Processing liquid for manufacturing semiconductor, method for cleaning object to be processed, and method for manufacturing semiconductor

Abstract

Provided is a processing liquid for semiconductor production, which has excellent ability to remove defects from a specific material when used for cleaning an object to be processed that contains at least one material (specific material) selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride. This processing liquid for semiconductor production contains a polycarboxylic acid and a polymer containing a repeating unit (A) derived from a nonionic monomer and a repeating unit (B) having an anionic group.

Description

Technical Field

[0001] The present invention relates to a processing liquid for semiconductor manufacturing, a method for cleaning a processed object, and a method for manufacturing a semiconductor. Background Art

[0002] In the development of semiconductor devices represented by semiconductor integrated circuits (LSI: large-scale integrated circuits), in order to achieve miniaturization and high speed, high density and high integration are required based on the miniaturization and lamination of wiring. Under these expectations, chemical mechanical polishing (CMP: chemical mechanical polishing) is used in the flattening of bare wafers, flattening of interlayer insulation films, formation of metal plugs, and formation of buried wiring in the manufacture of semiconductor devices.

[0003] In the CMP process, residues such as abrasive particles used in the CMP process, metal components of the polished wiring metal film and / or barrier metal, etc. may remain on the polished surface of the semiconductor substrate. Therefore, after the CMP process, a process using a processing liquid to remove these residues is usually performed.

[0004] In the manufacturing process of these semiconductor devices, there are various requirements for the characteristics and composition of the components used in the above-mentioned respective steps depending on the composition and application of the processed object.

[0005] Hereinafter, such a processing liquid used in the manufacturing process of a semiconductor device is also referred to as a "semiconductor manufacturing processing liquid."

[0006] For example, Patent Document 1 discloses a cleaning composition containing a predetermined organic acid, a fluoride compound, a polymer additive, and water.

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2022-009467 Summary of the invention

[0010] Technical issues to be solved by the invention

[0011] On the other hand, in recent years, there has been a demand for a processing liquid used in a workpiece that is commonly used as an insulating film and contains at least one selected from the group consisting of polycrystalline silicon (poly-Si), silicon carbide (SiC), and silicon carbonitride (SiCN). In particular, there is a demand for a processing liquid that is preferably used for cleaning the workpiece after CMP processing and polishing and cleaning the workpiece after CMP processing.

[0012] The present inventors have discovered that when the cleaning composition described in Patent Document 1 is applied to the cleaning of a workpiece (especially a workpiece containing a specific material after CMP treatment) comprising at least one material selected from the group consisting of polycrystalline silicon, silicon carbide and silicon carbonitride (hereinafter also referred to as "specific material"), the defect removal performance on the specific material needs to be further improved.

[0013] Therefore, an object of the present invention is to provide a processing liquid for semiconductor manufacturing that is excellent in defect removal performance on a specific material when used for cleaning a workpiece containing at least one (specific material) selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride.

[0014] Furthermore, the present invention aims to provide a method for cleaning an object to be processed and a method for manufacturing a semiconductor, which are related to the above-mentioned processing liquid for semiconductor manufacturing.

[0015] Means for solving technical problems

[0016] The present inventors have conducted intensive studies to solve the above-mentioned problems and have found that the problems can be solved by the following configuration.

[0017] [1] A processing liquid for semiconductor manufacturing, comprising:

[0018] Polycarboxylates; and

[0019] A polymer comprising a repeating unit A derived from a nonionic monomer and a repeating unit B having an anionic group.

[0020] [2] The semiconductor manufacturing processing liquid according to [1], wherein

[0021] The repeating unit A is a repeating unit represented by the formula (1) described below.

[0022] [3] The semiconductor manufacturing processing liquid according to [2], wherein:

[0023] L 1 Indicates -COO- or -CO-NR a -.

[0024] [4] The semiconductor manufacturing processing liquid according to any one of [1] to [3], wherein the ClogP of the nonionic monomer is -1.00 to 5.00.

[0025] [5] The semiconductor manufacturing processing liquid according to any one of [1] to [4], wherein the repeating unit B is a repeating unit represented by the formula (2) described below.

[0026] [6] The semiconductor manufacturing processing liquid according to any one of [1] to [5], wherein the anionic group is a carboxylic acid group, a sulfonic acid group or a phosphonic acid group.

[0027] [7] The semiconductor manufacturing processing liquid according to any one of [1] to [6], wherein the polycarboxylic acid has a hydroxyl group.

[0028] [8] The semiconductor manufacturing processing liquid according to any one of [1] to [7], wherein the weight average molecular weight of the polymer is 1,000 to 50,000.

[0029] [9] The semiconductor manufacturing processing liquid according to any one of [1] to [8], wherein the mass ratio of the content of the polycarboxylic acid to the content of the polymer is 1 to 30.

[0030]

[10] The semiconductor manufacturing processing liquid according to any one of [1] to [9], wherein the pH is 2.0 to 10.0.

[0031]

[11] The semiconductor manufacturing processing liquid according to any one of [1] to

[10] , further comprising an amino alcohol.

[0032]

[12] The semiconductor manufacturing processing liquid according to

[11] , wherein the amino alcohol has two or more hydroxyl groups.

[0033]

[13] The semiconductor manufacturing processing liquid according to

[11] or

[12] , wherein the mass ratio of the content of the polymer to the content of the amino alcohol is 0.005 to 0.5.

[0034]

[14] The semiconductor manufacturing processing liquid according to any one of [1] to

[13] , further comprising an antibacterial agent.

[0035]

[15] The semiconductor manufacturing process liquid according to

[14] , wherein the mass ratio of the content of the polymer to the content of the antibacterial agent is 5 to 100.

[0036]

[16] A semiconductor manufacturing processing liquid according to any one of [1] to

[15] , which is used for a processing object containing any one of polycrystalline silicon, silicon carbide and silicon carbonitride.

[0037]

[17] A method for cleaning a workpiece, comprising the steps of: using any one of the semiconductor manufacturing processing liquids described in [1] to

[15] to clean a workpiece containing at least one selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride.

[0038]

[18] A method for manufacturing a semiconductor, comprising the method for cleaning an object to be processed as described in

[17] .

[0039] Effects of the Invention

[0040] According to the present invention, a processing liquid for semiconductor manufacturing can be provided which is excellent in defect removal performance on a specific material when used for cleaning a workpiece containing at least one (specific material) selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride.

[0041] Furthermore, according to the present invention, a method for cleaning an object to be processed using the processing liquid for semiconductor manufacturing and a method for manufacturing a semiconductor can be provided. DETAILED DESCRIPTION

[0042] Hereinafter, the present invention will be described in detail.

[0043] The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0044] The meaning of each description in this specification is shown below.

[0045] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0046] The compounds described in the present specification may include isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes unless otherwise specified. Furthermore, the isomers and isotopes may include only one type or multiple types.

[0047] In this specification, unless otherwise specified, the bonding direction of the described divalent group (e.g., -COO-) is not limited. For example, when Y in a compound represented by the formula "XYZ" is -COO-, the compound may be "X-O-C0-Z" or "X-CO-OZ".

[0048] In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-converted values ​​of the standard substance measured by a gel permeation chromatography (GPC) analyzer using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all trade names manufactured by TOSOH CORPORATION) as a column, THF (tetrahydrofuran) as an eluent, a differential refractometer as a detector, and polystyrene as a standard substance.

[0049] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.

[0050] In this specification, a primary amino group refers to a group represented by -NH2, and a secondary amino group refers to a group represented by -NHR T The tertiary amino group refers to -N(R T )2 represents the base.

[0051] The above R T Each independently represents an alkyl group which may have a substituent.

[0052] R in the secondary amino group T It can be bonded to the structure of the bond bonded to the secondary amino group to form a ring. T can be bonded to each other to form a ring. T In the above, the atom directly bonded to the carbon atom having a bond to the nitrogen atom is a carbon atom or a hydrogen atom.

[0053] In the present specification, examples of the hetero atom include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.

[0054] In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0055] In this specification, the ClogP value refers to the value of the common logarithm logP of the partition coefficient P for 1-octanol and water obtained by calculation. The method and software for calculating the ClogP value can use a known method and software. In this specification, unless otherwise specified, the ClogP value is a value using the ClogP program incorporated into ChemBioDrawUltra12.0 of Cambridgesoft.

[0056] <Processing liquid>

[0057] The processing liquid of the present invention (hereinafter also referred to as "the present processing liquid") is a processing liquid for semiconductor manufacturing that contains a polycarboxylic acid and a polymer (hereinafter also referred to as a "specific polymer"), wherein the polymer contains a repeating unit A derived from a nonionic monomer and a repeating unit B having an anionic group.

[0058] The mechanism by which the problem of the present invention can be solved by adopting the above-mentioned structure in the present processing liquid is not clear, but the present inventors presume it as follows.

[0059] At least one (specific material) selected from the group consisting of polycrystalline silicon, silicon carbide and silicon carbonitride, which is used as a material for a semiconductor substrate (e.g., a gate electrode, etc.), has a surface that exhibits relative hydrophobicity compared to other general materials such as silicon dioxide or silicon nitride.

[0060] Therefore, organic residues showing hydrophobic properties are likely to remain on the surface of the specific material. In addition, since the specific material is easy to polish, the surface is usually protected with a surfactant or the like before CMP treatment, and the surfactant is also likely to remain as organic residues.

[0061] Furthermore, since compositions containing water as a main component that are generally used after CMP treatment have poor compatibility with the surface of specific materials, when the cleaning composition described in Patent Document 1 is used for post-CMP cleaning, defect removal performance on the surface of specific materials is not sufficient.

[0062] On the other hand, it is considered as follows: in the present treatment liquid, the specific polymer contains a repeating unit A derived from a nonionic monomer and a repeating unit B having an anionic group, so that while the base in the above-mentioned repeating unit A interacts with the organic residue (defects) on the surface of the specific material, the anionic group functions to move away from the surface of the specific material, thereby effectively removing the defects as a result.

[0063] Hereinafter, the components contained in the present treatment liquid are described in detail. In addition, when the present treatment liquid is used for cleaning a workpiece containing a specific material, the defect removal performance on the specific material is more excellent, which is also referred to as "the effect of the present invention is more excellent".

[0064] [Polycarboxylic acid]

[0065] The present treatment liquid contains polycarboxylic acid. Polycarboxylic acid is a compound having two or more carboxylic acid groups (carboxyl groups) in one molecule.

[0066] In addition, the polycarboxylic acid is a compound which is different from the specific polymer described later and does not contain a repeating unit.

[0067] The number of carboxyl groups in the polycarboxylic acid is not particularly limited as long as it is 2 or more, but is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0068] The molecular weight of the polycarboxylic acid is not particularly limited, but is preferably 50 to 750, more preferably 50 to 500, and even more preferably 100 to 350.

[0069] The polycarboxylic acid may be any of an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid. The aliphatic polycarboxylic acid is a polycarboxylic acid having no aromatic ring in the molecule, and the aromatic polycarboxylic acid is a polycarboxylic acid having an aromatic ring in the molecule. The aliphatic polycarboxylic acid may have an alicyclic structure.

[0070] Furthermore, the polycarboxylic acid may have a substituent other than the carboxyl group.

[0071] As the substituent possessed by the polycarboxylic acid, a hydroxyl group is preferred. That is, the polycarboxylic acid may be a hydroxypolycarboxylic acid. The number of hydroxyl groups possessed by the polycarboxylic acid is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0072] The polycarboxylic acid is preferably a compound represented by formula (X1).

[0073] L a -(COOH) na (X1)

[0074] In formula (X1), L a represents a single bond or an n-valent aliphatic hydrocarbon group which may have a substituent. n- represents an integer of 2 or greater.

[0075] From the viewpoint of more excellent effects of the present invention, na is preferably 2 to 5, more preferably 2 or 3.

[0076] The n-valent aliphatic hydrocarbon group is a group formed by removing n hydrogen atoms from an aliphatic hydrocarbon.

[0077] The n-valent aliphatic hydrocarbon group may be linear, branched or cyclic, and may have an unsaturated bond in the molecule.

[0078] The number of carbon atoms of the na-valent aliphatic hydrocarbon group (excluding the number of carbon atoms of the substituent) is not particularly limited, but is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 or 3 from the viewpoint of achieving a more excellent effect of the present invention.

[0079] The n-valent aliphatic hydrocarbon group is preferably a group obtained by removing two or three hydrogen atoms from an aliphatic saturated hydrocarbon.

[0080] The number of substituents that the n-valent aliphatic hydrocarbon group may have is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2.

[0081] Examples of the substituent that may have a n-valent aliphatic hydrocarbon group include a hydroxyl group, a halogen atom, and an alkoxycarbonyl group. Among them, a hydroxyl group is preferred.

[0082] In the above formula (X1), examples of the polycarboxylic acid (dicarboxylic acid) wherein na is 2 include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, eicosandioic acid, eicosadienoic acid, cyclopentanedicarboxylic acid, cyclopentenedicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, octane-4,5-dicarboxylic acid, nonane-1,3-dicarboxylic acid, 2-butylsuberic acid, hydroxymalonic acid, malic acid and tartaric acid.

[0083] From the viewpoint of more excellent effects of the present invention, the dicarboxylic acid is preferably malonic acid, succinic acid, malic acid or tartaric acid, and more preferably malic acid or tartaric acid.

[0084] In the above formula (X1), examples of the polycarboxylic acid (tricarboxylic acid) in which na is 3 include 1α,3α,5β-cyclohexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid and citric acid.

[0085] From the viewpoint of achieving more excellent effects of the present invention, the tricarboxylic acid is preferably citric acid.

[0086] The content of the polycarboxylic acid is preferably 12.5 ppm by mass or more, more preferably 50.0 ppm by mass or more, and even more preferably 150.0 ppm by mass, relative to the total mass of the treatment liquid.

[0087] The upper limit is preferably 25.0 mass % or less, more preferably 10.0 mass % or less, and further preferably 5.0 mass % or less.

[0088] Furthermore, the content of the polycarboxylic acid is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, and further preferably 20.0% by mass or more, relative to the total mass of the components of the treatment liquid excluding the solvent. The upper limit is not particularly limited, but is preferably 80.0% by mass or less, and more preferably 70.0% by mass or less.

[0089] In order to obtain more excellent effects of the present invention, the mass ratio of the content of the polycarboxylic acid to the content of the specific polymer described below is preferably 0.2 to 150, more preferably 0.2 to 50, further preferably 1 to 50, and particularly preferably 1 to 30.

[0090] The polycarboxylic acid may be used alone or in combination of two or more. Even when two or more polycarboxylic acids are used, it is preferred that the total content thereof be within the above-mentioned preferred range.

[0091] [Specific polymer]

[0092] The present treatment liquid contains a polymer (specific polymer) containing a repeating unit A derived from a nonionic monomer and a repeating unit B having an anionic group.

[0093] (Repeating unit A)

[0094] The repeating unit A is a repeating unit derived from a nonionic monomer.

[0095] In this specification, a nonionic monomer refers to a monomer that does not become an ion even if dissolved in water. In other words, it is a monomer that does not have an ionized group. In addition, in this specification, a group represented by -CO-NH2 is treated as a nonionic group.

[0096] The nonionic monomer may have either hydrophilicity or hydrophobicity, and preferably has hydrophobicity. Furthermore, the nonionic monomer may contain a hetero atom, and examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

[0097] The nonionic group of the nonionic monomer is not particularly limited, and examples thereof include a hydrocarbon group, a cyano group, a -CO-N(R a )(X 1 ) and a group containing a polymer chain described later. a and X 1 As described below.

[0098] The methylene group in the above hydrocarbon group may be substituted by -CO- or -O-.

[0099] The nonionic monomer preferably has a hydrocarbon group.

[0100] The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group.

[0101] The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but is preferably 1-10, more preferably 1-4.

[0102] The aliphatic hydrocarbon group may be linear, branched, or cyclic.

[0103] The aromatic hydrocarbon group may be a monocyclic or polycyclic ring.

[0104] The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6-18, more preferably 6-12.

[0105] The methylene group in the above hydrocarbon group may be substituted by -CO- or -O-.

[0106] Furthermore, the nonionic monomer also preferably has a polymer chain.

[0107] In addition, the polymer chain is a structure including a plurality of repeating units.

[0108] The polymer chain may be nonionic, and is preferably a polymer chain having at least one structure selected from the group consisting of a polyester structure, a poly(meth)acrylic acid structure, a polystyrene structure, a polyurethane structure, and a polyether structure. Among them, a polymer chain having a polyester structure is preferred.

[0109] Examples of the polyester structure include a polycaprolactone structure and a polyvalerolactone structure.

[0110] The polycaprolactone structure refers to a structure including a ring-opened ε-caprolactone structure as a repeating unit, and the polyvalerolactone structure refers to a structure including a ring-opened δ-valerolactone structure as a repeating unit.

[0111] From the viewpoint of achieving more excellent effects of the present invention, the repeating unit A is preferably a repeating unit represented by formula (1).

[0112] [Chemical formula 1]

[0113]

[0114] In formula (1), R 1 represents a hydrogen atom or an alkyl group.

[0115] L 1 Represents a single bond, -COO- or -CO-NR a -. R a represents a hydrogen atom or an alkyl group.

[0116] X 1 represents a hydrogen atom, a hydrocarbon group or a group containing a polymer chain. The methylene group in the above hydrocarbon group may be substituted by -CO- or -O-. 1 When L is a hydrogen atom, 1 Indicates -CO-NR a -.

[0117] By R 1 The alkyl group represented by may be linear, branched or cyclic, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.

[0118] Among them, as R 1 , preferably a hydrogen atom or a methyl group.

[0119] L 1 Represents a single bond, -COO- or -CO-NR a Among them, -COO- or -CO-NR a -.

[0120] R a represents a hydrogen atom or an alkyl group.

[0121] By R a The number of carbon atoms in the alkyl group represented by is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.

[0122] X 1 represents a hydrogen atom, a hydrocarbon group or a group comprising a polymer chain. The methylene group in the hydrocarbon group may be substituted by -CO- or -O-.

[0123] By X 1 Preferred embodiments of the hydrocarbon group represented by are the same as the preferred embodiments of the hydrocarbon group which the above-mentioned nonionic monomer may have.

[0124] By X 1 Preferred embodiments of the polymer chain-containing group represented by are the same as preferred embodiments of the polymer chain-containing group which the above-mentioned nonionic monomer may have.

[0125] In addition, X 1 When L is a hydrogen atom, 1 Indicates -CO-NR a -.

[0126] As described above, examples of the repeating unit A in the case where the nonionic monomer has a polymer chain include a repeating unit represented by the formula (1-1) or a repeating unit represented by the formula (1-2).

[0127] [Chemical formula 2]

[0128]

[0129] [Chemical formula 3]

[0130]

[0131] In formula (1-1) or formula (1-2), Q 1 is a group represented by any one of Formula (QX1), Formula (QNA) and Formula (QNB), Q 2 It is a group represented by any one of Formula (QX2), Formula (QNA) and Formula (QNB).

[0132] In formula (QX1), formula (QX2), formula (QNA) and formula (QNB), *a represents a bonding position on the main chain side, and *b represents a bonding position on the side chain side.

[0133] In formula (1-1) and formula (1-2), W 1 and W 2 Each independently represents a single bond, an oxygen atom or NH.

[0134] In formula (QX1) and formula (QX2), X 1 and X 2 Each independently represents a hydrogen atom or a monovalent organic group, X 1 and X 2 It is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0135] In formula (1-1) or formula (1-2), Y 1 and Y 2 Each independently represents a single bond or a divalent linking group, and examples of the divalent linking group include linking groups represented by formula (Y-1) to formula (Y-23).

[0136] [Chemical formula 4]

[0137]

[0138] In formula (Y-1) to formula (Y-23), A represents the same compound as W in formula (1-1) or formula (1-2). 1 or W 2 B represents the bonding position of W bonded to A. 1 or W 2 The bonding position of the group on the opposite side.

[0139] In formula (1-1) and formula (1-2), Z 1 and Z 2 Each independently represents a hydrogen atom or a monovalent organic group.

[0140] The structure of the monovalent organic group is not particularly limited, and specific examples thereof include hydroxyl groups, acyloxy groups (—O(C═O)R), alkyl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, alkyl thioether groups, aryl thioether groups, heteroaryl thioether groups, primary amino groups, secondary amino groups, and tertiary amino groups.

[0141] The acyloxy group, alkyl group, and alkoxy group may be linear, branched, or cyclic, and may have a substituent. Examples of the substituent include a hydroxyl group.

[0142] The monovalent organic group has preferably 5 to 24 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0143] Among them, as Z 1 and Z 2 The monovalent organic group represented by is preferably an acryloyl group, a hydroxyl group, an acyloxy group or an alkoxy group.

[0144] In the formula (1-1) and the formula (1-2), n and m each independently represent 2 to 20. Among them, 2 to 10 are preferred.

[0145] Furthermore, in Formula (1-1) and Formula (1-2), j and k each independently represent an integer of 2 to 8, preferably an integer of 4 to 6, and more preferably 5.

[0146] From the viewpoint of more excellent effects of the present invention, the ClogP of the nonionic monomer is preferably -1.00 to 5.00, more preferably 0.50 to 5.00, further preferably 1.00 to 5.00, and particularly preferably 0.50 to 3.00.

[0147] Specific examples of the nonionic monomer include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, N,N-dimethylacrylamide, diacetone acrylamide, and acrylamide.

[0148] In the specific polymer, the content of the repeating unit A is preferably 20 to 80 mol %, more preferably 25 to 70 mol %, and further preferably 30 to 60 mol % based on all the repeating units in the specific polymer.

[0149] The specific polymer may contain two or more types of repeating units A. In this case, the total content of all repeating units A is preferably within the above range.

[0150] (Repeating unit B)

[0151] The repeating unit B has an anionic group.

[0152] The anionic group is not particularly limited as long as it is a group that becomes an anion in water, but among them, an acid group is preferred, and a carboxylic acid group, a sulfonic acid group, or a phosphonic acid group is more preferred.

[0153] The number of anionic groups contained in the repeating unit B is not particularly limited, but is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0154] From the viewpoint of achieving more excellent effects of the present invention, the repeating unit B is preferably a repeating unit represented by formula (2).

[0155] [Chemical formula 5]

[0156]

[0157] In formula (2), R b represents a hydrogen atom or an anionic group.

[0158] R 2 represents a hydrogen atom or an alkyl group.

[0159] L 2 represents a single bond or a divalent linking group.

[0160] X 2 It represents an anionic group.

[0161] By R b The specific aspects and preferred aspects of the anionic group represented are the same as the specific aspects and preferred aspects of the anionic group described above.

[0162] And, about the 2 The specific embodiments and preferred embodiments of the anionic group represented are also the same as the specific embodiments and preferred embodiments of the anionic group described above.

[0163] By R 2 The alkyl group represented by may be linear, branched or cyclic, and is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.

[0164] Among them, as R 2 , preferably a hydrogen atom or a methyl group.

[0165] As L 2 The divalent linking group represented by the invention includes alkylene, arylene, -O-, -CO-, -NH-, -NR N2 -(R N2 represents an alkyl group having 1 to 6 carbon atoms. ) or a divalent linking group formed by combining these.

[0166] By L 2 The divalent linking group represented by may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom.

[0167] By L 2 The number of carbon atoms of the divalent linking group represented by is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2.

[0168] By L 2 The alkylene group represented by may be any of a linear, branched, and cyclic type. 2 The number of carbon atoms of the alkylene group represented by is preferably 1-10, more preferably 1-6, further preferably 1-3.

[0169] As L 2 Examples of the divalent alkylene group represented by include a methylene group, an ethylene group, and a propylene group.

[0170] By L 2 The arylene group represented by is preferably a phenylene group.

[0171] In the specific polymer, the content of the repeating unit B is preferably 20 to 80 mol %, more preferably 30 to 75 mol %, and even more preferably 40 to 70 mol % based on all the repeating units in the specific polymer.

[0172] The specific polymer may contain two or more types of repeating units B. In this case, the total content of all repeating units B is preferably within the above range.

[0173] The ratio of repeating unit A to repeating unit B in a specific polymer is not particularly limited, but from the perspective of achieving a more excellent effect of the present invention, the ratio a / b of the molar number a of repeating unit A to the molar number b of repeating unit B is preferably 1 / 99 or more, more preferably 5 / 95 or more, further preferably 10 / 90 or more, and particularly preferably 25 / 75 or more.

[0174] The upper limit of the ratio a / b is not particularly limited, but the ratio a / b is preferably 70 / 30 or less, more preferably 65 / 35 or less, further preferably 60 / 40 or less, and particularly preferably 55 / 45 or less.

[0175] In the specific polymer, the repeating unit A and the repeating unit B may be randomly bonded (so-called random copolymer), alternately bonded (so-called alternating copolymer), or bonded in blocks (so-called block copolymer).

[0176] The specific polymer may have a repeating unit different from either the repeating unit A or the repeating unit B.

[0177] The content of the repeating unit different from either the repeating unit A or the repeating unit B in the specific polymer is preferably 20 mol% or less, more preferably 0 to 10 mol%, and even more preferably 0 to 5 mol%, based on all repeating units in the specific polymer.

[0178] It is preferred that the specific polymer does not have a repeating unit different from either the repeating unit A or the repeating unit B.

[0179] The weight average molecular weight of the specific polymer is preferably 800 to 75,000, more preferably 1,000 to 50,000, and even more preferably 1,000 to 20,000.

[0180] The acid value of the specific polymer is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and further preferably 120 mgKOH / g or less. The lower limit is preferably 5 mgKOH / g or more.

[0181] The content of the specific polymer is preferably 0.1 ppm by mass or more, more preferably 15.0 ppm by mass or more, and even more preferably 50.0 ppm by mass or more, relative to the total mass of the treatment liquid.

[0182] The upper limit is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, and further preferably 1.0% by mass or less.

[0183] Furthermore, the content of the specific polymer is preferably 0.10% by mass or more, more preferably 0.45% by mass or more, further preferably 0.80% by mass or more, and particularly preferably 3.00% by mass or more, relative to the total mass of the components of the treatment liquid excluding the solvent. The upper limit is not particularly limited, but is preferably 60.0% by mass or less, more preferably 40.0% by mass or less, and further preferably 20.0% by mass or less.

[0184] The mass ratio of the content of the polymer to the content of the amino alcohol described below is preferably 0.001 to 2.0, more preferably 0.005 to 1.0, and even more preferably 0.005 to 0.5.

[0185] The mass ratio of the polymer content to the antibacterial agent content described below is preferably 0.1 to 200, more preferably 1 to 100, further preferably 0.3 to 90.0, particularly preferably 1.0 to 50.0, and most preferably 1.0 to 20.0.

[0186] The specific polymer may be used alone or in combination of two or more. Even when two or more specific polymers are used, it is preferred that the total content thereof be within the above-mentioned preferred range.

[0187] [Optional Ingredients]

[0188] The present treatment liquid may contain any components other than those described above. The optional components will be described in detail below.

[0189] (Amino alcohol)

[0190] From the viewpoint of further improving the effects of the present invention, the present treatment liquid preferably contains amino alcohol.

[0191] Amino alcohol refers to an organic compound having at least one group selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, and a hydroxyl group in the molecule.

[0192] The number of at least one group selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups possessed by the amino alcohol is not particularly limited, but is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.

[0193] From the viewpoint of more excellent effects of the present invention, the number of hydroxyl groups possessed by the amino alcohol is preferably 2 or more, more preferably 3 or more. The upper limit is not particularly limited, but is, for example, preferably 10 or less, more preferably 8 or less.

[0194] As the amino alcohol, a compound represented by the following formula (A1) or the following formula (A2) is preferred.

[0195] [Chemical formula 6]

[0196]

[0197] In formula (A1), R A1 R each independently represents a hydrogen atom or an alkyl group. A1 The number of carbon atoms of the alkyl group represented is preferably 1 to 3, more preferably 1 or 2.

[0198] In formula (A1), R H1 Each independently represents an alkyl group having at least one hydroxyl group. H1 The alkyl group having at least one hydroxyl group preferably has 1 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms.

[0199] R H1 The number of hydroxyl groups of the alkyl group having at least one hydroxyl group represented by the formula (I) is preferably 1-6, more preferably 1-3.

[0200] As R H1 Examples of the group represented include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2,3-dihydroxypropyl group, a bis(hydroxymethyl)methyl group, a tris(hydroxymethyl)methyl group, and a 2,3,4,5,6-pentahydroxyhexyl group.

[0201] In formula (A1), n1 represents an integer of 1 to 3, and m1 represents an integer of 0 to 2. n1 and m1 are selected so that the sum of n1 and m1 is 3. n1 is preferably 1 or 2. m1 is preferably 1 or 2.

[0202] Examples of the compound represented by formula (A1) include monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, trishydroxymethylaminomethane (also called tris or Tris), bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane (also called bis-tris or Bis-Tris), reduced glucosamine, and N-methyl reduced glucosamine.

[0203] In formula (A2), R A2 and R A3 R each independently represents a hydrogen atom or an alkyl group. A2 and R A3 The preferred embodiment of the group represented by is the same as R A1 The preferred embodiments of the groups represented are the same and thus their description is omitted.

[0204] In formula (A2), R H2 and R H3 Each independently represents an alkyl group having at least one hydroxyl group. H2 and R H3 The preferred embodiment of the group represented by is the same as R H1 The preferred embodiments of the groups represented are the same and thus their description is omitted.

[0205] In formula (A2), n2 represents an integer of 1 or 2, and m2 represents an integer of 0 or 1. However, n2 and m2 are selected so that the sum of n2 and m2 is 2.

[0206] In formula (A2), n3 represents an integer of 1 or 2, and m3 represents an integer of 0 or 1. However, n3 and m3 are selected so that the sum of n3 and m3 is 2.

[0207] In formula (A2), L A2 Represents a divalent linking group. A2 Preferably, it represents an alkylene group having 1 to 6 carbon atoms.

[0208] Examples of the compound represented by formula (A2) include 1,3-bis[tris(hydroxymethyl)methylamino]propane (also referred to as bis-tripropane).

[0209] Among them, the amino alcohol is preferably trishydroxymethylaminomethane, bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane or 1,3-bis[tris(hydroxymethyl)methylamino]propane.

[0210] The content of the amino alcohol is preferably 15.0 ppm by mass or more, more preferably 150 ppm by mass or more, and even more preferably 500 ppm by mass or more, relative to the total mass of the treatment liquid.

[0211] The upper limit is preferably 20.0 mass % or less, more preferably 15.0 mass % or less, and further preferably 5.0 mass % or less.

[0212] The amino alcohol content is preferably 10.0% by mass or more, more preferably 25.0% by mass or more, relative to the total mass of the components of the treatment liquid excluding the solvent. The upper limit is not particularly limited, but is preferably 90.0% by mass or less, more preferably 70.0% by mass or less.

[0213] The amino alcohol may be used alone or in combination of two or more. When two or more amino alcohols are used, it is also preferred that the total content thereof is within the above-mentioned preferred range.

[0214] (Antibacterial Agent)

[0215] From the viewpoint of further improving the effects of the present invention, it is preferred that the treatment liquid contains an antibacterial agent.

[0216] The antimicrobial agent is a compound that can inhibit the growth of microorganisms and is a compound different from the polycarboxylic acid and the specific polymer.

[0217] The molecular weight of the antibacterial agent is preferably 50 to 700, more preferably 100 to 600, and even more preferably 100 to 500.

[0218] Examples of the antibacterial agent include cationic antibacterial agents (quaternary ammonium antibacterial agents, etc.), carboxylic acid antibacterial agents, phenolic antibacterial agents, isothiazolinone antibacterial agents, biguanide antibacterial agents, sulfonamide antibacterial agents, peroxide antibacterial agents, imidazole antibacterial agents, ester antibacterial agents, alcohol antibacterial agents, carbamate antibacterial agents, iodine antibacterial agents, and antibiotics.

[0219] Examples of the quaternary ammonium antimicrobial agent include benzalkonium chloride, didecyldimethylammonium chloride (DDAC), cetylpyridinium chloride (CPC), 3,3′-(2,7-dioxaoctane)bis(1-dodecylpyridinium bromide) (Hygeria), benzethonium chloride, and domiphene bromide.

[0220] Among them, benzethonium chloride is preferred.

[0221] Examples of the carboxylic acid-based antibacterial agent include sorbic acid, dehydroacetic acid, benzoic acid, and salicylic acid, and sorbic acid, benzoic acid, and salicylic acid are preferred.

[0222] Examples of the phenolic antimicrobial agent include cresol, catechol, chlorovanillin, dichlorooxygenol and hexachlorophene.

[0223] Examples of isothiazolinone antibacterial agents include 2-methyl-4-isothiazolin-3-one (MIT), 2-octyl-4-isothiazolin-3-one (OIT), 1,2-benzisothiazol-3(2H)-one (BIT) and 5-chloro-2-methyl-4-isothiazolin-3-one (CIT).

[0224] Among them, MIT, OIT or BIT is preferred, and MIT or OIT is more preferred.

[0225] Examples of the imidazole antibacterial agent include 2-(4-thiazolyl)-benzimidazole (TBZ) and 2-benzimidazole carbamic acid methyl ester (PREVENTOL BCM).

[0226] Examples of biguanide antibacterial agents include bis(p-chlorophenylbiguanide)hexane digluconate (chlorhexidine gluconate) and poly(hexamethylene biguanide) hydrochloride (hexamethylene biguanide hydrochloride). Among these, chlorhexidine gluconate is preferred.

[0227] The content of the antibacterial agent is preferably 0.1 ppm by mass or more, more preferably 1.5 ppm by mass or more, and even more preferably 5.0 ppm by mass or more, relative to the total mass of the treatment liquid.

[0228] The upper limit is preferably 2.0% by mass or less, more preferably 1.0% by mass or less.

[0229] Among them, from the viewpoint of excellent defect removal performance on silicon nitride, the content of the antibacterial agent relative to the total mass of the treatment liquid is preferably 0.5 to 12.5 ppm by mass.

[0230] Furthermore, relative to the total mass of the components other than the solvent in the treatment liquid, the content of the antibacterial agent is preferably 0.01 mass % or more, more preferably 0.1 mass % or more, and further preferably 0.5 mass % or more. The upper limit is not particularly limited, and is preferably 15.0 mass % or less, more preferably 4.0 mass % or less, and further preferably 1.0 mass % or less.

[0231] Among them, from the viewpoint of excellent defect removal performance on silicon nitride, the content of the antibacterial agent is preferably 0.1 to 4.0% by mass based on the total mass of the components other than the solvent in the treatment liquid.

[0232] The antibacterial agent may be used alone or in combination of two or more. When two or more antibacterial agents are used, it is also preferred that the total content thereof is within the above-mentioned preferred range.

[0233] (Solvent)

[0234] The present treatment liquid preferably contains a solvent.

[0235] Examples of the solvent include water and organic solvents.

[0236] The organic solvent is preferably mixed with water at any ratio.

[0237] Examples of the organic solvent include alcohol solvents, glycol solvents, glycol ether solvents, ketone solvents, and sulfur-containing solvents.

[0238] As the organic solvent, for example, the compounds exemplified in paragraphs

[0135] to

[140] of International Publication No. 2022 / 044893 can be cited, and these contents are incorporated into the present specification.

[0239] The solvent is preferably water, and the water is preferably distilled water, deionized water, pure water or ultrapure water, and more preferably pure water or ultrapure water.

[0240] The content of the solvent is preferably 70.0% by mass or more, more preferably 80.0% by mass or more, and even more preferably 90.0% by mass or more, relative to the total mass of the treatment liquid.

[0241] The upper limit is preferably 99.999 mass % or less, more preferably 99.97 mass % or less, and even more preferably 99.7 mass % or less.

[0242] The solvent may be used alone or in combination of two or more. Even when two or more solvents are used, it is preferred that the total content thereof be within the above-mentioned preferred range.

[0243] (pH adjuster)

[0244] The present treatment liquid may contain a pH adjuster. The pH of the treatment liquid can be adjusted to a preferred pH range described below by the pH adjuster.

[0245] The pH adjuster is preferably a compound different from the above-mentioned compound. Examples of the pH adjuster include acidic compounds and basic compounds.

[0246] The acidic compound refers to an acidic compound that exhibits acidity (pH less than 7.0) in an aqueous solution.

[0247] Examples of the acidic compound include inorganic acids and salts thereof.

[0248] Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and salts thereof.

[0249] The content of the acidic compound is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 5.0% by mass, relative to the total mass of the treatment liquid.

[0250] The basic compound refers to a compound that exhibits alkalinity (pH exceeding 7.0) in an aqueous solution.

[0251] Examples of the basic compound include inorganic bases, organic bases, and salts thereof.

[0252] Examples of the inorganic base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, and ammonia.

[0253] Examples of the organic base include quaternary ammonium salts. The anion contained in the quaternary ammonium salt is preferably Cl, Br or OH, more preferably Cl or OH, and further preferably OH.

[0254] The content of the basic compound is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 5.0% by mass, relative to the total mass of the treatment liquid.

[0255] In addition to the above-mentioned components, the present treatment liquid may contain an oxidizing agent, a surfactant, and the like.

[0256] <Properties of treatment fluid>

[0257] Preferred properties of the treatment liquid of the present invention are described.

[0258] [pH]

[0259] The pH of the treatment liquid of the present invention is preferably 1.0 to 12.0, more preferably 2.0 to 10.0, and even more preferably 3.0 to 8.0.

[0260] It is considered that by setting the pH of the treatment liquid within the above-mentioned preferred range, the removability of defects derived from the residue is more excellent.

[0261] The pH of the treatment liquid can be measured using a known pH meter by a method in accordance with JIS Z8802-1984. The measurement temperature is set at 25°C.

[0262] [Insoluble particles]

[0263] The treatment liquid of the present invention preferably contains substantially no insoluble particles.

[0264] The above-mentioned “insoluble particles” correspond to particles of inorganic solid substances and organic solid substances, and are substances that do not finally dissolve in the treatment liquid and exist in the form of particles.

[0265] The above-mentioned “substantially contains no insoluble particles” means that the number of particles with a particle size of 50 nm or more contained in 1 mL of the measuring composition is 40,000 or less when the treating liquid is diluted 10,000 times in the solvent contained in the treating liquid. In addition, the number of particles contained in the measuring composition can be measured in the liquid phase using a commercially available particle counter.

[0266] As commercially available particle counters, devices manufactured by RION CO., LTD. and PMS can be used. Representative devices of the former include KS-19F, and representative devices of the latter include Chem 20. In order to measure larger coarse particles, devices such as KS-42 series and LiQuilaz II S series can be used.

[0267] Examples of insoluble particles include inorganic solid materials such as silica (including colloidal silica and fumed silica), alumina, zirconia, cerium dioxide, titanium dioxide, germanium oxide, manganese oxide, and silicon carbide; and particles of organic solid materials such as polystyrene, polyacrylic resin, and polyvinyl chloride.

[0268] As a method of removing insoluble particles from the treatment liquid, purification treatment such as filtration is mentioned, for example.

[0269] [Coarse particles]

[0270] The treatment liquid of the present invention may contain coarse particles, but the content thereof is preferably low.

[0271] The coarse particles are particles having a diameter (particle size) of 1 μm or more when the particle shape is regarded as a sphere. In addition, the particles included in the above-mentioned insoluble particles may be included in the coarse particles.

[0272] The content of coarse particles in the treatment liquid is preferably 100 or less, more preferably 50 or less, per 1 mL of the treatment liquid. The lower limit is preferably 0 or more, more preferably 0.01 or more, per 1 mL of the treatment liquid.

[0273] The coarse particles contained in the treatment liquid are particles of dust, dust, organic solid matter, inorganic solid matter, etc. contained as impurities in the raw materials, and particles of dust, dust, organic solid matter, inorganic solid matter, etc. brought in as contaminants during the preparation of the treatment liquid, corresponding to substances that are not dissolved in the final treatment liquid and exist as particles.

[0274] The number of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available particle counter.

[0275] As a method for removing coarse particles, for example, purification treatment such as filtration described later can be cited.

[0276] <Method for producing treatment liquid>

[0277] The processing liquid can be produced by a known method. Hereinafter, the method for producing the processing liquid will be described in detail.

[0278] [Liquid preparation process]

[0279] The treatment liquid can be prepared by mixing the above-mentioned components, for example.

[0280] The order and / or time of mixing the above-mentioned components are not particularly limited. For example, in a container containing a purified solvent (e.g., pure water), polycarboxylic acid, specific polymer and other components (amino alcohol and antibacterial agent, etc.) are sequentially added and stirred and mixed. Furthermore, after mixing, the pH of the mixed solution can be adjusted by adding a pH adjuster.

[0281] When adding the solvent and each component to the container, they may be added all at once or dividedly added a plurality of times.

[0282] The stirring device and stirring method used in the treatment liquid preparation may be a known device as a stirrer or a disperser. Examples of the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer. Examples of the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.

[0283] The mixing of the components in the treatment liquid preparation step, the purification treatment described later, and the storage of the produced treatment liquid are preferably performed at 40° C. or less, more preferably at 30° C. or less. The lower limit is preferably 5° C. or more, more preferably 10° C. or more. By preparing the treatment liquid and performing the treatment and / or storage within the above temperature range, the performance can be stably maintained for a long period of time.

[0284] (Purification treatment)

[0285] It is preferred that at least one of the raw materials used to prepare the treatment liquid is subjected to a purification treatment in advance. Examples of the purification treatment include known methods such as distillation, ion exchange, and filtering.

[0286] The degree of purification is preferably such that the purity of the raw material becomes 99% by mass or more, and more preferably such that the purity of the stock solution becomes 99.9% by mass or more.

[0287] (container)

[0288] As long as corrosivity etc. do not pose a problem, the treatment liquid (including a method of diluting the treatment liquid described below) can be filled in any container and stored, transported, and used.

[0289] As the container, for semiconductor applications, it is preferred that the cleanliness inside the container is high and impurities are suppressed from eluting into each liquid from the inner wall of the container's receiving portion. As such a container, various commercially available containers for semiconductor processing liquids can be cited, such as the "Clean-Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure Bottle" manufactured by KODAMAPLASTICS Co., Ltd., but the container is not limited to these.

[0290] Furthermore, as a container for storing the treatment liquid, it is preferable that the liquid contact portion such as the inner wall of the storage portion is formed of fluororesin (perfluororesin) or a metal treated to prevent rust and metal elution.

[0291] The inner wall of the container is preferably formed of one or more resins selected from the group consisting of polyethylene resins, polypropylene resins and polyethylene-polypropylene resins, or a different resin or a metal such as stainless steel, Hastelloy, Inconel and Monel alloy that has been treated to prevent rust and metal dissolution.

[0292] These containers are preferably cleaned before filling with the treatment liquid. The liquid used for cleaning preferably reduces the amount of metal impurities in the solution. The treatment liquid can be bottled in a container such as a gallon bottle or a coating bottle after production for transportation and storage.

[0293] In order to prevent the change of the components in the treatment liquid during storage, the container may be replaced with an inert gas (nitrogen or argon, etc.) with a purity of 99.99995% by volume or more. In particular, a gas with a low water content is preferred. In addition, the temperature may be controlled within a range of -20°C to 20°C during transportation and storage to prevent deterioration.

[0294] (Clean Room)

[0295] The manufacture of the treatment liquid, the opening and cleaning of the container, the operations including the filling of the treatment liquid, the treatment analysis and the measurement are preferably all performed in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferred to meet any one of ISO (International Organization for Standardization) grade 1, ISO grade 2, ISO grade 3 and ISO grade 4, more preferably ISO grade 1 or ISO grade 2, and even more preferably ISO grade 1.

[0296] [Dilution process]

[0297] The above-mentioned treatment liquid can be used as a diluted treatment liquid (diluted treatment liquid) after being subjected to a dilution step of diluting with a diluent. That is, after preparing a concentrated liquid, it can be diluted and used as a treatment liquid.

[0298] Furthermore, as long as the requirements of the present invention are satisfied, a diluted treatment liquid is also one embodiment of the treatment liquid of the present invention.

[0299] Examples of the diluent include water and an aqueous solution containing ammonia.

[0300] It is preferred that the dilution liquid used in the dilution step be purified in advance, and it is more preferred that the diluted liquid obtained in the dilution step be purified.

[0301] Examples of the purification treatment include the ion component reduction treatment using an ion exchange resin or RO membrane or the like and foreign matter removal using filtration described as the purification treatment for the treatment liquid. It is preferred to perform any of these treatments.

[0302] The dilution rate of the treatment liquid in the dilution process can be appropriately adjusted according to the type and content of each component, and the object and purpose of use of the treatment liquid. The ratio (dilution ratio) of the diluted treatment liquid to the treatment liquid before dilution is preferably 1.5 to 10,000 times, more preferably 2 to 2,000 times, and further preferably 50 to 1,000 times, in terms of volume ratio (volume ratio at 23° C.).

[0303] The change in pH before and after dilution (the difference between the pH of the treatment liquid before dilution and the pH of the diluted treatment liquid) is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.5 or less.

[0304] The pH of the treatment liquid before dilution and the pH of the diluted treatment liquid are preferably the above-mentioned preferred embodiments.

[0305] The specific method of the dilution step of diluting the treatment liquid may be carried out based on the above treatment liquid preparation step. The stirring device and stirring method used in the dilution step may also be carried out using the known stirring device mentioned in the above treatment liquid preparation step.

[0306] <Use of treatment fluid>

[0307] The processing liquid is used in various processes for manufacturing semiconductors. Among them, the processing liquid is preferably used in a cleaning step of cleaning a workpiece (preferably a semiconductor substrate) subjected to a chemical mechanical polishing (CMP) process.

[0308] As described above, for washing the object to be treated, a diluted treatment liquid obtained by diluting the treatment liquid can be used.

[0309] [Object to be processed]

[0310] The object to be processed preferably includes at least one (specific material) selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride.

[0311] The silicon carbonitride is a compound containing silicon (Si), carbon (C), and nitrogen (N), and the content ratio of silicon (Si), carbon (C), and nitrogen (N) is not particularly limited.

[0312] Examples of the object to be processed include a substrate having a layer containing polycrystalline silicon (polycrystalline silicon layer), a layer containing silicon carbide (silicon carbide layer), and a layer containing silicon carbonitride (silicon carbonitride layer).

[0313] In addition, when the substrate has the above-mentioned specific material, the location where the layer containing the specific material exists may be, for example, any one of the front and back surfaces, the side surfaces, and the grooves of the substrate. Furthermore, when the substrate has a layer containing a specific material, it includes not only the case where the layer containing the specific material is directly on the surface of the substrate, but also the case where the layer containing the specific material is on the substrate through other layers.

[0314] The layer containing the specific material may be disposed on only one main surface of the substrate or on both main surfaces of the substrate. Furthermore, the layer containing the specific material may be disposed on the entire main surface of the substrate or on a portion of the main surface of the substrate.

[0315] The present treatment liquid also exhibits good compatibility with materials that exhibit a high contact angle with water (eg, polycrystalline silicon, silicon carbide, and silicon carbonitride).

[0316] The object to be processed may include other insulating films besides the layer containing the specific material.

[0317] There is no particular limitation on the above-mentioned other insulating films. For example, an insulating film containing one or more materials selected from the group consisting of silicon nitride (SiN), silicon oxide, silicon oxycarbide (SiOC), silicon oxynitride, and TEOS (tetraethoxysilane) can be cited. Among them, as the above-mentioned materials, SiN or TEOS is preferably used. Also, the insulating film can be composed of multiple films.

[0318] The object to be processed may further have various layers and / or structures as desired in addition to the above. For example, when the object to be processed is a substrate, the object to be processed may have components such as a barrier layer (for example, a layer containing titanium, titanium nitride, tantalum, and tantalum nitride, etc.), metal wiring, an oxide film, a gate electrode, a source electrode, a drain electrode, an insulating layer, a ferromagnetic layer, an integrated circuit structure, and / or a non-magnetic layer.

[0319] <CMP process>

[0320] The CMP process is, for example, a process for planarizing the surface of an electrode film, a metal wiring film, a barrier metal, and a substrate having an insulating film by the combined action of the chemical action of a polishing slurry containing abrasive particles (abrasive grains) and mechanical polishing.

[0321] In the surface of the object to be processed on which the CMP process has been performed, there may remain abrasive grains (for example, silica and alumina, etc.) used in the CMP process, as well as non-metallic impurities and metal impurities derived from a polysilicon film, a silicon carbide film, a silicon carbonitride film, a metal wiring film, other insulating films, and a barrier metal. Also, organic residues derived from the CMP treatment liquid used during the CMP process sometimes remain.

[0322] In particular, when performing the CMP process on an object to be processed containing polysilicon, silicon carbide, or silicon carbonitride, the film containing polysilicon, silicon carbide, or silicon carbonitride is usually protected by a surfactant or the like to make it easy to polish, so that the above-mentioned surfactant or the like easily remains on the polysilicon, silicon carbide, or silicon carbonitride as organic residues.

[0323] These impurities may, for example, cause a short circuit between wirings and deteriorate the electrical characteristics of the object to be processed. Therefore, the object to be processed on which the CMP process has been performed is subjected to a cleaning process for removing these impurities from the surface.

[0324] Examples of the object to be processed on which the CMP process has been performed include the substrate on which the CMP process has been performed as described in Journal of Precision Engineering Vol.84, No.3, 2018, but are not limited thereto.

[0325] <Polishing process>

[0326] The object to be processed may be subjected to a polishing treatment after being subjected to a CMP treatment.

[0327] Polishing is a process for reducing impurities on the surface of the object to be processed using a polishing pad. Specifically, the surface of the object to be processed that has been subjected to CMP treatment is brought into contact with the polishing pad, and a polishing composition is supplied to the contact portion while the object to be processed and the polishing pad are made to slide relative to each other. As a result, impurities on the surface of the object to be processed are removed by the friction force based on the polishing pad and the chemical action based on the polishing composition.

[0328] As the polishing composition, a known polishing composition can be appropriately used according to the type of the object to be processed and the type and amount of impurities to be removed. Components included in the polishing composition include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid.

[0329] Furthermore, as one embodiment of the polishing treatment, it is preferable to perform the polishing treatment on the object to be treated using the above-mentioned treatment liquid as a polishing composition.

[0330] The grinding device and grinding conditions used in the polishing process can be appropriately selected from known devices and conditions according to the type of the object to be processed and the object to be removed. As a polishing process, for example, the process described in paragraphs

[0085] to

[0088] of International Publication No. 2017 / 169539 can be cited, and these contents are incorporated into this specification.

[0331] [Washing method for treated objects]

[0332] As described above, the processing liquid is preferably used for cleaning the object to be processed.

[0333] The method for cleaning an object to be processed preferably includes a cleaning step of cleaning the object to be processed which has been subjected to CMP processing using the present processing liquid.

[0334] The above-mentioned cleaning process can be carried out on the treated object by a known method, for example, brush cleaning in which a treatment liquid is supplied to the treated object and a cleaning component such as a brush is brought into physical contact with the surface of the treated object to remove residues, an immersion cleaning method in which the treated object is immersed in the treatment liquid, a spin (dripping) method in which the treated object is rotated and the treatment liquid is dripped, and a spray method in which the treatment liquid is sprayed, etc., which are methods commonly performed in this field.

[0335] In the immersion cleaning, it is preferable to subject the treatment liquid in which the treatment object is immersed to ultrasonic treatment from the viewpoint of being able to further reduce the impurities remaining on the surface of the treatment object.

[0336] The above-mentioned cleaning step may be performed only once or twice or more. When cleaning is performed twice or more, the same method may be repeated or different methods may be combined.

[0337] As a method for cleaning the object to be processed, either a single-wafer method or a batch method may be used.

[0338] The single sheet method refers to a method in which one sheet of the processed object is processed at a time, and the batch method refers to a method in which a plurality of processed objects are processed at the same time.

[0339] The temperature of the treatment liquid used in the cleaning of the treated object is not particularly limited as long as it is a temperature usually performed in this field. Usually, cleaning is performed at room temperature (about 25° C.), but in order to improve the cleaning property and suppress the damage to the parts, the temperature can be arbitrarily selected. For example, the temperature of the treatment liquid is preferably 10 to 60° C., and more preferably 15 to 50° C.

[0340] The pH of the treatment liquid is preferably the preferred embodiment of the pH of the treatment liquid described above. The pH of the diluted treatment liquid is also preferably the preferred embodiment of the pH of the treatment liquid described above.

[0341] The cleaning time in cleaning the treated object can be appropriately changed according to the types and contents of components contained in the treatment liquid, etc. Practically, it is preferably 10 seconds to 2 minutes, more preferably 20 seconds to 1 minute 30 seconds, and even more preferably 30 seconds to 1 minute.

[0342] The supply amount (supply rate) of the treatment liquid in the treatment object washing step is preferably 50 to 5000 mL / min, more preferably 500 to 2000 mL / min.

[0343] In cleaning the treated object, a mechanical stirring method may be used to further enhance the cleaning ability of the treatment liquid.

[0344] Examples of the mechanical stirring method include a method of circulating the treatment liquid on the treatment object, a method of flowing or spraying the treatment liquid on the treatment object, and a method of stirring the treatment liquid with ultrasonic waves or megasonic waves.

[0345] After the above-mentioned cleaning of the object to be processed, a step of rinsing the object to be processed with a solvent (hereinafter also referred to as a "rinsing step") may be performed.

[0346] The rinsing step is preferably performed continuously after the treatment object cleaning step and is a step of rinsing for 5 seconds to 5 minutes using a rinsing solvent (rinsing liquid). The rinsing step can be performed using the above-mentioned mechanical stirring method.

[0347] Examples of the rinse solvent include water (preferably deionized (DI) water), methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. In addition, an aqueous rinse solution having a pH exceeding 8.0 (such as diluted aqueous ammonium hydroxide) may be used.

[0348] As a method of bringing the rinse solvent into contact with the object to be processed, the method of bringing the above-mentioned processing liquid into contact with the object to be processed can also be applied in the same manner.

[0349] Furthermore, after the rinsing step, a drying step of drying the processed object may be performed.

[0350] Examples of the drying method include a spin drying method, a method of passing a dry gas over the workpiece, a method of heating the substrate by a heating mechanism such as a hot plate and an infrared lamp, a Marangoni drying method, a Notagoni drying method, an IPA (isopropyl alcohol) drying method, and any combination of these methods.

[0351] Example

[0352] Below, the present invention is further described in detail based on examples. The materials, usage amounts and ratios shown in the following examples can be appropriately changed as long as they do not depart from the purpose of the present invention. That is, the scope of the present invention is not limited to the following examples.

[0353] In the following examples, the pH of the concentrate described later was measured at 25° C. using a pH meter (eg, manufactured by HORIBA, Ltd., model “F-74”) in accordance with JIS Z8802-1984.

[0354] Furthermore, in the production of the treatment liquids of Examples and Comparative Examples, the handling of the containers, the preparation, filling, storage, and analysis of the treatment liquids were all performed in a clean room satisfying ISO Class 2 or lower.

[0355] [Raw materials of treatment fluid]

[0356] To prepare the treatment liquid, the following compounds were used.

[0357] Each component used in the examples was classified to a semiconductor grade or a component classified to a high purity grade equivalent thereto.

[0358] 〔Polycarboxylic acid〕

[0359] Citric acid

[0360] ·oxalic acid

[0361] Malonic acid

[0362] Succinic acid

[0363] Malic acid

[0364] Tartaric acid: L-tartaric acid

[0365] 〔Specific polymer〕

[0366] In the following specific polymers, when there is no description of the weight average molecular weight, Mw = 6000. In any specific polymer, the ratio a / b (copolymerization ratio) of the number of moles a of the repeating unit A to the number of moles b of the repeating unit B is 50 / 50.

[0367] Polymer-1a: acrylic acid-methyl acrylate copolymer (Mw=800)

[0368] Polymer-lb: acrylic acid-methyl acrylate copolymer (Mw=6000)

[0369] Polymer-1c: acrylic acid-methyl acrylate copolymer (Mw=30000)

[0370] Polymer-1d: acrylic acid-methyl acrylate copolymer (Mw=50000)

[0371] Polymer-1e: acrylic acid-methyl acrylate copolymer (Mw=75000)

[0372] Polymer-2: Acrylic acid-butyl acrylate copolymer

[0373] Polymer-3: acrylic acid-N, N-dimethylacrylamide copolymer

[0374] Polymer-4: Acrylic acid-2-ethylhexyl acrylate copolymer

[0375] Polymer-5: acrylic acid-acrylamide copolymer

[0376] Polymer-6: Maleic acid-ethyl acrylate copolymer

[0377] Polymer-7: Maleic acid-N, N-dimethylacrylamide copolymer

[0378] Polymer-8: Maleic acid-butyl acrylate copolymer

[0379] Polymer-9: Maleic acid-methyl acrylate copolymer

[0380] Polymer-10: Maleic acid-diacetone acrylamide copolymer

[0381] Polymer-11: Styrene sulfonic acid-butyl acrylate copolymer

[0382] Polymer-12: Styrene sulfonic acid-N, N-dimethylacrylamide copolymer

[0383] Polymer-13: Vinylphosphonic acid-butyl acrylate copolymer

[0384] Polymer-14: Vinylphosphonic acid-N, N-dimethylacrylamide copolymer

[0385] Polymer-15: Styrene-maleic acid copolymer

[0386] In addition, regarding the repeating unit A derived from the nonionic monomer in the above-mentioned specific polymer, the ClogP of the above-mentioned nonionic monomer is shown below.

[0387] Methyl acrylate: 0.79

[0388] Ethyl acrylate: 1.33

[0389] Butyl acrylate: 2.39

[0390] ·2-Ethylhexyl acrylate: 4.33

[0391] N, N-dimethylacrylamide: -0.59

[0392] Acrylamide: -0.79

[0393] [Resin (resin not corresponding to a specific polymer)]

[0394] Polyacrylic acid

[0395] Polyacrylamide

[0396] 〔Amino alcohol〕

[0397] ·Tris:Tris(hydroxymethyl)aminomethane

[0398] ·MEA: Monoethanolamine

[0399] ·DEA: Diethanolamine

[0400] MDEA: N-methyldiethanolamine

[0401] Bis-Tris: Bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane

[0402] Bis-TrisP: 1,3-Bis[tris(hydroxymethyl)methylamino]propane

[0403] 〔Antibacterial agent〕

[0404] MIT: 2-methyl-4-isothiazolin-3-one

[0405] ·Sorbic acid

[0406] MIT / OIT: A mixture of MIT and 2-octyl-4-isothiazoline-3-one (OIT) (mass ratio 1:5)

[0407] Cresol

[0408] Dehydroacetic acid

[0409] ·benzoic acid

[0410] Catechol

[0411] PHMB: Polyhexamethylene biguanide

[0412] CHG: Chlorhexidine gluconate

[0413] 〔pH adjuster and water〕

[0414] In the process of producing the treatment liquid in this embodiment, potassium hydroxide (KOH) or nitric acid (HNO 3 ) and ultrapure water are used as pH adjusters.

[0415] The content of the pH adjuster was 2% by mass or less relative to the total mass of the concentrated liquid when producing any of the treatment liquids in Examples and Comparative Examples.

[0416] [Manufacturing of treatment liquid]

[0417] The method for producing the treatment liquid of Example 1 will be described.

[0418] After adding citric acid, Polymer-1b, Tris and MIT to ultrapure water according to the table described below, a pH adjuster was added so that the pH of the prepared concentrated solution became 1.5. The obtained mixed solution was stirred thoroughly to obtain a concentrated solution.

[0419] The remainder of the concentrate (components other than citric acid, Polymer-1b, Tris, MIT, and the pH adjuster) was ultrapure water.

[0420] The obtained concentrated liquid was further diluted with ultrapure water at the dilution ratio described in the table, thereby obtaining the treatment liquid of Example 1.

[0421] The treatment liquids of each example and comparative example were prepared by the same manufacturing method as in Example 1 except that the types and contents of each component were adjusted according to the table described later. In each example and comparative example, a concentrated solution was prepared in the same manner as in Example 1 and diluted at a predetermined dilution ratio to prepare a predetermined treatment liquid.

[0422] [evaluate]

[0423] 〔Defect removal〕

[0424] The defect removal performance of the processing liquid of each example or comparative example prepared as described above when cleaning an object after CMP processing was evaluated.

[0425] -CMP treatment-

[0426] The object was subjected to CMP treatment using a device "FREX-300X" manufactured by EBARA CORPORATION as a polishing device while supplying slurry (polishing liquid). The object to be CMP treated, the composition of the polishing liquid, and the polishing conditions are as follows.

[0427] (Target object)

[0428] ·12-inch wafer with polycrystalline silicon (poly-Si) film formed on Si substrate

[0429] 12-inch wafer with silicon carbide (SiC) film formed on Si substrate

[0430] ·12-inch wafer with silicon carbonitride (SiCN) film formed on Si substrate

[0431] ·12-inch wafer with silicon nitride (SiN) film formed on Si substrate

[0432] (Grinding fluid composition)

[0433]

[0434] The polishing liquid was used after being adjusted to pH=10.0 using KOH / HNO 3 .

[0435] (Grinding conditions)

[0436]

[0437] - Defect Assessment -

[0438] The defect removal performance when cleaning treatment was performed on each of the above-mentioned CMP-processed objects (wafers with poly-Si, wafers with SiC, wafers with SiCN, or wafers with SiN) using the processing liquid was evaluated.

[0439] Using each process liquid, the object after the CMP process was cleaned for 30 seconds in the cleaning unit 1 (wafer cleaning by brush cleaning) and then cleaned for 30 seconds in the cleaning unit 2 (wafer cleaning by brush cleaning).

[0440] After the above cleaning treatment, a rinse treatment was performed using ultrapure water for 60 seconds, and finally, N2 was blown onto the wafer surface in a drying unit, and spin drying was performed at a rotation speed of 1000 rpm to implement wafer drying treatment.

[0441] The number of defects with a length of 0.1 μm or more in the polished surface of the obtained wafer was detected using a defect detection device (ComPlus II), and each defect was observed and classified using a SEM (scanning electron microscope). If necessary, the constituent elements were analyzed and the composition was determined using an EDX (energy dispersive X-ray analyzer). Thus, the number of defects based on the residue was obtained, and the cleaning performance was evaluated according to the following evaluation criteria (evaluation A is the best cleaning performance).

[0442] (Evaluation Criteria)

[0443] A: The number of defects per wafer is less than 100

[0444] B: The number of defects per wafer is more than 100 and less than 300

[0445] C: The number of defects per wafer is more than 300 and less than 500

[0446] D: The number of defects per wafer is more than 500 and less than 1000

[0447] E: The number of defects per wafer is more than 1,000

[0448] [result]

[0449] The following table shows the composition, dilution ratio and evaluation results of the concentrate of the treatment liquid of each example and comparative example. The content in the table is expressed as the concentration (unit: mass %) relative to the total mass of the concentrate of the treatment liquid.

[0450] In the table, the column "Mw" indicates the weight average molecular weight.

[0451] The column "A) / B)" shows the mass ratio of the content of the polycarboxylic acid to the content of the specific polymer.

[0452] The column "B) / C)" shows the mass ratio of the content of the specific polymer to the content of the amino alcohol.

[0453] The column "B) / D)" shows the mass ratio of the content of the specific polymer to the content of the antimicrobial agent.

[0454] The numerical value in the "pH" column indicates the pH of the concentrate at 25°C measured by the above-mentioned pH meter.

[0455] The column "Dilution ratio (times)" indicates the dilution ratio (volume ratio) when the concentrated solution of the composition described in the table is used in the test. For example, in Example 1, each evaluation was performed using a treatment solution obtained by diluting the concentrated solution of the composition described in Table 1 with ultrapure water to a volume ratio of 200 times.

[0456]

[0457]

[0458]

[0459]

[0460] From the results in the table, it was confirmed that the processing liquid of the example of the present invention was excellent in defect removal performance on poly-Si, SiC or SiCN.

[0461] On the other hand, the treatment liquid of the comparative example not containing the specific polymer did not obtain a sufficient effect on defect removal properties on poly-Si, SiC, or SiCN.

[0462] It was confirmed that when the weight average molecular weight of the specific polymer is 1000 to 50000, the effect of the present invention and the defect removal property on SiN are more excellent, and when it is 1000 to 20000, the effect of the present invention and the defect removal property on SiN are further excellent (comparison of Example 6, Example 28 and Examples 31 to 33).

[0463] It was confirmed that, in the specific polymer, when the nonionic monomer has an aliphatic hydrocarbon group, the effect of the present invention is more excellent (comparison of Examples 34 to 47, etc.).

[0464] It was confirmed that when the polycarboxylic acid has a hydroxyl group, defect removal properties on SiN are more excellent (comparison between Example 6 and Examples 66 to 70).

[0465] It was confirmed that when the mass ratio of the content of polycarboxylic acid to the content of polymer is 0.2 to 50, at least one of the effect of the present invention and the defect removal property on SiN is better, and when it is 1 to 30, the defect removal property on SiN is better (comparison of Example 6 and Examples 91 to 96, etc.).

[0466] It was confirmed that when the number of hydroxyl groups contained in the amino alcohol is 2 or more, the defect removal property on SiN is more excellent, and when the number of hydroxyl groups contained in the amino alcohol is 3 or more, the effect of the present invention is more excellent (comparison of Examples 97 to 101).

[0467] It was confirmed that when the mass ratio of the polymer content to the amino alcohol content was 0.005 to 0.5, the effect of the present invention and the defect removal property on SiN were more excellent (comparison of Examples 91 to 96, etc.).

[0468] It was confirmed that when the mass ratio of the content of the polymer to the content of the antibacterial agent was 1.0 to 20.0, the defect removal property on SiN was more excellent (comparison of Examples 91 to 96, etc.).

[0469] It was confirmed that in the defect removability evaluation test, when the copolymerization ratio of the specific polymer used in each example was changed from 50 / 50 to within the range of 25 / 75 to 55 / 45, the same evaluation results as those of the treatment liquids in each example were obtained.

[0470] In the above-mentioned defect removability evaluation test, the object to be processed (wafer with poly-Si, wafer with SiC, wafer with SiCN or wafer with SiN) after the above-mentioned CMP treatment was used, and the surface of the ground wafer was further subjected to a polishing treatment.

[0471] In the polishing process, the processing liquids of Examples 4 to 8 and 66 to 70 adjusted to room temperature (23° C.) as the polishing composition were used. In addition, the polishing process was performed using the polishing apparatus used in the above CMP process under the conditions of polishing pressure: 2.0 psi, supply rate of the polishing composition: 250 mL / min, and polishing time: 60 seconds.

[0472] Thereafter, the polished wafers were cleaned for 30 seconds using the treatment solutions of Examples 4 to 8 and 66 to 70 adjusted to room temperature (23° C.), and then dried. The treatment solution used in the polishing process was the same as the treatment solution used in the above cleaning.

[0473] It was confirmed that the cleaning performance of the treatment liquid was evaluated for the polished surface of the obtained wafer according to the above-mentioned evaluation test method of "defect removal performance", and the defect removal performance on poly-Si, SiC and SiCN showed an evaluation result one level higher than the evaluation of each example recorded in the table when each treatment liquid was used. For example, in the above-mentioned table, the evaluation of defect removal performance on poly-Si, SiC and SiCN of Example 4 was B, but when the treatment liquid of Example 4 was used in the above-mentioned polishing process and the subsequent cleaning process, the evaluation of defect removal performance on poly-Si, SiC and SiCN was A.

Claims

1. A processing liquid for semiconductor manufacturing, comprising: Polycarboxylates; and A polymer comprising a repeating unit A derived from a nonionic monomer and a repeating unit B having an anionic group.

2. The semiconductor manufacturing processing liquid according to claim 1, wherein The repeating unit A is a repeating unit represented by formula (1), In formula (1), R 1 represents a hydrogen atom or an alkyl group, L 1 Represents a single bond, -COO- or -C0-NR a -, R a represents a hydrogen atom or an alkyl group, X 1 represents a hydrogen atom, a hydrocarbon group or a group comprising a polymer chain, wherein the methylene group in the hydrocarbon group is optionally substituted by -C0- or -O-, Among them, X 1 When L is a hydrogen atom, 1 Indicates -CO-NR a -.

3. The semiconductor manufacturing processing liquid according to claim 2, wherein: L 1 Indicates -COO- or -C0-NR a -.

4. The semiconductor manufacturing processing liquid according to claim 1, wherein The ClogP of the nonionic monomer is -1.00 to 5.

00.

5. The semiconductor manufacturing processing liquid according to claim 1, wherein The repeating unit B is a repeating unit represented by formula (2), In formula (2), R b represents a hydrogen atom or an anionic group, R 2 represents a hydrogen atom or an alkyl group, L 2 represents a single bond or a divalent connecting group, X 2 It represents an anionic group.

6. The semiconductor manufacturing processing liquid according to claim 5, wherein The anionic group is a carboxylic acid group, a sulfonic acid group or a phosphonic acid group.

7. The semiconductor manufacturing processing liquid according to claim 1, wherein The polycarboxylic acid has a hydroxyl group.

8. The semiconductor manufacturing processing liquid according to claim 1, wherein The weight average molecular weight of the polymer is 1,000 to 50,000.

9. The semiconductor manufacturing processing liquid according to claim 1, wherein The mass ratio of the content of the polycarboxylic acid to the content of the polymer is 1 to 30.

10. The semiconductor manufacturing processing liquid according to claim 1, wherein the pH thereof is 2.0 to 10.

0. The semiconductor manufacturing processing liquid according to claim 1 , further comprising an amino alcohol.

12. The semiconductor manufacturing processing liquid according to claim 11, wherein The amino alcohol has 2 or more hydroxyl groups.

13. The semiconductor manufacturing processing liquid according to claim 11, wherein The mass ratio of the content of the polymer to the content of the amino alcohol is 0.005 to 0.

5. The semiconductor manufacturing processing liquid according to claim 1 , further comprising an antibacterial agent.

15. The semiconductor manufacturing processing liquid according to claim 14, wherein The mass ratio of the polymer content to the antibacterial agent content is 0.1 to 200. 16 . The semiconductor manufacturing processing liquid according to claim 1 , which is used for a processing object including at least one selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride.

17. A method for cleaning a treated object, comprising the following steps: An object to be processed containing at least one selected from the group consisting of polycrystalline silicon, silicon carbide, and silicon carbonitride is cleaned using the processing liquid for semiconductor manufacturing according to any one of claims 1 to 15.

18. A method for manufacturing a semiconductor, comprising the method for cleaning an object to be processed according to claim 17.

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