WO2013002281A1 - Sel neutre destiné à être utilisé dans un liquide de polissage, liquide de polissage de matériaux électroniques, procédé de polissage et procédé de fabrication de matériaux électroniques - Google Patents

Sel neutre destiné à être utilisé dans un liquide de polissage, liquide de polissage de matériaux électroniques, procédé de polissage et procédé de fabrication de matériaux électroniques Download PDF

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Publication number
WO2013002281A1
WO2013002281A1 PCT/JP2012/066424 JP2012066424W WO2013002281A1 WO 2013002281 A1 WO2013002281 A1 WO 2013002281A1 JP 2012066424 W JP2012066424 W JP 2012066424W WO 2013002281 A1 WO2013002281 A1 WO 2013002281A1
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Prior art keywords
polishing
acid
salt
polishing liquid
group
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PCT/JP2012/066424
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English (en)
Japanese (ja)
Inventor
山口　俊一郎
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三洋化成工業株式会社
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Priority to CN201280031168.8A priority Critical patent/CN103619982B/zh
Publication of WO2013002281A1 publication Critical patent/WO2013002281A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • 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

Definitions

  • the present invention relates to a neutralized salt used in a polishing step, a polishing liquid for electronic materials containing the neutralized salt, a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic materials, and an electron in this polishing method.
  • the present invention relates to a method for manufacturing an electronic material including a step of polishing a material intermediate.
  • a neutralized salt that is used in a polishing process during the manufacturing process of an electronic material has a better polishing rate than conventional methods, and improves the surface quality of the electronic material, and an electronic material containing the neutralized salt
  • the present invention relates to a polishing liquid for polishing, a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material, and a method for manufacturing an electronic material including a step of polishing the electronic material intermediate by the polishing method.
  • the magnetic disk manufacturing process includes a lapping process that is a process for chamfering a substrate plate, a substrate manufacturing process that is a process for creating a flattened substrate, and a medium that is a process for forming a magnetic layer on the substrate.
  • a lapping process that is a process for chamfering a substrate plate
  • a substrate manufacturing process that is a process for creating a flattened substrate
  • a medium that is a process for forming a magnetic layer on the substrate.
  • the lapping process the main surface and end face of the substrate are polished using a polishing pad and a polishing liquid in which a grindstone such as diamond is fixed with a resin in order to roughly chamfer the substrate, and then the substrate is cleaned in a subsequent cleaning process. After removing the polishing scraps on the main surface and end face of the substrate, the processed substrate is transported to the substrate manufacturing process through a drying process.
  • polishing with a polishing pad and polishing liquid containing polishing particles such as colloidal silica and cerium oxide was performed to flatten the substrate, and polishing particles generated on the substrate surface were generated in the subsequent cleaning process.
  • polishing particles generated on the substrate surface were generated in the subsequent cleaning process.
  • the processed substrate is packed in a predetermined container through a drying process and transported to a media process.
  • Abrasive particles and generated polishing debris in the polishing liquid are very fine and easily aggregate. These aggregates may affect the surface quality of the substrate in the step of polishing the substrate. For example, resistance may be generated between these aggregates and the substrate, and scratches may be generated on the substrate. Scratches generated on the substrate may cause, for example, a poor adhesion between the magnetic film and the substrate in a later media process, and may be a factor that hinders the increase in the capacity of the magnetic disk. Therefore, in order to suppress the above-described reduction in scratch generation and reduction in the polishing rate, polishing liquids containing azoles such as benzotriazole, maleic acid, and the like have been proposed (for example, Patent Documents 1 and 2).
  • Patent Document 3 a polishing liquid containing an aromatic sulfonate has been proposed for the purpose of improving the durability of the polishing rate.
  • Patent Document 4 a polishing liquid containing hydroxyethyl cellulose has been proposed.
  • Patent Documents 1 to 4 are not sufficient in suppressing the generation of scratches and adhesion of particles during polishing, and the substrate quality allowed to achieve high capacity is achieved. It could not be supported. Further, the polishing liquid of Patent Document 2 is not sufficient, although it has a slight effect on the sustainability of the polishing rate, and the substrate quality after polishing is not satisfactory. Therefore, there are fewer defects in the substrate such as scratches in the polishing process during the electronic material manufacturing process than in conventional polishing liquids, and polishing debris generated by polishing can be easily removed in the subsequent cleaning process.
  • a material capable of sustaining the polishing rate in the process a polishing liquid for electronic material containing the material, a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material, and an electronic material intermediate by this polishing method It is an object of the present invention to provide a method for manufacturing an electronic material including a polishing step.
  • the present invention relates to a specific neutralized salt (AB) used in the step of polishing an electronic material intermediate using a polishing pad, a polishing liquid for electronic material containing the neutralized salt (AB), and the electronic material
  • the neutralized salt (AB) includes an acidic compound (A) having at least one acid group (X) in the molecule, and nitrogen having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol.
  • the neutralized salt of the present invention used in the polishing step has an effect of significantly reducing surface defects generated on the surface of the object to be polished in the polishing step. Further, it has an effect of reducing adhesion of particles during polishing and facilitating removal of the particles from the substrate in the subsequent cleaning step. Moreover, the polishing liquid for electronic materials containing this neutralized salt is excellent in sustainability of the polishing rate, in addition to the above-described effects, as compared with the conventional polishing liquid. Therefore, an electronic material with few surface defects such as scratches or pits and / or residual particles can be stably produced.
  • the neutralized salt of the present invention is a specific neutralized salt (AB) used in the step of polishing an electronic material intermediate using a polishing pad.
  • the neutralized salt (AB) includes an acidic compound (A) having at least one acid group (X) in the molecule, and nitrogen having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol.
  • the electronic material in the present invention is not particularly limited as long as it is an electronic material manufactured by a process including a process of polishing using a polishing pad during the manufacturing process.
  • a magnetic disk substrate such as a hard disk glass substrate or a hard disk aluminum substrate whose surface is plated with nickel-phosphorus (Ni-P)
  • a semiconductor substrate such as a semiconductor element or a silicon wafer
  • Examples thereof include compound semiconductor substrates such as SiC substrates, GaAs substrates, GaN substrates, and AlGaAs substrates, and (4) sapphire substrates for LEDs.
  • a magnetic disk substrate is preferable from the viewpoint of improving production efficiency, and specifically, a glass substrate for hard disk or an aluminum substrate for hard disk plated with nickel-phosphorus (Ni-P).
  • the electronic material intermediate refers to an object to be polished before becoming an electronic material.
  • the glass substrate before lapping, or before rough polishing with cerium oxide or the like refers to a glass substrate, a glass substrate before being precisely polished with colloidal silica or the like, and all electronic materials before polishing processing mean an electronic material intermediate.
  • the polishing step in the present invention refers to a step of processing a material flat using a grindstone or abrasive particles, for example, a lapping step of rough chamfering using a polishing pad to which a grindstone is fixed, or using abrasive particles It includes a polishing process for precise planarization.
  • the polishing pad in the present invention is a pad made of polyurethane resin or polyester resin, and includes a pad on which a grindstone such as diamond is fixed. Further, it may be a foam type or a suede type, and various hardnesses can be used. These polishing pads are not particularly limited, and commercially available polishing pads can be used.
  • the polishing pad is used by being affixed to a surface plate of a polishing apparatus in the lapping step for rough chamfering described above or the polishing step for precise flattening using abrasive particles.
  • the neutralized salt (AB) in the present invention is a neutralized salt (AB1) of an acidic compound (A1) and a compound (B) and / or a neutralized salt of a polymer (A2) which is an acidic compound and a compound (B).
  • the neutralized salt (AB1) comprises at least an acid group (X1) of an acid having a heat of formation (Q1) in an acid dissociation reaction of 3 to 200 kcal / mol and a hydrophobic group (Y) having 1 to 36 carbon atoms, respectively.
  • a neutral salt of one acidic compound (A1) and a compound (B) having a heat of formation (Q2) of 10 to 152 kcal / mol in a proton addition reaction wherein (X1) is a sulfonic acid group, sulfuric acid
  • a neutralized salt which is at least one selected from the group consisting of a group, a carboxyl group, a carboxymethyloxy group, a carboxyethyloxy group, a (di) carboxymethylamino group and a (di) carboxyethylamino group
  • (AB2) includes a polymer (A2) that is an acidic compound having at least one acid group (X2) in the molecule, and a change in heat of formation (Q2) in the proton addition reaction. Is 0 ⁇ 152kcal / mol, compound (B) and neutralization salts.
  • the acidic compound (A1) includes at least one acid group (X1) of an acid having a heat of formation (Q1) in an acid dissociation reaction of 3 to 200 kcal / mol and a hydrophobic group (Y) having 1 to 36 carbon atoms.
  • the polymer (A2) has at least one acid group (X2) in the molecule.
  • the acid group (X2) also has a heat generation change (Q1) in the acid dissociation reaction of 3 to 200 kcal / mol.
  • the heat of formation (Q1) in the acid dissociation reaction of the acid groups (X1) and (X2) is the heat of formation of HX and the heat of formation of X ⁇ in the acid dissociation reaction of the acid (HX) represented by the following formula (1). Means the difference.
  • the change in the heat of formation in the acid dissociation reaction of the acid group (X1) is a value assuming that the hydrophobic group (Y) is a hydrogen atom.
  • the change in heat of formation in the acid dissociation reaction of the acid group (X2) is a value assuming that the polymer chain to which the acid group (X2) is bonded is a hydrogen atom.
  • the generated heat change (Q1) is expressed by the following formula (2).
  • Q1 ⁇ f H o HX ⁇ f H o X ⁇ (2)
  • ⁇ f H o HX and ⁇ f H o X ⁇ represent the heat of formation in vacuum for HX and X ⁇ in order, respectively.
  • the value of the heat of formation ( ⁇ f H o ) Chem. Soc. Perkin Trans. 2, p. 923 (1995), and can be calculated using the semiempirical molecular orbital method (MOPAC PM3 method).
  • the value of the generated heat can be calculated as generated heat (25 ° C.) in a vacuum using, for example, “CAChe Worksystem 6.01” manufactured by Fujitsu Limited. That is, the value of this heat of formation is calculated by writing the molecular structure to be calculated on “Work Space”, optimizing the structure with the molecular force field method “MM2 geometry”, and then “PM3 geometry” which is a semi-empirical molecular orbital method. Is obtained by calculation.
  • the heat of formation (Q1) (kcal / mol, 25 ° C.) in the acid dissociation reaction of the acid group (X1) or (X2) is 3 to 200, and is preferably 10 from the viewpoint of lowering the zeta potential.
  • To 150 then preferably 15 to 100, then preferably 20 to 80, particularly preferably 20 to 65.
  • carboxymethyloxy group —OCH 2 COOH
  • Q1 19 kcal / mol
  • (di) carboxymethylamino group —NRCH 2 COOH or —N (CH 2 COOH) 2 )
  • Q1 26 kcal / mol
  • sulfonic acid groups are preferable from the viewpoint of preventing re-adhesion of particles and easy industrial production, and the viewpoint of preventing hydrolysis of the neutralized salt (AB2). More preferably a sulfonic acid group or a carboxyl group.
  • a sulfonic acid group As the acid group (X1), among the acid groups (X2) exemplified above, a sulfonic acid group, a sulfuric acid group, a carboxyl group, a carboxymethyloxy group, a carboxyethyloxy group, a (di) carboxymethylamino group, ) Carboxyethylamino group and the like.
  • these acid groups sulfonic acid groups, sulfuric acid groups, carboxymethyloxy groups, or carboxyethyloxy groups are preferable from the viewpoint of preventing re-adhesion of particles and industrially easy production, and the neutral salt (AB1). From the viewpoint of preventing hydrolysis and the like, a sulfonic acid group, a carboxymethyloxy group or a carboxyethyloxy group is more preferable, and a sulfonic acid group is particularly preferable.
  • Examples of the hydrophobic group (Y) in the acidic compound (A1) include an aliphatic hydrocarbon group and an aromatic ring-containing hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, a cycloalkyl group having 3 to 36 carbon atoms, and the like (which may be linear or branched) ).
  • Examples of the alkyl group include methyl, ethyl, n- or i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like.
  • Alkenyl groups include n- or i-propenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl and
  • Examples of the cycloalkyl group having 3 to 36 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • aromatic ring-containing hydrocarbon group examples include aromatic hydrocarbons having 7 to 36 carbon atoms, such as methylphenyl, ethylphenyl, n- or i-propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, Examples include octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, octylnaphthyl, nonylnaphthyl, dodecylnaphthyl and the like.
  • an aliphatic hydrocarbon group or an aromatic ring-containing hydrocarbon group is preferable, and more preferable is octyl, nonyl, decyl, undecyl, dodecyl, octylphenyl, nonylphenyl, dodecylphenyl, octylnaphthyl, nonyl. Naphthyl and dodecylnaphthyl, particularly preferably octyl, nonyl, dodecyl, octylphenyl, dodecylphenyl and octylnaphthyl.
  • the number of carbon atoms of the hydrophobic group (Y) is 1 to 36, more preferably 4 to 24, and particularly preferably 8 to 24.
  • some or all of the hydrogen atoms are other atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) or functional groups (hydroxyl group, amino group, mercapto group, perfluoroalkyl group, carboxyl group) Or an organic group including an ether bond, an amide bond, or an ester bond), and the functional group may include one or more oxyalkylene groups.
  • Examples of the acidic compound (A1) include the following compounds.
  • Compound having sulfonic acid group (A1-1) Alkylsulfonic acid (octylsulfonic acid, decylsulfonic acid, dodecylsulfonic acid, myristylsulfonic acid, cetylsulfonic acid, stearylsulfonic acid, etc.), benzenesulfonic acid, alkylbenzenesulfonic acid (toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid) , Eicosylbenzenesulfonic acid, etc.), naphthalenesulfonic acid, sulfosuccinic acid, alkylnaphthalenesulfonic acid (methylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, eicosylnaphthalene
  • Alkyl sulfate (octyl sulfate, decyl sulfate, dodecyl sulfate, myristyl sulfate, cetyl sulfate, stearyl sulfate, etc.), polyoxyalkylene alkyl ether sulfate (polyoxyethylene octyl ether sulfate, polyoxyethylene lauryl) Ether sulfates, etc.), polyoxyalkylene alkyl aryl ether sulfates (polyoxyethylene octyl phenyl ether sulfates, polyoxyethylene nonyl phenyl ether sulfates, etc.), acylamide alkyl sulfates, and the like.
  • Alkylene alkyl ether sulfonic acid polyoxyalkylene alkyl aryl ether sulfonic acid, ⁇ -o Refin sulfonic acid, alkyloylaminoethyl sulfonic acid.
  • the HLB value of the acidic compound (A1) is preferably 5 to 30, more preferably 7 to 17, more preferably 9 to 16, particularly preferably 10 to 15, and most preferably 10.5 to 14.5.
  • the HLB value is a value calculated using the following formula (3) by the Oda method (Takehiko Fujimoto, Introduction to Surfactant (Sanyo Chemical Industry Co., Ltd.), p212 (2007)). .
  • HLB 10 ⁇ (inorganic / organic) (3)
  • organic property and inorganic property in a formula are the total value of the numerical value defined for every atom and functional group which comprise a molecule
  • the pKa of the acidic compound (A1) is preferably 8.0 or less, more preferably 7.0 or less, particularly preferably 5.5 or less, and most preferably 3.0 or less from the viewpoint of lowering the zeta potential. . Moreover, Preferably it is 0.5 or more.
  • pKa means the acid dissociation constant at the first stage.
  • pKa is a known method ⁇ for example, J.P. Am. Chem. Soc. , 1673 (1967) ⁇ and the like.
  • Examples of the polymer (A2) having at least one acid group (X2) include a polymer having a sulfonic acid group (A2-1) and a polymer having a sulfate group (A2-2) from the viewpoint of preventing reattachment of particles.
  • a polymer (A2-3) having a carboxyl group is preferable, and a polymer (A2-1) having a sulfonic acid group or a polymer (A2-3) having a carboxyl group is more preferable.
  • Examples of the polymer (A2-1) having a sulfonic acid group include a polymer (A2-1-1) obtained by radical polymerization using an unsaturated monomer (aX-1) having a sulfonic acid group, and a sulfonic acid group in the molecule. And a polymer (A2-1-2) obtained by a polycondensation reaction with formaldehyde using an aromatic compound (aY-1) having
  • Examples of the polymer (A2-2) having a sulfate group include a polymer (A2-2-1) obtained by radical polymerization using an unsaturated monomer (aX-2) having a sulfate group.
  • Examples of the polymer (A2-3) having a carboxyl group include a polymer (A2-3-1) obtained by radical polymerization using an unsaturated monomer (aX-3) having a carboxyl group.
  • polymers (A2) from the viewpoint of preventing particle reattachment, a polymer (A2-3) having a carboxyl group and a polymer (A2-1) having a sulfonic acid group are preferable, and (A2-3) is more preferable. -1), (A2-1-1) or (A2-1-2).
  • the polymer (A2) used for this invention may be used independently, it can also be used as a 2 or more types of mixture.
  • Examples of the unsaturated monomer (aX-1) having a sulfonic acid group include aliphatic unsaturated sulfonic acids having 2 to 20 carbon atoms (such as vinyl sulfonic acid and (meth) allyl sulfonic acid), and aromatics having 6 to 24 carbon atoms.
  • Unsaturated sulfonic acid (styrene sulfonic acid, p-nonyl styrene sulfonic acid, etc.), sulfonic acid group-containing (meth) acrylate ⁇ 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 3 -(Meth) acryloyloxypropanesulfonic acid, 2- (meth) acryloyloxybutanesulfonic acid, 4- (meth) acryloyloxybutanesulfonic acid, 2- (meth) acryloyloxy-2,2-dimethylethanesulfonic acid, p -(Meth) acryloyloxymethylbenzenesulfonic acid, etc. ⁇ , including sulfonic acid group (Meth) acrylamide ⁇ 2- (meth) acryloyl-aminoethanesulfonic
  • it contains an aliphatic unsaturated sulfonic acid having 2 to 20 carbon atoms, an aromatic unsaturated sulfonic acid having 6 to 24 carbon atoms or a sulfonic acid group (meta ) Acrylamide is preferred, and vinyl sulfonic acid, styrene sulfonic acid or 2- (meth) acryloylamino-2,2-dimethylethane sulfonic acid is more preferred.
  • Examples of the unsaturated monomer (aX-2) having a sulfate group include sulfate ester of a hydroxyl group-containing monomer. Of these, from the viewpoint of polymerizability and the like, a hydroxyl group-containing (meth) acrylic acid ester sulfate is preferable, and a 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate sulfate is more preferable. .
  • unsaturated monomer (aX-3) having a carboxyl group unsaturated monocarboxylic acid ⁇ (meth) acrylic acid, vinylbenzoic acid, allyl acetic acid, (iso) crotonic acid, cinnamic acid, 2-carboxyethyl acrylate, etc. ⁇ , Unsaturated dicarboxylic acid or anhydride of unsaturated dicarboxylic acid ⁇ (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. ⁇ .
  • unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or anhydride of unsaturated dicarboxylic acid is preferable from the viewpoint of polymerizability and hydrolysis resistance in water, and more preferably (meth) acrylic acid, (anhydrous) ) Maleic acid, fumaric acid or (anhydrous) itaconic acid.
  • Polymers (A2-1-1) to (A2-3-1) obtained by radical polymerization using unsaturated monomers include unsaturated monomers having sulfonic acid groups (aX-1) and unsaturated monomers having sulfuric acid groups.
  • a radically polymerizable unsaturated monomer other than the monomer (aX-2) and the unsaturated monomer having a carboxyl group (aX-3) can be copolymerized.
  • Monomers (aX-1) to (aX-3) may be used alone or as a mixture of two or more.
  • the structure may be either a random copolymer or a block copolymer.
  • polystyrene sulfonic acid examples include polystyrene sulfonic acid, styrene / styrene sulfonic acid copolymer, poly ⁇ 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid ⁇ , 2- ( (Meth) acryloylamino-2,2-dimethylethanesulfonic acid / styrene copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / acrylamide copolymer, or 2- (meth) acryloylamino -2,2-dimethylethanesulfonic acid / styrene / acrylamide copolymer.
  • polymer (A2-2-1) examples include poly ⁇ 2-hydroxyethyl (meth) acrylate sulfate ⁇ , 2-hydroxyethyl acrylate / 2-hydroxyethyl acrylate sulfate copolymer, 2-hydroxyethyl methacrylate. / 2-hydroxyethyl methacrylate sulfate copolymer and the like.
  • polymer (A2-3-1) examples include poly (meth) acrylic acid, (meth) acrylic acid / vinyl acetate copolymer, 2-hydroxyethyl methacrylate / (meth) acrylic acid copolymer, and the like. It is done.
  • a known radical polymerization method can be used.
  • a monomer comprising monomers (aX-1) to (aX-3) and other radical polymerizable unsaturated monomers as required, and a radical initiator (persulfate, azobisamidinopropane salt, azobisisobutylnitrile, etc.) Is polymerized at a temperature of 30 to 150 ° C. in a solvent such as water or an alcohol solvent using 0.1 to 30% by weight based on the monomer.
  • a chain transfer agent such as mercaptan may be used.
  • Examples of the aromatic compound (aY-1) having a sulfonic acid group used for the synthesis of the polymer (A2-1-2) include aryl sulfonic acid (benzenesulfonic acid, etc.), alkyl (carbon number 1 to 24) aryl sulfone.
  • Acids toluenesulfonic acid, dodecylbenzenesulfonic acid, monobutylbiphenylsulfonic acid, etc.
  • polycyclic aromatic sulfonic acids naphthalenesulfonic acid, anthracenesulfonic acid, hydroxynaphthalenesulfonic acid, hydroxyanthracenesulfonic acid, etc.
  • alkyl (C1-24) arylsulfonic acid, polycyclic aromatic sulfonic acid, and alkyl (C1-24) substituted polycyclic aromatic sulfonic acid are preferable from the viewpoint of preventing redeposition. More preferred are dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and dimethylnaphthalenesulfonic acid.
  • the polymer (A2-1-2) can contain other aromatic compound (aO), urea, or the like as necessary, if necessary.
  • aromatic compounds (aO) include benzene, alkylbenzene (alkyl group having 1 to 20 carbon atoms), naphthalene, alkylnaphthalene (alkyl group having 1 to 20 carbon atoms), phenol, cresol, hydroxynaphthalene, aniline, and the like. Can be mentioned.
  • polymer (A2-1-2) examples include naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, dimethyl naphthalene sulfonic acid formaldehyde condensate, octyl naphthalene sulfonic acid formaldehyde condensate, naphthalene sulfonic acid-methyl.
  • the reaction vessel is charged with the aromatic compound (aY-1) having the sulfonic acid group and, if necessary, other compounds (aO), urea, an acid (such as sulfuric acid) or an alkali (such as sodium hydroxide) used as a catalyst.
  • a predetermined amount of an aqueous formaldehyde solution (for example, 37% by weight aqueous solution) is dropped over 1 to 4 hours with stirring at 70 to 90 ° C., and after the dropwise addition, the mixture is stirred for 3 to 30 hours under reflux and cooled. .
  • the compound (aY-1) a polymer (A2-1-2) was synthesized at the same time using a compound in which a part or all of the sulfonic acid groups had been neutralized with the compound (B) in advance, and at the same time a directly neutralized salt ( AB2) may be obtained.
  • the molar ratio ((aY-1) / (aO) ⁇ of (aY-1) to (aO) is preferably 1 to 99/99 to 1, more preferably 10 ⁇ 90 / 90 ⁇ 10, particularly preferably 30 ⁇ 85 / 70 ⁇ 15, most preferably 50 ⁇ 80 / 50 ⁇ 20.
  • the molar ratio of (aY-1) to urea ⁇ (aY-1) / urea ⁇ is preferably 1 to 99/99 to 1, more preferably 10 to 90/90 to 10, particularly preferably. Is from 30 to 85/70 to 15, most preferably from 50 to 80/50 to 20.
  • (aY-1) or (aO) may be used as a mixture of two or more.
  • the pKa of the polymer (A2) is preferably 8.0 or less, more preferably 7.0 or less, particularly preferably 5.5 or less, and most preferably 3.0 or less from the viewpoint of lowering the zeta potential. pKa can be determined by the above method.
  • the weight average molecular weight (hereinafter abbreviated as Mw) of the polymer (A2) is preferably from 300 to 200,000, more preferably from 1,000 to 100, from the viewpoint of improving surface quality such as scratch reduction and low foaming properties. , 000.
  • the weight average molecular weight is a value measured by gel permeation chromatography (hereinafter abbreviated as GPC) at 40 ° C. using polyethylene oxide as a standard substance.
  • apparatus main body HLC-8120 manufactured by Tosoh Corporation
  • column TSKgel G5000 PWXL, G3000 PW XL manufactured by Tosoh Corporation
  • detector differential refractometer detector built in the apparatus main body
  • eluent 0.2 M sulfuric anhydride Sodium, 10% acetonitrile buffer
  • eluent flow rate 0.8 ml / min
  • column temperature 40 ° C.
  • sample 1.0 wt% eluent solution
  • injection volume 100 ⁇ l
  • standard substance TSK manufactured by Tosoh Corporation It can be measured under the conditions of SE-30, SE-15, SE-8, and SE-5.
  • the compound (B) constituting the neutralized salts (AB1) and (AB2) will be described.
  • a compound (B) having a heat generation change (Q2) in the proton addition reaction of 10 to 152 kcal / mol is used.
  • the change in heat of formation (Q2) in the proton addition reaction means the difference between the heat of formation of B and the heat of formation of H + B in the proton addition reaction of the compound (B) represented by the following formula (4). . B + H + ⁇ H + B (4)
  • Q2 is represented by the following formula (5).
  • Q2 ⁇ f H o H + B - ⁇ f H o B (5)
  • ⁇ f H o H + B , ⁇ f H o B are respectively a representing the generated heat in a vacuum for H + B, B.
  • the value of the heat of formation ( ⁇ f H o ) can be calculated using the semiempirical molecular orbital method (MOPAC PM3 method).
  • MOPAC PM3 method semiempirical molecular orbital method
  • the position where H + is added in calculating the heat of formation of H + B is on the nitrogen atom contained in the compound (B).
  • the heat of formation is calculated for each nitrogen atom, and the value when the difference between the heat of formation of B and the heat of formation of H + B is minimized is defined as the change in heat generation (Q2). .
  • the change in heat of formation (Q2) (kcal / mol, 25 ° C.) in the proton addition reaction of compound (B) is 10 to 152, preferably 30 to 148, more preferably 40 from the viewpoint of lowering the zeta potential.
  • the compound (B) is not limited as long as the change in heat of formation (Q2) in the proton addition reaction is in the range of 10 to 152 kcal / mol.
  • a compound (B-2) having at least one amidine skeleton in the molecule are not limited as long as the change in heat of formation (Q2) in the proton addition reaction.
  • the molecular volume (nm 3 ) of the compound (B) is preferably from 0.025 to 0.7, more preferably from 0.050 to 0.5, particularly preferably from 0.12 to 0.5 from the viewpoint of lowering the zeta potential. 0.36.
  • the molecular volume refers to the volume of the space formed on the isoelectronic density surface of the molecule, and is the molecular force field method MM2 (Allinger, NL, J. Am. Chem. Soc., 99, 8127 (1977). )))
  • PM3 Stepwart, J. J. P., J. Am. Chem. Soc., 10, 221 (1989)
  • R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an alkyl group having 6 to 30 carbon atoms.
  • R 7 and two R 8 may be the same or different and are bonded to each other (carbon-carbon bond, ether bond, etc.) to form a ring having 4 to 12 carbon atoms. Also good. m and n each independently represent an integer of 1 to 12. ]
  • alkyl group having 1 to 24 carbon atoms or the alkenyl group having 2 to 24 carbon atoms include those having 1 to 24 carbon atoms among the alkyl groups and alkenyl groups exemplified for the hydrophobic group (Y).
  • the alkynyl group having 2 to 30 carbon atoms may be linear or branched, and is ethynyl, 1-propynyl, 2-propynyl, 1- or 2-dodecynyl, 1- or 2-tridecynyl, 1- or 2 -Tetradecynyl, 1- or 2-hexadecynyl, 1- or 2-stearinyl, 1- or 2-nonadecynyl, 1- or 2-eicosinyl, 1- or 2-tetracosinyl and the like.
  • Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and methylnaphthyl.
  • Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl, 7-phenylheptyl, 8-phenyloctyl, 10 -Phenyldecyl, 12-phenyldodecyl, naphthylmethyl, naphthylethyl and the like.
  • two R 7 or two R 8 are divalent organic groups (alkylene having 4 to 12 carbon atoms).
  • alkylene group having 4 to 12 carbon atoms include butylene, pentylene, hexylene, heptylene, octylene, decylene and dodecylene, and these alkylene groups may be bonded by an ether bond or the like.
  • DBU 1,8-diazabicyclo [5.4.0] undecene-7
  • DBN 1,5-diazabicyclo [4.3.0] nonene-5
  • DBN 1,8-diazabicyclo [5.3.0] decene-7
  • compound (B) Preferred from the viewpoint of zeta potential and the like as compound (B) are guanidine, methylguanidine, ethylguanidine, (B-2) of (B-1), DBU and DBN, and more preferably DBU. Or DBN.
  • a compound (B) may be used independently and may be used as a 2 or more types of mixture.
  • the pKa of the compound (B) is preferably 11 to 40, more preferably 11.5 to 30, particularly preferably 12 to 25 from the viewpoint of lowering the zeta potential.
  • pKa of compound (B) is a known method ⁇ for example, Can. J. et al. Chem. 65, 626 (1987) ⁇ and the like.
  • the neutralized salt (AB1) of the acidic compound (A1) and the compound (B) and the neutralized salt (AB2) of the polymer (A2) and the compound (B) are the acid group (X1) or (X2 ) May be partially or completely neutralized with (B).
  • neutralized salt (AB1) include the following compounds. Alkylbenzenesulfonate (toluenesulfonate guanidine salt, toluenesulfonate DBU salt, toluenesulfonate DBN salt, xylenesulfonate guanidine salt, xylenesulfonate DBU salt, xylenesulfonate DBN salt, dodecylbenzenesulfonate guanidine salt, dodecylbenzene Sulfonic acid DBU salt, dodecylbenzene sulfonic acid DBN salt, etc.), naphthalene sulfonic acid salt (naphthalene sulfonic acid guanidine salt, naphthalene sulfonic acid DBU salt, naphthalene sulfonic acid DBN salt etc.), alkyl naphthalene sulfonic acid salt (methyl naphthalene
  • neutralized salt (AB2) include the following compounds.
  • Polyacrylate polyacrylic acid DBU salt, polyacrylic acid DBN salt, etc.
  • polystyrene sulfonate polystyrene sulfonic acid guanidine salt, polystyrene sulfonic acid DBU salt, polystyrene sulfonic acid DBN salt, etc.
  • alkyl naphthalene sulfonic acid formaldehyde condensate salt methyl naphthalene sulfonic acid formaldehyde condensate
  • the neutralized salt (AB1) is preferably such that the ratio ⁇ Q2 / (Q1 ⁇ p) ⁇ of (Q1) and (Q2) satisfies the formula (7) from the viewpoint of reducing the zeta potential, and more preferably It is preferable to satisfy the formula (8), particularly preferably the formula (9), and most preferably the formula (10).
  • the weight average molecular weight (Mw) of the neutralized salt (AB2) is preferably 1,000 to 1,000,000, more preferably 1,000 to 1,000, from the viewpoint of improving surface quality such as scratch reduction and low foaming properties. 200,000, particularly preferably 3,000 to 100,000.
  • Mw of neutralization salt (AB2) is a value obtained by GPC similarly to a polymer (A2).
  • the polishing liquid for electronic material of the present invention may contain at least one of neutralized salts (AB1) and (AB2), but contains neutralized salt (AB2) from the viewpoint of improving surface quality such as scratch reduction. Those are preferred.
  • the neutralized salt (AB1) or (AB2) can be obtained by a neutralization reaction between the acidic compound (A1) or polymer (A2) and the nitrogen-containing basic compound (B).
  • a neutralization reaction between the acidic compound (A1) or polymer (A2) and the nitrogen-containing basic compound (B).
  • an aqueous solution of (A1) and / or (A2) is charged into a reaction vessel capable of temperature control and stirring, and (B) (aqueous solution if necessary) is added at room temperature (about 25 ° C.) with stirring to mix uniformly. can do.
  • it can be obtained by mixing (A1) and / or (A2) and (B) simultaneously or separately into a reaction vessel preliminarily charged with water and mixing them uniformly.
  • the concentration during the neutralization reaction can be appropriately selected depending on the purpose.
  • the polishing liquid for electronic materials of the present invention has a high degree of dissociation of the acid groups (X1) and (X2), the zeta potential of the particles and the substrate can be effectively lowered, and the reattachment of particles can be prevented. it can.
  • the concentration of the neutralized salt (AB) in the polishing slurry for electronic materials is 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the weight of the polishing solution.
  • the water that is an essential component of the polishing liquid for electronic materials of the present invention is preferably pure water having an electrical resistivity of 18 M ⁇ ⁇ cm or more from the viewpoint of cleanliness, ultrapure water, ion exchange water, reverse osmosis water (RO water). And distilled water.
  • Another embodiment of the present invention is a polishing liquid for use in a step of polishing an electronic material intermediate using a polishing pad, which is a polishing liquid for an electronic material that requires neutralization salt (AB) and water as essential. .
  • AB neutralization salt
  • the polishing liquid for electronic materials of the present invention may contain abrasive particles (C) in addition to the neutralized salt (AB) and water described above.
  • abrasive particles (C) By containing the abrasive particles (C), an electronic material excellent in flatness can be produced.
  • abrasive particles (C) in the present invention commercially available abrasive particles for polishing electronic materials can be used and are not particularly limited.
  • the material for the abrasive particles (C) include colloidal silica, cerium oxide, alumina, zirconium oxide, diamond, manganese oxide, titanium oxide, silicon carbide, and boron nitride. From the viewpoint of the effect of reducing scratches, colloidal is preferable. Silica, cerium oxide, alumina or diamond.
  • the average particle diameter of the abrasive particles (C) varies depending on the abrasive particles used. In the case of colloidal silica, it is usually 5 nm to 100 nm, and in the case of cerium oxide, it is 0.1 ⁇ m to 3.0 ⁇ m. This is preferable from the viewpoint of substrate productivity.
  • the abrasive particles (C) in the polishing liquid for electronic materials is 0 to 20% by weight, preferably 0.5 to 20% by weight, based on the weight in the polishing liquid.
  • the polishing liquid for electronic materials of the present invention may contain a surfactant (D) other than the neutralized salt (AB) and water described above, in addition to the neutralized salt (AB). By containing the surfactant (D), it can be used in the lapping step.
  • a surfactant (D) other than the neutralized salt (AB) and water described above, in addition to the neutralized salt (AB).
  • surfactant (D) in the present invention examples include nonionic surfactants (D1) and anionic surfactants (D2) other than neutralized salts (AB).
  • Nonionic surfactant (D1) includes higher alcohol alkylene having 8 to 18 carbon atoms (2 to 4 carbon atoms) oxide adduct (D11), polyoxyethylene polyoxypropylene copolymer (D12), 8 carbon atoms.
  • Examples include an alkylene oxide adduct (D13) of aliphatic amine of ⁇ 36, a polyhydric alcohol type nonionic surfactant (D14), and the like.
  • Examples of the higher alcohol alkylene (carbon number 2 to 4) oxide adduct (D11) having 8 to 18 carbon atoms include octyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, and the like. Can be mentioned.
  • the polyoxyethylene polyoxypropylene copolymer (D12) may be a block type or a random type.
  • Examples of the alkylene oxide adduct (D13) of an aliphatic amine having 8 to 36 carbon atoms include an alkylene oxide adduct (D131) of an aliphatic primary amine having 8 to 24 carbon atoms, or an aliphatic oxide having 8 to 36 carbon atoms.
  • the starting aliphatic primary amine in the alkylene oxide adduct (D131) of an aliphatic primary amine having 8 to 24 carbon atoms may be linear, branched or cyclic, and may have a saturated or unsaturated bond. It is an aliphatic primary amine having 8 to 24 carbon atoms.
  • aliphatic primary amine examples include laurylamine, octylamine, decylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine , Heicosylamine, docosylamine, tricosylamine, tetracosylamine, octadecenylamine or octadecadienylamine, and mixtures thereof beef tallow amine, hardened tallow amine, coconut oil amine, palm oil amine or soybean oil amine Mention may be made of aliphatic primary amines derived from iso-animal vegetable oils. As the aliphatic primary amine, one kind or a mixture of two or more kinds may be used.
  • the starting aliphatic secondary amine in the alkylene oxide adduct (D132) of an aliphatic secondary amine having 8 to 36 carbon atoms may be linear, branched or cyclic, and may have a saturated or unsaturated bond. It is an aliphatic secondary amine having 8 to 36 carbon atoms.
  • aliphatic secondary amine examples include dioctylamine, dibutylamine, dihexylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, Mention may be made of diheptadecylamine or dioctadecylamine.
  • the aliphatic secondary amine one kind or a mixture of two or more kinds may be used.
  • Examples of the starting alkylene oxide in the aliphatic amine alkylene oxide adduct (D13) of the present invention include alkylene oxides having 2 to 12 carbon atoms, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, Examples include tetrahydrofuran and 3-methyltetrahydrofuran. Of these, ethylene oxide and 1,2-propylene oxide are preferable from the viewpoint of availability. These alkylene oxides may use only 1 type and may use 2 or more types together. When using 2 or more types together, random or a block may be sufficient.
  • the average number of moles of alkylene oxide added in (D131) or (D132) is preferably 3 to 100 moles, more preferably 3 to 70 moles, and particularly preferably 3 to 40 moles per mole of amine.
  • a known method or the like can be used as a method for producing (D131) and (D132). Specifically, the above-mentioned aliphatic primary amine or aliphatic secondary amine is charged into a stirrable pressure vessel, sufficiently substituted with an inert gas (nitrogen, argon, etc.), then dehydrated under reduced pressure, A method in which the alkylene oxide is added and reacted at a reaction temperature of about 80 to 160 ° C. can be used. Moreover, you may use a well-known catalyst as needed at the time of reaction. The catalyst may be added from the beginning of the reaction or from the middle.
  • an inert gas nitrogen, argon, etc.
  • the catalyst examples include a metal atom-free catalyst (a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, and a third such as tetramethylethylenediamine and 1,8-diazabicyclo [5.4.0] undecene-7. Secondary amines) and metal atom-containing catalysts (alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides and alkaline earth metal oxides).
  • a metal atom-free catalyst a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, and a third such as tetramethylethylenediamine and 1,8-diazabicyclo [5.4.0] undecene-7. Secondary amines
  • metal atom-containing catalysts alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides and alkaline earth metal oxides.
  • the concentration of the aliphatic amine alkylene oxide adduct (D13) in actual use is 0.001 to 10% by weight based on the weight in the polishing liquid.
  • polyhydric alcohol type nonionic surfactant (D14) examples include glycerin ethylene oxide adduct and sorbitan ethylene oxide adduct.
  • anionic surfactant (D2) examples include fatty acid surfactants (fatty acid (salt) having 8 to 18 carbon atoms or ether carboxylic acid (salt) of an aliphatic alcohol having 8 to 18 carbon atoms); phosphate ester Surfactants [phosphoric mono- or diesters (salts) of higher alcohols having 8 to 24 carbon atoms, or phosphoric mono- or diesters (salts) of alkylene oxide adducts of higher alcohols having 8 to 24 carbon atoms, etc.] .
  • a fatty acid amine salt is preferable from the viewpoint of lubricity, and the fatty acid amine salt is a fatty acid amine salt having 8 to 22 carbon atoms (for example, oleic acid) completely or completely with an amine.
  • the thing which neutralized a part is mentioned.
  • the amine include primary amines such as monoethanolamine; secondary amines such as diethanolamine; tertiary amines such as triethanolamine.
  • the concentration of the surfactant (D) in the polishing liquid for electronic materials is usually 0 to 90% by weight, preferably 0.001 to 80% by weight, more preferably 0.01 to 20% by weight.
  • the weight ratio of the neutralized salt (AB) to the weight of the surfactant (D) is 0.001 to 1.
  • the polishing liquid for electronic materials of the present invention may contain an organic reducing agent (E) as necessary.
  • an organic reducing agent (E) By mix
  • Examples of the organic reducing agent (E) include phenols (E1) and reductones (E2).
  • the organic reducing agent (E) a commercially available organic reducing agent can be used, and phenols (E1) and reductones (E2) are preferable from the viewpoint of polishing rate.
  • Examples of the phenols (E1) include compounds represented by the following general formula (11).
  • X 1 to X 5 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, an amino group or an alkyl group.
  • phenols (E1) represented by the general formula (11) include phenols in which all of X 1 to X 5 are hydrogen; polyhydric phenol compounds such as pyrocatechol, resorcinol, hydroquinone and pyrogallol (E11 ); Phenolic compounds containing carboxyl groups such as 2-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,6-dicarboxyphenol, and 2,4,6-tricarboxyphenol (E12); gallic acid, etc.
  • a polyhydric phenol compound containing a carboxyl group (E13); a phenolic compound containing an amino group such as 4-aminophenol (E14); a phenolic compound containing an alkyl group such as cresol (E15); or a salt thereof. It is done.
  • polyhydric phenol compounds (E11) and polyhydric phenol compounds containing carboxyl groups (E13) are preferred, and more preferred are polyhydric phenols containing carboxyl groups.
  • the reductones (E2) may be any compound having a ketoenediol group represented by the following general formula (12) in the molecule.
  • reductones (E2) include ascorbic acid (L-form, DL-form, D-form), isoascorbic acid, erythorbic acid, or esters thereof (L-ascorbic acid sulfate, L-ascorbine). Acid phosphate ester, L-ascorbic acid 2-glucoside, L-ascorbic acid palmitic acid ester, tetraisopalmitic acid L-ascorbyl, ascorbic acid isopalmitate, erythorbic acid phosphoric acid ester, erythorbic acid palmitic acid ester, tetraisopalmitin Erysovir acid); or a salt thereof.
  • L-ascorbic acid, isoascorbic acid, esters of L-ascorbic acid or esters of isoascorbic acid, or salts thereof are preferred from the viewpoint of polishing rate and particle adhesion prevention, and more preferably L-ascorbic acid or a salt thereof.
  • Examples of the salts of (E1) and (E2) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary ammonium salts. Is mentioned.
  • the concentration of the organic reducing agent (E) in the polishing liquid during use is preferably 0.01 to 1% by weight from the viewpoint of preventing adhesion of particles.
  • the polishing liquid of the present invention includes inorganic acids (nitric acid, sulfuric acid, phosphoric acid, etc.), chelating agents (phosphonic acid-based chelating agents [hydroxyethylidene diphosphonic acid (HEDP) or salts thereof, methyl diphosphones).
  • inorganic acids nitric acid, sulfuric acid, phosphoric acid, etc.
  • chelating agents phosphonic acid-based chelating agents [hydroxyethylidene diphosphonic acid (HEDP) or salts thereof, methyl diphosphones).
  • An additive such as an adduct may be contained. As these additives, those conventionally used as polishing liquids can be used, and are not particularly limited.
  • the polishing method of the present invention is a polishing method for polishing an electronic material intermediate using the polishing liquid for electronic material of the present invention in the production process of the electronic material.
  • Another embodiment of the present invention is an electronic material manufacturing method including a step of polishing an electronic material intermediate using the above-described polishing liquid in the polishing step.
  • a lapping process of a hard disk glass substrate will be described below as an example.
  • a glass substrate is set on a carrier of a polishing apparatus, and the glass substrate is sandwiched by a surface plate to which a polishing pad to which a diamond grindstone is fixed is attached.
  • a load is applied to rotate the surface plate and the carrier.
  • the rotation is stopped.
  • the substrate is dried.
  • a substrate process for a hard disk glass substrate will be described below as an example.
  • (1) The above-mentioned lapped glass substrate is set on a carrier of a polishing apparatus, and the glass substrate is sandwiched by a surface plate to which a polyurethane polishing pad is attached.
  • (2) A load is applied while supplying the polishing liquid of the present invention containing cerium oxide, and the surface plate and the carrier are rotated.
  • the glass substrate is rinsed with running water, taken out from the carrier, and dipped or scrubbed with a cleaning agent.
  • a glass substrate rinsed with running water is set on a carrier of a polishing apparatus and polished in the same manner as described above using the polishing liquid of the present invention containing colloidal silica.
  • a commercially available polishing apparatus can be used as the polishing apparatus, and is not particularly limited.
  • polishing conditions such as the number of rotations, polishing time, number of oscillations, load, etc.
  • the conditions for polishing with a conventional polishing liquid can be used.
  • Production Example 1 (Production of polyacrylic acid DBU salt) A reaction vessel capable of temperature control and stirring was charged with 300 parts of isopropyl alcohol and 100 parts of ultrapure water, and the reaction vessel was purged with nitrogen, and then heated to 75 ° C. While stirring at 30 rpm, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropyl alcohol solution of dimethyl 2,2′-azobisisobutyrate were simultaneously added dropwise over 3.5 hours. After completion of the dropwise addition, the mixture was stirred at 75 ° C.
  • polyacrylic acid aqueous solution was neutralized with 450 parts of DBU until the pH became 7.0, and the concentration was adjusted with ultrapure water to obtain a 40% aqueous solution of polyacrylic acid DBU salt (AB-1). .
  • the Mw of the polyacrylic acid DBU salt was 10,000.
  • Production Example 2 (Production of naphthalenesulfonic acid formaldehyde condensate DBU salt)
  • a reaction vessel with stirring was charged with 21 parts of naphthalenesulfonic acid and 10 parts of ultrapure water, and 8 parts of 37% formaldehyde was added dropwise over 3 hours while maintaining the temperature in the system at 80 ° C. with stirring.
  • the temperature was raised to 105 ° C. and reacted for 25 hours, then cooled to room temperature (about 25 ° C.), DBU was gradually added while adjusting to 25 ° C. in a water bath, and adjusted to pH 6.5 (DBU). Use about 15 parts).
  • Ultrapure water was added to adjust the solid content to 40% to obtain a 40% aqueous solution of DBU salt (AB-2) of naphthalenesulfonic acid formaldehyde condensate as an anionic surfactant.
  • the Mw of the DBU salt of (AB-2) was 5,000.
  • Production Example 3 (Production of polystyrene sulfonic acid guanidine salt) 100 parts of ethylene dichloride was charged into a reaction vessel with stirring capable of temperature control and refluxing, and after purging with nitrogen under stirring, the temperature was raised to 90 ° C. to reflux ethylene dichloride. 120 parts of styrene and an initiator solution prepared by dissolving 1.7 parts of 2,2′-azobisisobutyronitrile in 20 parts of ethylene dichloride are dropped into the reaction vessel separately for 6 hours, and the dropping is completed. Thereafter, polymerization was further performed for 1 hour. After the polymerization, the mixture was cooled to 20 ° C.
  • Production Example 4 (Production of polystyrene sulfonic acid guanidine salt) 80 parts of ethylene dichloride was charged into a reaction vessel with stirring capable of temperature control and refluxing, and the temperature was raised to 90 ° C. after stirring and purging with nitrogen, thereby refluxing ethylene dichloride. 200 parts of styrene and an initiator solution prepared by dissolving 1.0 part of 2,2′-azobisisobutyronitrile in 20 parts of ethylene dichloride were dropped into the reaction vessel separately over 6 hours, and the addition was completed. Thereafter, polymerization was further performed for 1 hour. After the polymerization, the mixture was cooled to 20 ° C.
  • Production Example 6 (Production of aliphatic amine ethylene oxide adduct) 185 parts (1.0 mole part) of laurylamine and 3.6 parts (0.01 mole part) of 25% TMAH aqueous solution were charged into a stainless steel autoclave equipped with a stirrer and a temperature controller, and 100 ° C., 4 kPa or less. For 30 minutes under reduced pressure. 308 parts (7.0 mole parts) of ethylene oxide was added dropwise over 3 hours while controlling the reaction temperature at 100 ° C., and then aged at 100 ° C. for 3 hours. Further, the mixture was stirred at 150 ° C. for 2 hours under a reduced pressure of 2.6 kPa or less to decompose and remove the remaining TMAH, and a nonionic surfactant laurylamine ethylene oxide 7 mol adduct (D-2) 490 parts were obtained.
  • D-2 nonionic surfactant laurylamine ethylene oxide 7 mol adduct
  • Comparative Production Example 1 (Production of polyacrylic acid Na salt) A reaction vessel capable of temperature control and stirring was charged with 300 parts of isopropyl alcohol and 100 parts of ultrapure water, and the reaction vessel was purged with nitrogen, and then heated to 75 ° C. While stirring at 30 rpm, 407 parts of a 75% aqueous solution of acrylic acid and 95 parts of a 15% isopropyl alcohol solution of dimethyl 2,2′-azobisisobutyrate were simultaneously added dropwise over 3.5 hours. After completion of the dropwise addition, the mixture was stirred at 75 ° C.
  • Examples 1 to 49 and Comparative Examples 1 to 19 Each component was blended so as to be a total of 100 parts with the composition described in Tables 1 to 6, and stirred for 20 minutes at 25 ° C. with a magnetic stirrer at 40 rpm to obtain the polishing liquid of the present invention and the polishing for comparison. A liquid was obtained. The following abrasive particles were used in the table.
  • Colloidal silica slurry “COMPOL80” manufactured by Fujimi Incorporated (average particle size 80 nm, active ingredient concentration 40% by weight)
  • Cerium oxide “HS-8005” manufactured by Showa Denko KK (average particle size 0.5 ⁇ m)
  • Alumina “WA # 20000” manufactured by Fujimi Incorporated (average particle size 0.4 ⁇ m)
  • Diamond “1/10 PCS-WB2” manufactured by Nano Factor Co., Ltd.
  • Polyoxyethylene polyoxypropylene copolymer New Pole GEP2800 manufactured by Sanyo Chemical Industries
  • Dioleyl phosphate Na salt NAS-546 manufactured by Sanyo Chemical Industries
  • Aromatic sulfonate hydroxynaphthyl sulfonic acid Na salt reagent was used.
  • the number of rotations was set to 30 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 50 g weight / cm 2 , and the above test solution was polished for 5 minutes while being poured onto the substrate at a rate of 1 mL / second.
  • the polished glass substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed, and then removed from the polishing apparatus and dried by nitrogen blowing to prepare an evaluation substrate.
  • a surface inspection device (made by Vision Cytec Co., Ltd.) that emphasizes and inspects fine scratches on the surface by applying light to scratches on the evaluation substrate and condensing and amplifying the weak scattered light generated.
  • the evaluation substrate surface was arbitrarily selected at five locations (10 mm ⁇ 10 mm square), the number of scratches within the range was counted, and the average value at the five locations was calculated.
  • the average number of scratches on the substrate of Comparative Example 1 (blank) was 50.
  • the number of scratches on each substrate was compared with the number of scratches on the substrate of Comparative Example 1 (blank), and the effect of suppressing the generation of scratches on the substrate surface was evaluated and determined according to the following criteria.
  • the results are shown in Table 1. 5: Less than 20% of blanks (50 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more
  • the number of particles on each substrate was compared with the number of particles on the substrate of Comparative Example 1, and the effect of reducing the adhesion of particles in the polishing process was evaluated and determined according to the following criteria.
  • the results are shown in Table 1. 5: Less than 20% of blanks (1950 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more
  • the number of rotations was set to 30 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 50 g weight / cm 2 , and the above test solution was polished for 5 minutes while being poured onto the substrate at a rate of 1 mL / second.
  • the polished aluminum substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed, and then removed from the polishing apparatus and dried by nitrogen blowing to prepare an evaluation substrate.
  • a surface inspection device (made by Vision Cytec Co., Ltd.) that emphasizes and inspects fine scratches on the surface by applying light to scratches on the evaluation substrate and condensing and amplifying the weak scattered light generated.
  • the evaluation substrate surface was arbitrarily selected at five locations (10 mm ⁇ 10 mm square), the number of scratches within the range was counted, and the average value at the five locations was calculated.
  • the average number of scratches on the substrate of Comparative Example 4 was 100.
  • the number of scratches on each substrate was compared with the number of scratches on the substrate of Comparative Example 4, and the effect of suppressing the generation of scratches on the substrate surface was evaluated and determined according to the following criteria.
  • the results are shown in Table 2. 5: Less than 20% of blank (100 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more
  • the number of particles on each substrate was compared with the number of particles on the substrate of Comparative Example 4, and the effect of reducing the adhesion of particles in the polishing process was evaluated and determined according to the following criteria.
  • the results are shown in Table 2. 5: Less than 20% of blanks (1200) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more
  • the number of rotations was set to 100 rpm, the number of oscillations was set to 60 times / minute, the pressing pressure was set to 100 g weight / cm 2 , and the above test solution was polished onto the substrate at a rate of 1 mL / second for 5 minutes.
  • the polished glass substrate was taken out from the polishing apparatus, rinsed with running water for 1 minute, rinsed, and then removed from the polishing apparatus and dried by nitrogen blowing to prepare an evaluation substrate.
  • the above surface inspection apparatus capable of inspecting fine residue on the surface by applying light to residual particles on the evaluation substrate, emphasizing and amplifying the weak scattered light generated, and amplifying it.
  • the number of particles on each substrate was compared with the number of particles on the substrate of Comparative Example 16, and the effect of reducing the adhesion of particles in the polishing process was evaluated and determined according to the following criteria.
  • the results are shown in Table 6. 5: Less than 20% of blanks (4500 pieces) 4: 20% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more
  • the polishing liquids of Examples 1 to 49 of the present invention can greatly reduce the amount of adhered particles and can maintain the polishing rate as compared with Comparative Examples 1 to 19. Further, the polishing liquids of the present invention of Examples 1 to 40 can greatly reduce the number of scratches compared to Comparative Examples 1 to 15.
  • the polishing liquids of Comparative Examples 3, 6, 9, 12, 15, and 18 have some effect of suppressing the adhesion of certain particles as compared with the blank, but the acceptable particle adhesion for high capacity is possible. It does not reach the amount. Further, the polishing liquids of Comparative Examples 3, 6, 9, 12, and 15 are somewhat effective in suppressing the occurrence of a certain scratch compared to the blank, but do not reach the number of scratches that can be allowed for higher capacity.
  • the polishing liquids of Comparative Examples 2, 5, 8, 11, and 14 using benzotriazole have almost the same number of scratches after polishing the glass substrate as compared with Comparative Examples 1, 4, 7, 10, and 13. The effect of suppressing the generation of scratches and particles is small.
  • the polishing liquid for electronic materials of the present invention is excellent in the effect of suppressing the occurrence of scratches during the polishing process, and is also excellent in the effect of reducing particle adhesion during polishing, so the polishing liquid for electronic materials including the polishing process in the manufacturing process
  • it is useful as a polishing liquid for producing glass substrates for magnetic disks, Ni-P plated aluminum substrates for magnetic disks, silicon substrates for semiconductors, and sapphire substrates for LEDs.
  • the method for producing an electronic material including the step of polishing using the polishing liquid of the present invention is a method for producing a magnetic disk because scratching during polishing is very small and particle adhesion during polishing is small. It can be used as a manufacturing method for glass substrates, Ni—P plated aluminum substrates for magnetic disks, silicon substrates for semiconductors, sapphire substrates for LEDs, and the like.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

Cette invention comprend : un sel neutre spécifique (AB) utilisé dans une étape consistant à polir un intermédiaire de matériau électronique à l'aide d'un tampon de polissage; un liquide de polissage de matériau électronique contenant ledit sel neutre (AB); un procédé de polissage pour polir un intermédiaire de matériaux électroniques à l'aide dudit liquide de polissage de matériau électronique; et un procédé de fabrication d'un matériau électronique comprenant une étape consistant à polir un intermédiaire de matériau électronique par ledit procédé de polissage. Ici, le sel neutre (AB) est un sel (A) d'un composé acide ayant au moins un radical acide (X) dans la molécule, et (B) d'un composé basique contenant de l'azote, ayant une chaleur de changement de formation (Q2) de 10-152 kcal/mole dans des réactions de protonation, ledit sel neutre ayant une chaleur de changement de formation (Q1) de 3-200 kcal/mole dans des réactions de dissociation d'acide du radical acide mentionné ci-dessus (X). Ainsi, le mode de réalisation selon l'invention permet d'obtenir un matériau qui, comparé aux liquides de polissage classiques, crée moins de défauts sur des subtrats, tels que des rayures, ce qui par la suite permet de faciliter l'élimination des débris de polissage dans une étape de lavage ultérieure, et permet de maintenir une vitesse de polissage lors de l'étape de polissage.
PCT/JP2012/066424 2011-06-29 2012-06-27 Sel neutre destiné à être utilisé dans un liquide de polissage, liquide de polissage de matériaux électroniques, procédé de polissage et procédé de fabrication de matériaux électroniques WO2013002281A1 (fr)

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US10640681B1 (en) * 2018-10-20 2020-05-05 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing composition and method for tungsten

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CN103619982A (zh) 2014-03-05
MY163071A (en) 2017-08-15

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