WO2019189124A1 - Composition de polissage - Google Patents

Composition de polissage Download PDF

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Publication number
WO2019189124A1
WO2019189124A1 PCT/JP2019/012773 JP2019012773W WO2019189124A1 WO 2019189124 A1 WO2019189124 A1 WO 2019189124A1 JP 2019012773 W JP2019012773 W JP 2019012773W WO 2019189124 A1 WO2019189124 A1 WO 2019189124A1
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Prior art keywords
surfactant
polishing
polishing composition
weight
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PCT/JP2019/012773
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English (en)
Japanese (ja)
Inventor
恵 谷口
貴俊 向井
公亮 土屋
Original Assignee
株式会社フジミインコーポレーテッド
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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 JP2020510875A priority Critical patent/JP7237933B2/ja
Publication of WO2019189124A1 publication Critical patent/WO2019189124A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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, the present invention relates to a polishing composition for prepolishing a silicon substrate.
  • This application claims priority based on Japanese Patent Application No. 2018-61125 filed on Mar. 28, 2018 and Japanese Patent Application No. 2018-61126 filed on Mar. 28, 2018. The entire contents of these applications are hereby incorporated by reference.
  • the polishing process typically includes a preliminary polishing process (preliminary polishing process) and a final polishing process (final polishing process).
  • the preliminary polishing step typically includes a rough polishing step (primary polishing step) and an intermediate polishing step (secondary polishing step).
  • the silicon substrate is irradiated with laser light on the front surface or back surface of the silicon substrate, whereby marks such as barcodes, numbers, symbols, etc. (hard laser marks; hereinafter referred to as “HLM”) may be used. May be added).
  • HLM hard laser marks
  • the application of the HLM is generally performed after the lapping process of the silicon substrate is finished and before the polishing process is started.
  • an altered layer is formed on the surface of the silicon substrate at the periphery of the HLM by irradiation with laser light for attaching the HLM.
  • the HLM portion of the silicon substrate itself is not used in the final product, but if the above-mentioned deteriorated layer is not properly polished in the polishing process after the HLM is applied, it may be raised and the yield may be reduced more than necessary. .
  • 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 bulge. It was difficult.
  • Patent Document 1 is cited as a technical document related to eliminating the HLM peripheral bulge (hereinafter also simply referred to as “bulge”).
  • bulge a technical document related to eliminating the HLM peripheral bulge
  • This invention is made
  • the polishing composition provided by the present invention contains abrasive grains, a basic compound, a surfactant and water.
  • the polishing composition contains a surfactant having a quaternary ammonium salt structure as the surfactant.
  • As the surfactant having the quaternary ammonium salt structure one or two or more surfactants corresponding to at least one of surfactant A1 and surfactant A2 described below are used.
  • the polishing composition is suitable as a polishing composition for use in a preliminary polishing step for a silicon substrate.
  • the polishing composition contains a surfactant A1 having a quaternary ammonium type betaine structure as the surfactant. According to the polishing composition having such a configuration, it is used in the preliminary polishing step of the silicon substrate, and the bulge at the periphery of the HLM can be preferably eliminated.
  • eliminating the bulge at 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 bulge.
  • the height from the reference surface around the HLM of the silicon substrate to the highest point of the bulge can be measured, for example, by the method described in the examples described later.
  • the surfactant A1 contains a linear or branched alkyl group having 1 to 15 carbon atoms. According to the polishing composition containing the surfactant A1, the bulge around the HLM edge can be more preferably eliminated.
  • the surfactant A1 contains one or more selected from the group consisting of alkyldimethylaminoacetic acid betaine, alkylaminodimethylsulfopropyl betaine and fatty acid amidopropyl betaine. According to the polishing composition containing the surfactant A1, the bulge around the HLM edge can be more preferably eliminated.
  • the content of the surfactant A1 is 0.0035 parts by weight or more and 3.5 parts by weight or less with respect to 100 parts by weight of the abrasive grains. . According to the polishing composition containing the surfactant A1 with such a content, it is possible to suitably eliminate the bulge at the periphery of the HLM while suppressing a decrease in polishing efficiency (polishing rate).
  • the polishing composition contains a surfactant A2 containing a quaternary ammonium salt structure and no oxyalkylene structure as the surfactant. According to the polishing composition having such a configuration, it is used in the preliminary polishing step of the silicon substrate, and the bulge at the periphery of the hard laser mark (HLM) can be preferably eliminated.
  • HLM hard laser mark
  • the surfactant A2 includes an amphoteric surfactant. According to the polishing composition containing the surfactant A2, the bulge at the periphery of the HLM can be more preferably eliminated.
  • the surfactant A2 contains a cationic surfactant. According to the polishing composition containing the surfactant A2, it is possible to suitably eliminate the bulge at the periphery of the HLM while suppressing a decrease in the polishing rate.
  • the surfactant A2 contains a linear or branched alkyl group having 1 to 15 carbon atoms. According to the polishing composition containing the surfactant A2, the bulge at the periphery of the HLM can be more preferably eliminated.
  • the content of the surfactant A2 is 0.0035 parts by weight or more and 3.5 parts by weight or less with respect to 100 parts by weight of the abrasive grains. . According to the polishing composition containing the surfactant A2 with such a content, it is possible to suitably eliminate the bulge at the periphery of the HLM while suppressing a decrease in polishing efficiency (polishing rate).
  • a polishing composition according to another preferred embodiment includes quaternary ammonium hydroxide or a salt thereof as the basic compound. According to the polishing composition having such a configuration, the polishing rate can be improved.
  • the abrasive grains are silica particles.
  • the effect of eliminating the bulge at the periphery of the HLM by the surfactant can be more effectively exhibited.
  • the polishing composition according to another preferred embodiment further contains a weak acid salt. Since the polishing composition having such a configuration has little pH fluctuation during polishing and can be excellent in maintenance efficiency of polishing efficiency, it is possible to more appropriately achieve both improvement of bulge elimination and maintenance of the polishing rate. .
  • the weak acid salt is potassium carbonate. According to the polishing composition containing such a weak acid salt, it tends to exhibit a good buffering action in a pH range suitable for polishing a silicon substrate, so that both improvement of bulge elimination and maintenance of the polishing rate are more appropriately achieved. be able to.
  • the particle diameter calculated by the equation of value (m 2 / g)).
  • the specific surface area can be measured using, for example, a surface area measuring device manufactured by Micromeritex Corporation, a trade name “Flow Sorb II 2300”.
  • the aspect ratio of each particle constituting an abrasive grain is the length of the short side of the same rectangle as the length of the smallest rectangle that circumscribes the image of the particle by a scanning electron microscope (SEM). It can be obtained by dividing by.
  • the average aspect ratio of the abrasive grains and the standard deviation of the aspect ratio are average values and standard deviations of the aspect ratios of a plurality of particles within the field of view of the scanning electron microscope, and these are calculated using general image analysis software. Can be obtained.
  • the circle equivalent diameter of a particle refers to a value obtained by measuring the area of the image of the particle with a scanning electron microscope (SEM) and determining the diameter of the circle having the same area.
  • the average circle-converted diameter and standard deviation of the circle-converted diameter of the particles constituting the abrasive grains are the average value and standard deviation of the circle-converted diameters of a plurality of particles within the field of view of the scanning electron microscope. It can be obtained using a simple image analysis software.
  • the polishing composition disclosed herein contains abrasive grains.
  • the abrasive grains serve 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 usage.
  • An abrasive grain may be used individually by 1 type, and may be used in combination of 2 or more type.
  • 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 polymethyl methacrylate (PMMA) particles and polyacrylonitrile particles. Of these, inorganic particles are preferable.
  • silica particles are exemplified.
  • the technique disclosed here can be preferably implemented, for example, in a mode in which the abrasive grains are substantially composed of silica particles.
  • substantially means 95% by weight or more (preferably 98% by weight or more, more preferably 99% by weight or more, or 100% by weight) of the particles constituting the abrasive grains. It means silica particles.
  • the silica particles include colloidal silica, fumed silica, precipitated silica and the like.
  • Silica particles can be used alone or in combination of two or more.
  • Colloidal silica is particularly preferable because scratches are unlikely to occur on the surface of the object to be polished and good polishing performance (performance for reducing surface roughness, bulge elimination, etc.) can be exhibited.
  • colloidal silica for example, colloidal silica produced using water glass (Na silicate) as a raw material by an ion exchange method or alkoxide colloidal silica can be preferably used.
  • the alkoxide colloidal silica is colloidal silica produced by hydrolysis condensation reaction of alkoxysilane. Colloidal silica can be used alone or in combination of two or more.
  • the true specific gravity of silica constituting the silica particles is preferably 1.5 or more, more preferably 1.6 or more, and even more preferably 1.7 or more. As the true specific gravity of silica increases, the polishing rate tends to increase. 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 is typically 2.3 or less, for example, 2.2 or less.
  • a measured value by a liquid substitution method using ethanol as a substitution liquid can be adopted.
  • the average primary particle diameter of the abrasive grains is not particularly limited, and can be appropriately selected from a range of about 10 nm to 200 nm, for example. From the viewpoint of improving the bulge elimination, the average primary particle size is preferably 20 nm or more, and more preferably 30 nm or more. In some embodiments, the average primary particle size may be, for example, greater than 40 nm, greater than 45 nm, and greater than 50 nm. From the viewpoint of preventing the occurrence of scratches, the average primary particle size 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 may be 75 nm or less, or 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 bowl shape, a confetti shape, a rugby ball shape, and the like.
  • the average aspect ratio of the abrasive grains is not particularly limited.
  • the average aspect ratio of the abrasive grains is theoretically 1.0 or more, and can be 1.05 or more and 1.1 or more. As the average aspect ratio increases, bulge resolution generally tends to improve.
  • the average aspect ratio of the abrasive grains is preferably 3.0 or less, more preferably 2.0 or less, from the viewpoint of reducing scratches and improving polishing stability. In some embodiments, the average aspect ratio of the abrasive grains may be, for example, 1.5 or less, 1.4 or less, or 1.3 or less.
  • the abrasive grains those having a volume ratio of particles having a circle-equivalent diameter of 50 nm or more and an aspect ratio of 1.2 or more can be employed.
  • the volume ratio may be 60% or more.
  • the abrasive grains may contain a relatively large number of particles having a size and aspect ratio that are particularly effective for eliminating the bulge. For this reason, it is possible to further improve the bulge elimination due to the mechanical action of the abrasive grains.
  • the average circular equivalent diameter of the abrasive grains may be, for example, 25 nm or more, 40 nm or more, 55 nm or more, or 70 nm or more.
  • the average circle-converted 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 suitably implemented using abrasive grains having such an average circle-equivalent diameter.
  • the content of the abrasive grains is not particularly limited and can be appropriately set depending on the purpose.
  • the content of the abrasive grains relative to the total weight of the polishing composition may be, for example, 0.01% by weight or more, 0.05% by weight or more, or 0.1% by weight or more. Due to the increase in the content of abrasive grains, the bulge resolution tends to generally improve.
  • the abrasive content may be 0.2 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.8 wt% or more, It may be 0.0% by weight or more, or 1.2% 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 content of abrasive grains is usually 50% by weight or less from the viewpoint of storage stability, filterability, and the like. It is suitable and it is more preferable that it is 40 weight% or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the abrasive grains is preferably 1% by weight or more, more preferably 5% by weight or more.
  • the polishing composition disclosed herein contains a surfactant.
  • the surfactant as used herein refers to a compound having at least one hydrophilic site (typically a hydrophilic group) and one or more hydrophobic sites (typically a hydrophobic group) in one molecule.
  • the polishing composition disclosed herein contains a compound having a quaternary ammonium type betaine structure (hereinafter also referred to as surfactant A1) as a surfactant.
  • the quaternary ammonium type betaine in the present specification refers to a betaine compound having a quaternary ammonium cation structure (or a quaternary ammonium salt structure).
  • the quaternary ammonium type betaine has a quaternary ammonium cation structure in the molecule, but has a negative charge at a position not adjacent to the nitrogen atom in the quaternary ammonium cation structure.
  • it is a compound (inner salt) having no charge as a whole molecule.
  • Surfactant A1 is a surfactant having a quaternary ammonium type betaine structure, and is typically a quaternary ammonium type betaine.
  • Surfactant A1 is typically an amphoteric surfactant.
  • the performance of eliminating the bulge at the periphery of the HLM is likely to be improved.
  • the surfactant A1 contributes to the improvement of the bulge removal property of the HLM periphery, but according to the surfactant A1, the periphery of the HLM in the silicon substrate is not required.
  • the surface of the object to be polished is selectively protected at a portion to which no HLM is applied and polishing is suppressed.
  • the surfactant A1 in the technique disclosed herein is not particularly limited, but a surfactant containing a linear or branched alkyl group having 1 to 20 carbon atoms in the molecule is preferably used.
  • the lower limit of the number of carbon atoms of the alkyl group in the molecule of the surfactant A1 is preferably 1 or more, more preferably 6 or more, for example 8 or more.
  • the alkyl group in the molecule of surfactant A1 may have 10 or more carbon atoms. In some other embodiments, the alkyl group in the molecule of the surfactant A1 may have 11 or more carbon atoms.
  • the upper limit of the number of carbon atoms of the alkyl group in the molecule of the surfactant A1 is preferably 20 or less, more preferably 15 or less, further preferably 14 or less, for example, 12 or less. is there. More preferably, the surfactant A1 is a surfactant containing a linear or branched alkyl group having 1 to 15 carbon atoms (for example, 1 to 14 carbon atoms) in the molecule. Particularly preferably, the surfactant A1 includes a linear or branched alkyl group having 6 to 12 carbon atoms (for example, 8 to 12 carbon atoms or 10 to 12 carbon atoms) in the molecule. It is an activator. According to the surfactant A1 in which the number of carbon atoms in the alkyl group is in the above range, the bulge elimination is more likely to be improved.
  • alkyl betaine surfactants include alkyl betaine surfactants and fatty acid amidopropyl betaine surfactants.
  • alkylbetaine surfactants include alkyldimethylaminoacetic acid betaines such as lauryldimethylaminoacetic acid betaine and stearyldimethylaminoacetic acid betaine; dodecylaminomethyldimethylsulfopropylbetaine, octadecylaminomethyldimethylsulfopropylbetaine, Examples include octylaminodimethylsulfopropylbetaine, caprylylaminodimethylsulfopropylbetaine, laurylaminodimethylsulfopropylbetaine, alkylaminodimethylsulfopropylbetaine such as myristylaminodimethylsulfopropylbetaine; anhydrous betaine and the
  • Non-limiting examples of fatty acid amidopropyl betaine surfactants include fatty acid amidopropyl betaines such as cocamidopropyl betaine, cocamidopropyl hydroxysultain, lauric acid amidopropyl betaine, octanoic acid amidopropyl betaine.
  • an alkylbetaine surfactant containing a linear or branched alkyl group having 1 to 20 carbon atoms in the molecule can be used as the surfactant A1.
  • the lower limit of the number of carbon atoms in the alkyl group in the alkylbetaine surfactant molecule is preferably 1 or more, more preferably 6 or more, further preferably 8 or more, for example 10 or more. is there.
  • the upper limit of the number of carbon atoms of the alkyl group in the molecule of the alkylbetaine surfactant is preferably 20 or less, more preferably 15 or less, still more preferably 14 or less, for example, 12 It is as follows.
  • the surfactant A1 is a straight-chain or molecular compound having 8 to 15 carbon atoms (for example, 8 to 14 carbon atoms) in the molecule from the viewpoint of achieving both reduction in polishing rate and relieving bulge. It is an alkylbetaine-type surfactant containing a branched alkyl group. Particularly preferably, the surfactant A1 is an alkylbetaine surfactant containing a linear or branched alkyl group having 10 to 12 carbon atoms (for example, 12 carbon atoms) in the molecule.
  • lauryldimethylaminoacetic acid betaine can be preferably used as surfactant A1.
  • the surfactant A1 is more preferably an alkyl containing a linear or branched alkyl group having 8 to 15 carbon atoms (for example, 8 to 14 carbon atoms) in the molecule.
  • Betaine type surfactant is more preferably an alkyl containing a linear or branched alkyl group having 8 to 15 carbon atoms (for example, 8 to 14 carbon atoms) in the molecule.
  • the surfactant A1 is an alkylbetaine type surfactant containing a linear or branched alkyl group having 10 to 14 carbon atoms (for example, 14 carbon atoms) in the molecule.
  • the surfactant A1 caprylylaminodimethylsulfopropylbetaine or myristylaminodimethylsulfopropylbetaine can be preferably used.
  • a fatty acid amidopropyl betaine type surfactant containing a linear or branched alkyl group having 1 to 20 carbon atoms in the molecule can be used as the surfactant A1.
  • the lower limit of the number of carbon atoms of the alkyl group in the molecule of the fatty acid amidopropyl betaine surfactant is preferably 1 or more, more preferably 6 or more, still more preferably 8 or more, for example 10 That's it.
  • the upper limit of the number of carbon atoms of the alkyl group in the molecule of the fatty acid amidopropyl betaine surfactant is preferably 20 or less, more preferably 15 or less, further preferably 14 or less, For example, it is 12 or less. More preferably, the surfactant A1 is a fatty acid amidopropyl betaine type surfactant containing a linear or branched alkyl group having 8 to 15 carbon atoms (for example, 8 to 12 carbon atoms) in the molecule.
  • the surfactant A1 is a fatty acid amidopropyl betaine type surfactant containing a linear or branched alkyl group having 11 to 12 carbon atoms (for example, 12 carbon atoms) in the molecule. is there.
  • the surfactant A1 it is possible to realize a polishing composition having improved bulge elimination while suppressing a decrease in the polishing rate.
  • lauric acid amidopropyl betaine and octanoic acid amidopropyl betaine can be preferably used as the surfactant A1.
  • lauric acid amidopropyl betaine is particularly preferable.
  • the surfactant A1 in the technology disclosed herein may be any one of the above-described compounds, or may be a mixture of two or more.
  • the content of the surfactant A1 in the polishing composition (the total amount thereof when a plurality of types of the surfactant A1 is contained) is not particularly limited, and a desired effect depending on the purpose of use and the use mode It can set suitably so that can be obtained.
  • the content of the surfactant A1 in the polishing composition can be, for example, 0.00005% by weight or more, and may be 0.0001% by weight or more from the viewpoint of better exhibiting the bulge eliminating effect. It is preferably 0.0005% by weight or more, more preferably 0.0008% by weight or more.
  • the content of the surfactant A1 in the polishing composition can be, for example, 0.05% by weight or less, and may be 0.01% by weight or less from the viewpoint of polishing efficiency or the like, or 0.005% by weight.
  • the following is preferable, 0.003% by weight or less is more preferable, and 0.0015% by weight or less (for example, 0.0012% by weight or less) is further preferable.
  • 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 surfactant A1 is usually 0.5% by weight or less from the viewpoint of storage stability, filterability, and the like. It is appropriate that it is 0.2 wt% or less. For example, it may be 0.1% by weight or less, or 0.05% by weight or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the surfactant A1 is preferably 0.0001% by weight or more, more preferably 0.0002% by weight or more, and further preferably 0.0005% by weight. That's it.
  • the content of the surfactant A1 in the polishing composition disclosed herein can be 0.0035 parts by weight or more with respect to 100 parts by weight of the abrasive grains, thereby eliminating the bulge. From the viewpoint of better exhibiting the effect, it may be 0.0075 parts by weight or more, preferably 0.035 parts by weight or more, and more preferably 0.06 parts by weight or more.
  • the content of the surfactant A1 in the polishing composition can be 3.5 parts by weight or less with respect to 100 parts by weight of the abrasive grains. It is preferably 0.35 parts by weight or less, more preferably 0.15 parts by weight or less (for example, 0.1 parts by weight or less).
  • the polishing composition disclosed herein may or may not contain a surfactant other than the surfactant A1 (hereinafter also referred to as a surfactant B1) as the surfactant.
  • the other surfactant B1 refers to a surfactant that does not meet the definition of the surfactant A1 (that is, a surfactant having a quaternary ammonium type betaine structure).
  • the surfactant B1 is not particularly limited as long as it does not have a quaternary ammonium type betaine structure, and any of amphoteric surfactants, cationic surfactants, anionic surfactants and nonionic surfactants is used. Is possible.
  • this surfactant B1 can be used individually by 1 type or in combination of 2 or more types.
  • anionic surfactant that can be used as the surfactant B1 include polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl sulfate, alkyl sulfate, polyoxyethylene alkyl sulfate, alkyl sulfate, alkyl benzene sulfonic acid, Alkyl phosphate ester, polyoxyethylene alkyl phosphate ester, polyoxyethylene sulfosuccinic acid, alkyl sulfosuccinic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, polyacrylic acid, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene Sodium
  • anionic surfactant that can be used as the surfactant B1 include naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate, benzene sulfonic acid formaldehyde condensate, etc.
  • Polyalkylaryl sulfonic acid compounds such as: melamine formalin resin sulfonic acid compounds such as melamine sulfonic acid formaldehyde condensates; lignin sulfonic acid compounds such as lignin sulfonic acid and modified lignin sulfonic acid; aminoaryl sulfonic acid-phenol-formaldehyde condensation Aromatic aminosulfonic acid compounds such as products.
  • the salt include alkali metal salts such as sodium salt and potassium salt.
  • polyoxyethylene alkyl ethers such as polyoxyethylene decyl ether, polyoxyethylene polyoxypropylene derivatives (eg, PEO-PPO-PEO, PPO-PEO).
  • -PPO polyoxyethylene polyoxypropylene derivatives
  • sorbitan fatty acid esters glycerin fatty acid esters
  • polyoxyethylene fatty acid esters polyoxyethylene alkylamines
  • amphoteric surfactant that can be used as the surfactant B1 include alkylamine oxide.
  • the content of the surfactant B1 is not particularly limited as long as the effects of the present invention are not significantly impaired.
  • the content of the surfactant B1 (the total amount when a plurality of types of the surfactant B1 is contained) is less than 50% by weight with respect to the total amount of the surfactant contained in the polishing composition. Alternatively, it may be 35% by weight or less, 10% by weight or less, or 1% by weight or less.
  • the polishing composition in which the content of the surfactant B1 is less than (or below) the above upper limit value while suppressing an increase in the blending amount of the surfactant containing the surfactant A1 and the surfactant B1, Since the compounding amount of the surfactant A1 can be increased, it is possible to improve the bulge resolution while suppressing a decrease in the polishing rate.
  • the polishing composition is substantially free of surfactant B1 as a surfactant.
  • the fact that the polishing composition does not substantially contain the surfactant B1 means that the surfactant B1 is not contained at least intentionally. Therefore, a trace amount (for example, the molar concentration of the surfactant B1 in the polishing composition is 0.0005 mol / L or less, preferably 0.0001 mol / L or less, more preferably 0.00 or less, derived from the raw material or the production method.
  • the polishing composition unavoidably containing the surfactant B1 in an amount of 100001 mol / L or less, particularly preferably 0.000001 mol / L or less, is a polishing substantially free of the surfactant B1. It can be included in the concept of a pharmaceutical composition. According to the polishing composition that does not contain the surfactant B1 as the surfactant, it is possible to further improve the bulge eliminating property while suppressing a decrease in the polishing rate.
  • the total content of the surfactant including the surfactant A1 and the surfactant B1 as an optional component is not particularly limited, and is desired depending on the purpose of use, the mode of use, and the like. It can set suitably so that the effect of this may be acquired.
  • the total content of the surfactant with respect to the total amount of the polishing composition can be set to, for example, 0.00005% by weight or more, and 0.0001% by weight or more from the viewpoint of better exhibiting the bulge eliminating effect. 0.0005% by weight or more is preferable, and 0.0008% by weight or more is more preferable.
  • the total content of the surfactant with respect to the total amount of the polishing composition can be, for example, 0.05% by weight or less, and may be 0.01% by weight or less from the viewpoint of polishing efficiency, etc. % Or less is preferable, and 0.003% by weight or less (for example, 0.002% by weight or less) is more preferable.
  • These contents can be preferably applied to the contents in the polishing liquid (working slurry) supplied to the object to be polished, for example.
  • surfactant A2 a compound satisfying both of the following conditions (a) and (b) (hereinafter also referred to as surfactant A2) can be used.
  • the surfactant A2 used in the present invention is a surfactant containing a quaternary ammonium salt structure and no oxyalkylene structure.
  • the surfactant A2 has a structure derived from a quaternary ammonium cation represented by the following general formula (1).
  • R 1 , R 2 , R 3 , and R 4 are all substituents that are not hydrogen atoms.
  • each of R 1 , R 2 , R 3 , and R 4 is a hydrocarbon group that does not include an oxyalkylene structure, or a substituent in which a characteristic group is added to a hydrocarbon group that does not include an oxyalkylene structure. is there.
  • a compound having a structure in which two of R 1 , R 2 , R 3 and R 4 are bonded to each other and form a ring together with the nitrogen atom to which they are bonded may be used.
  • a quaternary ammonium cation structure having a positive charge at the position of the nitrogen atom is shown, but the charged state of the surfactant A2 is not limited thereto.
  • the oxyalkylene structure that the surfactant A2 does not have is a structure derived from an oxyalkylene group or a polyoxyalkylene group.
  • the oxyalkylene structure is a structure represented by the following general formula (2).
  • m and n are each an integer of 1 or more.
  • the value of m is 2 or 3, but the value of m is not limited to this.
  • the performance of eliminating the bulge at the periphery of the HLM is likely to be improved.
  • the surfactant A2 contributes to the improvement of the bulge elimination of the HLM periphery, but according to the surfactant A2, the periphery of the HLM in the silicon substrate is not required.
  • the surface of the object to be polished is selectively protected at a portion to which no HLM is applied and polishing is suppressed.
  • it is not limited to this mechanism.
  • any type of surfactants such as amphoteric surfactants, cationic surfactants, anionic surfactants, and nonionic surfactants may be used. It can.
  • an amphoteric surfactant can be preferably used as the surfactant A2 from the viewpoint of improving the ridge elimination property.
  • surfactant A2 which is a cationic surfactant may be preferably used from a viewpoint of making the improvement of a ridge elimination property and suppression of a polishing rate fall suitable suitably.
  • Amphoteric surfactants preferably used as surfactant A2 include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, dodecylaminomethyldimethylsulfopropylbetaine, octadecylaminomethyldimethylsulfopropylbetaine, octylaminodimethylsulfopropylbetaine Alkylbetaines such as caprylylaminodimethylsulfopropylbetaine, laurylaminodimethylsulfopropylbetaine, myristylaminodimethylsulfopropylbetaine; anhydrous betaine; octanoic acid amidopropyl betaine, lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, coca Fatty acid amidopropyl betaines such as midpropyl betaine and cocamidoprop
  • alkylbetaines and fatty acid amidopropylbetaines can be preferably used.
  • the polishing compositions disclosed herein include lauryl dimethylaminoacetic acid betaine, lauric acid amidopropyl betaine, octoamidopropyl betaine, octylaminodimethylsulfopropyl betaine, caprylylaminodimethylsulfopropyl betaine, laurylaminodimethyl.
  • Sulfopropyl betaine, myristylaminodimethylsulfopropyl betaine and the like can be preferably used.
  • Examples of the cationic surfactant suitably used as the surfactant A2 include alkyltrimethylammonium salts such as lauryltrimethylammonium salt, stearyltrimethylammonium salt, and cetyltrimethylammonium salt; dialkyldimethylammonium salts such as distearyldimethylammonium salt; Examples include alkyldimethylethylammonium salts such as octyldimethylethylammonium ethyl salt; alkyldimethylbenzylammonium salts. Of these, alkyldimethylethylammonium salts can be preferably used. Examples of the alkyldimethylethylammonium salt that can be preferably used include octyldimethylethylammonium ethyl sulfate.
  • a surfactant containing a linear or branched alkyl group having 1 to 20 carbon atoms (for example, 1 to 15 carbon atoms) in the molecule is preferable.
  • the surfactant A2 is a surfactant containing a linear or branched alkyl group having 8 to 15 carbon atoms (for example, 8 to 12 carbon atoms) in the molecule, and is particularly preferable.
  • the surfactant A2 is a surfactant containing a linear or branched alkyl group having 11 to 12 carbon atoms (for example, 12 carbon atoms) in the molecule. According to the surfactant A2 in which the number of carbon atoms in the alkyl group is in the above range, the bulge elimination is more likely to be improved.
  • an amphoteric surfactant containing a linear or branched alkyl group having 6 to 20 carbon atoms in the molecule can be preferably used. More preferably, the surfactant A2 is an amphoteric surfactant containing a linear or branched alkyl group having 8 to 15 carbon atoms (for example, 8 to 12 carbon atoms) in the molecule, and is particularly preferable.
  • the surfactant A2 is an amphoteric surfactant containing a linear or branched alkyl group having 11 to 12 carbon atoms (for example, 12 carbon atoms) in the molecule. According to the surfactant A2, a polishing composition having excellent bulge eliminating properties can be realized.
  • the surfactant A2 a cationic surfactant containing a linear or branched alkyl group having 6 to 20 carbon atoms in the molecule can be used. More preferably, the surfactant A2 is a cationic surfactant containing a linear or branched alkyl group having 8 to 15 carbon atoms (for example, 8 to 12 carbon atoms) in the molecule. For example, it may be a cationic surfactant containing a linear or branched alkyl group having 8 carbon atoms in the molecule. According to the surfactant A2, it is possible to realize a polishing composition having improved bulge elimination while suppressing a decrease in the polishing rate.
  • the surfactant A2 in the technique disclosed herein may be any one of the above-described compounds, or may be a mixture of two or more.
  • the content of the surfactant A2 in the polishing composition (the total amount thereof when a plurality of types of the surfactant A2 is contained) is not particularly limited, and a desired effect depending on the purpose of use, use mode, and the like. It can set suitably so that can be obtained.
  • the content of the surfactant A2 in the polishing composition can be, for example, 0.00005% by weight or more, and 0.0001% by weight or more from the viewpoint of better exerting the bulge eliminating effect. It is preferably 0.0005% by weight or more, more preferably 0.0008% by weight or more.
  • the content of the surfactant A2 in the polishing composition can be, for example, 0.05% by weight or less, and may be 0.01% by weight or less from the viewpoint of polishing efficiency and the like, and may be 0.005% by weight.
  • the following is preferable, and 0.0015 weight% or less (for example, 0.0012 weight% or less) is more preferable.
  • 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 surfactant A2 is usually 0.5% by weight or less from the viewpoint of storage stability, filterability, and the like. It is appropriate that it is 0.2 wt% or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the surfactant A2 is preferably 0.0001% by weight or more, more preferably 0.0002% by weight or more, and further preferably 0.0005% by weight. That's it.
  • the content of the surfactant A2 in the polishing composition disclosed herein can be 0.0035 parts by weight or more with respect to 100 parts by weight of the abrasive grains, thereby eliminating the bulge. From the viewpoint of better exhibiting the effect, it may be 0.0075 parts by weight or more, preferably 0.035 parts by weight or more, and more preferably 0.06 parts by weight or more. Further, the content of the surfactant A2 in the polishing composition can be 3.5 parts by weight or less with respect to 100 parts by weight of the abrasive grains, and can be 0.75 parts by weight or less from the viewpoint of polishing efficiency and the like. It is preferably 0.35 parts by weight or less, more preferably 0.1 parts by weight or less (for example, 0.09 parts by weight or less).
  • the polishing composition disclosed herein may contain a surfactant B2 other than the surfactant A2 as the surfactant. Or polishing composition indicated here does not need to contain surfactant B2 other than surfactant A2 as surfactant.
  • the other surfactant B2 is a surfactant that does not meet the definition of the surfactant A2, and specifically, a surfactant that does not satisfy at least one of the following conditions (a) and (b): It is an agent.
  • A) The molecule contains at least one quaternary ammonium salt structure.
  • B) No oxyalkylene structure is contained in the molecule.
  • any of an amphoteric surfactant, a cationic surfactant, an anionic surfactant and a nonionic surfactant can be used.
  • this surfactant B2 can be used individually by 1 type or in combination of 2 or more types.
  • amphoteric surfactants such as amino acid type surfactants; cationic surfactants such as alkylamine salts and surfactants having a pyridine ring; Polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl sulfate ester, alkyl sulfate ester, polyoxyethylene alkyl sulfate, alkyl sulfate, alkylbenzene sulfonic acid, alkyl phosphate ester, polyoxyethylene alkyl phosphate ester, polyoxyethylene sulfosuccinic acid, Alkyl sulfosuccinic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, polyacrylic acid, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene
  • surfactant B2 having an oxyalkylene structure examples include cationic surfactants such as stearyldimethylhydroxyethylammonium p-toluenesulfonate; polyoxyethylene alkyl ether, polyoxyalkylphenyl ether, polyoxyethylene polyoxypropylene glycol and the like.
  • cationic surfactants such as stearyldimethylhydroxyethylammonium p-toluenesulfonate
  • polyoxyethylene alkyl ether examples include polyoxyethylene alkyl ether, polyoxyalkylphenyl ether, polyoxyethylene polyoxypropylene glycol and the like.
  • ether type nonionic surfactants such as oxyethylene polyoxypropylene derivatives (for example, PEO-PPO-PEO, PPO-PEO-PPO);
  • surfactant B2 may be any one of the above-described compounds. It may be a mixture of two or more.
  • the content of the surfactant B2 is not particularly limited as long as the effects of the present invention are not significantly impaired.
  • the content of surfactant B2 (the total amount of surfactants B2 when plural types of surfactants B2 are contained) is less than 50% by weight with respect to the total amount of surfactants contained in the polishing composition. Alternatively, it may be 35% by weight or less, 10% by weight or less, or 1% by weight or less.
  • the polishing composition in which the content of the surfactant B2 is less than (or below) the above upper limit value while suppressing an increase in the total amount of the surfactant including the surfactant A2 and the surfactant B2.
  • the blending amount of the surfactant A2 can be increased, it is possible to improve the bulge eliminating property while suppressing a decrease in the polishing rate.
  • the polishing composition is substantially free of surfactant B2 as a surfactant.
  • the fact that the polishing composition does not substantially contain the surfactant B2 means that the surfactant B2 is not contained at least intentionally. Therefore, a trace amount (for example, the molar concentration of the surfactant B2 in the polishing composition is 0.0005 mol / L or less, preferably 0.0001 mol / L or less, more preferably 0.00 or less, derived from the raw material or the production method.
  • the polishing composition unavoidably containing the surfactant B2 of 00001 mol / L or less, particularly preferably 0.000001 mol / L or less) is a polishing substantially free of the surfactant B2 referred to herein. It can be included in the concept of a pharmaceutical composition. According to the polishing composition that does not contain the surfactant B2 as the surfactant, it is possible to further improve the bulge eliminating property while suppressing a decrease in the polishing rate.
  • the polishing composition disclosed herein does not substantially contain surfactant B2 containing an oxyalkylene structure as a surfactant. According to the polishing composition containing the surfactant B2, the performance for eliminating the bulge at the periphery of the HLM is inferior, and the polishing rate tends to decrease.
  • the polishing composition disclosed herein is substantially free of surfactant B2 that does not contain a quaternary ammonium salt structure as a surfactant. According to the polishing composition containing such surfactant B2, there is a tendency to be inferior in the performance of eliminating the bulge at the periphery of the HLM.
  • the total content of the surfactant including the surfactant A2 and the surfactant B2 as an optional component is not particularly limited, and is desired depending on the purpose of use, the mode of use, and the like. It can set suitably so that the effect of this may be acquired.
  • the total content of the surfactant with respect to the total amount of the polishing composition can be set to, for example, 0.00005% by weight or more, and 0.0001% by weight or more from the viewpoint of better exhibiting the bulge eliminating effect. 0.0005% by weight or more is preferable, and 0.0008% by weight or more is more preferable.
  • the total content of the surfactant with respect to the total amount of the polishing composition can be, for example, 0.05% by weight or less, and may be 0.01% by weight or less from the viewpoint of polishing efficiency, etc. % Or less is preferable, and 0.003% by weight or less (for example, 0.002% by weight or less) is more preferable.
  • 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 total content of the surfactant is usually 0.5% by weight or less from the viewpoint of storage stability, filterability, and the like. It is appropriate that the content is 0.2% by weight or less. For example, it may be 0.1% by weight or less, or 0.05% by weight or less. From the viewpoint of taking advantage of the concentrated solution, the total content of the surfactant is preferably 0.0001% by weight or more, more preferably 0.0002% by weight or more, and further preferably 0.0005% by weight. That's it.
  • the total content of the surfactant in the polishing composition disclosed herein can be 0.0035 parts by weight or more with respect to 100 parts by weight of the abrasive grains, thereby eliminating the bulge. From the viewpoint of better exhibiting the effect, it may be 0.0075 parts by weight or more, preferably 0.035 parts by weight or more, and more preferably 0.06 parts by weight or more. Further, the total content of the surfactant in the polishing composition can be 5 parts by weight or less with respect to 100 parts by weight of the abrasive grains, and may be 3.5 parts by weight or less. It may be less than or equal to parts by weight, and may be less than or equal to 0.75 parts by weight. Preferably it is 0.5 weight part or less, More preferably, it is 0.35 weight part or less, More preferably, it is 0.15 weight part or less (for example, 0.1 weight part or less).
  • the polishing composition according to the present invention contains a basic compound.
  • the basic compound refers to a compound having a function of increasing the pH of the composition when added to the polishing composition.
  • the basic compound functions to chemically polish the surface to be polished, and can contribute to the improvement of the polishing rate.
  • an organic or inorganic basic compound containing nitrogen, an alkali metal or alkaline earth metal hydroxide, or the like can be used.
  • alkali metal hydroxide, quaternary ammonium hydroxide or a salt thereof, ammonia, amine and the like can be mentioned.
  • Specific examples of the alkali metal hydroxide include potassium hydroxide and sodium hydroxide.
  • Specific examples of the quaternary ammonium hydroxide or a salt thereof 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, guanidine, azoles such as imidazole and triazole, and the like.
  • quaternary ammonium hydroxide or a salt thereof can be mentioned. Particularly preferably used is tetramethylammonium hydroxide.
  • the said basic compound can be used individually by 1 type or in combination of 2 or more types.
  • the content of the basic compound with respect to the total amount of the polishing composition is preferably 0.01% by weight or more, more preferably 0.03% by weight or more, and still more preferably 0.05% by weight, from the viewpoints of the polishing rate and bulge elimination. % Or more. Stability can also be improved by increasing the content of the basic compound.
  • the upper limit of the content of the basic compound is suitably 1% by weight or less, and is preferably 0.5% by weight or less, more preferably 0.1% by weight or less from the viewpoint of surface quality and the like. It is.
  • the said content points out the total content of 2 or more types of basic compounds.
  • the content of the basic compound is usually 10% by weight or less from the viewpoint of storage stability, filterability, and the like. Is suitable, and is more preferably 5% by weight or less. Further, from the viewpoint of taking advantage of the concentrated liquid, the content of the basic compound is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and further preferably 0.9% by weight or more. It is.
  • the polishing composition disclosed herein may contain a weak acid salt as necessary.
  • the weak acid salt those capable of exhibiting a buffering action in combination with a basic compound are preferable. Since the polishing composition configured to exhibit such a buffering action has less pH fluctuation of the polishing composition during polishing and can be excellent in maintainability of polishing efficiency, The improvement and the maintenance of the polishing rate can both be more suitably achieved.
  • weak acid salts include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium orthosilicate, potassium orthosilicate, sodium acetate, potassium acetate, sodium propionate, potassium propionate, calcium carbonate, calcium bicarbonate , Calcium acetate, calcium propionate, magnesium acetate, magnesium propionate, zinc propionate, manganese acetate, cobalt acetate and the like.
  • Weak acid salts in which the anion component is carbonate ion or hydrogen carbonate ion are preferred, and weak acid salts in which the anion component is carbonate ion are particularly preferred.
  • alkali metal ions such as potassium and sodium, are suitable.
  • the weak acid salts can be used alone or in combination of two or more.
  • At least one of the acid dissociation constants (pKa) values is 8.0 to 11.8 (eg, 8.0 to Weak acid salts in the range 11.5) are preferred.
  • Suitable examples include carbonates, bicarbonates, borates, phosphates and phenol salts.
  • Particularly preferred weak acid salts include sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate. Of these, potassium carbonate (K 2 CO 3 ) is preferable.
  • the value of pKa the value of the acid dissociation constant at 25 ° C. described in known materials can be adopted.
  • the content of the weak acid salt is not particularly limited, but may be, for example, 0.001% by weight or more, 0.005% by weight or more, and 0.01% by weight based on the total weight of the polishing composition. % By weight or 0.03% by weight or more may be used. Further, from the viewpoint of easily obtaining higher bulge elimination, in some embodiments, the total content may be, for example, 5% by weight or less, 2% by weight or less, or 1% by weight or less, It may be 0.5% by weight or less, or 0.1% 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 weak acid salt is usually 10% by weight or less from the viewpoint of storage stability, filterability, and the like. It is appropriate and more preferably 5% by weight or less. Further, from the viewpoint of taking advantage of the concentrated solution, the content of the weak acid salt is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and further preferably 0.9% by weight or more. is there.
  • the polishing composition disclosed herein contains water.
  • water ion exchange water (deionized water), pure water, ultrapure water, distilled water and the like can be preferably used.
  • the water to be used preferably has, for example, a total content of transition metal ions of 100 ppb or less in order to avoid as much as possible the action of other components contained in the polishing composition.
  • the purity of water can be increased by operations such as removal of impurity ions with an ion exchange resin, removal of foreign matter with a filter, distillation, and the like.
  • 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 (typically a water-soluble polymer, an acid, a chelating agent, an antiseptic, an antifungal agent, etc.) as long as the effects of the present invention are not significantly hindered. May further contain a known additive that can be used in a polishing composition used in a polishing process of a silicon substrate, 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 include hydroxyethyl cellulose, pullulan, random copolymer or block copolymer of ethylene oxide and propylene oxide, polyvinyl alcohol, polyisoprene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyisoamylene sulfonic acid.
  • a water-soluble polymer can be used singly or in combination of two or more.
  • the polishing composition disclosed herein can also be preferably implemented in an embodiment that does not substantially contain a water-soluble polymer, that is, an embodiment that does not at least intentionally contain a water-soluble polymer.
  • the acids 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 , Organic acids such as 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); It is done.
  • 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 chelating agent include aminocarboxylic acid chelating agents and organic phosphonic acid chelating agents.
  • aminocarboxylic acid chelating agents include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid sodium, nitrilotriacetic acid, nitrilotriacetic acid sodium, nitrilotriacetic acid ammonium, hydroxyethylethylenediaminetriacetic acid, hydroxyethylethylenediamine sodium triacetate, diethylenetriaminepentaacetic acid Diethylenetriamine sodium pentaacetate, triethylenetetramine hexaacetic acid and sodium triethylenetetramine hexaacetate.
  • organic phosphonic acid chelating agents examples include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic).
  • ethylenediaminetetrakis methylenephosphonic acid
  • diethylenetriaminepenta methylenephosphonic acid
  • diethylenetriaminepentaacetic acid are preferable.
  • Particularly preferred chelating agents include ethylenediaminetetrakis (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid).
  • a chelating agent can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the chelating agent used is, for example, that the content of the chelating agent in the working slurry is about 0.0001 to 1% by weight, about 0.001 to 0.5% by weight, or about 0.005 to 0.1% by weight.
  • the present invention is not limited to this.
  • the content of the chelating agent is usually 1.5% by weight or less from the viewpoint of storage stability, filterability, and the like. It is appropriate that it is 1% by weight or less. From the viewpoint of taking advantage of the concentrated solution, the content of the chelating agent is preferably 0.003% by weight or more, more preferably 0.005% by weight or more, and further preferably 0.01% by weight or more. is there.
  • preservatives and fungicides examples include isothiazoline compounds, paraoxybenzoates, phenoxyethanol, and the like.
  • the polishing composition disclosed herein does not substantially contain an oxidizing agent. If the polishing composition contains an oxidizing agent, the supply of the composition may oxidize the surface of the silicon substrate to produce an oxide film, which may reduce the polishing rate. Because.
  • that the polishing composition substantially does not contain an oxidant means that at least intentionally no oxidant is blended, and a trace amount of oxidant is inevitably contained due to raw materials and manufacturing methods. It can be tolerated.
  • the 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 0.00.
  • the polishing composition according to a preferred embodiment does not contain an oxidizing agent.
  • the polishing composition disclosed herein can be preferably implemented in an embodiment that does not contain, for example, hydrogen peroxide, sodium persulfate, ammonium persulfate, and sodium dichloroisocyanurate.
  • the polishing composition disclosed herein is typically supplied to a polishing object in the form of a polishing liquid (working slurry) containing the polishing composition and used for polishing the polishing object.
  • the polishing composition disclosed herein may be used, for example, as a polishing liquid after being diluted (typically diluted with water) or as it is as a polishing liquid. Also good. That is, the concept of the polishing composition in the technology disclosed herein includes both a working slurry that is supplied to a polishing object and used for polishing the polishing object, and a concentrated solution (stock solution) of the working slurry. Is included.
  • the concentration ratio of the concentrated solution may be, for example, about 2 to 100 times on a volume basis, and usually about 5 to 50 times is appropriate.
  • the pH of the polishing composition is typically 8.0 or more, preferably 8.5 or more, more preferably 9.0 or more, still more preferably 9.5 or more, for example 10.0 or more.
  • pH becomes high it exists in the tendency for a polishing rate and a bulge elimination property to improve.
  • the pH of the polishing liquid is usually 12.0 or less. It is preferably 11.8 or less, more preferably 11.5 or less, and even more preferably 11.0 or less.
  • the pH of the polishing composition was measured using a pH meter (for example, a glass electrode type hydrogen ion concentration indicator (Model No. F-23) manufactured by Horiba, Ltd.) and a standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer pH: 6.86 (25 ° C), carbonate pH buffer pH: 10.01 (25 ° C)) It can be grasped by putting the glass electrode into the polishing composition and measuring the value after 2 minutes or more has been stabilized.
  • a pH meter for example, a glass electrode type hydrogen ion concentration indicator (Model No. F-23) manufactured by Horiba, Ltd.
  • a standard buffer solution phthalate pH buffer solution pH: 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 at an appropriate timing as necessary.
  • each component contained in the polishing composition may be mixed using a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer.
  • a well-known mixing device such as a blade-type stirrer, an ultrasonic disperser, or a homomixer.
  • the aspect which mixes these components is not specifically limited, For example, all the components may be mixed at once and may be mixed in the order set suitably.
  • the polishing composition disclosed herein can be used for polishing a polishing object, for example, in an embodiment including the following operations. That is, a working slurry containing any of the polishing compositions disclosed herein is prepared. Next, the polishing composition is supplied to the object to be polished and polished by a conventional method. For example, a polishing object is set in a general polishing apparatus, and the polishing composition is supplied to the surface (polishing object surface) of the polishing object through a 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, and both are relatively moved (for example, rotated). The polishing of the object to be polished is completed through this polishing step.
  • the polishing pad used in the above polishing process is not particularly limited.
  • any of polyurethane foam type, non-woven fabric type, suede type, those containing abrasive grains, and those not containing abrasive grains may be used.
  • the polishing apparatus a double-side polishing apparatus that simultaneously polishes both surfaces of an object to be polished, or a single-side polishing apparatus that polishes only one surface of the object to be polished may be used.
  • the above polishing composition may be used in a disposable form (so-called “flowing”) once used for polishing, or may be repeatedly used after circulation.
  • a method of circulating and using the polishing composition there is a method of collecting a 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 here is excellent in the performance (uplift-removability) of eliminating the bulge at the periphery of the HLM. Taking advantage of such features, the polishing composition can be preferably applied to polishing of a surface to be polished including a surface to which an HLM is applied.
  • the polishing composition disclosed herein can be particularly preferably used in the preliminary polishing step, that is, the first polishing step (primary polishing step) in the polishing step or the subsequent intermediate polishing step (secondary polishing step).
  • the silicon substrate Prior to the polishing step using the polishing composition disclosed herein, the silicon substrate has been subjected to general treatments that can be applied to the silicon substrate, such as lapping, etching, and HLM application as described above. Also 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 to which an HLM has been applied.
  • the polishing composition disclosed herein can be suitably used for polishing a polishing object having no HLM, and can effectively reduce the surface roughness of the surface of the polishing object.
  • a polishing composition for use in a preliminary polishing step of a silicon substrate Containing abrasive grains, basic compounds, surfactants and water, Polishing composition containing surfactant A1 which has quaternary ammonium type betaine structure as said surfactant.
  • the polishing composition according to (1) wherein the surfactant A1 contains a linear or branched alkyl group having 8 to 15 carbon atoms.
  • Polishing as described in said (1) or (2) whose content of said surfactant A1 is 0.0035 weight part or more and 3.5 weight part or less with respect to 100 weight part of said abrasive grains. Composition.
  • the content of the surfactant A2 is 0.0035 parts by weight or more and 3.5 parts by weight or less based on 100 parts by weight of the abrasive grains.
  • the polishing composition as described.
  • the polishing composition according to (11), wherein the weak acid salt is potassium carbonate.
  • A-1 Lauryldimethylaminoacetic acid betaine
  • A-2 Amidopropyl betaine laurate
  • A-3 Amidopropyl betaine octoate
  • A-4 Octylaminodimethylsulfopropyl betaine
  • A-5 Caprylylaminodimethylsulfopropyl betaine
  • A- 6 Laurylaminodimethylsulfopropylbetaine
  • A-7 Myristylaminodimethylsulfopropylbetaine
  • A-8 Anhydrous betaine
  • A-9 Octyldimethylethylammonium ethyl sulfate
  • B-1 Stearyldimethylhydroxyethylammonium paratoluenesulfonate
  • B-2 Polyoxyethylene polyoxypropylene derivative (PEO-PPO-PEO)
  • B-3 Polyoxyethylene decyl ether
  • the surfactants A-1 to A-8 are surfactants having a quaternary ammonium type betaine structure. Furthermore, surfactants A-1, A-2, and A-6 are surfactants having a quaternary ammonium type betaine structure containing an alkyl group having 12 carbon atoms. Surfactants A-1 to A-8 are amphoteric surfactants containing a quaternary ammonium salt structure and no oxyalkylene structure. Surfactant A-9 is a cationic surfactant containing a quaternary ammonium salt structure and no oxyalkylene structure. Surfactants B-1 to B-3 are surfactants having no quaternary ammonium type betaine structure.
  • Surfactant B-1 is a cationic surfactant containing a quaternary ammonium salt structure and an oxyalkylene structure.
  • Surfactants B-2 and B-3 are nonionic surfactants that do not contain a quaternary ammonium salt structure and contain an oxyalkylene structure.
  • Example 1 The content of colloidal silica as abrasive grains is 1.4% by weight, the content of potassium carbonate (K 2 CO 3 ) is 0.04% by weight, and the content of tetramethylammonium hydroxide (TMAH) is 0.07% by weight. %, And the surfactant and the ion-exchanged water were stirred and mixed at room temperature of about 25 ° C. for about 30 minutes so that the content of the surfactant was 0.001% by weight.
  • Example 2 The content of colloidal silica as abrasive grains is 1.4% by weight
  • the content of potassium carbonate (K 2 CO 3 ) is 0.04% by weight
  • TMAH tetramethylammonium hydroxide
  • the colloidal silica has an average primary particle diameter of 55 nm, an average circle conversion diameter by SEM observation of 93 nm, a standard deviation of the circle conversion diameter of 38.5, an average aspect ratio of 1.3, an aspect ratio The standard deviation of the ratio is 0.320, the volume ratio of particles having a circle-converted diameter of 50 nm or more and an aspect ratio of 1.2 or more is 77%, and the volume content of particles having a circle-converted diameter of 1 to 300 nm is 100%. %Met. Moreover, pH of the polishing composition which concerns on Example 1 was 10.4.
  • polishing compositions according to Examples 2 to 12 were prepared in the same manner as the polishing composition according to Example 1, except that the surfactant type was changed to that shown in Table 1.
  • Example 13 A polishing composition according to Example 13 was prepared in the same manner as the polishing composition according to Example 1 except that the surfactant was not used.
  • test piece a commercially available silicon single crystal wafer having a diameter of 100 mm after finishing lapping and etching (thickness: 525 ⁇ m, conductivity type: P type, crystal orientation: ⁇ 100>, resistivity: 0.1 ⁇ ⁇ cm to 100 ⁇ ⁇ cm Less).
  • the wafer is provided with an HLM.
  • Polishing device Single-side polishing device manufactured by Nippon Engis Co., Ltd. Model “EJ-380IN” Polishing pressure: 12 kPa Plate rotation speed: 50 rpm Head rotation speed: 40rpm Polishing pad: Product name "SUBA800", manufactured by Nitta Haas Polishing liquid supply rate: 100 mL / min (using pouring) Polishing environment holding temperature: 25 ° C Polishing allowance: 4 ⁇ m
  • ⁇ Uplift erasure evaluation> For the polished silicon wafer, the surface shape of the site including the HLM is measured using a stylus type surface roughness profile measuring machine (SURFCOM 1500DX, manufactured by Tokyo Seimitsu Co., Ltd.), and the highest rise from the reference surface around the HLM The height to the point was measured. The higher the bulge height, the worse the bulge resolution. The obtained results are shown in the column of “bump height” in Table 1.
  • ⁇ Polishing rate evaluation> The polishing rate [nm / min] in each example was calculated based on the time required for the polishing, that is, the time required for the polishing allowance to reach 4 ⁇ m. The obtained result was converted into a relative value (relative polishing rate) with the polishing rate of Example 13 as 100%. The obtained results are shown in the column of “Relative polishing rate” in Table 1.

Abstract

L'invention concerne une composition de polissage qui a une excellente capacité à éliminer un gonflement autour d'un HLM. Cette composition de polissage est destinée au pré-polissage d'un substrat de silicium. La composition de polissage contient des grains abrasifs, un composé basique, un tensioactif et de l'eau. Selon un mode de réalisation avantageux, la composition de polissage comprend, comme tensioactif, un tensioactif A1 qui a une structure de bétaïne d'ammonium quaternaire. Selon un autre mode de réalisation avantageux, la composition de polissage comprend, comme tensioactif, un tensioactif A2 qui comprend une structure de sel d'ammonium quaternaire mais qui ne comprend pas de structure oxyalkylène.
PCT/JP2019/012773 2018-03-28 2019-03-26 Composition de polissage WO2019189124A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2022154016A1 (fr) 2021-01-18 2022-07-21 株式会社フジミインコーポレーテッド Composition pour polissage
JP7375450B2 (ja) 2019-10-17 2023-11-08 Jsr株式会社 半導体処理用組成物及び処理方法

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JP2013251561A (ja) * 2008-02-01 2013-12-12 Fujimi Inc 研磨用組成物及びそれを用いた研磨方法
JP2016215336A (ja) * 2015-05-22 2016-12-22 株式会社フジミインコーポレーテッド 研磨方法及び組成調整剤
JP2017190363A (ja) * 2016-04-11 2017-10-19 花王株式会社 サファイア板用研磨液組成物
WO2018193916A1 (fr) * 2017-04-17 2018-10-25 日産化学株式会社 Composition de polissage contenant un tensioactif amphotère

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013251561A (ja) * 2008-02-01 2013-12-12 Fujimi Inc 研磨用組成物及びそれを用いた研磨方法
JP2016215336A (ja) * 2015-05-22 2016-12-22 株式会社フジミインコーポレーテッド 研磨方法及び組成調整剤
JP2017190363A (ja) * 2016-04-11 2017-10-19 花王株式会社 サファイア板用研磨液組成物
WO2018193916A1 (fr) * 2017-04-17 2018-10-25 日産化学株式会社 Composition de polissage contenant un tensioactif amphotère

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7375450B2 (ja) 2019-10-17 2023-11-08 Jsr株式会社 半導体処理用組成物及び処理方法
WO2022154016A1 (fr) 2021-01-18 2022-07-21 株式会社フジミインコーポレーテッド Composition pour polissage
KR20230134132A (ko) 2021-01-18 2023-09-20 가부시키가이샤 후지미인코퍼레이티드 연마용 조성물

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