Processing solution for semiconductor substrate

Abstract

The present invention aims to provide a processing solution for semiconductor substrates that exhibits excellent storage stability, excellent tungsten corrosion resistance, and excellent cleaning properties for CMP-treated tungsten-containing semiconductor substrates. The semiconductor substrate processing solution of the present invention comprises an amphoteric compound, an antibacterial agent, and an amino alcohol. The amphoteric compound comprises acid groups with a pKa less than 4.5 and base groups with a pKa greater than 4.5, with the number of base groups exceeding the number of acid groups.

Description

Technical Field

[0001] This invention relates to a processing liquid for semiconductor substrates. Prior Technology

[0002] Photolithography is used to form fine electronic circuit patterns on a substrate to manufacture semiconductor devices such as CCDs (Charge-Coupled Devices) and memory. Specifically, a photoresist film is formed on a stack of layers containing a metal film that serves as wiring material, an etch stop layer, and an interlayer insulating layer on the substrate, and photolithography and dry etching steps (such as plasma etching) are performed to manufacture semiconductor devices.

[0003] In the manufacture of semiconductor devices, chemical mechanical polishing (CMP) is performed to planarize the surface of a semiconductor substrate containing metal wiring films, barrier metals, and insulating films using an polishing slurry containing abrasive particles (e.g., silicon dioxide and aluminum oxide). During CMP processing, residues such as the abrasive particles used, the polished wiring films, and / or metal components derived from barrier metals can easily remain on the surface of the semiconductor substrate after CMP treatment. These residues can cause short circuits between wirings and may adversely affect the electrical properties of semiconductors. Therefore, a cleaning step is usually performed to remove these residues from the surface of the semiconductor substrate.

[0004] For example, Patent Document 1 discloses the following: "A composition for cleaning semiconductors or for chemical mechanical polishing of substrates containing cobalt, comprising component (A-1), at least one selected from the group consisting of component (A-2) and component (A-3), and component (B) selected from the group consisting of at least one of (A-1) glutamic acid, (A-2) histidine, (A-3) cysteine, (B) inorganic acid and its salt."

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-188090 Summary of the Invention

[0006] The inventors studied the semiconductor substrate processing solution described in Patent Document 1, etc., and found that at least one of (1) storage stability, (2) tungsten corrosion resistance, and (3) cleanability of CMP-treated tungsten semiconductor substrates was poor. Furthermore, the aforementioned storage stability refers to the ability to inhibit the growth of mold and bacteria in the processing solution when storing semiconductor substrates.

[0007] Therefore, the objective of this invention is to provide a processing solution for semiconductor substrates that exhibits excellent storage stability, excellent tungsten corrosion resistance, and excellent cleaning properties for CMP-treated tungsten-containing semiconductor substrates.

[0008] The inventors have discovered that the above-mentioned problems can be solved by the following structure.

[0009] [1] A processing solution for semiconductor substrates comprises an amphoteric compound, an antibacterial agent, and an amino alcohol. The aforementioned amphoteric compounds contain acid groups with pKa less than 4.5 and base groups with pKa greater than 4.5. The number of the above bases is greater than the number of the above acid groups. [2] The semiconductor substrate processing solution as described in [1], wherein The aforementioned amphoteric compounds contain basic amino acids. [3] The semiconductor substrate processing solution as described in [1] or [2], wherein The aforementioned antimicrobial agents include at least one antimicrobial agent selected from the group consisting of cationic antimicrobial agents, carboxylic acid antimicrobial agents, phenolic antimicrobial agents, isothiazolino antimicrobial agents, and alcoholic antimicrobial agents. [4] The semiconductor substrate processing solution described in any one of [1] to [3] further comprises an organic acid. [5] The semiconductor substrate processing solution as described in any one of [1] to [4], wherein the pH is 4.0 to 8.0. [6] The semiconductor substrate processing solution as described in any one of [1] to [5], wherein the mass ratio of the content of the above-mentioned amphoteric compound to the content of the above-mentioned antibacterial agent is 3.00 to 50.00. [7] The semiconductor substrate processing solution as described in any one of [1] to [6], wherein the mass ratio of the content of the above-mentioned amino alcohol to the content of the above-mentioned antibacterial agent is 10.00 to 150.00. [8] The semiconductor substrate processing solution described in any one of [1] to [7] is used to clean a tungsten semiconductor substrate that has undergone chemical mechanical polishing. [Invention Effects]

[0010] According to the present invention, a processing solution for semiconductor substrates can be provided, which has excellent storage stability, excellent tungsten corrosion resistance, and excellent cleaning properties for CMP-treated semiconductor substrates containing tungsten. Implementation

[0011] Hereinafter, an example of a form used to implement the present invention will be described. In this specification, the numerical range represented by "~" refers to the range including the values ​​recorded before and after "~" as the lower and upper limits.

[0012] In this specification, when a certain ingredient exists in two or more forms, the “content” of the ingredient refers to the total content of these two or more ingredients. Unless otherwise specified, the compounds described in this specification may contain structural isomers, optical isomers, and isotopes. Furthermore, structural isomers, optical isomers, and isotopes may be contained individually or in more than two forms.

[0013] In this instruction manual, psi refers to pound-force per square inch, which means 1 psi = 6894.76 Pa. In this specification, “ppm” means “parts-per-million(10⁻⁶): parts per million”, and “ppb” means “parts-per-billion(10⁻⁹): parts per billion”.

[0014] Unless otherwise specified, in this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​converted from the polystyrene of the standard material measured by gel permeation chromatography (GPC) using TSKgel GMHxL, TSKgel G4000HxL or TSKgel G2000HxL (all manufactured by TOSOH CORPORATION) as the column, tetrahydrofuran as the eluent, a differential refractometer as the detector, and polystyrene as the standard material. Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight average molecular weight.

[0015] In this specification, "total mass of components other than solvents in the treatment solution" refers to the total content of all components contained in the treatment solution, excluding solvents such as water and organic solvents.

[0016] [Processing solution for semiconductor substrates] The semiconductor substrate processing solution of the present invention (hereinafter also referred to as "processing solution") comprises an amphoteric compound (hereinafter also referred to as "specific compound"), an antibacterial agent, and an amino alcohol. The amphoteric compound comprises acid groups with a pKa less than 4.5 and base groups with a pKa greater than 4.5, wherein the number of base groups is greater than the number of acid groups.

[0017] The mechanism by which the above structure solves the problem of the present invention is not yet clear, but it is speculated that the various components work synergistically to achieve the desired effect. In particular, it is speculated that certain compounds contribute to the corrosion resistance of tungsten, antibacterial agents contribute to preservation stability, and amino alcohols contribute to the corrosion resistance of tungsten. Furthermore, by combining specific compounds and amino alcohols, a protective film can be synergistically formed on the surface of tungsten, which also contributes to the corrosion resistance of tungsten. Hereinafter, the superior performance of at least one of the following effects—stability, corrosion resistance of tungsten, and cleanability of CMP-treated tungsten semiconductor substrates—is also referred to as "superior performance of the present invention." The following is a detailed description of the various components that can be contained in the treatment solution.

[0018] [Specific compound] The treatment solution contains specific compounds. A specific compound is a compound that contains acid groups with a pKa less than 4.5 and base groups with a pKa greater than 4.5, and the number of the base groups is greater than the number of the acid groups. Certain compounds can be in the form of salts (e.g., well-known salts).

[0019] Certain compounds have acid groups with pKa less than 4.5. The pKa of the above-mentioned acid groups is preferably less than 4.5, less than 4.0, more preferably less than 3.5, and even more preferably less than 3.0. The lower limit is preferably 1.0 or above, and more preferably 1.5 or above. When one of the above-mentioned acid groups has a plurality of pKas, the lowest of the plurality of pKas is less than 4.5. Specifically, when one of the above-mentioned acid groups has, for example, three pKas: 1, 5, and 10, the lowest 1 pKa is less than 4.5, and therefore is equivalent to the above-mentioned acid group. When a particular compound has a plurality of acid groups, the particular compound has acid groups with a pKa less than 4.5, and if the number of bases with a pKa greater than 4.5 is greater than the number of acid groups with a pKa less than 4.5, then the particular compound may further have acid groups with a pKa greater than 4.5. The pKa values ​​of the aforementioned acid groups are calculated in water (at 25°C) using a Calculator Plugin (manufactured by Fujitsu Limited). Furthermore, in cases where the above-mentioned water measurement is not possible, the values ​​are calculated in dimethyl sulfoxide.

[0020] Examples of the aforementioned acid groups include carboxyl, thiol, sulfonic acid, sulfonamide, phosphonic acid, sulfonylidinylimino, and phenolic hydroxyl groups, with carboxyl being preferred.

[0021] Certain compounds have bases with a pKa greater than 4.5. The pKa of the above-mentioned bases is preferably above 4.5, above 5.0, even better above 6.0, and further better above 7.0. The upper limit is preferably below 13.0, and even better below 12.5. In a specific compound, if one of the aforementioned bases has multiple pKas, the highest pKa among the multiple pKas must exceed 4.5. Specifically, if the aforementioned base has three pKas: 1 pKa: 1, 2 pKa: 4, and 3 pKa: 10, the highest 3 pKa must exceed 4.5, and therefore be equivalent to the aforementioned base. Furthermore, when a particular compound has a plurality of bases, the particular compound may have bases with a pKa greater than 4.5, and the number of bases with a pKa greater than 4.5 may be greater than the number of acid groups with a pKa less than 4.5. The particular compound may further have bases with a pKa less than 4.5. The pKa of the above-mentioned bases can be calculated using the same method as that used for determining the pKa of acid groups. Furthermore, the pKa of the above-mentioned bases represents the pKa of the conjugate acid of the base.

[0022] Examples of such bases include those containing a nitrogen atom, specifically primary amino groups (-NH₂), secondary amino groups (>NH) such as guanidine groups, tertiary amino groups (>N-), quaternary ammonium salt groups, and heterocyclic groups with a nitrogen atom as a ring member. Furthermore, secondary, tertiary, and quaternary ammonium salt groups are classified as heterocyclic groups with a nitrogen atom as a ring member when they constitute a ring member, and are classified as the highest-order amino groups when they have different orders. A heterocyclic group having a nitrogen atom as a ring member can be either an aliphatic heterocyclic group having a nitrogen atom as a ring member or an aromatic heterocyclic group having a nitrogen atom as a ring member. Examples of heterocyclic groups include aliphatic heterocyclic groups such as pyrrolidine cyclic group and piperidine cyclic group, and aromatic heterocyclic groups such as pyridine cyclic group, imidazole cyclic group and indole cyclic group. It is preferable that the base comprises at least one group selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium salt groups and heterocyclic groups having a nitrogen atom as a ring member atom, and it is even more preferable that it comprises at least one group selected from the group consisting of primary amino groups, secondary amino groups and heterocyclic groups having a nitrogen atom as a ring member atom.

[0023] The number of bases with pKa greater than 4.5 is greater than the number of acid groups with pKa less than 4.5. Specifically, the value of subtracting the number of acid groups from the number of bases (the number of bases - the number of acid groups) is 1 or more, preferably 1 to 5, and even more preferably 1 or 2. The number of the above-mentioned acid groups is 1 or more, 1 to 10 is preferred, 1 to 3 is even better, and 1 is further preferred. The number of bases mentioned above is 2 or more, 2 to 11 is preferred, 2 to 4 is even better, and 2 is further preferred.

[0024] It is preferable that the specific compound contains a basic amino acid, more preferably that it contains at least one compound selected from the group consisting of arginine, histidine, lysine, ornithine, 2,4-diaminobutyric acid, tryptophan, asparagine and glutamine, further preferably that it contains at least one compound selected from the group consisting of arginine, histidine, lysine, ornithine and 2,4-diaminobutyric acid, and even more preferably that it contains at least one compound selected from the group consisting of arginine, histidine and lysine, and especially preferably that it contains arginine.

[0025] A particular compound may be used alone or in two or more forms, but it is preferable to use two or more (e.g., two types). The content of a particular compound is typically 0.01 to 70.0% by mass, 0.2 to 70.0% by mass is preferred, 1.0 to 50.0% by mass is even better, 3.0 to 40.0% by mass is further preferred, and 5.0 to 20.0% by mass is particularly preferred, relative to the total mass of the components in the treatment solution excluding the solvent.

[0026] [Antibacterial agents] The treatment solution contains an antibacterial agent. Antimicrobial agents are compounds that have antimicrobial activity against bacteria and / or antifungal activity against mold, and are compounds that are different from the specific compounds mentioned above and the various components described below. Antibacterial agents can be in the form of salts (e.g., known salts).

[0027] Examples of antibacterial agents include cationic antibacterial agents (antibacterial agents with a cationic structure), carboxylic acid antibacterial agents (antibacterial agents with a carboxyl group), phenolic antibacterial agents (antibacterial agents with a phenolic hydroxyl group), isothiazolinic antibacterial agents (antibacterial agents with an isothiazolinic structure), alcoholic antibacterial agents (antibacterial agents with a hydroxyl group), peracetic acid, and hydrogen peroxide. Furthermore, antibacterial agents with carboxyl groups and phenolic hydroxyl groups are classified as carboxylic acid antibacterial agents.

[0028] Examples of cationic antibacterial agents include alkyl dimethyl benzyl ammonium chloride, benzoxanil chloride, and domiphen bromide, with benzoxanil chloride being preferred. As carboxylic acid-based antibacterial agents, examples include unsaturated carboxylic acids such as sorbic acid, and aromatic carboxylic acids such as benzoic acid and salicylic acid, with sorbic acid, benzoic acid, or salicylic acid being preferred. Examples of phenolic antibacterial agents include cresol, chlorpyrifos, dichloroxylenol, and hexachlorophenol. As isothiazolinone-based antibacterial agents, such as methylchloroisothiazolinone and methylisothiazolinone. As alcohol-based antibacterial agents, such as phenoxyethanol, 1,2-pentanediol and 1,2-hexanediol.

[0029] The antimicrobial agent preferably includes at least one antimicrobial agent selected from the group consisting of cationic antimicrobial agents, carboxylic acid antimicrobial agents, phenolic antimicrobial agents, isothiazolinite antimicrobial agents, and alcoholic antimicrobial agents; more preferably, it includes at least one antimicrobial agent selected from the group consisting of chlorobenzanol, carboxylic acid antimicrobial agents, and isothiazolinite antimicrobial agents; and even more preferably, it includes at least one antimicrobial agent selected from the group consisting of chlorobenzanol, salicylic acid, benzoic acid, sorbic acid, methylchloroisothiazolinone, and methylisothiazolinone.

[0030] Antibacterial agents can be used alone or in combination, but it is better to use two or more (e.g., two types). The content of antibacterial agent is preferably 0.01 to 30.0% by mass relative to the total mass of the components other than the solvent in the treatment solution, more preferably 0.05 to 12.0% by mass, further preferably 0.1 to 10.0% by mass, and especially preferably 0.2 to 5.0% by mass.

[0031] [Amino alcohols] Amino alcohols are compounds having one or more amino groups selected from primary, secondary, and tertiary amino groups and one or more hydroxyl groups. Amino alcohols are compounds that differ from the various components mentioned above. Examples of amino alcohols include primary, secondary, and tertiary amino alcohols. Furthermore, amino alcohols with different degrees of amino groups are classified as those with the highest degree of amino groups.

[0032] Examples of primary amino alcohols include tris(hydroxymethyl)aminomethane (Tris), monoethanolamine (MEA), 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol, 2-amino-2-methyl-1-propanol (AMP), 3-amino-1-propanol, 1-amino-2-propanol, diethylene glycolamine (DEGA), and 2-(aminoethoxy)ethanol (AEE).

[0033] Examples of secondary amino alcohols include 1,3-bis[tris(hydroxymethyl)methylamino]propane, uracil, N-methylethanolamine, 2-(ethylamino)ethanol, 2-[(hydroxymethyl)amino]ethanol, 2-(propylamino)ethanol, N,N'-bis(2-hydroxyethyl)ethylenediamine, diethanolamine, 2-(2-aminoethylamino)ethanol (AAE), N-butylethanolamine, and N-cyclohexylethanolamine.

[0034] Examples of tertiary amino alcohols include bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane (Bis-Tris-Propane), N-methyldiethanolamine (MDEA), 2-(dimethylamino)ethanol (DMAE), N-ethyldiethanolamine (EDEA), 2-diethylaminoethanol, 2-(dibutylamino)ethanol, 2-[2-(dimethylamino)ethoxy]ethanol, 2-[2-(diethylamino)ethoxy]ethanol, triethanolamine, N-butyldiethanolamine (BDEA), and N-tertiary butyldiethanolamine. Ethanolamine (t-BDEA), 1-[bis(2-hydroxyethyl)amino]-2-propanol (Bis-HEAP), 1-(2-hydroxyethyl)piperidine (HEP), 1,4-bis(2-hydroxyethyl)piperidine (BHEP), 2-(N-ethylaniline)ethanol, N-phenyldiethanolamine (Ph-DEA), N-benzyldiethanolamine, p-tolyldiethanolamine, m-tolyldiethanolamine, 2-(dimethylamino)-1,3-propanediol, 2-[[2-(dimethylamino)ethyl]methylamino]ethanol, and stearyldiethanolamine.

[0035] It is preferable that the amino alcohols include those with quaternary carbon atoms. The aforementioned amino alcohols may have one or two or more quaternary carbon atoms. Examples of amino alcohols with quaternary carbon atoms include Tris, Bis-Tris, and Bis-Tris-Propane.

[0036] The amino alcohol preferably contains at least one compound selected from the group consisting of Tris, MEA, Bis-Tris, Bis-Tris-Propane, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 1,3-diamino-2-propanol and MDEA; more preferably, it contains at least one compound selected from the group consisting of Tris, Bis-Tris, Bis-Tris-Propane, 2-amino-1,3-propanediol and 3-amino-1,2-propanediol; and even more preferably, it contains at least one compound selected from the group consisting of Tris, Bis-Tris and Bis-Tris-Propane.

[0037] Aminols can be used alone or in combination with one or more, but it is preferable to use two or more (e.g., two types). The content of amino alcohol is preferably 0.01 to 80.0% by mass relative to the total mass of components other than solvent in the treatment solution, more preferably 2.0 to 72.0% by mass, further preferably 5.0 to 68.0% by mass, and especially preferably 10.0 to 60.0% by mass.

[0038] [Ratio of various components] The mass ratio of the content of the specific compound to the content of the antimicrobial agent (content of the specific compound / content of the antimicrobial agent) is usually 0.10~1000.00, 1.00~60.00 is preferred, 2.00~55.00 is even better, 3.00~50.00 is further preferred, and 3.00~30.00 is particularly preferred. The mass ratio of amino alcohol content to antibacterial agent content (amino alcohol content / antibacterial agent content) is usually 1.00~4000.00, with 4.00~180.00 being preferred and 10.00~150.00 being even better. The mass ratio of the content of a specific compound to the content of an amino alcohol (content of specific compound / content of amino alcohol) is typically 0.01 to 20.00, with 0.10 to 6.00 being preferred, 0.12 to 4.00 being even better, and 0.20 to 2.00 being further preferred.

[0039] [Organic acids] The treatment solution may contain organic acids. Organic acids are compounds that differ from the various components mentioned above. For example, organic acids that do not have antibacterial activity against bacteria or antifungal activity against mold can be cited. Examples of organic acids include aliphatic carboxylic acid organic acids and aromatic carboxylic acid organic acids, as well as phosphonic acid organic acids. Carboxylic acid organic acids are preferred, dicarboxylic acids or tricarboxylic acids are preferred, and tricarboxylic acids are even more preferred. Organic acids can be in the form of salts. Examples of such salts include sodium salts, potassium salts, ammonium salts, and organic amine salts.

[0040] Carboxylic acid organic acids are compounds that have one or more carboxyl groups. Carboxylic acid organic acids can further have hydroxyl groups as functional groups other than carboxyl groups. The number of carboxyl groups in carboxylic acid organic acids is preferably 1 to 10, more preferably 2 to 10, and even more preferably 3 to 5.

[0041] Examples of aliphatic carboxylic acid organic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, maleic acid, malic acid, citric acid, tartaric acid, glycolic acid, and gluconic acid. Citric acid, malic acid, tartaric acid, or oxalic acid are preferred, with citric acid being even better. Examples of aromatic carboxylic acid organic acids include phthalic acid, isophthalic acid, terephthalic acid, gallic acid, 1,2,4-benzenetricarboxylic acid, benzoic acid, and cinnamic acid, with 1,2,4-benzenetricarboxylic acid being preferred.

[0042] As phosphonic organic acids, for example, the compounds described in paragraphs

[0026] to

[0036] of International Publication No. 2018 / 020878 and the compounds described in paragraphs

[0031] to

[0046] of International Publication No. 2018 / 030006 are included in this specification.

[0043] The organic acid comprises at least one organic acid selected from the group consisting of citric acid, glycolic acid, malic acid, tartaric acid, gluconic acid, oxalic acid and 1,2,4-benzenetricarboxylic acid, preferably at least one organic acid selected from the group consisting of citric acid, malic acid, tartaric acid and oxalic acid, and even more preferably citric acid.

[0044] Organic acids can be used alone or in combination with two or more. The content of organic acid is preferably 5.0 to 98.0% by mass relative to the total mass of components other than solvent in the treatment solution, more preferably 10.0 to 60.0% by mass, and even more preferably 15.0 to 50.0% by mass.

[0045] 〔polymer〕 The treatment fluid may contain polymers. Water-soluble polymers are preferred as polymers. "Water-soluble polymer" refers to a compound in which two or more constituent units are linked by covalent bonds to form a linear or mesh-like structure, and which has a mass of more than 0.1g dissolved in 100g of water at 20°C.

[0046] Examples of water-soluble polymers include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinylsulfonic acid and their salts; copolymers of monomers such as styrene, α-methylstyrene and / or 4-methylstyrene with acid monomers such as (meth)acrylic acid and / or maleic acid, and their salts; polyglycerol; vinyl-based synthetic polymers such as polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylmethyleneamine, polyethyleneimine, polyvinylpyrazoline, polyvinylimazole and polyallylamine; and modified natural polysaccharides such as hydroxyethyl cellulose, carboxymethyl cellulose and processed starch.

[0047] A water-soluble polymer can be either a polymer that polymerizes one monomer or a copolymer that copolymerizes two or more monomers. As monomers, examples include monomers selected from the group consisting of monomers having a carboxyl group, monomers having a hydroxyl group, monomers having a polyethylene oxide chain, monomers having an amino group, and monomers having a heterocycle. The content of structural units derived from monomers selected from the above-mentioned group in the water-soluble polymer is preferably 95-100% by mass relative to the total mass of the water-soluble polymer, and more preferably 99-100% by mass.

[0048] As polymers, for example, the water-soluble polymers described in paragraphs

[0043] to

[0047] of Japanese Patent Application Publication No. 2016-171294 are also included in this specification.

[0049] The molecular weight (weight average molecular weight with molecular weight distribution) of the polymer is preferably 300 or higher, more preferably 600 or higher, further preferably 2,000 or higher, and especially preferably 10,000 or higher. The upper limit is preferably 1,500,000 or lower, and more preferably 1,000,000 or lower. When the polymer is a water-soluble polymer, it is preferable that the weight average molecular weight of the water-soluble polymer is 300 or more, more preferably 2,000 or more, and even more preferably 10,000 or more. The upper limit is preferably 1,500,000 or less, more preferably 1,200,000 or less, and even more preferably 1,000,000 or less. It is preferable that the polymer contains carboxyl-containing units (e.g., units derived from (meth)acrylic acid). The content of carboxyl-containing units relative to the total mass of the polymer is preferably 30-100% by mass, more preferably 70-100% by mass, and further preferably 85-100% by mass.

[0050] Polymers can be used alone or in combination with two or more polymers. The polymer content, relative to the total mass of components other than the solvent in the treatment solution, is preferably 0.000001~50% by mass, more preferably 0.00001~20% by mass, and further preferably 0.0001~10% by mass. When the polymer content is within the above range, the polymer is appropriately adsorbed onto the surface of the substrate, which helps to improve the metal corrosion resistance of the treatment solution, and the balance between the viscosity and / or cleaning performance of the treatment solution is also excellent.

[0051] [Solvent] The treatment fluid may contain solvents. Examples of solvents include water and organic solvents, with water being preferred. Examples of water types include distilled water, deionized water, and pure water (ultrapure water). From the perspective of minimizing the impact on the semiconductor substrate during the manufacturing process, pure water (ultrapure water) is preferable. The water content is not particularly limited as long as it is the residual portion of components that can be contained in the treatment solution. Specifically, relative to the total mass of the treatment solution, a water content of 1.0% by mass or more is preferred, 30.0% by mass or more is even more preferred, 50.0% by mass or more is further preferred, and 60.0% by mass or more is especially preferred. Relative to the total mass of the treatment solution, an upper limit of 99.99% by mass or less is preferred, 99.9% by mass or less is even more preferred, and 99.0% by mass or less is further preferred.

[0052] As an organic solvent, well-known organic solvents such as alcohols and ketones are preferred. Organic solvents, for example, can be described in paragraphs

[0043] to

[0060] of Japanese Patent Application Publication No. 2021-052186, the contents of which are incorporated herein by reference.

[0053] [Other ingredients] In addition to the components mentioned above, the treatment solution may contain other components. Other components include, for example, amine compounds, quaternary ammonium compounds, pH adjusters, surfactants, and fluorine compounds. Other ingredients may be used alone or in combination with two or more ingredients.

[0054] <Amine compounds> Amine compounds are compounds that are different from the various components that can be contained in the above-mentioned treatment solutions. Amine compounds are compounds having at least one amino group selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups. Furthermore, when amine compounds have amino groups of different orders, they are classified as amine compounds having the highest-order amino group. Examples of amine compounds include guanidine compounds other than aliphatic amines and arginine. The amine compounds mentioned above can be either chain-like (straight-chain or branched-chain) or cyclic.

[0055] (Aliphatic amines) Examples of aliphatic amines include primary aliphatic amines (aliphatic amines with primary amino groups), secondary aliphatic amines (aliphatic amines with secondary amino groups), and tertiary aliphatic amines (aliphatic amines with tertiary amino groups).

[0056] Examples of primary chain aliphatic amines include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, n-octylamine, and 2-ethylhexylamine. Examples of primary cyclic aliphatic amines include cyclohexylamine.

[0057] Examples of secondary chain aliphatic amines include ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine and 1,4-butanediamine, etc., as well as polyalkyl polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA) and tetraethylenepentamine. Examples of secondary cyclic aliphatic amines include piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, and 2,6-dimethylpiperazine.

[0058] Examples of tertiary aliphatic amines include those that have a tertiary amino group in the molecule but no aromatic ring group.

[0059] Examples of tertiary chain aliphatic amines include tertiary alkylamines such as trimethylamine and triethylamine, alkyl diamines such as 1,3-bis(dimethylamino)butane, and polyalkyl polyamines such as N,N,N',N'',N''-pentamethyldiethylenetriamine.

[0060] Examples of tertiary cyclic aliphatic amines include those with a nitrogen atom as a ring member and a non-aromatic heterocycle. Examples of tertiary cyclic aliphatic amines include cyclic amidine compounds and piperidine compounds.

[0061] (Cyclic amidine compounds) Cyclic amidine compounds are compounds that contain heterocyclic rings with amidine structures (>NC=N-) within the ring. The cyclic amidine compound preferably has 5 to 6 ring members in the aforementioned heterocycle, with 6 being more preferred. Examples of cyclic amidine compounds include diazabicycloundecene (1,8-diazabicyclo[5.4.0]undec-7-ene:DBU), diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene:DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimidino[1.2-a]acocoxine, 3,4,6,7,8,9-hexahydro-2H-pyridino[1.2-a]pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo[1.2-a]imidazole, 3-ethyl-2,3,4,6,7,8,9,10-octahydro-1-(benzyl)-pyrimidino[1,2-α]azapyridine chloride, and creatine anhydride, with DBU or DBN being preferred.

[0062] (piperazine compound) Piperidine compounds are heterocyclic 6-membered rings (piperidine rings) in which the -CH- group of the cyclohexane ring is replaced by a tertiary amino group (>N-).

[0063] Examples of piperidine compounds include 1-methylpiperidine, 1-ethylpiperidine, 1-propylpiperidine, 1-butylpiperidine, 1,4-dimethylpiperidine, 1-phenylpiperidine, N-(2-aminoethyl)piperidine (AEP), 1,4-bis(2-aminoethyl)piperidine (BAEP), 1,4-bis(3-aminopropyl)piperidine (BAPP), and 1,4-diazabicyclo[2.2.2]octane (DABCO), with DABCO being preferred.

[0064] Examples of tertiary cyclic aliphatic amines include compounds with heterocyclic 5-membered rings that do not possess aromaticity such as 1,3-dimethyl-2-imidazolidineone, and compounds with nitrogen 7-membered rings.

[0065] <Quaternary ammonium compounds> Quaternary ammonium compounds are compounds that are different from the components that can be contained in the aforementioned treatment solutions. Examples of quaternary ammonium compounds include quaternary ammonium hydroxides, quaternary ammonium fluorides, quaternary ammonium bromides, quaternary ammonium iodides, quaternary ammonium acetates, and quaternary ammonium carbonates.

[0066] Examples of quaternary ammonium compounds include tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH), tetramethylammonium hydroxide (TMAH), trimethylammonium hydroxide (TMEAH), dimethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), tetraethylammonium hydroxide (TEAH), and tetrapropylammonium hydroxide. Ammonium (TPAH), tetrabutylammonium hydroxide (TBAH), 2-hydroxyethyltrimethylammonium hydroxide (choline), bis(2-hydroxyethyl)dimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and hexadecylmethylammonium hydroxide, THEMAH are preferred. As a quaternary ammonium compound, for example, the compounds described in paragraph

[0021] of Japanese Patent Application Publication No. 2018-107353 can also be used, and these contents are incorporated in this specification.

[0067] Quaternary ammonium compounds with asymmetrical structures are also preferred. A "symmetric structure" in quaternary ammonium compounds means that the four substituents (such as hydrocarbons) substituted by the nitrogen atom are all different. As a quaternary ammonium compound having an asymmetric structure, for example, THEMAH, TMEAH, DEDMAH, TEMAH, choline, and bis(2-hydroxyethyl)dimethylammonium hydroxide can be cited.

[0068] <pH adjuster> The pH adjuster is a compound different from the components that can be contained in the above treatment liquid. As the pH adjuster, for example, basic compounds and acidic compounds can be cited. Furthermore, by adjusting the addition amounts of various components that can be contained in the above treatment liquid, the pH of the treatment liquid can be adjusted. As the pH adjuster, for example, paragraphs

[0053] to

[0054] of International Publication No. 2019-151141 and paragraph

[0021] of International Publication No. 2019-151001 can be cited, and these contents are incorporated into this specification.

[0069] The content of the pH adjuster is appropriately adjusted according to the types and amounts of other components and the target pH of the treatment liquid. Relative to the total mass of the components other than the solvent in the treatment liquid, the content of the pH adjuster is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and still more preferably 1.5 to 5.0% by mass.

[0070] <Surfactant> As the surfactant, it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule. As the surfactant, for example, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be cited.

[0071] As the surfactant, for example, the descriptions in paragraphs

[0091] to

[0109] of International Publication No. 2021 / 054009 can be cited, and these contents are incorporated into this specification.

[0072] Relative to the total mass of the components other than the solvent in the treatment liquid, the content of the surfactant is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, and still more preferably 10.0 to 20.0% by mass.

[0073] <Fluorine compound> As fluorine compounds, examples include those described in paragraphs

[0013] to

[0015] of Japanese Patent Application Publication No. 2005-150236, the contents of which are incorporated herein by reference.

[0074] The contents of various components that may be contained in the above-mentioned treatment solution can be determined by known methods such as gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and ion-exchange chromatography (IC).

[0075] [Physical properties of the treatment solution] <ph> The pH of the treatment solution is usually 1.0~13.0, with 4.0~8.0 being better and 5.0~7.0 being even better. The pH of the pre-diluted treatment solution is usually 1.0~13.0, with 3.0~9.0 being the best and 4.0~8.0 being even better. The pH of the diluted treatment solution (e.g., 200-fold dilution (volume ratio)) is typically 1.0–13.0, with 3.5–9.0 being preferred, 4.0–8.0 being even better, and 5.0–7.0 being even better. The pH of the treatment solution can be measured using a known pH meter in accordance with the method of JIS Z8802-1984. The pH values ​​mentioned above are measured at a temperature of 25°C.

[0076] <Content of metallic impurities> Regarding the content of metallic impurities (Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag metallic elements) (as an example concentration determination), it is preferable that any metallic impurity content be below 5 ppm by mass relative to the total mass of the processing solution, and even better, below 1 ppm by mass. From the viewpoint of manufacturing cutting-edge semiconductor devices, it is further preferable that the content of the aforementioned metallic impurities be below 100 ppb by mass relative to the total mass of the processing solution, and even better that it be below the detection limit. The lower limit relative to the total mass of the processing solution is typically above 0 ppb by mass.

[0077] Methods for reducing metal content include, for example, purification processes such as distillation and filtration using ion exchange resins or filters during the raw material stage of manufacturing the treatment solution or in the stage after manufacturing the treatment solution. As another method to reduce metal content, one can cite using containers that minimize the leaching of the impurities described later, which are used as containers for holding raw materials or manufactured processing solutions. Alternatively, one can cite lining the inner walls of piping with fluoropolymer resin to suppress the leaching of metal components from piping during the manufacture of the processing solution.

[0078] <Inorganic and Organic Particles> The total content of inorganic and organic particles relative to the total mass of the treatment solution is preferably below 1.0% by mass, more preferably below 0.1% by mass, further preferably below 0.01% by mass, and especially preferably below the detection limit. The lower limit relative to the total mass of the treatment solution is preferably above 0% by mass. The inorganic and organic particles that can be contained in the treatment liquid are particles such as organic solids and inorganic solids contained as impurities in the raw materials, as well as particles such as organic solids and inorganic solids introduced as pollutants during the preparation of the treatment liquid. They are equivalent to particles that do not dissolve in the treatment liquid in the end. The content of inorganic and organic particles present in the treatment liquid can be determined in the liquid phase using a commercially available measuring device that uses laser light as a light scattering type liquid particle measurement method. Methods for removing inorganic and organic particles include, for example, purification processes such as filtration, which will be described later.

[0079] [Manufacturing of the treatment fluid] The treatment fluid can be manufactured using known methods. The method for manufacturing the treatment solution is preferably one that includes a solution preparation step.

[0080] [Preparation steps] The preparation step of the treatment solution is, for example, adjusting the treatment solution by mixing the various components that can be contained in the above-mentioned treatment solution. There are no particular restrictions on the order and timing of mixing the various components. For example, as a solution preparation step, one could add the various components to a container filled with purified water (ultrapure water) and stir, and then add a pH adjuster as needed. The method of adding the purified water and the various components to the container can be either a single addition or a batch addition.

[0081] As a stirring method in the preparation step of the treatment liquid, for example, the method of stirring using a known mixer or a known disperser can be cited. Examples of the aforementioned mixers include industrial mixers, portable mixers, mechanical mixers, and magnetic mixers. Examples of the aforementioned dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

[0082] The mixing of the above-mentioned components in the preparation step of the treatment solution, the purification treatment described later, and the storage temperature of the manufactured treatment solution are preferably below 40°C, and more preferably below 30°C. The lower limit is preferably above 5°C, and more preferably above 10°C.

[0083] <Purification Process> It is preferable that at least one of the raw materials for the treatment solution is purified before the solution preparation step. The purity of the purified raw material is preferably 99% by mass or higher, and even better if it is 99.9% by mass or higher. The upper limit is preferably below 99.9999% by mass.

[0084] Purification processes include, for example, distillation, and filtration processes such as ion exchange resins, RO membranes (Reverse Osmosis Membrane), and filtration, which will be described later. Purification processes can be implemented by combining multiple of the above-described purification methods. For example, after a first purification process in which the raw material is passed through an RO membrane, a second purification process can be performed in which the obtained raw material is passed through a purification device composed of cation exchange resin, anion exchange resin, or mixed-bed ion exchange resin. Furthermore, purification processes can also be performed multiple times.

[0085] As a filter used for filtration, for example, a well-known filter can be cited. As for filter materials, from the viewpoint of being able to remove highly polar foreign matter that is prone to causing defects, examples include fluoropolymers such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density or ultra-high molecular weight). Polyethylene, polypropylene (including high-density polypropylene), fluoropolymers (including PTFE and PFA) or polyamide resins (including nylon) are preferred, with fluoropolymers being even more preferred.

[0086] A critical surface tension of 70-95 mN / m is preferred for the filter, and 75-85 mN / m is even better. Within this range, highly polar foreign matter, which is prone to causing defects, can be removed. The critical surface tension of the filter can be determined using the manufacturer's nominal value.

[0087] A filter pore size of 2-20 nm is preferred, and 2-15 nm is even better. When the filter pore size is within this range, clogging can be prevented, and fine foreign matter such as impurities and clumps can be removed. The filter pore size can be the manufacturer's nominal value.

[0088] Filtration can be performed once or twice or more. When filtration is performed more than twice, the filters used for filtration can be the same or different.

[0089] The filtration temperature is preferably below 25°C, more preferably below 23°C, and further preferably below 20°C. The lower limit is preferably above 0°C, more preferably above 5°C, and further preferably above 10°C. Filtration within the above ranges can remove foreign matter and impurities dissolved in the raw material.

[0090] <container> The treatment fluid (including the diluted treatment fluid described below) can be filled into any container for storage, transportation and use, provided it does not corrode the container.

[0091] As a container, it is preferable to use a container with high cleanliness for semiconductor applications, and a container that suppresses the leaching of impurities from the inner wall of the container's containment section into the processing liquid. Examples of containers used in this field include commercially available semiconductor processing fluid containers. Specifically, examples include the Clean Bottle series (manufactured by AICELLO CHEMICAL CO., LTD.) and the PURE BOTTLE (manufactured by KODAMA PLASTICS Co., Ltd.). Furthermore, as a container, it is preferable that the inner wall of the container's housing and the liquid contacting part are made of fluoropolymer (perfluoropolymer) or metal that has undergone rust prevention treatment and metal leaching prevention treatment. It is preferable that the inner wall of the container is made of at least one resin selected from the group consisting of polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, or a resin different from the above resins, or a metal formed by rust prevention treatment and metal leaching prevention treatment such as stainless steel, Herstal alloy, Ingonan nickel alloy and Monel alloy.

[0092] Of the different resins mentioned above, fluoropolymers (perfluorinated resins) are preferred. Containers with inner walls made of fluororesin are better able to suppress the leaching of ethylene and propylene oligomers compared to containers with inner walls made of polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. Examples of containers with fluoropolymer inner walls include pure fluorinated PFA composite drums (manufactured by Nihon Entegris KK), containers described in Japanese Patent Publication No. 3-502677, International Publication No. 2004 / 016526, and International Publication No. 99 / 046309.

[0093] Furthermore, in addition to the aforementioned fluororesin, it is also preferable for the inner wall of the container to be made of quartz and electrolytically polished metal materials (metal materials that have undergone electrolytic polishing). The metal material used to manufacture the metal material for the above-mentioned electrolytic polishing preferably includes at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is more than 25% by mass relative to the total mass of the metal material. For example, stainless steel and nickel-chromium alloys can be cited. The total chromium and nickel content in the metallic material should ideally be 30% by mass or more relative to the total mass of the metallic material. Ideally, it should be below 90% by mass relative to the total mass of the metallic material.

[0094] As a method for electrolytically grinding metal materials, well-known methods can be cited, specifically the methods described in paragraphs

[0011] to

[0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Publication No. 2008-264929.

[0095] It is best to clean the inside of the container before filling it with the treatment solution. As a cleaning method, well-known methods can be cited, for example. It is preferable to reduce the amount of metallic impurities in the cleaning liquid. The treatment solution can be transported and stored in containers such as gallon bottles and coated bottles after manufacturing.

[0096] When storing the solution, it is preferable to replace it with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher, and even better if the inert gas has a lower water content. The temperature for transportation and storage can be controlled at room temperature (25℃) or -20℃ to 20℃.

[0097] [Dilution steps] A dilution step can be implemented whereby the treatment solution obtained in the above-mentioned preparation step is diluted with a diluent such as water. The diluted solution obtained in the above dilution steps is a form of the solution of the present invention as long as it meets the requirements of the present invention.

[0098] The dilution ratio of the dilution solution in the dilution step can be appropriately adjusted according to the types and contents of various components that can be contained in the solution, as well as the semiconductor substrate to be cleaned. The dilution ratio between the diluent and the undiluted solution is expressed as a mass ratio or volume ratio (volume ratio at 23°C), with 10 to 10,000 times being preferred, 20 to 3,000 times being even better, and 50 to 1,000 times being even more preferred.

[0099] The pH change before and after dilution (the difference between the pH of the pre-dilution treatment solution and the diluted treatment solution) is preferably below 2.5, even better below 1.8, and further better below 1.5. The lower limit is preferably above 0.1.

[0100] As a dilution step, it can be carried out according to the above-described liquid preparation step. As for the stirring device and stirring method used in the dilution step, the known stirring devices and stirring methods listed above used in the above-described liquid preparation step can be cited.

[0101] It is preferable to purify the water used in the dilution step before use. Furthermore, it is also preferable to purify the diluted solution obtained through the dilution step. As a purification process, it is preferable to perform either the reduction of ionic components by using ion exchange resins or RO membranes, or the removal of foreign matter by filtration, as purification processes for the above-mentioned treated liquid.

[0102] Cleanroom It is best to conduct all operations, including the manufacturing of the treatment solution, the opening and cleaning of containers, the filling of the treatment solution, the treatment analysis, and the determination, in a clean room. Cleanrooms that meet the 14644-1 cleanroom standard are considered to be of good quality. Furthermore, it is preferred to meet any one of ISO (International Organization for Standardization) Level 1, ISO Level 2, ISO Level 3, or ISO Level 4; it is even better to meet ISO Level 1 or ISO Level 2; and it is even better to meet ISO Level 1.

[0103] [Applications of the treatment fluid] The processing solution is preferably used in the cleaning step of cleaning semiconductor substrates, and even more preferably in the cleaning step of cleaning tungsten semiconductor substrates that have undergone CMP treatment. Furthermore, the processing solution can also be used in the cleaning of semiconductor substrates during the semiconductor substrate manufacturing process. As mentioned above, a diluted treatment solution can also be used to obtain a diluted treatment solution in the cleaning of semiconductor substrates.

[0104] [Objects to be cleaned] For example, a semiconductor substrate having a metal film containing tungsten (W) on a semiconductor substrate can be used as a cleaning agent. In this specification, "on a semiconductor substrate" includes, for example, the front and back sides, sides, and grooves of the semiconductor substrate. Furthermore, the metal film on a semiconductor substrate includes not only cases where the metal film is directly present on the surface of the semiconductor substrate, but also cases where the metal film is present on the semiconductor substrate via other layers.

[0105] Metals contained in a metal film, for example, include W (tungsten). The metal film may contain metals other than W. Examples of such metals include at least one metal M selected from the group consisting of Cu (copper), Co (cobalt), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium).

[0106] Semiconductor substrates that are used as cleaning agents include, for example, substrates with metal wiring films, barrier metals, and insulating films on the surface of the wafer constituting the semiconductor substrate.

[0107] As a wafer constituting a semiconductor substrate, examples include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, and silicon-containing resin-based wafers (glass epoxy wafers), as well as gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium (InP) wafers. Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)) and p-type silicon wafers doped with trivalent atoms (e.g., boron (B) and gallium (Ga)). Silicon used in silicon wafers can be categorized as amorphous silicon, monocrystalline silicon, polycrystalline silicon, and polycrystalline silicon. As for the aforementioned wafers, wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and silicon-containing resin-based wafers (glass epoxy wafers) are preferred.

[0108] The semiconductor substrate further has an insulating film on the aforementioned wafer. Examples of insulating films include silicon oxide films (e.g., silicon dioxide (SiO 2) films and tetraethyl orthosilicate (Si(OC 2H 5) 4) films (TEOS films), silicon nitride films (e.g., silicon nitride (Si 3N 4) and silicon carbide nitride (SiNC)), and low dielectric constant (Low-k) films (e.g., carbon-doped silicon oxide (SiOC) films and silicon carbide (SiC) films).

[0109] As the metal film containing tungsten (tungsten-containing film), for example, a metal film composed only of metallic tungsten (tungsten metal film) and an alloy metal film composed of tungsten and a metal other than tungsten (tungsten alloy metal film) can be cited. As the tungsten alloy metal film, for example, a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film) can be cited. The tungsten-containing film can be used, for example, for a barrier metal or a connection portion between a via hole and wiring.

[0110] [[ID=⑨]] As a method for forming the above-mentioned insulating film and tungsten-containing film on a wafer constituting a semiconductor substrate, there is no particular limitation as long as it is a known method. As a method for forming the insulating film, for example, a method of forming a silicon oxide film by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen, then flowing in silane and ammonia gas, and forming a silicon nitride film by chemical vapor deposition (CVD: Chemical Vapor Deposition) can be cited. As a method for forming the tungsten-containing film, for example, a method of forming a circuit on a wafer having the above-mentioned insulating film by a known method such as a resist, and then forming a tungsten-containing film and a cobalt-containing film by methods such as plating and CVD method can be cited.

[0111] <CMP process> The CMP process is a process for planarizing the surface of a substrate having a metal wiring film, a barrier metal, and an insulating film by a combined action of chemical action and mechanical polishing using a polishing slurry containing abrasive particles (abrasive grains). Impurities such as abrasive grains (for example, silicon dioxide and alumina, etc.) used in the CMP process, the polished metal wiring film, and metal impurities (metal residues) derived from the barrier metal may remain on the surface of the semiconductor substrate after the CMP process is performed. Also, organic impurities derived from the CMP treatment liquid used during the CMP process may remain. These impurities cause, for example, a short circuit between wirings and deteriorate the electrical characteristics of the semiconductor substrate. Therefore, a cleaning process for removing these impurities from the surface is performed on the semiconductor substrate after the CMP process is performed. As a semiconductor substrate after the CMP process is performed, for example, a substrate after the CMP process described in the Journal of the Japan Society for Precision Engineering Vol.84, No.3, 2018 can be cited. It is preferable to use a polishing liquid during the CMP process. Examples of polishing slurries include polishing slurries containing iron ions and hydrogen peroxide, or polishing slurries containing chemically modified colloidal silica (such as cationized and anionized modified silica). As the aforementioned polishing fluid, polishing fluid comprising iron complexes as described in Japanese Patent Application Publication No. 2020-068378, Japanese Patent Application Publication No. 2020-015899 and US Patent No. 11043151, or polishing fluid comprising chemically modified colloidal silica as described in Japanese Patent Application Publication No. 2021-082645, is preferred.

[0112] Polishing The surface of a semiconductor substrate, which is the object to be cleaned by the processing liquid, can be polished after CMP treatment. Polishing is a process that uses a polishing pad to reduce impurities on the surface of a semiconductor substrate. Specifically, the surface of a semiconductor substrate that has undergone CMP treatment is brought into contact with a polishing pad, and a polishing composition is supplied to the contact area while the semiconductor substrate and the polishing pad slide relative to each other. As a result, impurities on the surface of the semiconductor substrate are removed by the frictional force based on the polishing pad and the chemical action based on the polishing composition.

[0113] As a polishing composition, known polishing compositions can be appropriately used depending on the type of semiconductor substrate and the type and amount of impurities to be removed. Examples of components included in polishing compositions include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid. Furthermore, as a polishing process, it is preferable to use the aforementioned processing solution as a polishing component to perform polishing treatment on the semiconductor substrate. Regarding the polishing apparatus and polishing conditions used in the polishing process, appropriate apparatus and conditions can be selected from known ones depending on the type of semiconductor substrate 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.

[0114] [Cleaning Method] The method of cleaning semiconductor substrates using a processing solution is preferred. There are no particular limitations on the method for cleaning semiconductor substrates, as long as it includes a cleaning step of cleaning the semiconductor substrate with the above-mentioned processing solution. As the aforementioned semiconductor substrate, a semiconductor substrate that has undergone CMP treatment is preferred. A method for cleaning semiconductor substrates that includes applying the diluted solution obtained in the above-mentioned dilution step to the semiconductor substrate that has undergone CMP treatment and then cleaning it is also preferable.

[0115] As a cleaning step for cleaning a semiconductor substrate using a processing solution, a known method for cleaning a semiconductor substrate that has undergone CMP treatment can be cited as an example. Specifically, among various immersion cleaning methods, such as brushing to remove residues by supplying a processing solution to a semiconductor substrate while physically contacting the surface of the semiconductor substrate with a cleaning component like a brush, immersion cleaning by immersing the semiconductor substrate in the processing solution, rotational (dropping) cleaning by adding the processing solution while rotating the semiconductor substrate, and spray cleaning by spraying the processing solution, it is preferable to apply ultrasonic treatment to the processing solution used to immerse the semiconductor substrate, from the viewpoint of further reducing impurities remaining on the surface of the semiconductor substrate. The above cleaning steps can be performed once or twice or more. If cleaning is performed more than twice, the same method can be repeated, or different methods can be combined.

[0116] The cleaning method for semiconductor substrates can be either a single-wafer method or a batch method. The single-chip method is a method of processing semiconductor substrates one by one, while the batch method is a method of processing multiple semiconductor substrates simultaneously.

[0117] There are no particular restrictions on the temperature of the processing solution used to clean semiconductor substrates. For example, room temperature (25°C) can be used as the temperature of the above-mentioned treatment liquid. However, from the viewpoint of improving cleaning performance and suppressing damage to components, 10~60°C is preferred, and 15~50°C is even better.

[0118] The optimal pH values ​​for the treatment solution and the diluted treatment solution are those found to be suitable for the pH values ​​mentioned above.

[0119] The cleaning time in the cleaning of semiconductor substrates can be appropriately varied depending on the type and content of the components contained in the processing solution. The cleaning time is preferably 10-120 seconds, more preferably 20-90 seconds, and further preferably 30-60 seconds.

[0120] The preferred supply rate (supply speed) of the treatment solution in the cleaning step of the semiconductor substrate is 50~5000mL / min, and even better is 500~2000mL / min.

[0121] In the cleaning of semiconductor substrates, mechanical stirring can be used to further improve the cleaning performance of the treatment solution. Examples of mechanical stirring methods include circulating the processing liquid on a semiconductor substrate, flowing or spraying the processing liquid over a semiconductor substrate, and stirring the processing liquid using ultrasound or megafrequency.

[0122] After cleaning the semiconductor substrate, a rinsing step of rinsing the semiconductor substrate with a solvent can be performed. The rinsing step is performed consecutively after the cleaning step of the semiconductor substrate, and it is preferable to rinse with rinsing solution for 5 to 300 seconds. The rinsing step can be carried out using the mechanical stirring method described above.

[0123] Examples of suitable rinsing solutions include water (preferably deionized water), methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Alternatively, aqueous rinsing solutions with a pH greater than 8.0 (e.g., diluted aqueous ammonium hydroxide) can be used. As a method for bringing the rinsing solvent into contact with the semiconductor substrate, for example, a method for bringing the above-mentioned treatment liquid into contact with the semiconductor substrate can be cited.

[0124] After the above rinsing step, a drying step to dry the semiconductor substrate can be performed. Examples of drying methods include rotary drying, methods of passing a drying gas over a semiconductor substrate, methods of heating the substrate by means of a heating mechanism such as a heating plate or an infrared lamp, Marangoni drying, Notagoni drying, IPA (isopropyl alcohol) drying, and combinations thereof.

[0125] [Semiconductor device manufacturing methods] Among the known methods for manufacturing semiconductor devices, the cleaning method described above is preferred. [Example]

[0126] The present invention will now be described in further detail with reference to the embodiments. The materials, amounts, and proportions shown in the following embodiments can be appropriately modified without departing from the spirit of the invention, and the scope of the invention is not limited to the embodiments shown below.

[0127] The pH of the treatment solutions in the examples and comparative examples was measured at 25°C using a pH meter (manufactured by HORIBA, Ltd., F-74) according to JIS Z8802-1984. Furthermore, the pKa of the acid groups and the pKa of the bases of specific compounds were calculated in water (at 25°C) using Calculator Plugins (manufactured by Fujitsu Limited), and the pKa of the bases was the value of the conjugate acid of the base. In the manufacturing of the treatment solutions in the examples and comparative examples, the use of containers, preparation, filling, storage and molecular determination of the treatment solutions were all carried out in a cleanroom that met ISO level 2 or lower.

[0128] [The various components of the treatment solution] The following components were used to manufacture the treatment fluid. All components used in the embodiments were classified as semiconductor grade or as high purity grade based on this.

[0129] [Specific compound] The following shows the chemical structure of a specific compound, the pKa of each acid group, and the pKa of each base group.

[0130] [Chemical Formula 1]

[0131] [Amino alcohols] Tris: Tris(hydroxymethyl)aminomethane MEA: Monoethanolamine • Bis-Tris: Bis(2-hydroxyethyl)aminotris(hydroxymethyl)methane ･Bis-Tris-Propane:1,3-Bis[tris(hydroxymethyl)methylamino]propane 2-Amino-1,3-propanediol 3-Amino-1,2-propanediol 1,3-Diamino-2-propanol MDEA: N-Methyldiethanolamine

[0132] [Antibacterial agents] Sorbic acid · Methylchloroisothiazolinone · Methylisothiazolinone Alkyl dimethyl benzyl ammonium chloride ·Benzoxanil Chloride Domiphen bromide Salicylic acid ·benzoic acid ·Phenoxyethanol 1,2-Pentanediol 1,2-Hexanediol · Cresol Chloramphenicol dichloroxylenol Hexachlorophenol

[0133] [Organic acids] Citric acid Glycolic acid Malic acid ·tartaric acid gluconic acid ·oxalic acid 1,2,4-Benzotricarboxylic acid

[0134] 〔additive〕 Nonionic system X: Compounds shown below

[0135] [Chemical Formula 2]

[0136] THEMAH: Tris(2-hydroxyethyl)methylammonium hydroxide • Aron A-10SL: Polyacrylic acid (Mw6,000), manufactured by Toagosei Company, Limited • NOPOL PWA-50W: Poly(cis-butadiene acid) (Mw2,000), manufactured by NOF CORPORATION ·Ethylenediamine

[0137] 〔water〕 Ultrapure water

[0138] pH adjuster The pH adjuster used was potassium hydroxide and / or sulfuric acid, depending on the requirements.

[0139] [Manufacturing of the treatment fluid] The treatment solution of Example 1 was manufactured according to the following steps. In ultrapure water, L-arginine, tris(hydroxymethyl)aminomethane, sorbic acid, citric acid, and a pH adjuster were added in the amounts listed in the table below to obtain the final treated solution, and the mixture was stirred thoroughly to obtain the treated solution of Example 1. Treated solutions other than those of Example 1 were prepared according to the manufacturing method of Example 1. The content of pH adjuster in all treatment solutions is less than 2% by mass relative to the total mass of the treatment solutions.

[0140] [Dilution treatment solution] One mL of each of the obtained treatment solutions was taken and diluted with ultrapure water to a volume ratio of 200 times to prepare each diluted treatment solution (200 mL).

[0141] [Maintaining stability] Storage stability was evaluated using each treatment solution (pre-dilution treatment solution). The Orion Corporation Easicult TTC (Easy Antimicrobial and Antifungal Test Kit) was used to immerse the obtained treatment solutions and treat them according to the method specified in the kit. The resulting culture media were then stored at 30°C for 48 hours. The antimicrobial activity was evaluated by comparing the states before and after treatment using the following criteria. A: The state of the culture medium remained unchanged before and after the treatment. B: The formation of colonies can be somewhat confirmed. C: The formation of colonies at 5-10 CFU / ml as indicated by the kit test results can be confirmed. D: Able to confirm the formation of colonies exceeding 10 CFU / ml but below 10 3 CFU / ml as indicated by the kit test. E: The formation of colonies exceeding 10³ CFU / ml but below 10⁴ CFU / ml, as indicated by the kit test, can be confirmed.

[0142] [Cleansing properties] The cleaning performance (residue removal performance) of cleaning CMP-treated metal films was evaluated using various treatment solutions (pre-diluted treatment solutions). Using a FREX300SIII (polishing equipment, manufactured by Ebara Corporation), the polishing slurry described below was used, and CMP was performed on a wafer (12 inches in diameter) with a tungsten metal film on its surface under the conditions of a polishing slurry supply rate of 200 mL / min, a polishing pressure of 1.5 psi, and a polishing time of 60 seconds. Next, the temperature of each processing solution was adjusted to room temperature (23°C), and the wafers were rinsed and cleaned for 60 seconds before drying. A defect detection device was used to count the number of defects on the polished surface of the obtained wafers. Each defect was observed and classified using SEM (Scanning Electron Microscopy). As needed, elemental analysis was performed using EDAX (Energy Dispersive X-ray Analysis). The number of defects based on residue was determined, and the cleaning performance was evaluated using the following criteria (A-series cleaning performance was rated as the best). Furthermore, except that each treatment solution was changed to a different diluted treatment solution, the cleaning performance was evaluated in the same order as described above.

[0143] The following shows the various components of the polishing fluid used in the examples and comparative examples. Furthermore, the content of each component is relative to the total mass of each grinding fluid.

[0144] <Polishing Fluid 1>: Examples 1-75, Comparative Examples 1-3, Examples 80-81 • Malonic acid: 0.30% by mass Ferric nitrate: 0.02% by mass • Hydrogen peroxide: 2.5% by mass PL-5 (unmodified colloidal silica, manufactured by Fuso Chemical Co., Ltd.): 1.5% by mass Water: Residual portion

[0145] <Grinding Fluid 2>: Examples 76-77 • Malonic acid: 0.30% by mass Ferric nitrate: 0.02% by mass • Hydrogen peroxide: 2.5% by mass PL-5D (Anion-modified colloidal silicon dioxide, manufactured by Fuso Chemical Co., Ltd.): 1.5% by mass Water: Residual portion

[0146] <Grinding Fluid 3>: Examples 78-79 • Malonic acid: 0.30% by mass Ferric nitrate: 0.02% by mass • Hydrogen peroxide: 2.5% by mass PL-5C (Cationic modified colloidal silicon dioxide, manufactured by Fuso Chemical Co., Ltd.): 1.5% by mass Water: Residual portion

[0147] A: Number of defects is less than 20 B: The number of defects is more than 20 but less than 50. C: The number of defects is more than 50 but less than 100 D: The number of defects is more than 100 but less than 200 E: The number of defects is more than 200.

[0148] [W (Tungsten) corrosion resistance] The corrosion resistance of W was evaluated using various treatment solutions (pre-dilution treatment solutions). Wafers (12 inches in diameter) were diced from a W-shaped surface, and 2 cm square wafer strips were prepared. The thickness of the W metal film was 100 nm. The wafer strips were immersed in various processing solutions, and each metal film was stirred at 250 rpm for 30 minutes at room temperature. After 30 minutes, the thickness of the vanished W metal film was measured to calculate the W corrosion rate per unit time. The W corrosion resistance of the processing solutions was evaluated using the following criteria. Furthermore, except that the treatment solutions were changed to the diluted treatment solutions, the corrosion resistance of W was evaluated in the same order as described above. The corrosion rate of A:W is below 0.3 Å / min. B:W corrosion rate exceeding 0.3 Å / min and less than 0.5 Å / min The C:W corrosion rate is greater than 0.5 Å / min and less than 1.0 Å / min. The corrosion rate of D:W is greater than 1.0 Å / min and less than 1.5 Å / min. The E:W corrosion rate is above 1.5 Å / min.

[0149] [result] In the table, the "Content (mass%)" column indicates the content (mass%) of each component relative to the total mass of the treatment solution (treatment solution before dilution). The "*1" in the "pH" column refers to the amount of pH adjuster to be added as needed, so that the pH of the final treated solution becomes the value in the "pH before dilution" column. The "residual portion" of "water" refers to the remaining components that are not explicitly stated as components of the treatment solution in the table. The "A / B" column indicates the mass ratio of the content of a specific compound to the content of an amino alcohol (content of specific compound / content of amino alcohol). The "A / C" column indicates the mass ratio of the content of a specific compound to the content of the antimicrobial agent (content of the specific compound / content of the antimicrobial agent). The "B / C" column indicates the mass ratio of the amino alcohol content to the antibacterial agent content (amino alcohol content / antibacterial agent content). The "pH before dilution" column indicates the pH of the treatment solution before dilution. The "pH after dilution" column indicates the pH of the diluted treatment solution (the treatment solution diluted 200 times). The pH values ​​mentioned above are all measured by a pH meter at 25°C for the treated solution or diluted treated solution.

[0150] [Table 1] Table 1 Treatment fluid (A) Specific compounds (B) Amino alcohols (C) Antibacterial agents (D) Organic acids type content (quality%) type content (quality%) type content (quality%) type content (quality%) Example 1 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 2 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 3 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 4 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 5 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 6 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 7 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 8 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 9 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 10 L-arginine 0.005 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 11 L-arginine 0.01 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 12 L-arginine 0.05 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 13 L-arginine 0.3 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 14 L-arginine 2.0 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 15 L-arginine 3.0 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 16 L-arginine 5.0 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 17 L-lysine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 18 L-histidine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 19 L-ornithine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 20 2,4-Diaminobutyric acid 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 21 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 0.5 Example 22 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 1.0 Example 23 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 5.0 Example 24 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 glycolic acid 3.0 Example 25 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 malic acid 3.0 Example 26 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 tartaric acid 3.0 Example 27 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 gluconic acid 3.0 Example 28 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 oxalic acid 3.0 Example 29 L-arginine 1.0 Tris 0.05 Sorbic acid 0.05 Citric acid 3.0 Example 30 L-arginine 1.0 Tris 0.1 Sorbic acid 0.05 Citric acid 3.0 Example 31 L-arginine 1.0 Tris 0.3 Sorbic acid 0.05 Citric acid 3.0 Example 32 L-arginine 1.0 Tris 0.5 Sorbic acid 0.05 Citric acid 3.0 Example 33 L-arginine 1.0 Tris 5.0 Sorbic acid 0.05 Citric acid 3.0 Example 34 L-arginine 1.0 Tris 8.0 Sorbic acid 0.05 Citric acid 3.0 Example 35 L-arginine 1.0 Tris 10.0 Sorbic acid 0.05 Citric acid 3.0 Example 36 L-arginine 1.0 Tris 12.0 Sorbic acid 0.05 Citric acid 3.0 Example 37 L-arginine 1.0 MEA 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 38 L-arginine 1.0 Bis-Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 39 L-arginine 1.0 Bis-Tris-Propane 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 40 L-arginine 1.0 2-Amino-1,3-propanediol 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 41 L-arginine 1.0 3-Amino-1,2-propanediol 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 42 L-arginine 1.0 1,3-Diamino-2-propanol 3.0 Sorbic acid 0.05 Citric acid 3.0 Example 43 L-arginine 1.0 Tris 3.0 Sorbic acid 0.001 Citric acid 3.0 Example 44 L-arginine 1.0 Tris 3.0 Sorbic acid 0.005 Citric acid 3.0 Example 45 L-arginine 1.0 Tris 3.0 Sorbic acid 0.01 Citric acid 3.0 Example 46 L-arginine 1.0 Tris 3.0 Sorbic acid 0.02 Citric acid 3.0 Example 47 L-arginine 1.0 Tris 3.0 Sorbic acid 0.3 Citric acid 3.0 Example 48 L-arginine 1.0 Tris 3.0 Sorbic acid 0.5 Citric acid 3.0 Example 49 L-arginine 1.0 Tris 3.0 Sorbic acid 1.0 Citric acid 3.0 Example 50 L-arginine 1.0 Tris 3.0 Sorbic acid 1.5 Citric acid 3.0 Example 51 L-arginine 1.0 Tris 3.0 Methylchloroisothiazolinone 0.05 Citric acid 3.0 Example 52 L-arginine 1.0 Tris 3.0 Methylisothiazolinone 0.05 Citric acid 3.0 Example 53 L-arginine 1.0 Tris 3.0 Alkyl dimethyl benzyl ammonium chloride 0.05 Citric acid 3.0 Example 54 L-arginine 1.0 Tris 3.0 Benzoxanil Chloride 0.05 Citric acid 3.0 Example 55 L-arginine 1.0 Tris 3.0 Domiphen bromide 0.05 Citric acid 3.0 Example 56 L-arginine 1.0 Tris 3.0 salicylic acid 0.05 Citric acid 3.0 Example 57 L-arginine 1.0 Tris 3.0 benzoic acid 0.05 Citric acid 3.0 Example 58 L-arginine 1.0 Tris 3.0 Phenoxyethanol 0.05 Citric acid 3.0 Example 59 L-arginine 1.0 Tris 3.0 1,2-Pentanediol 0.05 Citric acid 3.0 Example 60 L-arginine 1.0 Tris 3.0 1,2-Hexanediol 0.05 Citric acid 3.0 Example 61 L-arginine 1.0 Tris 3.0 Cresol 0.05 Citric acid 3.0 Example 62 L-arginine 1.0 Tris 3.0 Chloramphenicol 0.05 Citric acid 3.0 Example 63 L-arginine 1.0 Tris 3.0 dichloroxylenol 0.05 Citric acid 3.0 Example 64 L-arginine 1.0 Tris 3.0 hexachlorophenol 0.05 Citric acid 3.0

[0151] [Table 2] Table 2 Continued from Table 1 Treatment fluid result Before dilution After dilution pH adjuster water A / B A / C B / C pH before dilution pH after dilution Preservation stability Cleaning properties W corrosion resistance Cleaning properties W corrosion resistance Example 1 *1 Residual part 0.33 20.00 60.00 2.0 3.2 A D A D A Example 2 *1 Residual part 0.33 20.00 60.00 3.0 3.8 A C A C A Example 3 *1 Residual part 0.33 20.00 60.00 4.0 4.5 A B A B B Example 4 *1 Residual part 0.33 20.00 60.00 5.0 5.5 A A A B B Example 5 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A B B Example 6 *1 Residual part 0.33 20.00 60.00 7.0 6.8 A A A B B Example 7 *1 Residual part 0.33 20.00 60.00 8.0 7.6 A A B A B Example 8 *1 Residual part 0.33 20.00 60.00 9.0 8.5 A A C A C Example 9 *1 Residual part 0.33 20.00 60.00 10.0 9.2 A A D A D Example 10 *1 Residual part 0.01 0.10 10.00 6.0 6.3 A A D A D Example 11 *1 Residual part 0.02 0.20 10.00 6.0 6.4 A A C A D Example 12 *1 Residual part 0.10 1.00 10.00 6.0 6.3 A A B A C Example 13 *1 Residual part 0.60 6.00 10.00 6.0 6.2 A A A B B Example 14 *1 Residual part 4.00 40.00 10.00 6.0 6.3 A B A A A Example 15 *1 Residual part 6.00 60.00 10.00 6.0 6.4 A C A B A Example 16 *1 Residual part 10.00 100.00 10.00 6.0 6.5 A D A C A Example 17 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A A A B B Example 18 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A A A B B Example 19 *1 Residual part 0.33 20.00 60.00 6.0 6.5 A A B B C Example 20 *1 Residual part 0.33 20.00 60.00 6.0 6.4 A A B B C Example 21 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A B A C B Example 22 *1 Residual part 0.33 20.00 60.00 6.0 6.4 A A A B B Example 23 *1 Residual part 0.33 20.00 60.00 6.0 6.5 A A B B C Example 24 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A C A D B Example 25 *1 Residual part 0.33 20.00 60.00 6.0 6.5 A B A C B Example 26 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A B A C B Example 27 *1 Residual part 0.33 20.00 60.00 6.0 6.7 A C A D B Example 28 *1 Residual part 0.33 20.00 60.00 6.0 6.5 A B A C B Example 29 *1 Residual part 20.00 20.00 1.00 6.0 6.3 A A C B D Example 30 *1 Residual part 10.00 20.00 2.00 6.0 6.4 A A B B C Example 31 *1 Residual part 3.33 20.00 6.00 6.0 6.3 A A B B B Example 32 *1 Residual part 2.00 20.00 10.00 6.0 6.5 A A A B B Example 33 *1 Residual part 0.20 20.00 100.00 6.0 6.4 A A A B B Example 34 *1 Residual part 0.13 20.00 160.00 6.0 6.3 A B A B B Example 35 *1 Residual part 0.10 20.00 200.00 6.0 6.4 A B A C B Example 36 *1 Residual part 0.08 20.00 240.00 6.0 6.5 A C A D B Example 37 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A A C B B Example 38 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A A A B B Example 39 *1 Residual part 0.33 20.00 60.00 6.0 6.5 A A A B B Example 40 *1 Residual part 0.33 20.00 60.00 6.0 6.6 A A B B B Example 41 *1 Residual part 0.33 20.00 60.00 6.0 6.7 A A B B B Example 42 *1 Residual part 0.33 20.00 60.00 6.0 6.7 A A C B B Example 43 *1 Residual part 0.33 1000.00 3000.00 6.0 6.3 D A A B B Example 44 *1 Residual part 0.33 200.00 600.00 6.0 6.3 C A A B B Example 45 *1 Residual part 0.33 100.00 300.00 6.0 6.3 B A A B B Example 46 *1 Residual part 0.33 50.00 150.00 6.0 6.3 A A A B B Example 47 *1 Residual part 0.33 3.33 10.00 6.0 6.3 A A A B B Example 48 *1 Residual part 0.33 2.00 6.00 6.0 6.3 A B A B B Example 49 *1 Residual part 0.33 1.00 3.00 6.0 6.3 A C A B B Example 50 *1 Residual part 0.33 0.67 2.00 6.0 6.4 A D A C B Example 51 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A B B Example 52 *1 Residual part 0.33 20.00 60.00 6.0 6.4 A A A B B Example 53 *1 Residual part 0.33 20.00 60.00 6.0 6.3 B A A B B Example 54 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A B B Example 55 *1 Residual part 0.33 20.00 60.00 6.0 6.4 B A A B B Example 56 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A B B Example 57 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A B B Example 58 *1 Residual part 0.33 20.00 60.00 6.0 6.3 B A A B B Example 59 *1 Residual part 0.33 20.00 60.00 6.0 6.3 B A A B B Example 60 *1 Residual part 0.33 20.00 60.00 6.0 6.3 B A A B B Example 61 *1 Residual part 0.33 20.00 60.00 6.0 6.3 B A A B B Example 62 *1 Residual part 0.33 20.00 60.00 6.0 6.4 B A A B B Example 63 *1 Residual part 0.33 20.00 60.00 6.0 6.4 B A A B B Example 64 *1 Residual part 0.33 20.00 60.00 6.0 6.5 B A A B B

[0152] [Table 3] Table 3 Treatment fluid (A) Specific compounds (B) Amino alcohols (C) Antibacterial agents (D) Organic acids (E) Additives type content (quality%) type content (quality%) type content (quality%) type content (quality%) type content (quality%) Example 65 L-arginine L-lysine (1:1) 2.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 66 L-arginine L-lysine (1:1) 2.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 67 L-arginine 1.0 Tris 3.0 Sorbic acid Methylisothiazolinone (1:1) 0.01 Citric acid 3.0 - - Example 68 L-arginine 1.0 Tris 3.0 Methylchloroisothiazolinone Methylisothiazolinone (1:1) 0.01 Citric acid 3.0 - - Example 69 L-arginine 1.0 Tris Bis-Tris (1:1) 5.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 70 L-arginine 1.0 Tris Bis-Tris -Propane (1:1) 5.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 71 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Nonionic X 0.05 Example 72 L-arginine 1.0 MDEA 1.0 Sorbic acid 0.05 tartaric acid 3.0 THEMAH 3.0 Example 73 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 Aron A-10SL 0.1 Example 74 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 NOPOL PWA-50W 0.1 Example 75 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 1,2,4-Benzotricarboxylic acid (5:1) 0.6 - - Example 76 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 77 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 1,2,4-Benzotricarboxylic acid (30:1) 3.1 - - Example 78 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 79 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 1,2,4-Benzotricarboxylic acid (30:1) 3.1 - - Example 80 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 - - Example 81 L-arginine 1.0 Tris 3.0 Sorbic acid 0.05 Citric acid 1,2,4-Benzotricarboxylic acid (30:1) 3.1 - - Comparative Example 1 - - Tris 3.0 Sorbic acid 0.05 Citric acid 3.0 - - Comparative Example 2 L-arginine 1.0 - - Sorbic acid 0.05 Citric acid 3.0 ethylenediamine 2.0 Comparative Example 3 L-arginine 1.0 Tris 3.0 - - Citric acid 3.0 - -

[0153] [Table 4] Table 4 Continued from Table 3 Treatment fluid result Before dilution After dilution pH adjuster water A / B A / C B / C pH before dilution pH after dilution Preservation stability Cleaning properties W corrosion resistance Cleaning properties W corrosion resistance Example 65 *1 Residual part 0.67 40.00 60.00 6.0 6.3 A A A A A Example 66 *1 Residual part 0.67 40.00 60.00 6.0 6.4 A A A A A Example 67 *1 Residual part 0.33 100.00 300.00 6.0 6.5 A A A B B Example 68 *1 Residual part 0.33 100.00 300.00 6.0 6.4 A A A B B Example 69 *1 Residual part 0.20 20.00 100.00 6.0 6.3 A A A B A Example 70 *1 Residual part 0.20 20.00 100.00 6.0 6.3 A A A B A Example 71 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A A B Example 72 *1 Residual part 1.00 20.00 20.00 9.0 8.3 A A B A B Example 73 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A A B Example 74 *1 Residual part 0.33 20.00 60.00 6.0 6.4 A A A A B Example 75 *1 Residual part 0.33 20.00 60.00 6.0 6.3 A A A B B Example 76 *1 Residual part 0.33 20.00 60.00 6.0 6.0 A A A B A Example 77 *1 Residual part 0.33 20.00 60.00 6.0 6.0 A A A A A Example 78 *1 Residual part 0.33 20.00 60.00 6.0 6.0 A A A B A Example 79 *1 Residual part 0.33 20.00 60.00 6.0 6.0 A A A A A Example 80 *1 Residual part 0.33 20.00 60.00 6.0 6.0 A A A B A Example 81 *1 Residual part 0.33 20.00 60.00 6.0 6.0 A A A B A Comparative Example 1 *1 Residual part - - - 7.0 6.8 A A E A E Comparative Example 2 *1 Residual part - - - 6.0 6.9 A A E A E Comparative Example 3 *1 Residual part - - - 6.0 6.3 E A A E A

[0154] As shown in the table, the treatment solution of the present invention has been confirmed to achieve the desired effect. It was confirmed that the present invention is more effective when the pH of the treatment solution is 4.0 to 8.0 (Examples 1 to 9). The invention is more effective when a specific compound is found to contain at least one compound selected from the group including arginine, histidine, and lysine (Examples 5, 17-20). When the content of a specific compound is found to be 0.2 to 70.0% by mass relative to the total mass of components other than the solvent in the treatment solution, the effect of the present invention is even better (Examples 5, 10 to 16). When it is confirmed that the invention contains two or more specific compounds, the effect is even better (Examples 5, 14, 65-66). The present invention is even more effective when it is confirmed that the amino alcohol contains at least one compound selected from the group consisting of Tris, Bis-Tris, Bis-Tris-Propane, 2-amino-1,3-propanediol and 3-amino-1,2-propanediol (Examples 5, 37-42). When the content of amino alcohols relative to the total mass of components other than solvents in the treatment solution is confirmed to be 2.0 to 72.0% by mass, the effect of the present invention is even better (Examples 5, 29 to 36). It has been confirmed that the present invention is more effective when containing two or more amino alcohols (Examples 5, 33, 69-70). It has been confirmed that the present invention is more effective when the antimicrobial agent contains at least one antimicrobial agent selected from the group including chlorobenzonine, carboxylic acid antimicrobial agents and isothiazolinine antimicrobial agents (Examples 5, 51-64). It was confirmed that the effect of the present invention is better when the content of antibacterial agent is 0.05 to 12.0% by mass relative to the total mass of components other than solvent in the treatment solution (Examples 5, 43 to 50). When two or more antibacterial agents are identified, the effect of the present invention is even better (Examples 45, 67-68). When the mass ratio of the content of a specific compound to the content of an antibacterial agent (content of specific compound / content of antibacterial agent) is confirmed to be 1.50 to 60.00, the effect of the present invention is even better (Examples 5, 10 to 16, 43 to 50). When the content of amino alcohol to the mass ratio (content of amino alcohol / content of antibacterial agent) is confirmed to be 4.00~180.00, the effect of the present invention is even better (Examples 5, 29~36, 43~50). When the mass ratio of the content of a specific compound to the content of an amino alcohol (content of specific compound / content of amino alcohol) is confirmed to be 0.10 to 6.00, the effect of the present invention is even better (Examples 5, 10 to 16, 29 to 36). The present invention is even more effective when the organic acid contains at least one compound selected from the group including dicarboxylic acids and tricarboxylic acids (Examples 5, 24-28). When the content of organic acid relative to the total mass of components other than solvent in the treatment solution is confirmed to be 15.0 to 50.0% by mass, the effect of the present invention is even better (Examples 5, 21 to 23).< / ph>

Claims

1. A processing solution for a semiconductor substrate, comprising an amphoteric compound, an antibacterial agent, and an amino alcohol, wherein the amphoteric compound comprises acid groups with a pKa less than 4.5 and base groups with a pKa greater than 4.5, the number of base groups being greater than the number of acid groups, the antibacterial agent comprising at least one antibacterial agent selected from the group consisting of cationic antibacterial agents, carboxylic acid antibacterial agents, phenolic antibacterial agents, isothiazolino antibacterial agents, and alcoholic antibacterial agents, the mass ratio of the content of the amphoteric compound to the content of the antibacterial agent being 3.00 to 50.00, and the mass ratio of the content of the amino alcohol to the content of the aforementioned antibacterial agent being 10.00 to 150.

00.

2. The semiconductor substrate processing solution as described in claim 1, wherein the aforementioned amphoteric compound comprises a basic amino acid.

3. The semiconductor substrate processing solution as described in claim 1 or claim 2, further comprising an organic acid.

4. The semiconductor substrate processing solution as described in claim 1 or claim 2, wherein the pH is 4.0 to 8.

0.

5. The semiconductor substrate processing solution as described in claim 1 or claim 2, used for cleaning a tungsten semiconductor substrate that has undergone chemical mechanical polishing.