WO2020162144A1 - Polishing composition - Google Patents

Polishing composition Download PDF

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Publication number
WO2020162144A1
WO2020162144A1 PCT/JP2020/001646 JP2020001646W WO2020162144A1 WO 2020162144 A1 WO2020162144 A1 WO 2020162144A1 JP 2020001646 W JP2020001646 W JP 2020001646W WO 2020162144 A1 WO2020162144 A1 WO 2020162144A1
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WO
WIPO (PCT)
Prior art keywords
polishing
nitrogen
polishing composition
acid
organic compound
Prior art date
Application number
PCT/JP2020/001646
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French (fr)
Japanese (ja)
Inventor
誼之 田邉
恵 谷口
Original Assignee
株式会社フジミインコーポレーテッド
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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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 JP2020571070A priority Critical patent/JPWO2020162144A1/en
Publication of WO2020162144A1 publication Critical patent/WO2020162144A1/en

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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 composition. Specifically, it relates to a polishing composition for preliminarily polishing a silicon substrate.
  • This application claims priority based on Japanese Patent Application No. 2019-18930 filed on February 5, 2019, the entire content of which is incorporated herein by reference.
  • the polishing step typically includes a preliminary polishing step (preliminary polishing step) and a final polishing step (final polishing step).
  • the preliminary polishing step typically includes a rough polishing step (primary polishing step) and an intermediate polishing step (secondary polishing step).
  • Patent Document 1 can be cited.
  • a silicon substrate is irradiated with a laser beam on the front surface or the back surface of the silicon substrate for the purpose of identification or the like, so that a mark such as a bar code, a number or a symbol (hard laser mark; hereinafter referred to as “HLM”).
  • HLM hard laser mark
  • Irradiation of a laser beam for attaching an HLM usually causes an altered layer on the surface of the silicon substrate around the HLM.
  • the HLM portion itself of the silicon substrate is not used for the final product, but if the above-mentioned deteriorated layer is not properly polished in the polishing step after HLM application, it may become a ridge and the yield may be reduced more than necessary. ..
  • the conventional general polishing composition for a silicon substrate effectively suppresses the occurrence of the protrusion. Was difficult.
  • the above-mentioned HLM peripheral edge Areas other than those that are easily abraded are selectively abraded more than areas that are hard to be abraded at the peripheral edge of the HLM, and as a result, improvement of the elimination of the bulge at the peripheral edge of the HLM (hereinafter, also simply referred to as “protrusion”) is achieved. It was hard to be done. Therefore, there is a demand for a polishing composition that satisfies the practical required level of the polishing rate and is excellent in the ability to eliminate the bulge at the periphery of the HLM.
  • the present invention has been made in view of the above points, and is used for a pre-polishing step of a silicon substrate, and a polishing composition that can achieve both a high polishing rate and excellent HLM peripheral edge swelling elimination property.
  • the purpose is to provide.
  • a polishing composition for use in a pre-polishing step of a silicon substrate.
  • the polishing composition contains abrasive grains, a basic compound and a nitrogen-containing organic compound A.
  • the nitrogen-containing organic compound A is a compound in which at least one nitrogen atom contained in the nitrogen-containing organic compound A constitutes a ⁇ -conjugated system structure. According to the polishing composition having such a constitution, it can be used in a preliminary polishing step of a silicon substrate, and a polishing rate that is sufficiently high for practical use and an excellent ability to eliminate bulging of the HLM peripheral edge can be achieved at the same time.
  • eliminating the ridge on the periphery of the HLM means reducing the height from the reference plane (reference plane) around the HLM of the silicon substrate to the highest point of the ridge.
  • the height from the reference surface around the HLM of the silicon substrate to the highest point of the ridge can be measured, for example, by the method described in Examples below.
  • the polishing composition has at least the nitrogen-containing organic compound A selected from the group consisting of amidine derivative amines, nitrogen-containing heterocyclic aromatic amines, nitrogen-conjugated carboxy group-containing compounds and urea. Including one. According to the polishing composition containing such a nitrogen-containing organic compound A, it is possible to more suitably eliminate the protrusion on the peripheral edge of the HLM while maintaining a polishing rate that is sufficiently high in practical use.
  • the basic compound is an organic basic compound (organic alkali).
  • organic alkali organic basic compound
  • the dispersibility of abrasive grains in the polishing composition is improved, and the polishing rate is easily improved.
  • the polishing composition according to another preferred embodiment contains a quaternary ammonium compound as the basic compound. According to the polishing composition having such a configuration, the dispersibility of abrasive grains in the polishing composition is improved, and the polishing rate can be improved.
  • the polishing composition according to a preferred embodiment contains, as the nitrogen-containing organic compound A, at least one of arginine, histidine and tryptophan. According to the configuration including the nitrogen-containing organic compound A, it is possible to preferably eliminate the protrusion on the peripheral edge of the HLM while maintaining a polishing rate that is sufficiently high in practical use.
  • a polishing composition according to another preferred embodiment contains, as the nitrogen-containing organic compound A, at least one selected from the group consisting of imidazole, pyridine and derivatives thereof. According to the configuration including the nitrogen-containing organic compound A, both a high polishing rate and an excellent swelling eliminating property on the periphery of the HLM can be achieved at the same time.
  • a polishing composition according to another preferred embodiment contains urea as the nitrogen-containing organic compound A. According to the configuration including the nitrogen-containing organic compound A, both a high polishing rate and an excellent swelling eliminating property on the periphery of the HLM can be achieved at the same time.
  • the abrasive grains are silica particles.
  • the effect of eliminating the ridge at the HLM peripheral edge by the nitrogen-containing organic compound A can be more effectively exhibited.
  • Value (m 2 /g)) is the particle size calculated by the formula.
  • the specific surface area can be measured using, for example, a surface area measuring device manufactured by Micromeritex Co., Ltd. under the trade name of “Flow Sorb II 2300”.
  • the aspect ratio of each particle constituting the abrasive grain is defined by the length of the long side of the smallest rectangle circumscribing the image of the particle by a scanning electron microscope (SEM) to the length of the short side of the same rectangle. It can be obtained by dividing by.
  • the circle-converted diameter of a particle is a value obtained by measuring the area of the image of the particle with a scanning electron microscope (SEM) and determining the diameter of a circle having the same area.
  • SEM scanning electron microscope
  • the polishing composition disclosed herein contains abrasive grains.
  • the abrasive grains function to mechanically polish the surface of the object to be polished.
  • the material and properties of the abrasive grains are not particularly limited, and can be appropriately selected according to the purpose of use and the mode of use.
  • the abrasive grains may be used alone or in combination of two or more.
  • examples of the abrasive grains include inorganic particles, organic particles, and organic-inorganic composite particles.
  • the inorganic particles include silicon compound particles such as silica particles, silicon nitride particles, and silicon carbide particles, and diamond particles.
  • Specific examples of the organic particles include polymethylmethacrylate (PMMA) particles and polyacrylonitrile particles. Of these, inorganic particles are preferable.
  • Silica particles are mentioned as particularly preferable abrasive grains in the technology disclosed herein.
  • the technique disclosed herein can be preferably carried out, for example, in a mode in which the abrasive grains are substantially silica particles.
  • substantially means 95% by weight or more (preferably 98% by weight or more, more preferably 99% by weight or more, and even 100% by weight) of the particles constituting the abrasive grains. 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.
  • Colloidal silica is particularly preferable because it is unlikely to cause scratches on the surface of the object to be polished and can exhibit good polishing performance (performance to reduce surface roughness, swelling elimination property, etc.).
  • colloidal silica for example, colloidal silica produced from water glass (Na silicate) as a raw material by an ion exchange method or alkoxide method colloidal silica can be preferably used.
  • the alkoxide colloidal silica is colloidal silica produced by a hydrolysis condensation reaction of alkoxysilane.
  • Colloidal silica can be used individually by 1 type or in combination of 2 or more types.
  • the true specific gravity of silica constituting the silica particles is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more.
  • the polishing rate tends to increase due to an increase in the true specific gravity of silica.
  • silica particles having a true specific gravity of 2.0 or more are particularly preferable.
  • the upper limit of the true specific gravity of silica is not particularly limited, but 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 adopted.
  • the average primary particle diameter of the abrasive grains is not particularly limited, and can be appropriately selected from the range of, for example, about 10 nm to 200 nm. From the viewpoint of improving the swelling elimination property, the average primary particle diameter is preferably 20 nm or more, and more preferably 30 nm or more. In some embodiments, the average primary particle size can be, for example, greater than 40 nm, greater than 45 nm, and greater than 50 nm. Further, from the viewpoint of preventing the occurrence of scratches, the average primary particle diameter is usually advantageously 150 nm or less, preferably 120 nm or less, and more preferably 100 nm or less. In some embodiments, the average primary particle size of the abrasive grains may be 75 nm or less, and 60 nm or less.
  • the shape (outer shape) of the abrasive grains may be spherical or non-spherical.
  • specific examples of the non-spherical particles include a peanut shape, that is, a peanut shell shape, a cocoon shape, a projection shape such as a konpeito sugar shape, and a rugby ball shape.
  • the average aspect ratio of the abrasive grains is not particularly limited.
  • the average aspect ratio of the abrasive grains is 1.0 or more in principle, and can be 1.05 or more, or 1.1 or more.
  • the increase in average aspect ratio tends to generally improve ridge relief.
  • the average aspect ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, from the viewpoints of scratch reduction and polishing stability improvement.
  • the average aspect ratio of the abrasive grains can be, for example, 1.5 or less, 1.4 or less, or 1.3 or less.
  • the abrasive grains those having a circle-converted diameter of 50 nm or more and an aspect ratio of 1.2 or more and having a volume ratio of 50% or more can be adopted.
  • the volume ratio may be 60% or more.
  • the abrasive grains may contain a relatively large amount of particles having a size and aspect ratio that are particularly effective for eliminating the protrusion. For that reason, it is possible to further improve the swelling elimination property due to the mechanical action of the abrasive grains.
  • the average circle equivalent diameter of the abrasive grains may be, for example, 25 nm or more, 40 nm or more, 55 nm or more, and 70 nm or more.
  • the average circle conversion diameter of the abrasive grains may be, for example, 300 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less.
  • the polishing composition disclosed herein can be preferably carried out using abrasive grains having such an average circle conversion diameter.
  • the content of abrasive grains is not particularly limited and may be set appropriately according to the purpose.
  • the content of abrasive grains with respect to the total weight of the polishing composition may be, for example, 0.01% by weight or more, may be 0.05% by weight or more, and may be 0.1% by weight or more.
  • Increasing the content of abrasive grains generally tends to improve the swelling elimination property.
  • the content of abrasive grains may be 0.2 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0 It may be 0.8% by weight or more, or 0.85% by weight or more.
  • the content of abrasive grains may be, for example, 10% by weight or less, 5% by weight or less, or 3% by weight or less. It may be 2% by weight or less. These contents can be preferably applied to the contents in the polishing liquid (working slurry) supplied to the object to be polished, for example.
  • the polishing composition disclosed herein contains a nitrogen-containing organic compound A.
  • the nitrogen-containing organic compound A is an organic compound containing at least one nitrogen atom in the molecule, and at least one nitrogen atom contained in the nitrogen-containing organic compound A has a ⁇ -conjugated system structure ( It is a compound that constitutes a structure in which ⁇ electrons are delocalized). According to the polishing composition containing such a nitrogen-containing organic compound A, it is easy to achieve both a high polishing rate and an excellent bulge elimination property at the edge of the HLM.
  • the number of nitrogen atoms contained in the nitrogen-containing organic compound A may be 1 or more and is not particularly limited. In the technology disclosed herein, as the nitrogen-containing organic compound A, those containing 1 to 10 nitrogen atoms in the molecule can be preferably used. The number of nitrogen atoms contained in the nitrogen-containing organic compound A is more preferably 1 or more and 6 or less, still more preferably 1 or more and 5 or less, for example 1 or more and 4 or less.
  • the number of nitrogen atoms contained in the nitrogen-containing organic compound A is 2 or more, it is not necessary that all the nitrogen atoms contained in the nitrogen-containing organic compound A form a ⁇ -conjugated system structure. That is, it suffices that at least one nitrogen atom among the nitrogen atoms contained in the nitrogen-containing organic compound A constitutes a ⁇ -conjugated system structure.
  • the number of nitrogen atoms constituting the ⁇ -conjugated system structure contained in the nitrogen-containing organic compound A is 1 or more and 3 or less, and more preferably 1 or more and 2 or less. Is.
  • the structure of a structure in which a nitrogen atom constitutes a ⁇ -conjugated system structure is not particularly limited.
  • a structure in which a nitrogen atom constitutes part of alternating single bonds and multiple bonds for example, a nitrogen-containing unsaturated heterocyclic structure
  • a non-covalent structure of a nitrogen atom examples thereof include a structure in which an electron pair forms a conjugated system with an atom adjacent to the nitrogen atom.
  • the nitrogen-conjugated structure examples include an amidine structure, a nitrogen-containing unsaturated heterocyclic structure, and a urea (carbamide) structure. According to the polishing composition containing the nitrogen-containing organic compound A having such a structure in the molecule, the performance of eliminating the protrusion on the peripheral edge of the HLM is likely to be improved.
  • the nitrogen-containing organic compound A disclosed herein is not particularly limited in the constitution (structure, substituents, etc.) of the portion other than the nitrogen-conjugated system structure, as long as the nitrogen-containing organic compound A has a structure in which the nitrogen atom constitutes a ⁇ -conjugated system. ..
  • Specific examples of the nitrogen-containing organic compound A that can be suitably used in the technology disclosed herein include amidine derivative amines, nitrogen-containing heterocyclic aromatic amines, nitrogen-conjugated carboxy group-containing compounds, and urea.
  • the nitrogen-conjugated carboxy group-containing compound refers to a compound containing a nitrogen-conjugated structure in the molecule and at least one carboxy group.
  • amidine derivative amine examples include amines having an amidine moiety (for example, a heterocyclic amine having an amidine partial structure). Specific examples include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN). Among them, DBU is preferable from the viewpoint of eliminating the bulge at the periphery of the HLM.
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • DBN 1,5-diazabicyclo[4.3.0]-5-nonene
  • the above-mentioned nitrogen-containing heterocyclic aromatic amine refers to an amine containing at least one aromatic heterocycle containing a nitrogen atom in the molecule.
  • the size of the aromatic heterocycle is not particularly limited.
  • the aromatic heterocycle is preferably a 6-membered ring or less, and more preferably a 5-membered ring or a 6-membered ring.
  • the nitrogen-containing heterocyclic aromatic amine may have two or more unsaturated heterocycles (typically aromatic heterocycles) in the molecule.
  • the nitrogen-containing heterocyclic aromatic amine has one or two nitrogen-containing unsaturated heterocycles in the molecule.
  • nitrogen-containing heterocyclic aromatic amine examples include nitrogen-containing 6-membered aromatic amine and nitrogen-containing 5-membered aromatic amine.
  • nitrogen-containing 6-membered aromatic amine examples include pyridine and its derivatives.
  • pyridine derivative examples include 4-aminopyridine, picolinic acid, pyridine and the like. Of these, pyridine can be preferably used.
  • nitrogen-containing five-membered aromatic amine examples include imidazole and its derivatives.
  • the imidazole derivative include 1-(3-aminopropyl)imidazole and 2-methylimidazole. Among them, 1-(3-aminopropyl)imidazole can be preferably used.
  • Non-limiting examples of the nitrogen-conjugated carboxy group-containing compound include guanidine derivatives such as guanidinobenzoic acid, guanidinoglutaric acid, guanidinosuccinic acid, guanidinoacetic acid, creatine and guanidinopropionic acid, and imidazole derivatives such as 1-imidazoleacetic acid. , Picolinic acid and the like.
  • examples of the nitrogen-conjugated carboxy group-containing compound include nitrogen-conjugated amino acids.
  • the nitrogen-conjugated amino acid refers to an amino acid in which at least one nitrogen atom in the molecule constitutes a ⁇ -conjugated structure.
  • the nitrogen-conjugated amino acid can be preferably used from the viewpoint of the ability to eliminate ridges on the periphery of HLM.
  • Specific examples of the nitrogen-conjugated amino acid include arginine, histidine, tryptophan and the like.
  • the nitrogen-containing organic compound A in the technology disclosed herein may be any one of the above compounds or a mixture of two or more thereof.
  • the content of the nitrogen-containing organic compound A in the polishing composition (when a plurality of kinds of nitrogen-containing organic compounds A is contained, the total amount thereof) is not particularly limited, and may be desired depending on the purpose of use, usage mode, etc. It can be appropriately set so as to obtain the effect of.
  • the content of the nitrogen-containing organic compound A in the polishing composition can be, for example, 0.0001% by weight or more, and is 0.001% by weight or more from the viewpoint of better exerting the bump elimination effect.
  • the content is preferably 0.003% by weight or more, more preferably 0.004% by weight or more.
  • the content of the nitrogen-containing organic compound A in the polishing composition can be, for example, 0.5% by weight or less, and may be 0.1% by weight or less from the viewpoint of polishing efficiency and the like, and 0.05% by weight or less. % Or less, preferably 0.03% by weight or less, and more preferably 0.02% by weight or less. These contents can be preferably applied to the contents in the polishing liquid (working slurry) supplied to the object to be polished, for example.
  • the content of the nitrogen-containing organic compound A in the polishing composition disclosed herein can be 0.01 parts by weight or more with respect to 100 parts by weight of abrasive grains, and The amount may be 0.05 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, and still more preferably 0.5 parts by weight or more, from the viewpoint of better exerting the elimination effect. is there. Further, the content of the nitrogen-containing organic compound A in the polishing composition can be 20 parts by weight or less with respect to 100 parts by weight of the abrasive grains, and may be 15 parts by weight or less from the viewpoint of polishing efficiency and the like. Is 10 parts by weight or less, more preferably 5 parts by weight or less, still more preferably 3 parts by weight or less (for example, 2.5 parts by weight or less).
  • the polishing composition according to the present invention contains a basic compound.
  • the basic compound means a compound having a function of increasing the pH of the polishing composition by being added thereto.
  • the basic compound serves to chemically polish the surface to be polished, and can contribute to the improvement of the polishing rate.
  • the basic compound does not include the nitrogen-containing organic compound A in which a nitrogen atom forms a ⁇ -conjugated system structure.
  • an organic or inorganic basic compound containing nitrogen, an alkali metal or alkaline earth metal hydroxide, or the like can be used.
  • the basic compound include alkali metal hydroxides, quaternary ammonium hydroxide or salts thereof, ammonia, amines and the like.
  • Specific examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide.
  • Specific examples of the quaternary ammonium hydroxide or its salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like.
  • amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-( ⁇ -aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine. , Piperazine hexahydrate, 1-(2-aminoethyl)piperazine, N-methylpiperazine and the like.
  • an organic basic compound (organic alkali) is preferably used as the basic compound.
  • organic alkali organic alkali
  • the use of an organic alkali as the basic compound tends to improve the dispersibility of the abrasive grains and improve the polishing rate.
  • a quaternary ammonium compound is mentioned as a preferable basic compound from the viewpoint of improving the swelling elimination property.
  • a quaternary ammonium salt typically a strong base
  • a tetraalkylammonium salt or a hydroxyalkyltrialkylammonium salt can be preferably used.
  • the anion component in such a quaternary ammonium salt may be, for example, OH ⁇ , F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BH 4 ⁇ .
  • a preferable example is a quaternary ammonium salt having an anion of OH ⁇ , that is, a quaternary ammonium hydroxide.
  • a quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide and tetrahexylammonium hydroxide.
  • Tetraalkylammonium hydroxyalkyltrialkylammonium hydroxide such as 2-hydroxyethyltrimethylammonium hydroxide (also called choline); and the like. Particularly preferably used is tetraalkylammonium hydroxide (eg, tetramethylammonium hydroxide).
  • hydroxyalkyltrialkylammonium hydroxide such as 2-hydroxyethyltrimethylammonium hydroxide (also called choline); and the like.
  • Particularly preferably used is tetraalkylammonium hydroxide (eg, tetramethylammonium hydroxide).
  • the above basic compounds may be used alone or in combination of two or more.
  • the content of the basic compound relative to the total amount of the polishing composition is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, further preferably 0.03% by weight or more, from the viewpoint of promoting the polishing rate. Is.
  • the content of the basic compound is appropriately 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less from the viewpoint of surface quality and the like. ..
  • the said content points out the total content of 2 or more types of basic compounds.
  • the content of the basic compound in the polishing composition disclosed herein can be 0.01 parts by weight or more based on 100 parts by weight of the abrasive grains, and the polishing rate From the viewpoint of acceleration, the amount may be 0.05 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, still more preferably 0.5 parts by weight or more.
  • the content of the basic compound in the polishing composition can be 20 parts by weight or less with respect to 100 parts by weight of the abrasive grains, and may be 15 parts by weight or less from the viewpoint of surface quality and the like, preferably It is 12 parts by weight or less, and more preferably 10 parts by weight or less.
  • the content of the basic compound may be 8 parts by weight or less and may be 5 parts by weight or less with respect to 100 parts by weight of the abrasive grains.
  • the above content refers to the total content of the two or more basic compounds.
  • the polishing composition disclosed herein comprises water.
  • water ion exchanged water (deionized water), pure water, ultrapure water, distilled water or the like can be preferably used.
  • the water to be used preferably has a total content of transition metal ions of 100 ppb or less, for example, in order to prevent the functions of other components contained in the polishing composition from being hindered.
  • the purity of water can be increased by operations such as removing impurity ions with an ion exchange resin, removing foreign substances with 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.
  • 90% by volume or more of the solvent contained in the polishing composition is preferably water, and more preferably 95% by volume or more (typically 99 to 100% by volume) is water.
  • the polishing composition disclosed herein is a polishing composition such as a water-soluble polymer, a surfactant, an acid, a chelating agent, an antiseptic agent, an antifungal agent, etc. within a range in which the effects of the present invention are not significantly impaired.
  • a known additive that can be used in typically, a polishing composition used in a polishing step of a silicon substrate may be further contained, if necessary.
  • water-soluble polymer examples include cellulose derivatives, starch derivatives, polymers containing oxyalkylene units, polymers containing nitrogen atoms, vinyl alcohol polymers and the like. Specific examples of the water-soluble polymer, hydroxyethyl cellulose, pullulan, random copolymers and block copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, Examples thereof include polyisoamylene sulfonic acid, polystyrene sulfonate, polyacrylate, polyvinyl acetate, polyethylene glycol, polyvinyl imidazole, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl caprolactam, and polyvinyl piperidine.
  • the water-soluble polymers can be used alone or in combination of two or more.
  • the polishing composition disclosed herein can be preferably carried out even in a mode in which the water-soluble polymer is not substantially contained, that is, in a mode in which the water-soluble polymer is not contained at least intentionally.
  • the polishing composition disclosed herein can contain a surfactant (typically, a water-soluble organic compound having a molecular weight of less than 1 ⁇ 10 4 ) as an optional component.
  • a surfactant typically, a water-soluble organic compound having a molecular weight of less than 1 ⁇ 10 4
  • the use of a surfactant can improve the dispersion stability of the polishing composition.
  • the surfactants may be used alone or in combination of two or more.
  • anionic or nonionic one can be preferably adopted. From the viewpoint of low foaming property and easiness of pH adjustment, a nonionic surfactant is more preferable.
  • oxyalkylene polymers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid ester, polyoxyethylene glyceryl ether fatty acid.
  • Nonionic surfactants such as esters, polyoxyalkylene adducts such as polyoxyethylene sorbitan fatty acid esters; copolymers of plural kinds of oxyalkylenes (diblock type, triblock type, random type, alternating type);
  • the amount of the surfactant used is suitably 5 g or less, preferably 2 g or less, and more preferably 1 g or less, per 1 kg of abrasive grains.
  • the polishing composition disclosed herein can be preferably carried out even in an embodiment substantially containing no surfactant.
  • the acid examples include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, phosphonic acid, nitric acid, phosphinic acid, boric acid; acetic acid, itaconic acid, succinic acid, tartaric acid, citric acid, maleic acid, glycolic acid, malonic acid. , Methanesulfonic acid, formic acid, malic acid, gluconic acid, alanine, glycine, lactic acid, hydroxyethylidene diphosphonic acid (HEDP), nitrilotris [methylene phosphonic acid] (NTMP), phosphonobutane tricarboxylic acid (PBTC), and other organic acids; and the like.
  • the acid may be used in the form of a salt of the acid.
  • the acid salt may be, for example, an alkali metal salt such as a sodium salt or a potassium salt, or an ammonium salt.
  • Examples of the above chelating agents include aminocarboxylic acid type chelating agents and organic phosphonic acid type chelating agents.
  • Examples of aminocarboxylic acid-based chelating agents include ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetic acid, ammonium nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, sodium hydroxyethylethylenediaminetriacetate, diethylenetriaminepentaacetic acid. , Sodium diethylenetriamine pentaacetate, triethylenetetramine hexaacetic acid and sodium triethylenetetramine hexaacetate.
  • organic phosphonic acid-based chelating agent examples include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid).
  • ethylenediaminetetrakis methylenephosphonic acid
  • diethylenetriaminepenta methylenephosphonic acid
  • diethylenetriaminepentaacetic acid preferred are ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and diethylenetriaminepentaacetic acid.
  • Particularly preferred chelating agents include ethylenediaminetetrakis (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid).
  • the chelating agents may be used alone or in combination of two or more.
  • the amount of the chelating agent used is, for example, about 0.0001 to 1% by weight, about 0.001 to 0.5% by weight, or about 0.005 to 0.1% by weight of the content of the chelating agent in the working slurry.
  • the present invention is not limited to this.
  • the polishing composition disclosed herein can be preferably used even in an embodiment containing no chelating agent.
  • Examples of the above preservatives and fungicides include isothiazoline compounds, paraoxybenzoic acid esters, phenoxyethanol and the like.
  • the polishing composition disclosed herein preferably contains substantially no oxidizing agent.
  • the polishing composition may be supplied to oxidize the surface of the silicon substrate to form an oxide film, which may lower the polishing rate. This is because.
  • that the polishing composition does not substantially contain an oxidizing agent means that at least the oxidizing agent is not intentionally mixed, and a trace amount of the oxidizing agent is inevitably included due to the raw material, the manufacturing method, and the like. Can be allowed.
  • the above-mentioned trace amount means that 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 0.001 mol/L or less. 000001 mol/L or less).
  • the polishing composition according to a preferred embodiment does not contain an oxidizing agent.
  • the polishing composition disclosed herein can be preferably carried out, for example, in a mode containing neither hydrogen peroxide, sodium persulfate, ammonium persulfate nor sodium dichloroisocyanurate.
  • the polishing composition disclosed herein is typically supplied to the object to be polished in the form of a polishing liquid (working slurry) containing the composition for polishing and used for polishing the object to be polished.
  • the polishing composition disclosed herein may be, for example, diluted (typically diluted with water) and used as a polishing liquid, or may be used as it is as a polishing liquid.
  • the concept of the polishing composition in the technology disclosed herein includes both a working slurry that is supplied to the object to be polished and used for polishing the object to be polished, and a concentrated solution (stock solution) of the working slurry. Is included.
  • the concentration ratio of the concentrated liquid may be, for example, about 2 to 100 times on a volume basis, and normally about 5 to 50 times is appropriate.
  • the pH of the polishing composition is typically 8.0 or higher, preferably 8.5 or higher, more preferably 9.0 or higher, further preferably 9.5 or higher, for example 10.0 or higher.
  • the pH of the polishing liquid is usually appropriate to be 12.0 or less. , 11.8 or less, preferably 11.5 or less, and more preferably 11.0 or less.
  • pH of the polishing composition For the pH of the polishing composition, use a pH meter (for example, a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by Horiba Ltd.) and use a standard buffer solution (phthalate pH buffer solution pH: After three-point calibration using 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 putting the glass electrode in the polishing composition and measuring the value after the glass electrode has been stabilized for 2 minutes or more.
  • a pH meter for example, a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by Horiba Ltd.
  • standard buffer solution phthalate pH buffer solution pH: After three-point calibration using 4.01 (25°C), neutral phosphate pH buffer pH: 6.86 (25°C, carbonate pH buffer pH:10.01 (25°C)
  • the polishing composition disclosed herein may be a one-part type or a multi-part type including a two-part type.
  • the polishing liquid may be prepared by mixing Part A containing at least abrasive grains and Part B containing the remaining components, and diluting them at an appropriate timing as needed.
  • each component contained in the polishing composition may be mixed using a known mixing device such as a blade stirrer, an ultrasonic disperser, or a homomixer.
  • the mode of mixing these components is not particularly limited, and for example, all components may be mixed at once, or may be mixed in an appropriately set order.
  • the polishing composition disclosed herein can be used for polishing an object to be polished in a mode including the following operations, for example. That is, a working slurry containing any of the polishing compositions disclosed herein is prepared. Then, the polishing composition is supplied to an object to be polished and polished by a conventional method.
  • the object to be polished is set in a general polishing apparatus, and the polishing composition is supplied to the surface (surface to be polished) of the object to be polished through the polishing pad of the polishing apparatus.
  • the polishing pad is pressed against the surface of the object to be polished to relatively move (for example, rotationally move) the both. Through this polishing step, the polishing of the object to be polished is completed.
  • the polishing pad used in the above polishing process is not particularly limited.
  • any of foamed polyurethane type, non-woven fabric type, suede type, those containing abrasive grains, those not containing abrasive grains, etc. may be used.
  • a double-sided polishing device for simultaneously polishing both surfaces of the polishing target object may be used, or a single-sided polishing device for polishing only one surface of the polishing target object may be used.
  • the above-mentioned polishing composition may be used in a mode of being disposable once used for polishing (so-called “flowing over”), or may be circulated and repeatedly used.
  • a method of circulating and using the polishing composition there is a method of collecting the used polishing composition discharged from the polishing apparatus in a tank and supplying the recovered polishing composition to the polishing apparatus again. ..
  • the polishing composition disclosed herein is used in circulation, even if a new component, a component decreased by use or a component desired to be increased is added to the polishing composition in use at any time. Good.
  • a mode of adding components a mode in which only the nitrogen-containing organic compound A is added, only the basic compound is added, and any of these is added to the polishing composition in circulation use Are listed.
  • the polishing composition disclosed herein is excellent in the ability to eliminate the bulge at the peripheral edge of the HLM (protuberance elimination property). Taking advantage of such a feature, the polishing composition can be preferably applied to polishing a surface to be polished including a surface having an HLM.
  • the polishing composition disclosed herein can be particularly preferably used in the preliminary polishing step, that is, the first polishing step (primary polishing step) or the subsequent intermediate polishing step (secondary polishing step) in the polishing step.
  • the polishing composition disclosed herein is suitably used for polishing a silicon substrate.
  • the above-mentioned silicon substrate Prior to the polishing step using the polishing composition disclosed herein, the above-mentioned silicon substrate has been subjected to general treatments that can be applied to the silicon substrate, such as lapping, etching, and application of the above-mentioned HLM. Good.
  • the silicon substrate typically has a surface made of silicon.
  • a typical example of such a silicon substrate 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 is suitable for use in polishing a silicon single crystal wafer provided with HLM. Further, the polishing composition disclosed herein can be suitably used for polishing an object to be polished having no HLM.
  • Example 1 The content of colloidal silica (average primary particle diameter: 55 nm) as abrasive grains is 0.9% by weight, the content of tetramethylammonium hydroxide (TMAH) is 0.04% by weight, and L as nitrogen-containing organic compound A is L.
  • TMAH tetramethylammonium hydroxide
  • L nitrogen-containing organic compound A
  • Examples 2-6 The polishing compositions according to Examples 2 to 6 were prepared in the same manner as the polishing composition according to Example 1, except that the kind and content of the nitrogen-containing organic compound A were changed to those shown in Table 1. did.
  • Example 7 A polishing composition according to Example 7 was prepared in the same manner as the polishing composition according to Example 1 except that the nitrogen-containing organic compound A was not used.
  • Example 8-11 The polishing compositions according to Examples 8 to 11 were prepared in the same manner as the polishing composition according to Example 1 except that the type and content of the nitrogen-containing organic compound were changed to those shown in Table 1. ..
  • ⁇ Silicon substrate polishing> The polishing liquid according to each example was used as it was as a working slurry, and the surface of the object to be polished (test piece) was polished under the following conditions.
  • a commercially available silicon single crystal wafer with a diameter of 100 mm after lapping and etching (thickness: 525 ⁇ m, conductivity type: P type, crystal orientation: ⁇ 100>, resistivity: 0.1 ⁇ cm or more 100 ⁇ cm Less than) was used.
  • An HLM is attached to the wafer.
  • Polishing device One-sided polishing device manufactured by Nippon Engis Co., Ltd., model "EJ-380IN” Polishing pressure: 12kPa Plate rotation speed: 50 rpm Head rotation speed: 45 rpm Polishing pad: Nitta Haas, product name "SUBA800” Polishing liquid supply rate: 100 mL/min (use overflow) Holding temperature of polishing environment: 25°C Polishing allowance: 4 ⁇ m
  • Example 7 containing no nitrogen-containing organic compound A As compared with the polishing composition of No. 3, the polishing rate was maintained at a sufficiently high level and the swelling elimination property was remarkably improved.
  • the polishing compositions of Examples 8 to 11 which do not contain the nitrogen-containing organic compound A, but instead contain the nitrogen-containing organic compound in which the nitrogen atom does not form a ⁇ -conjugated system structure, contain the nitrogen-containing organic compound A.
  • the swelling elimination property was deteriorated.

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Abstract

Provided is a polishing composition which can achieve both a high polishing rate and excellent protrusion elimination properties at a periphery of an HLM. The polishing composition provided by the present invention is used in a preliminary polishing step for a silicon substrate. This polishing composition contains abrasive grains, a basic compound and a nitrogen-containing organic compound A. At least one nitrogen atom contained in the nitrogen-containing organic compound A forms a π-conjugated structure.

Description

研磨用組成物Polishing composition
　本発明は、研磨用組成物に関する。詳しくはシリコン基板を予備研磨するための研磨用組成物に関する。本出願は、２０１９年２月５日に出願された日本国特許出願２０１９－１８９３０号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。 The present invention relates to a polishing composition. Specifically, it relates to a polishing composition for preliminarily polishing a silicon substrate. This application claims priority based on Japanese Patent Application No. 2019-18930 filed on February 5, 2019, the entire content of which is incorporated herein by reference.
　従来、金属や半金属、非金属、その酸化物等の材料表面に対して研磨用組成物を用いた精密研磨が行われている。例えば、半導体製品の構成要素等として用いられるシリコン基板の表面は、一般的にラッピング工程やポリシング工程を経て高品位の鏡面に仕上げられる。上記ポリシング工程は、典型的には、予備ポリシング工程（予備研磨工程）とファイナルポリシング工程（最終研磨工程）とを含む。上記予備ポリシング工程は、典型的には、粗研磨工程（一次研磨工程）および中間研磨工程（二次研磨工程）を含んでいる。この種のシリコン基板の研磨に関連する技術文献として、特許文献１が挙げられる。 Conventionally, precision polishing using a polishing composition has been performed on the surface of a material such as metal, metalloid, nonmetal, or its oxide. For example, the surface of a silicon substrate used as a component of a semiconductor product or the like is generally finished to a high quality mirror surface through a lapping process and a polishing process. The polishing step typically includes a preliminary polishing step (preliminary polishing step) and a final polishing step (final polishing step). The preliminary polishing step typically includes a rough polishing step (primary polishing step) and an intermediate polishing step (secondary polishing step). As a technical document related to the polishing of this type of silicon substrate, Patent Document 1 can be cited.
日本国特許出願公開２０１５－１９１９６６号公報Japanese Patent Application Publication No. 2015-191966
　ところで、シリコン基板には、識別等の目的で、該シリコン基板の表面や裏面にレーザー光を照射することによって、バーコード、数字、記号等のマーク（ハードレーザーマーク；以下「ＨＬＭ」と表記することがある。）が付されることがある。ＨＬＭの付与は、一般に、シリコン基板のラッピング工程を終えた後、ポリシング工程を開始する前に行われる。通常、ＨＬＭを付すためのレーザー光の照射によって、ＨＬＭ周縁のシリコン基板表面には変質層が生じる。シリコン基板のうちＨＬＭの部分自体は最終製品には用いられないが、ＨＬＭ付与後のポリシング工程において上記変質層が適切に研磨されないと、***となって必要以上に歩留まりが低下することがあり得る。しかし、上記変質層はレーザー光のエネルギーによりポリシリコン等に変質して研磨されにくくなっているため、従来の一般的なシリコン基板用の研磨用組成物では上記***の発生を効果的に抑制することが困難であった。 By the way, a silicon substrate is irradiated with a laser beam on the front surface or the back surface of the silicon substrate for the purpose of identification or the like, so that a mark such as a bar code, a number or a symbol (hard laser mark; hereinafter referred to as “HLM”). Sometimes) is attached. Application of the HLM is generally performed after the lapping process of the silicon substrate is completed and before the polishing process is started. Irradiation of a laser beam for attaching an HLM usually causes an altered layer on the surface of the silicon substrate around the HLM. The HLM portion itself of the silicon substrate is not used for the final product, but if the above-mentioned deteriorated layer is not properly polished in the polishing step after HLM application, it may become a ridge and the yield may be reduced more than necessary. .. However, since the deteriorated layer is changed into polysilicon or the like by the energy of the laser beam and is difficult to be polished, the conventional general polishing composition for a silicon substrate effectively suppresses the occurrence of the protrusion. Was difficult.
　また、研磨効率の向上を期待して高い研磨レート（単位時間当たりに研磨対象物を除去する量）を示す研磨用組成物を用いてＨＬＭが付与されたシリコン基板を研磨した場合、上記ＨＬＭ周縁以外の研磨されやすい部位が該ＨＬＭ周縁部の研磨されにくい部位よりも選択的に研磨されてしまい、結果として上記ＨＬＭ周縁の***（以下、単に「***」ともいう。）の解消性向上が達成されにくいことがあった。このため、研磨レートに関する実用的な要求レベルを満足しつつ、ＨＬＭ周縁の***を解消する性能に優れた研磨用組成物が求められている。 Further, in the case of polishing a silicon substrate provided with an HLM with a polishing composition showing a high polishing rate (amount for removing an object to be polished per unit time) in the hope of improving polishing efficiency, the above-mentioned HLM peripheral edge Areas other than those that are easily abraded are selectively abraded more than areas that are hard to be abraded at the peripheral edge of the HLM, and as a result, improvement of the elimination of the bulge at the peripheral edge of the HLM (hereinafter, also simply referred to as “protrusion”) is achieved. It was hard to be done. Therefore, there is a demand for a polishing composition that satisfies the practical required level of the polishing rate and is excellent in the ability to eliminate the bulge at the periphery of the HLM.
　本発明は、かかる点に鑑みてなされたものであり、シリコン基板の予備研磨工程に使用されて、高い研磨レートと優れたＨＬＭ周縁の***解消性とを両立して達成し得る研磨用組成物を提供することを目的とする。 The present invention has been made in view of the above points, and is used for a pre-polishing step of a silicon substrate, and a polishing composition that can achieve both a high polishing rate and excellent HLM peripheral edge swelling elimination property. The purpose is to provide.
　本発明によると、シリコン基板の予備研磨工程に使用するための研磨用組成物が提供される。上記研磨用組成物は、砥粒、塩基性化合物および含窒素有機化合物Ａを含む。ここで上記含窒素有機化合物Ａは、該含窒素有機化合物Ａに含まれる少なくとも１つの窒素原子がπ共役系構造を構成している化合物である。かかる構成の研磨用組成物によると、シリコン基板の予備研磨工程に使用されて、実用上十分に高い研磨レートと優れたＨＬＭ周縁の***解消性とが両立して達成され得る。 According to the present invention, there is provided a polishing composition for use in a pre-polishing step of a silicon substrate. The polishing composition contains abrasive grains, a basic compound and a nitrogen-containing organic compound A. Here, the nitrogen-containing organic compound A is a compound in which at least one nitrogen atom contained in the nitrogen-containing organic compound A constitutes a π-conjugated system structure. According to the polishing composition having such a constitution, it can be used in a preliminary polishing step of a silicon substrate, and a polishing rate that is sufficiently high for practical use and an excellent ability to eliminate bulging of the HLM peripheral edge can be achieved at the same time.
　なお、本明細書においてＨＬＭ周縁の***を解消するとは、シリコン基板のＨＬＭ周辺の基準面（基準平面）から上記***の最高点までの高さを小さくすることをいう。シリコン基板のＨＬＭ周辺の基準面から上記***の最高点までの高さは、例えば、後述する実施例に記載の方法により測定することができる。 Note that, in this specification, eliminating the ridge on the periphery of the HLM means reducing the height from the reference plane (reference plane) around the HLM of the silicon substrate to the highest point of the ridge. The height from the reference surface around the HLM of the silicon substrate to the highest point of the ridge can be measured, for example, by the method described in Examples below.
　好ましい一態様において、上記研磨用組成物は、上記含窒素有機化合物Ａとして、アミジン誘導体アミン、含窒素複素環式芳香族アミン、窒素共役系カルボキシ基含有化合物および尿素からなる群から選択された少なくとも１種を含む。かかる含窒素有機化合物Ａを含む研磨用組成物によると、実用上十分に高い研磨レートを維持しつつ、ＨＬＭ周縁の***をより好適に解消することができる。 In a preferred embodiment, the polishing composition has at least the nitrogen-containing organic compound A selected from the group consisting of amidine derivative amines, nitrogen-containing heterocyclic aromatic amines, nitrogen-conjugated carboxy group-containing compounds and urea. Including one. According to the polishing composition containing such a nitrogen-containing organic compound A, it is possible to more suitably eliminate the protrusion on the peripheral edge of the HLM while maintaining a polishing rate that is sufficiently high in practical use.
　好ましい一態様において、上記塩基性化合物は有機の塩基性化合物（有機アルカリ）である。塩基性化合物として有機アルカリを使用すると、研磨用組成物における砥粒の分散性が向上し、研磨レートが向上しやすい。 In a preferred embodiment, the basic compound is an organic basic compound (organic alkali). When an organic alkali is used as the basic compound, the dispersibility of abrasive grains in the polishing composition is improved, and the polishing rate is easily improved.
　好ましい他の一態様に係る研磨用組成物は、上記塩基性化合物として、第四級アンモニウム化合物を含む。かかる構成の研磨用組成物によると、研磨用組成物における砥粒の分散性が向上し、研磨レートが向上し得る。 The polishing composition according to another preferred embodiment contains a quaternary ammonium compound as the basic compound. According to the polishing composition having such a configuration, the dispersibility of abrasive grains in the polishing composition is improved, and the polishing rate can be improved.
　好ましい一態様に係る研磨用組成物は、上記含窒素有機化合物Ａとして、アルギニン、ヒスチジンおよびトリプトファンの少なくとも１種を含む。かかる含窒素有機化合物Ａを含む構成によると、実用上十分に高い研磨レートが維持されつつ、ＨＬＭ周縁の***を好適に解消することができる。 The polishing composition according to a preferred embodiment contains, as the nitrogen-containing organic compound A, at least one of arginine, histidine and tryptophan. According to the configuration including the nitrogen-containing organic compound A, it is possible to preferably eliminate the protrusion on the peripheral edge of the HLM while maintaining a polishing rate that is sufficiently high in practical use.
　好ましい他の一態様に係る研磨用組成物は、上記含窒素有機化合物Ａとして、イミダゾール、ピリジンおよびこれらの誘導体からなる群から選択される少なくとも１種を含む。かかる含窒素有機化合物Ａを含む構成によると、高い研磨レートとＨＬＭ周縁の優れた***解消性が両立して達成されうる。 A polishing composition according to another preferred embodiment contains, as the nitrogen-containing organic compound A, at least one selected from the group consisting of imidazole, pyridine and derivatives thereof. According to the configuration including the nitrogen-containing organic compound A, both a high polishing rate and an excellent swelling eliminating property on the periphery of the HLM can be achieved at the same time.
　好ましい他の一態様に係る研磨用組成物は、上記含窒素有機化合物Ａとして、尿素を含む。かかる含窒素有機化合物Ａを含む構成によると、高い研磨レートとＨＬＭ周縁の優れた***解消性が両立して達成されうる。 A polishing composition according to another preferred embodiment contains urea as the nitrogen-containing organic compound A. According to the configuration including the nitrogen-containing organic compound A, both a high polishing rate and an excellent swelling eliminating property on the periphery of the HLM can be achieved at the same time.
　ここに開示される研磨用組成物の好ましい他の一態様では、上記砥粒はシリカ粒子である。砥粒としてシリカ粒子を用いる研磨において、上記含窒素有機化合物ＡによるＨＬＭ周縁の***解消効果がより効果的に発揮され得る。 In another preferable aspect of the polishing composition disclosed herein, the abrasive grains are silica particles. In the polishing using silica particles as the abrasive grains, the effect of eliminating the ridge at the HLM peripheral edge by the nitrogen-containing organic compound A can be more effectively exhibited.
　以下、本発明の好適な実施形態を説明する。なお、本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、当該分野における従来技術に基づく当業者の設計事項として把握され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。
　本明細書において、範囲を示す「Ｘ～Ｙ」は「Ｘ以上Ｙ以下」を意味する。 Hereinafter, preferred embodiments of the present invention will be described. It should be noted that matters other than matters particularly referred to in the present specification and matters necessary for implementing the present invention can be grasped as design matters of a person skilled in the art based on conventional technology in the field. The present invention can be carried out based on the contents disclosed in this specification and the common general technical knowledge in the field.
In the present specification, “X to Y” indicating a range means “X or more and Y or less”.
　この明細書において、砥粒の平均一次粒子径とは、ＢＥＴ法により測定される比表面積（ＢＥＴ値）から、平均一次粒子径（ｎｍ）＝６０００／（真密度（ｇ／ｃｍ３）×ＢＥＴ値（ｍ２／ｇ））の式により算出される粒子径をいう。例えばシリカ粒子の場合、平均一次粒子径（ｎｍ）＝２７２７／ＢＥＴ値（ｍ２／ｇ）により平均一次粒子径を算出することができる。比表面積の測定は、例えば、マイクロメリテックス社製の表面積測定装置、商品名「Ｆｌｏｗ　Ｓｏｒｂ　ＩＩ　２３００」を用いて行うことができる。 In this specification, the average primary particle diameter of the abrasive grains means the average primary particle diameter (nm)=6000/(true density (g/cm 3 )×BET from the specific surface area (BET value) measured by the BET method. Value (m 2 /g)) is the particle size calculated by the formula. For example, in the case of silica particles, the average primary particle diameter can be calculated from the average primary particle diameter (nm)=2727/BET value (m 2 /g). The specific surface area can be measured using, for example, a surface area measuring device manufactured by Micromeritex Co., Ltd. under the trade name of “Flow Sorb II 2300”.
　この明細書において、砥粒を構成する各粒子のアスペクト比は、走査型電子顕微鏡（ＳＥＭ）による当該粒子の画像に外接する最小の長方形の長辺の長さを同じ長方形の短辺の長さで除することにより求めることができる。 In this specification, the aspect ratio of each particle constituting the abrasive grain is defined by the length of the long side of the smallest rectangle circumscribing the image of the particle by a scanning electron microscope (SEM) to the length of the short side of the same rectangle. It can be obtained by dividing by.
　この明細書において、粒子の円換算径とは、走査型電子顕微鏡（ＳＥＭ）による当該粒子の画像の面積を計測し、それと同じ面積の円の直径を求めることにより得られる値をいう。 In this specification, the circle-converted diameter of a particle is a value obtained by measuring the area of the image of the particle with a scanning electron microscope (SEM) and determining the diameter of a circle having the same area.
　＜砥粒＞
　ここに開示される研磨用組成物は、砥粒を含む。砥粒は、研磨対象物の表面を機械的に研磨する働きをする。 <Abrasive grains>
The polishing composition disclosed herein contains abrasive grains. The abrasive grains function to mechanically polish the surface of the object to be polished.
　砥粒の材質や性状は特に制限されず、使用目的や使用態様等に応じて適宜選択することができる。砥粒は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。砥粒の例としては、無機粒子、有機粒子、および有機無機複合粒子が挙げられる。無機粒子の具体例としては、シリカ粒子、窒化ケイ素粒子、炭化ケイ素粒子等のシリコン化合物粒子や、ダイヤモンド粒子等が挙げられる。有機粒子の具体例としては、ポリメタクリル酸メチル（ＰＭＭＡ）粒子、ポリアクリロニトリル粒子等が挙げられる。なかでも無機粒子が好ましい。 The material and properties of the abrasive grains are not particularly limited, and can be appropriately selected according to the purpose of use and the mode of use. The abrasive grains may be used alone or in combination of two or more. Examples of the abrasive grains include inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include silicon compound particles such as silica particles, silicon nitride particles, and silicon carbide particles, and diamond particles. Specific examples of the organic particles include polymethylmethacrylate (PMMA) particles and polyacrylonitrile particles. Of these, inorganic particles are preferable.
　ここに開示される技術において特に好ましい砥粒として、シリカ粒子が挙げられる。ここに開示される技術は、例えば、上記砥粒が実質的にシリカ粒子からなる態様で好ましく実施され得る。ここで「実質的に」とは、砥粒を構成する粒子の９５重量％以上（好ましくは９８重量％以上、より好ましくは９９重量％以上であり、１００重量％であってもよい。）がシリカ粒子であることをいう。 Silica particles are mentioned as particularly preferable abrasive grains in the technology disclosed herein. The technique disclosed herein can be preferably carried out, for example, in a mode in which the abrasive grains are substantially silica particles. Here, “substantially” means 95% by weight or more (preferably 98% by weight or more, more preferably 99% by weight or more, and even 100% by weight) of the particles constituting the abrasive grains. It is a silica particle.
　シリカ粒子の具体例としては、コロイダルシリカ、フュームドシリカ、沈降シリカ等が挙げられる。シリカ粒子は、１種を単独でまたは２種以上を組み合わせて用いることができる。研磨対象物表面にスクラッチを生じにくく、かつ良好な研磨性能（表面粗さを低下させる性能や***解消性等）を発揮し得ることから、コロイダルシリカが特に好ましい。コロイダルシリカとしては、例えば、イオン交換法により水ガラス（珪酸Ｎａ）を原料として作製されたコロイダルシリカや、アルコキシド法コロイダルシリカを好ましく採用することができる。ここでアルコキシド法コロイダルシリカとは、アルコキシシランの加水分解縮合反応により製造されたコロイダルシリカである。コロイダルシリカは、１種を単独でまたは２種以上を組み合わせて用いることができる。 Specific examples of silica particles include colloidal silica, fumed silica, and precipitated silica. The silica particles may be used alone or in combination of two or more. Colloidal silica is particularly preferable because it is unlikely to cause scratches on the surface of the object to be polished and can exhibit good polishing performance (performance to reduce surface roughness, swelling elimination property, etc.). As the colloidal silica, for example, colloidal silica produced from water glass (Na silicate) as a raw material by an ion exchange method or alkoxide method colloidal silica can be preferably used. Here, the alkoxide colloidal silica is colloidal silica produced by a hydrolysis condensation reaction of alkoxysilane. Colloidal silica can be used individually by 1 type or in combination of 2 or more types.
　シリカ粒子を構成するシリカの真比重は、１．５以上であることが好ましく、より好ましくは１．６以上、さらに好ましくは１．７以上である。シリカの真比重の増大により、研磨レートは高くなる傾向にある。かかる観点から、真比重が２．０以上（例えば２．１以上）のシリカ粒子が特に好ましい。シリカの真比重の上限は特に限定されないが、典型的には２．３以下、例えば２．２以下である。シリカの真比重としては、置換液としてエタノールを用いた液体置換法による測定値を採用し得る。 The true specific gravity of silica constituting the silica particles is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more. The polishing rate tends to increase due to an increase in the true specific gravity of silica. From this viewpoint, silica particles having a true specific gravity of 2.0 or more (for example, 2.1 or more) are particularly preferable. The upper limit of the true specific gravity of silica is not particularly limited, but it is typically 2.3 or less, for example 2.2 or less. As the true specific gravity of silica, a value measured by a liquid replacement method using ethanol as a replacement liquid can be adopted.
　砥粒の平均一次粒子径は特に限定されず、例えば１０ｎｍ～２００ｎｍ程度の範囲から適宜選択し得る。***解消性向上の観点から、平均一次粒子径は、２０ｎｍ以上であることが好ましく、３０ｎｍ以上であることがより好ましい。いくつかの態様において、平均一次粒子径は、例えば４０ｎｍ超であってよく、４５ｎｍ超でもよく、５０ｎｍ超でもよい。また、スクラッチの発生防止の観点から、平均一次粒子径は、通常、１５０ｎｍ以下であることが有利であり、１２０ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましい。いくつかの態様において、砥粒の平均一次粒子径は、７５ｎｍ以下でもよく、６０ｎｍ以下でもよい。 The average primary particle diameter of the abrasive grains is not particularly limited, and can be appropriately selected from the range of, for example, about 10 nm to 200 nm. From the viewpoint of improving the swelling elimination property, the average primary particle diameter is preferably 20 nm or more, and more preferably 30 nm or more. In some embodiments, the average primary particle size can be, for example, greater than 40 nm, greater than 45 nm, and greater than 50 nm. Further, from the viewpoint of preventing the occurrence of scratches, the average primary particle diameter is usually advantageously 150 nm or less, preferably 120 nm or less, and more preferably 100 nm or less. In some embodiments, the average primary particle size of the abrasive grains may be 75 nm or less, and 60 nm or less.
　砥粒の形状（外形）は、球形であってもよく、非球形であってもよい。非球形をなす粒子の具体例としては、ピーナッツ形状すなわち落花生の殻の形状、繭型形状、金平糖形状等のような突起付き形状、ラグビーボール形状等が挙げられる。 The shape (outer shape) of the abrasive grains may be spherical or non-spherical. Specific examples of the non-spherical particles include a peanut shape, that is, a peanut shell shape, a cocoon shape, a projection shape such as a konpeito sugar shape, and a rugby ball shape.
　砥粒の平均アスペクト比は特に限定されない。砥粒の平均アスペクト比は、原理的に１．０以上であり、１．０５以上、または、１．１以上とすることができる。平均アスペクト比の増大により、***解消性は概して向上する傾向にある。また、砥粒の平均アスペクト比は、スクラッチ低減や研磨の安定性向上等の観点から、好ましくは３．０以下であり、より好ましくは２．０以下である。いくつかの態様において、砥粒の平均アスペクト比は、例えば１．５以下であってよく、１．４以下でもよく、１．３以下でもよい。 The average aspect ratio of the abrasive grains is not particularly limited. The average aspect ratio of the abrasive grains is 1.0 or more in principle, and can be 1.05 or more, or 1.1 or more. The increase in average aspect ratio tends to generally improve ridge relief. The average aspect ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, from the viewpoints of scratch reduction and polishing stability improvement. In some embodiments, the average aspect ratio of the abrasive grains can be, for example, 1.5 or less, 1.4 or less, or 1.3 or less.
　いくつかの態様において、砥粒としては、円換算径が５０ｎｍ以上でかつアスペクト比が１．２以上である粒子の体積割合が５０％以上であるものを採用することができる。上記体積割合は、６０％以上とすることもできる。上記体積割合の値が５０％以上である場合、さらに言えば６０％以上である場合には、***の解消に特に有効なサイズおよびアスペクト比の粒子が砥粒中に比較的多く含まれることが理由で、砥粒の機械的作用による***解消性をより向上させることができる。 In some embodiments, as the abrasive grains, those having a circle-converted diameter of 50 nm or more and an aspect ratio of 1.2 or more and having a volume ratio of 50% or more can be adopted. The volume ratio may be 60% or more. When the value of the volume ratio is 50% or more, and more specifically 60% or more, the abrasive grains may contain a relatively large amount of particles having a size and aspect ratio that are particularly effective for eliminating the protrusion. For that reason, it is possible to further improve the swelling elimination property due to the mechanical action of the abrasive grains.
　いくつかの態様において、砥粒の平均円換算径は、例えば２５ｎｍ以上であってよく、４０ｎｍ以上でもよく、５５ｎｍ以上でもよく、７０ｎｍ以上でもよい。また、砥粒の平均円換算径は、例えば３００ｎｍ以下であってよく、２００ｎｍ以下でもよく、１５０ｎｍ以下でもよく、１００ｎｍ以下でもよい。ここに開示される研磨用組成物は、このような平均円換算径を有する砥粒を用いて好適に実施され得る。 In some embodiments, the average circle equivalent diameter of the abrasive grains may be, for example, 25 nm or more, 40 nm or more, 55 nm or more, and 70 nm or more. The average circle conversion diameter of the abrasive grains may be, for example, 300 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less. The polishing composition disclosed herein can be preferably carried out using abrasive grains having such an average circle conversion diameter.
　砥粒の含有量は、特に限定されず、目的に応じて適宜設定し得る。研磨用組成物の全重量に対する砥粒の含有量は、例えば０．０１重量％以上であってよく、０．０５重量％以上でもよく、０．１重量％以上でもよい。砥粒の含有量の増大により、***解消性は概して向上する傾向にある。いくつかの態様において、砥粒の含有量は、０．２重量％以上でもよく、０．５重量％以上でもよく、０．６重量％以上でもよく、０．７重量％以上でもよく、０．８重量％以上でもよく、０．８５重量％以上でもよい。また、スクラッチ防止や砥粒の使用量節約の観点から、いくつかの態様において、砥粒の含有量は、例えば１０重量％以下であってよく、５重量％以下でもよく、３重量％以下でもよく、２重量％以下でもよい。これらの含有量は、例えば、研磨対象物に供給される研磨液（ワーキングスラリー）における含有量に好ましく適用され得る。 The content of abrasive grains is not particularly limited and may be set appropriately according to the purpose. The content of abrasive grains with respect to the total weight of the polishing composition may be, for example, 0.01% by weight or more, may be 0.05% by weight or more, and may be 0.1% by weight or more. Increasing the content of abrasive grains generally tends to improve the swelling elimination property. In some embodiments, the content of abrasive grains may be 0.2 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0 It may be 0.8% by weight or more, or 0.85% by weight or more. From the viewpoint of preventing scratches and saving the amount of abrasive grains used, in some embodiments, the content of abrasive grains may be, for example, 10% by weight or less, 5% by weight or less, or 3% by weight or less. It may be 2% by weight or less. These contents can be preferably applied to the contents in the polishing liquid (working slurry) supplied to the object to be polished, for example.
　＜含窒素有機化合物Ａ＞
　ここに開示される研磨用組成物は、含窒素有機化合物Ａを含む。ここで、上記含窒素有機化合物Ａとは、分子中に少なくとも１つの窒素原子を含む有機化合物であって、かつ該含窒素有機化合物Ａに含まれる少なくとも１つの窒素原子が、π共役系構造（π電子が非局在化している構造）を構成している化合物である。このような含窒素有機化合物Ａを含む研磨用組成物によると、高い研磨レートと優れたＨＬＭ周縁の***解消性とが両立して達成されやすい。 <Nitrogen-containing organic compound A>
The polishing composition disclosed herein contains a nitrogen-containing organic compound A. Here, the nitrogen-containing organic compound A is an organic compound containing at least one nitrogen atom in the molecule, and at least one nitrogen atom contained in the nitrogen-containing organic compound A has a π-conjugated system structure ( It is a compound that constitutes a structure in which π electrons are delocalized). According to the polishing composition containing such a nitrogen-containing organic compound A, it is easy to achieve both a high polishing rate and an excellent bulge elimination property at the edge of the HLM.
　上記含窒素有機化合物Ａに含まれる窒素原子の数は１以上であればよく、特に限定されない。ここに開示される技術において、上記含窒素有機化合物Ａとしては、分子中に窒素原子を１以上１０以下含むものを好ましく使用することができる。上記含窒素有機化合物Ａに含まれる窒素原子の数は、より好ましくは１以上６以下、さらに好ましくは１以上５以下、例えば１以上４以下である。 The number of nitrogen atoms contained in the nitrogen-containing organic compound A may be 1 or more and is not particularly limited. In the technology disclosed herein, as the nitrogen-containing organic compound A, those containing 1 to 10 nitrogen atoms in the molecule can be preferably used. The number of nitrogen atoms contained in the nitrogen-containing organic compound A is more preferably 1 or more and 6 or less, still more preferably 1 or more and 5 or less, for example 1 or more and 4 or less.
　ここで、含窒素有機化合物Ａに含まれる窒素原子の数が２以上である場合において、含窒素有機化合物Ａに含まれる窒素原子の全てがπ共役系構造を構成している必要はない。即ち、含窒素有機化合物Ａに含まれる窒素原子のうち少なくとも１つの窒素原子がπ共役系構造を構成していればよい。ここに開示される技術における好適な一態様において、上記含窒素有機化合物Ａに含まれるπ共役系構造を構成している窒素原子の数は１以上３以下であり、より好ましくは１以上２以下である。 Here, when the number of nitrogen atoms contained in the nitrogen-containing organic compound A is 2 or more, it is not necessary that all the nitrogen atoms contained in the nitrogen-containing organic compound A form a π-conjugated system structure. That is, it suffices that at least one nitrogen atom among the nitrogen atoms contained in the nitrogen-containing organic compound A constitutes a π-conjugated system structure. In a preferred aspect of the technology disclosed herein, the number of nitrogen atoms constituting the π-conjugated system structure contained in the nitrogen-containing organic compound A is 1 or more and 3 or less, and more preferably 1 or more and 2 or less. Is.
　ここに開示される技術において、窒素原子がπ共役系構造を構成している構造（以下、「窒素共役系構造」ともいう。）の構成は、特に限定されない。例えば、上記窒素共役系構造の例として、交互に位置する単結合および多重結合の一部を窒素原子が構成する構造（例えば、含窒素不飽和複素環構造など）や、窒素原子の有する非共有電子対が該窒素原子に隣り合う原子との間で共役系を構成する構造等が挙げられる。上記窒素共役系構造の具体例としては、アミジン構造、含窒素不飽和複素環構造、尿素（カルバミド）構造等が挙げられる。かかる構造を分子内に有する含窒素有機化合物Ａを含む研磨用組成物によると、ＨＬＭ周縁の***を解消する性能が向上しやすい。 In the technology disclosed herein, the structure of a structure in which a nitrogen atom constitutes a π-conjugated system structure (hereinafter, also referred to as “nitrogen-conjugated system structure”) is not particularly limited. For example, as examples of the above-mentioned nitrogen-conjugated system structure, a structure in which a nitrogen atom constitutes part of alternating single bonds and multiple bonds (for example, a nitrogen-containing unsaturated heterocyclic structure) or a non-covalent structure of a nitrogen atom Examples thereof include a structure in which an electron pair forms a conjugated system with an atom adjacent to the nitrogen atom. Specific examples of the nitrogen-conjugated structure include an amidine structure, a nitrogen-containing unsaturated heterocyclic structure, and a urea (carbamide) structure. According to the polishing composition containing the nitrogen-containing organic compound A having such a structure in the molecule, the performance of eliminating the protrusion on the peripheral edge of the HLM is likely to be improved.
　ここに開示される含窒素有機化合物Ａは、窒素原子がπ共役系を構成している構造を含む限りにおいて、当該窒素共役系構造以外の部分の構成（構造、置換基など）は特に限定されない。ここに開示される技術において好適に用いられ得る含窒素有機化合物Ａの具体例としては、アミジン誘導体アミン、含窒素複素環式芳香族アミン、窒素共役系カルボキシ基含有化合物、尿素等が挙げられる。なかでも、ＨＬＭ周縁の***解消性の観点から、含窒素複素環式芳香族アミン、窒素共役系カルボキシ基含有化合物および尿素からなる群から選択される１種または２種以上が好ましく用いられ得る。ここで、上記窒素共役系カルボキシ基含有化合物は、分子中に窒素共役系構造を含みつつ、少なくとも１つのカルボキシ基を含む化合物のことを指す。 The nitrogen-containing organic compound A disclosed herein is not particularly limited in the constitution (structure, substituents, etc.) of the portion other than the nitrogen-conjugated system structure, as long as the nitrogen-containing organic compound A has a structure in which the nitrogen atom constitutes a π-conjugated system. .. Specific examples of the nitrogen-containing organic compound A that can be suitably used in the technology disclosed herein include amidine derivative amines, nitrogen-containing heterocyclic aromatic amines, nitrogen-conjugated carboxy group-containing compounds, and urea. Among them, from the viewpoint of eliminating the bulge around the HLM, one or more selected from the group consisting of a nitrogen-containing heterocyclic aromatic amine, a nitrogen-conjugated carboxy group-containing compound and urea can be preferably used. Here, the nitrogen-conjugated carboxy group-containing compound refers to a compound containing a nitrogen-conjugated structure in the molecule and at least one carboxy group.
　上記アミジン誘導体アミンの例としては、アミジン部位を有するアミン（例えばアミジンの部分構造を有する複素環式アミン）が挙げられる。具体的には、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン（ＤＢＵ）、１，５－ジアザビシクロ［４．３．０］－５－ノネン（ＤＢＮ）等が挙げられる。なかでも、ＨＬＭ周縁の***解消性の観点から、ＤＢＵが好ましい。 Examples of the amidine derivative amine include amines having an amidine moiety (for example, a heterocyclic amine having an amidine partial structure). Specific examples include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN). Among them, DBU is preferable from the viewpoint of eliminating the bulge at the periphery of the HLM.
　上記含窒素複素環式芳香族アミンは、窒素原子を含む芳香族複素環を分子内に少なくとも１つ含むアミンのことを指す。ここで、上記芳香族複素環の大きさは特に限定されない。ここに開示される技術における好適な一態様において、上記芳香族複素環は六員環以下であることが好ましく、より好ましくは五員環または六員環である。上記含窒素複素環式芳香族アミンは、２以上の不飽和複素環（典型的には芳香族複素環）を分子内に有していてもよい。好ましくは、上記含窒素複素環式芳香族アミンは１つまたは２つの含窒素不飽和複素環を分子内に有する。 The above-mentioned nitrogen-containing heterocyclic aromatic amine refers to an amine containing at least one aromatic heterocycle containing a nitrogen atom in the molecule. Here, the size of the aromatic heterocycle is not particularly limited. In a preferred aspect of the technology disclosed herein, the aromatic heterocycle is preferably a 6-membered ring or less, and more preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocyclic aromatic amine may have two or more unsaturated heterocycles (typically aromatic heterocycles) in the molecule. Preferably, the nitrogen-containing heterocyclic aromatic amine has one or two nitrogen-containing unsaturated heterocycles in the molecule.
　上記含窒素複素環式芳香族アミンの例としては、含窒素六員環芳香族アミン、含窒素五員環芳香族アミン等が挙げられる。上記含窒素六員環芳香族アミンの好適例としては、ピリジンおよびその誘導体が挙げられる。ピリジン誘導体の好適例としては、４－アミノピリジン、ピコリン酸、ピリジン等が挙げられる。なかでも、ピリジンが好ましく用いられ得る。上記含窒素五員環芳香族アミンの好適例としては、イミダゾールおよびその誘導体が挙げられる。イミダゾール誘導体の好適例としては、１－（３－アミノプロピル）イミダゾール、２－メチルイミダゾール等が挙げられる。なかでも、１－（３－アミノプロピル）イミダゾールが好ましく用いられ得る。 Examples of the nitrogen-containing heterocyclic aromatic amine include nitrogen-containing 6-membered aromatic amine and nitrogen-containing 5-membered aromatic amine. Preferable examples of the nitrogen-containing 6-membered aromatic amine include pyridine and its derivatives. Preferable examples of the pyridine derivative include 4-aminopyridine, picolinic acid, pyridine and the like. Of these, pyridine can be preferably used. Preferable examples of the nitrogen-containing five-membered aromatic amine include imidazole and its derivatives. Preferable examples of the imidazole derivative include 1-(3-aminopropyl)imidazole and 2-methylimidazole. Among them, 1-(3-aminopropyl)imidazole can be preferably used.
　上記窒素共役系カルボキシ基含有化合物の非限定的な例としては、グアニジノ安息香酸、グアニジノグルタル酸、グアニジノコハク酸、グアニジノ酢酸、クレアチン、グアニジノプロピオン酸等のグアニジン誘導体、１－イミダゾール酢酸等のイミダゾール誘導体、ピコリン酸等が挙げられる。 Non-limiting examples of the nitrogen-conjugated carboxy group-containing compound include guanidine derivatives such as guanidinobenzoic acid, guanidinoglutaric acid, guanidinosuccinic acid, guanidinoacetic acid, creatine and guanidinopropionic acid, and imidazole derivatives such as 1-imidazoleacetic acid. , Picolinic acid and the like.
　さらに、上記窒素共役系カルボキシ基含有化合物の例として、窒素共役系アミノ酸が挙げられる。上記窒素共役系アミノ酸とは、分子内の少なくとも一つの窒素原子がπ共役系構造を構成しているアミノ酸のことを指す。上記窒素共役系アミノ酸は、ＨＬＭ周縁の***解消性の観点から好ましく用いられ得る。上記窒素共役系アミノ酸の具体例としては、アルギニン、ヒスチジン、トリプトファン等が挙げられる。 Further, examples of the nitrogen-conjugated carboxy group-containing compound include nitrogen-conjugated amino acids. The nitrogen-conjugated amino acid refers to an amino acid in which at least one nitrogen atom in the molecule constitutes a π-conjugated structure. The nitrogen-conjugated amino acid can be preferably used from the viewpoint of the ability to eliminate ridges on the periphery of HLM. Specific examples of the nitrogen-conjugated amino acid include arginine, histidine, tryptophan and the like.
　ここに開示される技術における含窒素有機化合物Ａは、上述のような化合物のいずれか１種であってもよく、２種以上の混合物であってもよい。 The nitrogen-containing organic compound A in the technology disclosed herein may be any one of the above compounds or a mixture of two or more thereof.
　上記研磨用組成物における含窒素有機化合物Ａの含有量（複数種類の含窒素有機化合物Ａを含有する場合にはそれらの合計量）は特に限定されず、使用目的や使用態様等に応じて所望の効果が得られるように適宜設定することができる。好ましい一態様において、研磨用組成物における含窒素有機化合物Ａの含有量は、例えば０．０００１重量％以上とすることができ、***解消効果をよりよく発揮する観点から０．００１重量％以上としてもよく、０．００３重量％以上が好ましく、０．００４重量％以上がより好ましい。また、研磨用組成物における含窒素有機化合物Ａの含有量は、例えば０．５重量％以下とすることができ、研磨効率等の観点から０．１重量％以下としてもよく、０．０５重量％以下が好ましく、より好ましくは０．０３重量％以下であり、さらに好ましくは０．０２重量％以下である。これらの含有量は、例えば、研磨対象物に供給される研磨液（ワーキングスラリー）における含有量に好ましく適用され得る。 The content of the nitrogen-containing organic compound A in the polishing composition (when a plurality of kinds of nitrogen-containing organic compounds A is contained, the total amount thereof) is not particularly limited, and may be desired depending on the purpose of use, usage mode, etc. It can be appropriately set so as to obtain the effect of. In a preferred embodiment, the content of the nitrogen-containing organic compound A in the polishing composition can be, for example, 0.0001% by weight or more, and is 0.001% by weight or more from the viewpoint of better exerting the bump elimination effect. The content is preferably 0.003% by weight or more, more preferably 0.004% by weight or more. The content of the nitrogen-containing organic compound A in the polishing composition can be, for example, 0.5% by weight or less, and may be 0.1% by weight or less from the viewpoint of polishing efficiency and the like, and 0.05% by weight or less. % Or less, preferably 0.03% by weight or less, and more preferably 0.02% by weight or less. These contents can be preferably applied to the contents in the polishing liquid (working slurry) supplied to the object to be polished, for example.
　特に限定されるものではないが、ここに開示される研磨用組成物における含窒素有機化合物Ａの含有量は、砥粒１００重量部に対して０．０１重量部以上とすることができ、***解消効果をよりよく発揮する観点から０．０５重量部以上としてもよく、好ましくは０．１重量部以上であり、より好ましくは０．３重量部以上、さらに好ましくは０．５重量部以上である。また、研磨用組成物における含窒素有機化合物Ａの含有量は、砥粒１００重量部に対して２０重量部以下とすることができ、研磨効率等の観点から１５重量部以下としてもよく、好ましくは１０重量部以下であり、より好ましくは５重量部以下、さらに好ましくは３重量部以下（例えば２．５重量部以下）である。 Although not particularly limited, the content of the nitrogen-containing organic compound A in the polishing composition disclosed herein can be 0.01 parts by weight or more with respect to 100 parts by weight of abrasive grains, and The amount may be 0.05 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, and still more preferably 0.5 parts by weight or more, from the viewpoint of better exerting the elimination effect. is there. Further, the content of the nitrogen-containing organic compound A in the polishing composition can be 20 parts by weight or less with respect to 100 parts by weight of the abrasive grains, and may be 15 parts by weight or less from the viewpoint of polishing efficiency and the like. Is 10 parts by weight or less, more preferably 5 parts by weight or less, still more preferably 3 parts by weight or less (for example, 2.5 parts by weight or less).
　＜塩基性化合物＞
　本発明に係る研磨用組成物は、塩基性化合物を含む。ここで塩基性化合物とは、研磨用組成物に添加されることによって該組成物のｐＨを上昇させる機能を有する化合物を指す。塩基性化合物は、研磨対象となる面を化学的に研磨する働きをし、研磨レートの向上に寄与し得る。なお、本発明において、上記塩基性化合物には、窒素原子がπ共役系構造を構成する含窒素有機化合物Ａは含まれない。 <Basic compound>
The polishing composition according to the present invention contains a basic compound. Here, the basic compound means a compound having a function of increasing the pH of the polishing composition by being added thereto. The basic compound serves to chemically polish the surface to be polished, and can contribute to the improvement of the polishing rate. In the present invention, the basic compound does not include the nitrogen-containing organic compound A in which a nitrogen atom forms a π-conjugated system structure.
　上記塩基性化合物としては、窒素を含む有機または無機の塩基性化合物、アルカリ金属またはアルカリ土類金属の水酸化物等を用いることができる。例えば、上記塩基性化合物としては、アルカリ金属の水酸化物、水酸化第四級アンモニウムまたはその塩、アンモニア、アミン等が挙げられる。アルカリ金属の水酸化物の具体例としては、水酸化カリウム、水酸化ナトリウム等が挙げられる。水酸化第四級アンモニウムまたはその塩の具体例としては、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム等が挙げられる。アミンの具体例としては、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、モノエタノールアミン、Ｎ－（β－アミノエチル）エタノールアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、無水ピペラジン、ピペラジン六水和物、１－（２－アミノエチル）ピペラジン、Ｎ－メチルピペラジン等が挙げられる。このように窒素原子がπ共役系構造を構成していない塩基性化合物と、含窒素有機化合物Ａとを組み合わせて使用すると、研磨レート向上とＨＬＭ周縁の***解消性向上とが両立して達成されやすい。 As the basic compound, an organic or inorganic basic compound containing nitrogen, an alkali metal or alkaline earth metal hydroxide, or the like can be used. Examples of the basic compound include alkali metal hydroxides, quaternary ammonium hydroxide or salts thereof, ammonia, amines and the like. Specific examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide. Specific examples of the quaternary ammonium hydroxide or its salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and the like. Specific examples of amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-aminoethyl)ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine. , Piperazine hexahydrate, 1-(2-aminoethyl)piperazine, N-methylpiperazine and the like. When the basic compound in which the nitrogen atom does not form a π-conjugated system structure and the nitrogen-containing organic compound A are used in combination as described above, improvement in the polishing rate and improvement in the elimination of the ridge at the edge of the HLM are achieved at the same time. Cheap.
　ここに開示される技術において、好ましく用いられる塩基性化合物としては、有機の塩基性化合物（有機アルカリ）が挙げられる。塩基性化合物として有機アルカリを用いると、砥粒の分散性が向上し、研磨レートが向上する傾向がある。 In the technique disclosed herein, an organic basic compound (organic alkali) is preferably used as the basic compound. The use of an organic alkali as the basic compound tends to improve the dispersibility of the abrasive grains and improve the polishing rate.
　***解消性向上等の観点から好ましい塩基性化合物として、第四級アンモニウム化合物が挙げられる。第四級アンモニウム化合物としては、テトラアルキルアンモニウム塩、ヒドロキシアルキルトリアルキルアンモニウム塩等の第四級アンモニウム塩（典型的には強塩基）を好ましく用いることができる。かかる第四級アンモニウム塩におけるアニオン成分は、例えば、ＯＨ－、Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－、ＣｌＯ４ －、ＢＨ４ －等であり得る。なかでも好ましい例として、アニオンがＯＨ－である第四級アンモニウム塩、すなわち水酸化第四級アンモニウムが挙げられる。水酸化第四級アンモニウムの具体例としては、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム、水酸化テトラペンチルアンモニウムおよび水酸化テトラヘキシルアンモニウム等の水酸化テトラアルキルアンモニウム；水酸化２－ヒドロキシエチルトリメチルアンモニウム（コリンともいう。）等の水酸化ヒドロキシアルキルトリアルキルアンモニウム；等が挙げられる。特に好ましく用いられるものとして水酸化テトラアルキルアンモニウム（例えば、水酸化テトラメチルアンモニウム）が挙げられる。上記塩基性化合物は、１種を単独でまたは２種以上を組み合わせて用いることができる。 A quaternary ammonium compound is mentioned as a preferable basic compound from the viewpoint of improving the swelling elimination property. As the quaternary ammonium compound, a quaternary ammonium salt (typically a strong base) such as a tetraalkylammonium salt or a hydroxyalkyltrialkylammonium salt can be preferably used. The anion component in such a quaternary ammonium salt may be, for example, OH − , F − , Cl − , Br − , I − , ClO 4 − , BH 4 − . Among them, a preferable example is a quaternary ammonium salt having an anion of OH −, that is, a quaternary ammonium hydroxide. Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide and tetrahexylammonium hydroxide. Tetraalkylammonium; hydroxyalkyltrialkylammonium hydroxide such as 2-hydroxyethyltrimethylammonium hydroxide (also called choline); and the like. Particularly preferably used is tetraalkylammonium hydroxide (eg, tetramethylammonium hydroxide). The above basic compounds may be used alone or in combination of two or more.
　研磨用組成物全量に対する塩基性化合物の含有量は、研磨レートの促進の観点から、好ましくは０．０１重量％以上、より好ましくは０．０２重量％以上、さらに好ましくは０．０３重量％以上である。塩基性化合物の含有量の増加によって、研磨用組成物の分散安定性も向上し得る。上記塩基性化合物の含有量は、１重量％以下とすることが適当であり、表面品質等の観点から、好ましくは０．５重量％以下であり、より好ましくは０．１重量％以下である。また、２種以上の塩基性化合物を組み合わせて用いる場合は、上記含有量は２種以上の塩基性化合物の合計含有量を指す。これらの含有量は、例えば、研磨対象物に供給される研磨液（ワーキングスラリー）における含有量に好ましく適用され得る。 The content of the basic compound relative to the total amount of the polishing composition is preferably 0.01% by weight or more, more preferably 0.02% by weight or more, further preferably 0.03% by weight or more, from the viewpoint of promoting the polishing rate. Is. By increasing the content of the basic compound, the dispersion stability of the polishing composition can be improved. The content of the basic compound is appropriately 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less from the viewpoint of surface quality and the like. .. Moreover, when using 2 or more types of basic compounds in combination, the said content points out the total content of 2 or more types of basic compounds. These contents can be preferably applied to the contents in the polishing liquid (working slurry) supplied to the object to be polished, for example.
　特に限定されるものではないが、ここに開示される研磨用組成物における塩基性化合物の含有量は、砥粒１００重量部に対して０．０１重量部以上とすることができ、研磨レートの促進の観点から０．０５重量部以上としてもよく、好ましくは０．１重量部以上であり、より好ましくは０．３重量部以上、さらに好ましくは０．５重量部以上である。また、研磨用組成物における塩基性化合物の含有量は、砥粒１００重量部に対して２０重量部以下とすることができ、表面品質等の観点から、１５重量部以下としてもよく、好ましくは１２重量部以下であり、より好ましくは１０重量部以下である。例えば、砥粒１００重量部に対して、塩基性化合物の含有量は、８重量部以下であってもよく、５重量部以下とすることもできる。２種以上の塩基性化合物を組み合わせて用いる場合は、上記含有量は２種以上の塩基性化合物の合計含有量を指す。 Although not particularly limited, the content of the basic compound in the polishing composition disclosed herein can be 0.01 parts by weight or more based on 100 parts by weight of the abrasive grains, and the polishing rate From the viewpoint of acceleration, the amount may be 0.05 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, still more preferably 0.5 parts by weight or more. Further, the content of the basic compound in the polishing composition can be 20 parts by weight or less with respect to 100 parts by weight of the abrasive grains, and may be 15 parts by weight or less from the viewpoint of surface quality and the like, preferably It is 12 parts by weight or less, and more preferably 10 parts by weight or less. For example, the content of the basic compound may be 8 parts by weight or less and may be 5 parts by weight or less with respect to 100 parts by weight of the abrasive grains. When two or more basic compounds are used in combination, the above content refers to the total content of the two or more basic compounds.
　＜水＞
　好ましい一態様において、ここに開示される研磨用組成物は水を含む。水としては、イオン交換水（脱イオン水）、純水、超純水、蒸留水等を好ましく用いることができる。使用する水は、研磨用組成物に含有される他の成分の働きが阻害されることを極力回避するため、例えば遷移金属イオンの合計含有量が１００ｐｐｂ以下であることが好ましい。例えば、イオン交換樹脂による不純物イオンの除去、フィルタによる異物の除去、蒸留等の操作によって水の純度を高めることができる。
　ここに開示される研磨用組成物は、必要に応じて、水と均一に混合し得る有機溶剤（低級アルコール、低級ケトン等）をさらに含有してもよい。通常は、研磨用組成物に含まれる溶媒の９０体積％以上が水であることが好ましく、９５体積％以上（典型的には９９～１００体積％）が水であることがより好ましい。 <water>
In a preferred embodiment, the polishing composition disclosed herein comprises water. As the water, ion exchanged water (deionized water), pure water, ultrapure water, distilled water or the like can be preferably used. The water to be used preferably has a total content of transition metal ions of 100 ppb or less, for example, in order to prevent the functions of other components contained in the polishing composition from being hindered. For example, the purity of water can be increased by operations such as removing impurity ions with an ion exchange resin, removing foreign substances with 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. Usually, 90% by volume or more of the solvent contained in the polishing composition is preferably water, and more preferably 95% by volume or more (typically 99 to 100% by volume) is water.
　＜その他の成分＞
　ここに開示される研磨用組成物は、本発明の効果が著しく妨げられない範囲で、水溶性高分子、界面活性剤、酸、キレート剤、防腐剤、防カビ剤等の、研磨用組成物（典型的には、シリコン基板のポリシング工程に用いられる研磨用組成物）に用いられ得る公知の添加剤を、必要に応じてさらに含有してもよい。 <Other ingredients>
The polishing composition disclosed herein is a polishing composition such as a water-soluble polymer, a surfactant, an acid, a chelating agent, an antiseptic agent, an antifungal agent, etc. within a range in which the effects of the present invention are not significantly impaired. A known additive that can be used in (typically, a polishing composition used in a polishing step of a silicon substrate) may be further contained, if necessary.
　上記水溶性高分子の例としては、セルロース誘導体、デンプン誘導体、オキシアルキレン単位を含むポリマー、窒素原子を含有するポリマー、ビニルアルコール系ポリマー等が挙げられる。上記水溶性高分子の具体例としては、ヒドロキシエチルセルロース、プルラン、エチレンオキサイドとプロピレンオキサイドとのランダム共重合体やブロック共重合体、ポリビニルアルコール、ポリイソプレンスルホン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリイソアミレンスルホン酸、ポリスチレンスルホン酸塩、ポリアクリル酸塩、ポリ酢酸ビニル、ポリエチレングリコール、ポリビニルイミダゾール、ポリビニルカルバゾール、ポリビニルピロリドン、ポリビニルカプロラクタム、ポリビニルピペリジン等が挙げられる。水溶性高分子は、１種を単独でまたは２種以上を組み合わせて用いることができる。ここに開示される研磨用組成物は、水溶性高分子を実質的に含まない態様、すなわち、少なくとも意図的には水溶性高分子を含有させない態様でも好ましく実施され得る。 Examples of the water-soluble polymer include cellulose derivatives, starch derivatives, polymers containing oxyalkylene units, polymers containing nitrogen atoms, vinyl alcohol polymers and the like. Specific examples of the water-soluble polymer, hydroxyethyl cellulose, pullulan, random copolymers and block copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, Examples thereof include polyisoamylene sulfonic acid, polystyrene sulfonate, polyacrylate, polyvinyl acetate, polyethylene glycol, polyvinyl imidazole, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl caprolactam, and polyvinyl piperidine. The water-soluble polymers can be used alone or in combination of two or more. The polishing composition disclosed herein can be preferably carried out even in a mode in which the water-soluble polymer is not substantially contained, that is, in a mode in which the water-soluble polymer is not contained at least intentionally.
　ここに開示される研磨用組成物には、任意成分として、界面活性剤（典型的には、分子量１×１０４未満の水溶性有機化合物）を含ませることができる。界面活性剤の使用により、研磨用組成物の分散安定性が向上し得る。界面活性剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。
　界面活性剤としては、アニオン性またはノニオン性のものを好ましく採用し得る。低起泡性やｐＨ調整の容易性の観点から、ノニオン性の界面活性剤がより好ましい。例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等のオキシアルキレン重合体；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレングリセリルエーテル脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等のポリオキシアルキレン付加物；複数種のオキシアルキレンの共重合体（ジブロック型、トリブロック型、ランダム型、交互型）；等のノニオン性界面活性剤が挙げられる。
　界面活性剤の使用量は、砥粒１ｋｇ当たり５ｇ以下とすることが適当であり、２ｇ以下とすることが好ましく、１ｇ以下とすることがより好ましい。ここに開示される研磨用組成物は、界面活性剤を実質的に含まない態様でも好ましく実施され得る。 The polishing composition disclosed herein can contain a surfactant (typically, a water-soluble organic compound having a molecular weight of less than 1×10 4 ) as an optional component. The use of a surfactant can improve the dispersion stability of the polishing composition. The surfactants may be used alone or in combination of two or more.
As the surfactant, anionic or nonionic one can be preferably adopted. From the viewpoint of low foaming property and easiness of pH adjustment, a nonionic surfactant is more preferable. For example, oxyalkylene polymers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid ester, polyoxyethylene glyceryl ether fatty acid. Nonionic surfactants such as esters, polyoxyalkylene adducts such as polyoxyethylene sorbitan fatty acid esters; copolymers of plural kinds of oxyalkylenes (diblock type, triblock type, random type, alternating type); To be
The amount of the surfactant used is suitably 5 g or less, preferably 2 g or less, and more preferably 1 g or less, per 1 kg of abrasive grains. The polishing composition disclosed herein can be preferably carried out even in an embodiment substantially containing no surfactant.
　上記酸の例としては、塩酸、リン酸、硫酸、ホスホン酸、硝酸、ホスフィン酸、ホウ酸等の無機酸；酢酸、イタコン酸、コハク酸、酒石酸、クエン酸、マレイン酸、グリコール酸、マロン酸、メタンスルホン酸、ギ酸、リンゴ酸、グルコン酸、アラニン、グリシン、乳酸、hydroxyethylidene diphosphonic acid（HEDP）、nitrilotris[methylene phosphonic acid]（NTMP）、phosphonobutane tricarboxylic acid（PBTC）等の有機酸；等が挙げられる。酸は、該酸の塩の形態で用いられてもよい。上記酸の塩は、例えば、ナトリウム塩やカリウム塩等のアルカリ金属塩や、アンモニウム塩等であり得る。 Examples of the acid include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, phosphonic acid, nitric acid, phosphinic acid, boric acid; acetic acid, itaconic acid, succinic acid, tartaric acid, citric acid, maleic acid, glycolic acid, malonic acid. , Methanesulfonic acid, formic acid, malic acid, gluconic acid, alanine, glycine, lactic acid, hydroxyethylidene diphosphonic acid (HEDP), nitrilotris [methylene phosphonic acid] (NTMP), phosphonobutane tricarboxylic acid (PBTC), and other organic acids; and the like. To be The acid may be used in the form of a salt of the acid. The acid salt may be, for example, an alkali metal salt such as a sodium salt or a potassium salt, or an ammonium salt.
　上記キレート剤の例としては、アミノカルボン酸系キレート剤および有機ホスホン酸系キレート剤が挙げられる。アミノカルボン酸系キレート剤の例には、エチレンジアミン四酢酸、エチレンジアミン四酢酸ナトリウム、ニトリロ三酢酸、ニトリロ三酢酸ナトリウム、ニトリロ三酢酸アンモニウム、ヒドロキシエチルエチレンジアミン三酢酸、ヒドロキシエチルエチレンジアミン三酢酸ナトリウム、ジエチレントリアミン五酢酸、ジエチレントリアミン五酢酸ナトリウム、トリエチレンテトラミン六酢酸およびトリエチレンテトラミン六酢酸ナトリウムが含まれる。有機ホスホン酸系キレート剤の例には、２－アミノエチルホスホン酸、１－ヒドロキシエチリデン－１，１－ジホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラキス（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、エタン－１，１－ジホスホン酸、エタン－１，１，２－トリホスホン酸、エタン－１－ヒドロキシ－１，１－ジホスホン酸、エタン－１－ヒドロキシ－１，１，２－トリホスホン酸、エタン－１，２－ジカルボキシ－１，２－ジホスホン酸、メタンヒドロキシホスホン酸、２－ホスホノブタン－１，２－ジカルボン酸、１－ホスホノブタン－２，３，４－トリカルボン酸およびα－メチルホスホノコハク酸が含まれる。これらのうち有機ホスホン酸系キレート剤がより好ましい。なかでも好ましいものとして、エチレンジアミンテトラキス（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）およびジエチレントリアミン五酢酸が挙げられる。特に好ましいキレート剤として、エチレンジアミンテトラキス（メチレンホスホン酸）およびジエチレントリアミンペンタ（メチレンホスホン酸）が挙げられる。キレート剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。キレート剤の使用量は、例えば、ワーキングスラリーにおけるキレート剤の含有量が０．０００１～１重量％程度、０．００１～０．５重量％程度、または０．００５～０．１重量％程度となるように設定することができるが、これに限定されない。ここに開示される研磨用組成物は、キレート剤を含まない態様においても好ましく使用され得る。 Examples of the above chelating agents include aminocarboxylic acid type chelating agents and organic phosphonic acid type chelating agents. Examples of aminocarboxylic acid-based chelating agents include ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetic acid, ammonium nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, sodium hydroxyethylethylenediaminetriacetate, diethylenetriaminepentaacetic acid. , Sodium diethylenetriamine pentaacetate, triethylenetetramine hexaacetic acid and sodium triethylenetetramine hexaacetate. Examples of the organic phosphonic acid-based chelating agent include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid). Acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid , Ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonic acid Contains nosuccinic acid. Of these, organic phosphonic acid-based chelating agents are more preferable. Of these, preferred are ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and diethylenetriaminepentaacetic acid. Particularly preferred chelating agents include ethylenediaminetetrakis (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid). The chelating agents may be used alone or in combination of two or more. The amount of the chelating agent used is, for example, about 0.0001 to 1% by weight, about 0.001 to 0.5% by weight, or about 0.005 to 0.1% by weight of the content of the chelating agent in the working slurry. However, the present invention is not limited to this. The polishing composition disclosed herein can be preferably used even in an embodiment containing no chelating agent.
　上記防腐剤および防カビ剤の例としては、イソチアゾリン系化合物、パラオキシ安息香酸エステル類、フェノキシエタノール等が挙げられる。 Examples of the above preservatives and fungicides include isothiazoline compounds, paraoxybenzoic acid esters, phenoxyethanol and the like.
　ここに開示される研磨用組成物は、酸化剤を実質的に含まないことが好ましい。研磨用組成物中に酸化剤が含まれていると、当該組成物が供給されることでシリコン基板の表面が酸化されて酸化膜が生じ、これにより研磨レートが低下してしまうことがあり得るためである。ここで、研磨用組成物が酸化剤を実質的に含有しないとは、少なくとも意図的には酸化剤を配合しないことをいい、原料や製法等に由来して微量の酸化剤が不可避的に含まれることは許容され得る。上記微量とは、研磨用組成物における酸化剤のモル濃度が０．０００５モル／Ｌ以下（好ましくは０．０００１モル／Ｌ以下、より好ましくは０．００００１モル／Ｌ以下、特に好ましくは０．０００００１モル／Ｌ以下）であることをいう。好ましい一態様に係る研磨用組成物は、酸化剤を含有しない。ここに開示される研磨用組成物は、例えば、過酸化水素、過硫酸ナトリウム、過硫酸アンモニウムおよびジクロロイソシアヌル酸ナトリウムをいずれも含有しない態様で好ましく実施され得る。 The polishing composition disclosed herein preferably contains substantially no oxidizing agent. When the polishing composition contains an oxidizing agent, the composition may be supplied to oxidize the surface of the silicon substrate to form an oxide film, which may lower the polishing rate. This is because. Here, that the polishing composition does not substantially contain an oxidizing agent means that at least the oxidizing agent is not intentionally mixed, and a trace amount of the oxidizing agent is inevitably included due to the raw material, the manufacturing method, and the like. Can be allowed. The above-mentioned trace amount means that 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 0.001 mol/L or less. 000001 mol/L or less). The polishing composition according to a preferred embodiment does not contain an oxidizing agent. The polishing composition disclosed herein can be preferably carried out, for example, in a mode containing neither hydrogen peroxide, sodium persulfate, ammonium persulfate nor sodium dichloroisocyanurate.
　＜研磨用組成物＞
　ここに開示される研磨用組成物は、典型的には該研磨用組成物を含む研磨液（ワーキングスラリー）の形態で研磨対象物に供給されて、その研磨対象物の研磨に用いられる。ここに開示される研磨用組成物は、例えば、希釈（典型的には、水により希釈）して研磨液として使用されるものであってもよく、そのまま研磨液として使用されるものであってもよい。すなわち、ここに開示される技術における研磨用組成物の概念には、研磨対象物に供給されて該研磨対象物の研磨に用いられるワーキングスラリーと、かかるワーキングスラリーの濃縮液（原液）との双方が包含される。上記濃縮液の濃縮倍率は、例えば、体積基準で２倍～１００倍程度であってよく、通常は５倍～５０倍程度が適当である。 <Polishing composition>
The polishing composition disclosed herein is typically supplied to the object to be polished in the form of a polishing liquid (working slurry) containing the composition for polishing and used for polishing the object to be polished. The polishing composition disclosed herein may be, for example, diluted (typically diluted with water) and used as a polishing liquid, or may be used as it is as a polishing liquid. Good. That is, the concept of the polishing composition in the technology disclosed herein includes both a working slurry that is supplied to the object to be polished and used for polishing the object to be polished, and a concentrated solution (stock solution) of the working slurry. Is included. The concentration ratio of the concentrated liquid may be, for example, about 2 to 100 times on a volume basis, and normally about 5 to 50 times is appropriate.
　研磨用組成物のｐＨは、典型的には８．０以上であり、好ましくは８．５以上、より好ましくは９．０以上、さらに好ましくは９．５以上、例えば１０．０以上である。ｐＨが高くなると、研磨レートや***解消性が向上する傾向にある。一方、砥粒（例えばシリカ粒子）の溶解を防ぎ、該砥粒による機械的な研磨作用の低下を抑制する観点から、研磨液のｐＨは、通常、１２．０以下であることが適当であり、１１．８以下であることが好ましく、１１．５以下であることがより好ましく、１１．０以下であることがさらに好ましい。これらのｐＨは、研磨対象物に供給される研磨液（ワーキングスラリー）およびその濃縮液のｐＨのいずれにも好ましく適用され得る。 The pH of the polishing composition is typically 8.0 or higher, preferably 8.5 or higher, more preferably 9.0 or higher, further preferably 9.5 or higher, for example 10.0 or higher. When the pH is high, the polishing rate and the swelling elimination property tend to be improved. On the other hand, from the viewpoint of preventing dissolution of abrasive grains (for example, silica particles) and suppressing deterioration of mechanical polishing action due to the abrasive grains, the pH of the polishing liquid is usually appropriate to be 12.0 or less. , 11.8 or less, preferably 11.5 or less, and more preferably 11.0 or less. These pHs can be preferably applied to both the pH of the polishing liquid (working slurry) supplied to the object to be polished and the concentrated liquid thereof.
　なお、研磨用組成物のｐＨは、ｐＨメーター（例えば、堀場製作所製のガラス電極式水素イオン濃度指示計（型番Ｆ－２３））を使用し、標準緩衝液（フタル酸塩ｐＨ緩衝液　ｐＨ：４．０１（２５℃）、中性リン酸塩ｐＨ緩衝液　ｐＨ：６．８６（２５℃）、炭酸塩ｐＨ緩衝液　ｐＨ：１０．０１（２５℃））を用いて３点校正した後で、ガラス電極を研磨用組成物に入れて、２分以上経過して安定した後の値を測定することにより把握することができる。 For the pH of the polishing composition, use a pH meter (for example, a glass electrode type hydrogen ion concentration indicator (model number F-23) manufactured by Horiba Ltd.) and use a standard buffer solution (phthalate pH buffer solution pH: After three-point calibration using 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 putting the glass electrode in the polishing composition and measuring the value after the glass electrode has been stabilized for 2 minutes or more.
　ここに開示される研磨用組成物は、一剤型であってもよく、二剤型を始めとする多剤型であってもよい。例えば、少なくとも砥粒を含むパートＡと、残りの成分を含むパートＢとを混合し、必要に応じて適切なタイミングで希釈することによって研磨液が調製されるように構成されていてもよい。 The polishing composition disclosed herein may be a one-part type or a multi-part type including a two-part type. For example, the polishing liquid may be prepared by mixing Part A containing at least abrasive grains and Part B containing the remaining components, and diluting them at an appropriate timing as needed.
　ここに開示される研磨用組成物の製造方法は特に限定されない。例えば、翼式攪拌機、超音波分散機、ホモミキサー等の周知の混合装置を用いて、研磨用組成物に含まれる各成分を混合するとよい。これらの成分を混合する態様は特に限定されず、例えば全成分を一度に混合してもよく、適宜設定した順序で混合してもよい。 The method for producing the polishing composition disclosed herein is not particularly limited. For example, each component contained in the polishing composition may be mixed using a known mixing device such as a blade stirrer, an ultrasonic disperser, or a homomixer. The mode of mixing these components is not particularly limited, and for example, all components may be mixed at once, or may be mixed in an appropriately set order.
　＜研磨＞
　ここに開示される研磨用組成物は、例えば以下の操作を含む態様で、研磨対象物の研磨に使用することができる。
　すなわち、ここに開示されるいずれかの研磨用組成物を含むワーキングスラリーを用意する。次いで、その研磨用組成物を研磨対象物に供給し、常法により研磨する。例えば、一般的な研磨装置に研磨対象物をセットし、該研磨装置の研磨パッドを通じて該研磨対象物の表面（研磨対象面）に研磨用組成物を供給する。典型的には、上記研磨用組成物を連続的に供給しつつ、研磨対象物の表面に研磨パッドを押しつけて両者を相対的に移動（例えば回転移動）させる。かかる研磨工程を経て研磨対象物の研磨が完了する。 <Polishing>
The polishing composition disclosed herein can be used for polishing an object to be polished in a mode including the following operations, for example.
That is, a working slurry containing any of the polishing compositions disclosed herein is prepared. Then, the polishing composition is supplied to an object to be polished and polished by a conventional method. For example, the object to be polished is set in a general polishing apparatus, and the polishing composition is supplied to the surface (surface to be polished) of the object to be polished through the polishing pad of the polishing apparatus. Typically, while continuously supplying the polishing composition, the polishing pad is pressed against the surface of the object to be polished to relatively move (for example, rotationally move) the both. Through this polishing step, the polishing of the object to be polished is completed.
　上記研磨工程で使用される研磨パッドは特に限定されない。例えば、発泡ポリウレタンタイプ、不織布タイプ、スウェードタイプ、砥粒を含むもの、砥粒を含まないもの等のいずれを用いてもよい。また、上記研磨装置としては、研磨対象物の両面を同時に研磨する両面研磨装置を用いてもよく、研磨対象物の片面のみを研磨する片面研磨装置を用いてもよい。 The polishing pad used in the above polishing process is not particularly limited. For example, any of foamed polyurethane type, non-woven fabric type, suede type, those containing abrasive grains, those not containing abrasive grains, etc. may be used. Further, as the polishing device, a double-sided polishing device for simultaneously polishing both surfaces of the polishing target object may be used, or a single-sided polishing device for polishing only one surface of the polishing target object may be used.
　上記研磨用組成物は、いったん研磨に使用したら使い捨てにする態様（いわゆる「かけ流し」）で使用されてもよいし、循環して繰り返し使用されてもよい。研磨用組成物を循環使用する方法の一例として、研磨装置から排出される使用済みの研磨用組成物をタンク内に回収し、回収した研磨用組成物を再度研磨装置に供給する方法が挙げられる。ここに開示される研磨用組成物を循環使用する場合、その使用中の研磨用組成物に、任意のタイミングで新たな成分、使用により減少した成分または増加させることが望ましい成分を添加してもよい。例えば、成分を添加する態様としては、循環使用中の研磨用組成物に対して、上記含窒素有機化合物Ａのみを添加する、上記塩基性化合物のみを添加する、これらいずれも添加する等の態様が挙げられる。 The above-mentioned polishing composition may be used in a mode of being disposable once used for polishing (so-called “flowing over”), or may be circulated and repeatedly used. As an example of a method of circulating and using the polishing composition, there is a method of collecting the used polishing composition discharged from the polishing apparatus in a tank and supplying the recovered polishing composition to the polishing apparatus again. .. When the polishing composition disclosed herein is used in circulation, even if a new component, a component decreased by use or a component desired to be increased is added to the polishing composition in use at any time. Good. For example, as a mode of adding components, a mode in which only the nitrogen-containing organic compound A is added, only the basic compound is added, and any of these is added to the polishing composition in circulation use Are listed.
　＜用途＞
　ここに開示される研磨用組成物は、ＨＬＭ周縁の***を解消する性能（***解消性）に優れる。かかる特長を活かして、上記研磨用組成物は、ＨＬＭの付された表面を含む研磨対象面の研磨に好ましく適用することができる。ここに開示される研磨用組成物は、予備研磨工程、すなわちポリシング工程における最初の研磨工程（一次研磨工程）あるいはその次の中間研磨工程（二次研磨工程）において特に好ましく使用され得る。 <Use>
The polishing composition disclosed herein is excellent in the ability to eliminate the bulge at the peripheral edge of the HLM (protuberance elimination property). Taking advantage of such a feature, the polishing composition can be preferably applied to polishing a surface to be polished including a surface having an HLM. The polishing composition disclosed herein can be particularly preferably used in the preliminary polishing step, that is, the first polishing step (primary polishing step) or the subsequent intermediate polishing step (secondary polishing step) in the polishing step.
　ここに開示される研磨用組成物は、シリコン基板の研磨に好適に使用される。上記シリコン基板には、ここに開示される研磨用組成物を用いる研磨工程の前に、ラッピングやエッチング、上述したＨＬＭの付与等の、シリコン基板に適用され得る一般的な処理が施されていてもよい。
　上記シリコン基板は、典型的には、シリコンからなる表面を有する。このようなシリコン基板の典型的はシリコン単結晶ウェーハであり、例えば、シリコン単結晶インゴットをスライスして得られたシリコン単結晶ウェーハである。ここに開示される研磨用組成物は、ＨＬＭが付されたシリコン単結晶ウェーハを研磨する用途に好適である。
　また、ここに開示される研磨用組成物は、ＨＬＭを有しない研磨対象物の研磨にも好適に使用することができる。 The polishing composition disclosed herein is suitably used for polishing a silicon substrate. Prior to the polishing step using the polishing composition disclosed herein, the above-mentioned silicon substrate has been subjected to general treatments that can be applied to the silicon substrate, such as lapping, etching, and application of the above-mentioned HLM. Good.
The silicon substrate typically has a surface made of silicon. A typical example of such a silicon substrate 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 is suitable for use in polishing a silicon single crystal wafer provided with HLM.
Further, the polishing composition disclosed herein can be suitably used for polishing an object to be polished having no HLM.
　以下、本発明に関するいくつかの実施例を説明するが、本発明をかかる実施例に示すものに限定することを意図したものではない。 Hereinafter, some examples of the present invention will be described, but it is not intended to limit the present invention to those shown in the examples.
　＜研磨用組成物の調製＞
　　（例１）
　砥粒としてのコロイダルシリカ（平均一次粒子径：５５ｎｍ）の含有量が０．９重量％、水酸化テトラメチルアンモニウム（ＴＭＡＨ）の含有量が０．０４重量％、含窒素有機化合物ＡとしてのＬ－アルギニンの含有量が０．０１６重量％になるように、上記各成分およびイオン交換水を、室温２５℃程度で約３０分間攪拌混合することにより、例１に係る研磨用組成物を調製した。 <Preparation of polishing composition>
(Example 1)
The content of colloidal silica (average primary particle diameter: 55 nm) as abrasive grains is 0.9% by weight, the content of tetramethylammonium hydroxide (TMAH) is 0.04% by weight, and L as nitrogen-containing organic compound A is L. -The polishing composition according to Example 1 was prepared by stirring and mixing the above components and ion-exchanged water at room temperature of about 25°C for about 30 minutes so that the content of arginine was 0.016% by weight. ..
　（例２～６）
　含窒素有機化合物Ａの種類と含有量を表１に記載したものに変えたこと以外は、例１に係る研磨用組成物と同様な方法で、例２～６に係る研磨用組成物を調製した。 (Examples 2-6)
The polishing compositions according to Examples 2 to 6 were prepared in the same manner as the polishing composition according to Example 1, except that the kind and content of the nitrogen-containing organic compound A were changed to those shown in Table 1. did.
　（例７）
　含窒素有機化合物Ａを使用しなかったこと以外は、例１に係る研磨用組成物と同様な方法で、例７に係る研磨用組成物を調製した。 (Example 7)
A polishing composition according to Example 7 was prepared in the same manner as the polishing composition according to Example 1 except that the nitrogen-containing organic compound A was not used.
　（例８～１１）
　含窒素有機化合物の種類と含有量を表１に記載したものに変えたこと以外は、例１に係る研磨用組成物と同様な方法で、例８～１１に係る研磨用組成物を調製した。 (Examples 8-11)
The polishing compositions according to Examples 8 to 11 were prepared in the same manner as the polishing composition according to Example 1 except that the type and content of the nitrogen-containing organic compound were changed to those shown in Table 1. ..
　＜シリコン基板の研磨＞
　各例に係る研磨液をそのままワーキングスラリーとして使用して、研磨対象物（試験片）の表面を下記の条件で研磨した。試験片としては、ラッピングおよびエッチングを終えた直径１００ｍｍの市販シリコン単結晶ウェーハ（厚さ：５２５μｍ、伝導型：Ｐ型、結晶方位：＜１００＞、抵抗率：０．１Ω・ｃｍ以上１００Ω・ｃｍ未満）を使用した。上記ウェーハにはＨＬＭが付されている。 <Silicon substrate polishing>
The polishing liquid according to each example was used as it was as a working slurry, and the surface of the object to be polished (test piece) was polished under the following conditions. As a test piece, a commercially available silicon single crystal wafer with a diameter of 100 mm after lapping and etching (thickness: 525 μm, conductivity type: P type, crystal orientation: <100>, resistivity: 0.1 Ω·cm or more 100 Ω·cm Less than) was used. An HLM is attached to the wafer.
　（研磨条件）
　研磨装置：日本エンギス株式会社製の片面研磨装置、型式「ＥＪ－３８０ＩＮ」
　研磨圧力：１２ｋＰａ
　定盤回転数：５０ｒｐｍ
　ヘッド回転数：４５ｒｐｍ
　研磨パッド：ニッタハース社製、商品名「ＳＵＢＡ８００」
　研磨液供給レート：１００ｍＬ／分（かけ流し使用）
　研磨環境の保持温度：２５℃
　研磨取り代：４μｍ (Polishing conditions)
Polishing device: One-sided polishing device manufactured by Nippon Engis Co., Ltd., model "EJ-380IN"
Polishing pressure: 12kPa
Plate rotation speed: 50 rpm
Head rotation speed: 45 rpm
Polishing pad: Nitta Haas, product name "SUBA800"
Polishing liquid supply rate: 100 mL/min (use overflow)
Holding temperature of polishing environment: 25℃
Polishing allowance: 4 μm
　＜***解消性評価＞
　研磨後のシリコンウェーハについて、触針式表面粗さ形状測定機（ＳＵＲＦＣＯＭ　１５００ＤＸ、株式会社東京精密製）を使用してＨＬＭを含むサイトの表面形状を測定し、ＨＬＭ周辺の基準面から***の最高点までの高さを計測した。***高さが大きいほど、***解消性が悪いとの評価結果になる。得られた結果を表１の「***高さ」の欄に示す。また、得られた各例の***高さを、例７の***高さを１００％とする相対値（相対***高さ）に換算した。得られた結果を表１の「相対***高さ」の欄に示す。
　＜研磨レート評価＞
　上記研磨に要した時間、すなわち研磨取り代が４μｍに到達するまでの所要時間に基づいて、各例における研磨レート［ｎｍ／分］を算出した。得られた結果を、例７の研磨レートを１００％とする相対値（相対研磨レート）に換算した。得られた結果を表１の「相対研磨レート」の欄に示す。 <Evaluation of swelling elimination>
For the polished silicon wafer, the surface shape of the site including the HLM was measured using a stylus type surface roughness profiler (SURFCOM 1500DX, manufactured by Tokyo Seimitsu Co., Ltd.), and the highest protrusion from the reference plane around the HLM. The height to the point was measured. The larger the ridge height, the poorer the bulge-eliminating property is. The obtained results are shown in the column of "protrusion height" in Table 1. In addition, the obtained ridge height of each example was converted into a relative value (relative ridge height) with the ridge height of Example 7 being 100%. The obtained results are shown in the column of "relative ridge height" in Table 1.
<Evaluation of polishing rate>
The polishing rate [nm/min] in each example was calculated based on the time required for polishing, that is, the time required for the polishing stock removal to reach 4 μm. The obtained results were converted into a relative value (relative polishing rate) with the polishing rate of Example 7 being 100%. The obtained results are shown in the column of "relative polishing rate" in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　なお、表１における略称は、以下の化合物を意味する。
　Ａｒｇ：Ｌ－アルギニン
　Ｈｉｓ：Ｌ－ヒスチジン
　Ｔｒｐ：Ｌ－トリプトファン
　ＡＰＰ：１－（３－アミノプロピル）イミダゾール
　Ｐｙ：ピリジン
　ＴＥＡ：トリエチルアミン
　ＡＥＰ：Ｎ－（２－アミノエチル）ピペラジン The abbreviations in Table 1 mean the following compounds.
Arg:L-arginine His:L-histidine Trp:L-tryptophan APP:1-(3-aminopropyl)imidazole Py:pyridine TEA:triethylamine AEP:N-(2-aminoethyl)piperazine
　表１に示されるように、窒素原子がπ共役系構造を構成している含窒素有機化合物Ａを含む例１～６に係る研磨用組成物によると、含窒素有機化合物Ａを含まない例７の研磨用組成物に比べて、研磨レートが十分に高いレベルで維持されつつ***解消性が顕著に向上した。 As shown in Table 1, according to the polishing compositions according to Examples 1 to 6 containing the nitrogen-containing organic compound A in which the nitrogen atom constitutes the π-conjugated system structure, Example 7 containing no nitrogen-containing organic compound A As compared with the polishing composition of No. 3, the polishing rate was maintained at a sufficiently high level and the swelling elimination property was remarkably improved.
　一方、含窒素有機化合物Ａを含有せず、代わりに窒素原子がπ共役系構造を構成していない含窒素有機化合物を含む例８～１１の研磨用組成物は、含窒素有機化合物Ａを含む例１～６に係る研磨用組成物に比べて、***解消性が悪化した。 On the other hand, the polishing compositions of Examples 8 to 11 which do not contain the nitrogen-containing organic compound A, but instead contain the nitrogen-containing organic compound in which the nitrogen atom does not form a π-conjugated system structure, contain the nitrogen-containing organic compound A. As compared with the polishing compositions according to Examples 1 to 6, the swelling elimination property was deteriorated.
　以上、本発明の具体例を詳細に説明したが、これらは例示にすぎず、請求の範囲を限定するものではない。請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 The specific examples of the present invention have been described above in detail, but these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

Claims (8)

  1. 　シリコン基板の予備研磨工程に使用するための研磨用組成物であって、
    　砥粒、塩基性化合物および含窒素有機化合物Ａを含み、
    　前記含窒素有機化合物Ａは、該含窒素有機化合物Ａに含まれる少なくとも１つの窒素原子がπ共役系構造を構成している化合物である、研磨用組成物。     A polishing composition for use in a preliminary polishing step of a silicon substrate,
    Containing abrasive grains, a basic compound and a nitrogen-containing organic compound A,
    The polishing composition wherein the nitrogen-containing organic compound A is a compound in which at least one nitrogen atom contained in the nitrogen-containing organic compound A constitutes a π-conjugated system structure.
  2. 　前記塩基性化合物は有機アルカリである、請求項１に記載の研磨用組成物。 The polishing composition according to claim 1, wherein the basic compound is an organic alkali.
  3. 　前記有機アルカリとして、第四級アンモニウム化合物を含む、請求項２に記載の研磨用組成物。 The polishing composition according to claim 2, which contains a quaternary ammonium compound as the organic alkali.
  4. 　前記含窒素有機化合物Ａは窒素共役系カルボキシ基含有化合物である、請求項１から３のいずれか一項に記載の研磨用組成物。 The polishing composition according to any one of claims 1 to 3, wherein the nitrogen-containing organic compound A is a nitrogen-conjugated carboxy group-containing compound.
  5. 　前記含窒素有機化合物Ａとして、アルギニン、ヒスチジンおよびトリプトファンの少なくとも１種を含む、請求項４に記載の研磨用組成物。 The polishing composition according to claim 4, wherein the nitrogen-containing organic compound A contains at least one of arginine, histidine and tryptophan.
  6. 　前記含窒素有機化合物Ａとして、イミダゾール、ピリジンおよびこれらの誘導体からなる群から選択される少なくとも１種を含む、請求項１から３のいずれか一項に記載の研磨用組成物。 The polishing composition according to any one of claims 1 to 3, wherein the nitrogen-containing organic compound A contains at least one selected from the group consisting of imidazole, pyridine and derivatives thereof.
  7. 　前記含窒素有機化合物Ａとして、尿素を含む、請求項１から３のいずれか一項に記載の研磨用組成物。 The polishing composition according to any one of claims 1 to 3, which contains urea as the nitrogen-containing organic compound A.
  8. 　前記砥粒はシリカ粒子である、請求項１から７のいずれか一項に記載の研磨用組成物。
          The polishing composition according to any one of claims 1 to 7, wherein the abrasive grains are silica particles.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011086713A (en) * 2009-10-14 2011-04-28 Nippon Chem Ind Co Ltd Composition for polishing semiconductor wafer and polishing method
WO2015019706A1 (en) * 2013-08-09 2015-02-12 株式会社フジミインコーポレーテッド Method for producing polished object and composition kit for polishing
JP2015191966A (en) * 2014-03-27 2015-11-02 株式会社フジミインコーポレーテッド Composition for polishing silicon material
JP2018053147A (en) * 2016-09-29 2018-04-05 株式会社フジミインコーポレーテッド Abrasive grain dispersion, packed abrasive grain dispersion and manufacturing method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011086713A (en) * 2009-10-14 2011-04-28 Nippon Chem Ind Co Ltd Composition for polishing semiconductor wafer and polishing method
WO2015019706A1 (en) * 2013-08-09 2015-02-12 株式会社フジミインコーポレーテッド Method for producing polished object and composition kit for polishing
JP2015191966A (en) * 2014-03-27 2015-11-02 株式会社フジミインコーポレーテッド Composition for polishing silicon material
JP2018053147A (en) * 2016-09-29 2018-04-05 株式会社フジミインコーポレーテッド Abrasive grain dispersion, packed abrasive grain dispersion and manufacturing method therefor

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