Surface treatment composition, surface treatment method, and method for producing semiconductor substrate

Abstract

This invention provides a method for effectively removing residues remaining on the surface of a polished object. The surface treatment composition of this invention comprises the following components (A) to (C), and has a pH value exceeding 7.0: (A) Composition: A quaternary nitrogen-containing onium salt compound having at least one of a straight-chain or branched alkyl group having 7 or more carbon atoms and a straight-chain or branched alkenyl group having 7 or more carbon atoms. (B) Components: Nonionic polymer (C) Composition: Formula: A-COO -NH The buffer represented by 4+.

Description

Technical field

[0001] The present invention relates to a surface treatment composition, a surface treatment method, and a method for manufacturing a semiconductor substrate. prior art

[0002] In recent years, with the multi-layer wiring on the surface of semiconductor substrates, when manufacturing components, the industry uses so-called chemical mechanical polishing (CMP) technology that physically polishes semiconductor substrates for planarization. CMP uses a polishing composition (slurry) containing abrasive grains such as silica, aluminum oxide, and cerium oxide, corrosion inhibitors, surfactants, etc., to planarize the surface of polishing objects (objects to be polished) such as semiconductor substrates. In this method, the object to be polished (object to be polished) is wires, plugs, etc. containing silicon, polycrystalline silicon, silicon oxide, silicon nitride, or metal.

[0003] A large amount of impurities (also called foreign matter or residue) remain on the surface of the semiconductor substrate after the CMP step. Impurities include: abrasive grains, metals, corrosion inhibitors, surfactants and other organic matter derived from the polishing composition used in CMP; silicon-containing materials used as polishing objects; generated by polishing metal wiring or plugs, etc. Silicon-containing materials or metals; and organic matter such as padding chips generated from various gaskets.

[0004] If the surface of the semiconductor substrate is contaminated by such impurities, the electrical characteristics of the semiconductor will be adversely affected, and the reliability of the component may be reduced. Therefore, it is ideal to introduce a cleaning step after the CMP step to remove such impurities from the surface of the semiconductor substrate.

[0005] As such a cleaning composition, for example, Japanese Patent Application Laid-Open No. 2020-203980 (corresponding to the specification of U.S. Patent Application Publication No. 2022 / 372329, the same below) discloses a rinse composition selected from the group consisting of: At least one compound from the group consisting of quaternary polyammonium salts, quaternary ammonium salts with more than 6 carbon atoms, and polymers with specific structures, and water-soluble polymers. Furthermore, Japanese Patent Application Laid-Open No. 2020-203980 discloses that the above-mentioned rinse composition can remove abrasives remaining on the polishing pad, and reduce the surface roughness of the base material in both pre-polishing and fine polishing. Haze. Contents of the invention

[0006] However, in the technology of Japanese Patent Application Laid-Open No. 2020-203980, there is a problem that foreign matter (residues) cannot be sufficiently removed during cleaning of the polished object.

[0007] Therefore, the present invention was made in view of the above-mentioned circumstances, and an object thereof is to provide a method that can sufficiently remove residue remaining on the surface of a polished object.

[0008] The present inventors have conducted diligent research in order to solve the above-mentioned problems. As a result, it was found that the above-mentioned problems can be solved by using an alkaline surface treatment composition. The alkaline surface treatment composition includes a quaternary nitrogen-containing onium salt compound having a specific structure, a nonionic polymer, and a Ammonium monocarboxylate acts as a buffer.

[0009] That is, one form used to achieve the above purpose is a surface treatment composition, which contains the following (A) ~ (C) components, and has a pH value exceeding 7.0: (A) Component: a quaternary nitrogen-containing onium salt compound having at least one of a linear or branched alkyl group with 7 or more carbon atoms and a linear or branched alkenyl group with 7 or more carbon atoms. (B) Ingredient: nonionic polymer (C) Component: Buffer represented by the formula: A-COO -NH 4 + (A is an alkyl group or phenyl group with a carbon number of 1 to 10). Implementation

[0010] Details of the invention will be described below. Furthermore, the present invention is not limited to the following forms, and various changes can be made within the scope of the patent application. In addition, the embodiments described in this specification can be arbitrarily combined to form other embodiments. The embodiments described in this specification can be arbitrarily combined to form other embodiments. Throughout this specification, expressions in the singular form shall be understood to include the concept of the plural form as well, unless specifically mentioned. Therefore, articles in the singular form (such as "a", "an", "the", etc. in the case of English) should be understood to include the concept of their plural form as long as they are not specifically mentioned. In addition, unless otherwise mentioned, the terms used in this specification should be understood to have the meaning commonly used in the field. Therefore, unless otherwise defined, all professional terms and scientific and technical terms used in this specification have the same meanings as commonly understood by those in the field to which the present invention belongs. In case of conflict, this specification (including definitions) shall prevail.

[0011] One aspect of the present invention provides a surface treatment composition, which contains the following (A) ~ (C) components and has a pH value exceeding 7.0: (A) Component: a quaternary nitrogen-containing onium salt compound having at least one of a linear or branched alkyl group with 7 or more carbon atoms and a linear or branched alkenyl group with 7 or more carbon atoms. (B) Ingredient: nonionic polymer (C) Component: Buffer represented by the formula: A-COO -NH 4 + (A is an alkyl group or phenyl group with a carbon number of 1 to 10).

[0012] According to this surface treatment composition according to one aspect of the present invention, residues (such as abrasive grain residues and organic matter residues) remaining on the surface of a polished object to be polished (especially a polished silicon nitride substrate) can be sufficiently removed. Furthermore, the etching rate of the polished object containing polycrystalline silicon can be suppressed to a low level.

[0013] The present inventors speculate as follows regarding the mechanism by which such a structure can remove residues on the surface of the polished object and further suppress the etching rate of the polished object containing polycrystalline silicon to a low level.

[0014] The surface treatment composition of the present invention contains specific components (A) to (C). Among them, component (A) does not show pKa in water and is positively charged. Therefore, regardless of the pH value, the zeta potential of the ground object (especially the ground silicon nitride substrate), abrasive residue, organic residue (such as pad chips, polymers), etc. is controlled to be positive. Due to electrostatic repulsion, it can suppress and prevent residues from being adsorbed on the polished object. In addition, component (B) improves the wettability of the surface of the polished object and easily forms a film of water molecules on the surface. Therefore, it not only inhibits hydrophobic organic residues from adhering to the surface of the polished object, but also prevents organic residues from re-adhering. Therefore, according to the surface treatment composition of the present invention, residues can be removed with high efficiency.

[0015] In addition, generally, before the cleaning step (surface treatment, rinse polishing), the surface of the semiconductor substrate is polished using an alkaline slurry (polishing slurry) in the CMP step. When such a polished semiconductor substrate (polished object) is washed (rinsed and polished) with a surface treatment composition, the pH value of the surface treatment composition will rise due to the alkaline polishing slurry. As a result, the change in the zeta potential of the residue induces the adhesion of the residue (especially the abrasive grain residue) and increases the etching rate of the polished object containing polycrystalline silicon. However, the presence of component (C) can suppress an increase in the pH value of the surface treatment composition during cleaning (rinsing and grinding). Therefore, the zeta potential of the polished object (especially the polished silicon nitride substrate), abrasive residue, organic residue (such as pad dust, polymer), etc. is controlled to the optimal state (positive), by Electrostatic repulsion can inhibit and prevent the adsorption of residues to the grinding object. Therefore, according to the surface treatment composition of the present invention, residues can be removed with high efficiency. Furthermore, under alkaline conditions, the etching rate of a polished object containing polycrystalline silicon changes significantly. However, due to the presence of component (C), the pH value of the surface treatment composition changes less during cleaning (rinsing and polishing) (it is less susceptible to the influence of alkaline polishing slurry). Therefore, the etching rate of the polished polishing object containing polycrystalline silicon can be suppressed to be low. Thus, according to the present invention, it is possible to provide a method that can sufficiently remove residue remaining on the surface of a polished object. Furthermore, according to the present invention, the etching rate of the polished polishing object containing polycrystalline silicon can be suppressed to a low level.

[0016] Furthermore, the above-mentioned mechanism is based on speculation, and the present invention is not limited by the above-mentioned mechanism.

[0017] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited only to the following embodiments. In this specification, unless otherwise stated, operations and physical properties are measured under the conditions of room temperature (above 20°C and below 25°C) / relative humidity of 40%RH or more and 50%RH or less. Moreover, "X and / or Y" means including each of X, Y and their combination.

[0018] [residue] In this specification, residue refers to foreign matter adhering to the surface of the polished object. Examples of the residue are not particularly limited, and examples thereof include residues derived from the object to be polished, organic residues described below, particulate residues derived from the abrasive grains contained in the polishing composition (abrasive grain residues), and residues containing particulate matter. And other residues such as residues of components other than organic residues, particulate residues, mixtures of organic residues, etc.

[0019] The total number of residues represents the total number of all residues regardless of type. The total number of residues can be measured using a wafer defect inspection device. In addition, the number of residues indicates the total number of specific residues. Details of the method for measuring the number of residues are described in the following Examples.

[0020] In this specification, organic residue refers to foreign matter adhering to the surface of the polished object (surface treatment object), including organic matter such as organic low molecular compounds or polymer compounds, or organic salts.

[0021] Examples of the organic residue adhering to the polished object include pad dust generated from the pad used in the following polishing step or rinse polishing step, or from the polishing composition used in the polishing step or rinse polishing. The ingredients of additives contained in the surface treatment composition used in the step, etc.

[0022] Furthermore, since the color and shape of organic residues are greatly different from other foreign matter, it can be visually judged whether the foreign matter is organic residue through SEM (Scanning Electron Microscope) observation. In addition, whether the foreign matter is an organic residue can be determined by elemental analysis using an energy dispersive X-ray analyzer (EDX) if necessary. The number of organic residues can be measured using a wafer defect inspection device and SEM or EDX elemental analysis.

[0023] [Grinded grinding object] In this specification, the ground object means the object that has been ground in the grinding step. The grinding step is not particularly limited, but the CMP step is preferred.

[0024] The material contained in the object to be polished in the present invention is not particularly limited, and examples thereof include carbon-containing silicon such as silicon oxide, silicon nitride (SiN), and silicon carbonitride (SiCN), polycrystalline silicon (polysilicon), Amorphous silicon, silicon materials doped with impurities, metal monomers, alloys, metal nitrides, SiGe and other compound semiconductors, etc. Among them, it is preferable to include at least one of silicon nitride, silicon oxide, and polycrystalline silicon.

[0025] As an example of a film containing silicon oxide, there may be mentioned a TEOS (Tetraethyl Orthosilicate, tetraethoxysilane) type silicon oxide film (hereinafter also referred to as "TEOS" for short) produced using tetraethyl orthosilicate as a precursor. Film"), HDP (High Density Plusma, high density plasma) film, USG (Undoped Silicate Glass, undoped silicate glass) film, PSG (Phosphorus Silicate Glass, phosphosilicate glass) film, BPSG (Boron -Phospho Silicate Glass, borophosphosilicate glass) film, RTO (Rapid Thermal Oxidation, rapid thermal oxidation) film, etc. The material contained in the object to be ground may be a single type, or may be a combination of two or more types.

[0026] The polished object is preferably a polished semiconductor substrate, more preferably a semiconductor substrate after the CMP step. The reason is that since the residue may cause damage to the semiconductor element, when the polished object is a polished semiconductor substrate, as a cleaning step of the semiconductor substrate, it is necessary to remove the residue as much as possible.

[0027] Furthermore, the surface treatment composition according to one aspect of the present invention can reduce residues on the surface even if the polished object contains both a hydrophilic material and a hydrophobic material. Here, hydrophilic materials refer to materials whose contact angle with water is less than 50°, and hydrophobic materials refer to materials whose contact angle with water is more than 50°. In addition, the contact angle with water is a value measured using a contact angle meter DropMaster (DMo-501) manufactured by Kyowa Interface Science Co., Ltd.

[0028] Specific examples of the hydrophilic material include silicon oxide, silicon nitride, silicon oxynitride, tungsten, titanium nitride, tantalum nitride, boron-containing silicon, and the like. One type of these hydrophilic materials may be used alone, or two or more types may be used in combination. According to a preferred embodiment of the present invention, the hydrophilic material is silicon oxide. According to a preferred embodiment of the present invention, the hydrophilic material is silicon nitride. Specific examples of the hydrophobic material include polycrystalline silicon, single crystal silicon, amorphous silicon, carbon-containing silicon, and the like. One type of these hydrophobic materials may be used alone, or two or more types may be used in combination. According to a preferred embodiment of the present invention, the hydrophobic material is polycrystalline silicon.

[0029] That is, according to a preferred embodiment of the present invention, the hydrophilic material is silicon oxide, and the hydrophobic material is polycrystalline silicon. Furthermore, according to a preferred embodiment of the present invention, the hydrophilic material is silicon nitride, and the hydrophobic material is polycrystalline silicon.

[0030] [Surface treatment composition] The surface treatment composition of one form of the present invention contains the following (A) ~ (C) components, and the pH value exceeds 7.0: (A) Component: a quaternary nitrogen-containing onium salt compound having at least one of a linear or branched alkyl group with 7 or more carbon atoms and a linear or branched alkenyl group with 7 or more carbon atoms. (B) Ingredient: nonionic polymer (C) Component: Buffer represented by the formula: A-COO -NH 4 + (A is an alkyl group or phenyl group with a carbon number of 1 to 10).

[0031] A surface treatment composition according to one aspect of the present invention is used to reduce residue on the surface of a polished object. Furthermore, the surface treatment composition of the present invention is used to suppress the etching rate of a polished object containing polycrystalline silicon to a low level.

[0032] In this specification, the quaternary nitrogen-containing onium salt compound as component (A) is also referred to as the "quaternary nitrogen-containing onium salt compound of the present invention" or the "quaternary nitrogen-containing onium salt compound". In addition, the nonionic polymer as the component (B) is also simply called "the nonionic polymer of the present invention" or "the nonionic polymer". The buffer represented by the formula: A-COO -NH 4 + (A is an alkyl group or phenyl group with a carbon number of 1 to 10) as component (C) is also referred to as the "buffer of the present invention" or " "Ammonium monocarboxylate" or "ammonium monocarboxylate" of the present invention.

[0033] <(A)Component> A surface treatment composition according to one aspect of the present invention contains a quaternary nitrogen-containing onium salt compound having at least one of a linear or branched alkyl group having 7 or more carbon atoms and a linear or branched alkenyl group having 7 or more carbon atoms. As component (A).

[0034] The quaternary nitrogen-containing onium salt compound includes the above-mentioned quaternary nitrogen-containing onium cation having a specific substituent, and an anion (counter anion).

[0035] Quaternary nitrogen-containing onium cations include linear or branched alkyl groups with 7 or more carbon atoms (hereinafter, sometimes referred to as "alkyl groups"), and linear or branched alkenyl groups with 7 or more carbon atoms (hereinafter, sometimes referred to as "alkyl groups"). Also referred to as "alkenyl") at least one of. The quaternary nitrogen-containing onium cation may contain two or more such alkyl groups and / or alkenyl groups. When it contains two or more such substituents, the substituents may be the same or different from each other.

[0036] As a preferred form of the quaternary nitrogen-containing onium cation, it is a quaternary ammonium cation in which at least one of the above-mentioned alkyl group or the above-mentioned alkenyl group is bonded to a nitrogen atom. More specifically, the quaternary ammonium cation is preferably represented by the following formula (I).

[0037]

[0038] In the above formula (I), R is a linear or branched alkyl group with 7 or more carbon atoms or a linear or branched alkenyl group with 7 or more carbon atoms, R' is an organic group, and n is an integer from 1 to 4. . Among them, when n is 2 or more, there are a plurality of R's that may be the same or different from each other. In addition, when n is 2 or less, there are plural R's which may be the same or different from each other.

[0039] In the above formula (I), specific examples of the linear or branched alkyl group having 7 or more carbon atoms as R include: n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-11 group. Alkyl, lauryl (n-dodecyl), n-tridecyl, myristyl (n-tetradecyl), n-pentadecyl, n-hexadecyl, n-heptadecyl, stearyl Linear alkyl groups such as n-octadecyl, n-eicosyl, n-eicosyl, etc.; 1-methylhexyl, 2-ethylhexyl, 4-methylhexyl, 5-methylhexyl , 1-ethylpentyl, 1-propylbutyl, 1-ethyl-1,2-dimethylpropyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 2-propylpentyl, 1-methyloctyl, 2,2-dimethylheptyl, 1-ethylheptyl, 3-ethylheptyl, 1-propylhexyl, 1-butylpentyl , 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl, 1-butylhexyl and other branched-chain alkyl groups.

[0040] Furthermore, specific examples of the linear or branched alkenyl group having 7 or more carbon atoms as R include: 1-heptenyl, 2-heptenyl, 5-heptenyl, 1-octenyl, 3-octenyl, 5-octenyl, 1-nonenyl, 1-decenyl, 1-undecenyl, 1-dodecenyl, 1-tridecenyl, 1-tetradecene base, 1-pentadecenyl, 1-hexadecenyl, 1-heptadecenyl, octadecenyl (such as oleyl ((Z)-octadec-9-en-1-yl)), ylidene Oleyl ((9Z,12Z)-octadecyl-9,12-dienoyl), α-linoleyl ((9Z,12Z,15Z)-octadeca-9,12,15-trienyl) ), γ-linenyl ((6Z,9Z,12Z)-octadeca-6,9,12-trienyl) and other linear alkenyl groups.

[0041] Among them, the above-mentioned alkyl group and the above-mentioned alkenyl group are preferably linear chains.

[0042] Regarding the above-mentioned alkyl group and the above-mentioned alkenyl group, the upper limit of the number of carbon atoms is not particularly limited. From the viewpoint of reducing organic residues, it is preferably 30 or less, more preferably 20 or less, further preferably 15 or less, especially 14 or less. . On the other hand, the lower limit of the number of carbon atoms is 7, but it is preferably 8 or more, more preferably 9 or more, and particularly preferably 10 or more. Therefore, as an example, the number of carbon atoms of the alkyl group or alkenyl group contained in the quaternary ammonium cation is preferably 7 or more and 30 or less, more preferably 8 or more and 20 or less, still more preferably 9 or more and 15 or less, especially Preferably, it is above 10 and below 14. Furthermore, the above-mentioned carbon number is optimally 12.

[0043] The above-mentioned alkyl group and the above-mentioned alkenyl group may be substituted or unsubstituted. In this specification, "substituted" unless otherwise defined means substituted by alkyl, cycloalkyl, hydroxyalkyl, alkoxyalkyl, alkoxy, cycloalkoxy, alkenyl, alkynyl, amine group, aryl group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxyl group (-OH), carboxyl group (-COOH), thiol group ( -SH), cyano (-CN) and other substitutions. Furthermore, when a certain group is substituted, the substitution form included in the definition of the substituted structure before it is substituted is excluded. For example, when the substituent is an alkyl group, the alkyl group as the substituent will not be further substituted by an alkyl group. Among them, from the viewpoint of minimizing the mixing of impurities, the above-mentioned alkyl group and the above-mentioned alkenyl group contained in the quaternary ammonium cation are preferably unsubstituted.

[0044] Among them, in the above formula (I), R is preferably a linear or branched alkyl group with a carbon number of 8 or more and 20 or less or a linear or branched alkenyl group with a carbon number of 8 or more and 20 or less, more preferably A straight chain or branched chain alkyl group with a carbon number of 9 or more and 15 or less, or a straight chain or branched alkenyl group with a carbon number of 9 or more and 15 or less, and more preferably a straight chain or branched chain alkenyl group with a carbon number of 9 or more and 15 or less. The branched chain alkyl group is particularly preferably a straight chain or branched chain alkyl group having a carbon number of 10 or more and 14 or less, and most preferably a straight chain or branched chain alkyl group having a carbon number of 12.

[0045] In the above formula (I), the organic group used as R' is not particularly limited, and is preferably a linear or branched chain alkyl group with a carbon number of 1 or more and 6 or less, or a linear or branched chain alkyl group with a carbon number of 2 or more and 6 or less. Alkenyl group, cyclic alkyl group with 3 to 20 carbon atoms, aryl group with 6 to 20 carbon atoms, aralkyl group with 7 to 20 carbon atoms, or hydroxyalkyl group with 1 to 6 carbon atoms base.

[0046] Specific examples of linear or branched chain alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and second-butyl. , tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, 1 -Isopropylpropyl, 1,2-dimethylbutyl, etc.

[0047] Specific examples of linear or branched alkenyl groups having 2 to 6 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, and 2-butene. base, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, etc.

[0048] Specific examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0049] Specific examples of the aryl group having 6 or more carbon atoms and 20 or less carbon atoms include phenyl group, naphthyl group, biphenyl group, benzyl group, anthracenyl group, pyrenyl group, and the like.

[0050] An aralkyl group refers to an alkyl group in which one hydrogen atom on the alkyl group is substituted with an aryl group. Specific examples of the aralkyl group having 7 to 20 carbon atoms include benzyl (phenylmethyl), Phenylethyl (phenylethyl), etc.

[0051] A hydroxyalkyl group with a carbon number of 1 to 6 means one in which at least one hydrogen atom on the alkyl group with a carbon number of 1 to 6 is substituted with a hydroxyl group. Specific examples thereof include a methanol group (-CH 2OH), and methylmethanol group (hydroxyethyl:-CH 2CH 2OH), etc.

[0052] Among them, R' is preferably a linear or branched chain alkyl group with a carbon number of 1 or more and 6 or less, a benzyl group, and a phenethyl group, and more preferably a linear or branched chain alkyl group with a carbon number of 1 or more and 6 or less. base and benzyl.

[0053] In the above formula (I), n represents the number of R bonded to the nitrogen atom. n is preferably an integer from 1 to 3, more preferably 1 or 2, particularly preferably 1.

[0054] Furthermore, as other preferred forms of the quaternary nitrogen-containing onium cation, there are the following forms.

[0055] Other preferred forms of quaternary nitrogen-containing onium cations have a heterocyclic ring containing nitrogen atoms, and the heterocyclic ring has a linear or branched alkyl group with a carbon number of 7 or more and a linear or branched alkene group with a carbon number of 7 or more. At least 1 of the bases.

[0056] Examples of the quaternary nitrogen-containing onium cation containing such a ring (heterocyclic) structure include imidazolium ion, pyrrolidinium ion, piperidinium ion, and the like.

[0057] Among them, the quaternary nitrogen-containing onium cation containing a ring (heterocyclic) structure is preferably an imidazolium ion. Furthermore, at this time, the quaternary imidazolium cation is preferably represented by the following formula (II).

[0058]

[0059] In the above formula (II), R'' is a linear or branched alkyl group having 7 or more carbon atoms or a linear or branched alkenyl group having 7 or more carbon atoms. In the above formula (II), examples of the alkyl group and alkenyl group as R″ include the same alkyl group and alkenyl group as described for R in the above formula (I), respectively. Moreover, the preferred form is also the same as described for the above-mentioned R. Among them, R'' is preferably a straight-chain or branched alkyl group with a carbon number of 8 or more and 20 or less or a straight-chain alkyl group with a carbon number of 8 or more and 20 or less. chain or branched alkenyl.

[0060] The anion (counteranion) constituting the quaternary nitrogen-containing onium salt compound is not particularly limited as long as it can form a salt with the quaternary nitrogen-containing onium cation. Examples of such anions include halide ions such as fluoride ion (F -), chloride ion (Cl -), bromide ion (Br -), and iodide ion (I -); hydrogen sulfate ion (HSO 4 -); sulfite ion (HSO 3 -); alkyl sulfate ion ((Alkyl)SO 4 -: Alkyl is an alkyl group with more than 1 and less than 8 carbon atoms (such as methyl, ethyl, n- Propyl, isopropyl, n-butyl, second butyl, third butyl, preferably ethyl); sulfate ion (SO 4 2-); nitrate ion (NO 3 -); dihydrogen phosphate Ion (H 2PO 4 -), hydrogen phosphate ion (HPO 4 2-), phosphate ion (PO 4 3-); perchlorate ion (ClO 4 -); hydroxide ion (OH -); citrate ion, Carboxylic acid-based anions such as acetate ion, malate ion, fumarate ion, lactate ion, glutarate ion and maleate ion, etc. Among them, the anion (counter anion) is preferably Halide ion, alkyl sulfate ion, nitrate ion, more preferably halide ion, alkyl sulfate ion, further preferably chloride ion, ethyl sulfate ion (C 2H 5SO 4 -), especially is the chloride ion.

[0061] The quaternary nitrogen-containing onium salt compound of the present invention preferably contains a quaternary nitrogen-containing onium cation represented by the above formula (I) or formula (II), and more preferably contains a quaternary ammonium cation represented by the above formula (I). .

[0062] Furthermore, the quaternary ammonium salt compound containing a quaternary ammonium cation is preferably a compound represented by the following formula (a). That is, the quaternary nitrogen-containing onium salt compound is preferably a quaternary ammonium salt compound represented by the following formula (a).

[0063]

[0064] In the above formula (a), R 11 is a linear or branched chain alkyl group with a carbon number of 9 or more and 15 or less, R 12, R 13 and R 14 are each independently a linear or branched chain alkyl group or a benzyl group with a carbon number of 1 or more and 6 or less; X is an anion.

[0065] In the above formula (a), specific examples of the linear or branched alkyl group having a carbon number of 9 to 15 include those having a carbon number of 9 to 15 as exemplified for R in the above formula (I). The following specific examples are the same. Specific examples of the linear or branched alkyl group having 1 or more carbon atoms and 6 or less carbon atoms are the same as those listed for R′ in the above formula (I). Furthermore, .

[0066] Among them, it is preferable that R 11 is a linear or branched alkyl group having a carbon number of 10 to 14, and R 12 , R 13 and R 14 are each independently a linear or branched alkyl group having a carbon number of 1 to 3. base or benzyl group, X is a halide ion or an alkyl sulfate ion. Furthermore, it is more preferred that R 11 is a linear or branched alkyl group having a carbon number of 10 to 14, and R 12 , R 13 and R 14 are each independently a linear or branched alkyl group having a carbon number of 1 to 3. base or benzyl group, X is chloride ion or ethyl sulfate ion. Furthermore, in each of the above forms, it is particularly preferred that any one of R 12 , R 13 and R 14 be a benzyl group. If the quaternary ammonium salt compound contains a benzyl group, it is easy to form a hydrophilic film (water molecule film) on the surface of the polished grinding object, abrasive grain residue, organic matter residue, etc. by utilizing π-π interaction, so it can be highly polished. Removes residue efficiently. In addition, it is particularly preferable that R 11 is a linear alkyl group having a carbon number of 10 to 14, R 12 is a benzyl group, R 13 and R 14 are each independently a linear alkyl group having a carbon number of 1 to 3, and X is the chloride ion.

[0067] The molecular weight of the fourth-grade nitrogen-containing onium salt compound is not particularly limited, but it is preferably less than 1,000, more preferably 800 or less, further preferably 600 or less, and most preferably 400 or less. On the other hand, the lower limit of the molecular weight is not particularly limited, but it is preferably 150 or more, more preferably 200 or more, and particularly preferably 300 or more. As an example, the molecular weight of the quaternary nitrogen-containing onium salt compound is preferably 150 or more and less than 1,000, more preferably 200 or more and 800 or less, still more preferably 200 or more and 600 or less, particularly preferably 300 or more and 400 or less.

[0068] Furthermore, the molecular weight of the quaternary nitrogen-containing onium salt compound (low molecular weight compound) can be measured by a known method such as gas chromatography-mass spectrometry (GC-MS). In addition, the structure of the compound can be determined by methods such as NMR (Nuclear Magnetic Resonance), and the molecular weight can be determined by performing calculations based on the structure.

[0069] The quaternary nitrogen-containing onium salt compound that can be used as the component (A) may be synthesized or may be a commercially available product. Examples of commercially available products include: CATIOGEN (registered trademark) BC-50, CATIOGEN (registered trademark) ES-L, CATIOGEN (registered trademark) TMS (all owned by Daiichi Industrial Pharmaceutical Co., Ltd.), NISSAN CATION ( Registered trademark) 2-OLR, NISSAN CATION (registered trademark) AR-4 (all owned by NOF Corporation), etc.

[0070] The quaternary nitrogen-containing onium salt compound as (A) component may be used individually by 1 type, or may be used in combination of 2 or more types.

[0071] The content of component (A) in the surface treatment composition is appropriately set depending on the type of component (A) used or the desired effect. Assuming that the total mass of the surface treatment composition is 100 mass % (relative to the surface treatment composition), the content of component (A) is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, and still more preferably more than 0.005 mass %. quality%. Furthermore, assuming that the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), the upper limit of the content of component (A) in the surface treatment composition is preferably 0.5 mass% or less, more preferably 0.3%. mass % or less, more preferably 0.1 mass % or less, still more preferably less than 0.1 mass %. By setting such an upper limit, the component (A) forms microcells and suppresses the component (A) itself from becoming a residue, and the residue can be efficiently removed.

[0072] In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the content of component (A) is 0.001 mass% or more and 0.5 mass% or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the content of component (A) is 0.005 mass% or more and 0.3 mass% or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), and the content of component (A) is more than 0.005% by mass and less than 0.1% by mass. In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the content of component (A) is more than 0.005 mass% and less than 0.1 mass%. In addition, when the surface treatment composition contains two or more types of (A) component, the content of (A) component means the total amount of these.

[0073] <(B)Component> The surface treatment composition of the present invention contains a nonionic polymer as component (B). The "nonionic polymer" mentioned here refers to a polymer that does not have anionic groups such as carboxylic acid groups, sulfonic acid groups, and phosphate groups; or cationic groups such as amine groups and quaternary ammonium groups in the molecule.

[0074] When the surface treatment composition contains an anionic polymer instead of the component (B), the component (A) and the anionic polymer aggregate, making it difficult to prepare a uniform surface treatment composition. Furthermore, when the surface treatment composition contains a cationic polymer such as polyethyleneimine instead of component (B), the cationic polymer repels the positive charge of component (A) on the surface of the polished object. , inhibits adsorption of component (A) on the surface of the polished object at the same time. Therefore, the effect of improving the wettability of the surface of the polished object becomes insufficient, and a film of water molecules cannot be efficiently formed on the surface, so organic residues tend to adhere easily.

[0075] For these polymers, non-ionic polymers can be used under conditions that do not hinder the control (positive charge) of the zeta potential of the polished object, abrasive grain residue, organic matter residue, etc. using the component (A). Next, the wettability of the surface of the grinding object is improved, thereby promoting the removal of residues on the surface of the grinding object.

[0076] Nonionic polymers are polymers that have the same (homopolymer; copolymer) or different (copolymer; copolymer) repeating structural units, and typically can be compounds with a weight average molecular weight (Mw) of more than 1,000. When the nonionic polymer is a copolymer, the form of the copolymer may be any of block copolymer, random copolymer, graft copolymer, and alternating copolymer.

[0077] Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyN-vinyl acetamide, polyamines, polyvinyl ethers (polyvinyl ethers) Vinyl methyl ether, polyethylene ether, polyethylene isobutyl ether, etc.), polyglycerol, polyethylene glycol, polypropylene glycol, hydroxyethyl cellulose and other water-soluble polysaccharides, alginate polyol ester, water-soluble urea resin, Dextrin derivatives, casein, etc. In addition, not only those having such a main chain structure, but also graft copolymers having a nonionic polymer structure in the side chain can be suitably used. Furthermore, copolymers such as ethylene-vinyl alcohol copolymers and butylene glycol-vinyl alcohol copolymers can also be used.

[0078] Among them, as the nonionic water-soluble polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyN-vinyl acetamide, polyethylene glycol, and hydroxyethyl fiber are preferred. and butylene glycol-vinyl alcohol copolymer. Therefore, the nonionic polymer as component (B) is preferably one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyN-vinyl acetamide, polyethylene glycol, and hydroxyethyl. At least one of the group consisting of base cellulose and butylene glycol-vinyl alcohol copolymer. Furthermore, as the nonionic polymer, polyvinyl alcohol and polyvinylpyrrolidone are more preferred. Furthermore, polyvinyl alcohol is particularly preferred from the viewpoint of having a high effect of retaining water molecules through hydrogen bonding and reducing the etching rate of polished objects containing polycrystalline silicon.

[0079] The lower limit of the weight average molecular weight (Mw) of the nonionic polymer is preferably 1,000 or more, more preferably 3,000 or more, further preferably more than 5,000, particularly preferably 10,000 or more. Furthermore, the upper limit of the weight average molecular weight (Mw) of the nonionic polymer is preferably 1,000,000 or less, more preferably 100,000 or less, further preferably 50,000 or less, particularly preferably 30,000 or less. As an example, the weight average molecular weight (Mw) of the nonionic polymer is preferably 1,000 or more and 1,000,000 or less, more preferably 3,000 or more and 100,000 or less, further preferably more than 5,000 and 100,000 or less, still more preferably more than 5,000 and 100,000 or less. 50,000 or less, preferably more than 5,000 and less than 30,000, most preferably more than 10,000 and less than 30,000.

[0080] In addition, the weight average molecular weight (Mw) of the nonionic polymer can be measured as a polyethylene glycol converted value using gel permeation chromatography (GPC). The details of the measurement method are described in the following implementation. Example.

[0081] The nonionic polymer that can be used as component (B) may be produced by synthesis or may be a commercial product. Examples of commercially available products include: JMR (registered trademark)-10HH, JMR (registered trademark)-3HH (both belong to JAPAN VAM & POVAL Co., Ltd.), PITZCOL (registered trademark) K30A, K30L (all belong to JAPAN VAM & POVAL Co., Ltd.), One Industrial Pharmaceutical Co., Ltd.), CMC Daicel (registered trademark) 1150, 1170 (both Daicel Miraizu Co., Ltd.), etc.

[0082] As the nonionic polymer as component (B), one type may be used alone, or two or more types may be used in combination.

[0083] The content of component (B) in the surface treatment composition is appropriately set depending on the type of component (B) used or the desired effect. Assuming that the total mass of the surface treatment composition is 100 mass % (relative to the surface treatment composition), the content of component (B) is preferably 0.00001 mass % or more, more preferably more than 0.0001 mass %, and still more preferably 0.01 mass % %above. Furthermore, assuming that the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), the upper limit of the content of component (B) in the surface treatment composition is preferably 2 mass% or less, more preferably 1.5 mass% or less, and more preferably 1.0 mass% or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), and the content of component (B) is 0.00001 mass% or more and 2 mass% or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the content of component (B) is more than 0.0001 mass% and 1.5 mass% or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the content of component (B) is 0.01 mass% or more and 1.0 mass% or less. In addition, when the surface treatment composition contains two or more types of (B) component, the content of (B) component means the total amount of these.

[0084] Instead of or in addition to the above, the mixing ratio of component (A) and component (B) in the surface treatment composition is appropriately set according to the type of component (A) or component (B) used and the desired effect. . The mixing ratio (mass ratio) of component (A) to component (B) ((A) component / (B) component content ratio) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably more than 0.05. The mixing ratio of component (A) to component (B) ((A) component / (B) component content ratio) (mass ratio) is preferably 200 or less, more preferably 10 or less, and still more preferably less than 1.0. Especially good is less than 0.50. In one embodiment of the present invention, the mixing ratio of component (A) to component (B) (component (A) / component (B) content ratio) (mass ratio) is 0.01 or more and 200 or less. In one embodiment of the present invention, the mixing ratio of component (A) to component (B) (component (A) / component (B) content ratio) (mass ratio) is 0.03 or more and 10 or less. In one embodiment of the present invention, the mixing ratio of component (A) to component (B) (component (A) / component (B) content ratio) (mass ratio) exceeds 0.05 and is less than 1.0. In one embodiment of the present invention, the mixing ratio of component (A) to component (B) (component (A) / component (B) content ratio) (mass ratio) exceeds 0.05 and does not reach 0.50.

[0085] <(C)Component> In addition to the above-mentioned (A) and (B) components, the surface treatment composition of the present invention also contains (C) component. (C) The component includes a buffer (ammonium monocarboxylate) represented by the formula: A-COO -NH 4 +. In this specification, "buffer" means a substance that imparts a buffering effect to the surface treatment composition (solution) in order to maintain a constant pH value.

[0086] Component (C) may contain components other than the buffer represented by the above formula: A-COO -NH 4 + (for example, a known buffer), but from the viewpoint of further improving the effect of the present invention, component (C) is preferred. It contains the buffer represented by the above formula: A-COO-NH4+ (component (C) is the buffer represented by the above formula: A-COO-NH4+). The presence of component (C) enables efficient removal of residue remaining on the surface of the polished object. Furthermore, the etching rate of the polished object containing polycrystalline silicon can be suppressed to a low level. That is, in a preferred aspect of the present invention, component (C) includes a buffer represented by the formula: A-COO-NH4+ (component (C) is a buffer represented by the formula: A-COO-NH4+ ).

[0087] In the above formula: A-COO -NH 4 +, A is an alkyl group or phenyl group with a carbon number of 1 to 10. Here, as the alkyl group, the same specific examples as those exemplified for R' in the above formula (I) can be exemplified. Among them, from the viewpoint of further improving the effect of the present invention, A is preferably a linear or branched alkyl group with a carbon number of 1 or more and 8 or less, and more preferably a linear or branched alkyl group with a carbon number of 1 or more and 3 or less. The branched alkyl group is more preferably methyl (ammonium acetate) or ethyl (ammonium propionate), and particularly preferably methyl (ammonium acetate). That is, in a preferred embodiment of the present invention, the buffering agent is represented by the above formula: A-COO -NH 4 + in which A is a linear or branched alkyl group having a carbon number of 1 to 8. In a more preferred aspect of the present invention, the buffering agent is represented by the above formula: A-COO -NH 4 + in which A is a linear or branched alkyl group having a carbon number of 1 to 3. In a further preferred form of the present invention, the buffering agent is represented by the above formula in which A is methyl or ethyl: A-COO -NH 4 + (the buffering agent is ammonium acetate or ammonium propionate). In a particularly preferred form of the invention, the buffering agent is ammonium acetate.

[0088] The content of component (C) in the surface treatment composition is appropriately set depending on the type of component (C) used or the desired effect. When the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), the content of component (C) is preferably 0.05% by mass or more, more preferably more than 0.1% by mass, and still more preferably 0.2% by mass. %above. Furthermore, assuming that the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), the upper limit of the content of component (C) in the surface treatment composition is preferably 2 mass% or less, more preferably 1.5 mass% or less, and more preferably 1.0 mass% or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass % (relative to the surface treatment composition), and the content of component (C) is 0.05 mass % or more and 2 mass % or less. In one embodiment of the present invention, the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), and the content of component (C) is more than 0.1% by mass and less than 1.5% by mass. In one embodiment of the present invention, the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the content of component (C) is 0.2 mass% or more and 1.0 mass% or less. In addition, when the surface treatment composition contains two or more types of (C) component, the content of (C) component means the total amount of these.

[0089] Instead of or in addition to the above, the mixing ratio of component (A) and component (C) in the surface treatment composition is appropriately set according to the type of component (A) or component (C) used and the desired effect. . The mixing ratio (mass ratio) of component (A) to component (C) ((A) component / (C) component content ratio) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably more than 0.03. The mixing ratio (mass ratio) of component (A) to component (C) ((A) component / (C) component content ratio) is preferably 1.0 or less, more preferably 0.5 or less, and still more preferably less than 0.5, Particularly preferred is less than 0.1. In one embodiment of the present invention, the mixing ratio of component (A) to component (C) (component (A) / component (C) content ratio) (mass ratio) is 0.01 or more and 1.0 or less. In one embodiment of the present invention, the mixing ratio of component (A) to component (C) (component (A) / component (C) content ratio) (mass ratio) is 0.02 or more and 0.5 or less. In one embodiment of the present invention, the mixing ratio of component (A) to component (C) (component (A) / component (C) content ratio) (mass ratio) is more than 0.03 and less than 0.5. In one embodiment of the present invention, the mixing ratio of component (A) to component (C) (component (A) / component (C) content ratio) (mass ratio) is more than 0.03 and less than 0.1.

[0090] <pH adjuster ((D) ingredient)> The surface treatment composition of the present invention must contain the above-mentioned components (A) to (C), but it is preferred to further contain a pH adjuster in addition to these. That is, in a preferred aspect of the present invention, the surface treatment composition further contains component (D): (D) Ingredient: pH adjuster.

[0091] The pH adjuster is not particularly limited. Known pH adjusters used in the field of surface treatment compositions can be used, and known acids, bases, or salts thereof can be used. Examples of pH adjusters include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, and palmitic acid. Pearlic acid, stearic acid, oleic acid, linoleic acid, hypolinolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, lactic acid, malic acid, citric acid, benzoic acid , phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, mellitic acid, cinnamic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , fumaric acid, maleic acid, aconitic acid, amino acids, anthranilic acid and other carboxylic acids, or organic acids such as sulfonic acid and organic phosphonic acid; nitric acid, carbonic acid, hydrochloric acid, phosphoric acid, hypophosphorous acid , phosphorous acid, phosphonic acid, boric acid, hydrofluoric acid, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid and other inorganic acids; potassium hydroxide (KOH), sodium hydroxide (NaOH) and other alkali metal hydrogen Oxides; carbonates of alkali metals such as potassium carbonate (K 2CO 3) and sodium carbonate (Na 2CO 3); hydroxides of Group 2 elements; ammonia (ammonium hydroxide); quaternary ammonium hydroxide compounds and other organic compounds Alkali etc. As a pH adjuster, synthetic products or commercial products can be used. In addition, these pH adjusters can be used alone, or two or more types can be used in combination. Among them, potassium hydroxide, sodium hydroxide, sodium carbonate, and ammonia are preferred, potassium hydroxide, sodium hydroxide, and ammonia are more preferred, and ammonia is particularly preferred. That is, in a preferred aspect of the present invention, the pH adjuster is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate and ammonia. In a more preferred form of the present invention, the pH adjuster is at least one selected from the group consisting of potassium hydroxide, sodium hydroxide and ammonia. In a particularly preferred form of the invention, the pH adjuster is ammonia.

[0092] The content of the pH adjuster in the surface treatment composition may be appropriately selected so as to achieve the required pH of the surface treatment composition as described in detail below.

[0093] <pH value of surface treatment composition> The pH value of the surface treatment composition of the present invention exceeds 7.0. If the pH value of the surface treatment composition is below 7.0, the residue remaining on the surface of the polished object cannot be sufficiently removed. From the viewpoint of further improving the effect of the present invention, the pH value of the surface treatment composition is preferably above 7.5, more preferably above 7.5, and particularly preferably above 8.5. The pH value of the surface treatment composition is preferably less than 11.0, more preferably less than 10.5, even more preferably less than 10.0. That is, in one embodiment of the present invention, the pH value of the surface treatment composition is 7.5 or more and less than 11.0. In one embodiment of the present invention, the pH value of the surface treatment composition is more than 7.5 and less than 10.5. In one embodiment of the present invention, the pH value of the surface treatment composition is more than 8.5 and less than 10.0. In addition, the pH value of the surface treatment composition adopts the value measured by the method described in the Example.

[0094] <Solvent> The surface treatment composition of the present invention preferably contains a solvent. Solvents have the function of dispersing or dissolving components. The solvent preferably contains water, more preferably only water. In addition, in order to disperse or dissolve each component, the solvent may also be a mixed solvent of water and organic solvent. In this case, examples of the organic solvent used include acetone, acetonitrile, ethanol, methanol, isopropyl alcohol, glycerol, ethylene glycol, propylene glycol, triethanolamine, etc. as organic solvents that are miscible with water. Alternatively, these organic solvents may be used without being mixed with water, each component may be dispersed or dissolved, and then mixed with water. These organic solvents can be used alone, or two or more types can be used in combination.

[0095] From the viewpoint of preventing contamination of the ground object and hindering the action of other components, the water is preferably water containing as little residue as possible. For example, water in which the total content of transition metal ions is 100 ppb or less is preferred. Here, the purity of water can be improved, for example, by using an ion exchange resin to remove residual ions, using a filter to remove foreign matter, distillation, and other operations. Specifically, for example, deionized water (ion exchange water), pure water, ultrapure water, distilled water, etc. are preferably used.

[0096] <Surfactant> The surface treatment composition of the present invention may further include a surfactant. The type of surfactant is not particularly limited and can be any of nonionic, anionic, cationic, and amphoteric surfactants.

[0097] Examples of nonionic surfactants include compounds other than the above component (B). Examples include alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene oil ether; polyoxyethylene octylbenzene. Alkyl phenyl ether types such as ether; alkyl ester types such as polyoxyethylene laurate; alkylamine types such as polyoxyethylene laurylamine ether; alkylamide types such as polyoxyethylene lauryl amide; polyoxyethylene polyamide Polypropylene glycol ether types such as oxypropylene ether; alkanolamide types such as oleic acid diethanolamide; allyl phenyl ether types such as polyoxyalkylene allyl phenyl ether, etc. In addition, propylene glycol, diethylene glycol, monoethanolamine, alcohol ethoxylate, alkylphenol ethoxylate, tertiary acetylene glycol, alkanolamide, etc. can also be used as nonionic surfactants. Furthermore, the above-mentioned component (B) may function as a nonionic surfactant, so it is not necessary to add another nonionic surfactant.

[0098] Examples of anionic surfactants include carboxylic acid types such as sodium myristate, sodium palmitate, sodium stearate, sodium laurate, and potassium laurate; sulfate ester types such as sodium octyl sulfate; laurel Phosphate ester types such as phosphoric acid and sodium lauryl phosphate; sulfonic acid types such as sodium dioctyl sulfosuccinate and sodium dodecyl benzene sulfonate.

[0099] Examples of the cationic surfactant include compounds other than the above-mentioned component (A), and examples thereof include amines such as laurylamine hydrochloride. Furthermore, since the above-mentioned component (A) can function as a cationic surfactant, it is not necessary to add another cationic surfactant.

[0100] Examples of amphoteric surfactants include lecithin, alkylamine oxides, alkyl betaines such as N-alkyl-N,N-dimethylammonium betaine, and sulfobetaine.

[0101] One type of surfactant may be used alone, or two or more types may be used in combination. In addition, as the surfactant, commercially available products or synthetic products may be used.

[0102] When the surface treatment composition contains a surfactant, the total mass of the surface treatment composition is set to 100 mass%, and the lower limit of the content of the surfactant is preferably 0.01 mass% or more, more preferably 0.05 mass% or more. Furthermore, assuming that the total mass of the surface treatment composition is 100 mass%, the upper limit of the content of the surfactant in the surface treatment composition is preferably 5 mass% or less, more preferably 1 mass% or less. Furthermore, when the surface treatment composition contains two or more surfactants, the content of the surfactants means the total amount of these surfactants.

[0103] <Chelating agent> The surface treatment composition of the present invention may further include a chelating agent. Examples of the chelating agent include aminocarboxylic acid-based chelating agents and organic phosphonic acid-based chelating agents. Examples of aminocarboxylic acid chelating agents include: ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, nitrilotriacetic acid, sodium nitrilotriacetate, ammonium nitrilotriacetate, and hydroxyethylethylenediamine. Triacetic acid, sodium hydroxyethylethylenediaminetriacetate, diethylenetriaminepentaacetic acid, sodium diethylenetriaminepentacetate, triethylenetetraminehexaacetic acid and sodium triethylenetetraminehexaacetate. Examples of organic phosphonic acid chelating agents include: 2-aminoethylphosphonic acid, 1-hydroxyethylene-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), ethylenediaminetetra( Methylenephosphonic acid) (EDTPO), diethylenetriaminepenta(methylenephosphonic acid), ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane- 1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methane hydroxyphosphine acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid and α-methylphosphonosuccinic acid. Among them, organic phosphonic acid-based chelating agents are more preferred. Among them, preferred ones include ethylenediaminetetrakis(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid), and diethylenetriaminepentacetic acid. Particularly preferred chelating agents include ethylenediaminetetrakis(methylenephosphonic acid) and diethylenetriaminepenta(methylenephosphonic acid).

[0104] One type of chelating agent may be used alone, or two or more types of chelating agents may be used in combination. In addition, as the chelating agent, commercially available products or synthetic products can be used.

[0105] When the surface treatment composition contains a chelating agent, the total mass of the surface treatment composition is set to 100 mass%, and the lower limit of the content of the chelating agent is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, and further preferably Preferably, it is 0.002 mass % or more. The upper limit of the content of the chelating agent is preferably 1 mass% or less, more preferably 0.5 mass% or less, further preferably 0.3 mass% or less, especially 0.15 mass% or less. Furthermore, when the surface treatment composition contains two or more kinds of chelating agents, the content of the chelating agents means the total amount thereof.

[0106] <Other additives> The surface treatment composition of one form of the present invention may also contain other additives in any ratio as necessary within the range that does not hinder the effect of the present invention. However, components other than the essential components of the surface treatment composition of one aspect of the present invention may cause foreign matter (residues), so it is preferable not to add them as much as possible. Therefore, it is better to add as little other additives as possible. Examples of other additives include antifungal agents (preservatives), dissolved gases, reducing agents, oxidizing agents, and the like. The surface treatment composition of the present invention contains nonionic polymers and is alkaline. Therefore, among them, the surface treatment composition of the present invention preferably contains an antifungal agent (preservative). When the surface treatment composition of the present invention contains an antifungal agent (preservative), the antifungal agent (preservative) that can be used is not particularly limited and can be selected according to the type of nonionic polymer ((B) component). Choose appropriately. Specific examples include: 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 1,2-benzisothiazole Isothiazoline-based preservatives such as -3(2H)-one (BIT), and phenoxyethanol, etc.

[0107] Alternatively, the antifungal agent (preservative) may be a compound represented by Chemical Formula 1 below.

[0108] (Chemical formula 1)

[0109] In the above Chemical Formula 1, R 1 to R 5 are each independently a hydrogen atom, or a substituent containing at least two atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms.

[0110] Examples of the substituent containing at least two kinds of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms include: hydroxyl group, carboxyl group, alkyl group having 1 to 20 carbon atoms, carbon A hydroxyalkyl group with a carbon number of 1 or more and 20 or less, an alkoxy group with a carbon number of 1 or more and 20 or less, a hydroxyalkoxy group with a carbon number of 1 or more and 20 or less, an alkoxycarbonyl group with a carbon number of 2 or more and 21 or less, carbon Aryl groups with 6 to 30 carbon atoms, aralkyl groups with 7 to 31 carbon atoms, aryloxy groups with 6 to 30 carbon atoms, aryloxycarbonyl groups with 6 to 30 carbon atoms, An aralkoxycarbonyl group having a carbon number of 8 to 32, a hydroxyl group having a carbon number of 2 to 20, a hydroxyl group having a carbon number of 2 to 20, etc.

[0111] More specifically, examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl. Linear alkyl groups such as n-nonyl, n-decyl, etc.; isopropyl, isobutyl, second butyl, third butyl, third pentyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl- Branched alkyl groups such as 2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl; cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Nor 𦯉 alkenyl and other cyclic alkyl groups, etc.

[0112] Examples of the hydroxyalkyl group having 1 to 20 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 2-hydroxyn-propyl, 3-hydroxyn-propyl, 2-hydroxyn-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 2-hydroxy-n-pentyl, 3-hydroxy-n-pentyl, 4-hydroxy-n-pentyl, 5-hydroxy-n-pentyl, 2-hydroxy-n-hexyl, 3- Hydroxy n-hexyl, 4-hydroxy n-hexyl, 5-hydroxy n-hexyl, 6-hydroxy n-hexyl, etc.

[0113] Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, and n-heptyloxy. , n-octoxy, n-nonyloxy, n-decyloxy and other linear alkoxy groups; isopropoxy, isobutoxy, second butoxy, third butoxy, third pentyloxy , neopentyloxy, 3-methylpentyloxy, 1,1-diethylpropoxy, 1,1-dimethylbutoxy, 1-methyl-1-propylbutoxy, 1 , 1-dipropylbutoxy, 1,1-dimethyl-2-methylpropoxy, 1-methyl-1-isopropyl-2-methylpropoxy and other branched alkoxy groups Base; cyclic alkoxy groups such as cyclobutoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, noralkenyloxy, etc.

[0114] Examples of the hydroxyalkoxy group having 1 to 20 carbon atoms include hydroxymethoxy, 2-hydroxyethoxy, 2-hydroxyn-propoxy, 3-hydroxyn-propoxy, 2- Hydroxy n-butoxy, 3-hydroxy n-butoxy, 4-hydroxy n-butoxy, 2-hydroxy n-pentyloxy, 3-hydroxy n-pentyloxy, 4-hydroxy n-pentyloxy, 5-hydroxy n-butoxy Pentyloxy, 2-hydroxyn-hexyloxy, 3-hydroxyn-hexyloxy, 4-hydroxyn-hexyloxy, 5-hydroxyn-hexyloxy, 6-hydroxyn-hexyloxy, etc.

[0115] Examples of the alkoxycarbonyl group having a carbon number of 2 or more and 21 or less include: methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentoxycarbonyl group, hexyloxycarbonyl group, Octyloxycarbonyl, decyloxycarbonyl, etc.

[0116] Examples of the aryl group having 6 or more carbon atoms and 30 or less carbon atoms include phenyl group, naphthyl group, anthracenyl group, pyrenyl group, and the like.

[0117] Examples of the aralkyl group having 7 to 31 carbon atoms include benzyl, phenylethyl (phenylethyl), etc. Examples of the aryloxy group having 6 to 30 carbon atoms are: Examples include phenoxy, naphthyloxy, anthryloxy, pyreneoxy, and the like.

[0118] Examples of the aryloxycarbonyl group having a carbon number of 7 to 31 include phenoxycarbonyl, naphthyloxycarbonyl, anthracenyloxycarbonyl, pyreneoxycarbonyl, and the like.

[0119] Examples of the aralkoxycarbonyl group having a carbon number of 8 or more and 32 or less include benzyloxycarbonyl group, phenethyloxycarbonyl group, and the like.

[0120] Examples of the ethyl group having a carbon number of 1 to 20 include methanoyl, ethanoyl, propyl, butyl, pentyl, hexyl, octyl, and decyl. base, benzyl group, etc.

[0121] Examples of the acyloxy group having a carbon number of 1 to 20 include formyloxy, acetyloxy, propyloxy, butyloxy, pentyloxy, hexyloxy, and octyloxy. Cyloxy group, decyloxy group, benzyloxy group, etc.

[0122] Furthermore, the antifungal agent represented by the above-mentioned Chemical Formula 1 is preferably at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1-a to 1-c.

[0123]

[0124] In the above chemical formulas 1-a to 1-c, R 1 to R 3 are each independently a substituent containing at least two kinds of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms.

[0125] Examples of the substituent containing at least two kinds of atoms selected from the group consisting of carbon atoms, hydrogen atoms, and oxygen atoms are the same as above, and therefore the description is omitted here.

[0126] More specific examples of the compound represented by the above-mentioned Chemical Formula 1 include: methyl p-hydroxybenzoate (Methyl p-hydroxybenzoate), ethyl p-hydroxybenzoate (Ethyl p-hydroxybenzoate), and butyl parahydroxybenzoate. (Butyl p-hydroxybenzoate), Benzyl p-hydroxybenzoate (Benzyl p-hydroxybenzoate) and other parahydroxybenzoates (p-hydroxybenzoate); salicylic acid, methyl salicylate, phenol, catechol, m- Quinone, hydroquinone, isopropylphenol, cresol, athymone, phenoxyethanol, phenylphenol (2-phenylphenol, 3-phenylphenol, 4-phenylphenol), 2 -Phenylethanol (phenylethanol), etc.

[0127] Among them, from the viewpoint of exerting the desired effect of the present invention more effectively, the compound represented by the above-mentioned Chemical Formula 1 is preferably selected from the group consisting of ethyl parahydroxybenzoate, butyl parahydroxybenzoate, and At least one of the group consisting of phenylphenols, preferably butyl parahydroxybenzoate.

[0128] Alternatively, the antifungal agent (preservative) may be an unsaturated fatty acid. Examples of unsaturated fatty acids include: monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, and ricinoleic acid; sorbic acid, linoleic acid, eicosadienoic acid, etc. Diunsaturated fatty acids; triunsaturated fatty acids such as linolenic acid, terpineic acid, and eleostearic acid; tetraunsaturated fatty acids such as stearidonic acid or arachidonic acid; heptapentenoic acid, eicosapentaene Pentaunsaturated fatty acids such as acid; hexaunsaturated fatty acids such as docosahexaenoic acid and herring acid, etc.

[0129] Among them, from the viewpoint of exerting the desired effects of the present invention more effectively, sorbic acid is preferred as the unsaturated fatty acid.

[0130] Moreover, in addition to the above, 1,2-alkanediol such as 1,2-pentanediol, 1,2-hexanediol, and 1,2-octanediol; 2-ethylhexylglyceryl ether (ethylhexylglyceryl ether) may also be used. Alkyl glyceryl ethers such as methylhexylglycerol); capric acid, dehydroacetic acid and other compounds are used as antifungal agents (preservatives).

[0131] The above-mentioned antifungal agents (preservatives) can be used alone, or two or more types can be used in combination.

[0132] When the surface treatment composition contains an antifungal agent (preservative), the lower limit of the content (concentration) of the antifungal agent (preservative) is not particularly limited. The total mass of the surface treatment composition is set to 100% by mass (relative to the surface treatment composition), preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, further preferably 0.005 mass% or more, particularly preferably 0.01 mass% or more. In addition, the upper limit of the content (concentration) of the antifungal agent (preservative) is not particularly limited, and the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), preferably 5% by mass or less. , more preferably 1 mass% or less, still more preferably 0.5 mass% or less, particularly preferably 0.1 mass% or less. That is, assuming that the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), the content (concentration) of the antifungal agent (preservative) in the surface treatment composition is preferably 0.0001% by mass or more and 5 mass% or less, more preferably 0.001 mass% or more and 1 mass% or less, further preferably 0.005 mass% or more and 0.5 mass% or less, particularly preferably 0.01 mass% or more and 0.1 mass% or less. If it is within this range, an effect sufficient to inert or destroy microorganisms can be obtained. Furthermore, when the surface treatment composition contains two or more antifungal agents (preservatives), the above-mentioned content means the total amount thereof.

[0133] In one embodiment of the present invention, the surface treatment composition essentially contains a quaternary nitrogen-containing onium salt compound (component (A)), a nonionic polymer (component (B)), and a buffer ((C)). Ingredients), pH adjuster ((D) ingredient) and water, and at least one of the group consisting of antifungal agents, organic solvents, surfactants and chelating agents. In one embodiment of the present invention, the surface treatment composition essentially contains a quaternary nitrogen-containing onium salt compound (component (A)), a nonionic polymer (component (B)), and a buffer (component (C)). , pH adjuster (component (D)) and water, and at least one of an antifungal agent and an organic solvent. In one embodiment of the present invention, the surface treatment composition essentially contains a quaternary nitrogen-containing onium salt compound (component (A)), a nonionic polymer (component (B)), and a buffer (component (C)). , pH adjuster ((D) ingredient) and water. In the above form, "the surface treatment composition substantially contains X" means that the total mass of the surface treatment composition is 100 mass% (relative to the surface treatment composition), and the total content of X exceeds 99 mass% (upper limit: 100% by mass). It is preferable that the surface treatment composition contains X (the above total content = 100 mass %). For example, "The surface treatment composition essentially contains a quaternary nitrogen-containing onium salt compound (component (A)), a nonionic polymer (component (B)), a buffer (component (C)), and a pH adjuster (component (A)). (D) Component) and water, and at least one of an antifungal agent and an organic solvent" means that the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), and the fourth grade nitrogen-containing onium Salt compound (component (A)), nonionic polymer (component (B)), buffer (component (C)), pH adjuster (component (D)) and water, antifungal agent and organic solvent The total content exceeds 99% by mass (upper limit: 100% by mass), preferably the surface treatment composition includes a fourth-grade nitrogen-containing onium salt compound ((A) component), a nonionic polymer ((B) component), and a buffer agent ((C) component), pH adjuster ((D) component) and water, and at least one of an antifungal agent and an organic solvent (the total content of the above = 100 mass%).

[0134] In order to further improve the residue (foreign matter) removal effect, the surface treatment composition of the present invention is preferably substantially free of abrasive particles. Here, "substantially does not contain abrasive grains" means that the content of abrasive grains is less than 0.01 mass % with respect to the entire surface treatment composition. That is, in one embodiment of the present invention, the total mass of the surface treatment composition is 100% by mass (relative to the surface treatment composition), and the content of the abrasive grains is less than 0.01% by mass (lower limit: 0% by mass).

[0135] <Production method of surface treatment composition> The manufacturing method of the surface treatment composition of the present invention is not particularly limited. For example, it can be obtained by the following method: component (A) (quaternary nitrogen-containing onium salt compound), (B) component (nonionic polymer) are selected from the group consisting of: ), (C) component (buffer), and if necessary (D) component (pH adjuster), surfactant, chelating agent, water, organic solvent, antifungal agent (preservative) and other additives At least one of the group is stirred and mixed. In one embodiment of the present invention, the composition is selected from the group consisting of (A) component (quaternary nitrogen-containing onium salt compound), (B) component (nonionic polymer), (C) component (buffer), ( D) Ingredient (pH adjuster), water, and at least one of the group consisting of an antifungal agent, an organic solvent, a surfactant, and a chelating agent are stirred and mixed to produce the surface treatment composition of the present invention. In one embodiment of the present invention, by combining (A) component (quaternary nitrogen-containing onium salt compound), (B) component (nonionic polymer), (C) component (buffer), (D) The ingredients (pH adjuster), water, and at least one of the antifungal agent and organic solvent are stirred and mixed to produce the surface treatment composition of the present invention. In one embodiment of the present invention, by combining (A) component (quaternary nitrogen-containing onium salt compound), (B) component (nonionic polymer), (C) component (buffer), (D) The ingredients (pH adjuster) and water are stirred and mixed to prepare the surface treatment composition of the present invention. The temperature when mixing each component is not particularly limited, but is preferably 10°C or more and 40°C or less. In order to increase the dissolution rate, heating may be performed. In addition, the mixing time is not particularly limited.

[0136] [Surface treatment method] According to the surface treatment composition of the present invention, residue remaining on the surface of the polished object can be sufficiently removed. Furthermore, the etching rate of the polished object containing polycrystalline silicon can be suppressed to a low level. Therefore, the present invention provides a surface treatment method, which includes the following steps: using the surface treatment composition of the present invention to perform surface treatment on a ground object. Here, the polished object may include at least one selected from the group consisting of silicon nitride, silicon oxide, and polycrystalline silicon. That is, the present invention provides a surface treatment method that uses the surface treatment composition of the present invention to polish a polished object containing at least one selected from the group consisting of silicon nitride, silicon oxide, and polycrystalline silicon. Perform surface treatment to reduce residue on the surface of the above-mentioned grinding object. Furthermore, in this specification, "surface treatment method" refers to a method of reducing residues on the surface of a polished object, and is a method of cleaning in a broad sense.

[0137] According to the surface treatment method of the present invention, the residue remaining on the surface of the polished object can be fully removed. That is, the present invention also provides a method for reducing the residue on the surface of the above-mentioned polished object, which has the following steps: using the surface treatment composition of the present invention, surface treatment is performed on the polished object. Furthermore, the present invention provides a method for reducing residues on the surface of the above-mentioned polished object, which has the following steps: using the surface treatment composition of the present invention, a compound selected from the group consisting of silicon nitride, silicon oxide, and polycrystalline silicon is used. Surface treatment is performed on at least one type of ground grinding object in the group.

[0138] The surface treatment method of the present invention is carried out by bringing the surface treatment composition of the present invention into direct contact with the polished object to be polished.

[0139] As surface treatment methods, main examples include: (I) method of flushing and grinding treatment, (II) method of using washing treatment. That is, in one embodiment of the present invention, the surface treatment method is a rinse and polishing treatment method or a cleaning treatment method (the above-mentioned surface treatment is performed by rinse and polishing treatment or cleaning treatment). Rinse polishing treatment and cleaning treatment are performed to remove foreign matter (abrasive grain (particle) residue, organic residue such as polymer or pad dust, metal contaminants, etc.) on the surface of the polished object and obtain a clean surface. Below, the above (I) and (II) are explained.

[0140] (I) Rinsing and grinding treatment The surface treatment composition of the present invention can be suitably used in flushing and polishing treatment. That is, the surface treatment composition of the present invention can be preferably used as a rinse and polishing composition. The flushing and polishing process is to perform final grinding (finish grinding) of the grinding object to obtain a ground grinding object. Then, in order to remove foreign matter on the surface of the ground grinding object, a grinding plate with a polishing pad ( on the pressure plate). At this time, flush polishing treatment is performed by bringing the surface treatment composition of the present invention into direct contact with the polished object to be polished. As a result, foreign matter on the surface of the polished object is removed by friction (physical action) of the polishing pad and chemical action of the surface treatment composition. Among foreign matter, especially abrasive grain (particle) residue or organic matter residue, it is easy to remove by physical action. Therefore, in the flushing and polishing process, by utilizing the friction with the polishing pad on the polishing platen (pressing plate), abrasive grain (particle) residue or organic matter residue can be effectively removed.

[0141] That is, in this specification, the rinse polishing treatment, the rinse polishing method and the rinse polishing step respectively refer to the treatment, method and step of using a polishing pad to reduce the residue on the surface of the surface treatment object.

[0142] Specifically, the rinse polishing process can be performed by the following method: placing the surface of the polished object after the polishing step on the polishing platen (pressing plate) of the polishing device, while bringing the polishing pad into contact with the polished semiconductor substrate. The surface treatment composition is supplied to the contact portion, while the polished polishing object and the polishing pad are relatively slid.

[0143] As the polishing device, a general polishing device can be used, which is equipped with a holder for holding the polishing object, a motor that can change the rotation speed, etc., and a polishing platen to which a polishing pad (polishing cloth) can be attached.

[0144] The flushing and grinding treatment can also be performed using either a single-sided grinding device or a double-sided grinding device. Moreover, it is preferable that the said polishing apparatus is equipped with the discharge nozzle of the surface treatment composition in addition to the discharge nozzle of the polishing composition. There are no special restrictions on the operating conditions of the grinding device during flushing and grinding. As long as the operator is the manufacturer, the conditions can be set appropriately.

[0145] As the polishing pad, general nonwoven fabrics, polyurethane, porous fluororesin, etc. can be used without particular limitation. Preferably, the polishing pad is processed with grooves for accumulating the surface treatment composition.

[0146] There are no special restrictions on flushing and grinding conditions. For example, the rotation speed of the grinding platen and the grinding head (carrier) are preferably above 10 rpm (0.17 s -1) and below 100 rpm (1.67 s -1). The pressure (polishing pressure) applied to the polished object is preferably 0.5 psi (3.4 kPa) or more and 10 psi (68.9 kPa) or less. The method of supplying the surface treatment composition to the polishing pad is not particularly limited. For example, a method of continuously supplying the composition using a pump (flush pouring) can be used. There is no limit to the supply amount, but it is preferable that the surface of the polishing pad is always covered with the surface treatment composition, and preferably it is 10 mL / min or more and 5000 mL / min or less. The flushing and grinding time is not particularly limited, but is preferably 5 seconds or more and 180 seconds or less.

[0147] After the surface treatment composition of the present invention is used for flushing and polishing, the polished object to be polished (surface treatment object) is preferably lifted and taken out while pouring the surface treatment composition of the present invention.

[0148] (II) Washing treatment The surface treatment composition of the present invention can be used in cleaning treatment. That is, the surface treatment composition of the present invention can be preferably used as a cleaning composition. The cleaning treatment is preferably performed after the final grinding (finish grinding) of the object to be polished, followed by the above-mentioned flushing and polishing treatment, or other flushing and polishing treatment using a flushing and polishing composition other than the surface treatment composition of the present invention. After obtaining the polished object to be polished (object to be cleaned), it is performed in order to remove foreign matter on the surface of the object to be polished (object to be cleaned). Furthermore, the cleaning treatment and the above-mentioned flushing and grinding treatment are classified according to the place where these treatments are performed. The cleaning treatment is a surface treatment performed on a place other than the grinding platen (pressure plate), preferably where the ground surface is ground. The surface treatment of the grinding object after it is removed from the grinding platen (pressing plate). During the cleaning process, the surface treatment composition of the present invention can also be brought into direct contact with the polished object to remove foreign matter on the surface of the object.

[0149] As an example of the method of performing the cleaning process, the following methods may be mentioned: (i) While maintaining the state of the polished polishing target, the cleaning brush is brought into contact with one or both sides of the polished polishing target. , a method of using a cleaning brush to rub and clean the surface of the object while supplying the surface treatment composition to the contact part; (ii) immersing the ground object in the surface treatment composition and performing ultrasonic treatment or Stirring method (immersion type). In this method, foreign matters on the surface of the polished object are removed by utilizing the friction force caused by the cleaning brush or the mechanical force caused by ultrasonic treatment or stirring, and the chemical action caused by the surface treatment composition.

[0150] In the method (i) above, the method for bringing the surface treatment composition into contact with the polished object is not particularly limited. An example of this is: flowing the surface treatment composition from a nozzle onto the polished object. , a rotary type that rotates the ground object to be polished at high speed; a spray type that sprays the surface treatment composition on the ground object and cleans it, etc.

[0151] From the perspective of more efficient removal of contamination in a short period of time, the cleaning treatment is preferably a rotary type or a spray type, and more preferably a rotary type.

[0152] As devices for performing such cleaning treatment, there are the following: a batch cleaning device, which simultaneously performs surface treatment on a plurality of polished grinding objects stored in a box; and a single-piece cleaning device, which In this method, a polished polishing object is mounted on a holder and surface treated. From the viewpoint of shortening the cleaning time, it is better to use a single-chip cleaning device.

[0153] Furthermore, an example of a device for performing the cleaning process is a polishing device that is equipped with a self-polishing platen (pressing plate). After removing the polished object to be polished, the object is cleaned by rubbing the object with a cleaning brush. Use equipment. By using this kind of grinding device, the grinding object can be cleaned more efficiently.

[0154] As such a polishing device, a general polishing device having a holder for holding the polished object to be polished, a motor capable of changing the rotation speed, a cleaning brush, etc. can be used. As the polishing device, either a single-side polishing device or a double-side polishing device can be used. Furthermore, when a flushing and grinding step is performed after the CMP step, it is more efficient and preferable to use the same grinding device as that used in the flushing and grinding step to perform the cleaning process.

[0155] The cleaning brush is not particularly limited, but is preferably made of resin. The material of the resin brush is not particularly limited, but PVA (polyvinyl alcohol) is preferred. The cleaning brush is preferably a sponge made of PVA.

[0156] The cleaning conditions are not particularly limited and can be appropriately set according to the type of surface treatment object (polished object) and the type and amount of residue to be removed. For example, the rotation speed of the cleaning brush is preferably not less than 10 rpm (0.17 s -1) and not more than 200 rpm (3.33 s -1), and the rotation speed of the object to be washed is preferably not less than 10 rpm (0.17 s -1) and not more than 100 rpm. rpm (1.67 s -1) or less. The method of supplying the surface treatment composition to the cleaning brush is not particularly limited. For example, a method of continuously supplying the composition using a pump (flushing) can be used. There is no limit to the supply amount, but it is preferable that the surface of the cleaning brush and the object to be cleaned is always covered with the surface treatment composition, and it is preferably 10 mL / min or more and 5000 mL / min or less. The cleaning time is not particularly limited, but the step of using the surface treatment composition of one aspect of the present invention is preferably 5 seconds or more and 180 seconds or less. If it is within this range, foreign matter can be removed more effectively.

[0157] The temperature of the surface treatment composition during cleaning is not particularly limited. It can usually be room temperature, or it can be heated to about 40°C or above and below 70°C within the range that does not impair the performance.

[0158] In the method (ii) above, the conditions for the cleaning method using immersion are not particularly limited, and known methods can be used.

[0159] Before surface treatment by the method (I) or (II) above, water can also be used for cleaning.

[0160] (After cleaning treatment) Furthermore, as the surface treatment method, it is preferable to further perform a cleaning treatment on the polished object after the surface treatment of (I) or (II) using the surface treatment composition of the present invention. In this specification, this cleaning process is called post-cleaning process. The post-cleaning treatment is not particularly limited, and examples include a method of only flushing the surface treatment object with water, a method of only immersing the surface treatment object in water, and the like. In addition, similar to the surface treatment using the method (II) described above, the following method can be exemplified: while maintaining the state of the surface treatment target object, the cleaning brush is applied to one or both sides of the surface treatment target object. Surface contact, one side supplies water or aqueous solution (such as NH 3 aqueous solution) to the contact part, or one side supplies water and aqueous solution (such as NH 3 aqueous solution), while using a cleaning brush to rub the surface of the surface treatment object (brush cleaning); a method of immersing the surface treatment object in water and performing ultrasonic treatment or stirring (immersion type). Among them, it is preferable to keep the surface treatment object in a state of keeping the surface treatment object in contact with one or both sides of the surface treatment object, and supply water or an aqueous solution (for example, NH 3 aqueous solution) to the contact part. , or a method of supplying water and aqueous solution (such as NH 3 aqueous solution) in any order (supplying water after supplying aqueous solution, or supplying water after supplying NH 3 aqueous solution), while rubbing the surface of the surface treatment object with a cleaning brush. Furthermore, as for the equipment and conditions of post-cleaning treatment, please refer to the description of surface treatment in (II) above. Here, as the water used in the post-cleaning treatment, it is particularly preferable to use deionized water.

[0161] By performing surface treatment with the surface treatment composition of one aspect of the present invention, residues can be easily removed. Therefore, by performing surface treatment using the surface treatment composition for surface treatment according to one aspect of the present invention, and then further washing the surface with water, the residue can be effectively removed.

[0162] [Manufacturing method of semiconductor substrate] The surface treatment method of the present invention can be suitably applied when the polished object is a polished semiconductor substrate. That is, the present invention also provides a method for manufacturing a semiconductor substrate, wherein the polished object is a polished semiconductor substrate. The method for manufacturing the semiconductor substrate includes the following steps: polishing the polished semiconductor substrate through the above-mentioned surface Treatment method to reduce residue on the surface of the polished semiconductor substrate.

[0163] At this time, the ground object includes at least one of silicon nitride, silicon oxide, and polycrystalline silicon. That is, the present invention also provides a method of manufacturing a semiconductor substrate, in which the polished object is a polished semiconductor substrate. The method of manufacturing the semiconductor substrate includes the following steps: a polishing step, which is performed by using a polishing machine containing abrasive grains. Using a composition to grind a pre-polished semiconductor substrate containing at least one selected from the group consisting of silicon nitride, silicon oxide, and polycrystalline silicon to obtain a ground semiconductor substrate; and a surface treatment step using the present invention The surface treatment composition reduces the residue containing the abrasive grains on the surface of the above-ground semiconductor substrate.

[0164] Details of the semiconductor substrate to which this manufacturing method is applied are as described in the description of the polished object subjected to surface treatment using the above-mentioned surface treatment composition.

[0165] Furthermore, the manufacturing method of a semiconductor substrate is not particularly limited as long as it includes a step (surface treatment step) of surface-treating the ground surface of the semiconductor substrate using the surface treatment composition of the present invention. Examples of this manufacturing method include a method including a polishing step and a cleaning step to form a polished semiconductor substrate. Furthermore, as another example, a method including, in addition to the grinding step and the washing step, a rinse grinding step between the grinding step and the washing step can be cited. Each of these steps is explained below.

[0166] <Grinding step> The polishing step that may be included in the manufacturing method of a semiconductor substrate is a step of polishing the semiconductor substrate to form a polished semiconductor substrate.

[0167] The polishing step is not particularly limited as long as it is a step of polishing the semiconductor substrate, and is preferably a chemical mechanical polishing (CMP, Chemical Mechanical Polishing) step. In addition, the grinding step may be a grinding step including a single step, or a grinding step including a plurality of steps. As a polishing step including a plurality of steps, for example, a pre-grinding step (coarse polishing step) is followed by a fine polishing step; or a polishing step is followed by one or two or more secondary polishing steps. , followed by the steps of fine grinding and so on. The surface treatment step using the surface treatment composition of the present invention is preferably performed after the above-mentioned fine grinding step.

[0168] As the polishing composition, a known polishing composition can be appropriately used according to the characteristics of the semiconductor substrate. The polishing composition is not particularly limited, and examples thereof include a polishing composition containing abrasive grains, a water-soluble polymer, a pH adjuster, and a solvent.

[0169] The abrasive particles may be any of inorganic particles, organic particles, and organic-inorganic composite particles. Specific examples of the inorganic particles include particles containing metal oxides such as silicon dioxide, aluminum oxide, cerium oxide, and titanium oxide, silicon nitride particles, silicon carbide particles, and boron nitride particles. Specific examples of organic particles include polymethylmethacrylate (PMMA) particles. In addition, a commercially available product or a synthetic product may be used as this abrasive grain. Furthermore, in this specification, unless otherwise mentioned, abrasive particles refer to those without surface modification. One type of abrasive grain may be used alone, or two or more types may be used in combination. Among these abrasive particles, silica is preferred, and colloidal silica is more preferred.

[0170] The lower limit of the average primary particle size of the abrasive grains is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more, particularly preferably 30 nm or more. If it is within this range, a high grinding speed can be maintained, so it can be suitably used in the rough grinding step. Furthermore, the upper limit of the average primary particle size of the abrasive grains is preferably 200 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. In some aspects, the average primary particle size may be below 75 nm, below 60 nm, or below 50 nm. If it is within this range, the occurrence of defects on the surface of the polished object after polishing can be further suppressed. In addition, the average primary particle diameter of abrasive grains is calculated based on the specific surface area of ​​abrasive grains measured by BET method, for example.

[0171] The lower limit of the average secondary particle size of the abrasive grains is preferably 15 nm or more, more preferably 30 nm or more, further preferably 40 nm or more, further preferably 50 nm or more, and particularly preferably 60 nm or more. If it is within this range, a higher grinding speed can be maintained. Furthermore, the upper limit of the average secondary particle size of the abrasive grains is preferably 300 nm or less, more preferably 200 nm or less, further preferably 150 nm or less, further preferably 100 nm or less, and particularly preferably 80 nm or less. If it is within this range, the occurrence of defects on the surface of the polished object after polishing can be further suppressed. The average secondary particle size of the abrasive grains can be measured by dynamic light scattering. For example, model "FPAR-1000" manufactured by Otsuka Electronics Co., Ltd. or its equivalent can be used for measurement.

[0172] When the polishing composition is directly used as a polishing liquid, the content of the abrasive grains relative to the polishing composition is preferably 0.1 mass% or more, more preferably 0.4 mass% or more, and further preferably 1.0 mass%. above. As the content of abrasive grains increases, the grinding speed increases. In addition, when the polishing composition is directly used as a polishing liquid, from the viewpoint of preventing scratches, etc., the content of the abrasive grains is usually 10% by mass or less, preferably 5% by mass or less, and more preferably 5% by mass or less. 3% by mass or less, more preferably 2% by mass or less. From an economic point of view, it is also better to reduce the content of abrasive particles. Furthermore, when two or more abrasive grains are used in combination, the above content refers to the total content of two or more abrasive grains.

[0173] Examples of water-soluble polymers include cellulose derivatives, starch derivatives, polymers containing oxyalkylene units, polymers containing nitrogen atoms, vinyl alcohol-based polymers, and the like. Specific examples include: hydroxyethyl cellulose, pullulan, random copolymers or block copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, acetalized polyvinyl alcohol, vinyl alcohol Copolymers with alkylene oxide, polyisoprene sulfonic acid, polyethylene sulfonic acid, polyallylsulfonic acid, polyisopentene sulfonic acid, polystyrene sulfonate, polyacrylate, polyvinyl acetate , polyethylene glycol, polyvinyl imidazole, polyvinyl carbazole, polyvinylpyrrolidone, polyethylene caprolactam, polyethylene piperidine, polyacrylamide, polyhydroxyacrylamide, etc. One type of water-soluble polymer may be used alone or two or more types may be used in combination. The polishing composition disclosed here can be preferably implemented even if it contains substantially no water-soluble polymer, that is, at least intentionally contains no water-soluble polymer.

[0174] When the polishing composition is directly used as a polishing liquid, the content of the water-soluble polymer is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and further preferably 0.2 mass% relative to the polishing composition. %above. Moreover, when the polishing composition is directly used as a polishing liquid, the content is preferably 3 mass% or less, more preferably 2 mass% or less, and still more preferably 1 mass% or less. Furthermore, when two or more water-soluble polymers are used in combination, the above content refers to the total content of two or more water-soluble polymers.

[0175] The pH adjuster and the solvent are the same as those specified in the above-mentioned items <pH adjuster ((D) component)> and <solvent>, respectively, so descriptions are omitted here. Among them, the pH adjuster is preferably potassium hydroxide, sodium hydroxide, or ammonia, and more preferably ammonia. Moreover, it is preferable that a solvent contains water, and it is more preferable that it is only water.

[0176] When the polishing composition is directly used as a polishing liquid, the pH value of the polishing composition is preferably higher than the pH value of the surface treatment composition of the present invention (exceeding 8.0), more preferably 8.5 or above, and further More preferably, it is 9.5 or more, and particularly preferably, it is 10.0 or more. If the pH value of the grinding composition increases, the grinding speed increases. On the other hand, when the polishing composition is directly used as a polishing liquid, the pH value of the polishing composition is preferably 12.0 or less, more preferably 11.5 or less. If the pH value of the polishing composition is 12.0 or less, the dissolution of the abrasive grains can be suppressed and the reduction of the mechanical polishing effect caused by the abrasive grains can be prevented. In addition, the pH value of the polishing composition was measured by the method described in the Examples.

[0177] As the polishing device, a general polishing device can be used, which is equipped with a holder for holding the polishing object, a motor that can change the rotation speed, etc., and a polishing platen to which a polishing pad (polishing cloth) can be attached. As the polishing device, either a single-side polishing device or a double-side polishing device can be used.

[0178] As the polishing pad, general nonwoven fabrics, polyurethane, porous fluororesin, etc. can be used without particular limitation. It is preferred that the polishing pad be provided with grooves for accumulating polishing liquid.

[0179] There are no special restrictions on the grinding conditions. For example, the rotation speed of the grinding platen and the grinding head (carrier) are preferably above 10 rpm (0.17 s -1) and below 100 rpm (1.67 s -1). For the grinding object The applied pressure (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 method of continuously supplying the polishing composition using a pump (flush pouring) can be used. There is no limit to the supply amount, but it is preferable that the surface of the polishing pad is always covered with the polishing composition, and it is preferably 10 mL / min or more and 5000 mL / min or less. The polishing time is not particularly limited, but the step of using the polishing composition is preferably 5 seconds or more and 180 seconds or less.

[0180] <Surface treatment steps> The surface treatment step refers to the step of using the surface treatment composition of the present invention to reduce the residue on the surface of the polished object. In the manufacturing method of a semiconductor substrate, a cleaning step as a surface treatment step may be performed after the rinsing and polishing step, or only the rinsing and polishing step, or only the cleaning step may be performed.

[0181] (rinsing and grinding step) The rinse and grinding step can also be provided between the grinding step and the cleaning step in the manufacturing method of the semiconductor substrate. The rinse polishing step is a step of reducing foreign matter on the surface of the polished polishing object (polished semiconductor substrate) by using the surface treatment method (rinsing polishing treatment method) of one aspect of the present invention.

[0182] Details of the rinse-grinding method used in the rinse-grinding step are as described in the above description of the rinse-grinding process.

[0183] (washing step) In the manufacturing method of the semiconductor substrate, the cleaning step can be provided after the grinding step or after the rinsing and grinding step. The cleaning step is a step of reducing foreign matter on the surface of the polished object (polished semiconductor substrate) by using the surface treatment method (cleaning method) of one aspect of the present invention.

[0184] The details of the washing method used in the washing step are the same as those in the above (post-washing treatment).

[0185] The embodiments of the present invention have been described in detail above. They are illustrative and illustrative and are not limiting. It is clear that the scope of the present invention should be interpreted in accordance with the appended patent application scope.

[0186] The present invention includes the following aspects and forms. 1. A surface treatment composition, which contains the following (A) ~ (C) components, and has a pH value exceeding 7.0: (A) Component: a quaternary nitrogen-containing onium salt compound having at least one of a linear or branched alkyl group with 7 or more carbon atoms and a linear or branched alkenyl group with 7 or more carbon atoms. (B) Ingredient: nonionic polymer (C) Component: Buffer represented by the formula: A-COO -NH 4 + (A is an alkyl group or phenyl group with a carbon number of 1 to 10). 2. The surface treatment composition as described in 1. above, wherein the content ratio of the component (A) to the component (C) is a mass ratio of 0.01 to 1.0. 3. The surface treatment composition as described in 1. or 2. above, wherein the content ratio of the component (A) to the component (B) is a mass ratio of 0.01 to 200. 4. The surface treatment composition as described in any one of the above 1. to 3., wherein the above-mentioned quaternary nitrogen-containing onium salt compound is a quaternary ammonium salt compound represented by the following formula (a): In the above formula (a), R 11 is a linear or branched chain alkyl group with a carbon number of 9 or more and 15 or less, R 12, R 13 and R 14 are each independently a linear or branched chain alkyl group or a benzyl group with a carbon number of 1 or more and 6 or less; X is an anion. 5. The surface treatment composition according to any one of 1. to 4. above, wherein the weight average molecular weight of the nonionic polymer is 10,000 or more. 6. The surface treatment composition as described in any one of 1. to 5. above, wherein the nonionic polymer contains polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyN-ethylene At least one of the group consisting of acetamide, polyethylene glycol, hydroxyethyl cellulose and butylene glycol-vinyl alcohol copolymer. 7. The surface treatment composition according to any one of 1. to 6. above, wherein the buffering agent is ammonium acetate. 8. The surface treatment composition according to any one of 1. to 7. above, which does not substantially contain abrasive particles. 9. The surface treatment composition according to any one of 1. to 8. above, further comprising the following component (D): (D) component: pH adjuster. 10. The surface treatment composition as described in 9. above, wherein the pH adjuster is ammonia. 11. A surface treatment method using the surface treatment composition as described in any one of 1. to 10. above, containing at least one member selected from the group consisting of silicon nitride, silicon oxide, and polycrystalline silicon. Surface treatment is performed on the ground grinding object to reduce residues on the surface of the ground grinding object. 12. The surface treatment method described in 11. above, which is a flushing and grinding treatment method or a cleaning treatment method. 13. A method of manufacturing a semiconductor substrate, wherein the ground object is a ground semiconductor substrate. The method of manufacturing the semiconductor substrate includes the following steps: The polishing step is to polish a pre-polished semiconductor substrate containing at least one selected from the group consisting of silicon nitride, silicon oxide, and polycrystalline silicon using a polishing composition containing abrasive grains to obtain a polished semiconductor substrate. Semiconductor substrates; and The surface treatment step uses the surface treatment composition as described in any one of 1. to 10. above to reduce the residue containing the abrasive grains on the surface of the above-ground semiconductor substrate. 14. The method for manufacturing a semiconductor substrate as described in 13. above, wherein the pH value of the polishing composition is 8.5 or more. [Example]

[0187] The present invention will be described in more detail using the following Examples and Comparative Examples. However, the technical scope of the present invention is not limited to the following examples. Furthermore, unless otherwise specified, "%" and "parts" mean "mass %" and "mass parts" respectively. In addition, in the following examples, unless otherwise stated, the operation was performed under the conditions of room temperature (25° C.) / relative humidity of 40% RH or more and 50% RH or less.

[0188] [Preparation of (A)~(D) ingredients] Prepare the following ingredients (A)~(D).

[0189] <(A) Ingredient: Quaternary nitrogen-containing onium salt compound> Lauryldimethylbenzylammonium chloride, molecular weight 340: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., product name: CATIOGEN (registered trademark) BC-50 Dodecyl ethyl dimethyl ammonium ethyl sulfate, molecular weight 368: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., product name: CATIOGEN (registered trademark) ES-L Methyl tri-n-octyl ammonium chloride, molecular weight 404: manufactured by Fujifilm Wako Pure Chemical Co., Ltd. Trimethylstearyl ammonium chloride, molecular weight 348: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., product name: CATIOGEN (registered trademark) TMS Dioleyldimethylammonium chloride, molecular weight 582: manufactured by NOF Co., Ltd., product name: NISSAN CATION (registered trademark) 2-OLR 1-Methyl-1-hydroxyethyl-2-tallow alkyl-imidazolinium chloride: manufactured by NOF Co., Ltd., product name: NISSAN CATION (registered trademark) AR-4.

[0190] <(A') Ingredient: Other chlorine compounds> Tetradecylamine acetate, molecular weight 273: manufactured by NOF Co., Ltd., product name: NISSAN CATION (registered trademark) MA.

[0191] <(B) Component: Nonionic polymer> Polyvinyl alcohol (PVA), Mw=10,000: Manufactured by JAPAN VAM & POVAL Co., Ltd., product name: JMR (registered trademark)-10HH Polyvinyl alcohol (PVA), Mw=5,000: Manufactured by JAPAN VAM & POVAL Co., Ltd., product name: JMR (registered trademark)-3HH Polyvinylpyrrolidone (PVP), Mw=45,000: Manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., product name: PITZCOL (registered trademark) K30A.

[0192] <(B')Ingredients: other polymers> Polyammonium acrylate (PAA), Mw=6,000: Manufactured by Dong Ya Gosei Co., Ltd., product name: A-30SL Polyethyleneimine, Mw=10,000: Manufactured by Nippon Shokubai Co., Ltd., product name: EPOMIN (registered trademark) SP-200.

[0193] <(C) Ingredients: pH buffer> Ammonium acetate, molecular weight 77: manufactured by Kanto Chemical Co., Ltd.

[0194] <(C') Ingredient: Other pH buffering agents> Diammonium hydrogen phosphate, molecular weight 132: manufactured by Fujifilm Wako Pure Chemical Co., Ltd. Ammonium bicarbonate, molecular weight 79: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0195] <(D) Ingredient: pH adjuster> Ammonia, molecular weight 17: manufactured by Kanto Chemical Co., Ltd., product name: EL ammonia.

[0196] [Measurement of weight average molecular weight (Mw)] The weight average molecular weight (Mw) of the said (B) component and (B') component is measured by the following method.

[0197] The weight average molecular weight (Mw) of component (B) and (B') component uses the value of the weight average molecular weight (polyethylene glycol conversion) measured by gel permeation chromatography (GPC). The weight average molecular weight is measured using the following equipment and conditions: GPC device: manufactured by Shimadzu Corporation Model: Prominence+ELSD (Evaporative Light Scattering Detector, evaporative light scattering detector) detector (ELSD-LTII) Column: VP-ODS (manufactured by Shimadzu Corporation) Mobile phase A: MeOH B: Acetic acid 1% aqueous solution Flow:1mL / min Detector: ELSD temperature 40℃, gain 8, nitrogen 350 kPa Oven temperature: 40℃ Injection volume: 40 μL.

[0198] [Measurement of pH value of surface treatment composition] The pH value of the surface treatment composition (liquid temperature: 25°C) was confirmed using a pH meter (manufactured by Horiba Manufacturing Co., Ltd., product name: LAQUA (registered trademark)). In addition, the pH value of the polishing composition described below was also measured by the same method.

[0199] [Preparation of surface treatment composition] (Example 1) Using lauryldimethylbenzylammonium chloride as component (A), polyvinyl alcohol (Mw=10,000) as component (B), ammonium acetate as component (C), ammonia as component (D), and distilled water as a solvent were stirred and mixed at 25° C. for 5 minutes, thereby preparing surface treatment composition 1.

[0200] Here, the content of each component is set as follows: relative to the total amount of surface treatment composition 1, the content of component (A) is set to 0.01 mass % (0.1 g / L), and the content of component (B) is set to 0.10% by mass (1 g / L), the content of component (C) is set to 0.25% by mass (2.5 g / L), and the content of component (D) (pH value adjuster) is set to the pH value of surface treatment composition 1 Become a 9.0.

[0201] (Examples 2 and 3) Surface treatment compositions were prepared in the same manner as in Example 1, except that the content (added amount) of component (D) was changed so that the pH value of each surface treatment composition became the value described in Table 1 below. 2 and 3.

[0202] (Example 4) Surface treatment composition 4 was prepared in the same manner as in Example 1, except that the content of component (A) was changed as shown in Table 1 below.

[0203] (Example 5) Surface treatment composition 5 was prepared in the same manner as in Example 1, except that the content of component (B) was changed as shown in Table 1 below.

[0204] (Example 6) Surface treatment composition 6 was prepared in the same manner as in Example 1, except that polyvinyl alcohol (Mw=10,000) as component (B) was changed to polyvinyl alcohol (Mw=5,000).

[0205] (Example 7) Surface treatment composition 7 was prepared in the same manner as in Example 1, except that polyvinyl alcohol (Mw=10,000) as component (B) was changed to polyvinylpyrrolidone (Mw=45,000).

[0206] (Example 8) A surface treatment composition was prepared in the same manner as in Example 1, except that lauryldimethylbenzylammonium chloride as the component (A) was changed to dodecylethyldimethylammonium ethyl sulfate. 8.

[0207] (Example 9) A surface treatment composition was prepared in the same manner as in Example 4, except that lauryldimethylbenzylammonium chloride as the component (A) was changed to dodecylethyldimethylammonium ethyl sulfate. 9.

[0208] (Example 10) A surface treatment composition was prepared in the same manner as in Example 7, except that lauryldimethylbenzylammonium chloride as the component (A) was changed to dodecylethyldimethylammonium ethyl sulfate. 10.

[0209] (Examples 11, 13, 15 and 17) Surface treatment compositions 11, 13, 15 and 17 were prepared in the same manner as in Example 1, except that the lauryldimethylbenzylammonium chloride as component (A) was changed to that described in Table 1. .

[0210] (Examples 12, 14, 16 and 18) Surface treatment compositions 12, 14, 16 and 18 were prepared in the same manner as in Example 7, except that the lauryldimethylbenzylammonium chloride as component (A) was changed to that described in Table 1. .

[0211] (Comparative example 1) Surface treatment composition 19 was prepared by stirring and mixing lauryldimethylbenzylammonium chloride as component (A), ammonia as component (D), and distilled water as solvent at 25° C. for 5 minutes.

[0212] Here, the content of each component is as follows: relative to the total amount of the surface treatment composition 19, the content of the component (A) is 0.01 mass % (0.1 g / L), and the content of the component (D) is 0.01% by mass (0.1 g / L). The pH value of the surface treatment composition 19 is 9.0.

[0213] (Comparative example 2) Surface treatment composition 20 was prepared by stirring and mixing polyvinyl alcohol (Mw=10,000) as component (B), ammonia as component (D), and distilled water as solvent at 25° C. for 5 minutes.

[0214] Here, the content of each component is set as follows: relative to the total amount of the surface treatment composition 20, the content of the component (B) is set to 0.10 mass % (1 g / L), and the content of the component (D) is set to The pH value of the surface treatment composition 20 is set to 9.0.

[0215] (Comparative Examples 3~5) Surface treatment compositions 21 to 23 were prepared in the same manner as in Example 1, except that component (B), component (A) and component (C) were not added respectively.

[0216] (Comparative Examples 6 and 7) Surface treatment compositions were prepared in the same manner as in Example 1, except that the ammonium acetate as component (C) was changed to that described in Table 1, and the addition amount was changed to that described in Table 1. 24 and 25.

[0217] (Comparative example 8) Surface treatment composition 26 was prepared in the same manner as in Example 1, except that lauryldimethylbenzylammonium chloride as the component (A) was changed to myristylamine acetate.

[0218] (Comparative Example 9) Surface treatment composition 27 was prepared in the same manner as in Example 7, except that lauryldimethylbenzylammonium chloride as the component (A) was changed to myristylamine acetate.

[0219] (Comparative Examples 10 and 11) Surface treatment compositions 28 and 29 were prepared in the same manner as in Example 1, except that polyvinyl alcohol (Mw=10,000) as component (B) was changed to that described in Table 1. In addition, the components contained in the surface treatment composition 28 were aggregated, and the following evaluation could not be performed.

[0220] Furthermore, the surface treatment compositions 1 to 29 prepared above do not contain abrasive particles (content of abrasive particles = 0% by mass).

[0221] Table 1 NO. (A) component or (A') component (B)component or (B')component (C)component or (C')component (D)Ingredients (A)component / (B)component (A)component / (C)component pH value compound molecular weight Content [quality%] compound molecular weight Ionicity Content [quality%] Buffer Content [quality%] pH adjuster [-] Example 1 1 Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 2 2 Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 8.0 Example 3 3 Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 10.0 Example 4 4 Lauryldimethylbenzylammonium chloride 325 0.1 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 1.0 0.4 9.0 Example 5 5 Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.0001 Ammonium acetate 0.25 Ammonia 100 0.04 9.0 Example 6 6 Lauryldimethylbenzylammonium chloride 325 0.01 PVA 5,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 7 7 Lauryldimethylbenzylammonium chloride 325 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 8 8 Dodecyl ethyl dimethyl ammonium ethyl sulfate 368 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 9 9 Dodecyl ethyl dimethyl ammonium ethyl sulfate 368 0.1 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 1.0 0.4 9.0 Example 10 10 Dodecyl ethyl dimethyl ammonium ethyl sulfate 368 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 11 11 Methyl trioctyl ammonium chloride 404 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 12 12 Methyl trioctyl ammonium chloride 404 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 13 13 Trimethylstearyl ammonium chloride 348 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 14 14 Trimethylstearyl ammonium chloride 348 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 15 15 dioleyldimethylammonium chloride 546 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 16 16 dioleyldimethylammonium chloride 546 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0

[0222] Table 1 (continued) NO. (A) component or (A') component (B)component or (B')component (C)component or (C')component (D)Ingredients (A)component / (B)component (A)component / (C)component pH value compound molecular weight Content [quality%] compound molecular weight Ionicity Content [quality%] Buffer Content [quality%] pH adjuster [-] Example 17 17 1-Methyl-1-hydroxyethyl-2-tallowalkyl-imidazolinium chloride NA 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Example 18 18 1-Methyl-1-hydroxyethyl-2-tallowalkyl-imidazolinium chloride NA 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Comparative example 1 19 Lauryldimethylbenzylammonium chloride 325 0.01 - - - - - - Ammonia - - 9.0 Comparative example 2 20 - - - PVA 10,000 Nonionic 0.1 - - Ammonia - - 9.0 Comparative example 3 twenty one Lauryldimethylbenzylammonium chloride 325 0.01 - - - - Ammonium acetate 0.25 Ammonia - 0.04 9.0 Comparative example 4 twenty two - - - PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia - - 9.0 Comparative example 5 twenty three Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.1 - - Ammonia 0.1 - 9.0 Comparative example 6 twenty four Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.1 Diammonium hydrogen phosphate 0.2 Ammonia 0.1 0.05 9.0 Comparative example 7 25 Lauryldimethylbenzylammonium chloride 325 0.01 PVA 10,000 Nonionic 0.1 ammonium bicarbonate 0.23 Ammonia 0.1 0.04 9.0 Comparative example 8 26 Tetradecylamine acetate 245 0.01 PVA 10,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Comparative example 9 27 Tetradecylamine acetate 245 0.01 PVP 45,000 Nonionic 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Comparative example 10 28 Lauryldimethylbenzylammonium chloride 325 0.01 PAA 6,000 anion 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0 Comparative example 11 29 Lauryldimethylbenzylammonium chloride 325 0.01 Polyethyleneimine 10,000 cation 0.1 Ammonium acetate 0.25 Ammonia 0.1 0.04 9.0

[0223] [Preparation of ground objects] A polished object to be polished (polished SiN substrate, polished polycrystalline Si substrate) polished by the following chemical mechanical polishing (CMP) step is prepared.

[0224] (CMP step) As the polishing object, prepare: silicon wafer (SiN substrate) (300 mm unpatterned wafer, manufactured by Advantec Co., Ltd.), which is formed with a thickness of 2500 Å on the surface by CVD (Chemical Vapor Deposition, chemical vapor deposition method) SiN film; and silicon wafer (polycrystalline Si substrate) (300 mm wafer, manufactured by Advance Materials Technology Co., Ltd.), which has a polycrystalline silicon film with a thickness of 5000 Å formed on the surface by CVD.

[0225] The SiN substrate and polycrystalline Si substrate prepared above were polished under the following conditions using the polishing composition of the following composition to obtain the polished polishing object (the polished SiN substrate and the polished polycrystalline Si substrate). crystalline Si substrate).

[0226] <Polishing composition> Prepare silica slurry (composition: colloidal silica (average primary particle diameter: 35 nm, average secondary particle diameter: 70 nm) 10% by mass, polyvinylpyrrolidone (PITZCOL (registered trademark) K30A, first Industrial Pharmaceutical Co., Ltd., Mw=45,000) 0.25 mass%, EL ammonia (concentration: 28.0%~30.0% (as NH 3)) (Kanto Chemical Co., Ltd.) 0.33 mass% (as NH 3), solvent: distilled water ). A polishing composition was prepared by diluting the above silica slurry 5 times with distilled water. The pH value of the polishing composition obtained was 10.0.

[0227] <Grinding device and grinding conditions> Grinding device: FREX300E manufactured by Ebara Seisakusho Co., Ltd. Polishing pad: Foamed polyurethane pad manufactured by FUJIBO HOLDINGS Co., Ltd. H800-Type1 Adjuster (trimmer): Nylon brush (manufactured by 3M Company) Grinding pressure: 2.0 psi (1 psi=6894.76 Pa, the same below) Grinding platen speed: 80 rpm Grinding head speed: 80 rpm Supply of grinding compositions: pouring Grinding composition supply volume: 200 mL / min Grinding time: 30 seconds.

[0228] [Rinse and grind] In the above CMP step, the surface of the polishing object (SiN substrate, polycrystalline Si substrate) is polished respectively, and then the polished polishing object (polished SiN substrate, polished polycrystalline Si substrate) is self-polished and pressed. Remove it from the plate (pressure plate). Then, in the same grinding device, the ground object was mounted on another grinding platen (pressing plate), and under the following conditions, each surface treatment composition prepared in the above examples and comparative examples was used. 1~29, rinse and grind the surface of the ground object.

[0229] <Rinsing and grinding device and flushing and grinding conditions> Grinding device: FREX300E manufactured by Ebara Seisakusho Co., Ltd. Polishing pad: Foamed polyurethane pad manufactured by FUJIBO HOLDINGS Co., Ltd. H800-Type1 Adjuster (trimmer): Nylon brush (manufactured by 3M Company) Grinding pressure: 1.0 psi Pressure plate speed: 80 rpm Grinding head speed: 80 rpm Supply of surface treatment composition: pouring Surface treatment composition supply volume: 300 mL / min Grinding time: 60 seconds.

[0230] [Post-washing treatment] After the rinse and grinding treatment, use a 0.3% NH 3 aqueous solution to clean the substrate surface with a brush for 20 seconds, and then use deionized water to clean it for 40 seconds, thereby obtaining a rinsed and polished grinding object (Usage Example and the rinsed and polished SiN substrates 1 to 29 of the surface treatment compositions 1 to 29 of the comparative examples, and the rinsed and polished polycrystalline Si substrates 1 to 29 of the surface treatment compositions 1 to 29 of the examples and comparative examples) .

[0231] [evaluate] (Residue evaluation) Under alkaline conditions, there are a large number of hydroxyl groups on the surface of the polycrystalline Si substrate, forming a water film on the surface. Therefore, defects (such as abrasive grain residues, pad dust, or organic residues such as polymers) are not easily attached or do not adhere to the surface of the polycrystalline Si substrate. On the other hand, defects (such as abrasive grain residue, pad dust, or organic residues such as polymers) easily adhere to the SiN substrate. Therefore, in this evaluation, the number of abrasive grain residues and the number of organic residues (pad chips, polymers, etc.) on the rinse-polished SiN substrate (SiN substrate after rinse-polishing treatment) were measured according to the following method. The results are shown in Table 2 below ("Number of defects on SiN" in the table).

[0232] The number of residues on the surface of the rinse-polished SiN substrate (polished SiN substrate after rinse-polishing treatment) was evaluated using the optical inspection machine Surfscan (registered trademark) SP5 manufactured by KLA-Tencor Co., Ltd. Specifically, the remaining portion other than the 5 mm wide portion (the area from 0 mm to 5 mm when the outer peripheral end is set to 0 mm) is removed from the outer peripheral end of one side of the rinsed and polished SiN substrate, Count the number of residues with a diameter exceeding 50 nm. Thereafter, the number of abrasive grain residues and the number of organic residues were measured by SEM observation using Review SEM RS6000 manufactured by Hitachi High-Technology Co., Ltd. about the rinsed and polished SiN substrate. First, through SEM observation, 100 pieces of residues present in the remaining portion except for the 5 mm wide portion removed from the outer peripheral end of one side of the rinsed and polished SiN substrate were sampled. Then, from the 100 residues sampled, the type of residue (abrasive grains or organic residues) was determined by visual SEM observation, and the abrasive grain residues (SiO 2 residues) and organic residues (pad chips or polymers) were analyzed. etc.) to determine their number. Furthermore, the number of abrasive grain residues (SiO 2 residues) is preferably as small as possible, and is acceptable if it is 30 or less, preferably 25 or less, and more preferably less than 20. It is also preferable to keep organic residues (mat chips, polymers, etc.) as small as possible. If it is less than 15, it is acceptable, preferably 10 or less, and more preferably 5 or less.

[0233] (Evaluation of zeta potential of abrasive grains) According to the following method, the zeta potential of the abrasive particles (colloidal silica, SiO 2) in each surface treatment composition was measured. The results are shown in Table 2 below ("ζ potential abrasive grain [mV]" in the table).

[0234] The zeta potential of the abrasive grain is a value measured by Zetasizer Nano ZSP manufactured by Spectris Co., Ltd. (Malvern Division). The zeta potential of the abrasive grains in rinse polishing using the surface treatment composition was set to the value measured in the model experiment described below.

[0235] To each surface treatment composition, a silica (SiO 2 ) particle dispersion (colloidal silica, average primary particle diameter: 35 nm, average secondary particle diameter) was added so that the silica particle concentration became 0.02% by mass. :70 nm, 19.5 mass% aqueous dispersion), prepare a measurement liquid with a silica particle concentration of 0.02 mass% (the content (concentration) of silica particles in the measurement liquid is 0.02 mass% relative to the total mass of the measurement liquid) . The obtained measurement liquid was filled into the special measurement tank of the above-mentioned device (Zetasizer Nano ZSP), and the zeta potential (mV) of the abrasive grains was measured. If the zeta potential (mV) of the abrasive grain is 30 mV or more, it is acceptable.

[0236] (Ze potential evaluation of SiN substrate and pad chips) The zeta potential of silicon nitride (SiN substrate) and padding (polyurethane) in each surface treatment composition was measured. The results are shown in Table 2 below ("ζ potential SiN [mV]" and "ζ potential pad [mV]" in the table). Furthermore, it is speculated that the zeta potential of silicon nitride will have a greater impact on the residue removal effect compared with the zeta potential of polycrystalline silicon. Therefore, in this evaluation, the zeta potential of the SiN substrate in the surface treatment composition was measured.

[0237] The zeta potential of the polished SiN substrate and the zeta potential of the pad chips were measured using a solid zeta potential measuring device SurPASS3 (zeta potentiometer) manufactured by Anton Paar Japan Co., Ltd., respectively. The zeta potential of the polished SiN substrate surface in rinse polishing using the surface treatment composition and the zeta potential of the pad chips in rinse polishing using the surface treatment composition were respectively set to values ​​measured in the model experiment described below. .

[0238] The zeta potential of the polished SiN substrate surface was measured using a silicon wafer (SiN substrate) (300 mm unpatterned wafer, manufactured by Advantec Co., Ltd.) cut into 60 mm square as the measurement object. The silicon wafer was borrowed from A SiN film with a thickness of 2500 Å is formed on the surface by CVD.

[0239] The zeta potential of the pad chips was measured using a polyurethane pad (foamed polyurethane pad, H800-Type1 manufactured by FUJIBO HOLDINGS Co., Ltd.) cut into 60 mm squares as the measurement object.

[0240] Each of these measurement objects is installed in a zeta potentiometer. Then, the surface treatment composition prepared above is passed into the object to be measured, and the zeta potential (mV) of the object to be measured is measured respectively.

[0241] (Etching rate evaluation) The etching rate of the polished SiN substrate in rinse polishing using each surface treatment composition and the etching rate of the polished polycrystalline Si substrate in rinse polishing using the surface treatment composition were respectively set to the following models. The value measured in the experiment. These equivalent values ​​are shown in Table 2 below ("SiN [Å / min]" and "Polycrystalline Si [Å / min]" in the table).

[0242] The etching rate of the polished SiN substrate was measured using a silicon wafer (SiN substrate) (300 mm unpatterned wafer, manufactured by Advantec Co., Ltd.) cut into 60 mm square as the measurement object. The silicon wafer was CVD forms a SiN film with a thickness of 2500 Å on the surface.

[0243] The etching rate of the polished polycrystalline Si substrate was measured using a silicon wafer (polycrystalline Si substrate) (300 mm, manufactured by Advance Materials Technology Co., Ltd.) cut into 60 mm square as the measurement object. The above-mentioned silicon wafer A polycrystalline silicon film with a thickness of 5000 Å is formed on the surface by CVD.

[0244] The thickness of the measurement objects (thickness before immersion (Å)) was measured using an optical film thickness measuring device (Lambda ACE VM-2030: manufactured by Dainippon Screen Manufacturing Co., Ltd.). Next, each of the measurement objects was immersed in the surface treatment composition prepared above for 30 minutes. Using an optical film thickness measuring device (Lambda ACE VM-2030: manufactured by Dainippon Screen Manufacturing Co., Ltd.), the thickness of the object to be measured (thickness after immersion (Å)) was measured after immersing for a specified time. By dividing the difference in thickness before and after immersion by the immersion time (min), the etching rate [= (thickness before immersion (Å) - thickness after immersion (Å)) / immersion time (min)] was calculated. Furthermore, the etching rate of the polished SiN substrate and the polished polycrystalline Si substrate is preferably as small as possible. If it does not reach 15 Å / min, it is acceptable. It is preferably less than 10 Å / min, and even more preferably it is not. up to 8 Å / min.

[0245] (ΔpH value evaluation) The difference in pH value (ΔpH value) of the surface treatment composition before and after the above-mentioned rinse polishing was measured on the SiN substrate as the polishing object [= (pH value of the surface treatment composition after rinse polishing) - (surface before rinse polishing) pH value of the treatment composition)]. Furthermore, the pH value of the surface treatment composition before flushing and polishing is the pH value of the surface treatment composition described in Table 1 above. These equivalent values ​​are shown in Table 2 below ("ΔpH value [-]" in the table). Furthermore, the ΔpH value (pH value change before and after rinsing and grinding) is preferably as small as possible. If it is less than 1.0, it is acceptable. It is preferably less than 0.8, and even more preferably less than 0.3.

[0246] Table 2 No. Zeta potential Number of defects on SiN ΔpH [-] Etch rate SiN [mV] abrasive grains [mV] Pad crumbs [mV] Abrasive grain residue [count] organic residue [count] Polycrystalline Si [Å / min] SiN [Å / min] Example 1 1 40 38 37 7 1 0 1 0 Example 2 2 40 38 37 10 4 0 0 0 Example 3 3 45 42 40 8 3 0 7 0 Example 4 4 38 35 34 16 8 0 1 0 Example 5 5 39 37 36 15 8 0 5 0 Example 6 6 38 37 34 14 9 0 3 0 Example 7 7 38 32 33 17 2 0 8 0 Example 8 8 30 31 30 28 3 0 5 0 Example 9 9 30 31 30 27 5 0 7 0 Example 10 10 32 31 31 28 6 0 9 0 Example 11 11 31 30 30 29 14 0 8 0 Example 12 12 32 30 31 28 13 0 9 0 Example 13 13 30 31 31 27 13 0 8 0 Example 14 14 31 31 32 27 14 0 9 0 Example 15 15 30 31 30 28 14 0 8 0 Example 16 16 31 31 32 29 14 0 9 0 Example 17 17 33 30 31 26 13 0 9 0 Example 18 18 30 30 31 27 14 0 8 0

[0247] Table 2 (continued) No. Zeta potential Number of defects on SiN ΔpH [-] Etch rate SiN [mV] abrasive grains [mV] Pad crumbs [mV] Abrasive grain residue [count] organic residue [count] Polycrystalline Si [Å / min] SiN [Å / min] Comparative example 1 19 twenty two twenty three twenty three 70 20 1.2 27 0 Comparative example 2 20 -38 -48 -30 85 25 1.2 20 0 Comparative example 3 twenty one twenty three twenty four twenty three 68 twenty one 0 16 0 Comparative example 4 twenty two -38 -48 -30 79 28 0 15 0 Comparative example 5 twenty three twenty four twenty one twenty three 31 18 1.2 twenty two 0 Comparative example 6 twenty four twenty three twenty two twenty four 31 16 0.8 17 0 Comparative example 7 25 twenty one twenty three twenty one 34 17 0.8 18 0 Comparative example 8 26 15 13 13 44 17 0 20 0 Comparative example 9 27 16 17 10 45 twenty one 0 25 0 Comparative example 10 28 Condensation occurs, so it cannot be prepared Comparative example 11 29 twenty three twenty one twenty two 77 60 0 10 0

[0248] As clearly seen from the above Table 2, the surface treatment composition according to the Example can fully remove the residue on the SiN substrate compared with the surface treatment composition of the Comparative Example. In addition, according to the surface treatment composition of the embodiment, the etching rate of the polycrystalline Si substrate can be suppressed to a low level. The above are the results of evaluation immediately after the surface treatment composition is produced. However, in the case of long-term preservation or storage, it is preferable to include an antifungal agent (preservative). Furthermore, antifungal agents (preservatives) have little or no influence on the above results. Therefore, the same results as above were observed for surface treatment compositions containing antifungal agents (preservatives).

[0249] In addition, Table 2 above shows the difference in pH value (ΔpH value) of the surface treatment composition before and after washing and polishing the SiN substrate as the polishing object. For the polycrystalline Si substrate or TEOS film as the polishing object, The difference in pH value of the surface treatment composition before and after rinse polishing is the same as the difference in pH value of the surface treatment composition before and after rinse polishing of the SiN substrate as the polishing object. This application is based on Japanese Patent Application No. 2022-053005 filed on March 29, 2022, and the entire disclosure thereof is incorporated into this specification by reference.

Claims

1. A surface treatment composition comprising the following components (A) to (C) and having a pH value exceeding 7.0: (A) Component: a quaternary nitrogen-containing onium salt compound having at least one of a straight-chain or branched alkyl group having 7 or more carbon atoms and a straight-chain or branched alkenyl group having 7 or more carbon atoms; (B) Component: a nonionic polymer; (C) Component: a buffer represented by the formula: A-COO-NH4+ (A is an alkyl group having 1 or more carbon atoms and less than 10 carbon atoms or a phenyl group).

2. The surface treatment composition of claim 1, wherein the content ratio of component (A) to component (C) is 0.01 or more and 1.0 or less by mass.

3. The surface treatment composition of claim 1 or 2, wherein the content ratio of component (A) to component (B) is 0.01 or more and 200 or less by mass.

4. The surface treatment composition of claim 1 or 2, wherein the molecular weight of the aforementioned fourth-order nitrogen-containing onium salt compound is less than 1,000.

5. The surface treatment composition of claim 1 or 2, wherein the aforementioned quaternary nitrogen-containing onium salt compound is a quaternary ammonium salt compound represented by the following formula (a): In the above formula (a), R11 is a straight-chain or branched alkyl group having 9 or more and 15 or less carbon atoms, R12, R13 and R14 are each independently a straight-chain or branched alkyl group or benzyl group having 1 or more and 6 or less carbon atoms; X is an anion.

6. The surface treatment composition of claim 1 or 2, wherein the weight average molecular weight of the nonionic polymer is 10,000 or more.

7. The surface treatment composition of claim 1 or 2, wherein the nonionic polymer comprises at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly(N-vinylacetamide), polyethylene glycol, hydroxyethyl cellulose, and butene glycol-vinyl alcohol copolymer.

8. The surface treatment composition of claim 1 or 2, wherein the buffer is ammonium acetate.

9. The surface treatment composition of claim 1 or 2 is substantially free of abrasive particles.

10. The surface treatment composition of claim 1 or 2 further comprises the following component (D): (D) component: pH adjuster.

11. The surface treatment composition of claim 10, wherein the pH adjuster is ammonia.

12. A surface treatment method comprising using a surface treatment composition as claimed in claim 1 or 2 to surface treat a polished abrasive object comprising at least one of silicon nitride, silicon oxide, and polycrystalline silicon, thereby reducing residue on the surface of the polished abrasive object.

13. The surface treatment method as described in claim 12 is a rinsing and grinding method or a cleaning method.

14. A method for manufacturing a semiconductor substrate, wherein the polished object is a polished semiconductor substrate, the method comprising the following steps: a polishing step, wherein a pre-polishing semiconductor substrate comprising at least one of silicon nitride, silicon oxide, and polycrystalline silicon is polished using a polishing composition comprising abrasive particles to obtain a polished semiconductor substrate; and a surface treatment step, wherein a surface treatment composition as claimed in claim 1 or 2 is used to reduce the residue comprising the abrasive particles on the surface of the polished semiconductor substrate.

15. The method for manufacturing a semiconductor substrate as claimed in claim 14, wherein the pH value of the polishing composition is 8.5 or higher.