WO2022065022A1 - Composition de polissage et utilisation associée - Google Patents

Composition de polissage et utilisation associée Download PDF

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Publication number
WO2022065022A1
WO2022065022A1 PCT/JP2021/032805 JP2021032805W WO2022065022A1 WO 2022065022 A1 WO2022065022 A1 WO 2022065022A1 JP 2021032805 W JP2021032805 W JP 2021032805W WO 2022065022 A1 WO2022065022 A1 WO 2022065022A1
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Prior art keywords
polishing
weight
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polishing composition
polymer
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PCT/JP2021/032805
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English (en)
Japanese (ja)
Inventor
修 後藤
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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Priority to JP2022551846A priority Critical patent/JPWO2022065022A1/ja
Publication of WO2022065022A1 publication Critical patent/WO2022065022A1/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
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a polishing composition and a polishing method using the polishing composition.
  • the surface of a silicon wafer used as a component of a semiconductor product is generally finished into a high-quality mirror surface through a wrapping step (rough polishing step) and a polishing step (precision polishing step).
  • the polishing step typically includes a pre-polishing step (pre-polishing step) and a finishing polishing step (final polishing step).
  • Patent Documents 1 and 2 Examples of documents disclosing the polishing composition include Patent Documents 1 and 2.
  • Patent Document 1 discloses a polishing slurry composition used for polishing an ITO film transparent substrate or the like.
  • Patent Document 2 discloses that a thermoplastic silicon, a silicon nitride film, and a silicon oxide film are polished by using a polishing composition.
  • an object of the present invention is to provide a polishing composition capable of reducing the haze of the substrate after polishing.
  • a polishing composition contains abrasive grains, a basic compound, water, and a compound represented by the following formula (I) (hereinafter, also referred to as a "urea-based compound” for convenience). According to such a polishing composition, haze on the surface of the substrate after polishing can be reduced.
  • R 1 , R 2 , R 3 and R 4 in the formula (I) are each independently selected from the group consisting of hydrogen, an alkyl group, a hydroxyl group, and a hydroxyalkyl group. (I) If there is no hydroxyl group in (I), the total number of carbon atoms of R 1 , R 2 , R 3 and R 4 is 1 or more.)
  • the content of the urea compound is 0.001% by weight or more and 0.1% by weight or less.
  • the haze reducing effect can be preferably exhibited.
  • the polishing composition further comprises a water-soluble polymer.
  • the haze reducing effect of the technique disclosed herein can be preferably exhibited in a composition containing a urea-based compound and a water-soluble polymer.
  • the pH of the polishing composition is 8.0 or more and 12.0 or less. In a composition having a pH in the above range, the effects of the techniques disclosed herein can be preferably exerted.
  • the polishing composition disclosed here is suitable for polishing a silicon wafer. By performing polishing on a silicon wafer using the above-mentioned polishing composition, haze can be reduced and a high-quality silicon wafer surface can be suitably realized.
  • the polishing composition disclosed herein can be preferably used in the finishing polishing step of a silicon wafer.
  • the polishing method includes a polishing step.
  • the substrate is polished using a polishing composition containing abrasive grains, a basic compound, water, and a urea-based compound represented by the above formula (I).
  • the polishing method provided herein is, in some embodiments, a method for polishing a silicon wafer. That is, the haze reduction effect of the technique disclosed herein is suitably realized in polishing a silicon wafer.
  • the polishing method comprises a pre-polishing step and a finishing polishing step.
  • polishing using the polishing composition disclosed herein is carried out.
  • polishing method in the finish polishing step, it is possible to obtain a higher quality silicon wafer surface in which the haze of the wafer surface after polishing is reduced.
  • the polishing composition disclosed herein comprises abrasive grains.
  • Abrasive grains serve to mechanically polish the surface of the substrate.
  • the material and properties of the abrasive grains are not particularly limited, and can be appropriately selected depending on the purpose and mode of use of the polishing composition.
  • Examples of abrasive grains include inorganic particles, organic particles, and organic-inorganic composite particles.
  • the inorganic particles include silica particles, alumina particles, cerium oxide particles, chromium oxide particles, titanium dioxide particles, zirconium oxide particles, magnesium oxide particles, manganese dioxide particles, zinc oxide particles, and oxide particles such as red iron oxide particles; Nitride particles such as silicon nitride particles and boron nitride particles; carbide particles such as silicon carbide particles and boron carbide particles; diamond particles; carbonates such as calcium carbonate and barium carbonate can be mentioned.
  • the organic particles include polymethylmethacrylate (PMMA) particles and poly (meth) acrylic acid particles (here, (meth) acrylic acid means to comprehensively refer to acrylic acid and methacrylic acid). , Polyacrylonitrile particles and the like. Such abrasive grains may be used alone or in combination of two or more.
  • abrasive grains inorganic particles are preferable, particles made of a metal or metalloid oxide are preferable, and silica particles are particularly preferable.
  • a polishing composition that can be used for polishing a substrate having a surface made of silicon (for example, finish polishing) such as a silicon wafer described later, it is particularly meaningful to use silica particles as abrasive grains.
  • the technique disclosed herein can be preferably carried out, for example, in an embodiment in which the abrasive grains are substantially composed of silica particles.
  • substantially means 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 means that it is a silica particle.
  • silica particles include colloidal silica, fumed silica, and precipitated silica.
  • the silica particles may be used alone or in combination of two or more.
  • the use of colloidal silica is particularly preferable because it is easy to obtain a polished surface having excellent surface quality after polishing.
  • colloidal silica for example, colloidal silica produced from water glass (Na silicate) by an ion exchange method or colloidal silica produced by an alkoxide method (coroidal silica produced by a hydrolysis condensation reaction of alkoxysilane) is preferably adopted. be able to.
  • Colloidal silica can be used alone or in combination of two or more.
  • the true specific gravity of the abrasive grain constituent material is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more.
  • the upper limit of the true specific gravity of silica is not particularly limited, but is typically 2.3 or less, preferably 2.2 or less, still more preferably 2.0 or less, and for example, 1.9 or less.
  • a measured value by a liquid replacement method using ethanol as a replacement liquid can be adopted.
  • the average primary particle diameter of the abrasive grains is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more from the viewpoint of polishing efficiency and the like. 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 is preferably 15 nm or more, and more preferably 20 nm or more (for example, more than 20 nm). Further, from the viewpoint of scratch prevention and the like, the average primary particle diameter of the abrasive grains is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 45 nm or less.
  • the average primary particle size of the abrasive grains may be 43 nm or less, less than 40 nm, less than 38 nm, less than 35 nm, less than 32 nm, from the viewpoint of facilitating a lower haze surface. It may be less than 30 nm.
  • the specific surface area can be measured using, for example, a surface area measuring device manufactured by Micromeritex, trade name "Flow Sorb II 2300".
  • the average secondary particle diameter of the abrasive grains is not particularly limited, and can be appropriately selected from the range of, for example, about 15 nm to 300 nm. From the viewpoint of improving the polishing efficiency, the average secondary particle diameter is preferably 30 nm or more, and more preferably 35 nm or more. In some embodiments, the average secondary particle size may be, for example, 40 nm or more, 42 nm or more, and preferably 44 nm or more. Further, the average secondary particle diameter is usually preferably 250 nm or less, preferably 200 nm or less, and more preferably 150 nm or less. In some preferred embodiments, the average secondary particle diameter is 120 nm or less, more preferably 100 nm or less, still more preferably 70 nm or less, for example 60 nm or less, or 50 nm or less.
  • the average secondary particle diameter means the particle diameter (volume average particle diameter) measured by the dynamic light scattering method.
  • the average secondary particle diameter of the abrasive grains can be measured, for example, by a dynamic light scattering method using "Nanotrack (registered trademark) UPA-UT151” manufactured by Nikkiso Co., Ltd.
  • the shape (outer shape) of the abrasive grains may be spherical or non-spherical.
  • the non-spherical particles include a peanut shape (that is, a peanut shell shape), a cocoon shape, a konpeito shape, a rugby ball shape, and the like.
  • abrasive grains in which many of the particles are peanut-shaped or cocoon-shaped can be preferably adopted.
  • the average value (average aspect ratio) of the major axis / minor axis ratio of the abrasive grains is, in principle, 1.0 or more, preferably 1.05 or more, and more preferably 1.1 or more. Is. Higher polishing efficiency can be achieved by increasing the average aspect ratio.
  • the average aspect ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.5 or less, from the viewpoint of scratch reduction and the like.
  • the shape (outer shape) and average aspect ratio of the abrasive grains can be grasped by, for example, observing with an electron microscope.
  • a specific procedure for grasping the average aspect ratio for example, for a predetermined number (for example, 200) of abrasive particles that can recognize the shape of independent particles using a scanning electron microscope (SEM), each particle is used.
  • the value obtained by dividing the length of the long side (value of the major axis) by the length of the short side (value of the minor axis) is the major axis / minor axis ratio (aspect ratio).
  • the average aspect ratio can be obtained by arithmetically averaging the aspect ratios of the predetermined number of particles.
  • the content of the abrasive grains in the polishing composition is not particularly limited, and is, for example, 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.10% by weight or more, still more preferably. Is 0.15% by weight or more. Higher polishing efficiency can be achieved by increasing the abrasive grain content.
  • the content is preferably 10% by weight or less, preferably 7% by weight or less, more preferably 5% by weight or less, still more preferably 2% by weight or less, and may be, for example, 1% by weight or less. It may be 0.5% by weight or less, or 0.4% by weight or less. This makes it possible to realize a surface with a lower haze.
  • the above-mentioned abrasive grain content can be preferably adopted in an embodiment in which the polishing composition is used in the form of a polishing liquid (working slurry).
  • the polishing composition disclosed herein contains a basic compound.
  • the term "basic compound” refers to a compound having a function of dissolving in water and raising the pH of an aqueous solution.
  • the basic compound 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.
  • phosphorus-containing basic compounds include quaternary phosphonium compounds. Such basic compounds may be used alone or in combination of two or more.
  • alkali metal hydroxides include potassium hydroxide, sodium hydroxide and the like.
  • specific examples of the carbonate or hydrogen carbonate include ammonium hydrogen carbonate, ammonium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate, 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 include quaternary phosphonium hydroxides such as tetramethylphosphonium hydroxide and tetraethylphosphonium hydroxide.
  • quaternary ammonium salt typically a strong base
  • a quaternary ammonium salt such as a tetraalkylammonium salt or a hydroxyalkyltrialkylammonium salt
  • the anionic component in such a quaternary ammonium salt can be, for example, OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , ClO 4- , BH 4- and the like.
  • examples of the quaternary ammonium compound include a quaternary ammonium salt having an anion of OH ⁇ , that is, a quaternary ammonium hydroxide.
  • quaternary ammonium hydroxide examples include hydroxylation of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide and tetrahexylammonium hydroxide.
  • At least one basic compound selected from alkali metal hydroxides, quaternary ammonium hydroxides and ammonia can be preferably used.
  • tetraalkylammonium hydroxide for example, tetramethylammonium hydroxide
  • ammonia is particularly preferable.
  • the content of the basic compound with respect to the total amount of the polishing composition is not particularly limited. From the viewpoint of improving polishing efficiency, it is usually appropriate to set the above content to 0.0005% by weight or more, preferably 0.001% by weight or more, and 0.003% by weight or more. Is even more preferable. Further, from the viewpoint of haze reduction and the like, the content is preferably less than 0.1% by weight, preferably less than 0.05% by weight, and less than 0.03% by weight (for example, 0. It is more preferably less than 025% by weight, more preferably less than 0.01% by weight). When two or more kinds are used in combination, the above-mentioned content refers to the total content of two or more kinds of basic compounds. These contents can be preferably applied to the content in the polishing liquid (working slurry) supplied to the substrate, for example.
  • ion-exchanged water deionized water
  • pure water ultrapure water
  • distilled water distilled water
  • the water used preferably has, for example, a total content of transition metal ions of 100 ppb or less in order to avoid hindering the action of other components contained in the polishing composition as much as possible.
  • the purity of water can be increased by operations such as removal of impurity ions by an ion exchange resin, removal of foreign substances by a filter, and distillation.
  • the polishing composition disclosed herein may further contain an organic solvent (lower alcohol, lower ketone, etc.) that can be uniformly mixed with water, if necessary. It is preferable that 90% by volume or more of the solvent contained in the polishing composition is water, and more preferably 95% by volume or more (for example, 99 to 100% by volume) is water.
  • the polishing composition disclosed herein contains a compound represented by the following formula (I) (a compound containing a urea structure, that is, a urea-based compound).
  • R 1 , R 2 , R 3 and R 4 in the following formula (I) are independently selected from the group consisting of hydrogen, an alkyl group, a hydroxyl group, and a hydroxyalkyl group. be.
  • the hydroxyl group is not present in the following formula (I)
  • the total carbon number of R 1 , R 2 , R 3 and R 4 is 1 or more.
  • the total carbon number of R1 , R2 , R3 and R4 may be 1 or more and less than 1 (that is, the total carbon number). May be 0).
  • one kind of urea-based compound represented by the following formula (I) may be used alone, or two or more kinds may be used in combination.
  • the total carbon number of R 1 , R 2 , R 3 and R 4 in the above formula (I) is 1 or more (for example, 1 to 10). ), For example, 2 or more, preferably 3 or more (for example, 3 to 10), more preferably 4 or more (for example, 4 to 8, preferably 4 to 6).
  • R 1 , R 2 , R 3 and R 4 in the above formula (I) contain 1 or 2 or more alkyl groups, the carbon number of each alkyl group is not particularly limited, and is preferably 1 to 10, for example. Is 1 to 4 (eg 1, 2, or 3).
  • the number of alkyl groups in the urea compound is selected from the range of 1 to 4 (eg, 2, 3 or 4).
  • R 1 , R 2 , R 3 and R 4 in the above formula (I) may or may not contain hydrogen.
  • the number of hydrogen is 1 to 3, for example 1 or 2.
  • Examples of such urea-based compounds include 1-methylurea, 1-ethylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1-propylurea, 1,1,3-trimethylurea and 1-butyl.
  • Examples thereof include urea, 1,1-diethyl urea, 1,3-diethyl urea, tetramethylurea and tetraethylurea.
  • 1-propylurea, 1,1,3-trimethylurea, 1-butylurea, 1,1-diethylurea, 1,3-diethylurea, tetramethylurea, tetraethylurea and the like can be preferably used.
  • R 1 , R 2 , R 3 and R 4 in the above formula (I) have one or more hydroxyl groups or hydroxyalkyl groups (1 or more). For example, 1 to 4, preferably 2 or 3) are included. From the viewpoint of effectively reducing haze, a urea-based compound containing a hydroxyl group is preferable.
  • all of R 1 , R 2 , R 3 and R 4 may be a hydroxyl group or a hydroxyalkyl group, and 1 or 2 of the above R 1 , R 2 , R 3 and R 4 may be used.
  • 3 has a group selected from a hydroxyl group and a hydroxyalkyl group.
  • the total carbon number of R 1 , R 2 , R 3 and R 4 may be 1 or more (for example, 1 to 10) and less than 1 (for example, 1 to 10). That is, the total number of carbon atoms may be 0).
  • the hydroxyalkyl group has, for example, 1 to 10 carbon atoms, preferably 1 to 4 (more preferably 1 or 2).
  • R 1 , R 2 , R 3 and R 4 in the above formula (I) may or may not contain an alkyl group.
  • the carbon number of each alkyl group is not particularly limited, and is, for example, 1 to 10, preferably 1 to 4 (for example, 1 to 4). 1, 2, or 3).
  • the number of alkyl groups in the urea compound is selected from the range of 0 to 3 (eg, 0, 1 or 2).
  • R 1 , R 2 , R 3 and R 4 in the above formula (I) do not have to be hydrogen, and at least one of R 1 , R 2 , R 3 and R 4 may be hydrogen.
  • R 1 , R 2 , R 3 and R 4 in the above formula (I) contain hydrogen
  • the number of hydrogen is 1 to 3, for example, 1 or 2.
  • urea-based compounds include hydroxyurea, 2-hydroxymethylurea, 2-hydroxyethylurea, 2-hydroxypropylurea, 2-hydroxybutylurea, 1,3- (hydroxymethyl) urea, and 1,3-. (Hydroxyethyl) urea and the like can be mentioned. Among them, 1,3- (hydroxymethyl) urea can be preferably used.
  • the molecular weight of the urea compound may be 74 or more, may be 76 or more, preferably 90 or more, more preferably 100 or more, and may be 110 or more.
  • the upper limit of the molecular weight is not limited to a specific range, and is, for example, 300 or less, and may be 200 or less or 150 or less from the viewpoint of solubility in a polishing composition or the like.
  • the molecular weight of the urea compound the molecular weight calculated from the chemical formula is adopted.
  • the content of the urea-based compound in the polishing composition is not particularly limited as long as the effect of the technique disclosed herein is exhibited, and from the viewpoint of exhibiting the effect of adding the urea-based compound (that is, the haze reducing effect). It can be 0.0001% by weight or more, preferably 0.001% by weight or more, and may be 0.002% by weight or more, or 0.003% by weight or more. In some preferred embodiments, the content of the urea compound in the polishing composition is 0.005% by weight or more, more preferably 0.01% by weight or more, still more preferably 0.03% by weight or more. ..
  • the upper limit of the content of the urea compound is not particularly limited, and is, for example, 1% by weight or less, preferably 0.1% by weight or less (less than 0.1% by weight), and more preferably 0. It is 08% by weight or less, and may be 0.06% by weight or less.
  • the content is the total content (weight-based content) of all the urea compounds contained in the polishing composition. To say.
  • the polishing composition disclosed herein may contain a water-soluble polymer.
  • the water-soluble polymer can be useful for protecting the surface of the substrate, improving the wettability of the surface of the substrate after polishing, and the like.
  • the water-soluble polymer is a compound containing a hydroxyl group, a carboxy group, an acyloxy group, a sulfo group, an amide structure, an imide structure, a quaternary ammonium structure, a heterocyclic structure, a vinyl structure, or the like. Can be mentioned.
  • the water-soluble polymer for example, a cellulose derivative, a starch derivative, a polymer containing an oxyalkylene unit, a polyvinyl alcohol-based polymer, a polymer containing a nitrogen atom, or the like is used, and as one embodiment of the polymer containing a nitrogen atom, N- Vinyl type polymers, N- (meth) acryloyl type polymers and the like can be used.
  • the water-soluble polymer may be a polymer derived from a natural product or a synthetic polymer. As the water-soluble polymer, one type may be used alone, or two or more types may be used in combination.
  • a polymer derived from a natural product is used as the water-soluble polymer.
  • examples of polymers derived from natural products include cellulose derivatives and starch derivatives.
  • the polymer derived from a natural product one kind may be used alone, or two or more kinds may be used in combination.
  • a cellulose derivative is used as the water-soluble polymer.
  • the cellulose derivative is a polymer containing ⁇ -glucose unit as a main repeating unit.
  • Specific examples of the cellulose derivative include hydroxyethyl cellulose (HEC), hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose and the like. Among them, HEC is preferable.
  • HEC hydroxyethyl cellulose
  • one type may be used alone, or two or more types may be used in combination.
  • the starch derivative is used as the water-soluble polymer.
  • the starch derivative is a polymer containing an ⁇ -glucose unit as a main repeating unit, and examples thereof include pregelatinized starch, pullulan, carboxymethyl starch, and cyclodextrin.
  • pregelatinized starch pullulan
  • carboxymethyl starch and cyclodextrin.
  • the starch derivative one type may be used alone, or two or more types may be used in combination.
  • synthetic polymers are used as water-soluble polymers.
  • the haze improving effect disclosed herein is preferably exhibited in an embodiment in which a synthetic polymer is used as the water-soluble polymer.
  • a synthetic polymer is used as the water-soluble polymer.
  • the synthetic polymer one kind may be used alone, or two or more kinds may be used in combination.
  • a polymer containing an oxyalkylene unit 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. Among them, a block copolymer of EO and PO or a random copolymer of EO and PO is preferable.
  • the block copolymer of EO and PO can be a diblock copolymer containing a PEO block and a polypropylene oxide (PPO) block, a triblock copolymer, or the like.
  • Examples of the above-mentioned triblock copolymers include PEO-PPO-PEO type triblock copolymers and PPO-PEO-PPO type triblock copolymers. Usually, PEO-PPO-PEO type triblock copolymer is more preferable.
  • copolymer in the present specification comprehensively refers to various copolymers such as random copolymers, alternate copolymers, block copolymers, and graft copolymers. be.
  • the molar ratio (EO / PO) of EO and PO constituting the copolymer is determined from the viewpoint of solubility in water, cleanability, and the like. It is preferably larger than 1, more preferably 2 or more, and even more preferably 3 or more (for example, 5 or more).
  • a polyvinyl alcohol-based polymer is used as the water-soluble polymer.
  • the effects of the techniques disclosed herein are more preferably realized in compositions containing polyvinyl alcohol polymers.
  • the polyvinyl alcohol-based polymer refers to a polymer containing a vinyl alcohol unit (hereinafter, also referred to as “VA unit”) as a repeating unit thereof.
  • VA unit vinyl alcohol unit
  • the polyvinyl alcohol-based polymer may contain only VA units as repeating units, and 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, may be a block copolymer, or may be 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 non-modified PVA is produced by hydrolyzing (saponifying) polyvinyl acetate, and is other than the repeating unit (-CH 2 -CH (OCOCH 3 )-) and the VA unit of the structure in which vinyl acetate is polymerized with vinyl.
  • the saponification degree of the non-modified PVA may be, for example, 60% or more, 70% or more, 80% or more, or 90% or more from the viewpoint of water solubility.
  • the polyvinyl alcohol-based polymer has a VA unit and at least one selected from an oxyalkylene group, a carboxy group, a sulfo group, an amino group, a hydroxyl group, an amide group, an imide group, a nitrile group, an ether group, an ester group, and salts thereof. It may be a modified PVA containing a non-VA unit having a structure.
  • the non-VA unit that can be contained in the modified PVA is, for example, a repeating unit derived from an N-vinyl type monomer or an N- (meth) acryloyl type monomer, which will be described later, a repeating unit derived from ethylene, or an alkyl vinyl ether.
  • N-vinyl type monomer N-vinylpyrrolidone.
  • N- (meth) acryloyl type monomer N- (meth) acryloyl morpholine.
  • the alkyl vinyl ether may be a vinyl ether having an alkyl group having 1 or more and 10 or less carbon atoms, such as propyl vinyl ether, butyl vinyl ether, and 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 carbon atoms and 7 or less carbon atoms, such as vinyl propanoate, vinyl butanoate, vinyl pentanate, vinyl hexanoate and the like.
  • the polyvinyl alcohol-based polymer may be a modified PVA in which a part of the VA unit contained in the polyvinyl alcohol-based polymer is acetalized with an aldehyde.
  • an alkyl aldehyde for example, an alkyl aldehyde can be preferably used, and an alkyl aldehyde having an alkyl group having 1 or more and 7 or less carbon atoms is preferable, and acetaldehyde, n-propyl aldehyde, n-butyl aldehyde, and n-pentyl aldehyde are particularly preferable. Is preferable.
  • a polyvinyl alcohol-based polymer a cationically modified polyvinyl alcohol having a cationic group such as a quaternary ammonium structure introduced may be used.
  • a cationic group derived from a monomer having a cationic group such as a diallyldialkylammonium salt or an N- (meth) acryloylaminoalkyl-N, N, N-trialkylammonium salt is introduced. The ones that have been done are listed.
  • 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 proportion of the number of moles of the VA unit may be 50% or more, 65% or more, 75% or more, or 80% or more. It may be 90% or more (for example, 95% or more, or 98% or more).
  • Substantially 100% of the repeating units constituting the polyvinyl alcohol-based polymer may be VA units.
  • substantially 100% means that the polyvinyl alcohol-based polymer does not contain non-VA units at least intentionally, and typically the number of moles of non-VA units in the number of moles of all repeating units.
  • the ratio of is less than 2% (for example, less than 1%), and includes the case where it is 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. However, it may be 70% or less.
  • the content of VA units (content based on weight) 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, more than 50% by weight).
  • 90% by weight or more, 95% by weight or more, or 98% by weight or more) may be used.
  • Substantially 100% by weight of the repeating units constituting the polyvinyl alcohol-based polymer may be VA units.
  • substantially 100% by weight means that the non-VA unit is not contained as a repeating unit constituting the polyvinyl alcohol-based polymer at least intentionally, and typically, the non-VA unit in the polyvinyl alcohol-based polymer is not contained. It means that the content of is less than 2% by weight (for example, less than 1% by weight). In some other embodiments, 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 a plurality of polymer chains having different contents of VA units in the same molecule.
  • the polymer chain refers to a portion (segment) constituting a part of a single molecule polymer.
  • polyvinyl alcohol-based polymers have a polymer chain A with a VA unit content of more than 50% by weight and a VA unit content of less than 50% by weight (ie, a non-VA unit content of more than 50% by weight).
  • Polymer chain B may be contained in the same molecule.
  • the polymer chain A may contain only VA units as repeating units, and 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 the polymer chain A may be 95% by weight or more, or 98% by weight 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, and may contain VA units in addition to non-VA units.
  • the content of the non-VA unit in the 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 the polymer chain B may be 95% by weight or more, or 98% by weight or more. Substantially 100% by weight of the repeating units constituting the polymer chain B may be non-VA units.
  • polyvinyl alcohol-based polymers containing the polymer chains A and the polymer chains 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), or the polymer chain A (side chain) may be attached to the polymer chain B (main chain). It may be a graft copolymer having a structure in which the chain) is grafted.
  • a polyvinyl alcohol-based polymer having a structure in which the polymer chain B is grafted to the polymer chain A can be used.
  • polymer chain B examples include a polymer chain having a repeating unit derived from an N-vinyl type monomer as a main repeating unit, and a polymer chain having a repeating unit derived from an N- (meth) acryloyl type monomer as a main repeating unit.
  • the main repeating unit means a repeating unit contained in excess of 50% by weight, unless otherwise specified.
  • a preferred example of the polymer chain B is a polymer chain having an N-vinyl type monomer as a main repeating unit, that is, an N-vinyl-based polymer chain.
  • the content of the repeating unit 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. It may be 95% by weight or more.
  • Substantially all of the polymer chain B may be a repeating unit derived from an N-vinyl type monomer.
  • examples of N-vinyl type monomers include monomers having a nitrogen-containing heterocycle (for example, a lactam ring) and N-vinyl chain amides.
  • Specific examples of the N-vinyllactam type monomer include N-vinylpyrrolidone, N-vinylpiperidone, N-vinylmorpholinone, N-vinylcaprolactam, N-vinyl-1,3-oxadin-2-one, and N-vinyl-. Examples thereof include 3,5-morpholindione.
  • Specific examples of the N-vinyl chain amide include N-vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide and the like.
  • the polymer chain B is, for example, an N-vinyl-based polymer chain in which more than 50% by weight (for example, 70% by weight or more, 85% by weight or more, or 95% by weight or more) of the repeating unit is an N-vinylpyrrolidone unit. obtain. Substantially all of the repeating units constituting the polymer chain B may be N-vinylpyrrolidone units.
  • polymer chain B is a polymer chain having a repeating unit derived from an N- (meth) acryloyl type monomer as a main repeating unit, that is, an N- (meth) acryloyl-based polymer chain.
  • the content of the repeating unit derived from the N- (meth) acryloyl type monomer in the N- (meth) acryloyl polymer chain is typically more than 50% by weight, may be 70% by weight or more, and may be 85% by weight. It may be 5% by weight or more, or 95% by weight or more.
  • Substantially all of the polymer chain B may be a repeating unit derived from an N- (meth) acryloyl type monomer.
  • examples of the N- (meth) acryloyl type monomer include a chain amide having an N- (meth) acryloyl group and a cyclic amide having an N- (meth) acryloyl group.
  • Examples of chain amides having an N- (meth) acryloyl group are (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl ( N-alkyl (meth) acrylamide such as meta) acrylamide, Nn-butyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) ) N, N-dialkyl (meth) acrylamide such as acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide; and the like.
  • Examples of cyclic amides having an N- (meth) acryloyl group include N- (meth) acryloy
  • polymer chain B is a polymer chain containing an oxyalkylene unit as a main repeating unit, that is, an oxyalkylene polymer chain.
  • the content of the oxyalkylene unit in the oxyalkylene polymer chain is typically more than 50% by weight, may be 70% by weight or more, may be 85% by weight or more, and may be 95% by weight or more. There may be. Substantially all of the repeating units contained in the polymer chain B may be oxyalkylene units.
  • the oxyalkylene unit examples include an oxyethylene unit, an oxypropylene unit, an oxybutylene unit and the like. Each such oxyalkylene unit can be a repeating unit derived from the corresponding alkylene oxide.
  • the oxyalkylene unit contained in the oxyalkylene polymer chain may be one kind or two or more kinds. For example, it may be an oxyalkylene polymer chain containing an oxyethylene unit and an oxypropylene unit in combination. In an oxyalkylene polymer chain containing two or more kinds of oxyalkylene units, the oxyalkylene units may be random copolymers of corresponding alkylene oxides, block copolymers, or alternating copolymers. It may be a polymer or a graft copolymer.
  • a polymer chain containing a repeating unit derived from an alkyl vinyl ether for example, a vinyl ether having an alkyl group having 1 or more and 10 or less carbon atoms
  • a monocarboxylic acid vinyl ester for example, the number of carbon atoms
  • examples thereof include a polymer chain containing a repeating unit derived from (vinyl ester of 3 or more monocarboxylic acids), a polymer chain into which a cationic group (for example, a cationic group having a quaternary ammonium structure) is introduced, and the like.
  • the polyvinyl alcohol-based polymer as the water-soluble polymer in the technique disclosed herein is preferably a modified polyvinyl alcohol which is a copolymer containing VA units and non-VA units.
  • the saponification degree of the polyvinyl alcohol-based 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 saponification degree of the polyvinyl alcohol-based polymer is 100 mol% or less.
  • the N-vinyl type polymer may be used as the water-soluble polymer.
  • N-vinyl type polymers include polymers containing repeating units derived from monomers having a nitrogen-containing heterocycle (eg, a lactam ring).
  • examples of such polymers include homopolymers and copolymers of N-vinyl lactam type monomers (for example, copolymers in which the copolymerization ratio of N-vinyl lactam type monomers exceeds 50% by weight), N-vinyl.
  • the homopolymer and the copolymer of the chain amide for example, the copolymer in which the copolymerization ratio of the N-vinyl chain amide exceeds 50% by weight) and the like are included.
  • N-vinyllactam type monomer that is, a compound having a lactam structure and an N-vinyl group in one molecule
  • N-vinylpyrrolidone VP
  • N-vinylpiperidone N-vinylmorpholinone
  • N. -Vinyl caprolactam VC
  • N-vinyl-1,3-oxadin-2-one N-vinyl-3,5-morpholindione and the like can be mentioned.
  • polymers containing N-vinyl lactam type monomer units include polyvinylpyrrolidone, polyvinylcaprolactam, random copolymers of VP and VC, one or both of VP and VC and other vinyl monomers (eg, acrylics). Examples include a random copolymer with (monomer, vinyl ester-based monomer, etc.), a block copolymer containing a polymer chain containing one or both of VP and VC, an alternate copolymer, a graft copolymer, and the like.
  • Specific examples of the N-vinyl chain amide include N-vinylacetamide, N-vinylpropionic acid amide, N-vinylbutyric acid amide and the like.
  • an N- (meth) acryloyl type polymer may 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 weight by weight. % (Copolymer) is included.
  • Examples of N- (meth) acryloyl-type monomers include chain amides having an N- (meth) acryloyl group and cyclic amides having an N- (meth) acryloyl group.
  • Examples of chain amides having an N- (meth) acryloyl group are (meth) acrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl ( N-alkyl (meth) acrylamide such as meta) acrylamide, Nn-butyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) ) N, N-dialkyl (meth) acrylamide such as acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide; and the like.
  • a copolymer of N-isopropylacrylamide and a copolymer of N-isopropylacrylamide for example, a copolymerization ratio of N-isopropylacrylamide Is a copolymer in excess of 50% by weight.
  • Examples of cyclic amides having an N- (meth) acryloyl group are N-acryloylmorpholine, N-acryloylthiomorpholine, N-acryloylpiperidin, N-acryloylpyridine, N-methacryloylmorpholine, N-methacryloylpiperidin, N-methacryloyl.
  • Examples include pyrrolidine.
  • An example of a polymer containing a cyclic amide having an N- (meth) acryloyl group as a monomer unit is an acryloyl morpholine polymer (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 composed of substantially 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 ⁇ 104 or less, and about 150 ⁇ 10 4 or less is appropriate, and from the viewpoint of detergency and the like, it is preferably about 100 ⁇ 104 or less, which is about 100 ⁇ 104 or less. It may be 50 ⁇ 10 4 or less.
  • the Mw of the water-soluble polymer may be, for example, 0.2 ⁇ 104 or more, preferably 0.5 ⁇ 104 or more.
  • the Mw of 1.0 ⁇ 10 4 or more is suitable, and may be 2 ⁇ 10 4 or more, for example, 5 ⁇ 10 4 or more.
  • the range of molecular weights of preferred water-soluble polymeric compounds may vary depending on the type of polymer used.
  • the Mw of the cellulose derivative and the starch derivative can be approximately 200 ⁇ 104 or less, respectively , and 150 ⁇ 104 or less is appropriate.
  • 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).
  • the Mw is, for example, about 0.2 ⁇ 104 or more, about 0.5 ⁇ 104 or more, and preferably about 1.0 ⁇ . It may be 104 or more, more preferably about 3.0 ⁇ 10 4 or more, still more preferably about 10 ⁇ 10 4 or more, and more preferably about 20 ⁇ 10 4 or more.
  • the Mw of the polyvinyl alcohol-based polymer and the polymer containing a nitrogen atom can be 100 ⁇ 10 4 or less, respectively, and 60 ⁇ 10 4 or less is appropriate.
  • 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.
  • Mw may be, for example, 0.2 ⁇ 104 or more, and usually 0.5 ⁇ 104 or more is preferable.
  • Mw of 1.0 ⁇ 104 or more is suitable, preferably 1.5 ⁇ 10 4 or more, more preferably 2 ⁇ 10 4 or more, still more preferably 3 ⁇ 10 4 or more.
  • it may be 4 ⁇ 10 4 or more, or 5 ⁇ 10 4 or more.
  • the Mw of the water-soluble polymer a molecular weight calculated from a value (water-based, in terms of polyethylene oxide) based on water-based gel permeation chromatography (GPC) can be adopted.
  • GPC gel permeation chromatography
  • the GPC measuring device it is preferable to use the model name "HLC-8320GPC" manufactured by Tosoh Corporation. The measurement can be performed under the following conditions, for example. The same method is adopted for the examples described later.
  • a nonionic polymer can be preferably adopted as the water-soluble polymer.
  • a synthetic polymer can be preferably adopted as the water-soluble polymer.
  • the polishing composition is one in which the polymer derived from a natural product is substantially not used as the water-soluble polymer. possible.
  • substantially not used means that the amount of the polymer derived from a natural product used is typically 3 parts by weight or less, preferably 1 part by weight or less, based on 100 parts by weight of the total content of the water-soluble polymer. This means 0 parts by weight or below the detection limit.
  • the content of the water-soluble polymer (content on a weight basis) in the polishing composition is not particularly limited. For example, it can be 1.0 ⁇ 10 -4 % by weight or more. From the viewpoint of haze reduction and the like, the preferable content is 5.0 ⁇ 10 -4 % by weight or more, more preferably 1.0 ⁇ 10 -3 % by weight or more, and further preferably 2.0 ⁇ 10 -3 % by weight. The above is, for example, 5.0 ⁇ 10 -3 % by weight or more. Further, from the viewpoint of polishing removal speed and the like, 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).
  • the polishing composition contains two or more kinds of water-soluble polymers
  • the above-mentioned content is the total content (weight-based content) of all the water-soluble polymers contained in the polishing composition. It means that.
  • These contents can be preferably applied to the content in the polishing liquid (working slurry) supplied to the substrate, for example.
  • the content of the water-soluble polymer (the total amount of two or more kinds of water-soluble polymers when they are contained) can also be specified by the relative relationship with the abrasive grains.
  • the content of the water-soluble polymer with respect to 100 parts by weight of the abrasive grains can be, for example, 0.01 part by weight or more, and is 0. It is appropriate that the amount is 1 part by weight or more, preferably 0.5 part by weight or more, more preferably 1 part by weight or more, still more preferably 3 parts by weight or more, and for example, 4 parts by weight or more.
  • the content of the water-soluble polymer with respect to 100 parts by weight of the abrasive grains may be, for example, 50 parts by weight or less, or 30 parts by weight or less.
  • the content of the water-soluble polymer with respect to 100 parts by weight of the abrasive grains is preferably 15 parts by weight or less, preferably 10 parts by weight. It may be 8 parts by weight or less, and may be 7 parts by weight or less.
  • the polishing compositions disclosed herein are, for example, surfactants, organic acids, organic acid salts, inorganic acids, inorganic acid salts, chelating agents, preservatives, antifungal agents, to the extent that the effects of the present invention are not significantly impaired.
  • a known additive that can be used in a polishing composition for example, a polishing composition used in a finishing polishing step of a silicon wafer
  • an agent may be further contained.
  • the polishing composition disclosed herein may contain a surfactant, if necessary.
  • a surfactant any of anionic, cationic, nonionic and amphoteric ones can be used.
  • anionic or nonionic surfactants may be preferably employed.
  • Nonionic surfactants are more preferable from the viewpoint of low foaming property and ease of pH adjustment.
  • oxyalkylene polymers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, polyoxyethylene fatty acid ester, polyoxyethylene glyceryl ether fatty acid.
  • Polyoxyalkylene derivatives such as esters and polyoxyethylene sorbitan fatty acid esters (eg, polyoxyalkylene adducts); copolymers of multiple oxyalkylenes (eg, diblock type copolymers, triblock type copolymers, etc.) Random type copolymers, alternate copolymers); and the like are nonionic surfactants.
  • the surfactant preferably contains a surfactant containing a polyoxyalkylene structure. The surfactant may be used alone or in combination of two or more.
  • nonionic surfactant containing a polyoxyalkylene structure examples include a block copolymer of ethylene oxide (EO) and propylene oxide (PO) (diblock type copolymer, PEO (polyethylene oxide) -PPO).
  • EO ethylene oxide
  • PO propylene oxide
  • PEO polyethylene oxide
  • block copolymers of EO and PO are preferable surfactants.
  • polyoxyethylene decyl ether are preferable surfactants.
  • the weight average molecular weight (Mws) of the surfactant is typically less than 2000, and is preferably 1900 or less (for example, less than 1800) from the viewpoint of filterability, detergency and the like. Further, the Mws of the surfactant is usually preferably 200 or more from the viewpoint of surface activity ability and the like, and preferably 250 or more (for example, 300 or more) from the viewpoint of haze reducing effect and the like. A more preferred range of Mws of the surfactant may also vary depending on the type of the surfactant. For example, when polyoxyethylene alkyl ether is used as the surfactant, its Mws is preferably 1500 or less, and may be 1000 or less (for example, 500 or less).
  • the Mws thereof may be, for example, 500 or more, 1000 or more, and further 1200 or more. May be good.
  • the molecular weight of the surfactant the weight average molecular weight (Mw) obtained by the above GPC or the molecular weight calculated from the chemical formula can be adopted.
  • the content of the surfactant in the polishing composition can be, for example, 1.0 ⁇ 10 -6 % by weight or more, and from the viewpoint of haze reduction, the above content can be 5.0 ⁇ 10 -6 % by weight or more. It is appropriate, preferably 1.0 ⁇ 10-5 % by weight or more, and more preferably 5.0 ⁇ 10-5 % by weight or more. Further, the content of the surfactant can be 0.5% by weight or less, and it is appropriate to set it to 0.25% by weight or less from the viewpoint of polishing efficiency, detergency and the like, and 0.1. It is preferably not more than the weight, more preferably 0.05% by weight or less.
  • the above-mentioned surfactant content can be preferably adopted in an embodiment in which the polishing composition is used in the form of a polishing liquid.
  • the content of the surfactant can also be specified by the relative relationship with the abrasive grains. Usually, from the viewpoint of detergency and the like, it is appropriate that the content of the surfactant with respect to 100 parts by weight of the abrasive grains is 20 parts by weight or less, preferably 15 parts by weight or less, and 10 parts by weight or less (for example, 6 parts by weight). (Parts or less) is more preferable. From the viewpoint of better exerting the effect of using the surfactant, the content of the surfactant with respect to 100 parts by weight of the abrasive grains is preferably 0.001 part by weight or more, preferably 0.005 part by weight or more, preferably 0.01. It may be more than 0.05 parts by weight or more than 0.05 parts by weight.
  • organic acid and its salt, and the inorganic acid and its salt can be used alone 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, tartrate acid, malic acid, maleic acid, fumaric acid and succinic acid.
  • Organic sulfonic acids such as acid, glycolic acid, malonic acid, gluconic acid, alanine, glycine, lactic acid, hydroxyethylidene diphosphate (HEDP), methanesulfonic acid, nitrilotris (methylenephosphate) (NTMP), phosphonobustan tricarbonate.
  • organic phosphonic acids such as acid (PBTC).
  • the organic acid salt include alkali metal salts (sodium salt, potassium salt, etc.) and ammonium salts of organic acids.
  • inorganic acids 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 agent may be used alone or in combination of two or more.
  • the chelating agent include an aminocarboxylic acid-based chelating agent and an organic phosphonic acid-based chelating agent.
  • Preferable examples of the chelating agent include, for example, ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and diethylenetriaminepentaacetic acid.
  • the preservatives and fungicides include isothiazolinone compounds, paraoxybenzoic acid esters, phenoxyethanol and the like.
  • the polishing composition disclosed herein preferably contains substantially no oxidant.
  • the polishing composition contains an oxidizing agent
  • the polishing composition is supplied to a substrate (for example, a silicon wafer) to oxidize the surface of the substrate to form an oxide film, which causes a polishing rate. This is because it may decrease.
  • a substrate for example, a silicon wafer
  • 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
  • the polishing composition inevitably containing an oxidizing agent of mol / L or less, particularly preferably 0.000001 mol / L or less, is the concept of the polishing composition substantially free of the oxidizing agent. Can be included in.
  • the pH of the polishing composition disclosed herein is not particularly limited, and an appropriate pH may be adopted depending on the substrate, abrasive grain type, and the like.
  • the pH of the polishing composition is preferably 8.0 or higher, preferably 8.5 or higher, more preferably 9.0 or higher.
  • the pH of the polishing composition increases, the polishing efficiency tends to improve.
  • the pH of the polishing composition is 12.0 or less. It is preferably 0.0 or less, more preferably 10.8 or less, and even more preferably 10.5 or less.
  • the pH of the polishing composition is a standard buffer solution (for example, a glass electrode type hydrogen ion concentration indicator (model number F-72) manufactured by Horiba Seisakusho). Phphthalate pH buffer pH: 4.01 (25 ° C), neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C)) It can be grasped by calibrating at three points using the pH, placing the glass electrode in the composition to be measured, and measuring the value after it has stabilized after 2 minutes or more.
  • a standard buffer solution for example, a glass electrode type hydrogen ion concentration indicator (model number F-72) manufactured by Horiba Seisakusho.
  • the polishing composition disclosed herein is typically supplied onto the surface of a substrate in the form of a polishing liquid containing the polishing composition and used for polishing the substrate.
  • the polishing liquid may be prepared, for example, by diluting (typically diluting with water) any of the polishing compositions disclosed herein.
  • the polishing composition may be used as it is as a polishing liquid. That is, the concept of the polishing composition in the technique disclosed herein includes a polishing liquid (working slurry) supplied to a substrate and used for polishing the substrate, and a concentrated liquid (polishing) diluted and used as the polishing liquid. Both with the undiluted solution of the solution) are included.
  • the polishing liquid containing the polishing composition disclosed herein there is a polishing liquid obtained by adjusting the pH of the composition.
  • the polishing composition disclosed herein may be in a concentrated form (ie, in the form of a concentrated solution of the polishing solution) before being supplied to the substrate.
  • the polishing composition in such a concentrated form is advantageous from the viewpoint of convenience and cost reduction in manufacturing, distribution, storage and the like.
  • the concentration ratio is not particularly limited, and can be, for example, about 2 to 100 times in terms of volume, and usually about 5 to 50 times (for example, about 10 to 40 times) is appropriate.
  • Such a concentrated liquid can be diluted at a desired timing to prepare a polishing liquid (working slurry), and the polishing liquid can be used in a mode of supplying the polishing liquid to the substrate.
  • the dilution can be performed, for example, by adding water to the concentrate and mixing.
  • the content of abrasive grains in the concentrated solution can be, for example, 25% by weight or less.
  • the content is usually preferably 20% by weight or less, more preferably 15% by weight or less.
  • the content of the abrasive grains may be 10% by weight or less, or 5% by weight or less.
  • the content of abrasive grains in the concentrate can be, for example, 0.1% by weight or more, preferably 0.5% by weight. % Or more, more preferably 0.7% by weight or more, still more preferably 1% by weight or more.
  • the polishing composition used in the technique disclosed herein may be a one-dosage form or a multi-dosage form including a two-dosage form.
  • part A containing at least abrasive grains among the constituents of the polishing composition and part B containing at least a part of the remaining components are mixed, and these are mixed and diluted at appropriate timings as necessary. This may be configured to prepare the polishing liquid.
  • the method for preparing the polishing composition is not particularly limited.
  • the mode in which these components are mixed is not particularly limited, and for example, all the components may be mixed at once, or may be mixed in an appropriately set order.
  • the polishing composition disclosed herein can be applied to the polishing of substrates having various materials and shapes.
  • the material of the substrate is, for example, a metal or semi-metal such as silicon, aluminum, nickel, tungsten, copper, tantalum, titanium, stainless steel, or an alloy thereof; a glassy substance such as quartz glass, aluminosilicate glass, and glassy carbon. It can be a ceramic material such as alumina, silica, sapphire, silicon nitride, tantalum nitride, titanium carbide; a compound semiconductor substrate material such as silicon carbide, gallium nitride, gallium arsenide; a resin material such as a polyimide resin; and the like.
  • a substrate made of a plurality of materials may be used.
  • the shape of the substrate is not particularly limited.
  • the polishing composition disclosed herein may be applied, for example, to polishing a substrate having a flat surface such as a plate or a polyhedron, or polishing an end portion of the substrate (for example, polishing a wafer edge).
  • the polishing composition disclosed herein can be particularly preferably used for polishing a surface made of silicon (typically polishing a silicon wafer).
  • 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 composition disclosed herein can be preferably applied to a polishing process of a substrate (for example, a silicon wafer).
  • the substrate may be subjected to general treatments such as wrapping and etching that may be applied to the substrate in a process upstream of the polishing process prior to the polishing step with the polishing composition disclosed herein.
  • the polishing composition disclosed herein is effective for use in the finishing step of a substrate (for example, a silicon wafer) or the polishing step immediately before the substrate (for example, silicon wafer), and is particularly preferably used in the finishing polishing step.
  • the finish polishing step refers to the final polishing step in the manufacturing process of the target product (that is, a step in which further polishing is not performed after the step).
  • the polishing composition disclosed herein also refers to a pre-polishing step upstream of finish polishing (a pre-polishing step between the rough polishing step and the final polishing step, typically comprising at least a primary polishing step. , Further may include polishing steps such as secondary, tertiary, etc.), for example, may be used in a polishing step performed immediately before finish polishing.
  • the polishing composition disclosed herein is, for example, to policing a silicon wafer (typically finish policing or immediately preceding policing) prepared by an upstream process to have a surface condition with a surface roughness of 0.01 nm to 100 nm. Is effective. Application to finish polishing is particularly preferred.
  • the surface roughness Ra of the substrate can be measured, for example, by using a laser scan type surface roughness meter "TMS-3000WRC" manufactured by Schmitt Measurement System Inc.
  • the polishing composition disclosed herein can be used for polishing a substrate, for example, in an embodiment including the following operations.
  • a preferred embodiment of a method of polishing a silicon wafer as a substrate by using the polishing composition disclosed herein will be described. That is, a polishing liquid containing any of the polishing compositions disclosed herein is prepared.
  • Preparing the polishing liquid may include preparing a polishing liquid by adding operations such as concentration adjustment (for example, dilution) and pH adjustment to the polishing composition.
  • concentration adjustment for example, dilution
  • pH adjustment for example, a polishing liquid
  • the polishing composition may be used as it is as a polishing liquid.
  • the polishing liquid is supplied to the substrate and polished by a conventional method.
  • the silicon wafer that has undergone the wrapping process is set in a general polishing device, and a polishing liquid is applied to the surface to be polished of the silicon wafer through the polishing pad of the polishing device.
  • Supply typically, while continuously supplying the polishing liquid, the polishing pad is pressed against the surface to be polished of the silicon wafer to relatively move (for example, rotationally move) the two.
  • the polishing of the substrate is completed through such a polishing step.
  • the polishing pad used in the above polishing process is not particularly limited.
  • a polishing pad such as a polyurethane foam type, a non-woven fabric type, or a suede type can be used.
  • Each polishing pad may or may not contain abrasive grains.
  • a polishing pad containing no abrasive grains is preferably used.
  • Substrates polished with the polishing composition disclosed herein are typically washed. Cleaning can be performed using a suitable cleaning solution.
  • the cleaning liquid used is not particularly limited, and for example, SC-1 cleaning liquid (ammonium hydroxide (NH 4 OH), hydrogen peroxide (H 2 O 2 ), and water (H 2 O), which are common in the field of semiconductors and the like. (Mixed solution of HCl), SC-2 cleaning solution (mixed solution of HCl, H 2 O 2 and H 2 O) and the like can be used.
  • the temperature of the cleaning liquid can be, for example, in the range of room temperature (typically about 15 ° C to 25 ° C) or higher and up to about 90 ° C. From the viewpoint of improving the cleaning effect, a cleaning liquid having a temperature of about 50 ° C. to 85 ° C. can be preferably used.
  • the technique disclosed herein includes a method for producing a polished product (for example, a method for producing a silicon wafer) including a polishing step (preferably finish polishing) by any of the above-mentioned polishing methods, and the method thereof.
  • a polishing step preferably finish polishing
  • the provision of manufactured abrasives may be included.
  • Example 1 Abrasive grains, a water-soluble polymer, a basic compound, a urea compound, a surfactant and deionized water were mixed to prepare a concentrated solution of the polishing composition according to this example.
  • Colloidal silica (average primary particle size: 27 nm) is used as the abrasive grains, and polyvinyl alcohol (hereinafter referred to as “PVA”) having a weight average molecular weight of about 7.0 ⁇ 104 is used as the water-soluble polymer.
  • PVA polyvinyl alcohol
  • Ammonia was used as the basic compound, hydroxyurea was used as the urea compound, and polyoxyethylene decyl ether (C10EO5) having 5 moles of ethylene oxide was used as the surfactant.
  • DIW deionized water
  • the concentration of the abrasive grains was 0.175%
  • the concentration of the water-soluble polymer was 0.00875%
  • the concentration was 0.00875%.
  • a polishing composition according to this example was obtained, wherein the concentration of the basic compound was 0.005%
  • the concentration of the urea compound was 0.030%
  • the concentration of the surfactant was 0.00015%.
  • Example 5 As the urea-based compound, the compound shown in the corresponding column of Table 1 was used, and the polishing composition according to each example was prepared in the same manner as in Example 1 except that the concentration shown in the corresponding column of Table 1 was used.
  • Example 6 As the water-soluble polymer, hydroxyethyl cellulose having a weight average molecular weight of about 2.8 ⁇ 105 (hereinafter referred to as “HEC”) was used, and as the urea-based compound, the compounds shown in the corresponding columns of Table 2 were used.
  • the polishing composition according to each example was prepared in the same manner as in Example 1 except that the concentrations shown in the corresponding columns of Table 2 were used.
  • a commercially available silicon single crystal wafer (conduction type: P type, crystal orientation: ⁇ 100>, COP (Crystal Organized Particle: crystal defect) free) having a diameter of 200 mm that has been wrapped and etched is prepared under the following polishing condition 1.
  • a polished silicon wafer was prepared.
  • Preliminary polishing was performed using a polishing solution containing 1.0% of abrasive grains (coloidal silica having an average primary particle diameter of 42 nm) and 0.068% of potassium hydroxide in deionized water.
  • Polishing device Single-wafer polishing device model "PNX-322" manufactured by Okamoto Machine Tool Mfg. Co., Ltd. Polishing load: 15kPa Surface plate rotation speed: 30 rpm Head (carrier) rotation speed: 30 rpm Polishing pad: Made by Fujibo Ehime Co., Ltd. Product name "FP55” Pre-polishing liquid supply rate: 550 mL / min Pre-polishing liquid temperature: 20 ° C Surface plate cooling water temperature: 20 ° C Polishing time: 3 min
  • polishing composition according to each example prepared above was used as a polishing liquid, and the silicon wafer after the pre-polishing was polished under the following polishing condition 2.
  • Polishing device Single-wafer polishing device model "PNX-322" manufactured by Okamoto Machine Tool Mfg. Co., Ltd. Polishing load: 15kPa Surface plate rotation speed: 30 rpm Head (carrier) rotation speed: 30 rpm Polishing pad: Made by Fujibo Ehime Co., Ltd. Product name "POLYPAS275NX” Abrasive liquid supply rate: 400 mL / min Abrasive liquid temperature: 20 ° C Surface plate cooling water temperature: 20 ° C Polishing time: 4min
  • SC-1 cleaning Specifically, two first and second washing tanks were prepared, and the washing liquid was contained in each of the washing tanks and kept at 60 ° C.
  • the polished silicon wafer is immersed in the first cleaning tank for 5 minutes, then immersed in ultrapure water to apply ultrasonic waves, and then immersed in the second cleaning tank for 5 minutes and then ultrapure water. It was dried using a spin dryer through a rinsing tank that was immersed in a silicon wafer and subjected to ultrasonic waves.

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

Abstract

L'invention concerne une composition de polissage capable de réduire le trouble post-polissage sur la surface d'un substrat. Cette composition de polissage contient des grains abrasifs, un composé basique, de l'eau et un composé représenté par la formule (I). R1, R2, R3, et R4 dans la formule (I) sont respectivement indépendamment un hydrogène, un groupe alkyle, un groupe hydroxyle et un groupe sélectionné dans le groupe constitué par des groupes hydroxyalkyle. Si le groupe hydroxyle n'existe pas dans la formule (I), le nombre total d'atomes de carbone dans R1, R2, R3, et R4 est supérieur ou égal à 1.　
PCT/JP2021/032805 2020-09-24 2021-09-07 Composition de polissage et utilisation associée WO2022065022A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017025231A (ja) * 2015-07-24 2017-02-02 株式会社Adeka 研磨液組成物及び研磨方法
WO2018131341A1 (fr) * 2017-01-11 2018-07-19 株式会社フジミインコーポレーテッド Composition de polissage
JP2018532828A (ja) * 2015-09-03 2018-11-08 キャボット マイクロエレクトロニクス コーポレイション 誘電体基板を加工するための方法及び組成物
JP2019119782A (ja) * 2017-12-28 2019-07-22 花王株式会社 研磨液組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017025231A (ja) * 2015-07-24 2017-02-02 株式会社Adeka 研磨液組成物及び研磨方法
JP2018532828A (ja) * 2015-09-03 2018-11-08 キャボット マイクロエレクトロニクス コーポレイション 誘電体基板を加工するための方法及び組成物
WO2018131341A1 (fr) * 2017-01-11 2018-07-19 株式会社フジミインコーポレーテッド Composition de polissage
JP2019119782A (ja) * 2017-12-28 2019-07-22 花王株式会社 研磨液組成物

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