Polishing composition and polishing method

Abstract

The invention provides a polishing composition and a polishing method. According to the present disclosure, provided is a solution whereby, when the pH of the polishing composition is less than 7, a high polishing speed of a material having a silicon-silicon bond can be achieved, and the ratio of the polishing speed of the material having a silicon-silicon bond to the polishing speed of a material having an oxygen-silicon bond is within a good range. The present disclosure pertains to: a polishing composition which contains the following component (A) and the following component (B) and has a pH of less than 7; component (A): surface-modified silica particles containing silica particles and a surface-modifying group that modifies the surface of the silica particles, the surface-modifying group including a polyoxyalkylene chain having a weight-average molecular weight of 80-7000 (inclusive); component (B): water.

Description

Technical Field

[0001] This invention relates to grinding compositions and grinding methods. Background Technology

[0002] In recent years, with the increasing prevalence of multilayer wiring on semiconductor substrates, chemical mechanical polishing (CMP) technology has been used in device manufacturing to planarize semiconductor substrates through physical grinding. CMP is, for example, a method of planarizing the surface of a workpiece such as a semiconductor substrate using a polishing composition (slurry) containing abrasive particles (e.g., silicon dioxide and / or cerium oxide) and additives (e.g., photoresist and / or surfactants). Specifically, CMP is used in processes such as shallow trench isolation (STI), planarization of interlayer insulating films (ILD films), tungsten plug formation, and / or the formation of multilayer wiring formed from copper and low-dielectric-constant films.

[0003] Japanese Patent Application Publication No. 2009-256184 discloses a colloidal silica surface-modified with polyethylene oxide of molecular weight of 15,000 or less and a grinding composition for CMP containing the same. Summary of the Invention

[0004] A scheme is required where the pH of the polishing composition is below 7 to increase the polishing speed of materials containing silicon-silicon bonds. However, the technology described in Japanese Patent Application Publication No. 2009-256184 is envisioned primarily for polishing wiring layers formed from copper-based wiring materials, barrier metal layers formed from tantalum-based materials, and / or insulating layers formed from silicon dioxide (silicon oxide)-based materials. Furthermore, the technology in Japanese Patent Application Publication No. 2009-256184 envisions a pH of 8 to 12 for the polishing composition used in CMP. Moreover, regarding the pH of the polishing composition for CMP, Japanese Patent Application Publication No. 2009-256184 discloses cases where insufficient polishing speed is sometimes not obtained when the pH of the polishing composition is 6 or higher but lower than 8, and cases where a barrier layer is formed when the pH of the polishing composition is lower than 6. However, Japanese Patent Application Publication No. 2009-256184 does not specifically disclose any effect on polishing materials containing silicon-silicon bonds. Furthermore, based on the technology disclosed in Japanese Patent Application Publication No. 2009-256184, when the pH of the grinding composition is below 7, there is a problem that the grinding speed of materials containing silicon-silicon bonds is sometimes insufficient.

[0005] Therefore, the present invention provides a scheme in which a high grinding speed of materials having silicon-silicon bonds can be achieved when the pH of the grinding composition is below 7, and the ratio of the grinding speed of materials having silicon-silicon bonds to the grinding speed of materials having oxygen-silicon bonds is within a good range.

[0006] To address the aforementioned issues, the inventors conducted repeated and in-depth research. Their findings revealed that by including specific surface-modified silica particles in a grinding composition with a pH below 7, at least one of the aforementioned issues could be resolved, thus completing this invention.

[0007] One aspect of the present invention for solving at least one of the above-mentioned problems relates to a grinding composition comprising component (A) and component (B) below, and having a pH below 7;

[0008] (A) Composition: Surface-modified silica particles, which contain silica particles and surface-modifying groups for surface modification of the aforementioned silica particles, wherein the surface-modifying groups contain polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less.

[0009] (B) Ingredient: Water. Detailed Implementation

[0010] <Grinding Composition>

[0011] One aspect of the present invention relates to a grinding composition comprising component (A) and component (B) below, and having a pH below 7.

[0012] (A) Composition: Surface-modified silica particles, which contain silica particles and surface-modifying groups for surface modification of the aforementioned silica particles, wherein the surface-modifying groups contain polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less.

[0013] (B) Ingredient: Water.

[0014] According to an embodiment of the present invention, a grinding composition comprising such a configuration can achieve a high grinding speed for materials having silicon-silicon bonds when the pH of the grinding composition is below 7, and the ratio of the grinding speed of materials having silicon-silicon bonds to the grinding speed of materials having oxygen-silicon bonds is within a favorable range.

[0015] The embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The embodiments described in this specification can be combined in any way to form other embodiments.

[0016] In this specification, the term "X~Y" indicating a numerical range is used to mean "above X and below Y," encompassing the values ​​(X and Y) listed before and after it. In this specification, "A and / or B" refers to both A and B individually and combinations thereof. Unless otherwise specified, in this specification, operations and measurements of physical properties are performed at room temperature (above 20°C and below 25°C) and relative humidity (above 40% RH and below 50% RH).

[0017] [(A) ingredient]

[0018] (A) The component is surface-modified silica particles, which contain silica particles and surface-modifying groups for surface modification of the silica particles, wherein the surface-modifying groups contain polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less.

[0019] In one embodiment, component (A) is suitable for use as an abrasive grain. In one embodiment, the abrasive composition preferably contains abrasive grains, and the abrasive grains contain component (A). In another embodiment, the abrasive composition more preferably contains abrasive grains, and the abrasive grains consist solely of component (A).

[0020] In this specification, the surface-modified silica particles are also referred to as "surface-modified silica particles of component (A)", wherein the surface-modified silica particles contain silica particles and surface-modifying groups for surface modification of the silica particles, and the surface-modifying groups contain polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less.

[0021] (Silica particles)

[0022] Examples of silica particles (hereinafter referred to as "silica particles") contained in the surface-modified silica particles of component (A) are not particularly limited, and examples include fumed silica, colloidal silica, etc. Colloidal silica particles are preferred. Examples of methods for manufacturing colloidal silica include the sodium silicate method and the sol-gel method. However, colloidal silica manufactured by any method is suitable for use. Among these, colloidal silica manufactured by the sol-gel method is preferred from the viewpoint of reducing metallic impurities. Colloidal silica manufactured by the sol-gel method tends to have a low content of corrosive ions (such as metallic impurities and / or chloride ions) that diffuse in semiconductors. The manufacture of colloidal silica based on the sol-gel method can be carried out using conventionally known methods. As a specific example, colloidal silica can be obtained by performing a hydrolysis-condensation reaction on a hydrolyzable silicon compound (such as an alkoxysilane or its derivative).

[0023] The lower limit of the average primary particle size of silica particles is not particularly limited, but it is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more. As the average primary particle size of the abrasive particles increases, the grinding speed of the object being ground based on the grinding composition increases. The upper limit of the average primary particle size of silica particles is not particularly limited, but it is preferably 100 nm or less, more preferably 75 nm or less, and even more preferably 50 nm or less. The average primary particle size of silica particles is calculated, for example, based on the specific surface area of ​​the silica particles measured by the BET method.

[0024] The lower limit of the average secondary particle size of silica particles is not particularly limited, but it is preferably 2 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, and particularly preferably 25 nm or more. Within these ranges, the resistance during grinding decreases, allowing for stable grinding. The upper limit of the average secondary particle size of silica particles is not particularly limited, but it is preferably 200 nm or less, more preferably 150 nm or less, further preferably 120 nm or less, and particularly preferably 90 nm or less. Within these ranges, the surface area per unit mass of the abrasive grains increases, the contact frequency with the object being ground increases, and the grinding speed further increases. Examples of ranges for the average secondary particle size of silica particles include 2 nm or more and 200 nm or less, 10 nm or more and 150 nm or less, 15 nm or more and 120 nm or less, and 25 nm or more and 90 nm or less. The average secondary particle size of silica particles can be determined by dynamic light scattering methods, such as laser diffraction scattering.

[0025] The average degree of association of the silica particles is not particularly limited, but is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. The average degree of association of the silica particles is not particularly limited, but is preferably 1.0 or more, more preferably 1.2 or more, and even more preferably 1.5 or more. The average degree of association of the silica particles is obtained by dividing the average secondary particle size of the silica particles by the average primary particle size of the silica particles.

[0026] The shape of silica particles is not particularly limited; they can be spherical or non-spherical. Various shapes can be cited as examples of non-spherical shapes. Examples of non-spherical shapes are not particularly limited, including polygonal prisms, cylinders, sack-shaped cylinders with a central bulge, donut-shaped discs with a central through-hole, plate-shaped discs, cocoon-shaped discs with a central contraction, associative spherical shapes consisting of multiple integrated particles, konpeito shapes with multiple protrusions on the surface, and rugby ball shapes. Examples of polygonal prisms are not particularly limited, including triangular prisms and square prisms.

[0027] (Surface-modifying groups)

[0028] The surface-modified silica particles of component (A) contain surface-modifying groups comprising polyoxyalkylene chains. The surface-modifying groups contained in the surface-modified silica particles of component (A) comprise polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less. In this specification, the polyoxyalkylene chains contained in the surface-modifying groups are also referred to as "polyoxyalkylene chains in the surface-modifying groups".

[0029] The polyoxyalkylene chain in the surface-modifying group may consist of only one type of alkylene oxide or two or more types of alkylene oxides. Examples of polyoxyalkylene chains in the surface-modifying group are not particularly limited, and may include polyoxyethylene chains, polyoxypropylene chains, polyoxytrimethylene chains, polyoxytetramethylene chains, polyoxyisobutylene chains, polyoxyethylene-polyoxypropylene chains, polyoxyethylene-polyoxytetramethylene chains, and polyoxyethylene-polyoxypropylene-polyoxyethylene chains. When the polyoxyalkylene chain in the surface-modifying group is formed by two or more types of alkylene oxides, the bonding mode of the two or more alkylene oxides may be random, alternating, block, periodic, or a combination thereof. Preferably, the polyoxyalkylene chain in the surface-modifying group includes at least one type of polyoxyalkylene chain selected from the group consisting of the polyoxyalkylene chains exemplified above. The polyoxyalkylene chain in the surface modification group is preferably selected from at least one of the following groups: polyoxyethylene chain, polyoxypropylene chain, polyoxyethylene-polyoxypropylene chain, and polyoxyethylene-polyoxypropylene-polyoxyethylene chain, more preferably a polyoxyethylene chain.

[0030] The polyoxyalkylene chain in the surface-modifying group can have a structure in which the ends of the polyoxyalkylene chain are capped. For example, the polyoxyalkylene chain in the surface-modifying group can have a structure in which the ends of the polyoxyalkylene chain are capped by an aliphatic hydrocarbon group. The hydrogen atom in the hydroxyl group at one end of the polyoxyalkylene chain in the surface-modifying group can be replaced by an aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups used to cap the ends of the polyoxyalkylene chain in the surface-modifying group are not particularly limited, and can include aliphatic hydrocarbon groups having 1 or more carbon atoms and 10 or fewer. Examples of aliphatic hydrocarbon groups having 1 or more carbon atoms and 10 or fewer are not particularly limited, and can include linear or branched alkyl groups, linear or branched alkenyl groups, alkynyl groups, etc. Examples of linear or branched alkyl groups are not particularly limited, and can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, etc. Examples of alkenyl groups, whether linear or branched, are not particularly limited and can include vinyl, allyl, etc. Examples of alkynyl groups are not particularly limited and can include ethynyl, propynyl, etc.

[0031] The weight-average molecular weight (Mw) of the polyoxyalkylene chains contained in the surface-modifying groups is 80 or more and 7000 or less. That is, the weight-average molecular weight (Mw) of the polyoxyalkylene chains in the surface-modifying groups, calculated as the weight-average molecular weight (Mw) of the compound containing the polyoxyalkylene chains, is 80 or more and 7000 or less. For example, the weight-average molecular weight (Mw) of the polyoxyalkylene chains in the surface-modifying groups, calculated as the weight-average molecular weight (Mw) of the compound containing the polyoxyalkylene chains, which is used as a raw material to constitute the polyoxyalkylene chains in the surface-modifying groups, is 80 or more and 7000 or less. When the weight-average molecular weight of the polyoxyalkylene chains in the surface-modifying groups is less than 80, the ratio of the grinding speed of materials with silicon-silicon bonds to the grinding speed of materials with oxygen-silicon bonds becomes smaller. When the weight-average molecular weight of the polyoxyalkylene chains in the surface-modifying groups exceeds 7000, aggregation of surface-modified silica particles sometimes occurs in grinding compositions with a pH below 7.

[0032] The lower limit of the weight-average molecular weight of the polyoxyalkylene chain in the surface-modifying group is not particularly limited as long as it is 80 or more, preferably 100 or more, more preferably 140 or more, further preferably 200 or more, and particularly preferably 300 or more. The upper limit of the weight-average molecular weight of the polyoxyalkylene chain in the surface-modifying group is not particularly limited as long as it is 7000 or less, preferably 5000 or less, more preferably 2000 or less, further preferably 600 or less, and particularly preferably 500 or less. In one embodiment, examples of the weight-average molecular weight of the polyoxyalkylene chain in the surface-modifying group are not particularly limited and can include: 80 or more and 5000 or less, 80 or more and 2000 or less, 80 or more and 600 or less, 80 or more and 500 or less, 100 or more and 5000 or less, 140 or more and 2000 or less, 200 or more and 600 or less, 300 or more and 500 or less, etc. If these ranges are met, the grinding speed of materials with silicon-silicon bonds is further increased when the pH of the grinding composition is below 7, and the ratio of the grinding speed of materials with silicon-silicon bonds to that of materials with oxygen-silicon bonds becomes a better range. The weight-average molecular weight of compounds containing polyoxyalkylene chains can be determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard.

[0033] The surface-modifying groups contained in the surface-modified silica particles of component (A) preferably include silicon atoms and linking groups. Examples of linking groups are described in the description of formulas (1) to (3) below. The surface-modifying groups contained in the surface-modified silica particles of component (A) are more preferably at least one group selected from the group shown in formula (1), formula (2) below and formula (3) below. The atomic bonds with wavy lines in formulas (1) to (3) below are bonded to the surface of the silica particles.

[0034]

[0035] In the above equations (1) to (3),

[0036] R 1 Each can independently represent a hydrogen atom or a hydrocarbon group with 1 or more carbon atoms but less than 30.

[0037] R 2 Each can be used independently to represent an alkylene group.

[0038] n are each independently an oxoalkylene chain [-(OR 2 The average degree of polymerization (number-mean degree of polymerization) of )-], and is a number greater than 2 and less than 200.

[0039] X can independently represent a single bond or a linking group (a divalent group with more than one atom).

[0040] R 3 and R 4 Each of the following groups independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 or more carbon atoms but less than 3 carbon atoms, or a group represented by formula (a) below.

[0041]

[0042] In equation (a) above, R A Each can be represented independently as [-X-(OR)] 2 ) n -OR 1 At this time, R A X and R in 1 R 2 And n are respectively related to X and R as defined in equations (1) to (3) above. 1 R 2 Like n, R 5 and R 6 Each of the following groups independently represents a hydrogen atom or an aliphatic hydrocarbon group with 1 to 3 carbon atoms, and l and m independently represent numbers greater than 0. It should be noted that in formula (a), the atomic bonds extending to the left from the silicon atom are bonded to the oxygen atom. The atomic bonds with wavy lines in formula (a) are bonded to the surface of the silicon dioxide particles.

[0043] In equations (1) to (3) above, R is used as... 1Examples of hydrocarbon groups with 1 or more carbon atoms and less than 30 carbon atoms are not particularly limited, and can include alkyl, alkenyl, phenyl, naphthyl, alkylaryl, arylalkyl, arylalyl, etc. Examples of the aforementioned alkyl groups are not particularly limited, and can include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, n-hexyl, cyclohexyl, cyclohexylmethyl, 2-cyclohexylethyl, n-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-heptadecyl, n-octadecyl, etc. Examples of the aforementioned alkenyl groups are not particularly limited and can include vinyl, 1-methylvinyl, 2-methylvinyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, pentadecenyl, 1-phenylpropen-3-yl, etc. Examples of the aforementioned alkylaryl groups are not particularly limited and can include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-ditert-butylphenyl, etc. Examples of the aforementioned arylalkyl groups are not particularly limited and may include benzyl, phenethyl, 2-phenylpropane-2-yl, diphenylmethyl, triphenylmethyl, etc. Examples of the aforementioned arylalyl groups are not particularly limited and may include styryl, cinnamyl, etc.

[0044] In equations (1) to (3) above, R 2 The term "alkylene" is preferred to be an alkylene with 1 or more but 4 or fewer carbon atoms. Examples of alkylenes with 1 or more but 4 or fewer carbon atoms are not particularly limited and include methylene, ethylene, propylene (methyl ethylene), trimethylene, butylene (tetramethylene), isobutylene, etc. Wherein, R... 2 Preferably ethylidene or propyleneide. Multiple R 2 They can be the same or different. Multiple R's 2 Under different conditions, the above oxyalkylene chains [-(OR 2 The bonding mode of )-] can be random, alternating, block, periodic, or a combination thereof.

[0045] In equations (1) to (3) above, n is an oxoalkylene chain [-(OR 2The average degree of polymerization (number-average degree of polymerization) of n is a number of 2 or more and 200 or less. n is preferably a number of 3 or more and 150 or less, more preferably a number of 4 or more and 100 or less, even more preferably a number of 5 or more and 50 or less, and particularly preferably a number of 6 or more and 10 or less. If it is within these ranges, when the pH of the grinding composition is less than 7, the grinding speed of the material having silicon-silicon bonds is further increased, and the ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having oxygen-silicon bonds becomes a better range.

[0046] In formulas (1) to (3) above, X represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group are not particularly limited, and can include divalent hydrocarbon groups, urethane bonds, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and groups formed by linking one or more of these (groups formed by linking at least one of these groups).

[0047] Examples of the divalent hydrocarbon groups mentioned above are not particularly limited and can include straight-chain alkylene groups with 1 or more and 18 or less carbon atoms, branched alkylene groups with 1 or more and 18 or less carbon atoms (e.g., branched alkylene groups with 3 or more and 18 or less carbon atoms), or cyclic alkylene groups with 1 or more and 18 or less carbon atoms (e.g., cyclic alkylene groups with 3 or more and 18 or less carbon atoms). Examples of linear alkylene compounds having 1 or more but less than 18 carbon atoms, branched alkylene compounds having 1 or more but less than 18 carbon atoms (e.g., branched alkylene compounds having 3 or more but less than 18 carbon atoms), or cyclic alkylene compounds having 1 or more but less than 18 carbon atoms (e.g., cyclic alkylene compounds having 3 or more but less than 18 carbon atoms) are not particularly limited, and examples include methylene, methylmethylene, dimethylmethylene, ethylene, propylene (methyl ethylene), trimethylene, butylene (tetramethylene), 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 2,4-dimethylbutylene, 1,3- Dimethylbutylene, n-pentane, n-hexane, n-heptane, n-octane, ethane-1,1-diyl, propane-2,2-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18-diyl, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,1-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, methylcyclohexane-1,4-diyl, cyclohexane-1,4-dimethyl, etc.

[0048] As the linking group described above, such as the linking group X, it is preferable to include a urethane bond for ease of synthesis, and more preferably a group containing a divalent hydrocarbon group (especially a straight-chain or branched alkylene group) and a urethane bond. Furthermore, it is preferable that the silicon atom in formulas (1) to (3) is directly bonded to the divalent hydrocarbon group (especially a straight-chain or branched alkylene group) in X. Specifically, the linking group described above, such as X, is more preferably -(CH2). k -NH-C(=O)- (the C on the left end is bonded to a silicon atom, and the C on the right end is bonded to an O atom in the polyoxyalkylene chain). It should be noted that in the above formula, k represents a number of 1 or more and 18 or less, preferably a number of 1 or more and 6 or less, and more preferably a number of 1 or more and 3 or less.

[0049] In the above formula (1), R 3 and R 4 Each group independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 or more but less than 3 carbon atoms. Examples of aliphatic hydrocarbon groups having 1 or more but less than 3 carbon atoms are not particularly limited and can include alkyl, alkenyl, ynyl, etc. Examples of alkyl groups are not particularly limited and can include methyl, ethyl, propyl, isopropyl, etc. Examples of alkenyl groups are not particularly limited and can include vinyl, allyl, etc. Examples of ynyl groups are not particularly limited and can include ethynyl, propynyl, etc. Among these, R... 3 and R 4 Each is preferably an alkyl group, R 3 and R 4 More preferably, all are alkyl groups. It should be noted that R in formula (2) 3 Also related to R in equation (1) 3 same.

[0050] In equation (a) above, R A It means [-X-(OR)] 2 ) n -OR 1 ]. R A X and R in 1 R 2 As and n are the same as those exemplified and explained in formulas (1) to (3) above, the preferred embodiments are also the same. Furthermore, for [-(OR] alkylene chains having two or more alkylene groups... 2 The bonding mechanism at the )-] is as described above. It should be noted that the atomic bonds extending to the left from the silicon atom are bonded to the oxygen atom. The atomic bonds with wavy lines in the formula are bonded to the surface of the silicon dioxide particles.

[0051] In equation (a) above, R 5 and R 6Each group independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 or more but less than 3 carbon atoms. Examples of these aliphatic hydrocarbon groups with 1 or more but less than 3 carbon atoms include straight-chain or branched alkyl groups, straight-chain or branched alkenyl groups, and ynyl groups. Examples of straight-chain or branched alkyl groups are not particularly limited and include methyl, ethyl, n-propyl, isopropyl, etc. Examples of straight-chain or branched alkenyl groups are not particularly limited and include vinyl, allyl, propenyl, etc. Examples of ynyl groups are not particularly limited and include ethynyl, propynyl, etc. Among these, R... 5 and R 6 Each is preferably a straight-chain or branched alkyl group, R 5 and R 6 More preferably, all are straight-chain or branched alkyl groups.

[0052] In equation (a) above, l and m each independently represent numbers greater than 0. The bonding order of the structural units with l and those with m is not particularly limited. That is, the silicon atom in equation (a) bonded to the oxygen atom in equation (1) or (2) can be a silicon atom in a structural unit with l or a silicon atom in a structural unit with m. Similarly, the silicon atom bonded to R in equation (a)... 6 The oxygen atom in the bonded formula (a) can be an oxygen atom in a structural unit with the number 1 or an oxygen atom in a structural unit with the number m. In addition, if one of 1 and m is 1 or more and the other is 2 or more, the bonding mode between the structural unit with the number 1 and the structural unit with the number m can be random, alternating, block, periodic, or a combination thereof.

[0053] (A) The surface-modified silica particles of the composition have multiple R 1 Multiple R 2 Multiple R 3 Multiple R 4 Multiple R 5 Multiple R 6 In the case of multiple X, multiple l, multiple m and / or multiple n, multiple R 1 Multiple R 2 Multiple R 3 Multiple R 4 Multiple R 5 Multiple R 6 Multiple X, multiple l, multiple m, and multiple n can be the same or different independently.

[0054] In equations (1) and (2) above, R 3 and / or R 4Structures containing hydrogen atoms, for example, represent structures where unreacted alkoxysilyl groups in surface-modifying groups bonded to silica particles have undergone hydrolysis. In formulas (1) and (2) above, R 3 and / or R 4 Structures consisting of aliphatic hydrocarbon groups with 1 or more but less than 3 carbon atoms, such as structures representing unreacted alkoxysilyl residues in surface-modifying groups bonded to silica particles. In formulas (1) and (2) above, R 3 and / or R 4 The structure of the group shown in formula (a) above can be represented by, for example, the following structures: a structure formed by reacting an unreacted alkoxysilyl group in a surface-modifying group bonded to silica particles with an unreacted silane coupling agent containing a polyoxyalkylene chain (described later); a structure formed by reacting an unreacted alkoxysilyl group in a surface-modifying group bonded to silica particles with an alkoxysilyl group in another surface-modifying group bonded to silica particles via dehydration condensation; or a structure formed by reacting an unreacted alkoxysilyl group in a surface-modifying group bonded to silica particles with an unreacted silane coupling agent containing a polyoxyalkylene chain (described later), and an alkoxysilyl group in another surface-modifying group bonded to silica particles via dehydration condensation; etc.

[0055] (A) The preferred composition contains silica particles on the surface of the particles having a compound containing a polyoxyalkylene chain fixed thereon by means of a silane coupling agent.

[0056] In silica particles where a compound containing a polyoxyalkylene chain is fixed to the surface of the particles by means of a silane coupling agent, the silane coupling agent is not particularly limited. Preferred examples of silane coupling agents include silane coupling agents containing isocyanate groups. In silica particles where a compound containing a polyoxyalkylene chain is fixed to the surface of the particles by means of a silane coupling agent, the silane coupling agent is not particularly limited, but it is preferable to contain a silane coupling agent containing an isocyanate group, and more preferably, it consists only of a silane coupling agent containing an isocyanate group. Examples of silane coupling agents containing isocyanate groups are not particularly limited, and examples include 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyldimethoxymethylsilane, 3-isocyanopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyldimethoxymethylsilane. These silane coupling agents can be used alone or in combination of two or more. The silane coupling agent preferably comprises at least one silane coupling agent selected from the group consisting of silane coupling agents exemplified above. The silane coupling agent is preferably an isocyanate-containing silane coupling agent, more preferably 3-isocyanate-propyltrimethoxysilane. The silane coupling agent can be commercially available or synthetic.

[0057] In one embodiment, silica particles containing a compound comprising polyoxyalkylene chains are fixed to the surface of the particles using a silane coupling agent. The compound comprising polyoxyalkylene chains is preferably a compound formed solely of polyalkylene glycol chains. The ends of the compound formed solely of polyalkylene glycol chains are uncapped. For example, the compound formed solely of polyalkylene glycol chains can be the same as the compound formed solely of polyalkylene glycol chains exemplified in the description below, which contains compounds comprising polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less. More preferably, the compound formed solely of polyalkylene glycol chains is at least one compound selected from the group consisting of polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers, and more preferably polyethylene glycol. The compound comprising polyoxyalkylene chains is preferably a polyalkylene glycol.

[0058] The lower limit of the average secondary particle size of the surface-modified silica particles in the grinding composition of one embodiment is not particularly limited, but is preferably 2 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, and particularly preferably 25 nm or more. If it falls within these ranges, the resistance during grinding decreases, and grinding can be performed stably. The upper limit of the average secondary particle size of the surface-modified silica particles in the grinding composition of one embodiment is not particularly limited, but is preferably 200 nm or less, more preferably 150 nm or less, further preferably 120 nm or less, and particularly preferably 90 nm or less. If it falls within these ranges, the surface area per unit mass of the abrasive grains increases, the contact frequency with the object being ground increases, and the grinding speed further increases. Examples of the range of the average secondary particle size of the surface-modified silica particles in the grinding composition of one embodiment include 2 nm or more and 200 nm or less, 10 nm or more and 150 nm or less, 15 nm or more and 120 nm or less, and 25 nm or more and 90 nm or less. The average secondary particle size of the surface-modified silica particles in the grinding composition of one embodiment can be determined, for example, by dynamic light scattering methods, such as laser diffraction scattering.

[0059] The content of component (A) in the grinding composition of one embodiment is not particularly limited. The lower limit of the content of component (A) relative to the total mass of the grinding composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more. For example, the lower limit of the content of component (A) relative to the total mass of the grinding composition can be 2% by mass or more. The upper limit of the content of surface-modified silica particles of component (A) (the upper limit of the content of component (A)) relative to the total mass of the grinding composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 8% by mass or less, even more preferably 6% by mass or less, and particularly preferably 5% by mass or less (the lower limit exceeds 0% by mass). If it is within these ranges, the cost can be suppressed and the grinding speed can be increased. Examples of the range of content of component (A) are not particularly limited, and can be 0.1% to 20% by mass or less, 0.2% to 15% by mass or less, 0.5% to 10% by mass or less, 1% to 8% by mass or less, 1.5% to 6% by mass or less, 2% to 5% by mass or less, etc., relative to the total mass of the grinding composition. When the grinding composition of one embodiment contains two or more types of surface-modified silica particles as component (A), the content of component (A) indicates their total content.

[0060] (Method for manufacturing surface-modified silica particles)

[0061] There are no particular limitations on the manufacturing method of surface-modified silica particles of component (A), and known methods may be used. Examples of manufacturing methods of surface-modified silica particles of component (A) include the method described below (a1) and the method described below (b1), etc.

[0062] Method (a1) includes the following steps:

[0063] The steps of pre-synthesizing a silane coupling agent containing a polyoxyalkylene chain (also referred to as a "surface modifier" in this specification) using a silane coupling agent having a group capable of reacting with terminal hydroxyl groups of a compound containing a polyoxyalkylene chain of 80 or more and 7000 or less, and a compound containing a polyoxyalkylene chain, and...

[0064] The step of reacting a silane coupling agent containing a polyoxyalkylene chain with silica particles (preferably colloidal silica);

[0065] Method (b1) includes the following steps: reacting a silane coupling agent having a group capable of reacting with terminal hydroxyl groups of a compound containing a polyoxyalkylene chain with a weight average molecular weight of 80 or more and 7000 or less with silica particles (preferably colloidal silica), followed by further reacting the compound containing a polyoxyalkylene chain with a weight average molecular weight of 80 or more and 7000 or less.

[0066] Of these, method (a1) is preferred from the perspective of ease of reaction control and potential reduction in manufacturing costs. The method (a1) will be explained below.

[0067] Process for synthesizing silane coupling agents containing polyoxyalkylene chains

[0068] In this process, a silane coupling agent having a group capable of reacting with the terminal hydroxyl groups of a compound containing a polyoxyalkylene chain is reacted with a compound containing a polyoxyalkylene chain with a weight average molecular weight of 80 or more and 7000 or less to synthesize a silane coupling agent (surface modifier) ​​containing a polyoxyalkylene chain.

[0069] The silane coupling agent having a group capable of reacting with the terminal hydroxyl group of a compound containing a polyoxyalkylene chain is not particularly limited, but isocyanate-containing silane coupling agents are preferred. Examples of isocyanate-containing silane coupling agents are not particularly limited, and include 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyldimethoxymethylsilane, 3-isocyanopropyltriethoxysilane, isocyanate methyltrimethoxysilane, isocyanate methyltriethoxysilane, isocyanate methyldimethoxymethylsilane, etc. These silane coupling agents can be used alone or in combination of two or more. The silane coupling agent preferably includes at least one silane coupling agent selected from the group consisting of the silane coupling agents exemplified above. The silane coupling agent is preferably an isocyanate-containing silane coupling agent, more preferably 3-isocyanopropyltrimethoxysilane. Commercially available or synthetic silane coupling agents can be used.

[0070] Examples of compounds containing polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less are not particularly limited, and include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyisobutylene glycol, ethylene glycol-propylene glycol copolymers, ethylene glycol-tetramethylene glycol copolymers, etc. It should be noted that the bonding mode of the copolymer can be random, alternating, block, periodic, or a combination thereof. These compounds containing polyoxyalkylene chains can be used alone or in combination of two or more. Preferably, the compound containing polyoxyalkylene chains contains at least one compound selected from the group consisting of the compounds containing polyoxyalkylene chains exemplified above. The compound containing polyoxyalkylene chains is preferably a polyalkylene glycol, more preferably at least one compound selected from the group consisting of polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers, and even more preferably polyethylene glycol. The preferred embodiment of the weight-average molecular weight of the compound containing the polyoxyalkylene chain is the same as the preferred embodiment of the weight-average molecular weight of the polyoxyalkylene chain described above.

[0071] For example, compounds containing polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less can have a structure in which one end of the polyoxyalkylene chain is capped. For example, compounds containing polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less can have a structure in which one end of the polyoxyalkylene chain is capped by an aliphatic hydrocarbon group. That is, the hydrogen atom in the hydroxyl group at one end of a compound containing polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less can be replaced by an aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups used to cap one end of a compound containing polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less are not particularly limited, and examples include aliphatic hydrocarbon groups with 1 or more carbon atoms and 10 or less. Examples of aliphatic hydrocarbon groups with 1 or more carbon atoms and 10 or less are not particularly limited, and examples include linear or branched alkyl groups, linear or branched alkenyl groups, alkynyl groups, etc. Examples of alkynyl groups are not specifically limited and can include ethynyl, propynyl, etc.

[0072] In one embodiment, the compound containing the polyoxyalkylene chain is preferably a polyalkylene glycol, a compound having a structure in which one end of the polyoxyalkylene chain is capped, or a combination thereof.

[0073] Compounds containing polyoxyalkylene chains can be commercially available or synthetic.

[0074] The reaction of the aforementioned silane coupling agent with compounds containing polyoxyalkylene chains is not particularly limited, and can be carried out, for example, in a solvent-free environment or in an organic solvent. Examples of usable organic solvents, without particular limitation, include aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, aprotic polar solvents, halogenated hydrocarbons, chain or cyclic ethers, esters, chain ketones, nitriles, etc. Examples of aliphatic hydrocarbons, without particular limitation, include hexane, heptane, octane, etc. Examples of aromatic hydrocarbons, without particular limitation, include benzene, toluene, xylene, etc. Examples of alicyclic hydrocarbons, without particular limitation, include cyclohexane, methylcyclohexane, etc. Examples of aprotic polar solvents, without particular limitation, include dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. Examples of halogenated hydrocarbons, without particular limitation, include chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, trifluoromethylbenzene, etc. Examples of chain or cyclic ethers are not particularly limited, and can include diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran (THF), dioxane, etc. Examples of esters are not particularly limited, and can include ethyl acetate, butyl acetate, etc. Examples of chain ketones are not particularly limited, and can include methyl ethyl ketone (MEK), methyl isobutyl ketone, etc. Examples of nitriles are not particularly limited, and can include acetonitrile, etc.

[0075] A surface modifier is obtained by mixing a silane coupling agent with a compound containing a polyoxyalkylene chain. As a mixing method, the following method is preferred: adding a silane coupling agent to the compound containing the polyoxyalkylene chain and mixing. In this case, the silane coupling agent can be added simultaneously, in batches, or continuously. When added continuously, the addition rate can be adjusted appropriately. If the compound containing the polyoxyalkylene chain is in solid form, it can be heated before mixing to liquefy it before mixing.

[0076] There is no particular limitation on the stirring speed during mixing; it can be set appropriately. The mixing time is preferably more than 15 minutes and less than 2 hours.

[0077] The reaction temperature after mixing is preferably above 20°C and below 200°C, more preferably above 50°C and below 150°C. The reaction time after mixing is as follows: when measuring the FT-IR spectrum of the surface modifier, preferably 2260 cm⁻¹. -1The time when the intensity of the peak derived from the isocyanate group of the silane coupling agent becomes less than 10% compared to immediately after mixing, and more preferably the time when the peak disappears. The reaction atmosphere can be any of air, nitrogen, argon, or other inert gas atmospheres, without particular limitation. Regarding the reaction pressure, it can be, for example, at atmospheric pressure, under pressure, or under reduced pressure, without particular limitation. The reaction can be carried out at atmospheric pressure; therefore, it is preferred to carry out the reaction at atmospheric pressure.

[0078] The molar ratio of the silane coupling agent to the compound containing the polyoxyalkylene chain (silane coupling agent / compound containing the polyoxyalkylene chain) is preferably 0.5 or more and 1.5 or less.

[0079] Thus, a surface modifier can be obtained. The structure of the surface modifier can be confirmed, for example, by measuring the infrared absorption spectrum using the total internal reflection method (ATR method) with a Fourier transform infrared spectrophotometer (FT-IR). Details of this method are described in the examples.

[0080] After this process, the surface modifier can be separated and purified, but the following process (the process of reacting silica particles with the surface modifier) ​​can be performed without separation and purification.

[0081] Process for reacting silica particles with surface modifiers

[0082] Preferably, the surface modifier obtained above is reacted with silica particles to obtain surface-modified silica particles of composition (A). The silica particles have silanol groups on their surface, which become reaction sites, forming siloxane bonds between them and the surface modifier.

[0083] The surface modifier (a silane coupling agent containing a polyoxyalkylene chain) is preferably a compound represented by the following formula (1'). This surface modifier can be used alone or in combination of two or more.

[0084]

[0085] In the above formula (1'), R 1 R 2 X, n, and n are the same as those shown and explained in equations (1) to (3) above, and the preferred scheme is also the same. When using two or more compounds as shown in equation (1') above, multiple R... 1 Multiple R 2 Multiple X's and multiple n's can be the same or different independently.

[0086] In the above formula (1'), R 7Each of these groups independently represents an aliphatic hydrocarbon group having 1 or more but 3 or fewer carbon atoms. Examples of these aliphatic hydrocarbon groups with 1 or more but 3 or fewer carbon atoms include linear or branched alkyl groups, linear or branched alkenyl groups, and ynyl groups. Examples of linear or branched alkyl groups are not particularly limited and include methyl, ethyl, propyl, and isopropyl groups. Examples of linear or branched alkenyl groups are not particularly limited and include vinyl, allyl, and propenyl groups. Examples of ynyl groups are not particularly limited and include ethynyl and propynyl groups. Among these, R... 7 Preferably, each alkyl group is independently linear or branched, R 7 More preferably, all of them are linear or branched alkyl groups.

[0087] The process of reacting the surface modifier with the silica particles is preferably carried out in a solvent. Examples of solvents are not particularly limited, and water, organic solvents, etc., can be included. One solvent may be used alone, or two or more may be used in combination. Examples of organic solvents are not particularly limited, and the substances exemplified in the description of the process for synthesizing silane coupling agents containing polyoxyalkylene chains, alcohols, etc., can be included. Examples of alcohols are not particularly limited, and methanol, ethanol, etc., can be included.

[0088] Preferably, the reaction is carried out while stirring a mixed solution containing silica particles, a surface modifier, and a solvent in a reaction vessel. The ratio of silica particles to surface modifier supplied for the reaction is appropriately selected according to the desired degree of surface modification. Taking an example of the ratio of silica particles to surface modifier, the amount of surface modifier used is preferably 0.1 parts by mass or more and 40 parts by mass or less, more preferably 0.5 parts by mass or more and 30 parts by mass or less, relative to 100 parts by mass of silica particles.

[0089] There are no particular limitations on the mixing method of silica particles and surface modifiers, but the following method is preferred: adding the surface modifier to the silica particles and mixing. In this case, the silica particles can be added simultaneously, in batches, or continuously. There are no particular limitations on the stirring speed during mixing, and it can be set appropriately.

[0090] The reaction temperature is preferably 20°C or higher and 200°C or lower, more preferably 30°C or higher and 150°C or lower. The reaction time is preferably 1 hour or higher and 50 hours or lower, more preferably 2 hours or higher and 30 hours or lower. The reaction atmosphere can be, for example, air, nitrogen, argon, or other inert gas atmospheres, and is not particularly limited. Regarding the reaction pressure, it can be, for example, at atmospheric pressure, under pressure, or under reduced pressure, and is not particularly limited. The reaction of the present invention can be carried out at atmospheric pressure; therefore, it is preferable to carry out the reaction at atmospheric pressure.

[0091] After a process of synthesizing a silane coupling agent (surface modifier) ​​containing a polyoxyalkylene chain and a process of reacting the surface modifier with silica particles, surface-modified silica particles of composition (A) are obtained.

[0092] If the dispersion of the surface-modified silica particles containing component (A) contains a dispersion medium other than water, the dispersion medium other than water may be replaced with water as needed. There are no particular limitations on the method of replacing the dispersion medium other than water; for example, a method may be used where water is added dropwise in fixed amounts while the dispersion of the surface-modified silica particles containing component (A) is heated. Alternatively, a method may be used where the surface-modified silica particles of component (A) are separated from the dispersion medium other than water by, for example, a combination of precipitation and separation, and / or centrifugation, and then re-dispersed in water.

[0093] The method for manufacturing surface-modified silica particles containing component (A) may further include other steps. Examples of other steps include: filtering a dispersion of surface-modified silica particles containing component (A); mixing the dispersion of surface-modified silica particles containing component (A) with other additives; and / or further filtering after mixing with other additives; etc.

[0094] (Amount of surface modifier)

[0095] (A) The surface-modified silica particles of component (A) can be silica particles modified with a surface modifier. The amount of surface modifier in the surface-modified silica particles of component (A) can be confirmed using a total organic carbon analyzer and a centrifugal separator. Details of this confirmation method are described in the examples.

[0096] (Structure of surface-modified silica particles)

[0097] (A) The structure of surface-modified silica particles can be achieved, for example, by using... 29The T2 component (in the manner described in formula (2) above) and / or the T3 component (in the manner described in formula (3) above) are confirmed by Si-NMR detection. In this specification, T refers to a Si atom with 3 atomic bonds bonded to O atoms and 1 atomic bond bonded (directly or indirectly) to a polyoxyalkylene chain. The numbers 2 and 3 represent the number of Si-O-Si bonds in which the Si atom participates, respectively. For example, the T2 component refers to a component having the following Si atoms: Si atoms with 3 atomic bonds bonded to O atoms, of which 2 participate in Si-O-Si bonds. In unmodified silica particles, the T2 and T3 components bonded (directly or indirectly) to a polyoxyalkylene chain were not detected, but in the surface-modified silica particles of component (A), the T2 and T3 components were detected.

[0098] [(B) Component]

[0099] The water used for component (B) is not particularly limited. In one embodiment, component (B) is suitable for use as a dispersion medium for dispersing component (A). Component (B) can also dissolve and / or disperse components other than component (A). A grinding composition of one embodiment preferably contains a dispersion medium, and the dispersion medium contains component (B). A grinding composition of one embodiment may contain a dispersion medium, and the dispersion medium consists only of component (B). From the viewpoint of preventing contamination of the object being ground and preventing interference with the action of other components, the water is preferably as free of impurities as possible. For example, water with a total transition metal ion content of 100 ppb or less is preferred. Here, the purity of the water can be improved, for example, by removing impurity ions using ion exchange resins, removing foreign matter based on filters, distillation, etc. Specifically, as preferred examples of water, there are no particular limitations, and deionized water (ion-exchanged water), pure water, ultrapure water, distilled water, etc., can be mentioned.

[0100] [(C) Component]

[0101] The grinding composition of one embodiment may further contain an acid as component (C), or may not contain an acid. The grinding composition of one embodiment preferably further contains an acid as component (C).

[0102] In one embodiment, component (C) is suitable for use as a pH adjuster. A grinding composition of one embodiment preferably contains a pH adjuster. A grinding composition of one embodiment preferably contains a pH adjuster, and the pH adjuster contains component (C). A grinding composition of one embodiment may contain a pH adjuster, and the pH adjuster consists solely of component (C).

[0103] (C) The acid in the component is not particularly limited. Examples of acids are not particularly limited and can include organic acids, inorganic acids, etc. Examples of organic acids are not particularly limited and can include aliphatic carboxylic acids, aromatic carboxylic acids, hydroxy acids, organic sulfonic acids, organic phosphonic acids, etc. Examples of aliphatic carboxylic acids are not particularly limited and can include aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, etc. Examples of aliphatic monocarboxylic acids are not particularly limited and can include formic acid, acetic acid, propionic acid, etc. Examples of aliphatic dicarboxylic acids are not particularly limited and can include maleic acid, fumaric acid, succinic acid, etc. Examples of aromatic carboxylic acids are not particularly limited and can include benzoic acid, phthalic acid, etc. Examples of hydroxy acids are not particularly limited and can include citric acid, oxalic acid, tartaric acid, malic acid, etc. Examples of inorganic acids are not particularly limited and can include sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, etc. These acids can be used alone or in combination of two or more. (C) The component preferably contains at least one acid selected from the group consisting of acids exemplified above. (C) The preferred component is an inorganic acid, and more preferably nitric acid. (C) The component may be a commercially available product or a synthetic product.

[0104] The grinding composition of one embodiment preferably further comprises component (C): acid, and the acid comprises an inorganic acid. The grinding composition of one embodiment more preferably further comprises component (C): acid, and the acid comprises nitric acid. The grinding composition of one embodiment further preferably further comprises component (C): acid, and the acid consists solely of nitric acid.

[0105] When the grinding composition of one embodiment contains component (C), the content of component (C) in the grinding composition is not particularly limited. The content of component (C) is preferably an amount in which the grinding composition can exhibit a desired pH. The content of component (C) relative to the total mass of the grinding composition is preferably 0.00001% by mass or more and 10% by mass or less, more preferably 0.0001% by mass or more and 10% by mass or less, further preferably 0.001% by mass or more and 1% by mass or less, further preferably 0.005% by mass or more and 0.5% by mass or less, further preferably 0.01% by mass or more and 0.25% by mass or less, and particularly preferably 0.01% by mass or more and 0.1% by mass or less. When the grinding composition of one embodiment contains two or more acids as component (C), the content of component (C) represents their total content.

[0106] [(D) component]

[0107] One embodiment of the grinding composition may further contain a compound comprising a polyoxyalkylene chain as component (D), or may not contain a compound comprising a polyoxyalkylene chain as component (D). Preferably, one embodiment of the grinding composition further contains a compound comprising a polyoxyalkylene chain as component (D).

[0108] In this specification, component (D) refers to a component present in the grinding composition that is independent of the surface-modifying groups of the surface-modified silica particles of component (A).

[0109] (D) The polyoxyalkylene chain in the compound containing the polyoxyalkylene chain may consist of only one type of oxyalkylene or two or more types of oxyalkylene. Examples of the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) are not particularly limited, and may include polyoxyethylene chains, polyoxypropylene chains, polyoxytrimethylene chains, polyoxytetramethylene chains, polyoxyisobutylene chains, polyoxyethylene-polyoxypropylene chains, polyoxyethylene-polyoxytetramethylene chains, polyoxyethylene-polyoxypropylene-polyoxyethylene chains, etc. When the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) consists of two or more types of oxyalkylene, the bonding mode of the two or more oxyalkylene groups may be random, alternating, block, periodic, or a combination thereof. Preferably, the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) comprises at least one type of polyoxyalkylene chain selected from the group consisting of the polyoxyalkylene chains exemplified above. (D) The polyoxyalkylene chain in the compound containing the polyoxyalkylene chain is preferably selected from at least one of the following groups: polyoxyethylene chain, polyoxypropylene chain, polyoxyethylene-polyoxypropylene chain, and polyoxyethylene-polyoxypropylene-polyoxyethylene chain, more preferably a polyoxyethylene chain.

[0110] For example, the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) may have a structure in which the ends of the polyoxyalkylene chain are capped. For example, the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) may have a structure in which one or both ends of the polyoxyalkylene chain are capped by an aliphatic hydrocarbon group. That is, the hydrogen atom in the hydroxyl group at one or both ends of the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) may be replaced by an aliphatic hydrocarbon group. Examples of aliphatic hydrocarbon groups used to cap the ends of the polyoxyalkylene chain in the compound containing the polyoxyalkylene chain of component (D) are not particularly limited, and examples include aliphatic hydrocarbon groups having 1 or more carbon atoms and 10 or fewer. Examples of aliphatic hydrocarbon groups having 1 or more carbon atoms and 10 or fewer are not particularly limited, and examples include linear or branched alkyl groups, linear or branched alkenyl groups, alkynyl groups, etc. Examples of linear or branched alkyl groups are not particularly limited, and can include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, etc. Examples of linear or branched alkenyl groups are not particularly limited, and can include vinyl, allyl, etc. Examples of alkynyl groups are not particularly limited, and can include ethynyl, propynyl, etc.

[0111] In one embodiment, (D) component: The compound comprising a polyoxyalkylene chain preferably comprises a polyalkylene glycol, a compound having a structure with one end of the polyoxyalkylene chain capped, a compound having a structure with both ends of the polyoxyalkylene chain capped, or a combination thereof, more preferably a polyalkylene glycol, a compound having a structure with one end of the polyoxyalkylene chain capped, a compound having a structure with both ends of the polyoxyalkylene chain capped, or a combination thereof.

[0112] Specific examples of component (D) are not particularly limited, and may include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, polyisobutylene glycol, ethylene glycol-propylene glycol copolymer, ethylene glycol-tetramethylene glycol copolymer, etc. It should be noted that the bonding mode of the copolymer can be random, alternating, block, periodic, or a combination thereof. These compounds containing polyoxyalkylene chains can be used alone or in combination of two or more. Component (D) preferably includes at least one compound containing a polyoxyalkylene chain selected from the group consisting of compounds containing polyoxyalkylene chains exemplified above. Component (D) is preferably a polyalkylene glycol, more preferably at least one compound selected from the group consisting of polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymer, and even more preferably polyethylene glycol.

[0113] The grinding composition of one embodiment preferably further contains component (D): a compound comprising a polyoxyalkylene chain, wherein the compound comprising the polyoxyalkylene chain comprises a polyalkylene glycol. The grinding composition of one embodiment more preferably further contains component (D): a compound comprising a polyoxyalkylene chain, wherein the compound comprising the polyoxyalkylene chain comprises polyethylene glycol. The grinding composition of one embodiment further preferably further contains component (D): a compound comprising a polyoxyalkylene chain, wherein the compound comprising the polyoxyalkylene chain consists solely of polyethylene glycol.

[0114] The weight-average molecular weight (Mw) of the compound containing polyoxyalkylene chains in component (D) is not particularly limited. The lower limit of the weight-average molecular weight of the compound containing polyoxyalkylene chains in component (D) is preferably 80 or more, more preferably 100 or more, further preferably 200 or more, and particularly preferably 300 or more. The upper limit of the weight-average molecular weight of the compound containing polyoxyalkylene chains in component (D) is preferably 1,000,000 or less, more preferably 100,000 or less, further preferably 10,000 or less, and particularly preferably less than 1,000. In one embodiment, examples of the weight-average molecular weight of the compound containing polyoxyalkylene chains in component (D) are not particularly limited, and examples include 80 or more and 1,000,000 or less, 100 or more and 100,000 or less, 200 or more and 10,000 or less, and 300 or more and less than 1,000. The weight-average molecular weight of the compound containing polyoxyalkylene chains can be determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard.

[0115] (D) The ingredients may be commercially available or synthetic products.

[0116] When the grinding composition of one embodiment contains component (D), the content of component (D) in the grinding composition is not particularly limited. The content of component (D) relative to the total mass of the grinding composition is preferably 0.0001% by mass or more and 1% by mass or less, more preferably 0.0005% by mass or more and 0.1% by mass or less, and even more preferably 0.001% by mass or more and 0.01% by mass or less. When the grinding composition of one embodiment contains two or more compounds comprising polyoxyalkylene chains as component (D), the content of component (D) represents their total content.

[0117] [(E) component]

[0118] The grinding composition of one embodiment may further contain a salt compound as component (E), or may not contain a salt compound as component (E). Preferably, the grinding composition of one embodiment further contains a salt compound as component (E).

[0119] In one embodiment, component (E) is suitable for use as a conductivity modifier. A grinding composition of one embodiment preferably contains a conductivity modifier. A grinding composition of one embodiment preferably contains a conductivity modifier, and the conductivity modifier contains component (E). A grinding composition of one embodiment may contain a conductivity modifier, and the conductivity modifier consists solely of component (E).

[0120] The salt compound can be a salt of an acid, a salt of a base, or a combination thereof. The salt compound can be an organic salt compound, an inorganic salt compound, or a combination thereof. Examples of salt compounds, without particular limitation, include potassium nitrate, ammonium nitrate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium sulfate, potassium chloride, sodium chloride, potassium bromide, potassium iodide, ammonium citrate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. These salt compounds can be used alone or in combination of two or more. (E) The component preferably contains at least one salt compound selected from the group consisting of the salt compounds exemplified above. (E) The component is preferably not a hydroxide. (E) The component is preferably an inorganic salt compound, particularly ammonium sulfate. (E) The component can be a commercially available product or a synthetic product.

[0121] The grinding composition of one embodiment preferably further comprises component (E): a salt compound, wherein the salt compound comprises an inorganic salt compound. The grinding composition of one embodiment more preferably further comprises component (E): a salt compound, wherein the salt compound comprises ammonium sulfate. The grinding composition of one embodiment further preferably further comprises component (E): a salt compound, wherein the salt compound consists solely of ammonium sulfate.

[0122] When the grinding composition of one embodiment contains component (E), the content of component (E) in the grinding composition is not particularly limited. The content of component (E) relative to the total mass of the grinding composition is preferably 0.01% by mass or more and 7.5% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and even more preferably 1% by mass or more and 5% by mass or less. When the grinding composition of one embodiment contains two or more salt compounds as component (E), the content of component (E) represents their total content.

[0123] (Other ingredients)

[0124] The grinding composition of one embodiment may further contain one or more other components (components other than those described in (A) to (E) above) as needed. Therefore, the grinding composition of one embodiment may contain one or more other components, or it may not contain any other components. These other components may be known additives that can be used in the grinding composition. Examples of other components are not particularly limited, but include water-soluble polymers (excluding compounds containing polyoxyalkylene chains), pH adjusters (excluding acids), oxidants, complexing agents, preservatives, fungicides, conductivity modifiers (excluding salt compounds), organic solvents, etc. Each of these other components may be used individually or in combination of two or more.

[0125] (Examples of the composition of preferred grinding compositions)

[0126] The grinding composition of a preferred embodiment can be substantially composed of

[0127] (A) Ingredients,

[0128] (B) Ingredients, and

[0129] (C) Composition.

[0130] The grinding composition of a preferred embodiment can be substantially composed of

[0131] (A) Ingredients;

[0132] (B) Ingredients;

[0133] (C) Components; and

[0134] It is composed of at least one component selected from the group consisting of components (D) and (E).

[0135] The grinding composition of a preferred embodiment can be substantially composed of

[0136] (A) Ingredients;

[0137] (B) Ingredients;

[0138] (C) Components; and

[0139] It is composed of at least one component selected from the group consisting of water-soluble polymers (excluding compounds containing polyoxyalkylene chains), pH adjusters (excluding acids), oxidants, complexing agents, preservatives, fungicides, conductivity adjusters (excluding salt compounds), and organic solvents.

[0140] The grinding composition of a preferred embodiment can be substantially composed of

[0141] (A) Ingredients;

[0142] (B) Ingredients;

[0143] (C) Components;

[0144] At least one component selected from the group consisting of components (D) and (E); and

[0145] It is composed of at least one component selected from the group consisting of water-soluble polymers (excluding compounds containing polyoxyalkylene chains), pH adjusters (excluding acids), oxidants, complexing agents, preservatives, fungicides, conductivity adjusters (excluding salt compounds), and organic solvents.

[0146] In these embodiments, "the grinding composition is substantially composed of X" means that the total content of X is more than 99% by mass (upper limit: 100% by mass) relative to the total mass of the grinding composition. In a preferred embodiment, the grinding composition is composed of only X (the above total content = 100% by mass).

[0147] In a preferred embodiment, the grinding composition may consist solely of...

[0148] (A) Ingredients,

[0149] (B) Ingredients, and

[0150] (C) Composition.

[0151] In a preferred embodiment, the grinding composition may consist solely of...

[0152] (A) Ingredients;

[0153] (B) Ingredients;

[0154] (C) Components; and

[0155] It consists of at least one of the components selected from the group consisting of components (D) and (E).

[0156] In a preferred embodiment, the grinding composition may consist solely of...

[0157] (A) Ingredients;

[0158] (B) Ingredients;

[0159] (C) Components; and

[0160] It is composed of at least one component selected from the group consisting of water-soluble polymers (excluding compounds containing polyoxyalkylene chains), pH adjusters (excluding acids), oxidants, complexing agents, preservatives, fungicides, conductivity adjusters (excluding salt compounds), and organic solvents.

[0161] In a preferred embodiment, the grinding composition may consist solely of...

[0162] (A) Ingredients;

[0163] (B) Ingredients;

[0164] (C) Components;

[0165] At least one component selected from the group consisting of components (D) and (E); and

[0166] It is composed of at least one component selected from the group consisting of water-soluble polymers (excluding compounds containing polyoxyalkylene chains), pH adjusters (excluding acids), oxidants, complexing agents, preservatives, fungicides, conductivity adjusters (excluding salt compounds), and organic solvents.

[0167] However, the grinding composition of this scheme is not limited to these.

[0168] (pH of the grinding composition)

[0169] The pH of the grinding composition in one embodiment is not particularly limited as long as it is below 7. From the viewpoint that the ratio of the grinding speed of materials having silicon-silicon bonds to the grinding speed of materials having oxygen-silicon bonds tends to be more favorable, the upper limit of the pH of the grinding composition in one embodiment is preferably 6 or less, more preferably less than 6. From the viewpoint that the ratio of the grinding speed of materials having silicon-silicon bonds to the grinding speed of materials having nitrogen-silicon bonds tends to be more favorable, the upper limit of the pH of the grinding composition in one embodiment is further preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less. From the viewpoint that there is a tendency to further increase the grinding speed of materials having silicon-silicon bonds, the lower limit of the pH of the grinding composition in one embodiment is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more. Examples of the pH range for the grinding composition as one embodiment are not particularly limited, and can include 1 or more and less than 7, 1 or more and less than 6, 1 or more and less than 6, 1 or more and less than 5, 1 or more and less than 4, 1 or more and less than 3, 1.5 or more and less than 7, 1.5 or more and less than 6, 1.5 or more and less than 6, 1.5 or more and less than 6, 1.5 or more and less than 5, 1.5 or more and less than 4, 1.5 or more and less than 3, 2 or more and less than 7, 2 or more and less than 6, 2 or more and less than 5, 2 or more and less than 4, 2 or more and less than 3, etc. The pH value of the grinding composition can be confirmed by a pH meter. Detailed methods for pH measurement are described in the examples.

[0170] (Conductivity of the grinding composition)

[0171] The electrical conductivity of the grinding composition in one embodiment is not particularly limited. Preferably, the electrical conductivity of the grinding composition in one embodiment is 0.1 mS / cm or more, more preferably 0.5 mS / cm or more, further preferably 1 mS / cm or more, more preferably 1.5 mS / cm or more, and particularly preferably 2 mS / cm or more. Furthermore, the electrical conductivity is preferably 20 mS / cm or less, more preferably 15 mS / cm or less, further preferably 10 mS / cm or less, further preferably 8 mS / cm or less, further preferably 6 mS / cm or less, and particularly preferably 4 mS / cm or less. For example, the electrical conductivity can be 3.5 mS / cm or less, or for example, 2 mS / cm or less. If it is within these ranges, the repulsion between the abrasive grains can be appropriately adjusted, ensuring stability. Examples of the conductivity range of the grinding composition as one embodiment are not particularly limited, and include 0.1 mS / cm or more and 20 mS / cm or less, 0.5 mS / cm or more and 15 mS / cm or less, 0.5 mS / cm or more and 10 mS / cm or less, 1 mS / cm or more and 10 mS / cm or less, 1.5 mS / cm or more and 8 mS / cm or less, 2 mS / cm or more and 6 mS / cm or less, 2 mS / cm or more and 4 mS / cm or less, 2 mS / cm or more and 3.5 mS / cm or less, more than 0 mS / cm and less than 3.5 mS / cm, more than 0 mS / cm and less than 2.0 mS / cm or less, etc. The conductivity of the grinding composition can be measured using a conductivity meter. Detailed methods for measuring conductivity are described in the examples. The conductivity can be adjusted according to the type and content of the grinding composition, for example, according to the type and content of a conductivity modifier.

[0172] (Method of using a grinding composition)

[0173] The grinding composition of one embodiment can be a single-component type or a multi-component type consisting of two or more components. The grinding composition of one embodiment can also be used directly for grinding. The grinding composition of one embodiment can be obtained, for example, by a method including the steps of: adding component (B) back into a concentrated solution of the grinding composition, or adding a further amount of component (B) and diluting. The grinding composition of one embodiment can also be, for example, a concentrated solution of a grinding composition.

[0174] (Method for manufacturing the grinding composition)

[0175] The method for manufacturing the grinding composition according to one embodiment is not particularly limited. As an example of the method for manufacturing the grinding composition according to one embodiment, a method including the following steps can be given: mixing the above-described component (A), the above-described component (B), the above-described component (C) as needed, the above-described component (D) as needed, the above-described component (E) as needed, and one or more other components as needed. A preferred method for manufacturing the grinding composition according to one embodiment includes the following steps: manufacturing component (A) by the above-described method for manufacturing surface-modified silica particles (preferably the above-described method (a1) or the above-described method (b1), more preferably the above-described method (a1); and mixing the above-described component (A), the above-described component (B), the above-described component (C) as needed, the above-described component (D) as needed, the above-described component (E) as needed, and one or more other components as needed.

[0176] (Object to be ground)

[0177] The object to be polished using the polishing composition of one embodiment is not particularly limited. The polishing object may consist of only one material or may combine two or more materials. The polishing composition of one embodiment is suitable for polishing polishing objects containing at least one material selected from the group consisting of materials having silicon-silicon bonds, materials having oxygen-silicon bonds, and materials having nitrogen-silicon bonds. In addition to at least one material selected from the group consisting of materials having silicon-silicon bonds, materials having oxygen-silicon bonds, and materials having nitrogen-silicon bonds, the polishing object may also contain one or two or more other materials. Examples of other materials are not particularly limited and include metals, resins, etc. The polishing composition of one embodiment is preferably used for polishing polishing objects containing materials having oxygen-silicon bonds and materials having silicon-silicon bonds. For example, the polishing composition of one embodiment is preferably used for polishing polishing objects containing layers having oxygen-silicon bonds and layers having silicon-silicon bonds. The polishing composition of one embodiment can also be used for polishing objects containing materials having oxygen-silicon bonds, materials having nitrogen-silicon bonds, and materials having silicon-silicon bonds. For example, the polishing composition of one embodiment can also be used for polishing objects containing layers having oxygen-silicon bonds, layers having nitrogen-silicon bonds, and layers having silicon-silicon bonds. With a view to achieving a high polishing speed for materials having silicon-silicon bonds, the polishing composition of one embodiment can also be used for polishing objects containing materials having silicon-silicon bonds. The polishing composition of one embodiment can also be used for polishing objects containing materials having nitrogen-silicon bonds, materials having silicon-silicon bonds, or combinations thereof.

[0178] Examples of materials with silicon-silicon bonds are not particularly limited and can include monocrystalline silicon, polycrystalline silicon, amorphous silicon, n-type doped monocrystalline silicon, p-type doped monocrystalline silicon, Si-based alloys, etc. Examples of materials with oxygen-silicon bonds are not particularly limited and can include silicon oxide, etc. Examples of materials with oxygen-silicon bonds are not particularly limited and can include: TEOS-type silicon oxide (also referred to as "TEOS" in this specification) generated using tetraethyl orthosilicate as a precursor, HDP (High Density Plasma), USG (Undoped Silicate Glass), PSG (Phosphorus Silicate Glass), BPSG (Boron-Phospho Silicate Glass), RTO (Rapid Thermal Oxidation), etc. Examples of materials with nitrogen-silicon bonds are not particularly limited and can include silicon nitride, silicon carbonitride (SiCN), etc. These materials can be used alone or in combination of two or more. The material to be ground preferably comprises at least one material selected from the group consisting of the materials described in the examples above. The material to be ground preferably comprises polycrystalline silicon, more preferably silicon oxide and polycrystalline silicon, and even more preferably TEOS and polycrystalline silicon. The material to be ground may comprise silicon oxide, silicon nitride, and polycrystalline silicon, or it may comprise TEOS, silicon nitride, and polycrystalline silicon.

[0179] The ratio of the grinding speed of the material with silicon-silicon bonds (preferably polycrystalline silicon; the same applies hereinafter to this paragraph) to the grinding speed of the material with oxygen-silicon bonds (preferably silicon oxide, more preferably TEOS; the same applies hereinafter to this paragraph) (grinding speed of the material with silicon-silicon bonds / grinding speed of the material with oxygen-silicon bonds) is not particularly limited. In one embodiment, the grinding composition preferably has the characteristic that the ratio of the grinding speed of the material with silicon-silicon bonds to the grinding speed of the material with oxygen-silicon bonds is 0.50 or more and 2.00 or less. More preferably, the ratio of the grinding speed of the material with silicon-silicon bonds to the grinding speed of the material with oxygen-silicon bonds is 0.80 or more and 1.90 or less, and even more preferably 0.90 or more and 1.90 or less. Sometimes, it is preferable that the grinding speed of the material with silicon-silicon bonds is the same as or slightly greater than the grinding speed of the material with oxygen-silicon bonds. The ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having oxygen-silicon bonds is further preferably 1.00 or more and 1.80 or less, further preferably 1.10 or more and 1.80 or less, further preferably 1.10 or more and 1.70 or less, further preferably 1.20 or more and 1.60 or less, further preferably 1.20 or more and 1.50 or less, and particularly preferably 1.30 or more and 1.50 or less.

[0180] The ratio of the grinding speed of the material having silicon-silicon bonds (preferably polycrystalline silicon; the same applies hereinafter regarding this paragraph) to the grinding speed of the material having nitrogen-silicon bonds (preferably silicon nitride; the same applies hereinafter regarding this paragraph) is not particularly limited (grinding speed of the material having silicon-silicon bonds / grinding speed of the material having nitrogen-silicon bonds). For the grinding composition in one embodiment, the grinding speed of the material having silicon-silicon bonds is sometimes preferably greater than that of the material having nitrogen-silicon bonds, but not excessively greater. Preferably, the ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having nitrogen-silicon bonds is 2.50 or more and 10.00 or less. The ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having nitrogen-silicon bonds is more preferably 2.50 or more and 9.00 or less, more preferably 3.00 or more and 8.50 or less, more preferably 3.00 or more and 8.00 or less, more preferably 4.00 or more and 7.50 or less, more preferably 5.00 or more and 7.50 or less, more preferably 6.00 or more and 7.00 or less, and particularly preferably 6.20 or more and 6.80 or less.

[0181] <Grinding Method and Semiconductor Substrate Manufacturing Method>

[0182] Another aspect of the present invention relates to a grinding method comprising the following steps: grinding an object to be ground using the grinding composition of the above-described embodiment.

[0183] According to a grinding method of one embodiment of the present invention comprising such a composition, when the pH of the grinding composition is below 7, a high grinding speed of materials having silicon-silicon bonds can be achieved, and the ratio of the grinding speed of materials having silicon-silicon bonds to the grinding speed of materials having oxygen-silicon bonds is within a good range.

[0184] The grinding object in this scheme is the same as that described for the grinding object using the grinding composition described above.

[0185] In one embodiment of the polishing method, the material to be polished preferably comprises a material having oxygen-silicon bonds and a material having silicon-silicon bonds. For example, in one embodiment of the polishing method, the material to be polished preferably comprises a layer having oxygen-silicon bonds and a layer having silicon-silicon bonds. In one embodiment of the polishing method, the material to be polished may also comprise a material having oxygen-silicon bonds, a material having nitrogen-silicon bonds, and a material having silicon-silicon bonds. For example, in one embodiment of the polishing method, the material to be polished may also comprise a layer having oxygen-silicon bonds, a layer having nitrogen-silicon bonds, and a layer having silicon-silicon bonds. In one embodiment of the polishing method, with the aim of achieving a high polishing speed of the material having silicon-silicon bonds in the polishing composition based on the above-described scheme, the material to be polished may also comprise a material having silicon-silicon bonds. In one embodiment of the polishing method, the material to be polished may also comprise a material having nitrogen-silicon bonds, a material having silicon-silicon bonds, or a combination thereof. As examples of materials having silicon-silicon bonds, materials having oxygen-silicon bonds, and materials having nitrogen-silicon bonds, the same substances as those exemplified in the description of the material to be polished described above can be given. In a preferred embodiment of the polishing method, the polishing material preferably comprises polycrystalline silicon, more preferably silicon oxide and polycrystalline silicon, and even more preferably TEOS and polycrystalline silicon. In another embodiment of the polishing method, the polishing material may comprise silicon oxide, silicon nitride, and polycrystalline silicon, or it may comprise TEOS, silicon nitride, and polycrystalline silicon.

[0186] The ratio of the grinding speed of the material with silicon-silicon bonds (preferably polycrystalline silicon; the same applies hereinafter regarding this paragraph) to the grinding speed of the material with oxygen-silicon bonds (preferably silicon oxide, more preferably TEOS; the same applies hereinafter regarding this paragraph) (grinding speed of the material with silicon-silicon bonds / grinding speed of the material with oxygen-silicon bonds) is not particularly limited. In one embodiment of the grinding method, the ratio of the grinding speed of the material with silicon-silicon bonds to the grinding speed of the material with oxygen-silicon bonds is preferably 0.50 or more and 2.00 or less. More preferably, the ratio is 0.80 or more and 1.90 or less, and even more preferably 0.90 or more and 1.90 or less. Sometimes, the grinding speed of the material with silicon-silicon bonds is preferably the same as or slightly greater than the grinding speed of the material with oxygen-silicon bonds. The ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having oxygen-silicon bonds is further preferably 1.00 or more and 1.80 or less, further preferably 1.10 or more and 1.80 or less, further preferably 1.10 or more and 1.70 or less, further preferably 1.20 or more and 1.60 or less, further preferably 1.20 or more and 1.50 or less, and particularly preferably 1.30 or more and 1.50 or less.

[0187] The ratio of the grinding speed of a material with silicon-silicon bonds (preferably polycrystalline silicon; the same applies hereinafter regarding this paragraph) to the grinding speed of a material with nitrogen-silicon bonds (preferably silicon nitride; the same applies hereinafter regarding this paragraph) (grinding speed of the material with silicon-silicon bonds / grinding speed of the material with nitrogen-silicon bonds) is not particularly limited. The grinding speed of the material with silicon-silicon bonds is sometimes preferably greater than that of the material with nitrogen-silicon bonds, but not excessively greater. In one embodiment of the grinding method, the ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having nitrogen-silicon bonds is preferably 2.50 or more and 10.00 or less, more preferably 2.50 or more and 9.00 or less, even more preferably 3.00 or more and 8.50 or less, even more preferably 3.00 or more and 8.00 or less, even more preferably 4.00 or more and 7.50 or less, even more preferably 5.00 or more and 7.50 or less, even more preferably 6.00 or more and 7.00 or less, and particularly preferably 6.20 or more and 6.80 or less.

[0188] Another aspect of the present invention relates to a method for manufacturing a semiconductor substrate, wherein the semiconductor substrate includes a workpiece for polishing, the manufacturing method comprising the step of polishing the workpiece using the polishing method described above. The workpiece for polishing in this aspect is also described in the same way as the workpiece for polishing using the polishing composition described above.

[0189] There are no particular limitations on the polishing apparatus. As an example of a polishing apparatus, a general polishing apparatus can be used, which is equipped with a holder for holding a substrate containing the object to be polished, a motor that can change the rotation speed, and a polishing plate for adhering a polishing pad (polishing cloth).

[0190] The abrasive pad is not particularly limited. Examples of materials for the abrasive pad are also not particularly limited, such as non-woven fabric, polyurethane, and porous fluoropolymer. It is preferable to perform a groove process on the abrasive pad to allow the abrasive fluid to accumulate.

[0191] There are no particular limitations on the grinding conditions. For example, the preferred rotational speed (rotational speed) of the grinding plate is 10 rpm (0.17 s). -1 ) or higher and 500rpm (8.33s) -1 Below that. For example, the preferred rotational speed (rotational speed) of the grinding head is 10 rpm (0.17 s). -1 ) or higher and 500rpm (8.33s) -1 The pressure applied to the substrate containing the object to be polished (polishing pressure) is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method of supplying the polishing composition to the polishing pad is not particularly limited; for example, a continuous supply method using a pump or the like can be used. The supply amount is not limited, but a supply amount in which the surface of the polishing pad is always covered by the polishing composition is preferred. The polishing time is not particularly limited; for example, a suitable polishing time can be selected to achieve the desired polishing effect.

[0192] After polishing, the substrate containing the polished object can be washed in running water, and the water droplets adhering to the substrate can be removed and dried using a rotary dryer or similar device.

[0193] Embodiments of the present invention have been described in detail, but are illustrative and exemplary and not limiting. It is obvious that the scope of the invention should be interpreted in accordance with the appended claims.

[0194] This invention includes, but is not limited to, the following schemes and methods:

[0195] [1] A grinding composition comprising component (A) and component (B) below, and having a pH below 7;

[0196] (A) Composition: Surface-modified silica particles, which contain silica particles and surface-modifying groups for surface modification of the aforementioned silica particles, wherein the surface-modifying groups contain polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less.

[0197] (B) Ingredient: Water.

[0198] [2] The grinding composition according to [1] above, wherein the weight average molecular weight of the aforementioned polyoxyalkylene chain is 80 or more and 600 or less.

[0199] [3] The grinding composition according to [1] or [2] above, wherein the aforementioned component (A) contains silica particles on the surface of the particles having a compound containing a polyoxyalkylene chain fixed thereon by means of a silane coupling agent.

[0200] [4] The grinding composition according to [3] above, wherein the aforementioned compound containing polyoxyalkylene chains is a compound formed only by polyalkylene glycol chains.

[0201] [5] The grinding composition according to [4] above, wherein the aforementioned compound formed solely by polyalkylene glycol chains is at least one compound selected from the group consisting of polyethylene glycol, polypropylene glycol and polyethylene glycol-polypropylene glycol copolymer.

[0202] [6] The grinding composition according to any one of [3] to [5] above, wherein the aforementioned silane coupling agent contains an isocyanate-containing silane coupling agent.

[0203] [7] The grinding composition according to any one of [1] to [6] above, wherein the pH is 1 or more and less than 6.

[0204] [8] The grinding composition according to any one of [1] to [7] above has an electrical conductivity of 0.5 mS / cm or more and 10 mS / cm or less.

[0205] [9] The grinding composition according to any one of [1] to [8] above has the following characteristics: the ratio of the grinding speed of the material having silicon-silicon bonds to the grinding speed of the material having oxygen-silicon bonds (grinding speed of the material having silicon-silicon bonds / grinding speed of the material having oxygen-silicon bonds) is 0.50 or more and 2.00 or less.

[0206]

[10] The grinding composition according to any one of [1] to [9] above is used for grinding a grinding object containing a material having oxygen-silicon bonds and a material having silicon-silicon bonds.

[0207]

[11] A grinding method wherein a grinding object comprising a material having oxygen-silicon bonds and a material having silicon-silicon bonds is ground using the grinding composition described in any one of [1] to

[10] above.

[0208]

[12] According to the grinding method described in

[11] above, the ratio of the grinding speed of the aforementioned material having silicon-silicon bonds to the grinding speed of the aforementioned material having oxygen-silicon bonds (grinding speed of the material having silicon-silicon bonds / grinding speed of the material having oxygen-silicon bonds) is 0.50 or more and 2.00 or less.

[0209] Example

[0210] The present invention will be further described in detail below with reference to the following embodiments and comparative examples. However, the scope of protection of the present invention should not be limited to the following embodiments. It should be noted that, unless otherwise specified, "%" and "parts" refer to "mass %" and "parts by mass," respectively.

[0211] <Manufacturing of Surface-Modified Silica Particles>

[0212] (Manufacturing Example 1)

[0213] Measure 36.3 g of polyethylene glycol 1 into a 100 mL sealed heat-resistant container. Place the container, along with the container, on an 80°C heated stirrer. Remove the lid and stir at 100 rpm. While stirring, add 18.7 g of 3-isocyanate-propyltrimethoxysilane at a rate of 0.03 g / s, maintaining a 1:1 molar ratio of polyethylene glycol 1 to 3-isocyanate-propyltrimethoxysilane. After adding the 3-isocyanate-propyltrimethoxysilane, seal the container and continue stirring at 100 rpm for 30 minutes. Remove the stirrer, seal the container again, and return it to an 80°C air bath (place the container in an 80°C air bath) for heating until the FT-IR spectrum reaches 2260 cm⁻¹. -1 The heating continued until the peaks of the isocyanate groups derived from the silane coupling agent disappeared. Heating was continued for a total of 26 hours to obtain the target surface modifier 1.

[0214] Separately, 4500g of a 5% (w / w) high-purity colloidal silica (average secondary particle size: 70nm, synthesized by sol-gel method) aqueous solution was prepared in a 5000mL flask and heated in a mantle heater until the liquid temperature reached 80°C. Once 80°C was reached, 50.8g of the surface modifier 1 obtained above was added at a rate of 0.03g / s while stirring the solution at 150rpm. The liquid temperature was then maintained at 80°C in the mantle heater, and the mixture was stirred at 150rpm for 30 minutes. The solution was then transferred to a sealed container, sealed, and returned to an air bath at 80°C (the sealed container was placed in an air bath at 80°C) for heating for 26 hours to obtain the target surface-modified colloidal silica 1.

[0215] (Manufacturing Examples 2-9)

[0216] In Example 1 above, as shown in Table 1, polyethylene glycol 1 was replaced with ethylene glycol, polyethylene glycol 2, polyethylene glycol 3, polyethylene glycol 4, polyethylene glycol 5, polyethylene glycol 6, polyethylene glycol 7, or polyethylene glycol 8. Otherwise, target surface-modified colloidal silica 2 to 9 were obtained respectively.

[0217] It should be noted that details of surface-modified colloidal silica and the alkylene glycols or compounds containing polyoxyalkylene chains used in their manufacture are shown in Table 1.

[0218] (Average secondary particle size of silica particles)

[0219] The average secondary particle size of silica particles was evaluated as follows: the concentration of a 5% by mass high-purity colloidal silica aqueous solution was determined by dynamic light scattering methods, such as laser diffraction scattering.

[0220] (Structural confirmation of surface modifiers)

[0221] The structure of the surface modifier 1 obtained above was confirmed using the following FT-IR apparatus:

[0222] Apparatus used: Fourier transform infrared spectrophotometer (Spectrum 100, manufactured by PerkinElmer Co., Ltd.)

[0223] Detection method: ATR (Attenuated Total Reflection) method.

[0224] Specifically, 1 g of 3-isocyanate-propyltrimethoxysilane was taken from the reaction system 10 minutes after being added to the reaction mixture of Manufacturing Example 1. The resulting sample was placed on a Spectrum 100 ATR measuring crystal, and the FT-IR spectrum was measured. The results confirmed that the FT-IR spectrum was within 2260 cm⁻¹. -1 There are peaks nearby derived from isocyanate groups of silane coupling agents.

[0225] Furthermore, at the end of the reaction, a 1g sample was taken from the reaction system. The resulting sample was placed on an ATR crystal of Spectrum 100, and the FT-IR spectrum was measured. The results confirmed that at 2260 cm⁻¹... -1 Nearby, the peak of the isocyanate group derived from the silane coupling agent disappeared. Therefore, it can be confirmed that a surface modifier 1, consisting of a compound containing a polyoxyalkylene chain bonded to a silane coupling agent, was generated.

[0226] It should be noted that, similarly, using an FT-IR apparatus, the surface modifiers 2 to 9 obtained in the above manufacturing examples 2 to 9 were also confirmed to be surface modifier 2 formed by bonding alkylene glycols and silane coupling agents, and surface modifiers 3 to 9 formed by bonding compounds containing polyoxyalkylene chains and silane coupling agents.

[0227] (The amount of modification of colloidal silica by the surface modifier)

[0228] The surface-modified colloidal silica 1 obtained above was used to confirm the amount of surface modifier used in the following total organic carbon analyzer and centrifugation apparatus. Specifically, the silica concentration of the surface-modified colloidal silica 1 was diluted with water to 0.175% by mass to prepare a diluent. The TOC value of the supernatant after centrifugation was subtracted from the TOC value of the diluent (i.e., the TOC value of the diluent minus the TOC value of the supernatant after centrifugation was calculated). As a result, it was confirmed that the colloidal silica was modified with surface modifier 1 at a mass of 8.4% relative to the silica mass.

[0229] It should be noted that the amount of surface-modified colloidal silica 2-9 obtained above can also be confirmed using the total organic carbon analyzer and centrifugal separation device described below.

[0230] Total Organic Carbon Analyzer

[0231] Device used: TOC-L CPH (manufactured by Shimadzu Corporation),

[0232] Measurement method: 680℃ combustion catalytic oxidation / NDIR detection.

[0233] Centrifugal Separation Device

[0234] Device used: Avanti HP-30I (manufactured by Beckman Coulter)

[0235] Speed: 26000 rpm

[0236] Centrifugation time: 30 minutes.

[0237] It should be noted that, by using 29 Si-NMR confirmed the structure of the surface-modified colloidal silica, thus confirming that the target surface-modified colloidal silica was obtained through the manufacturing method.

[0238] [Table 1]

[0239]

[0240] <Preparation of Grinding Composition>

[0241] (Examples 1-10 and Comparative Examples 1-5)

[0242] As described in Table 2, silica particles, acid or alkali, water, a compound containing an oxyalkylene chain as needed, and a salt compound as needed were mixed to obtain the grinding compositions of Examples 1-10 and Comparative Examples 1-5, respectively.

[0243] In Table 2, unmodified colloidal silica refers to colloidal silica (average secondary particle size: 70 nm, synthesized by sol-gel method). The unmodified colloidal silica used is the same type as the colloidal silica used as a raw material for surface-modified silica particles in the manufacture of the aforementioned surface-modified silica particles. In Table 2, polyethylene glycol 1 refers to the same type of polyethylene glycol as polyethylene glycol 1 used in the manufacture of surface-modified colloidal silica.

[0244] In Table 2, the contents of silica particles, acid or alkali, compounds containing polyoxyalkylene chains, and salt compounds are expressed as contents (mass%) relative to the total mass of the grinding composition.

[0245] In Table 2, ingredients marked with "-" in the category and content column indicate that the ingredient was not added.

[0246] <Evaluation of Grinding Compositions>

[0247] (pH of the grinding composition)

[0248] The pH of the grinding composition was determined using a pH meter (manufactured by Horiba Manufacturing Co., Ltd., product name: LAQUA (registered trademark)).

[0249] (Conductivity of the grinding composition)

[0250] The conductivity (EC) of the grinding composition was measured using a benchtop conductivity meter (manufactured by Horiba Manufacturing Co., Ltd., model: DS-71LAQUA (registered trademark)).

[0251] (Grinding performance)

[0252] The surface of an object to be ground was ground using an abrasive composition under the following abrasive conditions. In this evaluation, the object to be ground was one with a thick... Poly-Si film silicon wafers (300mm, blank wafers) with a thick film formed on the surface The silicon wafer (300 mm, blank wafer) of P-TEOS film (TEOS film (silica film) formed by plasma CVD) and the one with a thick silicon nitride (SiN) film formed on the surface (300 mm, blank wafer).

[0253] "Polishing Conditions"

[0254] Polishing apparatus: CMP single-sided polishing apparatus Mirra for 200 mm made by Applied Materials, Inc.

[0255] Polishing pad: Hard polyurethane pad IC1010 made by Nitta Haas Incorporated.

[0256] Polishing pressure: 2.0 psi

[0257] Polishing platen rotation speed: 63 rpm

[0258] Polishing head (carrier) rotation speed: 57 rpm

[0259] Supply of polishing composition: Overflow

[0260] Supply amount of polishing composition: 100 mL / minute

[0261] Polishing time: 60 seconds. <00…00617>The polishing speed is measured as follows: The thickness is obtained by an optical film thickness measuring instrument (RE-3500: manufactured by SCREEN Co., Ltd.), and (thickness before polishing) - (thickness after polishing) is divided by the polishing time for measurement. In addition, the ratio of the polishing speed of the polysilicon film ( / minute) to the polishing speed of the P-TEOS film ( / minute) (polishing speed of polysilicon film / polishing speed of P-TEOS film) is calculated as the selection ratio. In addition, the ratio of the polishing speed of the polysilicon film ( / minute) to the polishing speed of the silicon nitride film ( / minute) (polishing speed of polysilicon film / polishing speed of silicon nitride film) is calculated as the selection ratio.

[0263] The polishing speed of the polysilicon (Poly-Si) film obtained from the above evaluation ( / minute), the polishing speed of the P-TEOS film ( ' / minute) and the polishing speed of the silicon nitride (SiN) film ( The ratios (per minute) of these polishing speeds are shown in Table 3. Additionally, the selection ratios (ratios of polishing speeds) calculated from these polishing speeds are shown in Table 3. In Table 3, the ratio of the polishing speed of polysilicon to the polishing speed of P-TEOS (polysilicon polishing speed / P-TEOS polishing speed) is recorded as Poly-Si / P-TEOS, and the ratio of the polishing speed of polysilicon to the polishing speed of silicon nitride (polysilicon polishing speed / silicon nitride polishing speed) is recorded as Poly-Si / SiN.

[0264] In Table 3, evaluation items marked with "-" indicate that no evaluation was performed. It should be noted that the grinding composition of Comparative Example 3 exhibited aggregation; therefore, its grinding properties were not evaluated.

[0265] In this evaluation, the higher the grinding speed of polycrystalline silicon, the better.

[0266] In this evaluation, the ratio of the polishing speed of the polycrystalline silicon film to the polishing speed of the P-TEOS film is preferably 0.50 or more and 2.00 or less, more preferably 0.80 or more and 1.90 or less, even more preferably 0.90 or more and 1.90 or less, even more preferably 1.00 or more and 1.80 or less, even more preferably 1.10 or more and 1.80 or less, even more preferably 1.10 or more and 1.70 or less, even more preferably 1.20 or more and 1.60 or less, even more preferably 1.20 or more and 1.50 or less, and particularly preferably 1.30 or more and 1.50 or less.

[0267] In this evaluation, the ratio of the polishing speed of the polycrystalline silicon film to the polishing speed of the silicon nitride film is not particularly limited. However, in this evaluation, the ratio of the polishing speed of the polycrystalline silicon film to the polishing speed of the silicon nitride film is preferably 2.50 or more and 10.00 or less, more preferably 2.50 or more and 9.00 or less, further preferably 3.00 or more and 8.50 or less, further preferably 3.00 or more and 8.00 or less, further preferably 4.00 or more and 7.50 or less, further preferably 5.00 or more and 7.50 or less, further preferably 6.00 or more and 7.00 or less, and particularly preferably 6.20 or more and 6.80 or less.

[0268] [Table 2]

[0269]

[0270] [Table 3]

[0271] (Table 3) Evaluation results of grinding performance

[0272]

[0273] Based on the results of Comparative Example 1 and Examples 1-10, it was confirmed that by using a polishing composition comprising surface-modified silica particles and water, wherein the surface-modified silica particles contain surface-modifying groups comprising polyoxyalkylene chains having a specific weight-average molecular weight, it is possible to achieve a high polishing speed for materials with silicon-silicon bonds and to achieve a good ratio of the polishing speed of materials with oxygen-silicon bonds to the polishing speed of materials with silicon-silicon bonds.

[0274] The results of Example 4 and Comparative Example 4 confirm that the effects of the present invention cannot be obtained when the grinding composition simply contains a compound comprising a polyoxyalkylene chain. The effects of the present invention can be obtained when the grinding composition contains surface-modified silica particles, and the surface-modified silica particles contain surface-modifying groups comprising a polyoxyalkylene chain having a specific weight-average molecular weight.

[0275] The results of Examples 4 and 9, and Comparative Example 5, confirmed that the effects of the present invention can be obtained when the pH of the grinding composition is below 7, for example, pH 2.2 as in Example 4, and pH 5.2 as in Example 9. On the other hand, the effects of the present invention cannot be obtained when the pH of the grinding composition is high, for example, pH 8.1 as in Comparative Example 5.

[0276] This application is based on Japanese Patent Application No. 2024-170590, filed on September 30, 2024, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A grinding composition comprising component (A) and component (B) below, and having a pH below 7; (A) Composition: Surface-modified silica particles, which contain silica particles and surface-modifying groups for surface modification of the silica particles, wherein the surface-modifying groups contain polyoxyalkylene chains with a weight average molecular weight of 80 or more and 7000 or less. (B) Ingredient: Water.

2. The grinding composition according to claim 1, wherein, The weight-average molecular weight of the polyoxyalkylene chain is above 80 and below 600.

3. The grinding composition according to claim 1, wherein, The (A) component contains silica particles on the surface of the particles with a compound containing a polyoxyalkylene chain fixed by means of a silane coupling agent.

4. The grinding composition according to claim 3, wherein, The compound containing polyoxyalkylene chains is a compound formed solely of polyalkylene glycol chains.

5. The grinding composition according to claim 4, wherein, The compound formed solely by polyalkylene glycol chains is at least one compound selected from the group consisting of polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymers.

6. The grinding composition according to claim 3, wherein, The silane coupling agent contains an isocyanate group.

7. The grinding composition according to claim 1, wherein, The pH is above 1 and below 6.

8. The grinding composition according to claim 1, wherein the electrical conductivity is 0.5 mS / cm or more and 10 mS / cm or less.

9. The grinding composition according to claim 1, wherein the grinding speed of the material having silicon-silicon bonds is relative to the grinding speed of the material having oxygen-silicon bonds, i.e., the grinding speed of the material having silicon-silicon bonds / the grinding speed of the material having oxygen-silicon bonds, is 0.50 or more and 2.00 or less.

10. The grinding composition according to claim 1, used for grinding a grinding object comprising a material having oxygen-silicon bonds and a material having silicon-silicon bonds.

11. A grinding method, wherein, Using the grinding composition according to any one of claims 1 to 10, a grinding object comprising a material having oxygen-silicon bonds and a material having silicon-silicon bonds is ground.

12. The grinding method according to claim 11, wherein, The ratio of the grinding speed of the material with silicon-silicon bonds to the grinding speed of the material with oxygen-silicon bonds, i.e., the grinding speed of the material with silicon-silicon bonds / the grinding speed of the material with oxygen-silicon bonds, is 0.50 or more and 2.00 or less.

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