WO2021131198A1 - 分散剤及び研磨剤組成物 - Google Patents

分散剤及び研磨剤組成物 Download PDF

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WO2021131198A1
WO2021131198A1 PCT/JP2020/036577 JP2020036577W WO2021131198A1 WO 2021131198 A1 WO2021131198 A1 WO 2021131198A1 JP 2020036577 W JP2020036577 W JP 2020036577W WO 2021131198 A1 WO2021131198 A1 WO 2021131198A1
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Prior art keywords
polymer block
structural unit
group
polymer
dispersant
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English (en)
French (fr)
Japanese (ja)
Inventor
後藤　彰宏
紗知子 井村
駿 中野
隆太郎 坪内
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Toagosei Co Ltd
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Toagosei Co Ltd
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Application filed by Toagosei Co Ltd filed Critical Toagosei Co Ltd
Priority to KR1020227016045A priority Critical patent/KR102827839B1/ko
Priority to CN202080069040.5A priority patent/CN114641850B/zh
Priority to JP2021566824A priority patent/JP7255711B2/ja
Publication of WO2021131198A1 publication Critical patent/WO2021131198A1/ja
Priority to US17/830,285 priority patent/US12577431B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/52—Natural or synthetic resins or their salts
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing 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
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/22—Amides or hydrazides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H10P52/40—Chemomechanical polishing [CMP]
    • H10P52/402—Chemomechanical polishing [CMP] of semiconductor materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1472—Non-aqueous liquid suspensions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
    • H10P52/40—Chemomechanical polishing [CMP]
    • H10P52/403—Chemomechanical polishing [CMP] of conductive or resistive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P95/00—Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
    • H10P95/06—Planarisation of inorganic insulating materials
    • H10P95/062—Planarisation of inorganic insulating materials involving a dielectric removal step

Definitions

  • the present disclosure relates to a dispersant and an abrasive composition, and more particularly, for chemical mechanical polishing for flattening the surface of at least one of an insulating layer and a wiring layer formed on a wafer in a semiconductor manufacturing process.
  • dispersant and abrasive compositions are particularly, for chemical mechanical polishing for flattening the surface of at least one of an insulating layer and a wiring layer formed on a wafer in a semiconductor manufacturing process.
  • Chemical mechanical polishing (CMP) technology is important for realizing high-precision multilayer wiring formation, and at each stage such as flattening of insulating film, formation of metal plugs, and formation of embedded wiring in the manufacturing process of semiconductor devices. It's being used.
  • CMP Chemical mechanical polishing
  • an abrasive composition is used in order to improve the processing speed and processing accuracy.
  • the abrasive composition generally contains a water-soluble polymer as a dispersant together with abrasive grains and water (see, for example, Patent Document 1).
  • the water-soluble polymer is adsorbed on the surface of the abrasive grains to improve the dispersibility of the abrasive grains, thereby suppressing the occurrence of surface defects on the object to be polished. Further, the water-soluble polymer contributes to the improvement of the processing speed by adsorbing to the surface of the object to be polished to make the polished surface hydrophilic and increasing the contact frequency between the abrasive grains and the polished surface. On the other hand, the water-soluble polymer also has a function of protecting the surface of the object to be polished, thereby suppressing excessive polishing. Further, the effect of suppressing the adhesion of abrasive grains and foreign substances can be expected, and as a result, the surface smoothing of the object to be polished can be performed with high accuracy.
  • a water-soluble polymer as a dispersant in the polishing liquid composition, it is possible to perform surface smoothing of the object to be polished with high accuracy, while one molecule of the water-soluble polymer bridges the abrasive grains. It may be adsorbed on the surface of a plurality of abrasive grains so as to be bridged, causing aggregation of the abrasive grains.
  • Such agglomerated structures due to bridging between abrasive grains tend to occur more easily under strong shear forces.
  • cerium oxide when cerium oxide is used as the abrasive grains, when a strong shearing force is applied, the frequency of contact between the abrasive grains increases, and the abrasive grains tend to aggregate.
  • the present disclosure has been made in view of the above circumstances, and an object thereof is to provide a dispersant having high dispersion stability of abrasive grains and capable of suppressing aggregation of abrasive grains due to shearing force.
  • the present inventors diligently studied in order to solve the above problems, and focused on block copolymers having a specific structure. Then, they have found that the block copolymer can solve the above-mentioned problems. According to the present disclosure, the following means are provided.
  • the polymer block A has a structural unit UA derived from at least one selected from the group consisting of an amide group-containing vinyl monomer and an ester group-containing vinyl monomer.
  • B is a dispersant having a structural unit UB having an ionic functional group.
  • the heavy 5-combined block A and the polymer block B each have a structural unit having an ionic functional group, and the block copolymer (P) is one of the following conditions I and II.
  • Condition I The ionic functional group of the polymer block A and the ionic functional group of the polymer block B are different.
  • Condition II The content of the ionic functional group of the polymer block A and the content of the ionic functional group of the polymer block B are different.
  • the polymer block A and the polymer block B each have a structural unit derived from a vinyl monomer represented by the following formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are independently hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups, or R 2 and R 3 are bonded to each other R 2 and R 3 is a group which forms a ring with the nitrogen atom to which they are attached.
  • the polymer block A contains, as a structural unit derived from the vinyl monomer represented by the above formula (1), a structural unit having at least one of a primary amide group and a hydroxyl group. 4] Dispersant. [6]
  • the polymer block B contains a structural unit having at least one of a secondary amide group and a tertiary amide group as a structural unit derived from the vinyl monomer represented by the above formula (1). , The dispersant of the above [4] or [5]. [7] The dispersant according to any one of [4] to [6] above, wherein the polymer block B contains a structural unit having a carboxyl group.
  • the ratio (A / B) of the polymer block A and the polymer block B in the block copolymer (P) is 10/90 to 90/10 in terms of mass ratio.
  • the degree of molecular weight dispersion (Mw / Mn) represented by the ratio of the number average molecular weight Mn of the block copolymer (P) to the weight average molecular weight Mw is 2.0 or less.
  • An abrasive composition for chemical mechanical polishing used for surface flattening of at least one of an insulating layer and a wiring layer, which is oxidized with the dispersant according to any one of the above [1] to [10].
  • the block copolymer (P) has high dispersion stability of abrasive grains and can suppress aggregation of abrasive grains due to shearing force. Further, such an effect of suppressing the aggregates of abrasive grains is fully exhibited even when cerium oxide is used as the abrasive grains. Therefore, in the semiconductor manufacturing process, a semiconductor element having excellent surface flatness can be obtained by using it as a dispersant in an abrasive composition for chemical mechanical polishing for flattening the surface of an insulating layer or a wiring layer. ..
  • (meth) acrylic means acrylic and / or methacryl
  • (meth) acrylate means acrylate and / or methacrylate
  • (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
  • the dispersant of the present disclosure is a dispersant for chemical mechanical polishing used for flattening the surface of at least one of an insulating layer and a wiring layer formed on a wafer (for example, a silicon wafer) in a semiconductor manufacturing process.
  • the abrasive composition of the present disclosure contains cerium oxide (ceria) as abrasive grains and the dispersant of the present disclosure.
  • cerium oxide (ceria) as abrasive grains
  • the dispersant and abrasive composition of the present disclosure will be described.
  • the dispersant according to the first embodiment of the present disclosure contains a structural unit UA derived from at least one selected from the group consisting of an amide group-containing vinyl monomer and an ester group-containing vinyl monomer as a water-soluble polymer. It contains a block copolymer (P) containing a polymer block A having an ionic functional group and a polymer block B having a structural unit UB having an ionic functional group.
  • the polymer block A has a main chain composed of carbon-carbon bonds derived from a vinyl monomer.
  • the polymer block A having a main chain composed of carbon-carbon bonds has high adsorptivity to abrasive grains and appropriately adsorbs to a polishing object having a hydrophobic surface to impart good wettability to the polished surface. To do.
  • the amide group-containing vinyl monomer and the ester group-containing vinyl monomer constituting the structural unit UA are not particularly limited.
  • Examples of the amide group-containing vinyl monomer include (meth) acrylamide; N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-ethyl-N-methyl.
  • Alkylaminoalkylamides Alkylaminoalkylamides; heterocyclic-containing (meth) acrylamides such as 4- (meth) acryloylmorpholin; 2- (meth) acrylamide-containing (meth) acrylamides containing sulfonic acid groups such as -2-methylpropanesulfonic acid or salts thereof.
  • Classes; hydroxyl group-containing (meth) acrylamides such as 2-hydroxyethylacrylamide; N-vinylacetamide, N-vinylformamide, N-vinylisobutylamide, N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam, etc. N-vinylamides; etc.
  • ester group-containing vinyl monomer examples include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth) acrylic acid.
  • n-butyl isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylate (Meta) acrylic acid alkyl esters such as n-octyl, ethylhexyl (meth) acrylate, and n-decyl (meth) acrylate; Cyclohexyl (meth) acrylate, Methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, Cyclododecyl (meth) acrylate, Isobornyl (meth) acrylate, Adamanthyl (meth) acrylate, (meth) Adicyclic esters of (meth) acrylic acid such as
  • Alkoxyalkyls (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate; Hydroxyalkyls (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; N- [2- (methylamino) ethyl ] (Meta) acrylate, N- [2- (dimethylamino) ethyl] (meth) acrylate, N- [2- (ethylamino) ethyl] (meth) acrylate and N- [2- (diethylamino) ethyl] (meth) ) (Di) Alkylaminoalkyl (meth) acrylates such
  • the polymer block A preferably has at least a structural unit derived from an amide group-containing vinyl monomer as the structural unit UA. Since the polymer block A has a structural unit derived from an amide group-containing monomer, good dispersion stability can be imparted to abrasive grains (particularly cerium oxide), and the effect of suppressing abrasive grain aggregation due to shearing force can be enhanced. It is preferable in that it can be used.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are independently hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups, or R 2 and R 3 are bonded to each other R 2 and R 3 is a group which forms a ring with the nitrogen atom to which they are attached.
  • R 2 and R 3 when at least one of R 2 and R 3 is a substituted monovalent hydrocarbon group, it is used as the substituted monovalent hydrocarbon group.
  • examples include a group having a secondary amino group, a group having a tertiary amino group, and a hydroxyalkyl group.
  • Examples of the vinyl monomer represented by the above formula (1) include (meth) acrylamide, (di) alkyl (meth) acrylamide, (di) alkylaminoalkylamide, heterocyclic-containing (meth) acrylamide, and sulfonate. Examples thereof include acid group-containing (meth) acrylamides and hydroxyl group-containing (meth) acrylamides.
  • the structural unit UA contained in the polymer block A is preferably a structural unit derived from a water-soluble monomer.
  • the amide group-containing vinyl monomer is a preferable example of the vinyl monomer represented by the above formula (1), and at least one selected from the group consisting of N-vinyl-2-pyrrolidone. preferable.
  • the ester group-containing vinyl monomer is composed of methyl acrylate, hydroxyalkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms in the alkyl ester moiety, and polyoxyalkylene (meth) acrylates. At least one selected from the group is preferred.
  • the "water-soluble monomer” refers to a compound having a solubility of 2 g or more in 100 g of water at 20 ° C.
  • the polymer block A may be a block composed of only the structural unit UA, but the amide group-containing vinyl monomer and the ester group-containing vinyl monomer are not impaired as long as the action of the block copolymer (P) is not impaired. It may further have a structural unit derived from a monomer different from the above (hereinafter, also referred to as “other monomer M1”).
  • the other monomer M1 is not particularly limited as long as it is a monomer copolymerizable with the amide group-containing vinyl monomer and the ester group-containing vinyl monomer.
  • Examples of the other monomer M1 include alkyl vinyl ethers, vinyl alcohols, aromatic vinyl compounds, vinyl ester compounds, ⁇ -olefins, unsaturated acids, unsaturated acid anhydrides and the like.
  • the other monomeric M1 include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-hexyl vinyl ether, and 2 as alkyl vinyl ethers.
  • the content of the structural unit UA is preferably 70% by mass or more with respect to the total constituent monomer units of the polymer block A.
  • the content of the structural unit UA is 70% by mass or more, it is preferable that the polymer block A having excellent adsorptivity of abrasive grains can be obtained.
  • the content of the structural unit UA is more preferably 80% by mass or more, further preferably 90% by mass or more, more preferably 95% by mass or more, based on the total constituent monomer units of the polymer block A. It is more preferably mass% or more, and particularly preferably 99 mass% or more.
  • the content of the structural unit derived from the amide group-containing vinyl monomer in the polymer block A is equal to or equal to the content of the structural unit derived from the amide group-containing vinyl monomer in the polymer block B. More preferably than more, and more preferably more than the content of structural units derived from the amide group-containing vinyl monomer in the polymer block B.
  • the content of the structural unit derived from the amide group-containing vinyl monomer in the polymer block A is preferably 10% by mass or more, preferably 30% by mass or more, based on the total constituent monomer units of the polymer block A. By mass% or more is more preferable, 50% by mass or more is further preferable, 70% by mass or more is further preferable, and 90% by mass or more is particularly preferable.
  • the number average molecular weight (Mn) of the polymer block A is preferably in the range of 1,000 or more and 200,000 or less. When Mn is 1,000 or more, it is preferable that the effect of improving the adsorptivity of the abrasive grains by introducing the polymer block A is sufficiently exhibited. Further, when Mn is 200,000 or less, it is preferable that one molecule of the polymer can be sufficiently suppressed from adsorbing on the surfaces of a plurality of abrasive grains to form an aggregated structure of the abrasive grains.
  • the Mn of the polymer block A is more preferably 1,500 or more, still more preferably 2,000 or more.
  • the Mn of the polymer block A is more preferably 150,000 or less, further preferably 100,000 or less, and particularly preferably 70,000 or less.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are values in terms of sodium polyacrylate measured by gel permeation chromatography (GPC). Details are values measured by the method described in Examples described later.
  • the ionic functional group of the structural unit UB exhibits an appropriate adsorptivity to abrasive grains (particularly cerium oxide) and can impart good dispersion stability to the abrasive grains, and thus is a carboxyl group, a sulfonic acid group, or a phosphoric acid. It is preferably a group, a phosphonic acid group, an amino group or a salt thereof.
  • the ionic functional group is preferably an anionic functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group or a salt thereof, and is a carboxyl group, a sulfonic acid group or a salt of a carboxyl group or a sulfonic acid group. It is particularly preferable to have.
  • the structural unit UB may be introduced into the block copolymer (P) by polymerizing using a monomer having an ionic functional group (hereinafter, also referred to as “ionic group-containing monomer”).
  • a monomer having an ionic functional group hereinafter, also referred to as “ionic group-containing monomer”.
  • the ionic group-containing monomer is not particularly limited as long as it is a monomer copolymerizable with the constituent monomer of the polymer block A, but has an adsorptivity to abrasive grains and an object to be polished having a hydrophobic surface.
  • a vinyl monomer is preferable because it is good and the degree of freedom in selecting the monomer is high.
  • the ionic group-containing monomer examples include vinyl monomers having a carboxyl group, such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, and monobutyl maleate. Cyclohexendicarboxylic acid, salts thereof, etc .; as a vinyl monomer having a sulfonic acid group, for example, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acryloylethanesulfonic acid, or these.
  • vinyl monomers having a carboxyl group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, and monobutyl maleate. Cyclohexendicarboxylic acid, salts thereof, etc .
  • a vinyl monomer having a sulfonic acid group for example, 2- (meth) acryl
  • vinyl monomers having a phosphoric acid group or a phosphonic acid group for example, allylphosphonic acid, vinylphosphonic acid, acidphosphooxyethyl methacrylate, acidphosphooxypropyl methacrylate, 3-chloro-2-acidphosphooxypropyl.
  • Methacrylates, salts thereof, etc . as vinyl monomers having an amino group, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl.
  • the counterion of the cationic functional group includes, for example, chloride ion, bromide ion, iodide ion and the like; as the counterion of the anionic functional group, for example, sodium ion. , Magnesium ion, calcium ion, etc .; As the ionic group-containing monomer, one of these can be used alone or in combination of two or more.
  • the polymer block B may be a block composed of only the structural unit UB, but is a monomer different from the ionic group-containing monomer (hereinafter, as long as the action of the block copolymer (P) is not impaired). , Also referred to as “other monomer M2”).
  • the other monomer M2 is not particularly limited as long as it is a monomer copolymerizable with the ionic group-containing monomer, and for example, the amide group-containing vinyl monomer used for producing the polymer block A and the amide group-containing vinyl monomer.
  • the ester group-containing vinyl monomer and the other monomer M1 a vinyl monomer having no ionic functional group can be mentioned.
  • the other monomer M2 one of these can be used alone or in combination of two or more.
  • the polymer block B may contain a structural unit UB and a structural unit having an alkyl group having 1 to 10 carbon atoms in the side chain portion (hereinafter, also referred to as “structural unit UC”). Since the polymer block B has the structural unit UC, the hydrophobicity of the polymer block B is enhanced, and the adsorptivity to abrasive grains (particularly cerium oxide) can be further improved, which is preferable.
  • the alkyl group of the structural unit UC in the side chain portion preferably has 2 or more carbon atoms from the viewpoint of improving the dispersion stability of the abrasive grains.
  • the upper limit of the number of carbon atoms of the alkyl group of the structural unit UC in the side chain portion is preferably 8 or less, more preferably 7 or less, from the viewpoint of obtaining a polymer having high solubility in an aqueous system. is there.
  • the alkyl group is preferably bonded to the main chain via a linking group (-COO-, -CONH-, etc.).
  • the monomer constituting the structural unit UC is preferably at least one selected from the group consisting of an ester group-containing vinyl monomer and an amide group-containing vinyl monomer.
  • (meth) acrylic acid alkyl esters having an alkyl ester moiety having 1 to 10 carbon atoms and an N-alkyl group having 1 carbon atom have a high effect of improving the dispersion stability of abrasive grains.
  • At least one selected from the group consisting of N-alkyl (meth) acrylamides ranging from to 10 is preferable, and (meth) acrylic acid alkyl esters and N ⁇ which have an alkyl group having 2 to 10 carbon atoms in the alkyl ester moiety.
  • the polymer block B may have only one type of structural unit UC, or may have two or more types of structural unit UC.
  • the content of the structural unit UB is preferably 40% by mass or more with respect to the total constituent monomer units of the polymer block B.
  • the content of the structural unit UB is 40% by mass or more, it is preferable that the polymer block B having excellent dispersion stability of abrasive grains can be obtained.
  • the content of the structural unit UB is more preferably 50% by mass or more, further preferably 60% by mass or more, more preferably 70% by mass or more, based on the total constituent monomer units of the polymer block B. It is even more preferably mass% or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content of the structural unit UB is preferably 99% by mass or less with respect to the total constituent monomer units of the polymer block B. , 97% by mass or less, more preferably 95% by mass or less.
  • the content of the structural unit UC is 1 with respect to all the constituent monomer units of the polymer block B from the viewpoint of improving the adsorptivity to the abrasive grains and sufficiently obtaining the effect of improving the dispersion stability of the abrasive grains. It is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit of the content of the structural unit UC is preferably 50% by mass or less, more preferably 30% by mass or less, and 25% by mass, based on the total constituent monomer units of the polymer block B. The following is more preferable.
  • the polymer block B is a copolymer having an ionic functional group, but the polymer block A may further have an ionic functional group.
  • the polymer block A and the polymer block B preferably satisfy at least one of the following conditions I and II.
  • Condition I The ionic functional group of the polymer block A and the ionic functional group of the polymer block B are different.
  • Condition II The content of the ionic functional group of the polymer block A is smaller than the content of the ionic functional group of the polymer block B.
  • the ionic functional group exhibits appropriate adsorptivity to abrasive grains (particularly cerium oxide), and from the viewpoint of imparting good dispersion stability to the abrasive grains, from the viewpoint. It is preferably a sulfonic acid group or a carboxyl group, and more preferably a sulfonic acid group.
  • the combination of the ionic functional group of the polymer block A and the ionic functional group of the polymer block B is not particularly limited.
  • the ionic functional groups of each polymer block are as long as at least one type is a different ionic functional group.
  • Preferred specific examples of the combination satisfying the condition I include an embodiment in which the ionic functional group of the polymer block A is a sulfonic acid group and the ionic functional group of the polymerizable block B is a carboxyl group. ..
  • the content of the structural unit having an ionic functional group in the polymer block A is preferably 1000 mass by mass with respect to 100 parts by mass of the structural unit UB having an ionic functional group in the polymer block B. It is less than a part, more preferably 800 parts by mass or less.
  • the preferable range of the content of the structural unit having an ionic functional group in the polymer block A differs depending on whether or not the above condition I is satisfied.
  • the content of the structural unit having an ionic functional group in the polymer block A is 90 parts by mass or less with respect to 100 parts by mass of the structural unit UB having an ionic functional group in the polymer block B. It is preferably 80 parts by mass or less, and more preferably 80 parts by mass or less.
  • the content of the structural unit having an ionic functional group in the polymer block A is 75 parts by mass with respect to 100 parts by mass of the structural unit UB having an ionic functional group in the polymer block B. It is preferably less than or equal to, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less.
  • the difference in adsorptivity to abrasive grains and the object to be polished becomes larger in one molecule of the polymer, and grinding by shearing force becomes larger. This is preferable because the formation of aggregated structures of grains can be further suppressed.
  • the polymer block A has a structural unit UA, and preferably has a structural unit derived from an amide group-containing vinyl monomer.
  • the polymer block B may or may not have a structural unit derived from the amide group-containing vinyl monomer.
  • the polymer block A and the polymer block B are described above in that the formation of aggregated structures of abrasive grains due to shearing force is further reduced.
  • Condition II is preferably satisfied, and it is particularly preferable that the polymer block A has substantially no ionic functional group.
  • substantially free of an ionic functional group means that a compound having an ionic functional group is not used as a monomer raw material.
  • the number average molecular weight (Mn) of the polymer block B in terms of sodium polyacrylate measured by GPC is preferably in the range of 1,000 or more and 200,000 or less.
  • Mn is 1,000 or more, it is preferable in that the effect of improving the adsorptivity of the abrasive grains by introducing the polymer block B into the molecule is sufficiently exhibited.
  • Mn is 200,000 or less, in the obtained block copolymer (P), aggregation of abrasive grains due to shearing force can be suppressed, and dispersion stability of abrasive grains can be sufficiently ensured, which is preferable.
  • the Mn of the polymer block A is more preferably 1,500 or more, further preferably 2,000 or more, and particularly preferably 2,500 or more.
  • the upper limit of Mn of the polymer block A is more preferably 150,000 or less, further preferably 100,000 or less, and particularly preferably 70,000 or less.
  • the block copolymer (P) is not particularly limited in its production method, and is produced by adopting a known production method. Can be done. Specific examples of the method for producing the block copolymer (P) include various controlled polymerization methods such as living radical polymerization and living anionic polymerization, and a method of coupling polymers having functional groups with each other. Among these, the block copolymer (P) having high molecular weight dispersion (PDI) controllability and excellent dispersion stability of abrasive grains can be produced, and the operation is simple and a wide range of single amounts.
  • PDI molecular weight dispersion
  • the living radical polymerization method is preferable because it can be applied to a body.
  • the living radical polymerization method is adopted, the polymerization type is not particularly limited, and it can be carried out by various aspects such as bulk polymerization, solution polymerization, emulsion polymerization, mini-emulsion polymerization and suspension polymerization.
  • the block copolymer (P) when the block copolymer (P) is produced by solution polymerization by adopting the living radical polymerization method, an organic solvent and a monomer are charged in a reactor, a radical polymerization initiator is added, and the block copolymer (P) is preferably heated.
  • the desired block copolymer (P) can be obtained by carrying out the polymerization.
  • any process such as a batch process, a semi-batch process, a dry continuous polymerization process, or a continuous stirring tank type process (CSTR) may be adopted.
  • the living radical polymerization method In the production of the block copolymer (P), a known polymerization method can be adopted as the living radical polymerization method.
  • the living radical polymerization method to be used include a living radical polymerization method having an exchange chain mechanism, a living radical polymerization method having a bond-dissociation mechanism, and a living radical polymerization method having an atom transfer mechanism.
  • Specific examples of these include a reversible addition-cleavage chain transfer polymerization method (RAFT method), an iodine transfer polymerization method, a polymerization method using an organic tellurium compound (TERP method), and an organic antimony compound as living radical polymerization of an exchange chain mechanism.
  • SBRP method polymerization method using organic bismuth compound
  • BIRP method organic bismuth compound
  • NMP method nitroxy radical method
  • ATRP method atom transfer radical polymerization method
  • the living radical polymerization method having an exchange chain mechanism or a bond-dissociation mechanism is preferable because it can be applied to the widest range of vinyl monomers and has excellent polymerization controllability, and a metal or metalloid compound is mixed.
  • the RAFT method or the NMP method is preferable in that contamination of the object to be polished by the method can be avoided, and the RAFT method is particularly preferable from the viewpoint of ease of implementation.
  • the polymerization proceeds through a reversible chain transfer reaction in the presence of a polymerization control agent (RAFT agent) and a free radical polymerization initiator.
  • RAFT agent various known RAFT agents such as a dithioester compound, a zantate compound, a trithiocarbonate compound and a dithiocarbamate compound can be used. Of these, a trithiocarbonate compound and a dithiocarbamate compound are preferable in that a polymer having a smaller molecular weight dispersion can be obtained.
  • RAFT agent a monofunctional compound having only one active site may be used, or a polyfunctional compound having two or more active sites may be used. By using these compounds, a polymer having a narrower molecular weight dispersion can be obtained.
  • the amount of the RAFT agent used is appropriately adjusted depending on the monomer used, the type of RAFT agent, and the like.
  • the polymerization initiator used in the polymerization by the RAFT method known radical polymerization initiators such as azo compounds, organic peroxides and persulfates can be used.
  • the azo compound is preferable because it is easy to handle for safety and side reactions during radical polymerization are unlikely to occur.
  • Specific examples of the azo compound include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 4,4'-azobis (4-cyanovaleric acid).
  • radical polymerization initiator only one type may be used, or two or more types may be used in combination.
  • the amount of the radical polymerization initiator used is not particularly limited, but is preferably 0.5 mol or less, preferably 0.2 mol or less, with respect to 1 mol of the RAFT agent, from the viewpoint of obtaining a polymer having a smaller molecular weight dispersion. The following is more preferable.
  • the lower limit of the amount of the radical polymerization initiator used is preferably 0.01 mol or more, preferably 0.05 mol or more, with respect to 1 mol of the RAFT agent. Is more preferable.
  • the amount of the radical polymerization initiator used per 1 mol of the RAFT agent is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.2 mol.
  • the polymerization solvent includes aromatic compounds such as benzene, toluene, xylene and anisole; ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; and ketone compounds such as acetone and methyl ethyl ketone.
  • aromatic compounds such as benzene, toluene, xylene and anisole
  • ester compounds such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketone compounds such as acetone and methyl ethyl ketone.
  • dimethylformamide, acetonitrile, dimethylsulfoxide, alcohol, water and the like As the polymerization solvent, one of these may be used alone, or two or more thereof may be used in combination.
  • the reaction temperature is preferably 40 ° C. or higher and 100 ° C. or lower, more preferably 45 ° C. or higher and 90 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower.
  • the reaction temperature is 40 ° C. or higher, the polymerization reaction can proceed smoothly, and when the reaction temperature is 100 ° C. or lower, side reactions can be suppressed and restrictions on the initiators and solvents that can be used are relaxed. It is preferable in that it is done.
  • the reaction time can be appropriately set according to the monomer or the like used, but is preferably 1 hour or more and 48 hours or less, and more preferably 3 hours or more and 24 hours or less.
  • the polymerization may be carried out in the presence of a chain transfer agent (for example, an alkylthiol compound having 2 to 20 carbon atoms).
  • a chain transfer agent for example, an alkylthiol compound having 2 to 20 carbon atoms.
  • the storage container for the product or the like is a container made of a resin having corrosion resistance or the like.
  • the container is made of a material in which metal contamination due to dissolution of a filler or the like is suppressed.
  • the number average molecular weight (Mn) in terms of sodium polyacrylate measured by GPC is preferably in the range of 2,000 or more and 300,000 or less.
  • Mn is 2,000 or more, it is preferable in that it is possible to suppress a decrease in the polishing rate while sufficiently ensuring the wettability of the surface of the object to be polished.
  • Mn is 300,000 or less, aggregation of abrasive grains due to shearing force can be sufficiently suppressed, and defects such as scratches can be sufficiently suppressed during polishing, which is preferable.
  • the Mn of the block copolymer (P) is more preferably 2,500 or more, further preferably 3,000 or more, and even more preferably 3,500 or more.
  • the upper limit of Mn of the block copolymer (P) is more preferably 200,000 or less, further preferably 150,000 or less, further preferably 110,000 or less, and particularly preferably 100,000 or less.
  • the weight average molecular weight (Mw) of the block copolymer (P) in terms of sodium polyacrylate measured by GPC is preferably in the range of 3,000 or more and 400,000 or less.
  • the Mw of the block copolymer (P) is more preferably 4,000 or more, still more preferably 5,000 or more.
  • the upper limit of Mw of the block copolymer (P) is more preferably 300,000 or less, further preferably 220,000 or less, still more preferably 150,000 or less, and particularly preferably 100, It is 000 or less.
  • a polymer used as a dispersant for abrasive grains preferably has a narrow molecular weight distribution. From this viewpoint, it is preferable.
  • the PDI of the block copolymer (P) is more preferably 2.0 or less, still more preferably 1.8 or less, even more preferably 1.5 or less, and particularly preferably 1.3 or less. There is a lower limit of PDI, which is usually 1.0.
  • the ratio A / B (mass ratio) of the polymer block A and the polymer block B in one block copolymer (P) molecule is 5 / from the viewpoint of suppressing the formation of an aggregated structure of abrasive grains due to shearing force. It is preferably 95 to 95/5.
  • the ratio A / B is more preferably 10/90 to 90/10, further preferably 15/85 to 85/15, even more preferably 20/80 to 80/20, and particularly preferably 25. It is / 75 to 75/25.
  • the ratio A / B can be appropriately selected by adjusting the ratio of the monomer used for producing the polymer block A and the monomer used for producing the polymer block B. ..
  • the block copolymer (P) has the polymer block A and the polymer block B
  • the number and arrangement order of the polymer block A and the polymer block B in one molecule are not particularly limited.
  • Specific examples of the block copolymer (P) include (AB) diblock composed of polymer block A and polymer block B, and polymer block A / polymer block B / polymer block A (composed of polymer block A / polymer block B / polymer block A).
  • ABA triblocks
  • BAB triblocks composed of polymer block B / polymer block A / polymer block B, and the like can be mentioned.
  • the block copolymer (P) may be a multi-block copolymer having four or more polymer blocks, and further has a polymer block other than the polymer block A and the polymer block B. You may.
  • the block copolymer (P) has an AB-type structure in that it can efficiently produce a block copolymer (P) having sufficiently high dispersion stability of abrasive grains (particularly cerium oxide). It is preferably a block copolymer.
  • the dispersant of the present disclosure may be any one containing a block copolymer (P). Therefore, the dispersant may be in the form of a single component containing only the block copolymer (P), or may be different from the block copolymer (P) together with the block copolymer (P). It may be in a form containing a component (hereinafter, also referred to as “other component”).
  • the dispersant of the present disclosure may contain a solvent as another component.
  • the solvent include water, an organic solvent, and a mixed solvent of water and an organic solvent.
  • the solvent contained in the dispersant is preferably a solvent capable of dissolving the block copolymer (P) which is a water-soluble polymer, and water or a mixed solvent of water and an organic solvent soluble in water is preferable. More preferably, water is particularly preferable.
  • organic solvent used together with water examples include alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; alkylene glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether and propylene glycol.
  • Ethers such as monomethyl ether, ethylene glycol dimethyl ether and tetrahydrofuran; esters such as ethylene glycol monomethyl ether acetate and ethyl acetate; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; and the like.
  • the organic solvent one type can be used alone or two or more types can be used in combination.
  • the dispersant contains a block copolymer (P) and a solvent
  • the block copolymer (from the viewpoint of sufficiently contacting the surface of the object to be polished and the polishing pad with the block copolymer (P)).
  • the content of the block copolymer (P) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on the total mass of P) and the solvent. is there.
  • the upper limit of the content of the block copolymer (P) is the total mass of the block copolymer (P) and the solvent from the viewpoint of suppressing the decrease in handleability due to the viscosity becoming too high.
  • it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
  • the abrasive composition of the present disclosure contains cerium oxide (ceria) as abrasive grains and the above-mentioned dispersant.
  • Cerium oxide has an advantage that the polished surface can be polished at a higher polishing rate than silica, alumina and the like, and the hardness is lower than that of alumina and the like, and the occurrence of defects on the polished surface can be suppressed.
  • Cerium oxide is used in the form of particles.
  • the average particle size of cerium oxide is not particularly limited, but is generally 1 nm to 500 nm.
  • the average particle size is preferably 2 nm or more, more preferably 3 nm or more, from the viewpoint of ensuring a high polishing rate.
  • the upper limit of the average particle size is preferably 300 nm or less, more preferably 100 nm or less, from the viewpoint of suppressing the generation of scratches on the surface of the object to be polished.
  • the average particle size of cerium oxide is the primary particle size calculated using the specific surface area (m 2 / g) calculated by the BET (nitrogen adsorption) method.
  • the content of cerium oxide in the abrasive composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, from the viewpoint of achieving a high polishing rate.
  • the upper limit of the content of cerium oxide from the viewpoint of improving the smoothness of the object to be polished, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.
  • the content of the dispersant is preferably such that the solid content concentration of the block copolymer (P) is 0.001% by mass or more with respect to the total amount of the abrasive composition, and is 1% by mass or more. It is more preferable that the amount is as large as possible.
  • the solid content concentration of the block copolymer (P) is preferably 10% by mass or less based on the total amount of the abrasive composition, and is preferably 5% by mass or less. It is more preferable that the amount is as large as possible.
  • the abrasive composition may contain a solvent.
  • the solvent is preferably an aqueous solvent, and examples thereof include water or a mixed solvent of water and a solvent.
  • the solvent is preferably a solvent that is compatible with water, and examples thereof include alcohols such as ethanol.
  • the abrasive composition may further contain known additives such as a polishing accelerator, a pH adjuster, a surfactant, a chelating agent, and an anticorrosive agent as long as the effects of the present disclosure are not impaired. ..
  • the abrasive composition is usually prepared as a slurry-like mixture by mixing each component by a known method.
  • the viscosity of the abrasive composition at 25 ° C. can be appropriately selected depending on the object to be polished, the shear rate during polishing, and the like, but is preferably in the range of 0.1 to 10 mPa ⁇ s, 0.5. More preferably, it is in the range of about 5 mPa ⁇ s.
  • the abrasive composition of the present disclosure contains a block copolymer (P) as a dispersant, the dispersion stability of the abrasive grains (particularly ceria particles) is high, and the effect of suppressing the aggregation of the abrasive grains due to the shearing force is effective. high. Therefore, the abrasive composition of the present disclosure is used for flattening the surface of at least one of an insulating film and a metal wiring in the manufacturing process of a semiconductor element, specifically, oxidation during shallow trench separation (STI) preparation, for example.
  • STI shallow trench separation
  • polishing liquid for flattening films silicon oxide films, etc.
  • metal wiring made of copper, copper alloys, aluminum alloys, etc.
  • oxide films flattening the surface of interlayer insulating films (oxide films). Therefore, the occurrence of defects is reduced, and an insulating film and metal wiring having excellent surface smoothness can be obtained, which is preferable.
  • the obtained polymer was subjected to gel permeation chromatography (GPC) measurement under the following conditions to obtain a number average molecular weight (Mn) and a weight average molecular weight (Mw) in terms of sodium polyacrylate.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • PDI Mw / Mn
  • Azobis (4-cyanovaleric acid) (hereinafter also referred to as "ACVA") (0.035 g), 3-((((1-carboxyethyl) thio) carbonothio oil) thio) propanoic acid (1.29 g) as a RAFT agent ) (Manufactured by BORON MOLECULAR, hereinafter also referred to as "BM1429”) was sufficiently degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 70 ° C. After 4 hours, the reaction was stopped by water cooling.
  • Comparative Synthesis Example 2A, 3A The same operations as in Comparative Synthesis Example 1A were carried out except that the raw materials to be charged were changed as shown in Table 1, and polymers L1 and M1 were obtained, respectively.
  • Table 2 shows the results of determining the molecular weight of each polymer by GPC measurement.
  • Example 1A As a dispersant, an aqueous polymer solution containing the polymer A1 at a solid content concentration of 20% was prepared. To a 50 mL glass pressure resistant bottle, add 4.0 g of ceria nanoparticles (primary particle size 20 nm) and 2 g of a dispersant, mix well, and adjust the pH to 7 using a 0.5 mol / L HCl solution or a 25 mass% NH 3 aqueous solution. Adjusted to. Then, 20 g of zirconia beads having a diameter of 1 mm was added, and the mixture was stirred with a paint shaker for 30 minutes. After removing the beads by filtration, the beads were allowed to stand overnight to obtain a slurry-like abrasive composition. The following measurements and evaluations were carried out using the obtained abrasive composition. The results of measurement and evaluation are shown in Table 2.
  • ⁇ Slurry appearance> The appearance of the slurry was determined by visually confirming the appearance of the prepared abrasive composition.
  • a slurry-like abrasive composition was prepared as a reference sample by performing the same operation as in Example 1A except that the dispersant was not added. This reference sample was left to stand for 24 hours to measure the sedimentation thickness D, and the sedimentation degree [%] of the particles of each abrasive composition was calculated with the measured sedimentation thickness D as 100%.
  • the judgment criteria are as follows. The particles that had been allowed to stand overnight and settled were redispersed by shaking the container by hand, and the particle settling within 1 hour after the redispersion was confirmed.
  • Particle sedimentation within 1 hour is 5% or less
  • Particle sedimentation within 1 hour is greater than 5% and 15% or less
  • Particle sedimentation within 1 hour is greater than 15% and 30% or less
  • Within 1 hour Particle sedimentation is greater than 30%
  • Examples 2A to 10A, Comparative Examples 1A to 4A Dispersants were prepared in the same manner as in Example 1A except that the polymers used were changed as shown in Table 2, and slurry-like abrasive compositions were prepared in the same manner as in Example 1A. .. The obtained abrasive composition was measured for slurry viscosity and evaluated for slurry appearance in the same manner as in Example 1A. The results are shown in Table 2.
  • the numerical values of the monomer 1 and the monomer 2 in the "polymer block A” column and the “polymer block B” column are the respective weights calculated from the amount of the monomer charged at the time of polymerization. Represents the monomer composition (mass ratio) of the coalescence.
  • the "A / B mass ratio” represents the ratio (mass ratio) of the polymer block A and the polymer block B in each polymer calculated from the monomer composition of each polymer.
  • the numerical values in the "each block Mn” column are the design values of Mn of each polymer block A and the polymer block B, and the Mn, Mw and PDI in the "polymer / molecular weight physical properties” column are actual measurement values by GPC measurement. is there.
  • Example 5A in which the polymer block B uses the polymer E1 having a monomer unit derived from TBAM, Examples 9A and 10A using the polymers I1 and J1 having no monomer unit derived from TBAM, respectively.
  • the particles were less likely to settle and the slurry viscosity was smaller than that of the above.
  • the dispersant according to the second embodiment of the present disclosure is a water-soluble polymer having a polymer block A having a structural unit having an ionic functional group and a segment having a monomer composition different from that of the polymer block A and having ions. It contains a polymer block B having a structural unit having a sex functional group, and a block copolymer (P) having.
  • the structural unit having an ionic functional group of the polymer block A is "structural unit UA-2”
  • the structural unit of the polymer block B having an ionic functional group is "structural unit UB-". Also called "2".
  • the ionic functional group of the structural unit UA-2 exhibits appropriate adsorptivity to abrasive grains (particularly cerium oxide) and can impart good dispersion stability to the abrasive grains. It is preferably a phosphoric acid group, a phosphonic acid group, an amino group or a salt thereof. Among them, the ionic functional group is preferably an anionic functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group or a salt thereof, and particularly preferably a carboxyl group, a sulfonic acid group or a salt thereof. ..
  • the structural unit UA-2 may be introduced into the block copolymer (P) by polymerization using a monomer having an ionic functional group (hereinafter, also referred to as “ionic group-containing monomer”).
  • a monomer having an ionic functional group hereinafter, also referred to as “ionic group-containing monomer”.
  • the ionic group-containing monomer is preferably a vinyl monomer because it has good adsorptivity to abrasive grains and an object to be polished having a hydrophobic surface and has a high degree of freedom in selecting the monomer. Is. Since the block copolymer (P) has a main chain composed of carbon-carbon bonds, it has high adsorptivity to abrasive grains, and moderately adsorbs to a polishing object having a hydrophobic surface, which is good for the polished surface.
  • the ionic group-containing monomer is preferably a water-soluble monomer from the viewpoint of obtaining a polymer having high solubility in an aqueous system.
  • the "water-soluble monomer” refers to a compound having a solubility of 2 g or more in 100 g of water at 20 ° C.
  • ionic group-containing monomer that can be used in the production of the block copolymer (P) of the present embodiment and the description of the counter ion when the ionic functional group is a salt will be described in the first description above.
  • examples of the ionic group-containing monomer and the counter ion described in the polymer block B of the block copolymer (P) in the embodiment can be incorporated.
  • the polymer block A may be a block composed of only the structural unit UA-2, but is a monomer different from the ionic group-containing monomer as long as the action of the block copolymer (P) is not impaired. It may further have a structural unit derived from (hereinafter, also referred to as “other monomer M1-2”).
  • the other monomer M1-2 is not particularly limited as long as it is a monomer copolymerizable with the ionic group-containing monomer, but among them, an amide group-containing vinyl monomer and an ester group-containing vinyl monomer. At least one selected from the group consisting of is preferable.
  • the other monomer M1-2 is an ester group-containing vinyl monomer
  • an ester group-containing vinyl unit amount constituting the structural unit UA of the polymer block A in the first embodiment.
  • (Meta) acrylic acid alkyl esters exemplified as bodies, (meth) acrylic acid aliphatic cyclic esters, (meth) acrylic acid aromatic esters, (meth) acrylic acid alkoxyalkyls, (di) alkyl Aminoalkyl (meth) acrylates, epoxy group-containing (meth) acrylic acid esters, polyoxyalkylene (meth) acrylates; and the like can be mentioned.
  • the other monomer M1-2 one of these may be used alone, or two or more thereof may be used in combination.
  • the polymer block A may contain a structural unit (structural unit UC) having an alkyl group having 1 to 10 carbon atoms in the side chain portion together with the structural unit UA-2. Since the polymer block A has the structural unit UC, the hydrophobicity of the polymer block A is enhanced, and the adsorptivity to abrasive grains (particularly cerium oxide) can be further improved, which is preferable.
  • the alkyl group of the structural unit UC in the side chain portion preferably has 2 or more carbon atoms from the viewpoint of improving the dispersion stability of the abrasive grains.
  • the upper limit of the number of carbon atoms of the alkyl group of the structural unit UC in the side chain portion is preferably 8 or less, more preferably 7 or less, from the viewpoint of obtaining a polymer having high solubility in an aqueous system. is there.
  • the alkyl group is preferably bonded to the main chain via a linking group (-COO-, -CONH-, etc.).
  • the monomer constituting the structural unit UC is preferably at least one selected from the group consisting of an ester group-containing vinyl monomer and an amide group-containing vinyl monomer.
  • (meth) acrylic acid alkyl esters having an alkyl ester moiety having 1 to 10 carbon atoms and an N-alkyl group having 1 carbon atom have a high effect of improving the dispersion stability of abrasive grains.
  • At least one selected from the group consisting of N-alkyl (meth) acrylamides of ⁇ 10 is preferable, and (meth) acrylic acid alkyl esters and N- More preferably, at least one selected from the group consisting of N-alkyl (meth) acrylamides having an alkyl group having 2 to 10 carbon atoms is more preferable.
  • the polymer block A may have only one type of structural unit UC, or may have two or more types of structural unit UC.
  • the content of the structural unit UA-2 having an ionic functional group is preferably 30% by mass or more with respect to the total constituent monomer units of the polymer block A.
  • the content of the structural unit UA-2 is 30% by mass or more, it is preferable in that the dispersion stability of the abrasive grains can be further increased.
  • the content of the structural unit UA-2 is more preferably 40% by mass or more, and further preferably 50% by mass or more, based on the total constituent monomer units of the polymer block A. , 60% by mass or more is more preferable.
  • the upper limit of the content of the structural unit UA-2 when a structural unit derived from another monomer is introduced, it should be 99% by mass or less with respect to all the constituent monomer units of the polymer block A. Is more preferable, 98% by mass or less is more preferable, and 96% by mass or less is further preferable.
  • the content of the structural unit UC is 1 with respect to all the constituent monomer units of the polymer block A from the viewpoint of improving the adsorptivity to the abrasive grains and sufficiently obtaining the effect of improving the dispersion stability of the abrasive grains. It is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 4% by mass or more.
  • the upper limit of the content of the structural unit UC is preferably 70% by mass or less, more preferably 60% by mass or less, and 50% by mass, based on the total constituent monomer units of the polymer block A. The following is more preferable.
  • the number average molecular weight (Mn) of the polymer block A is preferably in the range of 1,000 or more and 100,000 or less. When Mn is 1,000 or more, it is preferable that the effect of improving the dispersion stability of the abrasive grains by introducing the polymer block A is sufficiently exhibited. Further, when Mn is 100,000 or less, it is preferable that one molecule of the polymer can be sufficiently suppressed from adsorbing on the surfaces of a plurality of abrasive grains to form an aggregated structure of the abrasive grains.
  • the Mn of the polymer block A is more preferably 1,500 or more, still more preferably 2,000 or more, and even more preferably 3,000 or more.
  • the Mn of the polymer block A is more preferably 70,000 or less, further preferably 50,000 or less, and particularly preferably 30,000 or less.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are values in terms of sodium polyacrylate measured by GPC. Details are values measured by the method described in Examples described later.
  • the ionic functional group of the structural unit UB-2 examples include functional groups exemplified as the ionic functional group of the structural unit UA-2.
  • the ionic functional group of the structural unit UB-2 is preferably an anionic functional group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phosphonic acid group or a salt thereof, and is preferably a carboxyl group, a sulfonic acid group or a salt thereof. It is particularly preferable that they are salts.
  • the structural unit UB-2 is preferably introduced into the block copolymer (P) by polymerizing using an ionic group-containing monomer.
  • the description of the polymer block A applies to specific examples and preferred examples of the ionic group-containing monomer.
  • the block copolymer (P) satisfies at least one of the following conditions I and II.
  • Condition I The ionic functional group of the polymer block A and the ionic functional group of the polymer block B are different.
  • Condition II The content of the ionic functional group of the polymer block A and the content of the ionic functional group of the polymer block B are different.
  • the combination of the ionic functional group of the polymer block A and the ionic functional group of the polymer block B is not particularly limited.
  • the ionic functional groups of each polymer block are as long as at least one type is a different ionic functional group.
  • Preferred specific examples of the combination satisfying the condition I include the following aspects [1] to [3]. [1] An embodiment in which one of the polymer block A and the polymer block B has a sulfonic acid group and the other has a carboxyl group.
  • the block copolymer (P) satisfies only the condition I, the content of the structural unit having an ionic functional group in the polymer block A and the content of the structural unit having an ionic functional group in the polymer block B
  • the ratio of is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and even more preferably 10/90 to 90/10 in terms of mass ratio.
  • the adsorptivity to the abrasive grains is appropriately adjusted, an appropriate electrostatic repulsive force is applied to the entire block copolymer (P), and an aggregated structure of the abrasive grains is formed by the shearing force. It is preferable in that the effect of suppressing static electricity can be enhanced.
  • the content of the structural unit UA-2 in the polymer block A and the content of the structural unit UB-2 in the polymer block B may be different.
  • the content of one of them is preferably 100 parts by mass, and the content of the other is preferably 100 parts by mass. It is 99 parts by mass or less, more preferably 98 parts by mass or less, and further preferably 96 parts by mass or less.
  • the lower limit of the content of one of the content of the structural unit UA-2 and the content of the structural unit UB-2 is 100 parts by mass, and the content of the other is preferably 2 parts by mass or more, more preferably 5. It is 10 parts by mass or more, more preferably 10 parts by mass or more.
  • any block of the polymer block A and the polymer block B may be increased.
  • the content of the structural unit derived from the ionic group-containing monomer in the polymer block B is higher than that of the polymer block A having the structural unit UC. It is preferable to do so.
  • the polymer block B may contain a structural unit (that is, a structural unit UC) having an alkyl group having 1 to 10 carbon atoms in the side chain portion, but the abrasive grains and the object to be polished are subjected to within one molecule of the polymer. It is preferable that the polymer block B has substantially no structural unit UC in that the difference in adsorptivity can be further increased and the formation of aggregated structures of abrasive grains due to shearing force can be further suppressed.
  • the content of the structural unit UC is preferably 0% by mass or more and 10% by mass or less, preferably 0% by mass, based on the total constituent monomer units of the polymer block B. It is more preferably% or more and 5% by mass or less, and further preferably 0% by mass or more and 1% by mass or less.
  • the number average molecular weight (Mn) of the polymer block B in terms of sodium polyacrylate measured by GPC is preferably in the range of 1,000 or more and 100,000 or less.
  • Mn is 1,000 or more, it is preferable that the effect of improving the dispersion stability of the abrasive grains by introducing the polymer block B is sufficiently exhibited.
  • Mn is 100,000 or less, it is preferable that one molecule of the polymer can be sufficiently suppressed from adsorbing on the surfaces of a plurality of abrasive grains to form an aggregated structure of the abrasive grains.
  • the Mn of the polymer block B is more preferably 1,500 or more, still more preferably 2,000 or more, and even more preferably 3,000 or more.
  • the Mn of the polymer block B is more preferably 70,000 or less, further preferably 50,000 or less, and particularly preferably 40,000 or less.
  • the block copolymer (P) of the present embodiment is not particularly limited in its production method as long as a block copolymer having two or more different segments can be obtained, and a known production method is adopted. Can be manufactured.
  • the description of the first embodiment can be referred to.
  • the living radical polymerization method having an exchange chain mechanism or a bond-dissociation mechanism is preferable, the RAFT method or the NMP method is more preferable, and the RAFT method is particularly preferable, as in the first embodiment. ..
  • the number average molecular weight (Mn) in terms of sodium polyacrylate measured by GPC is preferably in the range of 2,000 or more and 200,000 or less.
  • Mn is 2,000 or more, it is preferable in that it is possible to suppress a decrease in the polishing rate while sufficiently ensuring the wettability of the surface of the object to be polished.
  • Mn is 200,000 or less, aggregation of abrasive grains due to shearing force can be sufficiently suppressed, and defects such as scratches can be sufficiently suppressed during polishing, which is preferable.
  • the Mn of the block copolymer (P) is more preferably 2,500 or more, further preferably 3,000 or more, and even more preferably 4,000 or more.
  • the upper limit of Mn of the block copolymer (P) 100,000 or less is more preferable, 80,000 or less is further preferable, 70,000 or less is further preferable, and 60,000 or less is particularly preferable.
  • the weight average molecular weight (Mw) of the block copolymer (P) in terms of sodium polyacrylate measured by GPC is preferably in the range of 3,000 or more and 250,000 or less.
  • the Mw of the block copolymer (P) is more preferably 4,000 or more, still more preferably 6,000 or more, and even more preferably 10,000 or more.
  • the upper limit of Mw of the block copolymer (P) is more preferably 150,000 or less, further preferably 120,000 or less, and even more preferably 80,000 or less.
  • a polymer used as a dispersant for abrasive grains preferably has a narrow molecular weight distribution. From this viewpoint, it is preferable.
  • the PDI of the block copolymer (P) is more preferably 2.2 or less, still more preferably 2.0 or less, still more preferably 1.7 or less.
  • the lower limit of PDI is usually 1. It is 0.0.
  • the ratio A / B (mass ratio) of the polymer block A and the polymer block B in one block copolymer (P) molecule is 5 / from the viewpoint of suppressing the formation of an aggregated structure of abrasive grains due to shearing force. It is preferably 95 to 95/5.
  • the ratio A / B is more preferably 10/90 to 90/10, further preferably 15/85 to 85/15, even more preferably 20/80 to 80/20, and particularly preferably 25. It is / 75 to 75/25.
  • the ratio A / B can be appropriately selected by adjusting the ratio of the monomer used for producing the polymer block A and the monomer used for producing the polymer block B. ..
  • the block copolymer (P) has the polymer block A and the polymer block B
  • the number and arrangement order of the polymer block A and the polymer block B in one molecule are not particularly limited.
  • the description of the first embodiment can be incorporated.
  • the block copolymer (P) of the present embodiment is an AB type in that it can efficiently produce a block copolymer (P) having sufficiently high dispersion stability of abrasive grains (particularly cerium oxide). It is preferably a diblock copolymer having a structure.
  • the dispersant of the present disclosure may be any one containing a block copolymer (P). Therefore, the dispersant may be in the form of a single component containing only the block copolymer (P), or may be different from the block copolymer (P) together with the block copolymer (P). It may be in a form containing a component (other components).
  • the dispersant of the present disclosure may contain a solvent as another component.
  • the solvent include water, an organic solvent, and a mixed solvent of water and an organic solvent.
  • the solvent contained in the dispersant is preferably a solvent capable of dissolving the block copolymer (P) which is a water-soluble polymer, and water or a mixed solvent of water and an organic solvent soluble in water is preferable. More preferably, water is particularly preferable.
  • the organic solvent one type can be used alone or two or more types can be used in combination.
  • the dispersant contains a block copolymer (P) and a solvent
  • the block copolymer (from the viewpoint of sufficiently contacting the surface of the object to be polished and the polishing pad with the block copolymer (P)).
  • the content of the block copolymer (P) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on the total mass of P) and the solvent. is there.
  • the upper limit of the content of the block copolymer (P) is the total mass of the block copolymer (P) and the solvent from the viewpoint of suppressing the decrease in handleability due to the viscosity becoming too high.
  • it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
  • the abrasive composition of the present embodiment contains cerium oxide (ceria) as abrasive grains and the above-mentioned dispersant.
  • Cerium oxide has an advantage that the polished surface can be polished at a higher polishing rate than silica, alumina and the like, and the hardness is lower than that of alumina and the like, and the occurrence of defects on the polished surface can be suppressed.
  • the description of the cerium oxide to be used, the content of cerium oxide in the polishing agent composition, the solvent, the method for preparing the polishing agent composition, and the like can be referred to the description in the first embodiment.
  • the abrasive composition of the present embodiment contains the block copolymer (P) as a dispersant, the dispersion stability of the abrasive grains (particularly ceria particles) is high, and the effect of suppressing the aggregation of the abrasive grains due to the shearing force is achieved. Is high. Therefore, the abrasive composition of the present disclosure is used for flattening the surface of at least one of an insulating film and a metal wiring in the manufacturing process of a semiconductor element, specifically, oxidation during shallow trench separation (STI) preparation, for example.
  • STI shallow trench separation
  • polishing liquid for flattening films silicon oxide films, etc.
  • metal wiring made of copper, copper alloys, aluminum alloys, etc.
  • oxide films flattening the surface of interlayer insulating films (oxide films). Therefore, the occurrence of defects is reduced, and an insulating film and metal wiring having excellent surface smoothness can be obtained, which is preferable.
  • Azobis (4-cyanovaleric acid) (hereinafter also referred to as "ACVA”) (0.056 g), 3-((((1-carboxyethyl) thio) carbonothio oil) thio) propanoic acid (2.55 g) as a RAFT agent ) (Manufactured by BORON MOLECULAR, hereinafter also referred to as "BM1429”) was sufficiently degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 70 ° C. After 4 hours, the reaction was stopped by water cooling.
  • polymer C2 The molecular weights of the obtained water-soluble block copolymer (referred to as "polymer C2") were Mn18900 and Mw24600 as measured by GPC, and the PDI was 1.3.
  • Comparative Synthesis Example 2B The same operation as in Comparative Synthesis Example 1B was carried out except that the raw materials to be charged were changed as shown in Table 3, and the polymer K2 was obtained.
  • Table 4 shows the results of determining the molecular weight of the polymer K2 by GPC measurement.
  • Example 1B As a dispersant, an aqueous polymer solution containing the polymer A2 at a solid content concentration of 20% was prepared. To a 50 mL glass pressure resistant bottle, add 4.0 g of ceria nanoparticles (primary particle size 20 nm) and 2 g of a dispersant, mix well, and adjust the pH to 7 using a 0.5 mol / L HCl solution or a 25 mass% NH 3 aqueous solution. Adjusted to. Then, 20 g of zirconia beads having a diameter of 1 mm was added, and the mixture was stirred with a paint shaker for 30 minutes. After removing the beads by filtration, the beads were allowed to stand overnight to obtain a slurry-like abrasive composition. The following measurements and evaluations were carried out using the obtained abrasive composition. The results of measurement and evaluation are shown in Table 4.
  • ⁇ Slurry appearance> The appearance of the slurry was determined by visually confirming the appearance of the prepared abrasive composition.
  • a slurry-like abrasive composition was prepared as a reference sample by performing the same operation as in Example 1B except that the dispersant was not added. This reference sample was left to stand for 24 hours to measure the sedimentation thickness D, and the sedimentation degree [%] of the particles of each abrasive composition was calculated with the measured sedimentation thickness D as 100%.
  • the judgment criteria are as follows. The particles that had been allowed to stand overnight and settled were redispersed by shaking the container by hand, and the particle settling within 1 hour after the redispersion was confirmed.
  • Particle sedimentation within 1 hour is 5% or less
  • Particle sedimentation within 1 hour is greater than 5% and 15% or less
  • Particle sedimentation within 1 hour is greater than 15% and 30% or less
  • Within 1 hour Particle sedimentation is greater than 30%
  • Examples 2B to 9B, Comparative Examples 1B and 2B Dispersants were prepared in the same manner as in Example 1B except that the polymers used were changed as shown in Table 4, and slurry-like abrasive compositions were prepared in the same manner as in Example 1B. .. The obtained abrasive composition was measured for slurry viscosity and evaluated for slurry appearance in the same manner as in Example 1B. The results are shown in Table 4.
  • the numerical values of the monomer 1 and the monomer 2 in the "polymer block A” column and the “polymer block B” column are the respective weights calculated from the amount of the monomer charged at the time of polymerization. Represents the monomer composition (mass ratio) of the coalescence.
  • the "A / B mass ratio” represents the ratio (mass ratio) of the polymer block A and the polymer block B in each polymer calculated from the monomer composition of each polymer.
  • the numerical values in the "each block Mn” column are the design values of Mn of each polymer block A and the polymer block B, and the Mn, Mw and PDI in the "polymer / molecular weight physical properties” column are actual measurement values by GPC measurement. is there.
  • the dispersant according to the third embodiment of the present disclosure has a polymer block A having a structural unit derived from a vinyl monomer represented by the following formula (1) as a water-soluble polymer, and a polymer block A having a heavy monomer composition. It contains a block copolymer (P) having a polymer block B which is a segment different from the coalesced block A and has a structural unit derived from a vinyl monomer represented by the following formula (1).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are independently hydrogen atoms or substituted or unsubstituted monovalent hydrocarbon groups, or R 2 and R 3 are bonded to each other R 2 and R 3 is a group which forms a ring with the nitrogen atom to which they are attached.
  • the polymer block A is a structural unit derived from a vinyl monomer represented by the above formula (1) (hereinafter, also referred to as “specific vinyl monomer”) (hereinafter, also referred to as “structural unit UA-3”).
  • the specific vinyl monomer is a vinyl monomer having a primary amide group (-CONH 2 ), a secondary amide group (-CONHR 2 , -CONHR 3 ) or a tertiary amide group (-CONR 2 R 3 ). ..
  • R 2 and R 3 is a substituted monovalent hydrocarbon group
  • the substituted monovalent hydrocarbon group has a secondary amino group.
  • Examples thereof include a group having a tertiary amino group and a hydroxyalkyl group.
  • the group in which R 2 and R 3 are bonded to each other to form a ring together with a nitrogen atom may further contain a hetero atom such as an oxygen atom in addition to the nitrogen atom as an atom constituting the ring.
  • the specific vinyl monomer include (meth) acrylamide, (di) alkyl (meth) acrylamide, (di) alkylaminoalkylamides, heterocyclic (meth) acrylamide, and hydroxyl group-containing (meth) acrylamide.
  • Kind; etc. Specific examples of these are (meth) acrylamide, (di) alkyl (meth) acrylamide, and (di) alkylaminoalkyl exemplified as the amide group-containing vinyl monomer constituting the structural unit UA in the first embodiment. Examples thereof include amides, heterocyclic (meth) acrylamides and hydroxyl group-containing (meth) acrylamides.
  • a water-soluble monomer is preferable from the viewpoint of obtaining a polymer having high solubility in an aqueous system.
  • the specific vinyl monomer constituting the structural unit UA-3 is preferably a vinyl monomer having at least one of a primary amide group and a hydroxyl group, and is a group consisting of (meth) acrylamide and 2-hydroxyethyl acrylamide. At least one selected from is particularly preferable.
  • the "water-soluble monomer” refers to a compound having a solubility of 2 g or more in 100 g of water at 20 ° C.
  • the polymer block A may be a block composed of only the structural unit UA-3, but is a monomer different from the specific vinyl monomer (hereinafter, as long as the action of the block copolymer (P) is not impaired).
  • "Other monomers M1-3" may further have structural units.
  • the other monomer M1-3 is not particularly limited as long as it is a monomer copolymerizable with the specific vinyl monomer. Examples of the other monomer M1-3 include ester group-containing vinyl monomers, alkyl vinyl ethers, vinyl alcohols, aromatic vinyl compounds, vinyl ester compounds, ⁇ -olefins, unsaturated acids, and unsaturated acids. Anhydrous and the like can be mentioned.
  • the other monomer M1-3 include an ester group-containing vinyl monomer, for example, an ester group-containing vinyl monomer constituting the structural unit UA of the polymer block A in the first embodiment.
  • an ester group-containing vinyl monomer for example, an ester group-containing vinyl monomer constituting the structural unit UA of the polymer block A in the first embodiment.
  • examples thereof include alkyls, (di) alkylaminoalkyl (meth) acrylates, epoxy group-containing (meth) acrylic acid esters, polyoxyalkylene (meth) acrylates; and the like.
  • alkyl vinyl ethers, vinyl alcohols, aromatic vinyl compounds, vinyl ester compounds, ⁇ -olefins, unsaturated acids, and unsaturated acid anhydrides include the polymer block A in the first embodiment.
  • examples of other monomers M1 that may be used in the production include alkyl vinyl ethers, vinyl alcohols, aromatic vinyl compounds, vinyl ester compounds, ⁇ -olefins, unsaturated acids, and unsaturated acid anhydrides, respectively. be able to.
  • the other monomer M1-3 one type can be used alone or two or more types can be used in combination. Of these, the ester group-containing vinyl monomer is preferable as the other monomer M1-3.
  • the polymer block A may contain a structural unit (structural unit UC) having an alkyl group having 1 to 10 carbon atoms in the side chain portion together with the structural unit UA-3. Since the polymer block A has the structural unit UC, the hydrophobicity of the polymer block A is enhanced, and the adsorptivity to abrasive grains (particularly cerium oxide) can be further improved, which is preferable.
  • the alkyl group of the structural unit UC in the side chain portion preferably has 2 or more carbon atoms from the viewpoint of improving the dispersion stability of the abrasive grains.
  • the upper limit of the number of carbon atoms of the alkyl group of the structural unit UC in the side chain portion is preferably 8 or less, more preferably 7 or less, from the viewpoint of obtaining a polymer having high solubility in an aqueous system. is there.
  • the alkyl group is preferably bonded to the main chain via a linking group (-COO-, -CONH-, etc.).
  • the monomer constituting the structural unit UC is preferably an ester group-containing vinyl monomer, and among these, the alkyl group of the alkyl ester portion is carbon in that the effect of improving the dispersion stability of the abrasive grains is high.
  • Alkyl esters of (meth) acrylic acid having a number of 1 to 10 are preferable, and alkyl esters of (meth) acrylic acid having an alkyl group having 2 to 10 carbon atoms in the alkyl ester moiety are more preferable.
  • the polymer block A may have only one type of structural unit UC, or may have two or more types of structural unit UC.
  • the content of the structural unit UA-3 is preferably 30% by mass or more with respect to the total constituent monomer units of the polymer block A.
  • the content of the structural unit UA-3 is 30% by mass or more, it is preferable in that the dispersion stability of the abrasive grains can be further increased.
  • the content of the structural unit UA-3 is more preferably 40% by mass or more, and further preferably 50% by mass or more, based on the total constituent monomer units of the polymer block A. , 60% by mass or more is more preferable, and 80% by mass or more is particularly preferable.
  • the upper limit of the content of the structural unit UA-3 when a structural unit derived from another monomer is introduced, it should be 99% by mass or less with respect to all the constituent monomer units of the polymer block A. Is more preferable, 97% by mass or less is more preferable, and 95% by mass or less is further preferable.
  • the content of the structural unit UC improves the adsorptivity to the abrasive grains and sufficiently obtains the effect of improving the dispersion stability of the abrasive grains. It is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, based on all the constituent monomer units of the above.
  • the upper limit of the content of the structural unit UC is preferably 50% by mass or less, more preferably 40% by mass or less, and 20% by mass, based on the total constituent monomer units of the polymer block A. The following is more preferable.
  • the number average molecular weight (Mn) of the polymer block A is preferably in the range of 1,000 or more and 200,000 or less. When Mn is 1,000 or more, it is preferable that the effect of improving the adsorptivity of the abrasive grains by introducing the polymer block A is sufficiently exhibited. Further, when Mn is 200,000 or less, it is preferable that one molecule of the polymer can be sufficiently suppressed from adsorbing on the surfaces of a plurality of abrasive grains to form an aggregated structure of the abrasive grains.
  • the Mn of the polymer block A is more preferably 1,500 or more, still more preferably 2,000 or more, and even more preferably 3,000 or more.
  • the upper limit of Mn of the polymer block A is more preferably 150,000 or less, further preferably 100,000 or less, and particularly preferably 70,000 or less.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are values in terms of sodium polyacrylate measured by GPC. Details are values measured by the method described in Examples described later.
  • the polymer block B has a structural unit derived from the specific vinyl monomer (hereinafter, also referred to as “structural unit UB-3”).
  • specific vinyl monomer include the vinyl monomer exemplified in the description of the structural unit UA-3 possessed by the polymer block A.
  • the structural unit UA-3 and the structural unit UB-3 in one molecule of the polymer are derived from specific vinyl monomers different from each other. It is preferably a structural unit.
  • the structural unit derived from the specific vinyl monomer possessed by each polymer block is , At least one kind may be different, and it is preferable that all are different.
  • the specific vinyl monomer constituting the structural unit UB-3 is preferably a water-soluble monomer from the viewpoint of obtaining a polymer having high solubility in an aqueous system, and among them, at least one of a secondary amide group and a tertiary amide group.
  • a vinyl monomer having is preferable.
  • the specific vinyl monomers constituting the structural unit UB-3 are N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-.
  • At least one selected from the group consisting of diethyl (meth) acrylamide, N-ethyl-N-methyl (meth) acrylamide, 2-hydroxyethyl acrylamide, and 4- (meth) acryloylmorpholin is preferred.
  • the structural unit UA-3 has at least one of a primary amide group and a hydroxyl group and the structural unit UB-3 has at least one of a secondary amide group and a tertiary amide group
  • the abrasive grains and the object to be polished It is preferable because the difference in the adsorptivity to the object can be made larger between the segments and the effect of suppressing the formation of the aggregated structure of the abrasive grains by the shearing force can be enhanced.
  • the polymer block B may be a block composed of only the structural unit UB-3, but is a monomer different from the specific vinyl monomer (hereinafter, as long as the action of the block copolymer (P) is not impaired). , Also referred to as “other monomer M2-3”).
  • the other monomer M2-3 is not particularly limited as long as it is a monomer copolymerizable with the specific vinyl monomer. Specific examples of the other monomer M2-3 include the other monomer M1-3 exemplified in the description of the polymer block A.
  • the polymer block B may contain a structural unit having a carboxyl group (hereinafter, also referred to as “structural unit UD”) together with the structural unit UB-3.
  • the polymer block B having the structural unit UD is preferable in that the dispersion stability of the abrasive grains can be further improved.
  • the monomer constituting the structural unit UD is preferably a vinyl monomer having a carboxyl group, and examples thereof include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, and fumaric acid. Of these, (meth) acrylic acid is particularly preferable.
  • the carboxyl group of the structural unit UD may form a salt with a counter ion such as a sodium ion, a magnesium ion, or a calcium ion.
  • the polymer block B may have only one type of structural unit UD, or may have two or more types of structural unit UD.
  • the content of the structural unit UB-3 derived from the specific vinyl monomer is preferably 1% by mass or more with respect to the total constituent monomer units of the polymer block B.
  • the content of the structural unit UB-3 is 1% by mass or more, it is preferable in that the dispersion stability of the abrasive grains can be further increased.
  • the content of the structural unit UB-3 is more preferably 2% by mass or more, and further preferably 5% by mass or more, based on the total constituent monomer units of the polymer block B.
  • the upper limit of the content of the structural unit UB-3 can be set in the range of 100% by mass or less.
  • the content of the structural unit UD is the total constituent unit of the polymer block B from the viewpoint of sufficiently obtaining the effect of improving the dispersion stability of the abrasive grains by introducing the structural unit UD. It is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the polymer unit.
  • the upper limit of the content of the structural unit UD is not particularly limited, but is preferably 95% by mass or less with respect to all the constituent monomer units of the polymer block B.
  • the number average molecular weight (Mn) of the polymer block B is preferably in the range of 1,000 or more and 200,000 or less.
  • Mn is 1,000 or more, the effect of improving the dispersibility of the abrasive grains by introducing the polymer block B is sufficiently exhibited, which is preferable.
  • Mn is 200,000 or less, it is preferable that one molecule of the polymer can sufficiently suppress the formation of an aggregated structure of abrasive grains due to adsorption on the surfaces of a plurality of abrasive grains.
  • the Mn of the polymer block A is more preferably 1,500 or more, still more preferably 2,000 or more, and even more preferably 3,000 or more.
  • the upper limit of Mn of the polymer block B is more preferably 150,000 or less, further preferably 100,000 or less, and particularly preferably 70,000 or less.
  • the block copolymer (P) of the present embodiment is not particularly limited in its production method as long as a block copolymer having two or more different segments can be obtained, and a known production method is adopted. Can be manufactured.
  • the description of the first embodiment can be referred to.
  • the living radical polymerization method having an exchange chain mechanism or a bond-dissociation mechanism is preferable, the RAFT method or the NMP method is more preferable, and the RAFT method is particularly preferable, as in the first embodiment. ..
  • the number average molecular weight (Mn) in terms of sodium polyacrylate measured by GPC is preferably in the range of 1,000 or more and 150,000 or less.
  • Mn is 1,000 or more, it is preferable in that it is possible to suppress a decrease in the polishing rate while sufficiently ensuring the wettability of the surface of the object to be polished.
  • Mn is 150,000 or less, aggregation of abrasive grains due to shearing force can be sufficiently suppressed, and defects such as scratches can be sufficiently suppressed during polishing, which is preferable.
  • the Mn of the block copolymer (P) is more preferably 1,500 or more, further preferably 2,000 or more, and even more preferably 3,000 or more.
  • the upper limit of Mn of the block copolymer (P) 100,000 or less is more preferable, 80,000 or less is further preferable, 70,000 or less is further preferable, and 50,000 or less is particularly preferable.
  • the weight average molecular weight (Mw) of the block copolymer (P) in terms of sodium polyacrylate measured by GPC is preferably in the range of 1,500 or more and 150,000 or less.
  • the Mw of the block copolymer (P) is more preferably 2,500 or more, still more preferably 3,500 or more.
  • the upper limit of Mw of the block copolymer (P) is more preferably 100,000 or less, further preferably 80,000 or less, and even more preferably 70,000 or less.
  • a polymer used as a dispersant for abrasive grains preferably has a narrow molecular weight distribution. From this viewpoint, it is preferable.
  • the PDI of the block copolymer (P) is more preferably 2.0 or less, still more preferably 1.8 or less, even more preferably 1.5 or less, and particularly preferably 1.3 or less. There is a lower limit of PDI, which is usually 1.0.
  • the ratio A / B (mass ratio) of the polymer block A and the polymer block B in one block copolymer (P) molecule is 5 / from the viewpoint of suppressing the formation of an aggregated structure of abrasive grains due to shearing force. It is preferably 95 to 95/5.
  • the ratio A / B is more preferably 10/90 to 90/10, further preferably 15/85 to 85/15, and even more preferably 20/80 to 80/20.
  • the ratio A / B can be appropriately selected by adjusting the ratio of the monomer used for producing the polymer block A and the monomer used for producing the polymer block B. ..
  • the block copolymer (P) has the polymer block A and the polymer block B
  • the number and arrangement order of the polymer block A and the polymer block B in one molecule are not particularly limited.
  • the description of the first embodiment can be incorporated.
  • the block copolymer (P) of the present embodiment is an AB type in that it can efficiently produce a block copolymer (P) having sufficiently high dispersion stability of abrasive grains (particularly cerium oxide). It is preferably a diblock copolymer having a structure.
  • the dispersant of the present disclosure may be any one containing a block copolymer (P). Therefore, the dispersant may be in the form of a single component containing only the block copolymer (P), or may be different from the block copolymer (P) together with the block copolymer (P). It may be in a form containing a component (other components).
  • the dispersant of the present disclosure may contain a solvent as another component.
  • the solvent include water, an organic solvent, and a mixed solvent of water and an organic solvent.
  • the solvent contained in the dispersant is preferably a solvent capable of dissolving the block copolymer (P) which is a water-soluble polymer, and water or a mixed solvent of water and an organic solvent soluble in water is preferable. More preferably, water is particularly preferable.
  • the organic solvent one type can be used alone or two or more types can be used in combination.
  • the dispersant contains a block copolymer (P) and a solvent
  • the block copolymer (from the viewpoint of sufficiently contacting the surface of the object to be polished and the polishing pad with the block copolymer (P)).
  • the content of the block copolymer (P) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on the total mass of P) and the solvent. is there.
  • the upper limit of the content of the block copolymer (P) is the total mass of the block copolymer (P) and the solvent from the viewpoint of suppressing the decrease in handleability due to the viscosity becoming too high.
  • it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
  • the abrasive composition of the present embodiment contains cerium oxide (ceria) as abrasive grains and the above-mentioned dispersant.
  • Cerium oxide has an advantage that the polished surface can be polished at a higher polishing rate than silica, alumina and the like, and the hardness is lower than that of alumina and the like, and the occurrence of defects on the polished surface can be suppressed.
  • the description of the cerium oxide to be used, the content of cerium oxide in the polishing agent composition, the solvent, the method for preparing the polishing agent composition, and the like can be referred to the description in the first embodiment.
  • the abrasive composition of the present embodiment contains the block copolymer (P) as a dispersant, the dispersion stability of the abrasive grains (particularly ceria particles) is high, and the effect of suppressing the aggregation of the abrasive grains due to the shearing force is achieved. Is high. Therefore, the abrasive composition of the present disclosure is used for flattening the surface of at least one of an insulating film and a metal wiring in the manufacturing process of a semiconductor element, specifically, oxidation during shallow trench separation (STI) preparation, for example.
  • STI shallow trench separation
  • polishing liquid for flattening films silicon oxide films, etc.
  • metal wiring made of copper, copper alloys, aluminum alloys, etc.
  • oxide films flattening the surface of interlayer insulating films (oxide films). Therefore, the occurrence of defects is reduced, and an insulating film and metal wiring having excellent surface smoothness can be obtained, which is preferable.
  • V-65 2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter also referred to as "V-65”) (0.124 g), 3-((((1-carboxyethyl)) as a RAFT agent Thio) Carbonoti oil) Thio) Proanoic acid (manufactured by BORON MOLECULAR, hereinafter also referred to as "BM1429”) (1.07 g) was charged, sufficiently degassed by nitrogen bubbling, and polymerization was started in a constant temperature bath at 55 ° C. After 6 hours, the reaction was stopped by water cooling.
  • polymer A3 The molecular weight of the obtained water-soluble block copolymer (referred to as "polymer A3") was Mn20300 and Mw24400 as measured by GPC, and the PDI was 1.2.
  • Comparative Synthesis Example 2C The same operation as in Comparative Synthesis Example 1C was carried out except that the charged raw materials were changed as shown in Table 5, to obtain a polymer H3.
  • Table 6 shows the results of determining the molecular weight of the polymer H3 by GPC measurement.
  • Example 1C As a dispersant, an aqueous polymer solution containing the polymer A3 at a solid content concentration of 20% was prepared. To a 50 mL glass pressure resistant bottle, add 4.0 g of ceria nanoparticles (primary particle size 20 nm) and 2 g of a dispersant, mix well, and adjust the pH to 7 using a 0.5 mol / L HCl solution or a 25 mass% NH 3 aqueous solution. Adjusted to. Then, 20 g of zirconia beads having a diameter of 1 mm was added, and the mixture was stirred with a paint shaker for 30 minutes. After removing the beads by filtration, the beads were allowed to stand overnight to obtain a slurry-like abrasive composition. The following measurements and evaluations were carried out using the obtained abrasive composition. The results of measurement and evaluation are shown in Table 6.
  • ⁇ Slurry appearance> The appearance of the slurry was determined by visually confirming the appearance of the prepared abrasive composition.
  • a slurry-like abrasive composition was prepared as a reference sample by performing the same operation as in Example 1C except that the dispersant was not added. This reference sample was left to stand for 24 hours to measure the sedimentation thickness D, and the sedimentation degree [%] of the particles of each abrasive composition was calculated with the measured sedimentation thickness D as 100%.
  • the judgment criteria are as follows. The particles that had been allowed to stand overnight and settled were redispersed by shaking the container by hand, and the particle settling within 1 hour after the redispersion was confirmed.
  • Particle sedimentation within 1 hour is 5% or less
  • Particle sedimentation within 1 hour is greater than 5% and 15% or less
  • Particle sedimentation within 1 hour is greater than 15% and 30% or less
  • Within 1 hour Particle sedimentation is greater than 30%
  • Examples 2C to 6C, Comparative Examples 1C to 3C Dispersants were prepared in the same manner as in Example 1C except that the polymers used were changed as shown in Table 6, and slurry-like abrasive compositions were prepared in the same manner as in Example 1C. .. The obtained abrasive composition was measured for slurry viscosity and evaluated for slurry appearance in the same manner as in Example 1C. The results are shown in Table 6.
  • the numerical values of the monomer 1 and the monomer 2 in the "polymer block A” column and the “polymer block B” column are the single amount of each polymer calculated from the charged amount at the time of polymerization. Represents body composition (mass ratio).
  • the "A / B mass ratio” represents the ratio (mass ratio) of the polymer block A and the polymer block B in each polymer calculated from the monomer composition of each polymer.
  • the numerical values in the "each block Mn" column are theoretically calculated values of Mn of each polymer block A and polymer block B, and Mn, Mw and PDI in the "polymer / molecular weight physical properties” column are measured values by GPC measurement. Is.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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