably 140 times or less, still more preferably 100 times or less, still more preferably 70 times or less.
  • the concentrate of the polishing liquid composition of the present disclosure can be diluted with water so that the content of each component becomes the above-mentioned content (that is, the content at the time of use) at the time of use.
  • "when used" of the concentrate of the polishing liquid composition means a state in which the concentrate of the polishing liquid composition is diluted.
  • the polishing speed of the silicon substrate and the surface quality of the polished substrate are adjusted by changing the content ratio of the component A and the component B by using the polishing liquid composition of the present disclosure described above.
  • the effect of the polishing rate and the effect of the surface quality of the substrate can be changed by changing the ratio of the contents of the component A and the component B. Therefore, "adjusting the polishing speed of the silicon substrate and the surface quality of the substrate after polishing" means, in one or more embodiments, when polishing with the polishing liquid composition of the present disclosure, the polishing liquid composition.
  • the composition comprises setting the material to a composition in which the improvement of the polishing speed is prioritized over the improvement of the surface quality of the post-polishing substrate.
  • the polishing liquid composition is polished using the polishing liquid composition of the present disclosure, which comprises setting the polishing liquid composition to have a composition in which the improvement of the surface quality of the post-polishing substrate is prioritized over the improvement of the polishing speed. This includes making the polishing liquid composition a composition in which the improvement of the polishing speed and the improvement of the surface quality of the post-polishing substrate are balanced.
  • the adjusting method of the present disclosure is to be polished by one or more polishing liquid compositions in which the improvement of the polishing rate and the improvement of the surface quality of the post-polished substrate are adjusted as described above in the other one or more embodiments. It also includes adjusting the polishing speed of polishing and the surface quality of the substrate after polishing by polishing the silicon substrate.
  • the ratio of the component A in the polishing liquid composition of the present disclosure is preferably 50% by mass. % Or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably. It is mentioned that it is substantially 100% by mass.
  • the ratio [A / (A + B)] is substantially 100% by mass, which may be the case where component B is 0% by mass or intentionally not added or blended in one or more embodiments. ..
  • the ratio of the component B in the polishing liquid composition of the present disclosure is preferably 50% by mass. % Or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably. It is mentioned that it is substantially 100% by mass.
  • the ratio [B / (A + B)] of substantially 100% by mass may be 0% by mass or intentionally not added or blended with the component A in one or more embodiments. ..
  • the polishing liquid composition of the present disclosure contains silica particles (component C) in one or more embodiments.
  • a polishing liquid composition containing no silica particles (component C) may be used in one or more embodiments.
  • the adjustment method of the present disclosure is to polish using two or more polishing liquid compositions in which the improvement of the polishing speed and the improvement of the surface quality of the post-polishing substrate are adjusted as described above in one or more embodiments. Therefore, it also includes adjusting the improvement of the polishing speed of polishing in the polishing process and the improvement of the surface quality of the post-polishing substrate.
  • first polishing is performed using a polishing liquid composition having a high content ratio of component A, which gives priority to improving the polishing speed, and then the surface of the substrate after polishing is used.
  • polishing is performed using a polishing liquid composition having a high content ratio of component B, which gives priority to improving quality.
  • the adjusting method of the present disclosure is a polishing liquid composition in which the content ratio of the component A and the component B in two or more polishing liquid compositions is changed to shorten the polishing time until a predetermined surface quality is obtained. Includes choosing a combination of and polishing with them. By using these polishing liquids, it is possible to increase the production and reduce the cost of polishing.
  • the adjusting method of the present disclosure may include changing the total content of the component A and the component B in addition to changing the content ratio of the component A and the component B in the two or more polishing liquid compositions. ..
  • the adjustment method of the present disclosure may include selecting a combination of three or more abrasive liquid compositions.
  • polishing can be performed by switching and supplying two or more polishing liquid compositions to one polishing surface plate.
  • polishing can be performed by changing the polishing surface plate for each of two or more combinations of polishing liquid compositions.
  • components A and B are supplied from their respective storage containers on the same polishing surface plate using a tube or the like, mixed before being introduced into the polishing surface plate, and introduced into the polishing liquid, the components A and B are charged.
  • the form of polishing by changing the supply amount and continuously changing the content ratio may also be applicable to the case of polishing using two or more polishing liquid compositions of the adjustment method in the present disclosure.
  • the adjustment method of the present disclosure is preferably used in the finish polishing step in one or more embodiments from the viewpoint of achieving both improvement in polishing speed and improvement in surface quality.
  • the finish polishing step 2 for performing the finish polishing of the silicon substrate and the polishing step prior to the finish polishing step 2 are performed. It is preferable that the finish polishing step 1 is provided and the finish polishing step 1 and the finish polishing step 2 are performed in this order, and the finish polishing step 2 for performing the finish polishing of the silicon substrate and the finish polishing step 2 are preferable. It is more preferable to include a finish polishing step 1 which is a polishing step one step before the second step, and a polishing step in which the finish polishing step 1 and the finish polishing step 2 are continuous is more preferable.
  • the polishing liquid composition contains silica particles (component C), and the ratio of the content of component A to the total content of component A and component B [A / (A + B)] is high. It is preferable to polish with the composition, and in the finish polishing step 2, polish with a polishing liquid having a high ratio of the content of the component B to the total content of the component A and the component B [B / (A + B)].
  • the polishing liquid composition used in the finishing step 2 may or may not contain silica particles (component C). Further, in the finish polishing step 2, after polishing with a polishing liquid composition containing silica particles (component C), polishing may be performed with a polishing liquid composition not containing silica particles (component C).
  • the present disclosure includes a finish polishing step 2 for performing finish polishing of a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2, and includes a finish polishing step 1 and a finish polishing step.
  • 2 is the polishing method of the silicon substrate performed in this order.
  • the polishing liquid composition used in the finish polishing steps 1 and 2 contains at least one component selected from the group consisting of the component A and the component B, and in the finish polishing step 1, the polishing liquid composition contains the component C. Polish with a polishing liquid composition in which the ratio of the content of the component A to the total content of the component A and the component B is 50% by mass or more.
  • the finish polishing step 2 relates to a method for polishing a silicon substrate for polishing with a polishing liquid composition in which the ratio of the content of component B to the total content of component A and component B is 50% by mass or more. According to the method for polishing a silicon substrate according to this embodiment, the polishing speed and the surface quality can be improved.
  • the ratio [A / (A + B)] of the polishing liquid composition used in the finish polishing step 1 is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass, from the viewpoint of improving the polishing speed.
  • the above is more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass.
  • the ratio [B / (A + B)] of the polishing liquid composition used in the finish polishing step 2 is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80 from the viewpoint of improving the surface quality. It is mass% or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass.
  • the silicon substrate to be polished can be pressed against a surface plate to which a polishing pad is attached, and the silicon substrate to be polished can be polished with a polishing pressure of 3 to 20 kPa. ..
  • the polishing pressure means the pressure of the surface plate applied to the surface to be polished of the silicon substrate to be polished during polishing.
  • the silicon substrate to be polished is pressed against a surface plate to which a polishing pad is attached, and the polishing liquid composition and the polishing pad surface temperature of 15 ° C. or higher and 40 ° C. or lower are used.
  • the silicon substrate to be polished can be polished.
  • the temperature of the polishing liquid composition and the surface temperature of the polishing pad are preferably 15 ° C. or higher or 20 ° C. or higher, preferably 40 ° C. or lower, or 40 ° C. or lower, from the viewpoint of achieving both improvement in polishing speed and surface quality such as reduction of surface roughness (haze). It is preferably 30 ° C. or lower.
  • the finish polishing step 1 and the finish polishing step 2 can be performed on one polishing surface plate (same polishing surface plate).
  • the finish polishing step 1 and the finish polishing step 2 may be performed by changing the polishing surface plate, that is, the finish polishing step 2 may be performed by a polishing surface plate different from the polishing surface plate used in the finish polishing step 1. can.
  • the polishing liquid is supplied from each storage container of component A and component B using a tube or the like, and is mixed before being introduced into the polishing surface plate.
  • the supply amounts of the component A and the component B may be changed and the content ratio may be continuously changed for polishing by using the system introduced in the above.
  • the same polishing surface plate may be used.
  • the polishing step of polishing with the polishing liquid composition not containing silica particles (component C) is different from the polishing surface plate used in the step of polishing with the polishing liquid composition containing silica particles (component C). It can be done on the board.
  • the present disclosure relates to a method for manufacturing a semiconductor substrate (hereinafter, also referred to as "the method for manufacturing a semiconductor substrate of the present disclosure”), which comprises performing the preparation method of the present disclosure or the polishing method of the present disclosure in one aspect.
  • the semiconductor substrate manufacturing method of the present disclosure includes, in one or a plurality of embodiments, a step of polishing a silicon substrate to be polished using the polishing liquid composition of the present disclosure (hereinafter, also referred to as a “polishing step”).
  • a step of cleaning a silicon substrate hereinafter, also referred to as a “cleaning step” can be included.
  • the semiconductor substrate manufacturing method of the present disclosure by using the preparation method of the present disclosure or the polishing method of the present disclosure, both improvement of polishing speed and improvement of surface quality can be achieved, so that a high quality semiconductor substrate can be obtained. It can be manufactured with good yield, high productivity, and low cost.
  • the polishing steps in the semiconductor substrate manufacturing method of the present disclosure include, for example, a wrapping (rough polishing) step of flattening a single crystal silicon substrate obtained by slicing a single crystal silicon ingot into a thin disk shape, and a wrapping single crystal. After etching the silicon substrate, a finish polishing step of mirroring the surface of the single crystal silicon substrate can be included.
  • the adjustment method of the present disclosure is more preferably used in the above-mentioned finish polishing step from the viewpoint of achieving both improvement in polishing speed and improvement in surface quality. Examples of the finish polishing step in which the preparation method of the present disclosure is used include those described above.
  • polishing may be performed under the same conditions (polishing pressure, polishing composition, polishing pad surface temperature, etc.) as in the finish polishing steps 1 and 2 in the above-mentioned polishing method of the present disclosure. can.
  • the semiconductor substrate manufacturing method of the present disclosure may include, in one or more embodiments, a dilution step of diluting the concentrate of the polishing liquid composition before the polishing step.
  • a dilution step of diluting the concentrate of the polishing liquid composition before the polishing step For example, water can be used as the dilution medium.
  • the cleaning agent used for cleaning the inorganic substance include an inorganic cleaning agent containing at least one selected from hydrogen peroxide, ammonia, hydrochloric acid, sulfuric acid, hydrofluoric acid and ozone water.
  • the semiconductor substrate manufacturing method of the present disclosure may further include, in one or more embodiments, a step of rinsing the cleaned silicon substrate with water and drying it after the cleaning step.
  • the polishing step in the semiconductor substrate manufacturing method of the present disclosure is a polishing step in which the above-mentioned finish polishing step 1 and finish polishing step 2 are performed in this order, after performing the finish polishing step 1, cleaning and drying are performed. , The finish polishing step 2 may be performed. Further, after performing the finish polishing step 1, the finish polishing step 2 may be performed without washing and drying. From the viewpoint of improving productivity, it is preferable to perform the finish polishing step 2 without washing and drying after performing the finish polishing step 1.
  • ⁇ 1> Contains at least one component selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less.
  • ⁇ 2> Contains at least one component selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pH of 5 or more and 8.5 or less.
  • Component A is at least one selected from a reaction product of polyallylamine and a glycidol derivative and a compound containing a structural unit represented by the above formula (III), and component B is polyglycerin, polyglycerin alkyl ether, and the like.
  • ⁇ 1> or ⁇ 2 which is at least one selected from polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethyl acrylamide, and polyethylene glycol having a weight average molecular weight of 300 or more and 1,000 or less.
  • the method described in. ⁇ 4> The content of the component A in the polishing liquid composition is 0% by mass or more and 200% by mass, and the content of the component B in the polishing liquid composition is 0% by mass or more and 200% by mass.
  • ⁇ 5> The method according to any one of ⁇ 1> to ⁇ 4>, wherein the weight average molecular weight of the component A is 800 or more and 12000 or less, and the weight average molecular weight of the component B is 300 or more and 300,000 or less.
  • ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5>, wherein the polishing liquid composition further contains silica particles (component C).
  • the content of the component C in the polishing liquid composition is 0.07% by mass or more and 0.3% by mass or less, and the silicon substrate is a single crystal silicon substrate. The method described in any one.
  • a finish polishing step 2 for finish polishing a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2 are provided, and the finish polishing step 1 and the finish polishing step 2 are performed in this order. It is a method of polishing a silicon substrate that is performed.
  • the polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less.
  • a nonionic water-soluble polymer compound component B
  • the polishing liquid composition contains silica particles (component C) and is polished with a polishing liquid composition in which the ratio of the content of component A to the total content of component A and component B is 50% by mass or more.
  • finish polishing step 2 a method for polishing a silicon substrate, wherein the ratio of the content of the component B to the total content of the component A and the component B is 50% by mass or more with a polishing liquid composition.
  • a finish polishing step 2 for finish polishing a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2 are provided, and the finish polishing step 1 and the finish polishing step 2 are performed in this order. It is a method of polishing a silicon substrate that is performed.
  • the polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pH of 5 or more and 8.5 or less. It contains at least one component selected from the group consisting of, and the pH of the polishing liquid composition is 9 or more and 12 or less, and the difference between the pH and the pKa [pH-pKa] is 2 or more and 6 or less.
  • the polishing liquid composition contains silica particles (component C) and is polished with a polishing liquid composition in which the ratio of the content of component A to the total content of component A and component B is 50% by mass or more.
  • the method for polishing a silicon substrate according to ⁇ 9> wherein in the finish polishing step 2, the silicon substrate is polished with a polishing liquid composition in which the ratio of the content of the component B to the total content of the component A and the component B is 50% by mass or more.
  • Component A is at least one selected from a reaction product of polyallylamine and a glycidol derivative and a compound containing a structural unit represented by the above formula (III), and component B is polyglycerin, polyglycerin alkyl ether, and the like.
  • ⁇ 9> or ⁇ 10 which is at least one selected from polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethyl acrylamide, and polyethylene glycol having a weight average molecular weight of 300 or more and 1,000 or less.
  • the polishing method described in. ⁇ 12> The content of the component A in the polishing liquid composition is 0% by mass or more and 200% by mass, and the content of the component B in the polishing liquid composition is 0% by mass or more and 200% by mass.
  • ⁇ 13> The polishing method according to any one of ⁇ 9> to ⁇ 12>, wherein the weight average molecular weight of the component A is 800 or more and 12000 or less, and the weight average molecular weight of the component B is 300 or more and 300,000 or less.
  • ⁇ 14> Any of ⁇ 9> to ⁇ 13>, wherein the content of component C in the polishing liquid composition is 0.07% by mass or more and 0.3% by mass or less, and the silicon substrate is a single crystal silicon substrate.
  • ⁇ 15> The polishing method according to any one of ⁇ 9> to ⁇ 14>, wherein the finish polishing step 1 and the finish polishing step 2 are performed on one polishing surface plate.
  • ⁇ 16> The polishing method according to any one of ⁇ 9> to ⁇ 14>, wherein the finish polishing step 1 and the finish polishing step 2 are performed by changing the polishing surface plate.
  • polishing is performed with a polishing liquid composition containing silica particles (component C), and then polishing is performed with a polishing liquid composition containing no silica particles (component C), ⁇ 9> to ⁇ .
  • ⁇ 18> A method for manufacturing a semiconductor substrate, which comprises performing the method according to any one of ⁇ 1> to ⁇ 8> or the polishing method according to any one of ⁇ 9> to ⁇ 17>.
  • polishing liquid composition concentration of polishing liquid composition
  • Silica particles component C
  • amino group-containing water-soluble polymer compound component A
  • nonionic water-soluble polymer compound component B
  • ammonia component D
  • ultrapure water shown in Table 1
  • a concentrate 60 times
  • the pH of the concentrate at 25 ° C. was 10.3 to 11.0.
  • the concentrate was diluted 60-fold with ion-exchanged water to obtain the polishing liquid compositions (a1 to a6, b1 to b6) of Examples 1 to 12 (Table 1).
  • the content of each component in Table 1 is the content (mass% or mass ppm, effective content) of each component when the polishing liquid composition after dilution is used.
  • the content of ultrapure water is the residue excluding components A to D.
  • the pH of each polishing liquid composition (at the time of use) at 25 ° C. was 10.1 or 10.3.
  • the pH at 25 ° C. is a value measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and is a value 1 minute after immersing the electrode of the pH meter in the polishing liquid composition or its concentrate. Is.
  • the specific surface area S of the component C after performing the following [pretreatment], about 0.1 g of the measurement sample is concentrated in the measurement cell to 4 digits after the decimal point, and immediately before the measurement of the specific surface area, 30 in an atmosphere of 110 ° C. After drying for a minute, the measurement was carried out by the nitrogen adsorption method (BET method) using a specific surface area measuring device (micromeric automatic specific surface area measuring device "Flowsorb III2305", manufactured by Shimadzu Corporation).
  • BET method nitrogen adsorption method
  • Flowsorb III2305" micromeric automatic specific surface area measuring device "Flowsorb III2305", manufactured by Shimadzu Corporation.
  • the weight average molecular weight of the water-soluble polymer (Component A, Component B) is a chromatograph obtained by applying a gel permeation chromatography (GPC) method under the following conditions. Calculated based on peaks in the gram.
  • Polishing Liquid Compositions (a1 to a6, b1 to b6) (Examples 1 to 12) (1) Polishing method, etc. Each polishing liquid composition is filtered with a filter (compact cartridge filter "MCP-LX-C10S", manufactured by Advantech) immediately before polishing, and the following silicon to be polished under the following polishing conditions. The substrate was finished polished and cleaned.
  • a filter compact cartridge filter "MCP-LX-C10S", manufactured by Advantech
  • the single crystal silicon substrate was roughly polished in advance using a commercially available polishing liquid composition (manufactured by Fujimi Incorporated, GLANZOX 1302).
  • the haze of the single crystal silicon substrate that was subjected to rough polishing and finish polishing was 2 to 3 ppm.
  • Polishing machine Single-sided 8-inch polishing machine "GRIND-X SPP600s" (manufactured by Okamoto) Polishing pad: Suede pad (manufactured by Toray Industries, Inc., Asker hardness: 64, thickness: 1.37 mm, nap length: 450 ⁇ m, opening diameter: 60 ⁇ m) Silicon substrate polishing pressure: 100 g / cm 2 Surface plate rotation speed: 60 rpm Polishing time: 5 minutes Supply speed of polishing liquid composition: 150 g / min Abrasive composition temperature: 23 ° C Carrier rotation speed: 62 rpm
  • ozone cleaning and dilute hydrofluoric acid cleaning were performed on the silicon substrate as follows.
  • ozone cleaning an aqueous solution containing 20 ppm ozone was sprayed from a nozzle toward the center of a silicon substrate rotating at a flow rate of 1 L / min and 600 rpm for 3 minutes.
  • the temperature of ozone water was set to room temperature.
  • washing with dilute hydrofluoric acid was performed.
  • an aqueous solution containing 0.5% by mass of ammonium hydrogen fluoride (special grade, Nakaraitex Co., Ltd.) is sprayed from a nozzle toward the center of a silicon substrate rotating at a flow rate of 1 L / min and 600 rpm for 6 seconds. bottom.
  • a total of two sets of the above ozone cleaning and dilute hydrofluoric acid cleaning were performed as one set, and finally spin drying was performed. In spin drying, the silicon substrate was rotated at 1,500 rpm.
  • the weight of each silicon substrate before and after polishing was measured using a precision balance (“BP-210S” manufactured by Sartorius), and the obtained weight difference was measured as the density, area and polishing time of the silicon substrate. Divided by, the single-sided polishing rate per unit time was obtained. The results are shown in Table 1.
  • the weight of the silicon substrate after polishing is the weight of the silicon substrate after the finish polishing and cleaning.
  • the polishing liquid compositions of Examples 1, 2, 5, 7, 8 and 11 have the ratio of the content of component A to the total content of component A and component B [A / ( When the composition of A + B)] exceeds 50% by mass, the polishing speed of the silicon substrate is adjusted to take precedence over the surface quality (haze) of the polished substrate.
  • the polishing liquid compositions of Examples 3, 4, 6, 9, 10 and 12 have the ratio of the content of component B to the total content of component A and component B [B / (A + B)] has a composition of more than 50% by mass, so that the surface quality (haze) of the substrate after polishing is adjusted to take precedence over the polishing rate of the silicon substrate.
  • the weight of each silicon substrate before and after polishing was measured using a precision balance (“BP-210S” manufactured by Sartorius), and the obtained weight difference was measured by the density and area of the silicon substrate and polishing. Divided by time, the total polishing amount (nm) of the two-step polishing was obtained. The results are shown in Table 2.
  • the weight of the silicon substrate after polishing is the weight of the silicon substrate after the finish polishing and cleaning.
  • the polishing rate of the silicon substrate is prioritized as a composition in which the ratio [A / (A + B)] exceeds 50% by mass in the first finish polishing 1.
  • the total polishing amount (apparent polishing speed) can be improved. We were able to improve the surface quality at the same time.
  • the polishing liquid composition of the present disclosure is useful as a polishing liquid composition used in the manufacturing process of various semiconductor substrates, and above all, is useful as a polishing liquid composition for finish polishing of a silicon substrate.

Abstract

One aspect provides a method for adjusting the polishing speed of a silicon substrate and the surface quality of the polished silicon substrate.　In one aspect, this method is for adjusting the polishing speed of a silicon substrate and the surface quality of the polished substrate by: using a polishing liquid composition, which contains at least one component selected from the group consisting of an amino group-containing water‐soluble polymer compound (component A) having a pKa of 5-8.5 and a nonionic water‐soluble polymer compound (component B); and changing the content ratio of the component A and the component B.

Description

シリコン基板の研磨Polishing of silicon substrate
　本開示は、シリコン基板の研磨に関し、シリコン基板の研磨速度と研磨後の基板の表面品質の調整方法に関する。 This disclosure relates to the polishing of a silicon substrate, the polishing speed of the silicon substrate, and the method of adjusting the surface quality of the substrate after polishing.
　近年、半導体メモリの高記録容量化に対する要求の高まりから半導体装置のデザインルールは微細化が進んでいる。このため半導体装置の製造過程で行われるフォトリソグラフィーにおいて焦点深度は浅くなり、シリコン基板（ベアウェーハ）の欠陥低減や平滑性に対する要求はますます厳しくなっている。 In recent years, the design rules for semiconductor devices have been miniaturized due to the increasing demand for higher recording capacities in semiconductor memories. For this reason, the depth of focus becomes shallow in photolithography performed in the manufacturing process of semiconductor devices, and the demand for defect reduction and smoothness of silicon substrates (bare wafers) is becoming more and more strict.
　シリコン基板の品質を向上する目的で、シリコン基板の研磨は多段階で行われている。特に研磨の最終段階で行われる仕上げ研磨は、表面粗さ（ヘイズ）の抑制と研磨後のシリコン基板表面のぬれ性向上（親水化）によるパーティクルやスクラッチ、ピット等の表面欠陥（ＬＰＤ：Light point defects）の抑制とを目的として行われている。 For the purpose of improving the quality of the silicon substrate, the silicon substrate is polished in multiple stages. In particular, finish polishing, which is performed at the final stage of polishing, suppresses surface roughness (haze) and improves the wettability (hydrophilization) of the silicon substrate surface after polishing, resulting in surface defects (LPD: Light point) such as particles, scratches, and pits. It is done for the purpose of suppressing defects).
　シリコン基板表面について許容される表面欠陥のサイズは年々小さくなっており、通常この欠陥はレーザー光を基板表面に照射しそのときの散乱光を検出することで測定している。そのため、より微細な欠陥を測定するためには、シリコン基板の表面粗さ（ヘイズ）を低減し、欠陥測定時のＳ／Ｎ比を向上させなければならない。 The size of surface defects allowed on the surface of a silicon substrate is decreasing year by year, and these defects are usually measured by irradiating the surface of the substrate with laser light and detecting the scattered light at that time. Therefore, in order to measure finer defects, it is necessary to reduce the surface roughness (haze) of the silicon substrate and improve the S / N ratio at the time of defect measurement.
　仕上げ研磨に用いられる研磨液組成物としては、コロイダルシリカ、及びアルカリ化合物を用いた化学的機械研磨用の研磨液組成物が知られている。
　例えば、特開２００４－１２８０８９号公報には、ヘイズレベルを改善することを目的とした研磨液組成物として、ヒドロキシエチルセルロースやポリエチレンオキサイド等の水溶性高分子化合物を含有する研磨液組成物が報告されている。
　特開２００８－５３４１５号公報には、表面欠陥（ＬＰＤ）の数を低減することを目的とした研磨液組成物として、ポリビニルピロリドン及びポリＮ－ビニルホルムアミド等の窒素含有基を有する水溶性高分子化合物を含有する研磨液組成物が報告されている。 As a polishing liquid composition used for finish polishing, a polishing liquid composition for chemical mechanical polishing using colloidal silica and an alkaline compound is known.
For example, Japanese Patent Application Laid-Open No. 2004-128089 reports a polishing liquid composition containing a water-soluble polymer compound such as hydroxyethyl cellulose or polyethylene oxide as a polishing liquid composition for the purpose of improving the haze level. ing.
Japanese Patent Application Laid-Open No. 2008-53415 describes a water-soluble polymer having a nitrogen-containing group such as polyvinylpyrrolidone and polyN-vinylformamide as a polishing liquid composition for the purpose of reducing the number of surface defects (LPD). Abrasive liquid compositions containing compounds have been reported.
　また、シリコン基板を多段階で行う研磨方法が提案されている。
　例えば、特開２０１５－１８５６７２号公報には、多段階の研磨工程に用いる各研磨スラリーの水溶性ポリマーの濃度と重量平分子量との積の値の関係を規定したシリコン基板の研磨方法が提案されている。
　特開２０１５－１８５６７４号公報には、多段階の研磨工程に用いる各研磨スラリーの砥粒の濃度／体積平均粒子径の値の関係を規定したシリコン基板の研磨方法が提案されている。
　特開２０１６－４９５３号公報には、２段階の研磨工程に用いる各研磨スラリーの相対ヘイズの関係を規定したシリコン基板の研磨方法が提案されている。
　特開２０１７－１８３４７８号公報には、前研磨工程、リンス工程、仕上げ研磨工程の順で行う研磨方法おいて、前研磨工程に用いる研磨液組成物の親水性パラメータとリンス工程に用いるリンス剤の親水性パラメータの関係を規定したシリコン基板の研磨方法が提案されている。
　国際公開第２０１７／１６９１５４号には、前研磨工程に用いる研磨液組成物の親水パラメータ及び仕上げ精度パラメータの値、仕上げ研磨工程に用いる研磨液組成物の研磨加工性パラメータの値を規定した研磨用組成物セットが提案されている。
　上記５つの文献に記載されている研磨液組成物の水溶性ポリマーはヒドロキシエチルセルロース及び、ポリビニルピロリドンが用いられている。 Further, a polishing method in which a silicon substrate is performed in multiple stages has been proposed.
For example, Japanese Patent Application Laid-Open No. 2015-185672 proposes a method for polishing a silicon substrate, which defines the relationship between the product concentration of the water-soluble polymer concentration and the weight average molecular weight of each polishing slurry used in a multi-step polishing step. ing.
Japanese Unexamined Patent Publication No. 2015-185674 proposes a method for polishing a silicon substrate, which defines the relationship between the concentration of the abrasive grains of each polishing slurry used in the multi-step polishing step and the value of the volume average particle diameter.
Japanese Unexamined Patent Publication No. 2016-4953 proposes a method for polishing a silicon substrate, which defines the relationship of relative haze of each polishing slurry used in a two-step polishing step.
Japanese Patent Application Laid-Open No. 2017-183478 describes the hydrophilicity parameters of the polishing liquid composition used in the pre-polishing step and the rinsing agent used in the rinsing step in the polishing method performed in the order of the pre-polishing step, the rinsing step, and the finish polishing step. A method for polishing a silicon substrate that defines the relationship between hydrophilicity parameters has been proposed.
International Publication No. 2017/161954 defines the values of the hydrophilicity parameter and the finish accuracy parameter of the polishing liquid composition used in the pre-polishing process, and the value of the polishing processability parameter of the polishing liquid composition used in the finish polishing process for polishing. A composition set has been proposed.
Hydroxyethyl cellulose and polyvinylpyrrolidone are used as the water-soluble polymers of the polishing liquid compositions described in the above five documents.
　本開示は、一態様において、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有する研磨液組成物を用いて、成分Ａと成分Ｂの含有量比を変えることにより、シリコン基板の研磨速度と研磨後の基板の表面品質を調整する方法（以下、「本開示の調整方法」ともいう。）に関する。 The present disclosure is at least one selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less in one embodiment. A method for adjusting the polishing speed of a silicon substrate and the surface quality of the polished substrate by changing the content ratio of the component A and the component B using the polishing liquid composition containing the above-mentioned components (hereinafter, "the present disclosure"). Also referred to as "adjustment method").
　本開示は、一態様において、シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、該仕上げ研磨工程２よりも前の研磨工程である仕上げ研磨工程１とを備え、該仕上げ研磨工程１と該仕上げ研磨工程２とがこの順で行われるシリコン基板の研磨方法であって、仕上げ研磨工程１及び２において使用される研磨液組成物は、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有し、該仕上げ研磨工程１では、該研磨液組成物はシリカ粒子（成分Ｃ）を含有し、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合が５０質量％以上の研磨液組成物で研磨し、該仕上げ研磨工程２では、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合が５０質量％以上の研磨液組成物で研磨するシリコン基板の研磨方法（以下、「本開示の研磨方法」ともいう。）に関する。 The present disclosure comprises, in one embodiment, a finish polishing step 2 for performing a finish polishing of a silicon substrate, and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2, the finish polishing step 1 and the finishing. The polishing step 2 is a method for polishing a silicon substrate in this order, and the polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble substance having a pKa of 5 or more and 8.5 or less. It contains at least one component selected from the group consisting of a polymer compound (component A) and a nonionic water-soluble polymer compound (component B), and in the finish polishing step 1, the polishing liquid composition contains silica particles (components). C) is contained, and polishing is performed with a polishing liquid composition in which the ratio of the content of component A to the total content of component A and component B is 50% by mass or more, and in the finish polishing step 2, the components A and B are polished. The present invention relates to a method for polishing a silicon substrate (hereinafter, also referred to as “the polishing method of the present disclosure”) for polishing with a polishing liquid composition in which the ratio of the content of component B to the total content is 50% by mass or more.
　本開示は、一態様において、本開示の調整方法、又は、本開示の研磨方法を行うことを含む、半導体基板の製造方法に関する。 The present disclosure relates to, in one aspect, a method for manufacturing a semiconductor substrate, which comprises performing the adjusting method of the present disclosure or the polishing method of the present disclosure.
　表面欠陥等を低減するために、仕上げ研磨に用いられる研磨液には、より粒径の小さいコロイダルシリカが用いられ、研磨速度が遅くなる傾向にあり、研磨速度の向上に課題がある。
　しかし、特開２００４－１２８０８９号公報及び特開２００８－５３４１５号公報の研磨液組成物を用いた研磨では、研磨速度が十分とはいえない。
　また、特開２０１５－１８５６７２号公報、特開２０１５－１８５６７４号公報、特開２０１６－４９５３号公報、特開２０１７－１８３４７８号公報、及び、国際公開第２０１７／１６９１５４号のシリコン基板を多段階で行う研磨方法は、いずれも表面平滑性の向上や微小欠陥の発生抑制といった高品位の研磨表面を達成することを目的としており、研磨速度に関する言及はない。 In order to reduce surface defects and the like, colloidal silica having a smaller particle size is used as the polishing liquid used for finish polishing, and the polishing speed tends to be slow, and there is a problem in improving the polishing speed.
However, it cannot be said that the polishing speed is sufficient in the polishing using the polishing liquid compositions of JP-A-2004-128089 and JP-A-2008-53415.
Further, the silicon substrates of JP-A-2015-185672, JP-A-2015-185674, JP-A-2016-4953, JP-A-2017-183478, and International Publication No. 2017/169154 are used in multiple stages. All of the polishing methods to be performed are aimed at achieving a high-quality polished surface such as improvement of surface smoothness and suppression of generation of minute defects, and there is no mention of polishing speed.
　本開示は、シリコン基板の研磨速度と研磨後の基板の表面品質とを調整できる方法を提供する。 The present disclosure provides a method capable of adjusting the polishing speed of a silicon substrate and the surface quality of the substrate after polishing.
　本開示によれば、一態様において、シリコン基板の研磨において、研磨速度と、研磨後の基板表面品質（例えば、基板表面粗さ（ヘイズ））とを向上することができる。 According to the present disclosure, in one aspect, in polishing a silicon substrate, the polishing speed and the surface quality of the substrate after polishing (for example, the surface roughness (haze) of the substrate) can be improved.
　本開示の効果発現機構の詳細は明らかではないが、以下のように推察される。
　５以上８．５以下のｐＫａを有するアミノ基含有水溶性高分子（成分Ａ）は、カチオン性が低く、シリカ粒子（成分Ｃ）や被研磨シリコン基板に対し、アミノ基との静電相互作用よりも、主要因として分子全体のファンデルワールス力で吸着することでシリカ砥粒、シリコン基板間の静電斥力を抑制する。そのため静電相互作用に由来するシリカの凝集によるスクラッチ等の表面欠陥を新規に発生させることなく、高研磨速度を発現することで粗研磨工程由来の表面粗さの低減や表面欠陥の除去ができる。
　一方、ノニオン性水溶性高分子（成分Ｂ）はシリコン基板表面に吸着し、アルキレンオキサイドや水酸基などの親水基がシリコン基板表面に張り出すことで、アルカリによる過剰な腐食抑制とシリカ砥粒の接近を抑制する効果、すなわち、研磨後の基板表面品質を向上（例えば、ヘイズの低減等）の効果をもつ。
　両成分は主要因としてファンデルワールス力で吸着すると考えられ、その吸着力は同程度を考えられるために、お互いの吸着を阻害することなく、研磨液中の成分Ａと成分Ｂの比率に応じて、シリカ粒子（成分Ｃ）や被研磨シリコン基板に吸着する。
　その結果、成分Ａの研磨速度を向上する効果と成分Ｂの表面品質を向上する効果を阻害することなく、吸着量の割合、すなわち、成分Ａと成分Ｂの比率に応じて、成分Ａの効果と成分Ｂの効果を発現し、基板の研磨速度と表面品質を自由に調整することができると考えられる。
　ただし、本開示はこれらのメカニズムに限定して解釈されなくてもよい。 The details of the effect manifestation mechanism of the present disclosure are not clear, but it is inferred as follows.
The amino group-containing water-soluble polymer (component A) having a pKa of 5 or more and 8.5 or less has low cationicity, and has an electrostatic interaction with the amino group on the silica particles (component C) and the silicon substrate to be polished. Rather, it suppresses the electrostatic repulsive force between the silica abrasive grains and the silicon substrate by adsorbing with the van der Waals force of the whole molecule as the main factor. Therefore, it is possible to reduce the surface roughness derived from the rough polishing process and remove the surface defects by developing a high polishing rate without newly generating surface defects such as scratches due to the aggregation of silica derived from the electrostatic interaction. ..
On the other hand, the nonionic water-soluble polymer (component B) is adsorbed on the surface of the silicon substrate, and hydrophilic groups such as alkylene oxides and hydroxyl groups overhang on the surface of the silicon substrate, thereby suppressing excessive corrosion by alkali and approaching silica abrasive grains. That is, it has the effect of improving the surface quality of the substrate after polishing (for example, reducing haze).
It is thought that both components are adsorbed by van der Waals force as the main factor, and since the adsorption force is considered to be about the same, it does not interfere with the adsorption of each other and depends on the ratio of component A and component B in the polishing liquid. Then, it is adsorbed on the silica particles (component C) and the silicon substrate to be polished.
As a result, the effect of the component A depends on the ratio of the adsorption amount, that is, the ratio of the component A and the component B, without impairing the effect of improving the polishing rate of the component A and the effect of improving the surface quality of the component B. It is considered that the effect of component B can be exhibited and the polishing speed and surface quality of the substrate can be freely adjusted.
However, the present disclosure may not be construed as being limited to these mechanisms.
　［被研磨シリコン基板］
　本開示の調整方法又は研磨方法における研磨は、一又は複数の実施形態において、シリコン基板の研磨であり、一又は複数の実施形態において、半導体基板の製造方法における被研磨シリコン基板の研磨である。本開示の調整方法又は研磨方法において研磨される被研磨シリコン基板としては、一又は複数の実施形態において、シリコン基板等が挙げられ、一又は複数の実施形態において、単結晶シリコン基板が挙げられる。 [Silicon substrate to be polished]
The polishing in the adjusting method or polishing method of the present disclosure is, in one or more embodiments, polishing of a silicon substrate, and in one or more embodiments, polishing of a silicon substrate to be polished in a method of manufacturing a semiconductor substrate. Examples of the silicon substrate to be polished in the adjusting method or polishing method of the present disclosure include a silicon substrate and the like in one or more embodiments, and a single crystal silicon substrate in one or more embodiments.
　［研磨液組成物］
　本開示の調整方法又は研磨方法における研磨液組成物（以下、「本開示の研磨液組成物」ともいう。）は、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有する。
　本開示の研磨液組成物は、必要に応じて研磨砥粒を含有してもよい。研磨砥粒としては、一又は複数の実施形態において、シリカ粒子が挙げられる。
　本開示の研磨方法における「仕上げ研磨工程１」の研磨液組成物は、研磨速度と研磨後基板表面品質とを調整する観点から、研磨砥粒を含有することが好ましい。本開示の研磨方法における「仕上げ研磨工程２」の研磨液組成物は、研磨砥粒を含有してもよいし、しなくてもよい。 [Abrasive liquid composition]
The polishing liquid composition in the adjusting method or polishing method of the present disclosure (hereinafter, also referred to as “polishing liquid composition of the present disclosure”) is an amino group-containing water-soluble polymer compound having a pKa of 5 or more and 8.5 or less (hereinafter, also referred to as “polishing liquid composition of the present disclosure”). It contains at least one component selected from the group consisting of component A) and a nonionic water-soluble polymer compound (component B).
The polishing liquid composition of the present disclosure may contain polishing abrasive grains, if necessary. The abrasive grains include, in one or more embodiments, silica particles.
The polishing liquid composition of the "finish polishing step 1" in the polishing method of the present disclosure preferably contains polishing abrasive grains from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing. The polishing liquid composition of the "finish polishing step 2" in the polishing method of the present disclosure may or may not contain polishing abrasive grains.
　本開示において、研磨後の基板の表面品質の向上は、一又は複数の実施形態において、研磨後の基板の表面粗さ（ヘイズ）の低減である。 In the present disclosure, the improvement of the surface quality of the polished substrate is the reduction of the surface roughness (haze) of the polished substrate in one or more embodiments.
　［ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子（成分Ａ）］
　本開示の研磨液組成物は、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子（以下、「成分Ａ」ともいう）を含有しうる。成分Ａは、研磨砥粒の凝集を抑制し、研磨速度を向上させる効果を発揮しうる。本開示において、「水溶性」とは、水（２０℃）に対して０．５ｇ／１００ｍＬ以上の溶解度、好ましくは２ｇ／１００ｍＬ以上の溶解度を有することをいう。 [Amino group-containing water-soluble polymer having a pKa of 5 or more and 8.5 or less (component A)]
The polishing liquid composition of the present disclosure may contain an amino group-containing water-soluble polymer (hereinafter, also referred to as “component A”) having a pKa of 5 or more and 8.5 or less. The component A can exert the effect of suppressing the aggregation of the abrasive grains and improving the polishing rate. In the present disclosure, "water-soluble" means having a solubility of 0.5 g / 100 mL or more, preferably 2 g / 100 mL or more, in water (20 ° C.).
　成分ＡのｐＫａは、研磨速度を向上する観点から、５以上であって、５．５以上が好ましく、５．９以上がより好ましく、６．３以上が更に好ましく、６．８以上が更に好ましく、７．３以上が更に好ましく、７．５以上が更に好ましく、７．７以上が更に好ましく、そして、表面品質を向上する観点から、８．５以下であって、８．３以下が好ましく、８．１以下がより好ましく、８以下が更に好ましい。
　成分Ａが後述する成分Ａ１の場合、成分ＡのｐＫａは上記の範囲が好ましい。
　さらに、成分Ａが後述する成分Ａ２の場合、成分ＡのｐＫａは、研磨速度を向上する観点から、６．６以上が更に好ましく、６．９以上が更に好ましく、７．１以上が更に好ましく、そして、表面品質を向上する観点から、７．８以下が更に好ましく、７．６以下が更に好ましく、７．４以下が更に好ましい。 The pKa of the component A is 5 or more, preferably 5.5 or more, more preferably 5.9 or more, further preferably 6.3 or more, still more preferably 6.8 or more, from the viewpoint of improving the polishing rate. , 7.3 or more is more preferable, 7.5 or more is further preferable, 7.7 or more is further preferable, and from the viewpoint of improving the surface quality, 8.5 or less and 8.3 or less are preferable. 8.1 or less is more preferable, and 8 or less is further preferable.
When the component A is the component A1 described later, the pKa of the component A is preferably in the above range.
Further, when the component A is the component A2 described later, the pKa of the component A is more preferably 6.6 or more, further preferably 6.9 or more, still more preferably 7.1 or more, from the viewpoint of improving the polishing speed. From the viewpoint of improving the surface quality, 7.8 or less is further preferable, 7.6 or less is further preferable, and 7.4 or less is further preferable.
　成分Ａとしては、研磨速度と研磨後基板表面品質とを調整する観点から、アリルアミン及びジアリルアミンから選ばれる１種以上のモノマー由来の構成単位を含むことが好ましい。成分Ａは、入手性の観点から、一又は複数の実施形態において、アリルアミン由来の構成単位を含むアミノ基含有水溶性高分子（以下、「成分Ａ１」ともいう）であることが好ましく、一又は複数の実施形態において、ジアリルアミン由来の構成単位を含むアミノ基が含有水溶性高分子（以下、「成分Ａ２」ともいう）であることが好ましい。 The component A preferably contains a structural unit derived from one or more monomers selected from allylamine and diallylamine from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. From the viewpoint of availability, the component A is preferably an amino group-containing water-soluble polymer (hereinafter, also referred to as “component A1”) containing a structural unit derived from allylamine in one or more embodiments. In a plurality of embodiments, it is preferable that the amino group containing a structural unit derived from diallylamine is a water-soluble polymer (hereinafter, also referred to as “component A2”).
　（成分Ａ１：アリルアミン由来の構成単位を含むアミノ基含有水溶性高分子）
　アリルアミン由来の構成単位中のアミノ基の少なくとも一部は、一又は複数の実施形態において、研磨速度と研磨後基板表面品質とを調整する観点、及び、入手性の観点から、立体遮蔽基を有することが好ましい。本開示において、立体遮蔽基とは、成分Ａのアミノ基の窒素原子を遮蔽してカチオン化を抑制できる、すなわちｐＫａを低くする立体的な（嵩高い）置換基のことをいう。前記立体遮蔽基を有するアミノ基は、同様の観点から、水酸基を有する炭素数３以上１１以下の炭化水素基を含む第２級アミノ基又は第３級アミノ基であることが好ましい。前記炭化水素基の炭素数は、アミノ基の遮蔽性を向上する（アミノ基の窒素原子のカチオン化を抑制する）観点、及び、研磨速度と研磨後基板表面品質とを調整する観点から、３以上が好ましく、そして、水溶性を向上する観点、及び入手性の観点から、１１以下が好ましく、７以下がより好ましく、５以下が更に好ましく、４以下が更により好ましい。 (Component A1: Amino group-containing water-soluble polymer containing a structural unit derived from allylamine)
At least a part of the amino groups in the allylamine-derived structural unit has a steric shielding group in one or more embodiments from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing, and from the viewpoint of availability. Is preferable. In the present disclosure, the steric shielding group refers to a steric (bulky) substituent capable of shielding the nitrogen atom of the amino group of the component A to suppress cationization, that is, lowering pKa. From the same viewpoint, the amino group having a steric shielding group is preferably a secondary amino group or a tertiary amino group containing a hydrocarbon group having a hydroxyl group and having 3 or more carbon atoms and 11 or less carbon atoms. The number of carbon atoms of the hydrocarbon group is 3 from the viewpoint of improving the shielding property of the amino group (suppressing the cationization of the nitrogen atom of the amino group) and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. The above is preferable, and from the viewpoint of improving water solubility and availability, 11 or less is preferable, 7 or less is more preferable, 5 or less is further preferable, and 4 or less is further preferable.
　前記立体遮蔽基を有するアミノ基は、一又は複数の実施形態において、アミノ基に対するグリシドール誘導体による修飾基であり、一又は複数の実施形態において、アリルアミン由来の構成単位中のアミノ基とグリシドール誘導体とが反応して形成される基である。成分Ａ１の全アミノ基のうちの少なくとも一部のアミノ基がグリシドール誘導体によって変性され、立体遮蔽基を有するアミノ基となる。アリルアミン由来の構成単位中のアミノ基数（１当量）に対するグリシドール誘導体の当量（以下、「グリシドール変性率」ともいう）は、研磨速度と研磨後基板表面品質とを調整する観点から、０．３以上が好ましく、０．５以上がより好ましく、０．８以上が更に好ましく、１以上が更に好ましく、１．３以上が更に好ましく、１．５以上が更に好ましく、１．７以上が更に好ましく、そして、研磨速度を向上する観点から、４以下が好ましく、３以下がより好ましく、２．５以下が更に好ましく、２以下が更に好ましい。 The amino group having a steric shielding group is, in one or more embodiments, a modifying group with a glycidole derivative to the amino group, and in one or more embodiments, the amino group and the glycidol derivative in the allylamine-derived structural unit. Is a group formed by the reaction. At least a part of the amino groups of the total amino group of the component A1 is modified by the glycidol derivative to become an amino group having a steric shielding group. The equivalent of the glycidol derivative to the number of amino groups (1 equivalent) in the allylamine-derived structural unit (hereinafter, also referred to as "glycidol modification rate") is 0.3 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. Is preferable, 0.5 or more is more preferable, 0.8 or more is further preferable, 1 or more is further preferable, 1.3 or more is further preferable, 1.5 or more is further preferable, 1.7 or more is further preferable, and From the viewpoint of improving the polishing speed, 4 or less is preferable, 3 or less is more preferable, 2.5 or less is further preferable, and 2 or less is further preferable.
　本開示において、グリシドール変性率は、13Ｃ－ＮＭＲを用いて実施例に記載の方法により測定される値である。ただし、グリシドール変性率は、以下の方法（１）又は（２）によっても測定できる。
（１）反応原料に用いたアリルアミン重合体のアミノ基当量とグリシドール誘導体のモル数から求めることができる。
（２）グリシドール誘導体とアリルアミン重合体との反応物の窒素含有量Ｎ（質量％）を測定し、下記式から求めることができる。
　グリシドール変性率＝Ａ／Ｂ
　ここで、Ａ＝（１００－Ｎ×アリルアミン重合体の分子量／１４）／グリシドール誘導体分子量であり、Ｂ＝Ｎ／１４である。 In the present disclosure, the glycidol modification rate is a value measured by the method described in Examples using 13 C-NMR. However, the glycidol modification rate can also be measured by the following method (1) or (2).
(1) It can be obtained from the amino group equivalent of the allylamine polymer used as the reaction raw material and the number of moles of the glycidol derivative.
(2) The nitrogen content N (mass%) of the reaction product of the glycidol derivative and the allylamine polymer can be measured and calculated from the following formula.
Glycidol denaturation rate = A / B
Here, A = (100-N × molecular weight of allylamine polymer / 14) / glycidol derivative molecular weight, and B = N / 14.
　前記グリシドール誘導体としては、例えば、グリシドール、アルキルグリシジルエーテル等が挙げられ、入手性の観点、及び、研磨速度と研磨後基板表面品質とを調整する観点から、グリシドールが好ましい。前記アルキルグリシジルエーテルのアルキル基は、入手性の観点から、炭素数１～８のアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、２－エチルヘキシル基等が挙げられる。前記アルキルグリシジルエーテルとしては、メチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル等が挙げられる。 Examples of the glycidol derivative include glycidol, alkylglycidyl ether, and the like, and glycidol is preferable from the viewpoint of availability and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. The alkyl group of the alkylglycidyl ether is preferably an alkyl group having 1 to 8 carbon atoms from the viewpoint of availability, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a 2-ethylhexyl group. Examples of the alkyl glycidyl ether include methyl glycidyl ether and 2-ethylhexyl glycidyl ether.
　成分Ａ１としては、一又は複数の実施形態において、少なくとも一部のアミノ基が立体遮蔽基を有するポリアリルアミンが挙げられ、一又は複数の実施形態において、ポリアリルアミンとグリシドール誘導体との反応物が挙げられる。 The component A1 includes polyallylamine in which at least a part of the amino groups has a steric shielding group in one or more embodiments, and a reaction product of polyallylamine and a glycidol derivative in one or more embodiments. Be done.
　成分Ａ１としては、一又は複数の実施形態において、下記式（Ｉ）の構成単位を含む化合物（グリシドール変性ポリアリルアミン）が挙げられる。
Figure JPOXMLDOC01-appb-C000002
 Examples of the component A1 include a compound (glycidol-modified polyallylamine) containing the structural unit of the following formula (I) in one or more embodiments.
Figure JPOXMLDOC01-appb-C000002
　式（Ｉ）中、Ｒ1及びＲ2はそれぞれ、水素原子又は立体遮蔽基である。立体遮蔽基としては、グリシドール誘導体由来の修飾基が挙げられ、一又は複数の実施形態において、グリシドールの１モル付加体又は２モル付加体が挙げられ、一又は複数の実施形態において、－ＣＨ2ＣＨ（ＯＨ）ＣＨ2（ＯＨ）、－ＣＨ2ＣＨ（ＯＨ）ＣＨ2Ｏ－ＣＨ2ＣＨ（ＯＨ）ＣＨ2（ＯＨ）等が挙げられる。 In formula (I), R 1 and R 2 are hydrogen atoms or steric shielding groups, respectively. Examples of the steric shielding group include a modifying group derived from a glycidol derivative, and in one or more embodiments, a 1-molar adduct or a 2-molar adduct of glycidol can be mentioned, and in one or more embodiments, -CH 2 CH (OH) CH 2 (OH), −CH 2 CH (OH) CH 2 O—CH 2 CH (OH) CH 2 (OH) and the like can be mentioned.
　（成分Ａ２：ジアリルアミン由来の構成単位を含むアミノ基含有水溶性高分子）
　ジアリルアミン由来の構成単位中のアミノ基の少なくとも一部は、一又は複数の実施形態において、研磨速度と研磨後基板表面品質とを調整する観点から、アミノ基のβ位またはγ位に電子吸引基を有することが好ましい。電子吸引基としては、下記式（ＩＩ）で表される基等が挙げられる。 (Component A2: Amino group-containing water-soluble polymer containing a structural unit derived from diallylamine)
At least a part of the amino group in the constituent unit derived from diallylamine is an electron-withdrawing group at the β-position or the γ-position of the amino group from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing in one or more embodiments. It is preferable to have. Examples of the electron-withdrawing group include a group represented by the following formula (II).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　成分Ａ２としては、一又は複数の実施形態において、ジアリルアミン由来の構成単位及び二酸化硫黄由来の構成単位を含む化合物が挙げられ、例えば、下記式（ＩＩＩ）で表される構成単位を含む化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000004
 Examples of the component A2 include compounds containing a structural unit derived from diallylamine and a structural unit derived from sulfur dioxide in one or more embodiments, and examples thereof include a compound containing a structural unit represented by the following formula (III). Be done.
Figure JPOXMLDOC01-appb-C000004
　式（ＩＩＩ）中、Ｒ3は、水酸基を有してもよい炭素数１～３のアルキル基である。入手性及び経済性の観点の観点から、Ｒ3はメチル基が好ましい。また、ｎ＋ｍ＝１であり、ｎ、ｍは０又は１である。同様の観点から、ｍ＝１且つｎ＝０の化合物が好ましい。なお、ｍ＝１且つｎ＝０の化合物とｍ＝０且つｎ＝１の化合物の混合物でもよい。 In formula (III), R 3 is an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group. From the viewpoint of availability and economy, R 3 is preferably a methyl group. Further, n + m = 1, and n and m are 0 or 1. From the same viewpoint, a compound having m = 1 and n = 0 is preferable. A mixture of a compound having m = 1 and n = 0 and a compound having m = 0 and n = 1 may be used.
　成分Ａ２としては、一又は複数の実施形態において、下記式（ＩＶ）で表される構成単位を含む化合物が挙げられ、例えば、メチルジアリルアミン／二酸化硫黄共重合体が挙げられる。
Figure JPOXMLDOC01-appb-C000005
 Examples of the component A2 include compounds containing a structural unit represented by the following formula (IV) in one or more embodiments, and examples thereof include a methyldiallylamine / sulfur dioxide copolymer.
Figure JPOXMLDOC01-appb-C000005
　成分Ａの重量平均分子量は、研磨速度を向上する観点から、８００以上が好ましく、１，０００以上がより好ましく、１，５００以上が更に好ましく、２，０００以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、１００，０００以下が好ましく、５０，０００以下がより好ましく、３０，０００以下が更に好ましく、２０，０００以下が更に好ましく、１５，０００以下が更に好ましく、１２，０００以下が更に好ましい。本開示における成分Ａの重量平均分子量は、例えば、実施例に記載する方法により測定できる。 From the viewpoint of improving the polishing rate, the weight average molecular weight of the component A is preferably 800 or more, more preferably 1,000 or more, further preferably 1,500 or more, further preferably 2,000 or more, and the polishing rate. From the viewpoint of adjusting the surface quality of the substrate after polishing, 100,000 or less is preferable, 50,000 or less is more preferable, 30,000 or less is further preferable, 20,000 or less is further preferable, and 15,000 or less is further preferable. , 12,000 or less is more preferable. The weight average molecular weight of component A in the present disclosure can be measured, for example, by the method described in Examples.
　成分Ａが成分Ａ１である場合、成分Ａの重量平均分子量は、研磨速度を向上する観点から、８００以上が好ましく、１，０００以上がより好ましく、１，５００以上が更に好ましく、２，０００以上が更に好ましく、３，０００以上が好ましく、５，０００以上がより好ましく、６，０００以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、１００，０００以下が好ましく、５０，０００以下がより好ましく、３０，０００以下が更に好ましく、２０，０００以下が更に好ましく、１５，０００以下が更に好ましく、１２，０００以下が更に好ましい。 When the component A is the component A1, the weight average molecular weight of the component A is preferably 800 or more, more preferably 1,000 or more, further preferably 1,500 or more, and further preferably 2,000 or more from the viewpoint of improving the polishing rate. Is more preferable, 3,000 or more is preferable, 5,000 or more is more preferable, 6,000 or more is further preferable, and 100,000 or less is preferable from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing. 50,000 or less is more preferable, 30,000 or less is further preferable, 20,000 or less is further preferable, 15,000 or less is further preferable, and 12,000 or less is further preferable.
　成分Ａが成分Ａ２である場合、成分Ａの重量平均分子量は、研磨速度を向上する観点から、８００以上が好ましく、１，０００以上がより好ましく、１，５００以上が更に好ましく、２，０００以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、１００，０００以下が好ましく、５０，０００以下がより好ましく、３０，０００以下が更に好ましく、２０，０００以下が更に好ましく、１５，０００以下が更に好ましく、１２，０００以下が更に好ましく、１０，０００以下が更に好ましく、７，０００以下が更に好ましく、５，０００以下が更に好ましく、４，０００以下が更に好ましい。 When the component A is the component A2, the weight average molecular weight of the component A is preferably 800 or more, more preferably 1,000 or more, further preferably 1,500 or more, and further preferably 2,000 or more from the viewpoint of improving the polishing rate. Is more preferable, and from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing, 100,000 or less is preferable, 50,000 or less is more preferable, 30,000 or less is further preferable, and 20,000 or less is further preferable. It is preferable, 15,000 or less is further preferable, 12,000 or less is further preferable, 10,000 or less is further preferable, 7,000 or less is further preferable, 5,000 or less is further preferable, and 4,000 or less is further preferable.
　本開示の研磨液組成物中の成分Ａの含有量は、研磨速度と研磨後基板表面品質とを調整する観点から、一又は複数の実施形態において、１０質量ｐｐｍ以上、２０質量ｐｐｍ以上、又は３０質量ｐｐｍ以上が挙げられ、そして、同様の観点から、一又は複数の実施形態において、２００質量ｐｐｍ以下、１５０質量ｐｐｍ以下、又は１２０質量ｐｐｍ以下が挙げられる。なお、本開示において、１質量％は１０，０００質量ｐｐｍである（以下同じ）。 The content of component A in the polishing liquid composition of the present disclosure is 10% by mass or more, 20% by mass or more, or 20% by mass or more in one or more embodiments from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. 30 mass ppm or more, and from the same viewpoint, in one or more embodiments, 200 mass ppm or less, 150 mass ppm or less, or 120 mass ppm or less. In the present disclosure, 1% by mass is 10,000% by mass (the same applies hereinafter).
［ノニオン性水溶性高分子（成分Ｂ）］
　本開示の研磨液組成物は、一又は複数の実施形態において、研磨後の基板の表面品質を向上する観点から、ノニオン性水溶性高分子（以下、「成分Ｂ」ともいう）を含有しうる。成分Ｂとしては、同様の観点から、分子内にアルキレンオキサイド基、水酸基、又はアミド基を有するノニオン性水溶性高分子が好ましい。前記アルキレンオキサイド基としては、例えば、エチレンオキサイド基、プロピレンオキサイド基等が挙げられる。成分Ｂは、１種でもよいし、２種以上の組合せでもよい。 [Nonionic water-soluble polymer (component B)]
In one or more embodiments, the polishing liquid composition of the present disclosure may contain a nonionic water-soluble polymer (hereinafter, also referred to as “component B”) from the viewpoint of improving the surface quality of the substrate after polishing. .. From the same viewpoint, the component B is preferably a nonionic water-soluble polymer having an alkylene oxide group, a hydroxyl group, or an amide group in the molecule. Examples of the alkylene oxide group include an ethylene oxide group and a propylene oxide group. The component B may be one kind or a combination of two or more kinds.
　成分Ｂとしては、研磨速度と研磨後基板表面品質とを調整する観点から、ポリグリセリン、ポリグリセリンアルキルエーテル、ポリグリセリンアルキルエステル、ヒドロキシアルキルセルロース、ポリビニルアルコール、ポリビニルピロリドン、ポリヒドロキシエチルアクリルアミド、及び、重量平均分子量が３００以上１,０００以下のポリエチレングリコールから選ばれる少なくとも１種が挙げられる。
　前記ポリグリセリンアルキルエーテルのアルキル基は、研磨速度と研磨後基板表面品質とを調整する観点、及び、研磨液の泡立ち抑制の観点から、炭素数３以上２２以下のアルキル基が好ましく、炭素数５以上１６以下のアルキル基がより好ましく、炭素数７以上１２以下のアルキル基が更に好ましい。前記アルキル基は、直鎖アルキル基でもよいし、分岐鎖アルキル基でもよい。前記ポリグリセリンアルキルエーテルのグリセリン単位の平均重合度は、濡れ性向上の観点から、５以上であり、１０以上が好ましく、１５以上がより好ましく、１８以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、１００以下であり、６０以下が好ましく、４５以下がより好ましく、２５以下が更に好ましい。前記ポリグリセリンアルキルエーテルとしては、例えば、ポリグリセリンラウリルエーテル、ポリグリセリンデシルエーテル、ポリグリセリンミリスチルエーテル等が挙げられる。
　前記ポリグリセリンアルキルエステルのアルキル基は、研磨速度と研磨後基板表面品質とを調整する観点、及び、研磨液の泡立ち抑制の観点から、炭素数３以上２２以下のアルキル基が好ましく、炭素数５以上１６以下のアルキル基がより好ましく、炭素数７以上１２以下のアルキル基が更に好ましい。前記アルキル基は、直鎖アルキル基でもよいし、分岐鎖アルキル基でもよい。前記ポリグリセリンアルキルエステルのグリセリン単位の平均重合度は、濡れ性向上の観点から、５以上であり、１０以上が好ましく、１５以上がより好ましく、１８以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、１００以下であり、６０以下が好ましく、４５以下がより好ましく、２５以下が更に好ましい。前記ポリグリセリンアルキルエステルとしては、例えば、ポリグリセリンラウリルエステル、ポリグリセリンデシルエステル、ポリグリセリンミリスチルエステル等が挙げられる。
　前記ヒドロキシアルキルセルロースは、研磨速度と研磨後基板表面品質とを調整する観点から、ヒドロキシエチルセルロース（ＨＥＣ）、ヒドロキシプロピルセルロース、及びヒドロキシブチルセルロースから選ばれる少なくとも１種が好ましく、ヒドロキシエチルセルロース（ＨＥＣ）がより好ましい。
　これらの中でも、成分Ｂは、研磨速度と研磨後基板表面品質とを調整する観点から、ポリグリセリン、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（ＰＶＰ）、ヒドロキシエチルセルロース（ＨＥＣ）、重量平均分子量が３００以上１,０００以下のポリエチレングリコール（ＰＥＧ）から選ばれる少なくとも１種が好ましく、ポリグリセリンがより好ましい。 The component B includes polyglycerin, polyglycerin alkyl ether, polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethyl acrylamide, and polyhydroxyethyl acrylamide from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. At least one selected from polyethylene glycols having a weight average molecular weight of 300 or more and 1,000 or less can be mentioned.
The alkyl group of the polyglycerin alkyl ether is preferably an alkyl group having 3 or more and 22 or less carbon atoms, preferably 5 carbon atoms, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing and suppressing foaming of the polishing liquid. Alkyl groups having 16 or more carbon atoms are more preferable, and alkyl groups having 7 or more carbon atoms and 12 or less carbon atoms are further preferable. The alkyl group may be a linear alkyl group or a branched chain alkyl group. The average degree of polymerization of the polyglycerin alkyl ether in units of glycerin is 5 or more, preferably 10 or more, more preferably 15 or more, further preferably 18 or more, and the polishing rate and after polishing. From the viewpoint of adjusting the surface quality of the substrate, it is 100 or less, preferably 60 or less, more preferably 45 or less, still more preferably 25 or less. Examples of the polyglycerin alkyl ether include polyglycerin lauryl ether, polyglycerin decyl ether, and polyglycerin myristyl ether.
The alkyl group of the polyglycerin alkyl ester is preferably an alkyl group having 3 or more and 22 or less carbon atoms, preferably 5 carbon atoms, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing and suppressing foaming of the polishing liquid. Alkyl groups having 16 or more carbon atoms are more preferable, and alkyl groups having 7 or more carbon atoms and 12 or less carbon atoms are further preferable. The alkyl group may be a linear alkyl group or a branched chain alkyl group. The average degree of polymerization of the polyglycerin alkyl ester in units of glycerin is 5 or more, preferably 10 or more, more preferably 15 or more, further preferably 18 or more, and the polishing rate and after polishing. From the viewpoint of adjusting the surface quality of the substrate, it is 100 or less, preferably 60 or less, more preferably 45 or less, still more preferably 25 or less. Examples of the polyglycerin alkyl ester include polyglycerin lauryl ester, polyglycerin decyl ester, and polyglycerin myristyl ester.
The hydroxyalkyl cellulose is preferably at least one selected from hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, and hydroxybutyl cellulose from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing, and hydroxyethyl cellulose (HEC) is preferable. More preferred.
Among these, component B is polyglycerin, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hydroxyethyl cellulose (HEC), and has a weight average molecular weight of 300 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. At least one selected from 1,000 or less polyethylene glycol (PEG) is preferable, and polyglycerin is more preferable.
　成分Ｂの重量平均分子量は、研磨速度と研磨後基板表面品質とを調整する観点から、３００以上が好ましく、５００以上がより好ましく、１,０００以上が更に好ましく、１,５００以上が更に好ましく、２,０００以上が更に好ましく、そして、同様の観点、及び研磨液の濾過性の観点から、５０万未満が好ましく、４０万以下がより好ましく、３０万以下が更に好ましく、１５万以下が更に好ましく、１０万以下が更に好ましく、５万以下が更に好ましく、２万以下が更に好ましく、１万以下が更に好ましい。
　成分Ｂがポリグリセリンである場合、成分Ｂの重量平均分子量は、同様の観点から、１,０００以上が好ましく、１,５００以上がより好ましく、２,０００以上が更に好ましく、そして、１００００以下が好ましく、８０００以下がより好ましく、６０００以下が更に好ましい。
　成分Ｂがポリビニルアルコール（ＰＶＡ）である場合、成分Ｂの重量平均分子量は、同様の観点から、５,０００以上が好ましく、１０,０００以上がより好ましく、２０,０００以上が更に好ましく、そして、１５万以下が好ましく、１２万以下がより好ましく、１０万以下が更に好ましい。
　成分Ｂがポリビニルピロリドン（ＰＶＰ）である場合、成分Ｂの重量平均分子量は、同様の観点から、５０００以上が好ましく、１００００以上がより好ましく、２００００以上が更に好ましく、そして、１５万以下が好ましく、１２万以下がより好ましく、１０万以下が更に好ましい。
　成分Ｂがヒドロキシエチルセルロース（ＨＥＣ）である場合、成分Ｂの重量平均分子量は、同様の観点から、５万以上が好ましく、１０万以上がより好ましく、１５万以上が更に好ましく、そして、５０万以下が好ましく、４０万以下がより好ましく、３０万以下が更に好ましい。
　成分Ｂが重量平均分子量が３００以上１,０００以下のポリエチレングリコール（ＰＥＧ）である場合、成分Ｂの重量平均分子量は、同様の観点から、５００以上が好ましく、そして、９００以下が好ましく、８００以下がより好ましい。
　成分Ｂの重量平均分子量は後の実施例に記載の方法により測定できる。 The weight average molecular weight of the component B is preferably 300 or more, more preferably 500 or more, further preferably 1,000 or more, still more preferably 1,500 or more, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. More than 2,000 is more preferable, and from the same viewpoint and the filterability of the polishing liquid, less than 500,000 is preferable, 400,000 or less is more preferable, 300,000 or less is further preferable, and 150,000 or less is further preferable. 100,000 or less is further preferable, 50,000 or less is further preferable, 20,000 or less is further preferable, and 10,000 or less is further preferable.
When the component B is polyglycerin, the weight average molecular weight of the component B is preferably 1,000 or more, more preferably 1,500 or more, further preferably 2,000 or more, and 10,000 or less from the same viewpoint. It is preferable, 8000 or less is more preferable, and 6000 or less is further preferable.
When the component B is polyvinyl alcohol (PVA), the weight average molecular weight of the component B is preferably 5,000 or more, more preferably 10,000 or more, further preferably 20,000 or more, and more preferably 20,000 or more, from the same viewpoint. It is preferably 150,000 or less, more preferably 120,000 or less, and even more preferably 100,000 or less.
When the component B is polyvinylpyrrolidone (PVP), the weight average molecular weight of the component B is preferably 5,000 or more, more preferably 10,000 or more, further preferably 20,000 or more, and preferably 150,000 or less, from the same viewpoint. 120,000 or less is more preferable, and 100,000 or less is further preferable.
When the component B is hydroxyethyl cellulose (HEC), the weight average molecular weight of the component B is preferably 50,000 or more, more preferably 100,000 or more, further preferably 150,000 or more, and 500,000 or less from the same viewpoint. Is preferable, 400,000 or less is more preferable, and 300,000 or less is further preferable.
When the component B is polyethylene glycol (PEG) having a weight average molecular weight of 300 or more and 1,000 or less, the weight average molecular weight of the component B is preferably 500 or more, preferably 900 or less, and 800 or less from the same viewpoint. Is more preferable.
The weight average molecular weight of component B can be measured by the method described in a later example.
　本開示の研磨液組成物中の成分Ｂの含有量は、研磨速度と研磨後基板表面品質とを調整する観点から、一又は複数の実施形態において、０質量ｐｐｍ以上、２質量ｐｐｍ以上、１０質量ｐｐｍ以上、２０質量ｐｐｍ以上、３０質量ｐｐｍ以上、５０質量ｐｐｍ以上、又は１００質量ｐｐｍ以上が挙げられ、そして、１,０００質量ｐｐｍ以下、５００質量ｐｐｍ以下、３００質量ｐｐｍ以下、又は２００質量ｐｐｍ以下が挙げられる。成分Ｂが２種以上の組合せの場合、成分Ｂの含有量はそれらの合計含有量をいう。 The content of component B in the polishing liquid composition of the present disclosure is 0% by mass or more, 2% by mass or more, and 10 in one or more embodiments from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. Mass ppm or more, 20 mass ppm or more, 30 mass ppm or more, 50 mass ppm or more, or 100 mass ppm or more, and 1,000 mass ppm or less, 500 mass ppm or less, 300 mass ppm or less, or 200 mass ppm or more. The following is mentioned. When the component B is a combination of two or more kinds, the content of the component B means the total content thereof.
　本開示の研磨液組成物中の成分Ａと成分Ｂの合計含有量は、研磨速度と研磨後基板表面品質とを調整する観点から、２０質量ｐｐｍ以上が好ましく、４０質量ｐｐｍ以上がより好ましく、６０質量ｐｐｍ以上が更に好ましく、８０質量ｐｐｍ以上が更に好ましく、９０質量ｐｐｍ以上が更に好ましい。そして、同様の観点から、４００質量ｐｐｍ以下が好ましく、３５０質量ｐｐｍ以下がより好ましく、３００質量ｐｐｍ以下が更に好ましく、２６０質量ｐｐｍ以下が更に好ましく、２４０質量ｐｐｍ以下が更に好ましく、２２０質量ｐｐｍ以下が更に好ましい。本開示の研磨液組成物中の成分Ａと成分Ｂの合計含有量は、同様の観点から、２０質量ｐｐｍ以上４００質量ｐｐｍ以下が好ましく、４０質量ｐｐｍ以上３５０ｐｐｍ質量ｐｐｍ以下がより好ましく、６０質量ｐｐｍ以上３００質量ｐｐｍ以下が更に好ましく、８０質量ｐｐｍ以上２６０質量ｐｐｍ以下が更に好ましく、９０質量ｐｐｍ以上２４０質量ｐｐｍ以下が更に好ましく、９０質量ｐｐｍ以上２２０質量ｐｐｍ以下が更に好ましい。 The total content of the component A and the component B in the polishing liquid composition of the present disclosure is preferably 20% by mass or more, more preferably 40% by mass or more, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. 60% by mass or more is further preferable, 80% by mass or more is further preferable, and 90% by mass or more is further preferable. From the same viewpoint, 400 mass ppm or less is preferable, 350 mass ppm or less is more preferable, 300 mass ppm or less is further preferable, 260 mass ppm or less is further preferable, 240 mass ppm or less is further preferable, and 220 mass ppm or less. Is more preferable. From the same viewpoint, the total content of the component A and the component B in the polishing liquid composition of the present disclosure is preferably 20% by mass or more and 400% by mass or less, more preferably 40% by mass or more and 350ppm by mass or less, and more preferably 60% by mass. It is more preferably ppm or more and 300 mass ppm or less, further preferably 80 mass ppm or more and 260 mass ppm or less, further preferably 90 mass ppm or more and 240 mass ppm or less, and further preferably 90 mass ppm or more and 220 mass ppm or less.
　［研磨砥粒：シリカ粒子（成分Ｃ）］
　本開示の研磨液組成物に含まれうる研磨砥粒は、一又は複数の実施形態において、シリカ粒子（以下、「成分Ｃ」ともいう）である。成分Ｃとしては、コロイダルシリカ、フュームドシリカ、粉砕シリカ、又はそれらを表面修飾したシリカ等が挙げられ、研磨速度の向上と保存安定性とを両立する観点、及び、表面粗さ（ヘイズ）、表面欠陥及びスクラッチの低減等の表面品質の向上する観点から、コロイダルシリカが好ましい。成分Ｃは、１種でもよいし、２種以上の組合せでもよい。 [Abrasive abrasive grains: silica particles (component C)]
The polishing abrasive grains that can be contained in the polishing liquid composition of the present disclosure are silica particles (hereinafter, also referred to as “component C”) in one or more embodiments. Examples of the component C include colloidal silica, fumed silica, pulverized silica, and silica whose surface is modified thereof, from the viewpoint of achieving both improvement in polishing speed and storage stability, and surface roughness (haze). Colloidal silica is preferable from the viewpoint of improving surface quality such as reduction of surface defects and scratches. The component C may be one kind or a combination of two or more kinds.
　成分Ｃの使用形態としては、操作性の観点から、スラリー状が好ましい。本開示の研磨液組成物に含まれる成分Ｃがコロイダルシリカである場合、アルカリ金属やアルカリ土類金属等によるシリコン基板の汚染を防止する観点から、コロイダルシリカは、アルコキシシランの加水分解物から得たものであることが好ましい。アルコキシシランの加水分解物から得られるシリカ粒子は、従来から公知の方法によって作製できる。 As the usage form of the component C, a slurry is preferable from the viewpoint of operability. When the component C contained in the polishing liquid composition of the present disclosure is colloidal silica, colloidal silica is obtained from a hydrolyzate of alkoxysilane from the viewpoint of preventing contamination of the silicon substrate with an alkali metal, an alkaline earth metal, or the like. It is preferable that the material is silica. Silica particles obtained from a hydrolyzate of alkoxysilane can be produced by a conventionally known method.
　成分Ｃの平均一次粒子径は、研磨速度を維持する観点から、１０ｎｍ以上が好ましく、１５ｎｍ以上がより好ましく、２０ｎｍ以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、５０ｎｍ以下が好ましく、４５ｎｍ以下がより好ましく、４０ｎｍ以下が更に好ましい。同様の観点から、成分Ｃの平均一次粒子径は、１０ｎｍ以上５０ｎｍ以下が好ましく、１５ｎｍ以上４５ｎｍ以下がより好ましく、２０ｎｍ以上４０ｎｍ以下が更に好ましい。
　本開示において、成分Ｃの平均一次粒子径は、窒素吸着法（ＢＥＴ法）によって算出される比表面積Ｓ（ｍ2／ｇ）を用いて算出される。平均一次粒子径の値は、実施例に記載する方法で測定される値である。 The average primary particle size of the component C is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more from the viewpoint of maintaining the polishing rate, and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. , 50 nm or less is preferable, 45 nm or less is more preferable, and 40 nm or less is further preferable. From the same viewpoint, the average primary particle size of the component C is preferably 10 nm or more and 50 nm or less, more preferably 15 nm or more and 45 nm or less, and further preferably 20 nm or more and 40 nm or less.
In the present disclosure, the average primary particle size of the component C is calculated using the specific surface area S (m 2 / g) calculated by the nitrogen adsorption method (BET method). The value of the average primary particle size is a value measured by the method described in Examples.
　成分Ｃの平均二次粒子径は、研磨速度を維持する観点から、２０ｎｍ以上が好ましく、３０ｎｍ以上がより好ましく、４０ｎｍ以上が更に好ましく、研磨速度と研磨後基板表面品質とを調整する観点から、１００ｎｍ以下が好ましく、９０ｎｍ以下がより好ましく、８０ｎｍ以下が更に好ましい。同様の観点から、成分Ｃの平均二次粒子径は、２０ｎｍ以上１００ｎｍ以下が好ましく、３０ｎｍ以上９０ｎｍ以下がより好ましく、４０ｎｍ以上８０ｎｍ以下が更に好ましい。
　本開示において、平均二次粒子径は、動的光散乱（ＤＬＳ）法によって測定される値であり、実施例に記載する方法で測定される値である。 The average secondary particle diameter of the component C is preferably 20 nm or more, more preferably 30 nm or more, further preferably 40 nm or more from the viewpoint of maintaining the polishing rate, and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. It is preferably 100 nm or less, more preferably 90 nm or less, and even more preferably 80 nm or less. From the same viewpoint, the average secondary particle diameter of the component C is preferably 20 nm or more and 100 nm or less, more preferably 30 nm or more and 90 nm or less, and further preferably 40 nm or more and 80 nm or less.
In the present disclosure, the average secondary particle size is a value measured by a dynamic light scattering (DLS) method and is a value measured by the method described in Examples.
　成分Ｃの会合度は、研磨速度と研磨後基板表面品質とを調整する観点から、３以下が好ましく、２．５以下がより好ましく、２．３以下が更に好ましく、そして、同様の観点から、１．１以上が好ましく、１．５以上がより好ましく、１．８以上が更に好ましい。 The degree of association of the component C is preferably 3 or less, more preferably 2.5 or less, further preferably 2.3 or less, and from the same viewpoint, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. 1.1 or more is preferable, 1.5 or more is more preferable, and 1.8 or more is further preferable.
　本開示において、成分Ｃの会合度とは、シリカ粒子の形状を表す係数であり、下記式により算出される。
会合度＝平均二次粒子径／平均一次粒子径 In the present disclosure, the degree of association of component C is a coefficient representing the shape of silica particles, and is calculated by the following formula.
Association = average secondary particle size / average primary particle size
　成分Ｃの会合度の調整方法としては、例えば、特開平６－２５４３８３号公報、特開平１１－２１４３３８号公報、特開平１１－６０２３２号公報、特開２００５－０６０２１７号公報、特開２００５－０６０２１９号公報等に記載の方法を採用することができる。 Examples of the method for adjusting the degree of association of the component C include JP-A-6-254383, JP-A-11-214338, JP-A-11-60232, JP-A-2005-060217, and JP-A-2005-060219. The method described in the publication can be adopted.
　成分Ｃの形状は、研磨速度と研磨後基板表面品質とを調整する観点から、いわゆる球型及び／又はいわゆるマユ型であることが好ましい。 The shape of the component C is preferably a so-called spherical shape and / or a so-called eyebrows shape from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing.
　本開示の研磨液組成物中の成分Ｃの含有量は、研磨速度と研磨後基板表面品質とを調整する観点から、ＳｉＯ2換算で、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．０７質量％以上が更に好ましく、そして、同様の観点から、２．５質量％以下が好ましく、１質量％以下がより好ましく、０．８質量％以下が更に好ましく、０．５質量％以下が更により好ましく、０．３質量％以下が更により好ましい。本開示の研磨液組成物中の成分Ｃの含有量は、０．０１質量％以上２．５質量％以下が好ましく、０．０５質量％以上１質量％以下がより好ましく、０．０５質量％以上０．８質量％以下がより好ましく、０．０５質量％以上０．５質量％以下がより好ましく、０．０７質量％以上０．３質量％以下が更により好ましい。成分Ｃが２種以上の組合せの場合、成分Ｃの含有量はそれらの合計含有量をいう。 The content of component C in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, preferably 0.05% by mass, in terms of SiO 2 from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. The above is more preferable, 0.07% by mass or more is further preferable, and from the same viewpoint, 2.5% by mass or less is preferable, 1% by mass or less is more preferable, 0.8% by mass or less is further preferable, and 0. It is even more preferably 5.5% by mass or less, and even more preferably 0.3% by mass or less. The content of component C in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more and 2.5% by mass or less, more preferably 0.05% by mass or more and 1% by mass or less, and more preferably 0.05% by mass. More than 0.8% by mass is more preferable, 0.05% by mass or more and 0.5% by mass or less is more preferable, and 0.07% by mass or more and 0.3% by mass or less is even more preferable. When the component C is a combination of two or more kinds, the content of the component C means the total content thereof.
　本開示の研磨液組成物中における成分Ｃの含有量に対する成分Ａの含有量の比（質量比Ａ／Ｃ）は、研磨速度と研磨後基板表面品質とを調整する観点から、０．００１以上が好ましく、０．００５以上がより好ましく、０．００８以上が更に好ましく、そして、同様の観点から、０．２以下が好ましく、０．１８以下がより好ましく、０．１６以下が更に好ましい。 The ratio of the content of component A to the content of component C in the polishing liquid composition of the present disclosure (mass ratio A / C) is 0.001 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. Is preferable, 0.005 or more is more preferable, 0.008 or more is further preferable, and from the same viewpoint, 0.2 or less is preferable, 0.18 or less is more preferable, and 0.16 or less is further preferable.
　本開示の研磨液組成物中における成分Ｃの含有量に対する成分Ｂの含有量の比（質量比Ｂ／Ｃ）は、研磨速度と研磨後基板表面品質とを調整する観点から、０．０００５以上が好ましく、０．００１以上がより好ましく、０．００１２以上が更に好ましく、そして、０．４以下が好ましく、０．２以下がより好ましく、０．１８以下が更に好ましく、０．１７以下が更に好ましい。 The ratio of the content of component B to the content of component C in the polishing liquid composition of the present disclosure (mass ratio B / C) is 0.0005 or more from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. Is more preferable, 0.001 or more is more preferable, 0.0012 or more is further preferable, 0.4 or less is more preferable, 0.2 or less is more preferable, 0.18 or less is further preferable, and 0.17 or less is further preferable. preferable.
　［水］
　本開示の研磨液組成物は、一又は複数の実施形態において、水を含んでいてもよい。水としては、例えば、イオン交換水や超純水等の水が挙げられる。本開示の研磨液組成物中の水の含有量は、例えば、成分Ａ、成分Ｂ、成分Ｃ及び後述する任意成分の残余とすることができる。 [water]
The polishing liquid composition of the present disclosure may contain water in one or more embodiments. Examples of water include water such as ion-exchanged water and ultrapure water. The content of water in the polishing liquid composition of the present disclosure can be, for example, the residue of component A, component B, component C and any component described later.
　［含窒素塩基性化合物（成分Ｄ）］
　本開示の研磨液組成物は、一又は複数の実施形態において、ｐＨを調整する観点から、含窒素塩基性化合物（以下、「成分Ｄ」ともいう）をさらに含有することが好ましい。成分Ｄとしては、研磨速度の向上と保存安定性とを両立する観点、及び、表面品質を向上する観点から、水溶性の含窒素塩基性化合物であることが好ましい。本開示において、「水溶性の含窒素塩基性」とは、水に溶解したときに塩基性を示す含窒素化合物をいう。成分Ｄは、一又は複数の実施形態において、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子（成分Ａ）を含めないものとする。成分Ｄは、１種でもよいし、２種以上の組合せでもよい。 [Nitrogen-containing basic compound (component D)]
In one or more embodiments, the polishing liquid composition of the present disclosure preferably further contains a nitrogen-containing basic compound (hereinafter, also referred to as “component D”) from the viewpoint of adjusting the pH. The component D is preferably a water-soluble nitrogen-containing basic compound from the viewpoint of achieving both improvement in polishing speed and storage stability and improvement in surface quality. In the present disclosure, "water-soluble nitrogen-containing basic" means a nitrogen-containing compound that exhibits basicity when dissolved in water. Component D does not include the amino group-containing water-soluble polymer (component A) having a pKa of 5 or more and 8.5 or less in one or more embodiments. The component D may be one kind or a combination of two or more kinds.
　成分Ｄとしては、一又は複数の実施形態において、アミン化合物及びアンモニウム化合物から選ばれる少なくとも１種が挙げられる。成分Ｄとしては、例えば、アンモニア、水酸化アンモニウム、炭酸アンモニウム、炭酸水素アンモニウム、ジメチルアミン、トリメチルアミン、ジエチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ一メチルエタノールアミン、Ｎ－メチル－Ｎ，Ｎ一ジエタノ－ルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－ジブチルエタノールアミン、Ｎ－（β－アミノエチル）エタノ－ルアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、エチレンジアミン、ヘキサメチレンジアミン、ピペラジン・六水和物、無水ピペラジン、１－（２－アミノエチル）ピペラジン、Ｎ－メチルピペラジン、ジエチレントリアミン、水酸化テトラメチルアンモニウム、及びヒドロキシアミンから選ばれる１種又は２種以上の組合せが挙げられる。なかでも、研磨速度と研磨後基板表面品質とを調整する観点から、成分Ｄとしては、アンモニア、又は、アンモニアとヒドロキシアミンの混合物が好ましく、アンモニアがより好ましい。 The component D includes at least one selected from an amine compound and an ammonium compound in one or more embodiments. Examples of component D include ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogencarbonate, dimethylamine, trimethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, and N-methyl-N. , N-dietanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (β-aminoethyl) ethanolamine, monoisopropanolamine, diisopropanolamine , Triisopropanolamine, ethylenediamine, hexamethylenediamine, piperazine / hexahydrate, anhydrous piperazine, 1- (2-aminoethyl) piperazine, N-methylpiperazin, diethylenetriamine, tetramethylammonium hydroxide, and hydroxyamine. One type or a combination of two or more types can be mentioned. Among them, as the component D, ammonia or a mixture of ammonia and hydroxyamine is preferable, and ammonia is more preferable, from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing.
　本開示の研磨液組成物が成分Ｄを含む場合、本開示の研磨液組成物中の成分Ｄの含有量は、研磨速度を向上する観点から、５質量ｐｐｍ以上が好ましく、１０質量ｐｐｍ以上がより好ましく、２０質量ｐｐｍ以上が更に好ましく、研磨速度と研磨後基板表面品質とを調整する観点から、５００質量ｐｐｍ以下が好ましく、３００質量ｐｐｍ以下がより好ましく、１５０質量ｐｐｍ以下が更に好ましく、１００質量ｐｐｍ以下が更に好ましい。同様の観点から、成分Ｄの含有量は、５質量ｐｐｍ以上５００質量ｐｐｍ以下が好ましく１０質量ｐｐｍ以上３００質量ｐｐｍ以下がより好ましく、２０質量ｐｐｍ以上１５０質量ｐｐｍ以下が更に好ましく、２０質量ｐｐｍ以上１００質量ｐｐｍ以下が更に好ましい。成分Ｄが２種以上の組合せの場合、成分Ｄの含有量はそれらの合計含有量をいう。 When the polishing liquid composition of the present disclosure contains a component D, the content of the component D in the polishing liquid composition of the present disclosure is preferably 5% by mass or more, preferably 10% by mass or more, from the viewpoint of improving the polishing rate. More preferably, 20 mass ppm or more is further preferable, and from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing, 500 mass ppm or less is more preferable, 300 mass ppm or less is more preferable, 150 mass ppm or less is further preferable, and 100 by mass is 100. More preferably, the mass is ppm or less. From the same viewpoint, the content of the component D is preferably 5 mass ppm or more and 500 mass ppm or less, more preferably 10 mass ppm or more and 300 mass ppm or less, further preferably 20 mass ppm or more and 150 mass ppm or less, and further preferably 20 mass ppm or more. It is more preferably 100 mass ppm or less. When the component D is a combination of two or more kinds, the content of the component D means the total content thereof.
　本開示の研磨液組成物が成分Ｄを含む場合、本開示の研磨液組成物中における成分Ｃの含有量に対する成分Ｄの含有量の比Ｄ／Ｃ（質量比Ｄ／Ｃ）は、研磨速度を向上する観点から、０．００２以上が好ましく、０．０１以上がより好ましく、０．０１５以上が更に好ましく、そして、研磨速度と研磨後基板表面品質とを調整する観点から、１以下が好ましく、０．５以下がより好ましく、０．１以下が更に好ましく、０．０８以下が更に好ましい。同様の観点から、質量比Ｄ／Ｃは、０．００２以上１以下が好ましく、０．０１以上０．５以下がより好ましく、０．０１５以上０．１以下が更に好ましく、０．０１５以上０．０８以下が更に好ましい。 When the polishing liquid composition of the present disclosure contains the component D, the ratio D / C (mass ratio D / C) of the content of the component D to the content of the component C in the polishing liquid composition of the present disclosure is the polishing rate. 0.002 or more is preferable, 0.01 or more is more preferable, 0.015 or more is further preferable, and 1 or less is preferable from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. , 0.5 or less is more preferable, 0.1 or less is further preferable, and 0.08 or less is further preferable. From the same viewpoint, the mass ratio D / C is preferably 0.002 or more and 1 or less, more preferably 0.01 or more and 0.5 or less, further preferably 0.015 or more and 0.1 or less, and 0.015 or more and 0. It is more preferably .08 or less.
　［その他の成分］
　本開示の研磨液組成物は、本開示の効果が妨げられない範囲で、その他の成分をさらに含んでもよい。その他の成分としては、一又は複数の実施形態において、成分Ａ，Ｂ以外の水溶性高分子、成分Ｄ以外のｐＨ調整剤、防腐剤、アルコール類、キレート剤、及び酸化剤等が挙げられる。 [Other ingredients]
The polishing liquid composition of the present disclosure may further contain other components as long as the effects of the present disclosure are not impaired. Examples of other components include, in one or more embodiments, water-soluble polymers other than components A and B, pH adjusters other than component D, preservatives, alcohols, chelating agents, oxidizing agents and the like.
　［ｐＨ］
　本開示の研磨液組成物のｐＨは、研磨速度と研磨後基板表面品質とを調整する観点から、８．５超であり、９以上が好ましく、９．５以上が更に好ましく、１０以上が更に好ましく、そして、同様の観点から、１４以下であり、１３以下が好ましく、１２．５以下がより好ましく、１２以下が更に好ましく、１１．５以下が更に好ましく、１１以下が更に好ましい。同様の観点から、本開示の研磨液組成物のｐＨは、８．５超以上１４以下であり、９以上１３以下が好ましく、９．５以上１２．５以下がより好ましく、９．５以上１２以下が更に好ましく、９．５以上１１．５以下が更に好ましく、１０以上１１以下が更に好ましい。本開示の研磨液組成物のｐＨは、成分Ｄや公知のｐＨ調整剤を用いて調整できる。本開示において、上記ｐＨは、実施例に記載する方法で測定される値である。 [PH]
The pH of the polishing liquid composition of the present disclosure is more than 8.5, preferably 9 or more, more preferably 9.5 or more, still more preferably 10 or more, from the viewpoint of adjusting the polishing speed and the surface quality of the substrate after polishing. It is preferable, and from the same viewpoint, it is 14 or less, preferably 13 or less, more preferably 12.5 or less, further preferably 12 or less, further preferably 11.5 or less, still more preferably 11 or less. From the same viewpoint, the pH of the polishing liquid composition of the present disclosure is more than 8.5 and 14 or less, preferably 9 or more and 13 or less, more preferably 9.5 or more and 12.5 or less, and 9.5 or more and 12 or less. The following is more preferable, 9.5 or more and 11.5 or less is further preferable, and 10 or more and 11 or less is further preferable. The pH of the polishing liquid composition of the present disclosure can be adjusted by using component D or a known pH adjuster. In the present disclosure, the pH is a value measured by the method described in Examples.
　［ｐＨ－ｐＫａ］
　本開示の研磨液組成物のｐＨは、研磨速度と研磨後基板表面品質とを調整する観点から、成分ＡのｐＫａより大きいことが好ましい。ｐＨとｐＫａとの差（ｐＨ－ｐＫａ）は、同様の観点から、０超が好ましく、０．５以上がより好ましく、１以上が更に好ましく、１．５以上が更に好ましく、２以上が更に好ましく、そして、同様の観点から、７以下が好ましく、６以下がより好ましく、５．５以下が更に好ましく、５以下が更に好ましく、４．５以下が更に好ましい。 [PH-pKa]
The pH of the polishing liquid composition of the present disclosure is preferably larger than the pKa of the component A from the viewpoint of adjusting the polishing rate and the surface quality of the substrate after polishing. From the same viewpoint, the difference between pH and pKa (pH-pKa) is preferably more than 0, more preferably 0.5 or more, further preferably 1 or more, further preferably 1.5 or more, still more preferably 2 or more. From the same viewpoint, 7 or less is preferable, 6 or less is more preferable, 5.5 or less is further preferable, 5 or less is further preferable, and 4.5 or less is further preferable.
　本開示の研磨液組成物は、例えば、成分Ａ及び成分Ｂと、さらに所望により、水、成分Ｃ及び成分Ｄ並びにその他の成分とを公知の方法で配合することにより製造できる。すなわち、本開示の研磨液組成物は、例えば、少なくとも成分Ａと成分Ｂとを配合することにより製造できる。したがって、本開示は、その他の態様において、少なくとも成分Ａ、及び成分Ｂを配合する工程を含む、研磨液組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ、成分Ｂ、並びに、必要に応じて水、成分Ｃ及びその他の成分を同時に又は任意の順に混合することを含む。前記配合は、例えば、ホモミキサー、ホモジナイザー、超音波分散機、湿式ボールミル、又はビーズミル等の撹拌機等を用いて行うことができる。上記本開示の研磨液組成物の製造方法における各成分の好ましい配合量は、上述した本開示の研磨液組成物中の各成分の好ましい含有量と同じとすることができる。 The polishing liquid composition of the present disclosure can be produced, for example, by blending component A and component B, and if desired, water, component C and component D, and other components by a known method. That is, the polishing liquid composition of the present disclosure can be produced, for example, by blending at least component A and component B. Therefore, the present disclosure relates to a method for producing an abrasive liquid composition, which comprises, in other embodiments, at least a step of blending component A and component B. In the present disclosure, "blending" includes mixing component A, component B, and optionally water, component C and other components simultaneously or in any order. The compounding can be carried out using, for example, a stirrer such as a homomixer, a homogenizer, an ultrasonic disperser, a wet ball mill, or a bead mill. The preferable blending amount of each component in the method for producing the polishing liquid composition of the present disclosure can be the same as the preferable content of each component in the polishing liquid composition of the present disclosure described above.
　本開示において、「研磨液組成物中の各成分の含有量」は、使用時、すなわち、研磨液組成物の研磨への使用を開始する時点における各成分の含有量をいう。 In the present disclosure, "content of each component in the polishing liquid composition" means the content of each component at the time of use, that is, at the time when the polishing liquid composition is started to be used for polishing.
　本開示の研磨液組成物は、貯蔵及び輸送の観点から、濃縮物として製造され、使用時に希釈されてもよい。希釈倍率としては、製造及び輸送コストの観点から、好ましくは２倍以上であり、より好ましくは１０倍以上、更に好ましくは３０倍以上、更に好ましくは５０倍以上であり、保存安定性の観点から、好ましくは１８０倍以下であり、より好ましくは１４０倍以下、更に好ましくは１００倍以下、更に好ましくは７０倍以下である。本開示の研磨液組成物の濃縮物は、使用時に各成分の含有量が、上述した含有量（すなわち、使用時の含有量）となるように水で希釈して使用することができる。本開示において研磨液組成物の濃縮物の「使用時」とは、研磨液組成物の濃縮物が希釈された状態をいう。 The polishing liquid composition of the present disclosure may be produced as a concentrate from the viewpoint of storage and transportation, and may be diluted at the time of use. The dilution ratio is preferably 2 times or more, more preferably 10 times or more, still more preferably 30 times or more, still more preferably 50 times or more, from the viewpoint of manufacturing and transportation costs, and from the viewpoint of storage stability. It is preferably 180 times or less, more preferably 140 times or less, still more preferably 100 times or less, still more preferably 70 times or less. The concentrate of the polishing liquid composition of the present disclosure can be diluted with water so that the content of each component becomes the above-mentioned content (that is, the content at the time of use) at the time of use. In the present disclosure, "when used" of the concentrate of the polishing liquid composition means a state in which the concentrate of the polishing liquid composition is diluted.
　［調整方法］
　本開示の調整方法は、上述した本開示の研磨液組成物を用いて、成分Ａと成分Ｂの含有量比を変えることにより、シリコン基板の研磨速度と研磨後の基板の表面品質を調整する方法である。本開示の調整方法によれば、成分Ａと成分Ｂの含有量の比を変えることにより、研磨速度の効果と基板の表面品質の効果を変えることができる。よって、「シリコン基板の研磨速度と研磨後の基板の表面品質を調整する」とは、一又は複数の実施形態において、本開示の研磨液組成物を用いて研磨をする際に、研磨液組成物を、研磨後基板の表面品質の向上よりも研磨速度の向上を優先した組成とすることを含み、一又は複数の実施形態において、本開示の研磨液組成物を用いて研磨をする際に、研磨液組成物を、研磨速度の向上よりも研磨後基板の表面品質の向上を優先した組成とすることを含み、一又は複数の実施形態において、本開示の研磨液組成物を用いて研磨をする際に、研磨液組成物を、研磨速度の向上と研磨後基板の表面品質の向上のバランスがとれた組成とすることを含む。
　本開示の調整方法は、その他の一又は複数の実施形態において、上述のように研磨速度の向上と研磨後基板の表面品質の向上とが調整された一又は複数の研磨液組成物により被研磨シリコン基板の研磨することで、研磨の研磨速度の向上と研磨後基板の表面品質の向上とを調整することも含む。 [Adjustment method]
In the adjustment method of the present disclosure, the polishing speed of the silicon substrate and the surface quality of the polished substrate are adjusted by changing the content ratio of the component A and the component B by using the polishing liquid composition of the present disclosure described above. The method. According to the adjustment method of the present disclosure, the effect of the polishing rate and the effect of the surface quality of the substrate can be changed by changing the ratio of the contents of the component A and the component B. Therefore, "adjusting the polishing speed of the silicon substrate and the surface quality of the substrate after polishing" means, in one or more embodiments, when polishing with the polishing liquid composition of the present disclosure, the polishing liquid composition. When polishing with the polishing liquid composition of the present disclosure in one or more embodiments, the composition comprises setting the material to a composition in which the improvement of the polishing speed is prioritized over the improvement of the surface quality of the post-polishing substrate. In one or more embodiments, the polishing liquid composition is polished using the polishing liquid composition of the present disclosure, which comprises setting the polishing liquid composition to have a composition in which the improvement of the surface quality of the post-polishing substrate is prioritized over the improvement of the polishing speed. This includes making the polishing liquid composition a composition in which the improvement of the polishing speed and the improvement of the surface quality of the post-polishing substrate are balanced.
The adjusting method of the present disclosure is to be polished by one or more polishing liquid compositions in which the improvement of the polishing rate and the improvement of the surface quality of the post-polished substrate are adjusted as described above in the other one or more embodiments. It also includes adjusting the polishing speed of polishing and the surface quality of the substrate after polishing by polishing the silicon substrate.
　研磨速度の向上を優先した組成とする場合、一又は複数の実施形態において、本開示の研磨液組成物における成分Ａの比率を高くすることが挙げられる。
　成分Ａの比率と高くする場合、一又は複数の実施形態において、研磨液組成物中の成分Ａと成分Ｂの合計含有量に対する成分Ａの割合［Ａ／（Ａ＋Ｂ）］を、好ましくは５０質量％以上、より好ましくは７０質量％以上、更に好ましくは８０質量％以上、より更に好ましくは９０質量％以上、より更に好ましくは９５質量％以上、より更に好ましくは９８質量％以上、より更に好ましくは実質的に１００質量％とすることが挙げられる。
　本開示において、割合［Ａ／（Ａ＋Ｂ）］が実質的に１００質量％とは、一又は複数の実施形態において、成分Ｂが０質量％あるいは意図的に添加又は配合されていない場合が挙げられる。 When the composition gives priority to the improvement of the polishing rate, it is possible to increase the ratio of the component A in the polishing liquid composition of the present disclosure in one or more embodiments.
When the ratio of the component A is increased, in one or more embodiments, the ratio of the component A to the total content of the component A and the component B in the polishing liquid composition [A / (A + B)] is preferably 50% by mass. % Or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably. It is mentioned that it is substantially 100% by mass.
In the present disclosure, the ratio [A / (A + B)] is substantially 100% by mass, which may be the case where component B is 0% by mass or intentionally not added or blended in one or more embodiments. ..
　研磨後基板の表面品質の向上を優先した組成とする場合、一又は複数の実施形態において、本開示の研磨液組成物における成分Ｂの比率を高くすることが挙げられる。
　成分Ｂの比率と高くする場合、一又は複数の実施形態において、研磨液組成物中の成分Ａと成分Ｂの合計含有量に対する成分Ｂの割合［Ｂ／（Ａ＋Ｂ）］を、好ましくは５０質量％以上、より好ましくは７０質量％以上、更に好ましくは８０質量％以上、より更に好ましくは９０質量％以上、より更に好ましくは９５質量％以上、より更に好ましくは９８質量％以上、より更に好ましくは実質的に１００質量％とすることが挙げられる。
　本開示において、割合［Ｂ／（Ａ＋Ｂ）］が実質的に１００質量％とは、一又は複数の実施形態において、成分Ａが０質量％あるいは意図的に添加又は配合されていない場合が挙げられる。 When the composition gives priority to improving the surface quality of the polished substrate, it is possible to increase the ratio of the component B in the polishing liquid composition of the present disclosure in one or more embodiments.
When the ratio of the component B is increased, in one or more embodiments, the ratio of the component B to the total content of the component A and the component B in the polishing liquid composition [B / (A + B)] is preferably 50% by mass. % Or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably. It is mentioned that it is substantially 100% by mass.
In the present disclosure, the ratio [B / (A + B)] of substantially 100% by mass may be 0% by mass or intentionally not added or blended with the component A in one or more embodiments. ..
　研磨速度の向上を優先した組成とする場合、一又は複数の実施形態において、本開示の研磨液組成物はシリカ粒子（成分Ｃ）を含有することが好ましい。
　研磨後基板の表面品質の向上を優先した組成とする場合、一又は複数の実施形態において、シリカ粒子（成分Ｃ）を含有しない研磨液組成物を用いることもできる。 When the composition gives priority to improving the polishing rate, it is preferable that the polishing liquid composition of the present disclosure contains silica particles (component C) in one or more embodiments.
When the composition gives priority to improving the surface quality of the polished substrate, a polishing liquid composition containing no silica particles (component C) may be used in one or more embodiments.
　［研磨工程の調整］
　本開示の調整方法は、一又は複数の実施形態において、上述のように研磨速度の向上と研磨後基板の表面品質の向上とが調整された２以上の研磨液組成物を用いて研磨することで、研磨工程における研磨の研磨速度の向上と研磨後基板の表面品質の向上とを調整することも含む。
　一又は複数の実施形態において、ある表面品質の基板を得るにあたり、最初は研磨速度の向上を優先した成分Ａの含有比率の高い研磨液組成物を用いて研磨し、次に研磨後基板の表面品質の向上を優先した成分Ｂの含有比率の高い研磨液組成物を用いて研磨を行う。このように、本開示の調整方法は、２以上の研磨液組成物中の成分Ａ及び成分Ｂの含有比率を変更して、所定の表面品質を得るまでの研磨時間が短くなる研磨液組成物の組み合わせを選ぶこと、及びそれらを用いて研磨することを含む。これらの研磨液を用いることにより、生産を高めることができ、研磨にかかるコストを下げることができる。
　本開示の調整方法は、２以上の研磨液組成物中の成分Ａ及び成分Ｂの含有比率を変更することに加えて、成分Ａ及び成分Ｂの合計の含有量を変更することを含んでもよい。
　本開示の調整方法は、３以上の研磨液組成物の組み合わせを選ぶことを含みうる。 [Adjustment of polishing process]
The adjustment method of the present disclosure is to polish using two or more polishing liquid compositions in which the improvement of the polishing speed and the improvement of the surface quality of the post-polishing substrate are adjusted as described above in one or more embodiments. Therefore, it also includes adjusting the improvement of the polishing speed of polishing in the polishing process and the improvement of the surface quality of the post-polishing substrate.
In one or more embodiments, in order to obtain a substrate of a certain surface quality, first polishing is performed using a polishing liquid composition having a high content ratio of component A, which gives priority to improving the polishing speed, and then the surface of the substrate after polishing is used. Polishing is performed using a polishing liquid composition having a high content ratio of component B, which gives priority to improving quality. As described above, the adjusting method of the present disclosure is a polishing liquid composition in which the content ratio of the component A and the component B in two or more polishing liquid compositions is changed to shorten the polishing time until a predetermined surface quality is obtained. Includes choosing a combination of and polishing with them. By using these polishing liquids, it is possible to increase the production and reduce the cost of polishing.
The adjusting method of the present disclosure may include changing the total content of the component A and the component B in addition to changing the content ratio of the component A and the component B in the two or more polishing liquid compositions. ..
The adjustment method of the present disclosure may include selecting a combination of three or more abrasive liquid compositions.
　本開示の研磨液組成物を２以上の組み合わせで使用して研磨する場合、１つの研磨定盤に２以上の研磨液組成物を切り替えて供給することで研磨することができる。あるいは、２以上の組み合わせの研磨液組成物ごとに研磨定盤を変えて研磨することもできる。
　同じ研磨定盤において成分Ａ及び成分Ｂのそれぞれの貯蔵容器からチューブ等を用いて供給し、研磨定盤に導入する前に混合して研磨液に導入するシステムを用い、成分Ａと成分Ｂの供給量を変更して連続的に含有比率を変えて研磨する形態も、本開示における調整方法の２以上研磨液組成物を用いて研磨する場合に該当しうる。 When polishing using the polishing liquid composition of the present disclosure in a combination of two or more, polishing can be performed by switching and supplying two or more polishing liquid compositions to one polishing surface plate. Alternatively, polishing can be performed by changing the polishing surface plate for each of two or more combinations of polishing liquid compositions.
Using a system in which components A and B are supplied from their respective storage containers on the same polishing surface plate using a tube or the like, mixed before being introduced into the polishing surface plate, and introduced into the polishing liquid, the components A and B are charged. The form of polishing by changing the supply amount and continuously changing the content ratio may also be applicable to the case of polishing using two or more polishing liquid compositions of the adjustment method in the present disclosure.
　［シリコン基板の研磨方法］
　本開示の調整方法は、一又は複数の実施形態において、研磨速度の向上と表面品質の向上とを両立する観点から、仕上げ研磨工程で用いられることが好ましい。 [How to polish a silicon substrate]
The adjustment method of the present disclosure is preferably used in the finish polishing step in one or more embodiments from the viewpoint of achieving both improvement in polishing speed and improvement in surface quality.
　本開示の調整方法が用いられる仕上げ研磨工程としては、本開示の効果がより発揮される観点から、シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、該仕上げ研磨工程２よりも前の研磨工程である仕上げ研磨工程１とを備え、該仕上げ研磨工程１と該仕上げ研磨工程２とがこの順で行われる研磨工程が好ましく、シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、該仕上げ研磨工程２の１段階前の研磨工程である仕上げ研磨工程１を備え、該仕上げ研磨工程１と該仕上げ研磨工程２とが連続する研磨工程がより好ましい。 As the finish polishing step in which the adjustment method of the present disclosure is used, from the viewpoint of further exerting the effect of the present disclosure, the finish polishing step 2 for performing the finish polishing of the silicon substrate and the polishing step prior to the finish polishing step 2 are performed. It is preferable that the finish polishing step 1 is provided and the finish polishing step 1 and the finish polishing step 2 are performed in this order, and the finish polishing step 2 for performing the finish polishing of the silicon substrate and the finish polishing step 2 are preferable. It is more preferable to include a finish polishing step 1 which is a polishing step one step before the second step, and a polishing step in which the finish polishing step 1 and the finish polishing step 2 are continuous is more preferable.
　仕上げ研磨工程１では、研磨液組成物は、シリカ粒子（成分Ｃ）を含有し、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合［Ａ／（Ａ＋Ｂ）］が高い研磨液組成物で研磨し、仕上げ研磨工程２では、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合［Ｂ／（Ａ＋Ｂ）］の高い研磨液で研磨することが好ましい。
　仕上げ工程２で用いる研磨液組成物はシリカ粒子（成分Ｃ）を含有しても、しなくてもよい。また、仕上げ研磨工程２において、シリカ粒子（成分Ｃ）を含有する研磨液組成物で研磨した後、シリカ粒子（成分Ｃ）を含有しない研磨液組成物で研磨してもよい。 In the finish polishing step 1, the polishing liquid composition contains silica particles (component C), and the ratio of the content of component A to the total content of component A and component B [A / (A + B)] is high. It is preferable to polish with the composition, and in the finish polishing step 2, polish with a polishing liquid having a high ratio of the content of the component B to the total content of the component A and the component B [B / (A + B)].
The polishing liquid composition used in the finishing step 2 may or may not contain silica particles (component C). Further, in the finish polishing step 2, after polishing with a polishing liquid composition containing silica particles (component C), polishing may be performed with a polishing liquid composition not containing silica particles (component C).
　よって、本開示は一態様において、シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、仕上げ研磨工程２よりも前の研磨工程である仕上げ研磨工程１とを備え、仕上げ研磨工程１と仕上げ研磨工程２とがこの順で行われるシリコン基板の研磨方法であって、
　仕上げ研磨工程１及び２において使用される研磨液組成物は成分Ａ及び成分Ｂからなる群から選ばれる少なくとも一方の成分を含有し、該仕上げ研磨工程１では、該研磨液組成物は成分Ｃを含有し、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合が５０質量％以上の研磨液組成物で研磨し、
　仕上げ研磨工程２では、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合が５０質量％以上の研磨液組成物で研磨するシリコン基板の研磨方法に関する。本態様のシリコン基板の研磨方法によれば、研磨速度と表面品質を向上することができる。 Therefore, in one embodiment, the present disclosure includes a finish polishing step 2 for performing finish polishing of a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2, and includes a finish polishing step 1 and a finish polishing step. 2 is the polishing method of the silicon substrate performed in this order.
The polishing liquid composition used in the finish polishing steps 1 and 2 contains at least one component selected from the group consisting of the component A and the component B, and in the finish polishing step 1, the polishing liquid composition contains the component C. Polish with a polishing liquid composition in which the ratio of the content of the component A to the total content of the component A and the component B is 50% by mass or more.
The finish polishing step 2 relates to a method for polishing a silicon substrate for polishing with a polishing liquid composition in which the ratio of the content of component B to the total content of component A and component B is 50% by mass or more. According to the method for polishing a silicon substrate according to this embodiment, the polishing speed and the surface quality can be improved.
　仕上げ研磨工程１で用いる研磨液組成物の割合［Ａ／（Ａ＋Ｂ）］は、研磨速度を向上させる観点から、好ましくは５０質量％以上、より好ましくは７０質量％以上、更に好ましくは８０質量％以上、より更に好ましくは９０質量％以上、より更に好ましくは９５質量％以上、より更に好ましくは９８質量％以上、より更に好ましくは実質的に１００質量％である。
　また、仕上げ研磨工程２で用いる研磨液組成物の割合［Ｂ／（Ａ＋Ｂ）］は、表面品質を向上させる観点から、好ましくは５０質量％以上、より好ましくは７０質量％以上、更に好ましくは８０質量％以上、より更に好ましくは９０質量％以上、より更に好ましくは９５質量％以上、より更に好ましくは９８質量％以上、より更に好ましくは実質的に１００質量％である。 The ratio [A / (A + B)] of the polishing liquid composition used in the finish polishing step 1 is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass, from the viewpoint of improving the polishing speed. The above is more preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass.
Further, the ratio [B / (A + B)] of the polishing liquid composition used in the finish polishing step 2 is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80 from the viewpoint of improving the surface quality. It is mass% or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably substantially 100% by mass.
　本開示の研磨方法における仕上げ研磨工程１及び２では、例えば、研磨パッドを貼り付けた定盤に被研磨シリコン基板を押し付けて、３～２０ｋＰａの研磨圧力で被研磨シリコン基板を研磨することができる。本開示において、研磨圧力とは、研磨時に被研磨シリコン基板の被研磨面に加えられる定盤の圧力をいう。 In the finish polishing steps 1 and 2 in the polishing method of the present disclosure, for example, the silicon substrate to be polished can be pressed against a surface plate to which a polishing pad is attached, and the silicon substrate to be polished can be polished with a polishing pressure of 3 to 20 kPa. .. In the present disclosure, the polishing pressure means the pressure of the surface plate applied to the surface to be polished of the silicon substrate to be polished during polishing.
　本開示の研磨方法における仕上げ研磨工程１及び２では、例えば、研磨パッドを貼り付けた定盤に被研磨シリコン基板を押し付けて、１５℃以上４０℃以下の研磨液組成物及び研磨パッド表面温度で被研磨シリコン基板を研磨することができる。研磨液組成物の温度及び研磨パッド表面温度としては、研磨速度向上と表面粗さ（ヘイズ）低減等の表面品質との両立の観点から、１５℃以上又は２０℃以上が好ましく、４０℃以下又は３０℃以下が好ましい。 In the finish polishing steps 1 and 2 in the polishing method of the present disclosure, for example, the silicon substrate to be polished is pressed against a surface plate to which a polishing pad is attached, and the polishing liquid composition and the polishing pad surface temperature of 15 ° C. or higher and 40 ° C. or lower are used. The silicon substrate to be polished can be polished. The temperature of the polishing liquid composition and the surface temperature of the polishing pad are preferably 15 ° C. or higher or 20 ° C. or higher, preferably 40 ° C. or lower, or 40 ° C. or lower, from the viewpoint of achieving both improvement in polishing speed and surface quality such as reduction of surface roughness (haze). It is preferably 30 ° C. or lower.
　仕上げ研磨工程１と仕上げ研磨工程２は、１つの研磨定盤（同じ研磨定盤）で行うことができる。あるいは、仕上げ研磨工程１と仕上げ研磨工程２は、研磨定盤を変えて行う、すなわち、仕上げ研磨工程２を、仕上げ研磨工程１で使用した研磨定盤とは別の研磨定盤で行うこともできる。
　仕上げ研磨工程１と仕上げ研磨工程２を同じ研磨定盤で行う場合、成分Ａ及び成分Ｂのそれぞれの貯蔵容器からチューブ等を用いて供給し、研磨定盤に導入する前に混合して研磨液に導入するシステムを用いて、成分Ａと成分Ｂの供給量を変更して連続的に含有比率を変えて研磨してもよい。
　仕上げ研磨工程２において、シリカ粒子（成分Ｃ）を含有する研磨液組成物で研磨した後、シリカ粒子（成分Ｃ）を含有しない研磨液組成物で研磨する場合、同じ研磨定盤で行うことができる。あるいは、シリカ粒子（成分Ｃ）を含有しない研磨液組成物で研磨する工程を、シリカ粒子（成分Ｃ）を含有する研磨液組成物で研磨する工程で使用した研磨定盤とは別の研磨定盤で行うことができる。 The finish polishing step 1 and the finish polishing step 2 can be performed on one polishing surface plate (same polishing surface plate). Alternatively, the finish polishing step 1 and the finish polishing step 2 may be performed by changing the polishing surface plate, that is, the finish polishing step 2 may be performed by a polishing surface plate different from the polishing surface plate used in the finish polishing step 1. can.
When the finish polishing step 1 and the finish polishing step 2 are performed on the same polishing surface plate, the polishing liquid is supplied from each storage container of component A and component B using a tube or the like, and is mixed before being introduced into the polishing surface plate. The supply amounts of the component A and the component B may be changed and the content ratio may be continuously changed for polishing by using the system introduced in the above.
In the finish polishing step 2, when polishing with a polishing liquid composition containing silica particles (component C) and then polishing with a polishing liquid composition not containing silica particles (component C), the same polishing surface plate may be used. can. Alternatively, the polishing step of polishing with the polishing liquid composition not containing silica particles (component C) is different from the polishing surface plate used in the step of polishing with the polishing liquid composition containing silica particles (component C). It can be done on the board.
　［半導体基板の製造方法］
　本開示は、一態様において、本開示の調製方法、又は、本開示の研磨方法を行うことを含む、半導体基板の製造方法（以下、「本開示の半導体基板製造方法」ともいう）に関する。本開示の半導体基板製造方法は、一又は複数の実施形態において、本開示の研磨液組成物を用いて被研磨シリコン基板を研磨する工程（以下、「研磨工程」ともいう）と、研磨されたシリコン基板を洗浄する工程（以下、「洗浄工程」ともいう）と、を含むことができる。本開示の半導体基板製造方法によれば、本開示の調製方法、又は、本開示の研磨方法を用いることで、研磨速度向上と表面品質の向上とを両立できるため、高品質の半導体基板を高収率で、生産性よく、安価に製造できる。 [Manufacturing method of semiconductor substrate]
The present disclosure relates to a method for manufacturing a semiconductor substrate (hereinafter, also referred to as "the method for manufacturing a semiconductor substrate of the present disclosure"), which comprises performing the preparation method of the present disclosure or the polishing method of the present disclosure in one aspect. The semiconductor substrate manufacturing method of the present disclosure includes, in one or a plurality of embodiments, a step of polishing a silicon substrate to be polished using the polishing liquid composition of the present disclosure (hereinafter, also referred to as a “polishing step”). A step of cleaning a silicon substrate (hereinafter, also referred to as a “cleaning step”) can be included. According to the semiconductor substrate manufacturing method of the present disclosure, by using the preparation method of the present disclosure or the polishing method of the present disclosure, both improvement of polishing speed and improvement of surface quality can be achieved, so that a high quality semiconductor substrate can be obtained. It can be manufactured with good yield, high productivity, and low cost.
　本開示の半導体基板製造方法における研磨工程は、例えば、単結晶シリコンインゴットを薄円板状にスライスすることにより得られた単結晶シリコン基板を平面化するラッピング（粗研磨）工程と、ラッピング単結晶されたシリコン基板をエッチングした後、単結晶シリコン基板表面を鏡面化する仕上げ研磨工程とを含むことができる。本開示の調整方法は、研磨速度の向上と表面品質の向上とを両立する観点から、上記仕上げ研磨工程で用いられるとより好ましい。本開示の調製方法が用いられる仕上げ研磨工程としては、上述したものが挙げられる。本開示の半導体基板製造方法における研磨工程では、上述した本開示の研磨方法における仕上げ研磨工程１及び２と同様の条件（研磨圧力、研磨組成物及び研磨パッド表面温度等）で研磨を行うことができる。 The polishing steps in the semiconductor substrate manufacturing method of the present disclosure include, for example, a wrapping (rough polishing) step of flattening a single crystal silicon substrate obtained by slicing a single crystal silicon ingot into a thin disk shape, and a wrapping single crystal. After etching the silicon substrate, a finish polishing step of mirroring the surface of the single crystal silicon substrate can be included. The adjustment method of the present disclosure is more preferably used in the above-mentioned finish polishing step from the viewpoint of achieving both improvement in polishing speed and improvement in surface quality. Examples of the finish polishing step in which the preparation method of the present disclosure is used include those described above. In the polishing step in the semiconductor substrate manufacturing method of the present disclosure, polishing may be performed under the same conditions (polishing pressure, polishing composition, polishing pad surface temperature, etc.) as in the finish polishing steps 1 and 2 in the above-mentioned polishing method of the present disclosure. can.
　本開示の半導体基板製造方法は、一又は複数の実施形態において、前記研磨工程の前に、研磨液組成物の濃縮物を希釈する希釈工程を含んでいてもよい。希釈媒には、例えば、水を用いることができる。 The semiconductor substrate manufacturing method of the present disclosure may include, in one or more embodiments, a dilution step of diluting the concentrate of the polishing liquid composition before the polishing step. For example, water can be used as the dilution medium.
　本開示の半導体基板製造方法における洗浄工程では、シリコン基板表面上の残留物低減の観点から、無機物洗浄を行うことが好ましい。無機物洗浄で用いる洗浄剤としては、例えば、過酸化水素、アンモニア、塩酸、硫酸、フッ酸及びオゾン水から選ばれる少なくとも１種を含む無機物洗浄剤が挙げられる。 In the cleaning step in the semiconductor substrate manufacturing method of the present disclosure, it is preferable to perform inorganic substance cleaning from the viewpoint of reducing residues on the surface of the silicon substrate. Examples of the cleaning agent used for cleaning the inorganic substance include an inorganic cleaning agent containing at least one selected from hydrogen peroxide, ammonia, hydrochloric acid, sulfuric acid, hydrofluoric acid and ozone water.
　本開示の半導体基板製造方法は、一又は複数の実施形態において、前記洗浄工程の後に、洗浄後のシリコン基板を水でリンスし、乾燥する工程を更に含むことができる。 The semiconductor substrate manufacturing method of the present disclosure may further include, in one or more embodiments, a step of rinsing the cleaned silicon substrate with water and drying it after the cleaning step.
　本開示の半導体基板製造方法における研磨工程が、上述した仕上げ研磨工程１と仕上げ研磨工程２とがこの順で行われる研磨工程である場合、仕上げ研磨工程１を行った後、洗浄、乾燥を行い、仕上げ研磨工程２を行ってもよい。また、仕上げ研磨工程１を行った後、洗浄、乾燥を行なわずに、仕上げ研磨工程２を行ってもよい。生産性向上の観点から、仕上げ研磨工程１を行った後、洗浄、乾燥を行なわずに、仕上げ研磨工程２を行うことが好ましい。 When the polishing step in the semiconductor substrate manufacturing method of the present disclosure is a polishing step in which the above-mentioned finish polishing step 1 and finish polishing step 2 are performed in this order, after performing the finish polishing step 1, cleaning and drying are performed. , The finish polishing step 2 may be performed. Further, after performing the finish polishing step 1, the finish polishing step 2 may be performed without washing and drying. From the viewpoint of improving productivity, it is preferable to perform the finish polishing step 2 without washing and drying after performing the finish polishing step 1.
　本開示は、さらに以下の一又は複数の実施形態に関する。
＜１＞　ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有する研磨液組成物を用いて、成分Ａと成分Ｂの含有量比を変えることにより、シリコン基板の研磨速度と研磨後の基板の表面品質を調整する方法。
＜２＞　ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有し、研磨液組成物のｐＨが９以上１２以下であり、該ｐＨと該ｐＫａの差［ｐＨ－ｐＫａ］が２以上６以下する研磨液組成物を用いて、成分Ａと成分Ｂの含有量比を変えることによる、＜１＞に記載の方法。
＜３＞　成分Ａがポリアリルアミンとグリシドール誘導体との反応物及び上記式（ＩＩＩ）で表される構成単位を含む化合物から選ばれる少なくとも１種であり、成分Ｂがポリグリセリン、ポリグリセリンアルキルエーテル、ポリグリセリンアルキルエステル、ヒドロキシアルキルセルロース、ポリビニルアルコール、ポリビニルピロリドン、ポリヒドロキシエチルアクリルアミド、及び、重量平均分子量が３００以上１,０００以下のポリエチレングリコールから選ばれる少なくとも１種である、＜１＞または＜２＞に記載の方法。
＜４＞　前記研磨液組成物中の成分Ａの含有量が０質量ｐｐｍ以上２００質量ｐｐｍであり、前記研磨液組成物中の成分Ｂの含有量が０質量ｐｐｍ以上２００質量ｐｐｍである、＜１＞乃至＜３＞の何れか１つに記載の方法。
＜５＞　成分Ａの重量平均分子量が８００以上１２０００以下であり、成分Ｂの重量平均分子量が３００以上３０万以下である、＜１＞乃至＜４＞の何れか１つに記載の方法。
＜６＞　前記研磨液組成物がさらにシリカ粒子（成分Ｃ）を含有する、＜１＞乃至＜５＞の何れか１つに記載の方法。
＜７＞　前記研磨液組成物中の成分Ｃの含有量が０．０７質量％以上０．３質量％以下、であり、シリコン基板が単結晶シリコン基板である、＜１＞乃至＜６＞の何れか１つに記載の方法。
＜８＞　前記研磨液組成物中の成分Ｃの含有量が０．１質量％以上０．８質量％以下、であり、シリコン基板がポリシリコン基板である、＜１＞乃至＜６＞の何れか１つに記載の方法。
＜９＞　シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、仕上げ研磨工程２よりも前の研磨工程である仕上げ研磨工程１とを備え、仕上げ研磨工程１と仕上げ研磨工程２とがこの順で行われるシリコン基板の研磨方法であって、
　仕上げ研磨工程１及び２において使用される研磨液組成物は、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有し、
　仕上げ研磨工程１では、研磨液組成物はシリカ粒子（成分Ｃ）を含有し、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合が５０質量％以上の研磨液組成物で研磨し、
　仕上げ研磨工程２では、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合が５０質量％以上の研磨液組成物で研磨する、シリコン基板の研磨方法。
＜１０＞　シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、仕上げ研磨工程２よりも前の研磨工程である仕上げ研磨工程１とを備え、仕上げ研磨工程１と仕上げ研磨工程２とがこの順で行われるシリコン基板の研磨方法であって、
　仕上げ研磨工程１及び２において使用される研磨液組成物は、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有し、研磨液組成物のｐＨが９以上１２以下であり、該ｐＨと該ｐＫａの差［ｐＨ－ｐＫａ］が２以上６以下であり、
　仕上げ研磨工程１では、研磨液組成物はシリカ粒子（成分Ｃ）を含有し、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合が５０質量％以上の研磨液組成物で研磨し、
　仕上げ研磨工程２では、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合が５０質量％以上の研磨液組成物で研磨する、＜９＞に記載のシリコン基板の研磨方法。
＜１１＞　成分Ａがポリアリルアミンとグリシドール誘導体との反応物及び上記式（ＩＩＩ）で表される構成単位を含む化合物から選ばれる少なくとも１種であり、成分Ｂがポリグリセリン、ポリグリセリンアルキルエーテル、ポリグリセリンアルキルエステル、ヒドロキシアルキルセルロース、ポリビニルアルコール、ポリビニルピロリドン、ポリヒドロキシエチルアクリルアミド、及び、重量平均分子量が３００以上１,０００以下のポリエチレングリコールから選ばれる少なくとも１種である、＜９＞または＜１０＞に記載の研磨方法。
＜１２＞　前記研磨液組成物中の成分Ａの含有量が０質量ｐｐｍ以上２００質量ｐｐｍであり、前記研磨液組成物中の成分Ｂの含有量が０質量ｐｐｍ以上２００質量ｐｐｍである、＜９＞乃至＜１１＞の何れか１つに記載の研磨方法。
＜１３＞　成分Ａの重量平均分子量が８００以上１２０００以下であり、成分Ｂの重量平均分子量が３００以上３０万以下である、＜９＞乃至＜１２＞の何れか１つに記載の研磨方法。
＜１４＞　前記研磨液組成物中の成分Ｃの含有量が０．０７質量％以上０．３質量％以下であり、シリコン基板が単結晶シリコン基板である、＜９＞乃至＜１３＞の何れか１つに記載の研磨方法。
＜１５＞　前記仕上げ研磨工程１と前記仕上げ研磨工程２を１つの研磨定盤で行う、＜９＞乃至＜１４＞の何れか１つに記載の研磨方法。
＜１６＞　前記仕上げ研磨工程１と前記仕上げ研磨工程２を研磨定盤を変えて行う、＜９＞乃至＜１４＞の何れか１つに記載の研磨方法。
＜１７＞　前記仕上げ研磨工程２において、シリカ粒子（成分Ｃ）を含有する研磨液組成物で研磨した後、シリカ粒子（成分Ｃ）を含有しない研磨液組成物で研磨する、＜９＞乃至＜１６＞の何れか１つに記載の研磨方法。
＜１８＞　＜１＞から＜８＞のいずれかに記載の方法、又は、＜９＞から＜１７＞のいずれかに記載の研磨方法を行うことを含む、半導体基板の製造方法。 The present disclosure further relates to one or more embodiments below.
<1> Contains at least one component selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less. A method of adjusting the polishing speed of a silicon substrate and the surface quality of the substrate after polishing by changing the content ratio of the component A and the component B using the polishing liquid composition.
<2> Contains at least one component selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pH of 5 or more and 8.5 or less. , The content ratio of the component A to the component B using the polishing liquid composition in which the pH of the polishing liquid composition is 9 or more and 12 or less and the difference [pH-pKa] between the pH and the pKa is 2 or more and 6 or less. The method according to <1> by changing.
<3> Component A is at least one selected from a reaction product of polyallylamine and a glycidol derivative and a compound containing a structural unit represented by the above formula (III), and component B is polyglycerin, polyglycerin alkyl ether, and the like. <1> or <2, which is at least one selected from polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethyl acrylamide, and polyethylene glycol having a weight average molecular weight of 300 or more and 1,000 or less. > The method described in.
<4> The content of the component A in the polishing liquid composition is 0% by mass or more and 200% by mass, and the content of the component B in the polishing liquid composition is 0% by mass or more and 200% by mass. The method according to any one of 1> to <3>.
<5> The method according to any one of <1> to <4>, wherein the weight average molecular weight of the component A is 800 or more and 12000 or less, and the weight average molecular weight of the component B is 300 or more and 300,000 or less.
<6> The method according to any one of <1> to <5>, wherein the polishing liquid composition further contains silica particles (component C).
<7> Of <1> to <6>, the content of the component C in the polishing liquid composition is 0.07% by mass or more and 0.3% by mass or less, and the silicon substrate is a single crystal silicon substrate. The method described in any one.
<8> Any of <1> to <6>, wherein the content of component C in the polishing liquid composition is 0.1% by mass or more and 0.8% by mass or less, and the silicon substrate is a polysilicon substrate. The method described in one.
<9> A finish polishing step 2 for finish polishing a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2 are provided, and the finish polishing step 1 and the finish polishing step 2 are performed in this order. It is a method of polishing a silicon substrate that is performed.
The polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less. Contains at least one ingredient selected from the group consisting of
In the finish polishing step 1, the polishing liquid composition contains silica particles (component C) and is polished with a polishing liquid composition in which the ratio of the content of component A to the total content of component A and component B is 50% by mass or more. death,
In the finish polishing step 2, a method for polishing a silicon substrate, wherein the ratio of the content of the component B to the total content of the component A and the component B is 50% by mass or more with a polishing liquid composition.
<10> A finish polishing step 2 for finish polishing a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2 are provided, and the finish polishing step 1 and the finish polishing step 2 are performed in this order. It is a method of polishing a silicon substrate that is performed.
The polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pH of 5 or more and 8.5 or less. It contains at least one component selected from the group consisting of, and the pH of the polishing liquid composition is 9 or more and 12 or less, and the difference between the pH and the pKa [pH-pKa] is 2 or more and 6 or less.
In the finish polishing step 1, the polishing liquid composition contains silica particles (component C) and is polished with a polishing liquid composition in which the ratio of the content of component A to the total content of component A and component B is 50% by mass or more. death,
The method for polishing a silicon substrate according to <9>, wherein in the finish polishing step 2, the silicon substrate is polished with a polishing liquid composition in which the ratio of the content of the component B to the total content of the component A and the component B is 50% by mass or more.
<11> Component A is at least one selected from a reaction product of polyallylamine and a glycidol derivative and a compound containing a structural unit represented by the above formula (III), and component B is polyglycerin, polyglycerin alkyl ether, and the like. <9> or <10, which is at least one selected from polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethyl acrylamide, and polyethylene glycol having a weight average molecular weight of 300 or more and 1,000 or less. > The polishing method described in.
<12> The content of the component A in the polishing liquid composition is 0% by mass or more and 200% by mass, and the content of the component B in the polishing liquid composition is 0% by mass or more and 200% by mass. The polishing method according to any one of 9> to <11>.
<13> The polishing method according to any one of <9> to <12>, wherein the weight average molecular weight of the component A is 800 or more and 12000 or less, and the weight average molecular weight of the component B is 300 or more and 300,000 or less.
<14> Any of <9> to <13>, wherein the content of component C in the polishing liquid composition is 0.07% by mass or more and 0.3% by mass or less, and the silicon substrate is a single crystal silicon substrate. The polishing method described in one.
<15> The polishing method according to any one of <9> to <14>, wherein the finish polishing step 1 and the finish polishing step 2 are performed on one polishing surface plate.
<16> The polishing method according to any one of <9> to <14>, wherein the finish polishing step 1 and the finish polishing step 2 are performed by changing the polishing surface plate.
<17> In the finish polishing step 2, polishing is performed with a polishing liquid composition containing silica particles (component C), and then polishing is performed with a polishing liquid composition containing no silica particles (component C), <9> to <. The polishing method according to any one of 16>.
<18> A method for manufacturing a semiconductor substrate, which comprises performing the method according to any one of <1> to <8> or the polishing method according to any one of <9> to <17>.
　以下、実施例により本開示をさらに詳細に説明するが、これらは例示的なものであって、本開示はこれら実施例に制限されるものではない。 Hereinafter, the present disclosure will be described in more detail by way of examples, but these are exemplary and the present disclosure is not limited to these examples.
　１．研磨液組成物の調製
　（研磨液組成物の濃縮物）
　表１に示すシリカ粒子（成分Ｃ）、アミノ基含有水溶性高分子化合物（成分Ａ）、ノニオン性水溶性高分子化合物（成分Ｂ）、アンモニア（成分Ｄ）、及び超純水を撹拌混合して、研磨液組成物の濃縮物（６０倍）を得た。濃縮物の２５℃におけるｐＨは１０．３～１１．０であった。
　（研磨液組成物）
　上記濃縮物をイオン交換水で６０倍希釈して、実施例１～１２の研磨液組成物（ａ１～ａ６、ｂ１～ｂ６）を得た（表１）。表１中の各成分の含有量は、希釈後の研磨液組成物の使用時における各成分の含有量（質量％又は質量ｐｐｍ、有効分）である。超純水の含有量は、成分Ａ～Ｄを除いた残余である。各研磨液組成物（使用時）の２５℃におけるｐＨは、１０．１又は１０．３であった。
　２５℃におけるｐＨは、ｐＨメータ（東亜電波工業株式会社、ＨＭ－３０Ｇ）を用いて測定した値であり、ｐＨメータの電極を研磨液組成物又はその濃縮物へ浸漬して１分後の数値である。 1. 1. Preparation of polishing liquid composition (concentrate of polishing liquid composition)
Silica particles (component C), amino group-containing water-soluble polymer compound (component A), nonionic water-soluble polymer compound (component B), ammonia (component D), and ultrapure water shown in Table 1 are stirred and mixed. A concentrate (60 times) of the polishing liquid composition was obtained. The pH of the concentrate at 25 ° C. was 10.3 to 11.0.
(Abrasive liquid composition)
The concentrate was diluted 60-fold with ion-exchanged water to obtain the polishing liquid compositions (a1 to a6, b1 to b6) of Examples 1 to 12 (Table 1). The content of each component in Table 1 is the content (mass% or mass ppm, effective content) of each component when the polishing liquid composition after dilution is used. The content of ultrapure water is the residue excluding components A to D. The pH of each polishing liquid composition (at the time of use) at 25 ° C. was 10.1 or 10.3.
The pH at 25 ° C. is a value measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and is a value 1 minute after immersing the electrode of the pH meter in the polishing liquid composition or its concentrate. Is.
　各研磨液組成物の調製に用いた成分Ａ、成分Ｂ、成分Ｃ及び成分Ｄには下記のものを用いた。
（成分Ａ）
Ａ１：メチルジアリルアミン・二酸化硫黄共重合体［ニットーボーメディカル社製、重量平均分子量３，０００、ｐＫａ７．２］
Ａ２：グリシドール変性ポリアリルアミン（グリシドール変性率：２．０）［ニットーボーメディカル社製、重量平均分子量１１，０００、ｐＫａ６．１］
（成分Ｂ）
Ｂ１：ポリグリセリン［ダイセル社製の「ＸＰＷ」、重合度４０、重量平均分子量２，９８０］
（成分Ｃ）
Ｃ１：コロイダルシリカ［平均一次粒子径３５ｎｍ、平均二次粒子径７０ｎｍ、会合度２．０］
Ｃ２：コロイダルシリカ［平均一次粒子径２５ｎｍ、平均二次粒子径４９ｎｍ、会合度２．０］
（成分Ｄ）
アンモニア［２８質量％アンモニア水、キシダ化学社製、試薬特級］ The following components A, B, C and D used in the preparation of each polishing liquid composition were used.
(Component A)
A1: Methyl diallylamine / sulfur dioxide copolymer [manufactured by Nittobo Medical Co., Ltd., weight average molecular weight 3,000, pKa7.2]
A2: Glycidol-modified polyallylamine (glycidol modification rate: 2.0) [manufactured by Nittobo Medical Co., Ltd., weight average molecular weight 11,000, pKa6.1]
(Component B)
B1: Polyglycerin [Daicel's "XPW", degree of polymerization 40, weight average molecular weight 2,980]
(Component C)
C1: Colloidal silica [average primary particle diameter 35 nm, average secondary particle diameter 70 nm, degree of association 2.0]
C2: Colloidal silica [average primary particle diameter 25 nm, average secondary particle diameter 49 nm, degree of association 2.0]
(Component D)
Ammonia [28% by mass ammonia water, manufactured by Kishida Chemical Co., Ltd., reagent special grade]
　２．各種パラメータの測定方法
　（１）シリカ粒子（成分Ｃ）の平均一次粒子径の測定
　成分Ｃの平均一次粒子径（ｎｍ）は、ＢＥＴ（窒素吸着）法によって算出される比表面積Ｓ（ｍ2／ｇ）を用いて下記式で算出した。
平均一次粒子径（ｎｍ）＝２７２７／Ｓ 2. 2. Measurement method of various parameters (1) Measurement of average primary particle size of silica particles (component C) The average primary particle size (nm) of component C is the specific surface area S (m 2 /) calculated by the BET (nitrogen adsorption) method. It was calculated by the following formula using g).
Average primary particle size (nm) = 2727 / S
　成分Ｃの比表面積Ｓは、下記の［前処理］をした後、測定サンプル約０．１ｇを測定セルに小数点以下４桁まで精量し、比表面積の測定直前に１１０℃の雰囲気下で３０分間乾燥した後、比表面積測定装置（マイクロメリティック自動比表面積測定装置「フローソーブＩＩＩ２３０５」、島津製作所製）を用いて窒素吸着法（ＢＥＴ法）により測定した。
［前処理］
（ａ）スラリー状の成分Ｃを硝酸水溶液でｐＨ２．５±０．１に調整する。
（ｂ）ｐＨ２．５±０．１に調整されたスラリー状の成分Ｃをシャーレにとり１５０℃の熱風乾燥機内で１時間乾燥させる。
（ｃ）乾燥後、得られた試料をメノウ乳鉢で細かく粉砕する。
（ｄ）粉砕された試料を４０℃のイオン交換水に懸濁させ、孔径１μｍのメンブランフィルタで濾過する。
（ｅ）フィルタ上の濾過物を２０ｇのイオン交換水（４０℃）で５回洗浄する。
（ｆ）濾過物が付着したフィルタをシャーレにとり、１１０℃の雰囲気下で４時間乾燥させる。
（ｇ）乾燥した濾過物（成分Ｃ）をフィルタ屑が混入しないようにとり、乳鉢で細かく粉砕して測定サンプルを得た。 For the specific surface area S of the component C, after performing the following [pretreatment], about 0.1 g of the measurement sample is concentrated in the measurement cell to 4 digits after the decimal point, and immediately before the measurement of the specific surface area, 30 in an atmosphere of 110 ° C. After drying for a minute, the measurement was carried out by the nitrogen adsorption method (BET method) using a specific surface area measuring device (micromeric automatic specific surface area measuring device "Flowsorb III2305", manufactured by Shimadzu Corporation).
[Preprocessing]
(A) The slurry-like component C is adjusted to pH 2.5 ± 0.1 with an aqueous nitric acid solution.
(B) The slurry-like component C adjusted to pH 2.5 ± 0.1 is taken in a petri dish and dried in a hot air dryer at 150 ° C. for 1 hour.
(C) After drying, the obtained sample is finely pulverized in an agate mortar.
(D) The pulverized sample is suspended in ion-exchanged water at 40 ° C. and filtered through a membrane filter having a pore size of 1 μm.
(E) The filtrate on the filter is washed 5 times with 20 g of ion-exchanged water (40 ° C.).
(F) Take the filter to which the filter adheres on a petri dish and dry it in an atmosphere of 110 ° C. for 4 hours.
(G) The dried filtrate (component C) was taken so as not to be mixed with filter waste, and finely pulverized in a mortar to obtain a measurement sample.
　（２）シリカ粒子（成分Ｃ）の平均二次粒子径
　成分Ｃの平均二次粒子径（ｎｍ）は、成分Ｃの濃度が０．２５質量％となるように研磨材をイオン交換水に添加した後、得られた水分散液をＤｉｓｐｏｓａｂｌｅ Ｓｉｚｉｎｇ Ｃｕｖｅｔｔｅ（ポリスチレン製 １０ｍｍセル）に下底からの高さ１０ｍｍまで入れ、動的光散乱法（装置名：「ゼータサイザーＮａｎｏ ＺＳ」、シスメックス社製）を用いて測定した。 (2) Average secondary particle diameter of silica particles (component C) For the average secondary particle diameter (nm) of component C, a polishing material is added to ion-exchanged water so that the concentration of component C is 0.25% by mass. After that, the obtained aqueous dispersion was put into a Disposable Particle Cuvette (10 mm cell made of polystyrene) up to a height of 10 mm from the lower bottom, and a dynamic light scattering method (device name: "Zetasizer Nano ZS", manufactured by Sysmex). Was measured using.
　（３）水溶性高分子の重量平均分子量の測定
　水溶性高分子（成分Ａ、成分Ｂ）の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法を下記の条件で適用して得たクロマトグラム中のピークに基づき算出した。
＜アミノ基含有水溶性高分子（成分Ａ）＞
装置：ＨＬＣ－８３２０　ＧＰＣ（東ソー社製、検出器一体型）
カラム：ＧＳ－２２０ＨＱ＋ＧＳ－６２０ＨＱ
溶離液：０．４Ｍ ＮａＣｌ
流量：１．０ｍＬ／ｍｉｎ
カラム温度：３０℃
検出器：ショーデックスＲＩ　ＳＥ－６１示差屈折率検出器
標準物質：分子量が既知の単分散ポリエチレングリコール
＜ノニオン性水溶性高分子（成分Ｂ）＞
装置：ＨＬＣ－８３２０　ＧＰＣ（東ソー社製、検出器一体型）
カラム：ＧＭＰＷＸＬ＋ＧＭＰＷＸＬ（アニオン）
溶離液：０．２Ｍリン酸バッファー／ＣＨ3ＣＮ＝９／１
流量：０．５ｍＬ／ｍｉｎ
カラム温度：４０℃
検出器：ショーデックスＲＩ　ＳＥ－６１示差屈折率検出器
標準物質：分子量が既知の単分散ポリエチレングリコール (3) Measurement of Weight Average Molecular Weight of Water-Soluble Polymer The weight average molecular weight of the water-soluble polymer (Component A, Component B) is a chromatograph obtained by applying a gel permeation chromatography (GPC) method under the following conditions. Calculated based on peaks in the gram.
<Amino group-containing water-soluble polymer (component A)>
Equipment: HLC-8320 GPC (manufactured by Tosoh, integrated detector)
Column: GS-220HQ + GS-620HQ
Eluent: 0.4M NaCl
Flow rate: 1.0 mL / min
Column temperature: 30 ° C
Detector: Shodex RI SE-61 Differential Refractometer Detector Standard Material: Monodisperse Polyethylene Glycol with Known Molecular Weight <Nonionic Water Soluble Polymer (Component B)>
Equipment: HLC-8320 GPC (manufactured by Tosoh, integrated detector)
Column: GMPWXL + GMPWXL (anion)
Eluent: 0.2M phosphate buffer / CH 3 CN = 9/1
Flow rate: 0.5 mL / min
Column temperature: 40 ° C
Detector: Shodex RI SE-61 Differential Refractometer Detector Standard Material: Monodisperse Polyethylene Glycol with Known Molecular Weight
　（４）ｐＫａの測定
　ＨＭ－４１Ｋ型ｐＨメーター（東亜ＤＫＫ(株)）用いて、１Ｍに調整した成分Ｂの水溶液を０．１Ｍ－塩酸により室温で電位差滴定を行った。得られた滴定曲線からｐＫａを算出した。 (4) Measurement of pKa Using an HM-41K type pH meter (Toa DKK Co., Ltd.), an aqueous solution of component B adjusted to 1M was potentiometrically titrated with 0.1M-hydrochloric acid at room temperature. The pKa was calculated from the obtained titration curve.
　（５）グリシドール変性率
　グリシドール変性率は、13Ｃ－ＮＭＲを用いて求めた。
＜測定条件＞
試料：グリシドール変性ポリアリルアミン　２００ｍｇを重水０．６ｍＬに溶解
使用装置：　４００ＭＨｚ　13Ｃ－ＮＭＲ（アジレント・テクノロジー株式会社製「Ａｇｉｌｅｎｔ　４００－ＭＲ　ＤＤ２」）
測定条件：13Ｃ－ＮＭＲ測定、パルス間隔時間５秒、テトラメチルシランを標準ピーク（σ：０．０ｐｐｍ）として測定
積算回数：５０００回
積分に用いる各ピーク範囲：
Ａ：７１．０～７２．３ｐｐｍ（アミノ基と反応したグリシドールの２級水酸基が結合したＣのピークの積分値）
Ｂ：３２．０～４１．０ｐｐｍ（アリルアミンの主鎖Ｃのピークの積分値）
＜グリシドール変性率＞
グリシドール変性率（アミノ基の当量に対するグリシドールの当量比）は以下の式で求める。
グリシドール変性率（当量比）＝　２Ａ／Ｂ (5) Glycidol modification rate The glycidol modification rate was determined using 13 C-NMR.
<Measurement conditions>
Sample: Dissolve 200 mg of glycidol-modified polyallylamine in 0.6 mL of heavy water Equipment used: 400 MHz 13 C-NMR ("Agilent 400-MR DD2" manufactured by Agilent Technologies, Inc.)
Measurement conditions: 13 C-NMR measurement, pulse interval time 5 seconds, measurement with tetramethylsilane as the standard peak (σ: 0.0 ppm) Number of integrations: 5000 times Each peak range used for integration:
A: 71.0 to 72.3 ppm (integral value of the peak of C to which the secondary hydroxyl group of glycidol reacted with the amino group is bonded)
B: 32.0 to 41.0 ppm (integral value of peak of main chain C of allylamine)
<Glycidol denaturation rate>
The glycidol modification rate (equivalent ratio of glycidol to amino group equivalent) is calculated by the following formula.
Glycidol denaturation rate (equivalent ratio) = 2A / B
　３．研磨液組成物（ａ１～ａ６、ｂ１～ｂ６）の評価（実施例１～１２）
　（１）研磨方法等
　各研磨液組成物について、それぞれ研磨直前にフィルタ（コンパクトカートリッジフィルタ「ＭＣＰ－ＬＸ－Ｃ１０Ｓ」、アドバンテック社製）にてろ過を行い、下記の研磨条件で下記の被研磨シリコン基板に対して仕上げ研磨及び洗浄を行った。
　＜被研磨シリコン基板＞
単結晶シリコン基板［直径２００ｍｍのシリコン片面鏡面基板、伝導型：Ｐ、結晶方位：１００、抵抗率：０．１Ω・ｃｍ以上１００Ω・ｃｍ未満］
　上記単結晶シリコン基板を市販の研磨液組成物(フジミインコーポレーテッド製、ＧＬＡＮＺＯＸ 1302)を用いて予め粗研磨を実施した。粗研磨を終了し仕上げ研磨に供した単結晶シリコン基板のヘイズは、２～３ｐｐｍであった。 3. 3. Evaluation of Polishing Liquid Compositions (a1 to a6, b1 to b6) (Examples 1 to 12)
(1) Polishing method, etc. Each polishing liquid composition is filtered with a filter (compact cartridge filter "MCP-LX-C10S", manufactured by Advantech) immediately before polishing, and the following silicon to be polished under the following polishing conditions. The substrate was finished polished and cleaned.
<Silicon substrate to be polished>
Single crystal silicon substrate [Silicon single-sided mirror substrate with a diameter of 200 mm, conduction type: P, crystal orientation: 100, resistivity: 0.1 Ω · cm or more and less than 100 Ω · cm]
The single crystal silicon substrate was roughly polished in advance using a commercially available polishing liquid composition (manufactured by Fujimi Incorporated, GLANZOX 1302). The haze of the single crystal silicon substrate that was subjected to rough polishing and finish polishing was 2 to 3 ppm.
　＜仕上げ研磨条件＞
研磨機：片面８インチ研磨機「ＧＲＩＮＤ－Ｘ　ＳＰＰ６００ｓ」（岡本工作製）
研磨パッド：スエードパッド（東レ　コーテックス社製、アスカー硬度：６４、厚さ：１．３７ｍｍ、ナップ長：４５０μｍ、開口径：６０μｍ）
シリコン基板研磨圧力：１００ｇ／ｃｍ2
定盤回転速度：６０ｒｐｍ
研磨時間：５分
研磨液組成物の供給速度：１５０ｇ／ｍｉｎ
研磨液組成物の温度：２３℃
キャリア回転速度：６２ｒｐｍ <Finishing conditions>
Polishing machine: Single-sided 8-inch polishing machine "GRIND-X SPP600s" (manufactured by Okamoto)
Polishing pad: Suede pad (manufactured by Toray Industries, Inc., Asker hardness: 64, thickness: 1.37 mm, nap length: 450 μm, opening diameter: 60 μm)
Silicon substrate polishing pressure: 100 g / cm 2
Surface plate rotation speed: 60 rpm
Polishing time: 5 minutes Supply speed of polishing liquid composition: 150 g / min
Abrasive composition temperature: 23 ° C
Carrier rotation speed: 62 rpm
　＜洗浄方法＞
　仕上げ研磨後、シリコン基板に対して、オゾン洗浄と希フッ酸洗浄を下記のとおり行った。オゾン洗浄では、２０ｐｐｍのオゾンを含んだ水溶液をノズルから流速１Ｌ／ｍｉｎ、６００ｒｐｍで回転するシリコン基板の中央に向かって３分間噴射した。このときオゾン水の温度は常温とした。次に希フッ酸洗浄を行った。希フッ酸洗浄では、０．５質量％のフッ化水素アンモニウム（特級、ナカライテクス株式会社）を含んだ水溶液をノズルから流速１Ｌ／ｍｉｎ、６００ｒｐｍで回転するシリコン基板の中央に向かって６秒間噴射した。上記オゾン洗浄と希フッ酸洗浄を１セットとして計２セット行い、最後にスピン乾燥を行った。スピン乾燥では１，５００ｒｐｍでシリコン基板を回転させた。 <Washing method>
After finish polishing, ozone cleaning and dilute hydrofluoric acid cleaning were performed on the silicon substrate as follows. In ozone cleaning, an aqueous solution containing 20 ppm ozone was sprayed from a nozzle toward the center of a silicon substrate rotating at a flow rate of 1 L / min and 600 rpm for 3 minutes. At this time, the temperature of ozone water was set to room temperature. Next, washing with dilute hydrofluoric acid was performed. In dilute hydrofluoric acid washing, an aqueous solution containing 0.5% by mass of ammonium hydrogen fluoride (special grade, Nakaraitex Co., Ltd.) is sprayed from a nozzle toward the center of a silicon substrate rotating at a flow rate of 1 L / min and 600 rpm for 6 seconds. bottom. A total of two sets of the above ozone cleaning and dilute hydrofluoric acid cleaning were performed as one set, and finally spin drying was performed. In spin drying, the silicon substrate was rotated at 1,500 rpm.
　（２）研磨速度の評価
　研磨前後の各シリコン基板の重さを精密天秤（Ｓａｒｔｏｒｉｕｓ社製「ＢＰ－２１０Ｓ」）を用いて測定し、得られた重量差をシリコン基板の密度、面積および研磨時間で除して、単位時間当たりの片面研磨速度を求めた。結果を表１に示す。なお、研磨後のシリコン基板の重さとは、上記仕上げ研磨及び洗浄を行った後のシリコン基板の重さである。 (2) Evaluation of polishing speed The weight of each silicon substrate before and after polishing was measured using a precision balance (“BP-210S” manufactured by Sartorius), and the obtained weight difference was measured as the density, area and polishing time of the silicon substrate. Divided by, the single-sided polishing rate per unit time was obtained. The results are shown in Table 1. The weight of the silicon substrate after polishing is the weight of the silicon substrate after the finish polishing and cleaning.
　（３）シリコン基板の表面粗さ（ヘイズ）の測定
　上記仕上げ研磨及び洗浄を行った後のシリコン基板の表面粗さを、表面粗さ測定装置「Ｓｕｒｆｓｃａｎ　ＳＰ１－ＤＬＳ」（ＫＬＡ　Ｔｅｎｃｏｒ社製）を用いて測定される、暗視野ワイド斜入射チャンネル（ＤＷＯ）での値（ＤＷＯヘイズ）を用いた。結果を表１に示す。ヘイズの値は小さいほど平坦性が高いと評価できる。 (3) Measurement of Surface Roughness (Haze) of Silicon Substrate The surface roughness of the silicon substrate after the above finish polishing and cleaning is measured by using the surface roughness measuring device "Surfscan SP1-DLS" (manufactured by KLA Tencor). The value (DWO haze) at the dark field wide oblique incident channel (DWO) measured using was used. The results are shown in Table 1. It can be evaluated that the smaller the haze value, the higher the flatness.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表１に示されるように、実施例１、２、５、７、８、及び１１の研磨液組成物は、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合［Ａ／（Ａ＋Ｂ）］が５０質量％を超える組成となることで、シリコン基板の研磨速度が研磨後基板の表面品質（ヘイズ）よりも優先するように調整された。また、表１に示されるように、実施例３，４，６，９，１０及び１２の研磨液組成物は、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合［Ｂ／（Ａ＋Ｂ）］が５０質量％を超える組成となることで、研磨後基板の表面品質（ヘイズ）がシリコン基板の研磨速度よりも優先するように調整された。 As shown in Table 1, the polishing liquid compositions of Examples 1, 2, 5, 7, 8 and 11 have the ratio of the content of component A to the total content of component A and component B [A / ( When the composition of A + B)] exceeds 50% by mass, the polishing speed of the silicon substrate is adjusted to take precedence over the surface quality (haze) of the polished substrate. Further, as shown in Table 1, the polishing liquid compositions of Examples 3, 4, 6, 9, 10 and 12 have the ratio of the content of component B to the total content of component A and component B [B / (A + B)] has a composition of more than 50% by mass, so that the surface quality (haze) of the substrate after polishing is adjusted to take precedence over the polishing rate of the silicon substrate.
　４．２段階仕上げ研磨の評価（実施例２－１、２－２、比較例２－１）
　（１）連続研磨
　仕上げ研磨を、表２に示す研磨液組成物の組み合わせを用いて行った。仕上げ研磨１を行った後、洗浄および乾燥を行わずに、研磨機（研磨定盤）を変えて仕上げ研磨２を連続して行った以外は、上記３．と同様の研磨条件で行った。 4.2 Evaluation of 2-step finish polishing (Examples 2-1 and 2-2, Comparative Example 2-1)
(1) Continuous polishing Finish polishing was performed using the combination of the polishing liquid compositions shown in Table 2. 3. After performing the finish polishing 1, the above 3. The polishing conditions were the same as above.
　（２）合計研磨量の評価
　研磨前後の各シリコン基板の重さを精密天秤（Ｓａｒｔｏｒｉｕｓ社製「ＢＰ－２１０Ｓ」）を用いて測定し、得られた重量差をシリコン基板の密度及び面積および研磨時間で除して、２段階研磨の合計研磨量（ｎｍ）を求めた。結果を表２に示す。なお、研磨後のシリコン基板の重さとは、上記仕上げ研磨及び洗浄を行った後のシリコン基板の重さである。 (2) Evaluation of total polishing amount The weight of each silicon substrate before and after polishing was measured using a precision balance (“BP-210S” manufactured by Sartorius), and the obtained weight difference was measured by the density and area of the silicon substrate and polishing. Divided by time, the total polishing amount (nm) of the two-step polishing was obtained. The results are shown in Table 2. The weight of the silicon substrate after polishing is the weight of the silicon substrate after the finish polishing and cleaning.
　（３）シリコン基板の表面粗さ（ヘイズ）の測定
　上記仕上げ研磨及び洗浄を行った後のシリコン基板の表面粗さを、上述と同様に測定した。結果を表２に示す。 (3) Measurement of Surface Roughness (Haze) of Silicon Substrate The surface roughness of the silicon substrate after the above finish polishing and cleaning was measured in the same manner as described above. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表２に示されるように、実施例２－１及び２－２では、最初の仕上げ研磨１で割合［Ａ／（Ａ＋Ｂ）］が５０質量％を超える組成としてシリコン基板の研磨速度を優先し、最後の仕上げ研磨２で割合［Ｂ／（Ａ＋Ｂ）］が５０質量％を超える組成として研磨後の基板の表面品質を優先するよう調整することで、合計研磨量（見かけの研磨速度）の向上と表面品質の向上を両立できた。 As shown in Table 2, in Examples 2-1 and 2-2, the polishing rate of the silicon substrate is prioritized as a composition in which the ratio [A / (A + B)] exceeds 50% by mass in the first finish polishing 1. By adjusting the composition so that the ratio [B / (A + B)] exceeds 50% by mass in the final finish polishing 2 and giving priority to the surface quality of the substrate after polishing, the total polishing amount (apparent polishing speed) can be improved. We were able to improve the surface quality at the same time.
　本開示の研磨液組成物を用いれば、シリコン基板の研磨速度と研磨後のシリコン基板の表面品質とを調整できる。よって、本開示の研磨液組成物は、様々な半導体基板の製造過程で用いられる研磨液組成物として有用であり、なかでも、シリコン基板の仕上げ研磨用の研磨液組成物として有用である。 By using the polishing liquid composition of the present disclosure, the polishing speed of the silicon substrate and the surface quality of the silicon substrate after polishing can be adjusted. Therefore, the polishing liquid composition of the present disclosure is useful as a polishing liquid composition used in the manufacturing process of various semiconductor substrates, and above all, is useful as a polishing liquid composition for finish polishing of a silicon substrate.

Claims (17)

  1. 　ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有する研磨液組成物を用いて、成分Ａと成分Ｂの含有量比を変えることにより、シリコン基板の研磨速度と研磨後の基板の表面品質を調整する方法。 Abrasive liquid composition containing at least one component selected from the group consisting of an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less. A method of adjusting the polishing speed of a silicon substrate and the surface quality of the substrate after polishing by changing the content ratio of the component A and the component B using a substance.
  2. 　研磨液組成物のｐＨが、成分ＡのｐＫａよりも大きい、請求項１に記載の方法。 The method according to claim 1, wherein the pH of the polishing liquid composition is higher than the pKa of the component A.
  3. 　研磨液組成物のｐＨと前記アミノ基含有水溶性高分子化合物のｐＫａの差が０超７以下ある、請求項１又は２に記載の方法。 The method according to claim 1 or 2, wherein the difference between the pH of the polishing liquid composition and the pKa of the amino group-containing water-soluble polymer compound is more than 0 and 7 or less.
  4. 　成分Ａは、アリルアミン及びジアリルアミンから選ばれる１種以上のモノマー由来の構成単位を含む、請求項１から３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, wherein the component A contains a structural unit derived from one or more monomers selected from allylamine and diallylamine.
  5. 　アリルアミン由来の構成単位中のアミノ基の少なくとも一部は、立体遮蔽基を有する、請求項４に記載の方法。 The method according to claim 4, wherein at least a part of the amino groups in the structural unit derived from allylamine has a steric shielding group.
  6. 　アリルアミン由来の構成単位中のアミノ基の少なくとも一部は、水酸基を有する炭素数３以上１１以下の炭化水素基を含む第２級アミノ基又は第３級アミノ基である、請求項４又は５に記載の方法。 Claim 4 or 5, wherein at least a part of the amino group in the structural unit derived from allylamine is a secondary amino group or a tertiary amino group containing a hydrocarbon group having a hydroxyl group and having 3 or more and 11 or less carbon atoms. The method described.
  7. 　成分Ａは、ポリアリルアミンとグリシドール誘導体との反応物である、請求項１から６のいずれかに記載の方法。 The method according to any one of claims 1 to 6, wherein the component A is a reaction product of polyallylamine and a glycidol derivative.
  8. 　ジアリルアミン由来の構成単位中のアミノ基の少なくとも一部は、β位又はγ位に電子吸引基を有する、請求項４に記載の方法。 The method according to claim 4, wherein at least a part of the amino groups in the constituent unit derived from diallylamine has an electron-withdrawing group at the β-position or the γ-position.
  9. 　成分Ａは、下記式（ＩＩＩ）で表される構成単位を含む化合物である、請求項１から４、及び８のいずれかに記載の方法。
    Figure JPOXMLDOC01-appb-C000001
     　式（ＩＩＩ）中、Ｒ3は、水酸基を有してもよい炭素数１～３のアルキル基であり、ｎ＋ｍ＝１である。     The method according to any one of claims 1 to 4, and 8, wherein the component A is a compound containing a structural unit represented by the following formula (III).
    Figure JPOXMLDOC01-appb-C000001
     In formula (III), R 3 is an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, and n + m = 1.
  10. 　成分Ｂは、分子内にアルキレンオキサイド基、水酸基、又はアミド基を有する水溶性高分子である、請求項１から９のいずれかに記載の方法。 The method according to any one of claims 1 to 9, wherein the component B is a water-soluble polymer having an alkylene oxide group, a hydroxyl group, or an amide group in the molecule.
  11. 　成分Ｂは、ポリグリセリン、ポリグリセリンアルキルエーテル、ポリグリセリンアルキルエステル、ヒドロキシアルキルセルロース、ポリビニルアルコール、ポリビニルピロリドン、ポリヒドロキシエチルアクリルアミド、及び、重量平均分子量が３００以上１,０００以下のポリエチレングリコールから選ばれる少なくとも１種である、請求項１から１０のいずれかに記載の方法。 Component B is selected from polyglycerin, polyglycerin alkyl ether, polyglycerin alkyl ester, hydroxyalkyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyhydroxyethylacrylamide, and polyethylene glycol having a weight average molecular weight of 300 or more and 1,000 or less. The method according to any one of claims 1 to 10, which is at least one kind.
  12. 　研磨液組成物は、さらに、シリカ粒子（成分Ｃ）を含有する、請求項１から１１のいずれかに記載の方法。 The method according to any one of claims 1 to 11, wherein the polishing liquid composition further contains silica particles (component C).
  13. 　シリコン基板の仕上げ研磨を行う仕上げ研磨工程２と、仕上げ研磨工程２よりも前の研磨工程である仕上げ研磨工程１とを備え、仕上げ研磨工程１と仕上げ研磨工程２とがこの順で行われるシリコン基板の研磨方法であって、
    　仕上げ研磨工程１及び２において使用される研磨液組成物は、ｐＫａが５以上８．５以下であるアミノ基含有水溶性高分子化合物（成分Ａ）及びノニオン性水溶性高分子化合物（成分Ｂ）からなる群から選ばれる少なくとも一方の成分を含有し、
    　仕上げ研磨工程１では、研磨液組成物はシリカ粒子（成分Ｃ）を含有し、成分Ａ及び成分Ｂの合計含有量に対する成分Ａの含有量の割合が５０質量％以上の研磨液組成物で研磨し、
    　仕上げ研磨工程２では、成分Ａ及び成分Ｂの合計含有量に対する成分Ｂの含有量の割合が５０質量％以上の研磨液組成物で研磨する、シリコン基板の研磨方法。     A finish polishing step 2 for finish polishing a silicon substrate and a finish polishing step 1 which is a polishing step prior to the finish polishing step 2 are provided, and the finish polishing step 1 and the finish polishing step 2 are performed in this order. It ’s a method of polishing the substrate.
    The polishing liquid composition used in the finish polishing steps 1 and 2 has an amino group-containing water-soluble polymer compound (component A) and a nonionic water-soluble polymer compound (component B) having a pKa of 5 or more and 8.5 or less. Contains at least one ingredient selected from the group consisting of
    In the finish polishing step 1, the polishing liquid composition contains silica particles (component C) and is polished with a polishing liquid composition in which the ratio of the content of component A to the total content of component A and component B is 50% by mass or more. death,
    In the finish polishing step 2, a method for polishing a silicon substrate, wherein the ratio of the content of the component B to the total content of the component A and the component B is 50% by mass or more with a polishing liquid composition.
  14. 　前記仕上げ研磨工程１と前記仕上げ研磨工程２を１つの研磨定盤で行う、請求項１３に記載の研磨方法。 The polishing method according to claim 13, wherein the finish polishing step 1 and the finish polishing step 2 are performed on one polishing surface plate.
  15. 　前記仕上げ研磨工程１と前記仕上げ研磨工程２を研磨定盤を変えて行う、請求項１３に記載の研磨方法。 The polishing method according to claim 13, wherein the finish polishing step 1 and the finish polishing step 2 are performed by changing the polishing surface plate.
  16. 　前記仕上げ研磨工程２において、シリカ粒子（成分Ｃ）を含有する研磨液組成物で研磨した後、シリカ粒子（成分Ｃ）を含有しない研磨液組成物で研磨する、請求項１３から１５のいずれかに記載の研磨方法。 Any of claims 13 to 15, wherein in the finish polishing step 2, polishing is performed with a polishing liquid composition containing silica particles (component C), and then polishing is performed with a polishing liquid composition containing no silica particles (component C). The polishing method described in.
  17. 　請求項１から１２のいずれかに記載の方法、又は、請求項１３から１６のいずれかに記載の研磨方法を行うことを含む、半導体基板の製造方法。 A method for manufacturing a semiconductor substrate, which comprises performing the method according to any one of claims 1 to 12 or the polishing method according to any one of claims 13 to 16.
PCT/JP2020/038345 2020-10-09 2020-10-09 Polishing of silicon substrate WO2022074835A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN202080104227.4A CN116034149A (en) 2020-10-09 2020-10-09 Polishing of silicon substrates
PCT/JP2020/038345 WO2022074835A1 (en) 2020-10-09 2020-10-09 Polishing of silicon substrate
JP2022555239A JPWO2022074835A1 (en) 2020-10-09 2020-10-09
KR1020237005732A KR20230082605A (en) 2020-10-09 2020-10-09 Polishing of silicon substrate
TW110137561A TW202221099A (en) 2020-10-09 2021-10-08 Polishing of silicon substrate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2020/038345 WO2022074835A1 (en) 2020-10-09 2020-10-09 Polishing of silicon substrate

Publications (1)

Publication Number Publication Date
WO2022074835A1 true WO2022074835A1 (en) 2022-04-14

Family

ID=81126359

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/038345 WO2022074835A1 (en) 2020-10-09 2020-10-09 Polishing of silicon substrate

Country Status (5)

Country Link
JP (1) JPWO2022074835A1 (en)
KR (1) KR20230082605A (en)
CN (1) CN116034149A (en)
TW (1) TW202221099A (en)
WO (1) WO2022074835A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006352042A (en) * 2005-06-20 2006-12-28 Nitta Haas Inc Composition for polishing semiconductor
WO2009131133A1 (en) * 2008-04-23 2009-10-29 日立化成工業株式会社 Polishing agent and method for polishing substrate using the polishing agent
WO2016143323A1 (en) * 2015-03-11 2016-09-15 株式会社フジミインコーポレーテッド Composition for grinding, and method for grinding silicon substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006352042A (en) * 2005-06-20 2006-12-28 Nitta Haas Inc Composition for polishing semiconductor
WO2009131133A1 (en) * 2008-04-23 2009-10-29 日立化成工業株式会社 Polishing agent and method for polishing substrate using the polishing agent
WO2016143323A1 (en) * 2015-03-11 2016-09-15 株式会社フジミインコーポレーテッド Composition for grinding, and method for grinding silicon substrate

Also Published As

Publication number Publication date
KR20230082605A (en) 2023-06-08
JPWO2022074835A1 (en) 2022-04-14
CN116034149A (en) 2023-04-28
TW202221099A (en) 2022-06-01

Similar Documents

Publication Publication Date Title
JP5893706B2 (en) Polishing liquid composition for silicon wafer
JP6422325B2 (en) Polishing liquid composition for semiconductor substrate
JP2018078287A (en) Rinse agent composition for silicon wafer
JP6655354B2 (en) Polishing composition for silicon wafer or polishing composition kit for silicon wafer
JP2016213216A (en) Polishing liquid composition for silicon wafers
JP6087143B2 (en) Polishing liquid composition for silicon wafer
JP6039419B2 (en) Polishing liquid composition for silicon wafer
JP6489690B2 (en) Polishing liquid composition for silicon wafer
JP6893835B2 (en) Finish polishing liquid composition for silicon wafer
JP2018074048A (en) Polishing liquid composition for silicon wafer
JP2018006538A (en) Polishing liquid composition for silicon wafer
JP7105089B2 (en) Silicon wafer manufacturing method
WO2022074835A1 (en) Polishing of silicon substrate
JP2015084379A (en) Polishing liquid composition for silicon wafers
JP2022063116A (en) Polishing method
JP2022063115A (en) Polishing method
JP2022063112A (en) Polishing method
JP2022063233A (en) Polishing liquid composition for silicon substrate
WO2022074831A1 (en) Polishing liquid composition for silicon substrate
JP2023154963A (en) Polishing liquid composition for silicon substrate
JP2022063113A (en) Polishing liquid composition
JP6792413B2 (en) Abrasive liquid composition for silicon wafer
JP2022063114A (en) Method for increasing volume of liquid passed through filter
JP2023020529A (en) Polishing liquid composition
JP6168984B2 (en) Polishing liquid composition for silicon wafer

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20956782

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022555239

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20956782

Country of ref document: EP

Kind code of ref document: A1