WO2020162144A1 - 研磨用組成物 - Google Patents

研磨用組成物 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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Prior art keywords
polishing
nitrogen
polishing composition
acid
organic compound
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PCT/JP2020/001646
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English (en)
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
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Priority to JP2020571070A priority Critical patent/JPWO2020162144A1/ja
Publication of WO2020162144A1 publication Critical patent/WO2020162144A1/ja

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    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
PCT/JP2020/001646 2019-02-05 2020-01-20 研磨用組成物 WO2020162144A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011086713A (ja) * 2009-10-14 2011-04-28 Nippon Chem Ind Co Ltd 半導体ウエハ研磨用組成物および研磨方法
WO2015019706A1 (ja) * 2013-08-09 2015-02-12 株式会社フジミインコーポレーテッド 研磨済研磨対象物の製造方法および研磨用組成物キット
JP2015191966A (ja) * 2014-03-27 2015-11-02 株式会社フジミインコーポレーテッド シリコン材料研磨用組成物
JP2018053147A (ja) * 2016-09-29 2018-04-05 株式会社フジミインコーポレーテッド 砥粒分散液、容器入り砥粒分散液およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011086713A (ja) * 2009-10-14 2011-04-28 Nippon Chem Ind Co Ltd 半導体ウエハ研磨用組成物および研磨方法
WO2015019706A1 (ja) * 2013-08-09 2015-02-12 株式会社フジミインコーポレーテッド 研磨済研磨対象物の製造方法および研磨用組成物キット
JP2015191966A (ja) * 2014-03-27 2015-11-02 株式会社フジミインコーポレーテッド シリコン材料研磨用組成物
JP2018053147A (ja) * 2016-09-29 2018-04-05 株式会社フジミインコーポレーテッド 砥粒分散液、容器入り砥粒分散液およびその製造方法

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