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WO2022209758A1 - Procédé de polissage et ensemble de composition de polissage - Google Patents

Procédé de polissage et ensemble de composition de polissage Download PDF

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Publication number
WO2022209758A1
WO2022209758A1 PCT/JP2022/010879 JP2022010879W WO2022209758A1 WO 2022209758 A1 WO2022209758 A1 WO 2022209758A1 JP 2022010879 W JP2022010879 W JP 2022010879W WO 2022209758 A1 WO2022209758 A1 WO 2022209758A1
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WO
WIPO (PCT)
Prior art keywords
polishing
abrasive grains
less
weight
polishing composition
Prior art date
Application number
PCT/JP2022/010879
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English (en)
Japanese (ja)
Inventor
大輝 市坪
公亮 土屋
Original Assignee
株式会社フジミインコーポレーテッド
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Filing date
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Application filed by 株式会社フジミインコーポレーテッド filed Critical 株式会社フジミインコーポレーテッド
Priority to JP2023510833A priority Critical patent/JPWO2022209758A1/ja
Publication of WO2022209758A1 publication Critical patent/WO2022209758A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a polishing method and a polishing composition set.
  • This application claims priority based on Japanese Patent Application No. 2021-57915 filed on March 30, 2021, the entire contents of which are incorporated herein by reference.
  • Precise polishing using polishing compositions is performed on the surfaces of materials such as metals, semi-metals, non-metals, and their oxides.
  • the surface of a silicon wafer used as a component of a semiconductor device or the like is generally finished to a high-quality mirror surface through a lapping process (rough polishing process) and a polishing process (precise polishing process).
  • the polishing process typically includes a preliminary polishing process (preliminary polishing process) and a final polishing process (final polishing process).
  • Patent Documents 1 to 5 are cited as technical documents relating to polishing compositions that are mainly used for polishing semiconductor substrates such as silicon wafers.
  • semiconductor substrates such as silicon wafers and other substrates have been required to have higher quality surfaces.
  • a polishing composition used in a final polishing step for semiconductor substrates such as silicon wafers and other substrates is required to have the ability to realize a surface exhibiting excellent surface quality after polishing.
  • the accuracy of evaluating the surface quality after polishing is also increasing.
  • an object of the present invention is to provide a polishing method capable of reducing defects on the surface of an object to be polished even when highly accurate evaluation is being performed.
  • Another object of the present invention is to provide a polishing composition set that can be preferably used in such a polishing method.
  • a method of polishing an object to be polished is provided.
  • the polishing composition S1 containing abrasive grains A1 and the polishing composition S2 containing abrasive grains A2 are supplied in this order onto the same polishing surface plate to polish the object to be polished.
  • the abrasive grains A1 have a particle diameter converted from the specific surface area measured by the BET method, D1 A1 , and an average particle diameter measured by the dynamic light scattering method, D2 A1 .
  • A1 ratio (D2 A1 /D1 A1 ) is 1.5 or more.
  • the abrasive grains A2 have a particle diameter converted from the specific surface area measured by the BET method as D1 A2 and an average particle diameter measured by the dynamic light scattering method as D2 A2, D2 A2 to D1 A2 ratio (D2 A2 /D1 A2 ) is less than 1.5. According to such a polishing method, the reduction of defects on the polished surface can be achieved with high precision.
  • D1 A1 is 5 nm or more and 100 nm or less. By using such abrasive grains A1, good defect reduction properties can be exhibited.
  • D1 A2 is 5 nm or more and 100 nm or less.
  • the content of the abrasive grains A1 in the polishing composition S1 is 0.01% by weight or more and 1% by weight or less.
  • the content of the abrasive grains A2 in the polishing composition S2 is 0.01% by weight or more and 1% by weight or less.
  • the polishing composition S2 further contains a water-soluble polymer.
  • a polishing composition S2 is more excellent in protecting the polished surface, and can improve the surface quality of the surface to be polished.
  • the polishing composition S1 also contains a water-soluble polymer. According to this aspect, the surface quality of the surface to be polished can be further improved.
  • the technology disclosed here is preferably applied to polishing using silica particles as both abrasive grains A1 and abrasive grains A2.
  • polishing by applying the technology disclosed herein, it is easy to achieve a polished surface with suitably reduced defects.
  • the technique disclosed here is preferably applied to polishing using colloidal silica as both abrasive grains A1 and abrasive grains A2.
  • colloidal silica as both abrasive grains A1 and abrasive grains A2.
  • the relationship between the time t1 for supplying the polishing composition S1 for polishing and the time t2 for supplying the polishing composition S2 for polishing is t2/ It satisfies t1 ⁇ 1. That is, by performing polishing using the polishing composition S1 for a relatively long polishing time t1, good defect reduction is achieved, and then polishing using the polishing composition S2 for a relatively short polishing time t2. By performing the above, it is possible to suitably remove the damage after processing and improve the surface quality.
  • the polishing method disclosed here is suitable for polishing surfaces made of silicon. By polishing a surface made of silicon using the above-described polishing method, a surface with reduced defects can be suitably achieved.
  • the object to be polished is a silicon wafer.
  • polishing composition generally refers to the polishing composition used in the polishing method disclosed herein, regardless of which polishing stage the polishing composition is used. ” is sometimes used. Also, hereinafter, the polishing surface plate may be abbreviated as “surface plate”.
  • the polishing method disclosed herein includes a polishing step in which a polishing composition S1 containing abrasive grains A1 and a polishing composition S2 containing abrasive grains A2 are supplied in this order to polish an object to be polished.
  • the step of supplying the polishing composition S1 for polishing may be referred to as the first step
  • the step of supplying the polishing composition S2 for polishing may be referred to as the second step.
  • the first step and the second step are performed without moving the object to be polished onto another polishing apparatus or another surface plate during the process. That is, the first stage and the second stage are performed on the same platen.
  • the first stage and the second stage are performed sequentially, ie step by step, on the same object to be polished. However, polishing a plurality of objects to be polished simultaneously (in parallel) in each polishing step is not prevented.
  • performing the first step and the second step sequentially means that the starting points of these steps are sequential, and it is prohibited to start the second step before the end of the first step. do not have. That is, the first and second stages may partially overlap.
  • the abrasive grains A1 contained in the polishing composition S1 supplied in the first stage and the abrasive grains A2 contained in the polishing composition S2 supplied in the second stage are as follows. has the characteristics of That is, the abrasive grains A1 have a ratio (D2 A1 / D1 A1 ) is 1.5 or more. Further, the abrasive grains A2 have a ratio (D2 A2 / D1 A2 ) is less than 1.5.
  • the ratio of the average particle size (D2) measured by the dynamic light scattering method to the particle size (D1) converted from the specific surface area of the abrasive grains contained in the polishing composition measured by the BET method ( D2/D1) represents the degree of association of abrasive grains.
  • D2/D1 the ratio of the average particle size (D2) measured by the dynamic light scattering method to the particle size (D1) converted from the specific surface area of the abrasive grains contained in the polishing composition measured by the BET method
  • the polishing method disclosed herein provides a polished surface with highly reduced defects.
  • the specific surface area can be measured using, for example, a surface area measuring device manufactured by Micromeritex under the trade name “Flow Sorb II 2300”.
  • the true density can be measured, for example, using a pycnometer.
  • the particle diameter (D1) of the abrasive grains can be regarded as the "average primary particle diameter" of the abrasive grains measured by the same method as described above. Therefore, in this specification, the particle diameter (D1) of abrasive grains is also referred to as "average primary particle diameter (D1)".
  • the average particle size (D2) of abrasive grains refers to the average particle size measured by the dynamic light scattering method.
  • the value of this average particle size (D2) can be measured, for example, using model "UPA-UT151” manufactured by Nikkiso Co., Ltd. The same applies to the examples described later.
  • the average particle diameter (D2) of the abrasive grains can be regarded as the "average secondary particle diameter" of the abrasive grains measured by the same method as described above. Therefore, in this specification, the average particle size (D2) of abrasive grains is also referred to as "average secondary particle size (D2)".
  • (D2 A1 /D1 A1 ) is 1.55 or greater, more preferably 1.60 or greater, and even more preferably 1.65 or greater.
  • the upper limit of (D2 A1 /D1 A1 ) is not particularly limited. From the viewpoint of suppressing damage due to processing, in a preferred embodiment, (D2 A1 /D1 A1 ) is 3.0 or less, more preferably 2.8 or less, and still more preferably 2.5 or less.
  • (D2 A2 /D1 A2 ) is 1.45 or less, more preferably 1.40 or less, and even more preferably 1.35 or less.
  • the lower limit of (D2 A2 /D1 A2 ) is not particularly limited. From the viewpoint of availability, etc., the above (D2 A2 /D1 A2 ) may be greater than 1.0, may be 1.1 or more, or may be 1.2 or more.
  • the polishing composition S1 used for the first-stage polishing contains abrasive grains A1. Any of inorganic particles, organic particles, and organic-inorganic composite particles can be used as the abrasive grains A1.
  • inorganic particles include oxide particles such as alumina particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconium oxide particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and red iron oxide particles; silicon nitride particles , nitride particles such as boron nitride particles; carbide particles such as silicon carbide particles and boron carbide particles; diamond particles; carbonates such as calcium carbonate and barium carbonate; Examples of alumina constituting the alumina particles include ⁇ -alumina, intermediate alumina other than ⁇ -alumina, and composites thereof.
  • the intermediate alumina is a general term for alumina other than ⁇ -alumina, and specific examples thereof include ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina and composites thereof.
  • organic particles include polymethyl methacrylate particles, poly(meth)acrylic acid particles, polyacrylonitrile particles, and the like.
  • (meth)acrylic acid is a generic term for acrylic acid and methacrylic acid. These can be used individually by 1 type or in combination of 2 or more types.
  • silica particles refer to particles containing silica as a main component.
  • the silica particles are typically particles in which 90-100%, preferably 95-100%, eg 98-100% by weight of the particles are silica.
  • a polishing composition that can be used for polishing (for example, final polishing) a polishing object having a surface made of silicon such as a silicon wafer to be described later, it is particularly significant to employ silica particles as abrasive grains.
  • the technique disclosed here can be preferably implemented, for example, in a mode in which the abrasive grains A1 are substantially composed of silica particles.
  • substantially means that 95% by weight or more (preferably 98% by weight or more, more preferably 99% by weight or more, and may be 100% by weight) of the particles constituting the abrasive grains It refers to silica particles.
  • silica particles include colloidal silica, fumed silica, and precipitated silica.
  • a silica particle can be used individually by 1 type or in combination of 2 or more types. The use of colloidal silica is particularly preferred because it facilitates obtaining a polished surface with excellent surface quality after polishing.
  • colloidal silica include colloidal silica produced from water glass (sodium silicate) by an ion exchange method, colloidal silica produced by an alkoxide method (colloidal silica produced by a hydrolytic condensation reaction of alkoxysilane), and the like. Colloidal silica synthesized through particle growth in an aqueous phase can be preferably employed.
  • Abrasive grains A1 may contain one type of such silica particles alone or in combination of two or more types.
  • the true specific gravity of the abrasive grain-constituting material is preferably 1.5 or more, more preferably 1.6 or more, and still more preferably 1.7 or more.
  • the upper limit of the true specific gravity of the abrasive grain constituent material is not particularly limited, it is typically 2.3 or less, for example, 2.2 or less.
  • a value measured by a liquid replacement method using ethanol as a replacement liquid can be employed.
  • the technique disclosed here can be preferably implemented in a mode in which the abrasive grains A1 do not substantially contain particles other than silica particles (non-silica particles).
  • the proportion of non-silica particles in the entire abrasive grains A1 is 1% by weight or less, more preferably 0.5% by weight or less, typically It means 0.1% by weight or less, and includes the case where the proportion of non-silica particles is 0% by weight.
  • the application effects of the present invention can be favorably exhibited.
  • the average primary particle size (D1 A1 ) of the abrasive grains A1 is not particularly limited as long as it satisfies the relationship with the average secondary particle size (D2 A1 ) described above, but from the viewpoint of polishing efficiency etc. Therefore, it is preferably 5 nm or more, more preferably 10 nm or more. From the viewpoint of obtaining a higher polishing effect (for example, effects such as haze reduction and defect removal), the average primary particle diameter (D1 A1 ) of the abrasive grains A1 is preferably 15 nm or more, and preferably 20 nm or more (for example, more than 20 nm). more preferred.
  • the average primary particle diameter (D1 A1 ) of the abrasive grains A1 is preferably 100 nm or less, more preferably 75 nm or less, and even more preferably 50 nm or less. Since the technology disclosed herein makes it easy to obtain a high-quality surface (for example, a surface with a small number of defects detected by a highly accurate evaluation method), it is applied to polishing that requires a high-quality surface after polishing. preferably.
  • Abrasive grains A1 used in such a polishing method can have, for example, an average primary particle diameter (D1 A1 ) of 35 nm or less, 35 nm or less, 32 nm or less, or 30 nm or less.
  • the average primary particle diameter (D1 A1 ) of the abrasive grains A1 depends on the selection of the abrasive grains used as the abrasive grains A1, and when using multiple types of abrasive grains as the abrasive grains A1, the combination and amount of these abrasive grains used. ratio, etc.
  • the average secondary particle size (D2 A1 ) of the abrasive grains A1 is not particularly limited as long as it satisfies the relationship with the above-described average primary particle size (D1 A1 ). Therefore, it is preferably 5 nm or more, more preferably 10 nm or more. From the viewpoint of increasing the polishing rate, the average secondary particle diameter (D2 A1 ) of the abrasive grains A1 is preferably 15 nm or more, more preferably 20 nm or more (for example, more than 20 nm).
  • the average secondary particle diameter (D2 A1 ) of abrasive grains A1 is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 100 nm or less. Since the technique disclosed herein can easily obtain a high-quality surface, it is preferably applied to polishing that requires a high-quality surface after polishing. Abrasive grains A1 used in such a polishing method can have, for example, an average secondary particle diameter (D2 A1 ) of 75 nm or less, 65 nm or less, 60 nm or less, or less than 50 nm.
  • the average secondary particle diameter (D2 A1 ) of the abrasive grains A1 depends on the selection of the abrasive grains used as the abrasive grains A1, and the combination and use of those abrasive grains when using multiple types of abrasive grains as the abrasive grains A1. It can be adjusted by the amount ratio, etc.
  • the shape (outer shape) of the abrasive grains A1 is not particularly limited as long as the average primary particle size (D1 A1 ) and the average secondary particle size (D2 A1 ) satisfy the above relationship, and may be spherical or non- It may be spherical.
  • Specific examples of non-spherical particles include peanut-shaped (that is, peanut shell-shaped), cocoon-shaped, confetti-shaped, and rugby ball-shaped particles. Among them, non-spherical particles can be cited as shapes in which the average primary particle size (D1 A1 ) and the average secondary particle size (D2 A1 ) easily satisfy the above-described relationship regarding the abrasive grains A1.
  • abrasive grains A1 abrasive grains most of which are peanut-shaped or cocoon-shaped can be preferably employed.
  • the content of abrasive grains A1 in polishing composition S1 is not particularly limited, and is, for example, 0.005% by weight or more, and may be 0.01% by weight or more. Higher polishing efficiency can be achieved by increasing the abrasive content.
  • the above content is suitably 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, and even more preferably 0.5% by weight or less. As a result, a polished surface with fewer defects can be achieved.
  • Polishing composition S1 disclosed here contains a water-soluble polymer in a preferred embodiment.
  • a water-soluble polymer can be useful for protecting the surface to be polished and improving the wettability of the surface to be polished after polishing.
  • Examples of water-soluble polymers include compounds containing hydroxyl groups, carboxyl groups, acyloxy groups, sulfo groups, amide structures, imide structures, quaternary ammonium structures, heterocyclic structures, vinyl structures, etc. in their molecules.
  • Examples of water-soluble polymers include cellulose derivatives, starch derivatives, polymers containing oxyalkylene units, polyvinyl alcohol-based polymers, polymers containing nitrogen atoms, and the like.
  • the water-soluble polymer may be a polymer derived from natural products or a synthetic polymer.
  • One type of water-soluble polymer may be used alone, or two or more types may be used in combination.
  • polymers derived from natural products are used as water-soluble polymers.
  • Polymers derived from natural products include cellulose derivatives and starch derivatives. Natural product-derived polymers may be used singly or in combination of two or more.
  • a cellulose derivative is used as the water-soluble polymer.
  • cellulose derivatives are polymers containing ⁇ -glucose units as main repeating units.
  • Specific examples of cellulose derivatives include hydroxyethylcellulose (HEC), hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, methylcellulose, ethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose and the like.
  • HEC hydroxyethylcellulose
  • a cellulose derivative may be used individually by 1 type, and may be used in combination of 2 or more types.
  • a starch derivative is used as the water-soluble polymer.
  • Starch derivatives are polymers containing ⁇ -glucose units as main repeating units, such as pregelatinized starch, pullulan, carboxymethyl starch, cyclodextrin, and the like.
  • a starch derivative may be used individually by 1 type, and may be used in combination of 2 or more types.
  • a synthetic polymer is used as the water-soluble polymer.
  • the haze-improving effect disclosed herein is preferably exhibited in an embodiment using a synthetic polymer as the water-soluble polymer.
  • Synthetic polymers may be used singly or in combination of two or more.
  • a polymer containing oxyalkylene units is used as the water-soluble polymer.
  • polymers containing oxyalkylene units include polyethylene oxide (PEO), block copolymers of ethylene oxide (EO) and propylene oxide (PO) or butylene oxide (BO), and random copolymers of EO and PO or BO. etc. are exemplified.
  • block copolymers of EO and PO or random copolymers of EO and PO are preferred.
  • Block copolymers of EO and PO can be diblock copolymers, triblock copolymers, or the like, comprising PEO blocks and polypropylene oxide (PPO) blocks.
  • the triblock copolymers include PEO-PPO-PEO type triblock copolymers and PPO-PEO-PPO type triblock copolymers. PEO-PPO-PEO type triblock copolymers are usually more preferred.
  • copolymer is used to comprehensively refer to various copolymers such as random copolymers, alternating copolymers, block copolymers, and graft copolymers, unless otherwise specified. be.
  • the molar ratio (EO/PO) of EO and PO constituting the copolymer is It is preferably greater than 1, more preferably 2 or more, and even more preferably 3 or more (eg, 5 or more).
  • a polyvinyl alcohol-based polymer is used as the water-soluble polymer.
  • a polyvinyl alcohol-based polymer refers to a polymer containing a vinyl alcohol unit (hereinafter also referred to as "VA unit") as a repeating unit.
  • VA unit vinyl alcohol unit
  • the polyvinyl alcohol-based polymer may contain only VA units as repeating units, or may contain repeating units other than VA units (hereinafter also referred to as "non-VA units”) in addition to VA units.
  • the polyvinyl alcohol-based polymer may be a random copolymer containing VA units and non-VA units, a block copolymer, an alternating copolymer or a graft copolymer.
  • the polyvinyl alcohol-based polymer may contain only one type of non-VA unit, or may contain two or more types of non-VA units.
  • the polyvinyl alcohol-based polymer may be unmodified polyvinyl alcohol (non-modified PVA) or modified polyvinyl alcohol (modified PVA).
  • the unmodified PVA is a repeating unit (—CH 2 —CH(OCOCH 3 )—) of a structure produced by hydrolyzing (saponifying) polyvinyl acetate and vinyl-polymerizing vinyl acetate, and other than VA units.
  • the degree of saponification of the non-modified PVA may be, for example, 60% or more, or from the viewpoint of water solubility, 70% or more, 80% or more, or 90% or more.
  • the polyvinyl alcohol-based polymer contains at least one selected from VA units, oxyalkylene groups, carboxy groups, sulfo groups, amino groups, hydroxyl groups, amide groups, imide groups, nitrile groups, ether groups, ester groups, and salts thereof. It may also be a modified PVA containing non-VA units having a structure.
  • non-VA units that can be contained in the modified PVA include, for example, repeating units derived from N-vinyl type monomers and N-(meth)acryloyl type monomers described later, repeating units derived from ethylene, and alkyl vinyl ether-derived units.
  • the alkyl vinyl ether may be a vinyl ether having an alkyl group having 1 to 10 carbon atoms, such as propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether.
  • the vinyl ester of a monocarboxylic acid having 3 or more carbon atoms is a vinyl ester of a monocarboxylic acid having 3 or more and 7 or less carbon atoms, such as vinyl propanoate, vinyl butanoate, vinyl pentanoate, and vinyl hexanoate.
  • the polyvinyl alcohol-based polymer may be modified PVA in which some of the VA units contained in the polyvinyl alcohol-based polymer are acetalized with aldehyde.
  • aldehyde for example, an alkyl aldehyde can be preferably used, and an alkyl aldehyde having an alkyl group having 1 to 7 carbon atoms is preferable.
  • Cation-modified polyvinyl alcohol into which a cationic group such as a quaternary ammonium structure is introduced may be used as the polyvinyl alcohol-based polymer.
  • a cationic group derived from a monomer having a cationic group such as diallyldialkylammonium salt, N-(meth)acryloylaminoalkyl-N,N,N-trialkylammonium salt is introduced. What was done is mentioned.
  • Modified PVA acetalized PVA (ac-PVA) in which a portion of the VA units contained in the polyvinyl alcohol polymer is acetalized with aldehyde is an aldehyde compound or a ketone compound in which a portion of the hydroxy groups of the polyvinyl alcohol polymer is It can be obtained by reacting with and acetalizing.
  • an acetalized polyvinyl alcohol polymer is obtained by an acetalization reaction between a polyvinyl alcohol polymer and an aldehyde compound.
  • the aldehyde compound has 1 to 7 carbon atoms, more preferably 2 to 7 carbon atoms.
  • aldehyde compound examples include formaldehyde; linear or branched alkyl aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, t-butyraldehyde, and hexylaldehyde; or aromatic aldehydes; These may be used alone or in combination of two or more.
  • formaldehyde one or more hydrogen atoms may be substituted with halogen or the like.
  • straight-chain or branched alkylaldehydes are preferable because they have high solubility in water and are easy to acetalize.
  • acetaldehyde, n-propylaldehyde, n-butyraldehyde and n-pentylaldehyde. is more preferable.
  • aldehyde compounds having 8 or more carbon atoms such as 2-ethylhexylaldehyde, nonylaldehyde, and decylaldehyde may be used.
  • the acetalized polyvinyl alcohol-based polymer comprises a VA unit, which is a structural portion represented by the following chemical formula: —CH 2 —CH(OH)—; and an acetalized structure represented by the following general formula (1) unit (hereinafter also referred to as “VAC unit”).
  • R is a hydrogen atom or a linear or branched alkyl group, and the alkyl group may be substituted with a functional group.
  • R in formula (1) above is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
  • R may be one of these, or may be a combination of two or more.
  • R is preferably a linear or branched alkyl chain having 1 to 6 carbon atoms.
  • the acetalization degree of the acetalized polyvinyl alcohol polymer can be 1 mol% or more, may be 5 mol% or more, preferably 10 mol% or more, and more preferably. 15 mol % or more, more preferably 20 mol % or more, particularly preferably 25 mol % or more (for example, 27 mol % or more).
  • the acetalization degree of the acetalized polyvinyl alcohol polymer is preferably less than 60 mol%, more preferably 50 mol% or less, more preferably 40 mol% or less, and particularly preferably 35 mol% or less. (for example, 33 mol % or less).
  • the ratio of the number of moles of VA units to the number of moles of all repeating units constituting the polyvinyl alcohol polymer may be, for example, 5% or more, 10% or more, 20% or more, or 30% or more. .
  • the ratio of the number of moles of the VA units may be 50% or more, 65% or more, 75% or more, or 80% or more, It may be 90% or more (eg, 95% or more, or 98% or more).
  • Substantially 100% of the repeating units constituting the polyvinyl alcohol polymer may be VA units.
  • substantially 100% means that the polyvinyl alcohol-based polymer does not contain non-VA units at least intentionally, typically the number of moles of non-VA units in the number of moles of all repeating units is less than 2% (eg, less than 1%), including 0%.
  • the ratio of the number of moles of VA units to the number of moles of all repeating units constituting the polyvinyl alcohol polymer may be, for example, 95% or less, 90% or less, or 80% or less. , or 70% or less.
  • the content of VA units (content on a weight basis) in the polyvinyl alcohol-based polymer may be, for example, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more.
  • the content of the VA unit may be 50% by weight or more (for example, more than 50% by weight), 70% by weight or more, or 80% by weight or more ( For example, 90% by weight or more, 95% by weight or more, or 98% by weight or more).
  • Substantially 100% by weight of the repeating units constituting the polyvinyl alcohol-based polymer may be VA units.
  • substantially 100% by weight refers to at least intentionally not containing non-VA units as repeating units constituting the polyvinyl alcohol-based polymer, typically non-VA units in the polyvinyl alcohol-based polymer is less than 2% by weight (for example, less than 1% by weight).
  • the content of VA units in the polyvinyl alcohol-based polymer may be, for example, 95% by weight or less, 90% by weight or less, 80% by weight or less, or 70% by weight or less. .
  • the polyvinyl alcohol-based polymer may contain multiple polymer chains with different VA unit contents in the same molecule.
  • the polymer chain refers to a portion (segment) that constitutes a part of one molecule of polymer.
  • a polyvinyl alcohol-based polymer has a polymer chain A containing more than 50% by weight of VA units and a polymer chain A containing less than 50% by weight of VA units (i.e., more than 50% by weight of non-VA units). ) and the polymer chain B in the same molecule.
  • the polymer chain A may contain only VA units as repeating units, or may contain non-VA units in addition to VA units.
  • the content of VA units in the polymer chain A may be 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more. In some embodiments, the content of VA units in polymer chain A may be 95 wt% or more, or 98 wt% or more. Substantially 100% by weight of the repeating units constituting the polymer chain A may be VA units.
  • the polymer chain B may contain only non-VA units as repeating units, or may contain VA units in addition to non-VA units.
  • the content of non-VA units in polymer chain B may be 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more. In some embodiments, the content of non-VA units in polymer chain B may be 95 wt% or greater, or 98 wt% or greater. Substantially 100% by weight of the repeating units constituting polymer chain B may be non-VA units.
  • polyvinyl alcohol-based polymers containing polymer chain A and polymer chain B in the same molecule include block copolymers and graft copolymers containing these polymer chains.
  • the graft copolymer may be a graft copolymer having a structure in which the polymer chain B (side chain) is grafted to the polymer chain A (main chain), and the polymer chain A (side chain) is attached to the polymer chain B (main chain). chain) may be graft copolymers.
  • a polyvinyl alcohol-based polymer having a structure in which a polymer chain B is grafted onto a polymer chain A can be used.
  • polymer chain B examples include a polymer chain whose main repeating unit is a repeating unit derived from an N-vinyl type monomer, and a polymer chain whose main repeating unit is a repeating unit derived from an N-(meth)acryloyl type monomer. , a polymer chain having an oxyalkylene unit as a main repeating unit, and the like.
  • the main repeating unit means a repeating unit containing more than 50% by weight unless otherwise specified.
  • a suitable example of the polymer chain B is a polymer chain having an N-vinyl type monomer as the main repeating unit, that is, an N-vinyl polymer chain.
  • the content of repeating units derived from the N-vinyl type monomer in the N-vinyl polymer chain is typically more than 50% by weight, may be 70% by weight or more, and may be 85% by weight or more. may be 95% by weight or more.
  • Substantially all of the polymer chain B may be repeating units derived from an N-vinyl type monomer.
  • examples of N-vinyl type monomers include monomers having a nitrogen-containing heterocyclic ring (eg, lactam ring) and N-vinyl chain amides.
  • Specific examples of N-vinyllactam type monomers include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylmorpholinone, N-vinylcaprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl- 3,5-morpholinedione and the like.
  • Specific examples of N-vinyl chain amides include N-vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide and the like.
  • Polymer chain B is, for example, an N-vinyl polymer chain in which more than 50% by weight (for example, 70% by weight or more, or 85% by weight or more, or 95% by weight or more) of the repeating units are N-vinylpyrrolidone units. obtain. Substantially all of the repeating units constituting the polymer chain B may be N-vinylpyrrolidone units.
  • polymer chain B is a polymer chain whose main repeating unit is a repeating unit derived from an N-(meth)acryloyl-type monomer, that is, an N-(meth)acryloyl-based polymer chain.
  • the content of repeating units derived from N-(meth)acryloyl type monomers in the N-(meth)acryloyl polymer chain is typically more than 50% by weight, and may be 70% by weight or more. It may be at least 95% by weight.
  • Substantially all of the polymer chain B may be repeating units derived from N-(meth)acryloyl type monomers.
  • examples of N-(meth)acryloyl-type monomers include linear amides having an N-(meth)acryloyl group and cyclic amides having an N-(meth)acryloyl group.
  • chain amides having an N-(meth)acryloyl group include (meth)acrylamide; N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl ( meth)acrylamide, N-alkyl (meth)acrylamide such as Nn-butyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide ) N,N-dialkyl(meth)acrylamides such as acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-but
  • polymer chain B is a polymer chain containing an oxyalkylene unit as a main repeating unit, that is, an oxyalkylene-based polymer chain.
  • the content of oxyalkylene units in the oxyalkylene-based polymer chain is typically greater than 50% by weight, and may be 70% by weight or more, may be 85% by weight or more, or may be 95% by weight or more. There may be. Substantially all of the repeating units contained in polymer chain B may be oxyalkylene units.
  • oxyalkylene units include oxyethylene units, oxypropylene units, and oxybutylene units. Each such oxyalkylene unit may be a repeat unit derived from the corresponding alkylene oxide.
  • the oxyalkylene units contained in the oxyalkylene-based polymer chain may be of one type or of two or more types. For example, it may be an oxyalkylene polymer chain containing a combination of oxyethylene units and oxypropylene units. In the oxyalkylene-based polymer chain containing two or more types of oxyalkylene units, the oxyalkylene units may be random copolymers, block copolymers, or alternating copolymers of corresponding alkylene oxides. It may be a polymer or a graft copolymer.
  • polymer chain B examples include polymer chains containing repeating units derived from alkyl vinyl ethers (for example, vinyl ethers having an alkyl group having 1 to 10 carbon atoms), monocarboxylic acid vinyl esters (for example, Examples thereof include polymer chains containing repeating units derived from 3 or more monocarboxylic acid vinyl esters), polymer chains introduced with cationic groups (for example, cationic groups having a quaternary ammonium structure), and the like.
  • alkyl vinyl ethers for example, vinyl ethers having an alkyl group having 1 to 10 carbon atoms
  • monocarboxylic acid vinyl esters for example, Examples thereof include polymer chains containing repeating units derived from 3 or more monocarboxylic acid vinyl esters
  • polymer chains introduced with cationic groups for example, cationic groups having a quaternary ammonium structure
  • the polyvinyl alcohol-based polymer as the water-soluble polymer in the technology disclosed herein is preferably modified polyvinyl alcohol, which is a copolymer containing VA units and non-VA units.
  • the degree of saponification of the polyvinyl alcohol polymer as the water-soluble polymer is usually 50 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more, for example 75 mol% or more. In principle, the degree of saponification of the polyvinyl alcohol-based polymer is 100 mol % or less.
  • an N-vinyl polymer can be used as the water-soluble polymer.
  • N-vinyl type polymers include polymers containing repeat units derived from monomers having nitrogen-containing heterocycles (eg, lactam rings).
  • examples of such polymers include homopolymers and copolymers of N-vinyllactam-type monomers (eg, copolymers in which the proportion of copolymerization of N-vinyllactam-type monomers is greater than 50% by weight), N-vinyl It includes homopolymers and copolymers of linear amides (for example, copolymers in which the copolymerization ratio of N-vinyl linear amides exceeds 50% by weight).
  • N-vinyllactam type monomers that is, compounds having a lactam structure and an N-vinyl group in one molecule
  • N-vinylpyrrolidone VP
  • N-vinylpiperidone N-vinylmorpholinone
  • N -vinylcaprolactam VC
  • N-vinyl-1,3-oxazin-2-one N-vinyl-3,5-morpholinedione and the like.
  • polymers containing N-vinyllactam type monomer units include polyvinylpyrrolidone, polyvinylcaprolactam, random copolymers of VP and VC, one or both of VP and VC and other vinyl monomers (e.g., acrylic monomers, vinyl ester-based monomers, etc.), block copolymers containing polymer chains containing one or both of VP and VC, alternating copolymers, graft copolymers, and the like.
  • N-vinyl chain amides include N-vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide and the like.
  • an N-(meth)acryloyl-type polymer can be used as the water-soluble polymer.
  • N-(meth)acryloyl type polymers include homopolymers and copolymers of N-(meth)acryloyl type monomers (typically, the copolymerization ratio of N-(meth)acryloyl type monomers is 50 wt. % of copolymers).
  • Examples of N-(meth)acryloyl-type monomers include linear amides having an N-(meth)acryloyl group and cyclic amides having an N-(meth)acryloyl group.
  • chain amides having an N-(meth)acryloyl group include (meth)acrylamide; N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl ( meth)acrylamide, N-alkyl (meth)acrylamide such as Nn-butyl (meth)acrylamide; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide ) N,N-dialkyl(meth)acrylamides such as acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide;
  • polymers containing linear amides having N-(meth)acryloyl groups as monomer units include homopolymers of N-isopropylacrylamide and copolymers of N-
  • Examples of cyclic amides having an N-(meth)acryloyl group include N-acryloylmorpholine, N-acryloylthiomorpholine, N-acryloylpiperidine, N-acryloylpyrrolidine, N-methacryloylmorpholine, N-methacryloylpiperidine, N-methacryloyl pyrrolidine and the like.
  • Examples of polymers containing cyclic amides having N-(meth)acryloyl groups as monomer units include acryloylmorpholine polymers (PACMO).
  • acryloylmorpholine-based polymers include homopolymers of N-acryloylmorpholine (ACMO) and copolymers of ACMO (for example, copolymers in which the copolymerization ratio of ACMO exceeds 50% by weight).
  • ACMO N-acryloylmorpholine
  • the ratio of the number of moles of ACMO units to the number of moles of all repeating units is usually 50% or more, and 80% or more (for example, 90% or more, typically 95% or more). is appropriate.
  • All repeating units of the water-soluble polymer may be substantially composed of ACMO units.
  • the weight average molecular weight (Mw) of the water-soluble polymer is not particularly limited.
  • the Mw of the water-soluble polymer may be, for example, about 200 ⁇ 10 4 or less, suitably about 150 ⁇ 10 4 or less, and preferably about 100 ⁇ 10 4 or less, or about It may be 50 ⁇ 10 4 or less.
  • the Mw of the water-soluble polymer is preferably 0.5 ⁇ 10 4 or more.
  • Mw is suitably 1.0 ⁇ 10 4 or more, may be 2 ⁇ 10 4 or more, and may be, for example, 5 ⁇ 10 4 or more.
  • the preferred molecular weight range of the water-soluble polymer compound may vary depending on the type of polymer used.
  • the Mw of the cellulose derivative and starch derivative can each be about 200 ⁇ 10 4 or less, and 150 ⁇ 10 4 or less is suitable.
  • the Mw may be about 100 ⁇ 10 4 or less, or about 50 ⁇ 10 4 or less (for example, about 30 ⁇ 10 4 or less).
  • Mw is, for example, about 0.5 ⁇ 10 4 or more, preferably about 1.0 ⁇ 10 4 or more, and more preferably about 3.0.
  • ⁇ 10 4 or more more preferably approximately 10 ⁇ 10 4 or more, and may be approximately 20 ⁇ 10 4 or more.
  • the Mw of the polyvinyl alcohol-based polymer (including acetalized polyvinyl alcohol-based polymer) and the nitrogen atom-containing polymer can each be 100 ⁇ 10 4 or less, preferably 60 ⁇ 10 4 or less. is. From the viewpoint of concentration efficiency, etc., the Mw may be 30 ⁇ 10 4 or less, preferably 20 ⁇ 10 4 or less, for example 10 ⁇ 10 4 or less, typically 8 ⁇ 10 4 or less. good. Moreover, from the viewpoint of suitably protecting the polished surface and reducing haze, Mw is preferably 0.5 ⁇ 10 4 or more, for example.
  • Mw is suitably 1.0 ⁇ 10 4 or more, preferably 1.5 ⁇ 10 4 or more, more preferably 2 ⁇ 10 4 or more, and still more preferably 3 ⁇ 10 4 or more, For example, it may be 4 ⁇ 10 4 or more, or 5 ⁇ 10 4 or more.
  • Mw of the water-soluble polymer a molecular weight calculated from a value based on aqueous gel permeation chromatography (GPC) (aqueous system, converted to polyethylene oxide) can be used.
  • GPC gel permeation chromatography
  • model name "HLC-8320GPC” manufactured by Tosoh Corporation may be used. Measurement can be performed, for example, under the following conditions. A similar method is adopted for the examples described later.
  • a nonionic polymer can be preferably used as the water-soluble polymer from the viewpoint of reducing aggregates and improving washability.
  • synthetic polymers can be preferably employed as water-soluble polymers.
  • the polishing composition does not substantially use a polymer derived from a natural product as the water-soluble polymer.
  • substantially not used means that the amount of the natural product-derived polymer used is typically 3 parts by weight or less, preferably 1 part by weight or less, relative to the total content of 100 parts by weight of the water-soluble polymer. It includes 0 parts by weight or below the detection limit.
  • the content (content by weight) of the water-soluble polymer in the polishing composition is not particularly limited. For example, it can be 1.0 ⁇ 10 ⁇ 4 wt % or more. From the viewpoint of reducing haze, etc., the content is preferably 5.0 ⁇ 10 ⁇ 4 wt % or more, more preferably 1.0 ⁇ 10 ⁇ 3 wt % or more, and still more preferably 2.0 ⁇ 10 ⁇ 3 wt %. or more, for example, 5.0 ⁇ 10 ⁇ 3 wt % or more. Further, from the viewpoint of polishing removal rate, etc., the content is preferably 0.2% by weight or less, more preferably 0.1% by weight or less, and 0.05% by weight or less (for example, 0.02% by weight). % by weight or less). When the polishing composition contains two or more types of water-soluble polymers, the content is the total content of all water-soluble polymers contained in the polishing composition (content on a weight basis). That's what I mean.
  • the content of water-soluble polymers (the total amount when two or more types of water-soluble polymers are included) can also be specified by the relative relationship with the abrasive grains.
  • the content of the water-soluble polymer relative to 100 parts by weight of the abrasive grains can be, for example, 0.001 parts by weight or more, and from the viewpoint of haze reduction, etc., it is 0.001 part by weight. 01 parts by weight or more, preferably 0.05 parts by weight or more.
  • the content of the water-soluble polymer relative to 100 parts by weight of the abrasive grains may be, for example, 50 parts by weight or less, or may be 40 parts by weight or less.
  • the content of the water-soluble polymer with respect to 100 parts by weight of the abrasive grains is suitably 30 parts by weight or less, preferably 20 parts by weight. parts or less, and may be 15 parts by weight or less.
  • the polishing composition disclosed herein contains a basic compound.
  • a basic compound refers to a compound that dissolves in water and has the function of raising the pH of an aqueous solution.
  • Examples of basic compounds include organic or inorganic basic compounds containing nitrogen, basic compounds containing phosphorus, alkali metal hydroxides, alkaline earth metal hydroxides, various carbonates and hydrogen carbonates, and the like. can be used.
  • nitrogen-containing basic compounds include quaternary ammonium compounds, ammonia, amines (preferably water-soluble amines), and the like.
  • Examples of basic compounds containing phosphorus include quaternary phosphonium compounds. Such a basic compound can be used individually by 1 type or in combination of 2 or more types.
  • alkali metal hydroxides include potassium hydroxide and sodium hydroxide.
  • Specific examples of carbonates or hydrogencarbonates include ammonium hydrogencarbonate, ammonium carbonate, potassium hydrogencarbonate, potassium carbonate, sodium hydrogencarbonate, sodium carbonate and the like.
  • Specific examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-( ⁇ -aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and anhydrous piperazine.
  • quaternary phosphonium compound examples include quaternary phosphonium hydroxides such as tetramethylphosphonium hydroxide and tetraethylphosphonium hydroxide.
  • quaternary ammonium salts such as tetraalkylammonium salts and hydroxyalkyltrialkylammonium salts
  • the anionic component in such quaternary ammonium salts can be, for example, OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BH 4 ⁇ and the like.
  • Examples of the above quaternary ammonium compounds include quaternary ammonium salts in which the anion is OH—, ie quaternary ammonium hydroxides.
  • quaternary ammonium hydroxides include hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide and tetrahexylammonium hydroxide.
  • tetraalkylammonium; hydroxyalkyltrialkylammonium hydroxide such as 2-hydroxyethyltrimethylammonium hydroxide (also referred to as choline);
  • At least one basic compound selected from alkali metal hydroxides, quaternary ammonium hydroxides and ammonia can be preferably used.
  • tetraalkylammonium hydroxide eg, tetramethylammonium hydroxide
  • ammonia is particularly preferred.
  • the content of the basic compound relative to the total amount of the polishing composition is not particularly limited. From the viewpoint of improving the polishing rate, etc., the above content is usually appropriate to be 0.0001% by weight or more, preferably 0.001% by weight or more, and 0.003% by weight or more. is more preferred. In addition, from the viewpoint of haze reduction, etc., the content is suitably less than 1% by weight, preferably less than 0.05% by weight, and less than 0.03% by weight (for example, 0.025% by weight %) is more preferable. In addition, when using 2 or more types in combination, the said content points out the total content of 2 or more types of basic compounds.
  • ion-exchanged water deionized water
  • pure water ultrapure water
  • distilled water distilled water
  • the water used preferably has a total transition metal ion content of, for example, 100 ppb or less, in order to avoid as much as possible inhibition of the functions of other components contained in the polishing composition.
  • the purity of water can be increased by removing impurity ions using an ion exchange resin, removing foreign substances using a filter, and performing operations such as distillation.
  • the polishing composition disclosed herein may, if necessary, further contain an organic solvent (lower alcohol, lower ketone, etc.) that can be uniformly mixed with water.
  • 90% by volume or more of the solvent contained in the polishing composition is preferably water, and more preferably 95% by volume or more (eg, 99 to 100% by volume) is water.
  • the polishing composition disclosed herein contains, for example, a surfactant, an organic acid, an organic acid salt, an inorganic acid, an inorganic acid salt, a chelating agent, an antiseptic, and an antifungal agent, as long as the effects of the present invention are not significantly hindered.
  • Known additives that can be used in polishing compositions for example, polishing compositions used in the final polishing step of silicon wafers, such as agents, may be further contained as necessary.
  • the polishing composition disclosed herein may contain a surfactant as an optional component within a range that does not impair the effects of the present invention.
  • any of anionic, cationic, nonionic and amphoteric surfactants can be used as surfactants.
  • Anionic or nonionic surfactants can be employed.
  • a nonionic surfactant may be used from the viewpoint of low foaming properties and ease of pH adjustment.
  • the surfactant for example, an organic compound having an Mw of less than 0.5 ⁇ 10 4 is used.
  • the Mw of the surfactant is preferably less than 0.1 ⁇ 10 4 from the standpoint of filterability of the polishing liquid, cleaning ability of the object to be polished, and the like. In a preferred embodiment of the technology disclosed herein, Mw of the surfactant is 100 or more, more preferably 200 or more, and even more preferably 250 or more.
  • the Mw of the surfactant may employ a molecular weight calculated from the chemical formula, or a value based on aqueous gel permeation chromatography (GPC) (converted to polyethylene oxide), similar to the water-soluble polymer described above. ) may be employed.
  • GPC gel permeation chromatography
  • surfactants include oxyalkylene polymers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene fatty acid esters, poly Polyoxyalkylene derivatives (e.g., polyoxyalkylene adducts) such as oxyethylene glyceryl ether fatty acid esters and polyoxyethylene sorbitan fatty acid esters; copolymers of multiple types of oxyalkylenes (e.g., diblock copolymers, triblock type copolymer, random type copolymer, alternating copolymer); The surfactant may include a surfactant containing a polyoxyalkylene structure. Surfactants can be used singly or in combination of two or more.
  • the polishing composition disclosed herein contains a surfactant
  • its content is not particularly limited as long as it does not significantly impair the effects of the present invention.
  • the content of the surfactant with respect to 100 parts by weight of the abrasive grains is, for example, 20 parts by weight or less, may be less than 10 parts by weight, may be less than 3 parts by weight, or may be less than 2 parts by weight (for example, 1.8 parts by weight less than) is acceptable.
  • the polishing composition disclosed herein can preferably be carried out in a manner substantially free of the surfactant.
  • organic acid and its salt and the inorganic acid and its salt can be used singly or in combination of two or more.
  • organic acids include fatty acids such as formic acid, acetic acid and propionic acid, aromatic carboxylic acids such as benzoic acid and phthalic acid, itaconic acid, citric acid, oxalic acid, tartaric acid, malic acid, maleic acid, fumaric acid, and succinic acid.
  • organic acids examples include alkali metal salts (sodium salt, potassium salt, etc.) and ammonium salts of organic acids.
  • inorganic acids examples include hydrochloric acid, phosphoric acid, sulfuric acid, phosphonic acid, nitric acid, phosphinic acid, boric acid, carbonic acid, and the like.
  • inorganic acid salts include alkali metal salts (sodium salt, potassium salt, etc.) and ammonium salts of inorganic acids.
  • the above chelating agents may be used singly or in combination of two or more.
  • the chelating agents include aminocarboxylic acid-based chelating agents and organic phosphonic acid-based chelating agents.
  • Suitable examples of chelating agents include, for example, ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) and diethylenetriaminepentaacetic acid.
  • the antiseptic and antifungal agents include isothiazoline compounds, paraoxybenzoic acid esters, phenoxyethanol, and the like.
  • the polishing composition disclosed herein is preferably substantially free of oxidizing agents.
  • the polishing composition contains an oxidizing agent
  • the surface of the substrate is oxidized to form an oxide film, thereby reducing the polishing rate.
  • the oxidizing agent include hydrogen peroxide (H 2 O 2 ), sodium persulfate, ammonium persulfate, sodium dichloroisocyanurate and the like.
  • the fact that the polishing composition does not substantially contain an oxidizing agent means that it does not contain an oxidizing agent at least intentionally.
  • a trace amount for example, the molar concentration of the oxidizing agent in the polishing composition is 0.0005 mol / L or less, preferably 0.0001 mol / L or less, more preferably 0.00001 mol/L or less, particularly preferably 0.000001 mol/L or less
  • the oxidizing agent is inevitably contained in the concept of the polishing composition substantially free of the oxidizing agent.
  • the pH of the polishing composition disclosed herein is not particularly limited, and an appropriate pH can be adopted according to the substrate, abrasive grain type, and the like.
  • the pH of the polishing composition is suitably 8.0 or higher, preferably 8.5 or higher, more preferably 9.0 or higher. Polishing efficiency tends to improve as the pH of the polishing composition increases.
  • the pH of the polishing composition is usually suitably 12.0 or less. It is preferably 0.0 or less.
  • the pH of the polishing composition is measured using a pH meter (for example, a glass electrode hydrogen ion concentration indicator (model number F-72) manufactured by Horiba, Ltd.), and a standard buffer solution ( Phthalate pH buffer solution pH: 4.01 (25°C), neutral phosphate pH buffer solution pH: 6.86 (25°C), carbonate pH buffer solution pH: 10.01 (25°C)
  • a pH meter for example, a glass electrode hydrogen ion concentration indicator (model number F-72) manufactured by Horiba, Ltd.
  • a standard buffer solution Phthalate pH buffer solution pH: 4.01 (25°C), neutral phosphate pH buffer solution pH: 6.86 (25°C), carbonate pH buffer solution pH: 10.01 (25°C)
  • the polishing composition S2 used for the second-stage polishing contains abrasive grains A2.
  • abrasive grains A2 one or more selected from the same grains as those exemplified as the grains that can be used for the abrasive grains A1 can be used.
  • the abrasive grains A2 preferably contain at least silica particles.
  • the content of silica particles in the abrasive grains A2 is preferably 50% by weight or more of the entire abrasive grains A2, may be 70% by weight or more, may be 90% by weight or more, may be 95% by weight or more, or may be 99% by weight. % or more, or 100% by weight.
  • silica particles that can be used for the abrasive grains A2 include the same silica particles that can be used for the abrasive grains A1. Among them, colloidal silica is preferred. By using colloidal silica as the abrasive grains A2, a surface with high surface precision can be suitably realized.
  • the content of colloidal silica in the abrasive grains A2 may be, for example, 50% by weight or more, 70% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight of the entire abrasive grains A2. % or more, or 100% by weight.
  • the abrasive grains A2 may consist of only one or more colloidal silicas.
  • the average primary particle size (D1 A2 ) of the abrasive grains A2 is not particularly limited as long as it satisfies the relationship with the average secondary particle size (D2 A2 ) described above, but from the viewpoint of polishing efficiency, etc. Therefore, it is preferably 5 nm or more, more preferably 10 nm or more. From the viewpoint of obtaining a higher polishing effect (for example, effects such as reduction of haze and removal of defects), the average primary particle diameter (D1 A2 ) of the abrasive grains A2 is preferably 15 nm or more, and preferably 20 nm or more (for example, more than 20 nm). more preferred.
  • the average primary particle diameter (D1 A2 ) of the abrasive grains A2 is preferably 100 nm or less, more preferably 75 nm or less, and even more preferably 50 nm or less. Since the technique disclosed herein can easily obtain a high-quality surface, it is preferably applied to polishing that requires a high-quality surface after polishing. Abrasive grains A2 used in such a polishing method can have, for example, an average primary particle diameter (D1 A2 ) of 35 nm or less, 35 nm or less, 32 nm or less, or 30 nm or less.
  • the average primary particle diameter (D1 A2 ) of the abrasive grains A2 depends on the selection of the abrasive grains used as the abrasive grains A2, and when using multiple types of abrasive grains as the abrasive grains A2. ratio, etc.
  • the average secondary particle size (D2 A2 ) of the abrasive grains A2 is not particularly limited as long as it satisfies the relationship with the above-described average primary particle size (D1 A2 ), but from the viewpoint of polishing efficiency, etc. Therefore, it is preferably 5 nm or more, more preferably 10 nm or more. From the viewpoint of increasing the polishing rate, the average secondary particle diameter (D2 A2 ) of the abrasive grains A2 is preferably 15 nm or more, more preferably 20 nm or more (for example, more than 20 nm).
  • the average secondary particle size (D2 A2 ) of abrasive grains A2 is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. Since the technique disclosed herein can easily obtain a high-quality surface, it is preferably applied to polishing that requires a high-quality surface after polishing. Abrasive grains A2 used in such a polishing method can have, for example, an average secondary particle diameter (D2 A2 ) of 75 nm or less, 65 nm or less, 60 nm or less, or less than 50 nm.
  • the average secondary particle diameter (D2 A2 ) of the abrasive grains A2 depends on the selection of the abrasive grains used as the abrasive grains A2, and the combination and use of those abrasive grains when multiple types of abrasive grains are used as the abrasive grains A2. It can be adjusted by the amount ratio, etc.
  • the shape (outer shape) of the abrasive grains A2 is not particularly limited as long as the average primary particle size (D1 A2 ) and the average secondary particle size (D2 A2 ) satisfy the above relationship, and may be spherical or non- It may be spherical.
  • Specific examples of non-spherical particles include peanut-shaped (that is, peanut shell-shaped), cocoon-shaped, confetti-shaped, and rugby ball-shaped particles.
  • a spherical shape can be given as a shape that easily satisfies the above-described relationship regarding the abrasive grains A2 between the average primary particle size (D1 A2 ) and the average secondary particle size (D2 A2 ).
  • the abrasive grains A2 most of the abrasive grains are spherical.
  • the content of the abrasive grains A2 in the polishing composition S2 is not particularly limited, and is, for example, 0.005% by weight or more, and may be 0.01% by weight or more. Higher polishing efficiency can be achieved by increasing the abrasive content.
  • the above content is suitably 5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less, and even more preferably 0.5% by weight or less. As a result, a polished surface with fewer defects can be achieved.
  • the abrasive grain content described above can be preferably employed in an embodiment in which the polishing composition is used in the form of a polishing liquid (working slurry).
  • the polishing composition S2 can contain a water-soluble polymer, a basic compound, water, a surfactant and other components as necessary. Examples of the materials that can be used as these components and the amounts used are substantially the same as those of the polishing composition S1, so overlapping descriptions will be omitted.
  • the technology disclosed herein can be preferably implemented in a mode in which at least one kind of water-soluble polymer is contained in both the polishing composition S1 and the polishing composition S2. That is, it can be carried out preferably in a mode in which at least one type of water-soluble polymer is commonly contained in both the polishing composition S1 and the polishing composition S2. All of the water-soluble polymers contained in the polishing compositions S1 and S2 may be common.
  • the polishing composition S1 and the polishing composition S2 coexist at least temporarily on the platen. can.
  • a common water-soluble polymer in the polishing composition S1 and the polishing composition S2 is advantageous from the viewpoint of improving dispersion stability and suppressing the generation of aggregates when these polishing compositions coexist. obtain.
  • the content of the common water-soluble polymer in the polishing composition S1 and the content in the polishing composition S2 may be the same or different.
  • the technology disclosed herein can be preferably carried out in a mode in which at least one type of basic compound is commonly contained in both polishing composition S1 and polishing composition S2.
  • the content of the common basic compound in the polishing composition S1 and the content in the polishing composition S2 may be about the same or different.
  • the technology disclosed herein can be preferably implemented in a mode in which at least one surfactant is commonly contained in both the polishing composition S1 and the polishing composition S2.
  • the content of the common surfactant in the polishing composition S1 and the content in the polishing composition S2 may be about the same or different.
  • the technology disclosed herein can be applied to polishing substrates having various materials and shapes.
  • Materials of the substrate include, for example, metals or semimetals such as silicon, aluminum, nickel, tungsten, copper, tantalum, titanium, and stainless steel, or alloys thereof; vitreous substances such as quartz glass, aluminosilicate glass, and vitreous carbon; ceramic materials such as alumina, silica, sapphire, silicon nitride, tantalum nitride and titanium carbide; compound semiconductor substrate materials such as silicon carbide, gallium nitride and gallium arsenide; resin materials such as polyimide resin;
  • the substrate may be made of a plurality of materials among these materials.
  • the shape of the substrate is not particularly limited.
  • the technology disclosed herein can be applied, for example, to polishing a substrate having a flat surface such as a plate-like or polyhedral shape, or polishing an edge of a substrate (for example, polishing a wafer edge).
  • the polishing method disclosed here can be particularly preferably used for polishing surfaces made of silicon (typically for polishing silicon wafers).
  • a typical example of the silicon wafer referred to here is a silicon single crystal wafer, for example, a silicon single crystal wafer obtained by slicing a silicon single crystal ingot.
  • the polishing method disclosed herein includes a polishing step of supplying polishing composition S1 and polishing composition S2 in this order to an object to be polished on the same platen to polish the object to be polished.
  • the polishing process performed on the same platen can be performed, for example, as follows. However, the following description does not limit the embodiments of the polishing process.
  • the object to be polished (typically a substrate) is set in the polishing device. Then, the supply of the polishing composition S1 to the object to be polished is started, and the first step of polishing the object to be polished is performed.
  • the polishing composition S1 is supplied to the object to be polished, for example, through a polishing pad fixed to the surface plate of the polishing apparatus.
  • the first-stage polishing is typically performed by continuously supplying the polishing composition S1 while pressing the polishing pad against the surface of the object to be polished and moving the two relative to each other. The relative movement can be, for example, rotational movement. After a predetermined time t1 has passed since the start of supply of the polishing composition S1, the supply of the polishing composition S1 is stopped.
  • the supply of the polishing composition S2 is started at an appropriate time after the supply of the polishing composition S1 is started, and the second stage of polishing by supplying the polishing composition S2 to the surface to be polished is performed for a predetermined time t2. over a period of time. After the first stage and the second stage thus performed, the polishing process is completed.
  • the supply of the polishing composition S2 may be started substantially at the same time as the supply of the polishing composition S1 is stopped, or may be started at an interval after the supply of the polishing composition S1 is stopped.
  • the supply of the polishing composition S2 may be started before the supply of the polishing composition S1 is stopped. That is, the supply timing of the polishing composition S1 and the supply timing of the polishing composition S2 may partially overlap.
  • the supply amount may be changed gradually, stepwise, or may be changed all at once.
  • supplying the polishing compositions S1 and S2 in this order means that the supply of the polishing composition S2 is started later than the supply of the polishing composition S1.
  • the supply of the polishing composition S2 is started after the supply of the polishing composition S1 is started, and the supply of the polishing composition S2 is stopped.
  • An example is an embodiment in which the supply of the polishing composition S1 is stopped before.
  • a period for polishing by supplying the polishing composition S1 without supplying the polishing composition S2 and a period for supplying the polishing composition S2 without supplying the polishing composition S1 have in this order. It is preferable that the supply of the polishing composition S2 is started at approximately the same time as or before the supply of the polishing composition S1 is stopped.
  • the relationship between the first stage polishing time t1 and the second stage polishing time t2 is not particularly limited.
  • the first stage polishing time t1 can be longer than the second stage polishing time t2. That is, in the polishing method disclosed herein, the time t2 for supplying the polishing composition S2 to the object to be polished and polishing is longer than the time t1 for supplying the polishing composition S1 to the object to be polished and polishing. It can be implemented in a short mode (that is, the ratio of polishing time t2 to polishing time t1 (t2/t1) is less than 1).
  • the technology disclosed herein can efficiently improve surface accuracy in the second step. As a result, even if the time for polishing with the polishing composition S2 is relatively shortened, it is possible to favorably remove post-processing damage and improve the surface quality.
  • the ratio of polishing time t2 to polishing time t1, ie, t2/t1, may be, for example, less than 0.5, less than 0.4, or less than 0.3. Also, from the viewpoint of improving the surface accuracy, t2/t1 is preferably 0.01 or more, and may be 0.02 or more.
  • the polishing time t2 is usually appropriate to be 5 seconds or more from the viewpoint of improving the surface accuracy and easiness of process control, and may be 10 seconds or more, or 20 seconds or more. Further, from the viewpoint of suppressing a decrease in the polishing rate of the polishing process as a whole, the polishing time t2 can be, for example, 5 minutes or less, 3 minutes or less, or 1.5 minutes or less. In some aspects, the polishing time t2 may be 1 minute or less, 0.75 minutes or less, or 0.6 minutes or less.
  • the total length of the first stage polishing time t1 and the second stage polishing time t2, ie, t1+t2, is not particularly limited. From the viewpoint of improving productivity, in some aspects, t1+t2 may be, for example, 30 minutes or less, 20 minutes or less, or 10 minutes or less. Also, from the viewpoint of improving the surface precision, in some aspects, t1+t2 can be set to, for example, 0.25 minutes or longer, 0.5 minutes or longer, or 1 minute or longer.
  • Each polishing slurry may be in a concentrated form before being supplied to the object to be polished.
  • the concentrated form is the form of a concentrated solution of the polishing slurry, and can also be understood as the undiluted solution of the polishing slurry.
  • Such a concentrate is advantageous from the viewpoints of convenience and cost reduction in manufacturing, distribution, storage, and the like.
  • the concentrate can be diluted at a desired timing to prepare a polishing slurry (working slurry), and the polishing slurry can be supplied to an object to be polished.
  • the dilution can be performed, for example, by adding water to the concentrate and mixing.
  • the concentration ratio of the concentrate is not particularly limited.
  • the concentration ratio can be, for example, about 2 to 100 times in terms of volume, may be about 5 to 50 times, and may be, for example, about 10 to 40 times.
  • the polishing slurry or its concentrate used in the technology disclosed herein may be a single-component type or a multi-component type including a two-component type.
  • the polishing slurry is prepared by mixing part A containing at least abrasive grains and part B containing the remaining components among the components of the polishing slurry, and diluting at an appropriate timing as necessary. may be configured.
  • each component contained in the polishing slurry or its concentrate may be mixed using a well-known mixing device such as a blade stirrer, an ultrasonic disperser, or a homomixer.
  • a well-known mixing device such as a blade stirrer, an ultrasonic disperser, or a homomixer.
  • the manner in which these components are mixed is not particularly limited. For example, all the components may be mixed at once, or they may be mixed in an appropriately set order.
  • the polishing slurry can be used in a so-called "flow-through" manner, that is, in a manner that is disposable once used for polishing.
  • the polishing slurry may be circulated and used repeatedly.
  • a mode of recycling polishing slurry there is a mode in which used polishing slurry discharged from a polishing apparatus is recovered in a tank and the recovered polishing slurry is supplied to the polishing apparatus again.
  • the polishing method disclosed herein can be preferably carried out in a mode in which both the polishing composition S1 and the polishing composition S2 are used in a free-flowing manner.
  • the polishing pad used in the polishing method disclosed here is not particularly limited.
  • a polyurethane foam type, non-woven fabric type, suede type polishing pad can be used.
  • Each polishing pad may or may not contain abrasive grains.
  • a polishing pad containing no abrasive grains is preferably used.
  • the polishing method disclosed herein can be part of the manufacturing process of a polished object (eg, silicon wafer). Therefore, according to this specification, there is provided a method for manufacturing a polished object (for example, a silicon wafer), which includes the polishing method described above. This specification also provides a polished object (for example, a silicon wafer) obtained by applying the above polishing method or manufacturing method.
  • a polished object for example, a silicon wafer
  • the above-described polishing step of supplying polishing composition S1 and polishing composition S2 in this order onto the same platen for polishing is performed by, for example, It can be a step of polishing (typically final polishing or polishing just before) a silicon wafer whose surface state has an Ra of 0.01 nm to 100 nm.
  • Ra is the arithmetic mean roughness measured by a device such as a laser scanning surface roughness meter "TMS-3000WRC" manufactured by Schmitt Measurement System Inc., for example.
  • the final polishing step refers to the last polishing step in the manufacturing process of the object (that is, a step in which no further polishing is performed after that step).
  • the polishing composition disclosed herein also refers to a polishing step (a pre-polishing step between the rough polishing step and the final polishing step) upstream of the final polishing step. , and may also include secondary, tertiary, etc. polishing steps.), for example, it may be used in a polishing step that is performed immediately before final polishing.
  • the first step of supplying the polishing composition S1 and polishing is regarded as a final polishing step
  • the second step of supplying and polishing the polishing composition S2 is regarded as a rinsing step. It may be grasped. That is, in the technology disclosed herein, for example, the first stage of polishing by supplying the polishing composition S1 is performed as a final polishing process or a part thereof, and the second stage is performed by supplying the polishing composition S2. It can be implemented in a mode performed as a rinse step or a part thereof.
  • the first stage of polishing by supplying the polishing composition S1 is performed as a preliminary polishing process or a part thereof, and the second stage is performed by supplying the polishing composition S2. It can be carried out in a manner performed as a final polishing step or a part thereof.
  • the polishing apparatus used in the above-described polishing step in which the polishing composition S1 and the polishing composition S2 are supplied in this order onto the same platen to polish both surfaces of the object to be polished. It may be a double-sided polishing machine that polishes simultaneously, or a single-sided polishing machine that polishes only one side of the object to be polished.
  • a single-sided polishing device can be preferably employed as the polishing device for performing the polishing step.
  • a double-sided polishing apparatus can be preferably employed as the polishing apparatus for performing the preliminary polishing process.
  • each polishing apparatus may be one or two or more.
  • Each polishing apparatus may be a single-wafer type polishing apparatus configured to polish one polishing object at a time, or may be configured to simultaneously polish a plurality of polishing objects on the same surface plate.
  • a batch-type polishing apparatus may also be used.
  • Substrates polished with the polishing compositions disclosed herein are typically washed. Washing can be performed using a suitable washing liquid.
  • the cleaning solution to be used is not particularly limited. (mixture of HCl, H 2 O 2 and H 2 O), SC-2 cleaning solution (mixture of HCl, H 2 O 2 and H 2 O).
  • the temperature of the cleaning solution can range, for example, from room temperature (typically about 15°C to 25°C) to about 90°C. From the viewpoint of improving the cleaning effect, a cleaning solution having a temperature of about 50°C to 85°C can be preferably used.
  • a polishing composition set that can be preferably used in the polishing method disclosed herein.
  • the polishing composition set includes at least a first composition and a second composition that are stored separately from each other.
  • the first composition may be the polishing composition S1 or its concentrate.
  • the second composition may be the polishing composition S2 or its concentrate.
  • the polishing method disclosed herein can be suitably carried out using such a polishing composition set. Therefore, the above-mentioned polishing composition set can be preferably used for the polishing method disclosed herein, a method for manufacturing a polished article including carrying out the polishing method, and the like.
  • Each of the first composition and the second composition that constitute the polishing composition set may be of a one-component type or a multi-component type including a two-component type.
  • the multi-component composition is stored separately, for example, in part A containing at least abrasive grains among the constituent components of each composition, and part B containing the remaining components, and the part A and the part B are stored separately.
  • a polishing slurry may be prepared by mixing and diluting at appropriate times as needed.
  • the abrasive grains A1 have an average particle diameter (average secondary particle diameter (average secondary particle diameter ( D2 A1 )) ratio (D2 A1 /D1 A1 ) is 1.5 or more
  • the abrasive grains A2 have an average particle diameter (average secondary particle diameter (average secondary particle diameter ( D2 A2 )) ratio (D2 A2 /D1 A2 ) is less than 1.5.
  • polishing composition S1 further contains a water-soluble polymer.
  • polishing composition S2 further contains a water-soluble polymer.
  • abrasive grains A1 are silica particles (preferably colloidal silica).
  • the abrasive grains A2 are silica particles (preferably colloidal silica).
  • the polishing step is a final polishing step for an object to be polished (for example, a silicon wafer), Further comprising, prior to the final polishing step, a preliminary polishing step of supplying a preliminary polishing composition to the object to be polished on a polishing platen different from the polishing platen to polish the object to be polished.
  • the polishing method according to any one of (15).
  • a method for producing an object to be polished eg, a silicon wafer
  • polishing the object eg, a silicon wafer
  • Ammonia was used as the basic compound.
  • the surfactant polyoxyethylene (ethylene oxide addition mole number: 5) decyl ether (hereinafter referred to as "C10EO5") having a molecular weight of 378 was used.
  • a slurry a was obtained by diluting the concentrated liquid of the polishing composition with water. The content of each component in the slurry a is 0.10% abrasive, 0.006% PACMO, 0.003% PVA, 0.005% basic compound, and 0.0006% surfactant. there were.
  • Slurry b and slurry c Colloidal silica having an average primary particle diameter (D1) and an average secondary particle diameter (D2) of the values shown in Table 1 is used as abrasive grains, and the content of abrasive grains is as shown in Table 1.
  • Slurries b and slurries c were prepared in the same manner as slurry a, except for the above.
  • the content of each component other than abrasive grains in slurry b and slurry c is 0.006% for PACMO, 0.003% for PVA, 0.005% for basic compound, and 0.0006% for surfactant. %Met.
  • a polishing composition comprising abrasive grains, PACMO as a water-soluble polymer and an acetalized polyvinyl alcohol polymer (hereinafter referred to as "ac-PVA"), a basic compound, a surfactant, and the balance being water.
  • ac-PVA acetalized polyvinyl alcohol polymer
  • Colloidal silica having an average primary particle size (D1) of 40 nm and an average secondary particle size (D2) of 52 nm was used as abrasive grains.
  • PACMO with Mw of 35 ⁇ 10 4 was used.
  • the ac-PVA used had an Mw of 1.3 ⁇ 10 4 and a degree of acetalization of 30 mol %.
  • Ammonia was used as the basic compound.
  • C10EO5 with a molecular weight of 378 was used as a surfactant.
  • a slurry d was obtained by diluting the concentrated liquid of the polishing composition with water. The content of each component in slurry d is 0.11% abrasive grains, 0.004% PACMO, 0.003% ac-PVA, 0.005% basic compound, and 0.001 surfactant. %Met.
  • Pre-polishing composition containing 0.6% abrasive grains, 0.08% tetramethylammonium hydroxide (TMAH) as a basic compound, 0.0002% hydroxyethyl cellulose (HEC) as a water-soluble polymer, and the balance being water
  • TMAH tetramethylammonium hydroxide
  • HEC hydroxyethyl cellulose
  • a concentrate was prepared.
  • Colloidal silica having a BET diameter of 35 nm was used as abrasive grains.
  • a polishing liquid obtained by diluting this pre-polishing composition with water was used as a working slurry to polish a silicon wafer under the following pre-polishing conditions.
  • As the silicon wafer a commercially available silicon single crystal wafer (conductivity type: P type, crystal orientation: ⁇ 100>, COP free) with a diameter of 300 mm was used.
  • Polishing device Sheet-fed polishing machine manufactured by Okamoto Machine Tool Co., Ltd., model "PNX-332B” Polishing load: 20kPa Surface plate rotation speed: 20 rpm Head (carrier) rotation speed: 20 rpm Polishing pad: manufactured by Fujibo Ehime Co., Ltd., product name “FP55” Polishing liquid supply rate: 1 liter/min Polishing liquid temperature: 20°C Surface plate cooling water temperature: 20°C Polishing time: 240 seconds
  • Example 1 The silicon wafer that had undergone the pre-polishing step was polished under the following polishing conditions. Specifically, on the same platen of the polishing apparatus described below, slurry a as the first polishing composition S1 and slurry b as the second polishing composition S2 are supplied, and the pre-polishing step is performed. The finished silicon wafer was polished.
  • Polishing device Sheet-fed polishing machine manufactured by Okamoto Machine Tool Co., Ltd., model "PNX-332B” Polishing load: 20kPa Surface plate rotation speed: 52 rpm Head (carrier) rotation speed: 50 rpm Polishing pad: manufactured by Fujibo Ehime Co., Ltd., product name “POLYPAS275NX” Polishing liquid supply rate: 1.5 liters/min Polishing liquid temperature: 20°C Surface plate cooling water temperature: 20°C
  • the silicon wafer that had undergone the pre-polishing step was set in the polishing apparatus under the above polishing conditions, slurry a was supplied, and polishing was started under the above polishing conditions. After 210 seconds from the start of supply of slurry a, the supply of slurry a was stopped, and at the same time the supply of slurry b was started to further polish the silicon wafer under the above polishing conditions. 30 seconds after the start of supply of slurry b, the supply of slurry b and the operation of the polishing apparatus were stopped, and polishing was completed.
  • SC-1 wash More specifically, a first cleaning tank equipped with an ultrasonic oscillator is prepared, the cleaning solution is contained in the first cleaning tank, the temperature is maintained at 70° C., and the polished silicon wafer is immersed in the cleaning tank for 6 minutes. did. After that, the silicon wafer was immersed in a second cleaning tank containing ultrapure water for 15 minutes, then immersed again in the first cleaning tank for 6 minutes and in the second cleaning tank for 16 minutes, and then dried.
  • Examples 2-6 Silicon wafers were polished in the same manner as in Example 1, except that the types of the polishing composition S1 used in the first liquid and the polishing composition S2 used in the second liquid were as shown in Table 1.

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Abstract

L'invention concerne un procédé de polissage permettant de réduire les défauts sur la surface d'un objet à polir. Le procédé de polissage comprend une étape de polissage consistant à fournir une composition de polissage S1 contenant des grains abrasifs A1 et une composition de polissage S2 contenant des grains abrasifs A2 dans cet ordre sur la même plaque de polissage pour polir un objet d'intérêt. Par rapport aux grains abrasifs A1, le rapport (D2A1/D1A1) d'un diamètre moyen de grain (D2A1) qui est mesuré par le procédé de diffusion dynamique de lumière sur un diamètre de grain (D1A1) qui est converti à partir d'une surface spécifique mesurée par la méthode BET est de 1,5 ou plus. Par rapport aux grains abrasifs A2, le rapport (D2A2/D1A2) d'un diamètre moyen de grain (D2A2) qui est mesuré par le procédé de diffusion dynamique de lumière sur un diamètre de grain (D1A2) qui est converti à partir d'une surface spécifique mesurée par la méthode BET est inférieur à 1,5.
PCT/JP2022/010879 2021-03-30 2022-03-11 Procédé de polissage et ensemble de composition de polissage WO2022209758A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010080499A (ja) * 2008-09-24 2010-04-08 Fujifilm Corp 研磨液
WO2015019706A1 (fr) * 2013-08-09 2015-02-12 株式会社フジミインコーポレーテッド Procédé pour produire un objet poli et ensemble de compositions pour le polissage
WO2019017407A1 (fr) * 2017-07-21 2019-01-24 株式会社フジミインコーポレーテッド Procédé de polissage d'un substrat, et ensemble de composition de polissage
WO2019043890A1 (fr) * 2017-08-31 2019-03-07 株式会社Sumco Procédé de fabrication d'une plaquette de semi-conducteur
WO2019077687A1 (fr) * 2017-10-17 2019-04-25 株式会社Sumco Procédé de polissage de tranche de silicium
JP2020158752A (ja) * 2019-03-22 2020-10-01 株式会社フジミインコーポレーテッド 研磨用組成物および研磨方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010080499A (ja) * 2008-09-24 2010-04-08 Fujifilm Corp 研磨液
WO2015019706A1 (fr) * 2013-08-09 2015-02-12 株式会社フジミインコーポレーテッド Procédé pour produire un objet poli et ensemble de compositions pour le polissage
WO2019017407A1 (fr) * 2017-07-21 2019-01-24 株式会社フジミインコーポレーテッド Procédé de polissage d'un substrat, et ensemble de composition de polissage
WO2019043890A1 (fr) * 2017-08-31 2019-03-07 株式会社Sumco Procédé de fabrication d'une plaquette de semi-conducteur
WO2019077687A1 (fr) * 2017-10-17 2019-04-25 株式会社Sumco Procédé de polissage de tranche de silicium
JP2020158752A (ja) * 2019-03-22 2020-10-01 株式会社フジミインコーポレーテッド 研磨用組成物および研磨方法

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