Semiconductor processing liquid and method for manufacturing semiconductor device

Abstract

The present invention addresses the problem of providing a semiconductor processing liquid in which dissolution of cobalt is suppressed, and occurrence of defects after processing a silicon substrate and then further performing water rinse processing is suppressed. A semiconductor processing liquid according to the present invention comprises water, an organic solvent, an anticorrosive, a chelating agent, and a basic compound, and does not comprise either hydroxylamine or a salt thereof, wherein the basic compound is a basic inorganic compound or a basic organic compound having a molecular weight of 150 or less and having at least one group selected from the group consisting of -NH2, -NHRN, -NRN 2, and -N+RN 3 X-, and the content of the organic solvent is 0.1-9.5 mass% with respect to the total mass of the semiconductor processing liquid.

Description

Semiconductor processing solution, semiconductor device manufacturing method

[0001] The present invention relates to a semiconductor processing solution and a method for manufacturing a semiconductor device.

[0002] As semiconductor devices become increasingly miniaturized, there is an increasing demand for efficient and accurate removal of unnecessary layers and residues generated during the semiconductor device manufacturing process. Semiconductor devices are manufactured, for example, by arranging a laminate including a metal layer serving as wiring material, an etching stop film, and an insulating film on a substrate, forming a resist film on the laminate, and then performing photolithography and etching processes. In the above processes, for example, when dry etching is performed, residues derived from the metal layer and / or interlayer insulating film may adhere to the laminate. To remove such etching residues, cleaning using a semiconductor processing solution is often performed. Furthermore, the resist film used as a mask during etching is subsequently removed from the laminate by a dry method (dry ashing) or a wet method. Semiconductor processing solutions may also be used to remove residues generated during dry ashing and as a wet method for removing the resist film. As described above, semiconductor processing solutions are used in the semiconductor device manufacturing process to remove residues (etching residues, ashing residues, etc.), resist films, and the like.

[0003] As an example of such a semiconductor processing liquid, Patent Document 1 discloses a processing liquid containing water, a remover, and a resin, in which the resin has a first repeating unit having at least one selected from the group consisting of a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium cation, and a second repeating unit different from the first repeating unit.

[0004] International Publication No. 2022 / 044893

[0005] In recent years, there has been an increasing demand for suppressing defects after processing of semiconductor substrates, and it is required that the occurrence of defects after processing a semiconductor substrate using a semiconductor processing solution and then performing a water rinse treatment be suppressed. The present inventors have studied the processing solutions specifically disclosed in the above-mentioned documents and found that further improvement is necessary to achieve a desired level of both suppression of cobalt dissolution and defect suppression performance after processing a silicon substrate and then performing a water rinse treatment.

[0006] Therefore, an object of the present invention is to provide a semiconductor processing solution that suppresses dissolution of cobalt and suppresses the occurrence of defects after processing a silicon substrate and subsequent water rinsing treatment. Another object of the present invention is to provide a method for manufacturing a semiconductor device using the semiconductor processing solution.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A semiconductor processing solution containing water, an organic solvent, a corrosion inhibitor, a chelating agent, and a basic compound, and not containing any of hydroxylamine and its salts, wherein the basic compound is a basic inorganic compound or -NH ２ , -NHR Ｎ , -NR Ｎ ２ , and -N ＋ R Ｎ ３ X － and a content of the organic solvent is 0.1 to 9.5 mass % based on the total mass of the semiconductor processing solution. Ｎ each independently represents a hydrocarbon group; X －represents a monovalent anion. [2] The semiconductor processing solution according to [1], further comprising an oxidizing agent. [3] The semiconductor processing solution according to [1] or [2], wherein the content of the water is 90.0 mass % or more, based on the total mass of the semiconductor processing solution. [4] The semiconductor processing solution according to any one of [1] to [3], wherein the organic solvent comprises a glycol ether solvent. [5] The semiconductor processing solution according to any one of [1] to [4], wherein the organic solvent comprises 2-butoxyethanol. [6] The semiconductor processing solution according to any one of [1] to [5], wherein the corrosion inhibitor comprises a compound having an azole structure. [7] The semiconductor processing solution according to any one of [1] to [6], wherein the corrosion inhibitor comprises a benzotriazole having a substituent. [8] The semiconductor processing solution according to any one of [1] to [7], wherein the corrosion inhibitor comprises 5-methylbenzotriazole. [9] The semiconductor processing liquid according to any one of [1] to [8], wherein the content of the anticorrosive agent is 0.12 to 0.21 mass % relative to the total mass of the semiconductor processing liquid.

[10] The semiconductor processing liquid according to any one of [1] to [9], wherein the chelating agent contains a compound having a carboxylic acid group.

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

[10] , wherein the chelating agent contains a polyaminocarboxylic acid.

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

[11] , wherein the chelating agent contains diethylenetriaminepentaacetic acid.

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

[12] , wherein the content of the chelating agent is 0.3 to 0.8 mass % relative to the total mass of the semiconductor processing liquid.

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

[13] , wherein the basic compound contains ammonia.

[15] The semiconductor processing solution according to any one of [1] to

[14] , wherein the content of the basic compound is 0.01 to 0.2 mass % relative to the total mass of the semiconductor processing solution.

[16] The semiconductor processing solution according to any one of [1] to

[15] , further comprising an aminocarboxylic acid having a cyano group.

[17] The semiconductor processing solution according to

[16] , wherein the aminocarboxylic acid having a cyano group comprises a compound represented by formula (1) described below.

[18] The semiconductor processing solution according to any one of [1] to

[17] , which is used for processing a semiconductor substrate containing at least one selected from the group consisting of cobalt and tungsten.

[19] A method for manufacturing a semiconductor device, comprising a step of processing a semiconductor substrate using the semiconductor processing solution according to any one of [1] to

[18] .

[0009] According to the present invention, there is provided a semiconductor processing solution that suppresses dissolution of cobalt and suppresses the occurrence of defects after processing a silicon substrate and then performing a water rinsing process.The present invention also provides a method for manufacturing a semiconductor device using the semiconductor processing solution.

[0010] 1 is a cross-sectional view showing an example of a laminate that is an object to be treated with the semiconductor treatment solution of the present invention.

[0011] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0012] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0013] In this specification, the "total mass of components in the semiconductor processing solution excluding the solvent" means the total mass of all components contained in the semiconductor processing solution other than the solvent, such as water and organic solvent.

[0014] In this specification, "ppm" means "parts-per-million (10 －６) and "ppb" stands for "parts-per-billion (10 －９ ) and "ppt" stands for "parts-per-trillion (10 －１２ In this specification, 1 Å (angstrom) corresponds to 0.1 nm.

[0015] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-equivalent values ​​measured by Gel Permeation Chromatography (GPC) measurement using a GPC apparatus (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0016] Unless otherwise specified, the compounds described herein may contain structural isomers, optical isomers, and isotopes. Furthermore, the structural isomers, optical isomers, and isotopes may be contained singly or in combination of two or more. Unless otherwise specified, each component of the semiconductor processing solution described herein may be ionized in the semiconductor processing solution or may form a salt.

[0017] [Semiconductor Processing Solution] The semiconductor processing solution of the present invention (hereinafter also simply referred to as "semiconductor processing solution") will be described in detail below. The semiconductor processing solution of the present invention contains water, an organic solvent, an anticorrosive agent, a chelating agent, and a basic compound (hereinafter also referred to as "specific basic compound"), and does not contain any of hydroxylamine and its salts. The specific basic compound is a basic inorganic compound or -NH ２ , -NHR Ｎ , -NR Ｎ ２ , and -N ＋ R Ｎ ３ X －and the organic solvent is a basic organic compound having a molecular weight of 150 or less and having at least one group selected from the group consisting of:

[0018] While the reason why the semiconductor processing solution having the above-described configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The semiconductor processing solution of the present invention contains an anticorrosive agent but does not contain hydroxylamine or its salts, which are highly corrosive to cobalt and other substances, thereby suppressing cobalt dissolution. Furthermore, the semiconductor processing solution of the present invention contains water, a chelating agent, a specific basic compound, and the like, and therefore has excellent ability to remove residues from the substrate surface. Here, since the specific basic compound is an inorganic basic compound or a predetermined organic basic compound with a small molecular weight, it is thought that it is unlikely to remain on the silicon substrate after a water rinse process, thereby reducing the likelihood of defects resulting from the semiconductor processing solution. Furthermore, since the semiconductor processing solution contains a predetermined amount or more of an organic solvent, precipitation of components such as the anticorrosive agent and their remaining on the silicon substrate after a water rinse process are suppressed, and since the organic solvent content is not more than a predetermined amount, the occurrence of watermarks is also suppressed. As a result, it is believed that the occurrence of defects after a silicon substrate is treated with the semiconductor processing solution and then further rinsed with water is also suppressed. Hereinafter, the fact that the defect suppression performance after a silicon substrate is treated and then rinsed with water is superior is also simply referred to as "superior post-rinse defect suppression performance." Furthermore, the fact that at least one of the ability to further suppress cobalt dissolution and the ability to further suppress post-rinse defects is achieved is also simply referred to as "superior effect of the present invention."

[0019] [Water] The semiconductor processing solution contains water. Examples of water include distilled water, ion-exchanged water, and pure water, with ultrapure water used in the manufacture of semiconductor devices being preferred. Water with reduced inorganic anions and metal ions is also preferred, with water having a reduced concentration of ions derived from metal atoms selected from Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn being more preferred, and water adjusted to the order of ppt or less (in one embodiment, a metal content of less than 0.001 ppt by mass) when used to prepare the semiconductor processing solution being even more preferred. Preferred methods for adjustment include purification using a filtration membrane or ion exchange membrane, or purification by distillation. Examples of methods for adjustment include the methods described in paragraphs

[0074] to

[0084] of JP 2011-110515 A and the methods described in JP 2007-254168 A.

[0020] In order to obtain the desired effects of the present invention more remarkably, it is preferable that the water described above be used not only as a component of the semiconductor processing solution, but also for cleaning containers, the manufacturing process of the semiconductor processing solution, component measurement, and evaluation measurements.

[0021] The water content is preferably 80.0 mass % or more, more preferably 90.0 mass % or more, and even more preferably 93.0 mass % or more, based on the total mass of the semiconductor processing solution, from the viewpoint of obtaining superior effects of the present invention. The upper limit is less than 99.9 mass %, and preferably 98.0 mass % or less, from the viewpoint of obtaining superior effects of the present invention.

[0022] [Organic Solvent] The semiconductor processing solution contains an organic solvent. The organic solvent is preferably a water-miscible organic solvent that is miscible with water in any ratio at 25° C. Examples of the organic solvent include glycol ether-based solvents, alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents. In terms of superior post-rinsing defect suppression properties, glycol ether-based solvents or ester-based solvents are preferred, and glycol ether-based solvents are more preferred.

[0023] The glycol ether solvent is an organic solvent containing a glycol ether structure. Examples of the glycol ether solvent include glycol monoethers and glycol diethers, with glycol monoethers being preferred. Examples of the glycol monoether include alkylene glycol monoethers such as 2-butoxyethanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, and ethylene glycol monobenzyl ether, as well as diethylene glycol mono. Examples of suitable glycol diethers include polyalkylene glycol monoethers such as butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and diethylene glycol monobenzyl ether. Alkylene glycol monoethers are preferred, and 2-butoxyethanol is more preferred. Examples of suitable glycol diethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. The glycol ether solvent preferably has 2 to 20 carbon atoms, more preferably 3 to 10, and even more preferably 4 to 7.

[0024] Examples of alcohol-based solvents include glycol-based solvents such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, and pinacol; and monohydric alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, isopropanol (isopropyl alcohol), 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol, 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

[0025] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0026] Examples of ester-based solvents include ethyl acetate, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0027] Examples of sulfone solvents, sulfoxide solvents, nitrile solvents, and amide solvents include sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfoxide, acetonitrile, N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide. Examples of organic solvents include those described in

[0043] to

[0057] of JP 2021-052186 A.

[0028] The organic solvent preferably contains at least one selected from the group consisting of glycol ether solvents and ester solvents, more preferably a glycol ether solvent, and particularly preferably 2-butoxyethanol.

[0029] The organic solvent may be used alone or in combination of two or more. The content of the organic solvent is 0.1 to 9.5 mass% relative to the total mass of the semiconductor processing solution. If the content of the organic solvent is less than 0.1 mass% or more than 9.5 mass% relative to the total mass of the semiconductor processing solution, this is not preferred because the defect suppression after rinsing is inferior. The content of the organic solvent is preferably 1.0 to 7.0 mass%, more preferably 2.0 to 5.0 mass%, relative to the total mass of the semiconductor processing solution, in order to further enhance the effects of the present invention.

[0030] [Anti-corrosion Agent] The semiconductor processing solution contains an anti-corrosion agent. The anti-corrosion agent has the function of inhibiting corrosion of a metal layer (particularly a cobalt-containing layer) that becomes wiring or the like of a semiconductor device. Examples of the anti-corrosion agent include aromatic heterocyclic compounds, and nitrogen-containing aromatic heterocyclic compounds are preferred. The aromatic heterocyclic compound can inhibit corrosion of the metal layer by coordinating to the surface of the above-mentioned metal layer to form a film. The nitrogen-containing heterocyclic compound is preferably a compound having an azole structure. The number of nitrogen atoms contained in the azole structure is preferably 1 to 4, more preferably 1 to 3, and even more preferably 3. Examples of compounds having an azole structure include imidazole compounds in which one of the atoms constituting the azole structure is a nitrogen atom, pyrazole compounds in which two of the atoms constituting the azole structure are nitrogen atoms, thiazole compounds in which one of the atoms constituting the azole structure is a nitrogen atom and the other is a sulfur atom, triazole compounds in which three of the atoms constituting the azole structure are nitrogen atoms, and tetrazole compounds in which four of the atoms constituting the azole structure are nitrogen atoms. Imidazole compounds or triazole compounds are preferred, and triazole compounds are more preferred. Compounds having an azole structure may have the azole structure as a single ring or may have a fused ring structure consisting of the azole structure and another ring. Compounds having an azole structure may have a substituent on the ring containing the azole structure. Examples of the substituent include optionally substituted alkyl groups, acyl groups, hydroxy groups, carboxylic acid groups, mercapto groups, amino groups, and 2-imidazolyl groups. Examples of substituents that the alkyl groups may have include hydroxy groups, carboxylic acid groups, amino groups, and halogen atoms. The alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 4 carbon atoms.

[0031] Examples of triazole compounds include triazoles which may have a substituent and benzotriazoles which may have a substituent, with benzotriazoles which have a substituent being preferred. Examples of the substituents which the triazoles and benzotriazoles may have include the substituents exemplified above as the substituents which the ring containing the azole structure may have. An alkyl group, a hydroxy group, or a carboxylic acid group which may have a substituent is preferred, with an alkyl group having 1 to 4 carbon atoms being more preferred. The substituent in the benzotriazole which has a substituent may be substituted on the azole structure or on the benzene ring. Examples of triazoles which may have a substituent include 1,2,4-triazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole, 1,2,3-triazole, and 1-methyl-1,2,3-triazole. Examples of the optionally substituted benzotriazole include benzotriazole, 5-methyl-benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, and 2,2'-{[(5-methyl-benzotriazol-1-yl)methyl]imino}diethanol, with 5-methylbenzotriazole being preferred.

[0032] Examples of imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazolecarboxylic acid, histamine, and benzimidazole. Examples of pyrazole compounds include 3,5-dimethylpyrazole, benzopyrazole, and 1-methylindazole-3-carboxylic acid. Examples of thiazole compounds include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole. Examples of tetrazole compounds include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 1,5-pentamethylenetetrazole, 5-mercapto-1-phenyltetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole, with 5-mercapto-1-phenyltetrazole being preferred.

[0033] Among these, the corrosion inhibitor preferably contains a compound having an azole structure, more preferably contains a benzotriazole having a substituent, and further preferably contains 5-methylbenzotriazole, in that it can further suppress the dissolution of cobalt.

[0034] The anticorrosive agent may be used alone or in combination of two or more. The content of the anticorrosive agent is preferably 0.01 to 1.0 mass %, and more preferably 0.12 to 0.21 mass %, relative to the total mass of the semiconductor processing solution, in terms of achieving a superior effect of the present invention and suppressing the dissolution of tungsten. The mass ratio of the content of the anticorrosive agent to the content of the organic solvent is preferably 0.05 to 5.0, and more preferably 0.2 to 1.0.

[0035] [Chelating Agent] The semiconductor processing solution contains a chelating agent. The chelating agent is a compound having a functional group (coordinating group) that can function as a ligand. However, the chelating agent is a compound different from the above-mentioned anticorrosive agent. An example of the coordinating group is an acid group. Examples of the acid group include a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxy group. A carboxylic acid group or a phosphonic acid group is preferred, and a carboxylic acid group is more preferred. As the chelating agent, a compound having a carboxylic acid group or a phosphonic acid group is preferred, in terms of better post-rinse defect suppression properties, and a compound having a carboxylic acid group is more preferred.

[0036] The chelating agent preferably has a low molecular weight. Specifically, the molecular weight of the chelating agent is preferably 1,000 or less, more preferably 600 or less. The lower limit is preferably 50 or more, more preferably 100 or more, and even more preferably more than 150. The number of carbon atoms in the chelating agent is preferably 1 to 15, more preferably 2 to 15.

[0037] <Compound Having a Carboxylic Acid Group> Examples of the compound having a carboxylic acid group include aminocarboxylic acids, polycarboxylic acids, and hydroxycarboxylic acids, with aminocarboxylic acids being preferred.

[0038] (Aminocarboxylic acid) Aminocarboxylic acid is a compound having one or more amino groups and one or more carboxylic acid groups in the molecule.As the aminocarboxylic acid, polyaminocarboxylic acid having two or more amino groups and one or more carboxylic acid groups in the molecule, aminopolycarboxylic acid having one amino group and two or more carboxylic acid groups in the molecule, and amino acid having one amino group and one carboxylic acid group in the molecule can be mentioned, polyaminocarboxylic acid or aminopolycarboxylic acid is preferred, and polyaminocarboxylic acid is more preferred.

[0039] Examples of polyaminocarboxylic acids include diethylenetriaminepentaacetic acid (DTPA), butylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (Cy-DTA), ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanol tetraacetic acid, (hydroxyethyl)ethylenediaminetriacetic acid, and glycol ether diaminetetraacetic acid (GEDTA), with diethylenetriaminepentaacetic acid being preferred.

[0040] Examples of aminopolycarboxylic acids include hydroxyethyliminodiacetic acid (HIDA), iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and N,N-bis(2-hydroxyethyl)glycine (DHEG), with hydroxyethyliminodiacetic acid or nitrilotriacetic acid being preferred.

[0041] Examples of amino acids include glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), L-lysine, leucine, isoleucine, cystine, ethionine, threonine, tryptophan, tyrosine, valine, histidine, histidine derivatives, asparagine, aspartic acid, glutamine, glutamic acid, L-arginine, proline, methionine, phenylalanine, and the compounds described in paragraphs

[0021] to

[0023] of JP-A No. 2016-086094, as well as salts thereof. Examples of histidine derivatives include compounds described in JP-A Nos. 2015-165561 and 2015-165562, the contents of which are incorporated herein by reference. Examples of salts include alkali metal salts such as sodium salts and potassium salts, ammonium salts, carbonates, and acetates.

[0042] (Polycarboxylic Acid) Polycarboxylic acid is a compound that does not have an amino group in the molecule but has two or more carboxylic acid groups. Examples of polycarboxylic acids include citric acid, malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, and oxalic acid.

[0043] (Hydroxycarboxylic Acid) Hydroxycarboxylic acid is a compound having one carboxylic acid group and one or more hydroxy groups in the molecule. Examples of hydroxycarboxylic acid include gluconic acid, heptonic acid, glycolic acid, and lactic acid.

[0044] <Compound Having a Phosphonic Acid Group> Examples of compounds having a phosphonic acid group include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDP), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTMP or ATMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminebis(methylenephosphonic acid) (EDDP), 1,3-propylenediaminebis(methylenephosphonic acid), N,N,N Examples of suitable amines include ',N'-ethylenediaminetetrakis(methylenephosphonic acid) (EDTMP), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPP), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylenetetraminehexa(ethylenephosphonic acid). As the compound having a phosphonic acid group, the compounds described in paragraphs

[0026] to

[0036] of WO 2018 / 020878 and the compounds ((co)polymers) described in paragraphs

[0031] to

[0046] of WO 2018 / 030006 can also be used, the contents of which are incorporated herein by reference.

[0045] Among these, the chelating agent preferably contains a compound having a carboxylic acid group, more preferably contains an aminocarboxylic acid, further preferably contains a polyaminocarboxylic acid, and particularly preferably contains diethylenetriaminepentaacetic acid, in terms of better post-rinse defect suppression properties.

[0046] The chelating agent may be used alone or in combination of two or more. The content of the chelating agent is preferably 0.1 to 5.0 mass %, more preferably 0.3 to 0.8 mass %, and even more preferably 0.5 to 0.8 mass %, based on the total mass of the semiconductor processing solution, in terms of more excellent effects of the present invention.

[0047] [Specific Basic Compound] The semiconductor processing solution contains a specific basic compound. The specific basic compound is a basic inorganic compound or a —NH ２ , -NHR Ｎ , -NR Ｎ ２ , and -N ＋ R Ｎ ３ X － R Ｎ and X － The specific basic compound will be described later. The specific basic compound is a compound different from the above-mentioned chelating agent and anticorrosive agent. The specific basic compound is a compound that exhibits basicity (pH greater than 7.0) in an aqueous solution. The specific basic compound may be ionized in the semiconductor processing solution or may form a salt.

[0048] <Inorganic Basic Compound> Examples of inorganic basic compounds include ammonia, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides, and ammonia is preferred. Ammonia is ammonium hydroxide (NH ４The ammonia may be used in the form of (OH). When producing the semiconductor processing solution of the present invention, either aqueous ammonia or ammonia gas may be used to add ammonia, with aqueous ammonia being preferred in terms of ease of preparation. The ammonia content in the semiconductor processing solution can be determined from the ammonium cation content measured using ion chromatography.

[0049] <Specific organic basic compound> The specific organic basic compound is -NH ２ , -NHR Ｎ , -NR Ｎ ２ , and -N ＋ R Ｎ ３ X － R has at least one group (hereinafter also referred to as "specific basic group") selected from the group consisting of Ｎ each independently represents a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, with an aliphatic hydrocarbon group being preferred. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group being preferred. The aliphatic hydrocarbon group may be linear, branched, or cyclic, with a linear or branched chain being preferred. The aliphatic hydrocarbon group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Examples of the aromatic hydrocarbon group include a phenyl group. The hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and a specific basic group. -NR Ｎ ２ and -N ＋ R Ｎ ３ X － Among them, there are multiple R Ｎ may be the same or different. － represents a monovalent anion. Examples of the monovalent anion include hydroxide ion, halide ions such as chloride ion and fluoride ion, and acid anions such as nitrate ion and acetate ion, with hydroxide ion being preferred.

[0050] The number of specific basic groups possessed by the specific organic basic compound is 1 or more, and is preferably 1 to 6, more preferably 1 to 3, in terms of better effects of the present invention. The specific organic basic compound may have a functional group other than the specific basic group. Examples of functional groups other than the specific basic group include a hydroxy group. The specific organic basic compound may be either chain (linear or branched) or cyclic, but is preferably chain.

[0051] The specific organic basic compound includes a compound represented by formula (A). Ａ -(X) ｎ Formula (A) In formula (A), R Ａ represents an aliphatic hydrocarbon group which may have an (n+1)-valent hydroxy group. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and is preferably linear or branched. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. Each X independently represents a specific basic group. n represents an integer of 1 or more, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

[0052] The molecular weight of the specific organic basic compound is 150 or less, preferably 110 or less, and more preferably 50 or less. There is no particular lower limit, and the molecular weight is often 30 or more. If the molecular weight exceeds 150, the basic compound remains on the substrate even after a semiconductor substrate is treated with the semiconductor treatment solution and then further rinsed with water, which is undesirable in that the defect suppression after rinsing is poor.

[0053] -NH ２ , -NHR Ｎ , and -NR Ｎ ２Examples of the specific organic basic compound having a group selected from the group consisting of include amino alcohols such as 2-aminoethanol, diethanolamine, monomethyldiethanolamine, 2-(2-aminoethylamino)ethanol, diglycolamine, 2-(dimethylamino)ethanol, 2-amino-2-methyl-1-propanol, DL-1-amino-2-propanol, tris(hydroxymethyl)aminomethane, and 3-amino-4-octanol, as well as aliphatic amines having no hydroxy group such as N,N-dimethylethylenediamine, N-methylethylenediamine, ethylenediamine, and 1,3-diaminopropane, with diglycolamine being preferred. ＋ R Ｎ ３ X － Examples of the specific organic basic compound having the formula (I) include tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), diethyldimethylammonium hydroxide (DEDMAH), triethylmethylammonium hydroxide (TEMAH), tetraethylammonium hydroxide (TEAH), and 2-hydroxyethyltrimethylammonium hydroxide (choline), with tetramethylammonium hydroxide being preferred.

[0054] The specific basic compound preferably includes an inorganic basic compound, and more preferably includes ammonia.

[0055] The specific basic compound may be used alone or in combination of two or more. The content of the specific basic compound is preferably 0.01 to 5.0 mass %, more preferably 0.01 to 2.0 mass %, and even more preferably 0.01 to 0.2 mass %, based on the total mass of the semiconductor processing solution, in terms of more excellent effects of the present invention.

[0056] [Hydroxylamine and its salts] The semiconductor processing solution contains hydroxylamine (NH ２hydroxylamine and its salts are not contained. The salts include both inorganic and organic acid salts. "Not containing hydroxylamine and its salts" means that the content of hydroxylamine and its salts is 100 ppm by mass or less, preferably 50 ppm or less, based on the total mass of the semiconductor processing solution. The lower limit is preferably 0. The content of hydroxylamine and its salts can be measured using ion chromatography under the following conditions. Column: Dionex IonPac CS16 (5 x 250 mm) Column temperature: 40°C Flow rate: 1.0 mL / min Eluent: 30 mM methanesulfonic acid aqueous solution Injection volume: 25 μL Detector: Electrical conductivity detector (with suppressor)

[0057] Optional components that may be contained in the semiconductor processing solution will be described below.

[0058] [Oxidizing Agent] The semiconductor processing solution preferably contains an oxidizing agent, as this provides superior solubility for titanium nitride. A semiconductor processing solution with excellent solubility for titanium nitride can be suitably used as an etching solution for resist films containing titanium nitride. Examples of oxidizing agents include peroxides such as hydrogen peroxide, percarbonates, permanganates, cerium compounds such as ammonium peroxodisulfate and cerium ammonium nitrate, and ferricyanides such as potassium ferricyanide. Examples of oxidizing agents include peroxyacids such as peracetic acid and perbenzoic acid, persulfides such as monopersulfuric acid and dipersulfuric acid, oxide halides such as chloric acid, perchloric acid, chlorous acid, hypochlorous acid, iodides, periodides, iodic acid, and periodic acid, perboric acid, nitric acid, nitrous acid, sulfuric acid, and salts thereof. Hydrogen peroxide is preferred as the oxidizing agent.

[0059] The oxidizing agent may be used alone or in combination of two or more. The content of the oxidizing agent is preferably 1.0 to 20.0 mass %, more preferably 10.0 to 20.0 mass %, based on the total mass of the semiconductor processing solution.

[0060] [Aminocarboxylic Acid Having a Cyano Group] The semiconductor processing solution preferably further contains an aminocarboxylic acid having a cyano group, since this provides better post-rinsing defect suppression and can suppress tungsten dissolution. The aminocarboxylic acid having a cyano group is a compound having one or more cyano groups, one or more amino groups, and one or more carboxylic acid groups in the molecule. It is preferable that the aminocarboxylic acid having a cyano group and the chelating agent described above are different compounds. That is, the semiconductor processing solution preferably contains a chelating agent and an aminocarboxylic acid having a cyano group that is a compound different from the chelating agent. The number of carboxylic acid groups in the aminocarboxylic acid having a cyano group is 1 or more, preferably 1 to 6, and more preferably 2 to 5. The number of amino groups in the aminocarboxylic acid having a cyano group is 1 or more, preferably 2 or more, and more preferably 3 or more. In other words, the aminocarboxylic acid having a cyano group is preferably a polyaminocarboxylic acid having a cyano group. There is no particular upper limit on the number of amino groups, but it is often 6 or less.

[0061] The polyaminocarboxylic acid having a cyano group is preferably a compound represented by the following formula (1).

[0062]

[0063] In formula (1), each R is independently a hydrogen atom, —CH ２ —COOH or —CH ２ -CN, provided that at least one of the five R's is -CH ２ -COOH, and at least one is -CH ２ In formula (1), at least two of the five Rs represent —CH ２ In formula (1), at least two of the five R's preferably represent -CH ２ It also preferably represents —CN.

[0064] The aminocarboxylic acid having a cyano group may form a salt. Examples of the salt include a metal salt and an ammonium salt. Examples of the metal cation in the metal salt include Na ＋, Cr ２＋ , Ca ２＋ , and Zn ２＋ Examples include:

[0065] Specific examples of the aminocarboxylic acid having a cyano group include the following compounds and salts thereof:

[0066]

[0067] The aminocarboxylic acid having a cyano group preferably includes a compound represented by formula (1), and more preferably includes at least one selected from the group consisting of compound A and compound B described above.

[0068] The aminocarboxylic acid having a cyano group may be used alone or in combination of two or more thereof. The content of the aminocarboxylic acid having a cyano group is preferably 1 to 1000 ppm by mass, more preferably 10 to 500 ppm by mass, based on the total mass of the semiconductor processing solution.

[0069] [Other Components] The semiconductor processing solution may contain other components in addition to those described above. Examples of the other components include acidic compounds, surfactants, antifoaming agents, antibacterial agents, rust inhibitors, and antiseptics. In addition, from the viewpoint of post-rinse defect suppression, it is also preferable that the semiconductor processing solution does not contain basic compounds with a molecular weight of more than 150 (e.g., amine compounds and quaternary ammonium compounds).

[0070] <Acidic Compound> The semiconductor processing solution may contain an acidic compound to adjust the pH of the semiconductor processing solution. Examples of the acidic compound include acidic inorganic compounds. Examples of the acidic inorganic compound include sulfuric acid, hydrochloric acid, nitric acid, boric acid, phosphonic acid, and phosphoric acid. The acidic compound used as the pH adjuster may be a salt of an acidic compound, as long as it becomes an acid or an acid ion (anion) in an aqueous solution.

[0071] <Surfactant> The semiconductor processing liquid may contain a surfactant. The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, and examples thereof include nonionic surfactants, cationic surfactants, and anionic surfactants. The surfactant often has at least one hydrophobic group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof. The total carbon number of the surfactant is preferably 16 to 100.

[0072] Examples of the nonionic surfactant include ester-type nonionic surfactants, ether-type nonionic surfactants, and ester-ether-type nonionic surfactants, and ether-type nonionic surfactants are preferred. Examples of the nonionic surfactant include the compounds exemplified in paragraph

[0126] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0073] Examples of cationic surfactants include primary to tertiary alkylamine salts (e.g., monostearyl ammonium chloride, distearyl ammonium chloride, tristearyl ammonium chloride, etc.) and modified aliphatic polyamines (e.g., polyethylene polyamine, etc.).

[0074] Examples of anionic surfactants include sulfonic acid surfactants having a sulfonic acid group, sulfate ester surfactants having a sulfate ester group, and carboxylic acid surfactants having a carboxylic acid group. Examples of anionic surfactants include the compounds exemplified in paragraphs

[0116] to

[0123] of WO 2022 / 044893, the contents of which are incorporated herein by reference.

[0075] <Antifoaming Agent> The semiconductor processing liquid may contain an antifoaming agent. Surfactants may cause foaming depending on how they are used. Therefore, it is preferable that a semiconductor processing liquid containing a surfactant contains an antifoaming agent that suppresses the generation of foaming, shortens the lifespan of the generated foam, and suppresses the residual foam. The antifoaming agent is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include silicone-based antifoaming agents, acetylene diol-based antifoaming agents, fatty acid ester-based antifoaming agents, and long-chain aliphatic alcohol-based antifoaming agents. Among these, silicone-based antifoaming agents are preferred because of their superior effect of suppressing residual foam. It should be noted that the antifoaming agent does not include compounds contained in the above-mentioned surfactants.

[0076] <Metal Component> The semiconductor processing solution may contain a metal component. Examples of the metal component include metal particles and metal ions. For example, the content of the metal component refers to the total content of the metal particles and metal ions. The semiconductor processing solution may contain either metal particles or metal ions, or both. Examples of metal atoms contained in the metal component include metal atoms selected from the group consisting of Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sn, Sr, Ti, and Zn. The metal component may contain one type of metal atom or two or more types of metal atoms. The metal particles may be a simple substance or an alloy, or the metal may exist in a form associated with an organic substance. The metal component may be a metal component that is inevitably contained in each component (raw material) contained in the semiconductor processing solution, a metal component that is inevitably contained during the production, storage, and / or transportation of the semiconductor processing solution, or a metal component that is intentionally added.

[0077] When a semiconductor processing solution contains a metal component, the content of the metal component is often 0.01 mass ppt to 10 mass ppm, preferably 0.1 mass ppt to 1 mass ppm, and more preferably 0.1 mass ppt to 100 mass ppb, relative to the total mass of the semiconductor processing solution. The type and content of the metal component in the semiconductor processing solution can be measured using SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). SP-ICP-MS uses the same equipment as conventional ICP-MS (Inductively Coupled Plasma Mass Spectrometry), with the only difference being the data analysis. Data analysis for SP-ICP-MS can be performed using commercially available software. In ICP-MS, the content of the target metal component is measured regardless of its form. Therefore, the total mass of the target metal particles and metal ions is quantified as the content of the metal component. On the other hand, SP-ICP-MS can measure the content of metal particles. Therefore, the content of metal ions in a sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample.

[0078] As a measurement method using the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies can be used, and the measurement can be performed by the method described in the Examples. As an alternative to the above, PerkinElmer NexION350S and Agilent 8900 manufactured by Agilent Technologies can also be used.

[0079] The content of each metal component in the semiconductor processing solution can be adjusted, for example, by performing a known process for removing metal from the semiconductor processing solution and / or from raw materials containing each component used in preparing the semiconductor processing solution, thereby reducing the content of the metal component in the semiconductor processing solution. Alternatively, the content of the metal component in the semiconductor processing solution can be increased by adding a compound containing a metal ion to the semiconductor processing solution.

[0080] [Physical Properties of Semiconductor Processing Solution] <pH> In terms of achieving better effects of the present invention, the pH of the semiconductor processing solution is preferably 7 to 11, and more preferably 8 to 10. The pH of the semiconductor processing solution is a pH value obtained by measuring at 25°C using a known pH meter according to a method in accordance with JIS Z8802-1984.

[0081] <Coarse Particles> The semiconductor processing solution may contain coarse particles, but the content thereof is preferably low. Coarse particles refer to particles having a diameter (particle size) of 1 μm or more when the particle shape is considered as a sphere. The coarse particles contained in the semiconductor processing solution include particles such as dust, dirt, organic solids, and inorganic solids contained as impurities in raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids brought in as contaminants during the preparation of the semiconductor processing solution, which ultimately exist as particles without dissolving in the semiconductor processing solution.

[0082] The content of coarse particles in the semiconductor processing solution is preferably 100 or less, more preferably 50 or less, particles with a particle size of 1 μm or more per mL of the semiconductor processing solution. The lower limit is preferably 0 or more, more preferably 0.01 or more, per mL of the semiconductor processing solution. The content of coarse particles present in the semiconductor processing solution can be measured in the liquid phase using a commercially available measuring device that employs a light scattering liquid particle measuring method using a laser as a light source. Methods for removing coarse particles include, for example, purification processes such as filtering, which will be described later.

[0083] It is also preferred that the semiconductor processing fluid does not contain abrasive particles.

[0084] [Kit and Concentrated Solution] The semiconductor processing solution may be prepared as a kit by dividing the raw materials thereof into a plurality of parts. Although not particularly limited, a specific method for preparing the semiconductor processing solution as a kit may include, for example, preparing a liquid composition containing water, an organic solvent, an anticorrosive, a chelating agent, and a specific basic compound as a first liquid, and preparing a liquid composition containing an oxidizing agent as a second liquid.

[0085] The contents of each component contained in the first and second liquids provided in the kit are not particularly limited, but are preferably amounts such that the contents of each component in the semiconductor processing liquid prepared by mixing the first and second liquids are the above-mentioned preferred contents. The pH of the first and second liquids provided in the kit is not particularly limited, as long as the pH of each liquid is adjusted so that the pH of the semiconductor processing liquid prepared by mixing the first and second liquids is the desired value.

[0086] The semiconductor processing solution may also be prepared as a concentrated solution. In this case, the diluted solution obtained by diluting with a dilution liquid before use is used. That is, the kit may include the semiconductor processing solution in the form of a concentrated solution and the dilution liquid. The dilution liquid is preferably a liquid selected from the group consisting of water, isopropanol, a mixture of water and isopropanol, and a solvent containing ammonium hydroxide, more preferably water, isopropanol, or a mixture of water and isopropanol, and even more preferably water. The dilution ratio of the semiconductor processing solution is not particularly limited, but is preferably 1 to 2000 times, more preferably 1 to 100 times.

[0087] A composition (hereinafter also referred to as a "diluted solution") containing each component in an amount obtained by dividing the preferred content of each component (excluding water) that can be contained in the semiconductor processing solution by a dilution ratio within the above range (e.g., 100) can also be suitably used. The preferred content of each component (excluding water) relative to the total mass of the diluted solution is, for example, the amount described as the preferred content of each component relative to the total mass of the semiconductor processing solution before dilution divided by a dilution ratio within the above range (e.g., 100). The specific method for the dilution step of diluting the semiconductor processing solution may be performed in accordance with the semiconductor processing solution preparation step described below. The stirring device and stirring method used in the dilution step may also be performed using the known stirring device mentioned in the semiconductor processing solution preparation step described below.

[0088] [Methods for Producing Semiconductor Processing Solutions, Concentrates, and Kits] The semiconductor processing solutions can be produced by known methods. Hereinafter, methods for producing semiconductor processing solutions will be described.

[0089] [Semiconductor Processing Solution Preparation Step] The method for producing the semiconductor processing solution is not particularly limited, and the semiconductor processing solution can be produced by a known production method. For example, a method including at least a semiconductor processing solution preparation step of mixing the above-mentioned components to prepare the semiconductor processing solution can be mentioned. In the semiconductor processing solution preparation step, the order in which the components are mixed is not particularly limited. The concentrated solution and each solution provided in the kit are preferably produced by the same method as above. The method for producing the kit is not particularly limited, and for example, the first solution and the second solution can be prepared, and then the first solution and the second solution can be placed in different containers to produce a kit for preparing a semiconductor processing solution.

[0090] [Filtration Step] The above production method preferably includes a filtration step of filtering the liquid to remove foreign matter, coarse particles, etc. from the liquid. The filtration method is not particularly limited, and any known filtration method can be used. Among them, filtering using a filter is preferred.

[0091] The filter used for filtering can be any filter conventionally used for filtering purposes, without any particular limitations. Examples of materials constituting the filter include filters made of fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, materials selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesins (including PTFE and PFA), and polyamide resins (including nylon) are preferred, with fluororesin filters being more preferred. Filtering raw materials using filters made of these materials can effectively remove highly polar contaminants that are likely to cause defects.

[0092] The critical surface tension of the filter is preferably 70 to 95 mN / m, and more preferably 75 to 85 mN / m. The critical surface tension values ​​are nominal values ​​provided by the manufacturer. By using a filter with a critical surface tension in the above range, highly polar foreign matter that is likely to cause defects can be more effectively removed from semiconductor processing solutions.

[0093] The pore size of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.02 to 0.5 μm, and even more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above range, it becomes possible to reliably remove fine foreign matter contained in the semiconductor processing liquid while suppressing clogging. When using filters, different filters may be combined.

[0094] The filter used is preferably treated before filtering the semiconductor processing liquid. The liquid used for this treatment is not particularly limited, but is preferably a liquid containing components contained in the semiconductor processing liquid, concentrated liquid, or liquid composition.

[0095] When filtering is performed, the upper limit of the temperature during filtering is preferably room temperature (25° C.) or lower, more preferably 23° C. or lower, and even more preferably 20° C. or lower. The lower limit of the temperature during filtering is preferably 0° C. or higher, more preferably 5° C. or higher, and even more preferably 10° C. or higher. Filtering can remove particulate foreign matter and / or impurities, and when filtering is performed at the above temperatures, the amount of particulate foreign matter and / or impurities dissolved in the semiconductor processing solution is reduced, so filtering is performed more efficiently.

[0096] The above-mentioned production method may further include a static elimination step of eliminating static electricity from at least one selected from the group consisting of a semiconductor processing solution, a concentrated solution, and a kit.

[0097] All steps of the above manufacturing method are preferably carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable that the clean room meets any one of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0098] [Container] The container for containing the semiconductor processing solution, concentrated solution, or kit described above is not particularly limited, and any known container can be used as long as corrosiveness by the solution is not an issue. For semiconductor applications, the container is preferably one with a high level of cleanliness within the container and low impurity elution. Specific examples of the container include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. Furthermore, for the purpose of preventing impurities from being mixed in (contaminated) with raw materials and semiconductor processing solutions, it is also preferable to use a multilayer container whose inner wall has a six-layer structure made of six types of resin, or a multilayer container whose inner wall has a seven-layer structure made of six types of resin. Examples of such containers include, but are not limited to, the containers described in JP 2015-123351 A. Furthermore, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used, and the contents of these containers are incorporated herein by reference.

[0099] It is preferable to wash the inside of these containers before filling them. The liquid used for washing may be appropriately selected depending on the application, but is preferably a semiconductor processing liquid, a liquid obtained by diluting a semiconductor processing liquid, or a liquid containing at least one of the components added to the semiconductor processing liquid.

[0100] To prevent changes in the components of the semiconductor processing solution during storage, the container may be filled with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or higher. A gas with a low water content is particularly preferred. The container may be transported or stored at room temperature, but the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0101] [Uses] The semiconductor processing liquid is a composition for semiconductor devices. In this specification, "for semiconductor devices" means that it is used in the manufacture of semiconductor devices. The semiconductor processing liquid can be used in any process for manufacturing semiconductor devices, for example, in the process of treating a semiconductor substrate included in the method of manufacturing a semiconductor device. More specifically, the semiconductor processing liquid can be used to treat insulating films, resists, anti-reflective films, etching residues, ashing residues, and residues derived from resist films such as photoresists and metal hard masks present on a substrate. The semiconductor processing liquid can also be used as an etching liquid for etching to remove metal-containing materials (including metal oxides and composite oxides composed of multiple metal oxides) from a substrate. It can also be used as a cleaning liquid to remove residues such as metal impurities, abrasive particles, and polishing liquid components from a substrate after chemical mechanical polishing. The semiconductor processing liquid can also be used as a prewet liquid applied to a substrate before the step of forming a resist film using an actinic ray- or radiation-sensitive composition in order to improve the coatability of the composition, a cleaning liquid used for removing residues adhering to a metal layer, a solution used for removing various resist films for pattern formation (e.g., a remover and a stripper), and a solution used for removing permanent films (e.g., a color filter, a transparent insulating film, and a resin lens) from a semiconductor substrate (e.g., a remover and a stripper). Note that the semiconductor substrate after removal of the permanent film may be reused in a semiconductor device, and therefore removal of the permanent film is considered to be included in the manufacturing process of the semiconductor device.

[0102] The semiconductor processing liquid may be used for only one of the above-mentioned uses, or for two or more uses. In particular, the semiconductor processing liquid can be suitably used as a cleaning liquid for semiconductor substrates that have been subjected to etching treatment, or an etching liquid for removing metal inclusions on semiconductor substrates, and is more suitably used as a cleaning liquid for semiconductor substrates that have been subjected to dry etching treatment, or an etching liquid for metal resist. The semiconductor processing liquid can also be suitably used as a residue treatment liquid or an etching liquid for resist films containing silicon oxide or titanium nitride. A diluted solution obtained by diluting the semiconductor processing liquid can also be used for the above-mentioned uses.

[0103] [Method for treating object to be treated] In a method for treating a substrate using a semiconductor treatment liquid (hereinafter also simply referred to as "this treatment method"), the semiconductor treatment liquid can be used by contacting it with an object to be treated (typically, a substrate having metal inclusions, which are materials containing metals).

[0104] [Workpiece] The workpiece to be treated with the semiconductor treatment solution is not particularly limited as long as it is a member used in the manufacturing process of a semiconductor device, and examples thereof include semiconductor substrates. The semiconductor substrate is preferably a semiconductor substrate containing metal inclusions, and more preferably a semiconductor substrate having metal inclusions on the substrate. The workpiece may contain multiple types of metal inclusions. Note that, in this specification, "on the substrate" includes, for example, the front and back surfaces, side surfaces, and grooves of the substrate. Furthermore, "metal inclusions on the substrate" includes not only cases where metal inclusions are present directly on the surface of the substrate, but also cases where metal inclusions are present on the substrate via another layer. Furthermore, "substrate" in this specification includes, for example, a semiconductor substrate consisting of a single layer and a semiconductor substrate consisting of a multilayer.

[0105] The metal inclusion is a material containing a metal (metal atom) as a main component. Examples of the metal contained in the metal inclusion include at least one metal M selected from the group consisting of Co (cobalt), W (tungsten), Ti (titanium), Cu (copper), 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] The metal-containing substance may be any substance containing a metal (metal atom), and examples thereof include substances composed of at least one selected from the group consisting of a simple substance of metal M, an alloy containing metal M, an oxide of metal M, a nitride of metal M, and an oxynitride of metal M, with a simple substance of metal M or an alloy containing metal M being preferred.

[0107] The metal inclusion preferably contains a metal M, more preferably at least one selected from the group consisting of Co, W, Mo, Cu, Ti, Ta, and Ru, even more preferably at least one selected from the group consisting of Co and W, and particularly preferably at least one selected from the group consisting of Co and Co alloys. In other words, the semiconductor substrate to be processed preferably contains at least one selected from the group consisting of Co and W, and more preferably contains Co.

[0108] The metal inclusions may be disposed on only one main surface of the substrate, or may be disposed on both main surfaces. The metal inclusions may be disposed over the entire main surface of the substrate, or may be disposed over a portion of the main surface of the substrate. The form of the metal inclusions is not particularly limited, and may be, for example, either a film-like form (metal film) or a particulate form (metal particles). The metal film may be in the form of a sheet, or may be in the form of a wiring (wiring film).

[0109] Examples of metal-containing materials containing Co include a metal film consisting only of metallic cobalt (Co metal film) and a metal film made of an alloy consisting of metallic cobalt and other metals (Co alloy metal film). Specific examples of Co alloy metal films include a metal film made of an alloy consisting of Co and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, examples include a CoTi alloy metal film, a CoCr alloy metal film, a CoFe alloy metal film, a CoNi alloy metal film, a CoMo alloy metal film, a CoPd alloy metal film, a CoTa alloy metal film, and a CoW alloy metal film. Among Co-containing films, a Co metal film is often used as a wiring film, and a Co alloy metal film is often used as a barrier metal.

[0110] Examples of the metal-containing material containing W include a metal film made of tungsten only (W metal film) and a metal film made of an alloy of tungsten and another metal (W alloy metal film). Specific examples of the W alloy metal film include a WTi alloy metal film and a WCo alloy metal film. W-containing films are often used as wiring films or barrier metals.

[0111] A more specific example of the workpiece is a laminate having a metal layer, an insulating film, and a metal hard mask on a substrate, in this order. The laminate may further have holes formed from the surface (openings) of the metal hard mask toward the substrate, exposing the surface of the metal layer, by undergoing a dry etching process or the like. The method for producing such a laminate having holes is not particularly limited. Typically, a method involves performing a dry etching process using the metal hard mask as a mask on a pre-processed laminate having a substrate, a metal layer, an insulating film, and a metal hard mask in this order, to etch the insulating film so as to expose the surface of the metal layer, thereby forming holes penetrating the metal hard mask and the insulating film. The method for producing a metal hard mask is not particularly limited. For example, a metal layer containing a predetermined component is first formed on an insulating film, and a resist film with a predetermined pattern is then formed thereon. Next, the metal layer is etched using the resist film as a mask, thereby producing a metal hard mask (i.e., a film with a patterned metal layer). The laminate may also have layers other than the above-mentioned layers, such as an etching stop film or an anti-reflective film.

[0112] Fig. 1 is a schematic cross-sectional view showing an example of a laminate that is a workpiece of this processing method. The laminate 10 shown in Fig. 1 includes a substrate 1, a metal layer 2, an etching stop layer 3, an insulating film 4, and a metal hard mask 5, in this order, and a hole 6 that exposes the metal layer 2 at a predetermined position formed by a dry etching process or the like. That is, the workpiece shown in Fig. 1 is a laminate that includes the substrate 1, the metal layer 2, the etching stop layer 3, the insulating film 4, and the metal hard mask 5, in this order, and includes a hole 6 that penetrates from the surface of the metal hard mask 5 to the surface of the metal layer 2 at the position of the opening. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a consisting of the etching stop layer 3, the insulating film 4, and the metal hard mask 5, and a bottom wall 11b consisting of the exposed metal layer 2, and has dry etching residue 12 attached thereto.

[0113] This processing method can be suitably used for removing these dry etching residues 12. That is, it is excellent in removing the dry etching residues 12 (residue removal property) and also in preventing corrosion of the inner wall 11 (e.g., metal layer 2, etc.) of the processing target object. The above-mentioned substrate processing method may also be performed on a laminate that has been subjected to a dry ashing step after the dry etching step. The materials constituting each layer of the above-mentioned laminate will be described below.

[0114] <Metal Hard Mask> The metal hard mask may be made of copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum nitride oxide, titanium aluminum, titanium aluminum carbide, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy (preferably YSiO ｘ ) wherein x is preferably a number of 1 to 3. Examples of the material for the metal hard mask include TiN, TiAl, TiAlC, and WO ２ and ZrO ２ Among these, TiN is preferred.

[0115] <Insulating Film> The material of the insulating film is not particularly limited, and examples thereof include those having a dielectric constant k of preferably 3.0 or less, more preferably 2.6 or less. Specific insulating film materials include SiO ｘ , SiN, SiOC, and organic polymers such as polyimide; and SiO ｘ Preferably, x is a number of 1 to 3. The insulating film may be composed of a plurality of films. An example of an insulating film composed of a plurality of films is an insulating film formed by combining a film containing silicon oxide and a film containing silicon carbide oxide.

[0116] <Etching Stop Layer> The material of the etching stop layer is not particularly limited. Specific examples of the material of the etching stop layer include SiN, SiON, SiOCN-based materials, and AlO ｘ and the like metal oxides.

[0117] <Metal Layer> The material forming the metal layer serving as the wiring material and / or plug material is not particularly limited, but preferably contains at least one selected from the group consisting of cobalt, tungsten, and copper, more preferably at least one selected from the group consisting of cobalt and tungsten, and even more preferably cobalt. The material forming the metal layer may also be an alloy of cobalt, tungsten, or copper with another metal. The metal layer may further contain a metal other than cobalt, tungsten, and copper, a metal nitride, and / or an alloy. Examples of metals other than cobalt, tungsten, and copper that may be contained in the metal layer include titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. The metal layer may contain at least one dopant selected from the group consisting of carbon, nitrogen, boron, and phosphorus in addition to one or more selected from the group consisting of cobalt, tungsten, and copper. The metal layer is also preferably a metal-containing material as described above.

[0118] <Substrate> Specific examples of wafers constituting the substrate include wafers made of silicon-based materials such as silicon (Si) wafers, silicon carbide (SiC) wafers, and silicon-containing resin wafers (glass epoxy wafers), as well as gallium phosphide (GaP) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers. Since the semiconductor processing solution of the present invention has excellent defect suppression performance after processing a silicon substrate and then performing a water rinse treatment, the substrate to be processed is preferably a silicon wafer. The silicon wafer may be an n-type silicon wafer doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb)), or a p-type silicon wafer doped with trivalent atoms (e.g., boron (B), gallium (Ga), etc.). The silicon of the silicon wafer may be, for example, amorphous silicon, single crystal silicon, or polycrystalline silicon (polysilicon).

[0119] The workpiece may contain various layers and / or structures as desired, in addition to those described above. For example, the substrate may contain metal wiring, gate electrodes, source electrodes, drain electrodes, insulating layers, ferromagnetic layers, and / or nonmagnetic layers. The substrate may also contain exposed integrated circuit structures, such as interconnect mechanisms, such as metal wiring and dielectric materials. Examples of metals and alloys used for interconnect mechanisms include aluminum, copper-aluminum alloys, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The substrate may also contain layers of silicon oxide, silicon nitride, silicon carbide, and / or carbon-doped silicon oxide.

[0120] The method for manufacturing the workpiece is not particularly limited as long as it is a method commonly used in this field. Examples of methods for forming the insulating film on a wafer constituting a substrate include a method in which a silicon oxide film is formed by heat treating the wafer constituting the substrate in the presence of oxygen gas, and then a silicon nitride film is formed by chemical vapor deposition (CVD) using silane and ammonia gases. Examples of methods for forming the metal layer on a wafer constituting a substrate include a method in which a circuit is formed on a wafer having the insulating film by a known method such as resist, and then a metal layer is formed by plating, sputtering, CVD, molecular beam epitaxy (MBE), or the like.

[0121] The workpiece may be a substrate that has been subjected to a planarization process such as CMP after providing an insulating film, a barrier metal, and a metal-containing film on a wafer. CMP is a process for planarizing the surface of a substrate having a metal-containing 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). Specific examples of substrates that have been subjected to CMP include, but are not limited to, substrates that have been subjected to CMP described in Journal of the Japan Society for Precision Engineering, Vol. 84, No. 3, 2018.

[0122] [Step A: Contacting Step] The treatment method of the present invention includes, for example, a contacting step (Step A) of contacting a semiconductor treatment solution with an object to be treated. This allows for the removal of metal-containing materials such as residues or metal resists from the object to be treated. Details of the object to be treated are as described above. Among these, a semiconductor substrate containing a metal-containing material is preferred, and a semiconductor substrate containing at least one selected from the group consisting of Co and W is more preferred.

[0123] The method for contacting the workpiece with the semiconductor processing solution is not particularly limited, and examples thereof include a method of immersing the workpiece in the semiconductor processing solution contained in a tank, a method of spraying the semiconductor processing solution onto the workpiece, a method of flowing the semiconductor processing solution onto the workpiece, or any combination thereof. The immersion treatment may be a batch method in which multiple workpieces are immersed and treated in a treatment tank, or a single-wafer method.

[0124] Furthermore, in order to further improve the processing capacity of the semiconductor processing liquid, a mechanical stirring method may be used, such as a method of circulating the semiconductor processing liquid above the workpiece, a method of passing or spraying the semiconductor processing liquid above the workpiece, or a method of stirring the semiconductor processing liquid by ultrasonic waves or megasonics.

[0125] The treatment time can be adjusted depending on the time for contacting the workpiece with the semiconductor treatment solution and the temperature of the semiconductor treatment solution, but is preferably 0.25 to 10 minutes, and more preferably 0.5 to 2 minutes. The temperature of the semiconductor treatment solution during treatment is not particularly limited, but the lower limit is preferably 15°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher. The upper limit of the temperature is preferably 90°C or lower, more preferably 80°C or lower, and even more preferably 70°C or lower.

[0126] Specific examples of the contact step include step A1 of recess-etching wiring made of metal inclusions disposed on a substrate using a semiconductor processing solution, step A2 of removing a film from the outer edge of a substrate on which a film made of metal inclusions is disposed, step A3 of removing metal inclusions adhering to the back surface of a substrate on which a film made of metal inclusions is disposed, step A4 of removing metal inclusions on a substrate after dry etching, and step A5 of removing metal inclusions on a substrate after chemical mechanical polishing. For the above steps A1 to A5, the description in paragraphs

[0049] to

[0072] of the specification of International Publication No. 2019 / 138814 can be cited, and the contents thereof are incorporated herein by reference.

[0127] [Step B: Rinse Step] The present processing method preferably includes a rinse step (Step B) in which the workpiece (substrate having metal inclusions) is rinsed with a rinse liquid (rinsed with a solvent to clean it) after Step A. The rinse step is preferably performed consecutively to the contact step, and is a step in which the workpiece is rinsed with the rinse liquid for 5 seconds to 5 minutes. Step B may be performed using the mechanical stirring method described above.

[0128] Examples of the rinse liquid include water (preferably deionized (DI) water), methanol, ethanol, isopropanol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. The rinse liquid is preferably water, methanol, ethanol, isopropanol, or a mixture thereof, more preferably water, and even more preferably DI water. That is, the present processing method preferably includes a step of performing a water rinse treatment after step A.

[0129] The method of bringing the rinse solution into contact with the workpiece can be the same as the method of bringing the semiconductor processing solution into contact with the workpiece described above. The temperature of the rinse solvent in the rinsing step is preferably 16 to 27°C.

[0130] [Step C: Drying Step] The present processing method may include a drying step (step C) of drying the object to be processed after step B. Examples of drying methods include spin drying, a method of passing a dry gas over the object to be processed, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, Marangoni drying, Rotagoni drying, IPA (isopropanol) drying, and any combination thereof.

[0131] In step C, the substrate is preferably dried by heating it with a heating means. The heating temperature is not particularly limited, but is preferably 50 to 350° C., more preferably more than 100° C. and less than 400° C., and even more preferably 150 to 250° C. The drying time in step C can be adjusted depending on the drying method, and is preferably, for example, 20 seconds to 5 minutes.

[0132] [Method for Manufacturing a Semiconductor Device] The present invention also includes a method for manufacturing a semiconductor device. The semiconductor device manufacturing method of the present invention preferably includes a substrate processing method having the above-described step A. The processing method of the present invention may be performed before or after other steps in the semiconductor device manufacturing method. The processing method of the present invention may be incorporated into other steps during the implementation of the processing method, or may be incorporated into other steps. Examples of other steps include formation steps (layer formation, etching, chemical mechanical polishing, modification, etc.) of structures such as metal wiring, gate structures, source structures, drain structures, insulating layers, ferromagnetic layers, and / or nonmagnetic layers, resist formation steps, exposure steps and removal steps, heat treatment steps, cleaning steps, and inspection steps. The processing method of the present invention may be performed at any stage of the back-end process (BEOL), middle-end process (MOL), or front-end process (FEOL).

[0133] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0134] In the following examples, the pH of the semiconductor processing solution was measured at 25°C using a pH meter (Horiba, Ltd., Model "F-74") in accordance with JIS Z8802-1984. In addition, in producing the semiconductor processing solutions of the examples and comparative examples, handling of containers, preparation, filling, storage, and analytical measurements of the semiconductor processing solutions were all carried out in a clean room meeting ISO Class 2 or lower.

[0135] [Raw Materials for Semiconductor Processing Solution] The following compounds were used to produce the semiconductor processing solution. Note that all of the components used in the Examples and Comparative Examples were classified as semiconductor grade or equivalent high purity grade.

[0136] [Basic compounds] Ammonia Tetramethylammonium hydroxide (TMAH) 2-aminoethanol Diethanolamine Monomethyldiethanolamine (MDEA) 2-(2-aminoethylamino)ethanol (AEEA) Diglycolamine N,N-dimethylethylenediamine (DMAEA) 2-(dimethylamino)ethanol (DMAE) 2-amino-2-methyl-1-propanol (AMP) DL-1-amino-2-propanol (DL-MIPA) Tris(hydroxymethyl)aminomethane (Tris) 3-amino-4-octanol Diazabicycloundecene (comparison compound, DBU) ε-caprolactam (comparison compound)

[0137] [Components other than basic compounds] ・2-butoxyethanol (organic solvent) ・Diethylene glycol monobutyl ether (BDG, organic solvent) ・Propylene glycol monomethyl ether acetate (PGMEA, organic solvent) ・Dimethyl sulfoxide (DMSO, organic solvent) ・5-methylbenzotriazole (5-MBTA, corrosion inhibitor) ・Benzotriazole (BTA, corrosion inhibitor) ・Benzimidazole (corrosion inhibitor) ・Diethylenetriaminepentaacetic acid (DTPA, chelating agent) ・Hydroxyethyliminodiacetic acid (HIDA, product name "HP-HIDA", manufactured by Cherest Co., Ltd., chelating agent) ・Citric acid (chelating agent) ・Oxalic acid (chelating agent) ・1-hydroxyethylidene-1,1'-diphosphonic acid (HEDP, chelating agent) ・Nitrilotris(methylenephosphonic acid) (ATMP, chelating agent) Phosphonobutanetricarboxylic acid (PBTC) N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) (EDTMP) Compound A (the compound shown below, an aminocarboxylic acid having a cyano group) Compound B (the compound shown below, an aminocarboxylic acid having a cyano group) Hydrogen peroxide (oxidizing agent)

[0138]

[0139] [Preparation of semiconductor processing solution] The semiconductor processing solution of Example 1 was prepared by mixing the raw materials so that the contents of 2-butoxyethanol, 5-methylbenzotriazole, diethylenetriaminepentaacetic acid, ammonia, and ultrapure water were the values ​​shown in the table, and then thoroughly stirring the resulting mixture using a stirrer. 20% by mass aqueous ammonia was used to add ammonia. According to the method for preparing the semiconductor processing solution of Example 1, the semiconductor processing solutions of Examples 2 to 20 and Comparative Examples 1 to 4, each having the composition shown in the table, were prepared. The pH at 25°C of the prepared semiconductor processing solutions of the Examples and Comparative Examples was all within the range of 7 to 12.

[0140] [Evaluation] Using the obtained semiconductor processing solution, the dissolution rates of cobalt, tungsten, and titanium nitride, and the defect suppression ability after rinsing were evaluated as follows.

[0141] [Metal Layer Dissolution Rate] A substrate having a 20 nm thick Co film (Co film), a substrate having a 20 nm thick W film (W film), and a substrate having a 20 nm thick TiN film (TiN film) were each prepared and cut into 2 x 2 cm squares to produce test specimens, which were substrates having metal layers. Each test specimen was immersed in the semiconductor processing solution of each Example or Comparative Example for 10 minutes. The semiconductor processing solution was adjusted to approximately 40°C. Before and after the immersion test, the thickness of each film was measured using an XRF AZX 400 X-ray fluorescence analyzer (manufactured by Rigaku Corporation). The dissolution rate (Å / min) of each film when using the semiconductor processing solution was calculated from the measured film thicknesses before and after immersion. A low dissolution rate of cobalt and tungsten is preferable because it can suppress the inhibition of cobalt and tungsten dissolution. In addition, a high dissolution rate of TiN is also preferable because the semiconductor processing liquid can be used as an etching liquid for TiN and has excellent TiN removability. In the table below, "< 1" in the TiN dissolution rate column indicates that the calculated film dissolution rate is less than 1 Å / min.

[0142] [Post-Rinse Defect Suppression] Using a wafer surface inspection device (SP-5, manufactured by KLA-Tencor Corporation), the number of particles with a diameter of 32 nm or more present on the surface of a 300 mm diameter silicon substrate and the address of each particle were measured. Next, the wafer, on which the number of foreign particles present on the silicon substrate surface had been measured, was set in a spin-rotation wafer processing device (manufactured by EKC Technologies Inc.). Each semiconductor processing solution of the Examples and Comparative Examples was ejected onto the surface of the set wafer at a flow rate of 1.5 L / min for 1 minute. Subsequently, rinsing with ultrapure water was performed for 15 seconds, also at a flow rate of 1.5 L / min, and then the wafer was spin-dried. For the dried wafer obtained, the number of particles with a diameter of 32 nm or more on the wafer and the address of each particle were measured using a wafer surface inspection device. From the obtained particle count, the increase in the number of particles before and after processing was calculated, and the post-rinse defect suppression was evaluated according to the following evaluation criteria. In practical terms, post-rinse defect suppression is preferably C or higher.

[0143] A: The increase in the number of particles with a diameter of 32 nm or more is 0 or more and less than 100. B: The increase in the number of particles with a diameter of 32 nm or more is 100 or more and less than 500. C: The increase in the number of particles with a diameter of 32 nm or more is 500 or more and less than 1000. D: The increase in the number of particles with a diameter of 32 nm or more is 1000 or more.

[0144] [Results] The compositions and evaluation results of the semiconductor processing solutions of the examples and comparative examples are shown in the table below. The content of each component in each semiconductor processing solution (all on a mass basis, unit: wt% (mass%)) is as shown in the table. The content of water is the remainder of all components shown in the table. "Mw." indicates the molecular weight of the compound used.

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] From the results shown in the table, it was confirmed that the semiconductor processing solution of the present invention can suppress the dissolution of cobalt and also suppresses the occurrence of defects after processing a silicon substrate and then performing a water rinsing process.

[0152] A comparison of Examples 1 to 13 confirmed that when the specific basic compound contained ammonia, post-rinse defect suppression was more excellent. A comparison of Examples 1 to 13 with Examples 14 to 16 confirmed that when the semiconductor processing solution contained an aminopolycarboxylic acid containing a cyano group, tungsten dissolution could be further suppressed. A comparison of Examples 17 to 19 with other Examples confirmed that when the organic solvent content was 1.0 to 7.0 mass%, post-rinse defect suppression was more excellent. A comparison of Example 20 with other Examples confirmed that when the semiconductor processing solution contained an oxidizing agent, titanium nitride solubility was excellent. A comparison of Examples 1 and 21 to 23 confirmed that when the organic solvent contained a glycol ether-based solvent, post-rinse defect suppression was more excellent, and when the organic solvent contained 2-butoxyethanol, post-rinse defect suppression was even more excellent. A comparison of Examples 1 and 24 to 25 confirmed that when the chelating agent was a compound having a carboxylic acid group, cobalt dissolution could be further suppressed, and when the chelating agent was an aminocarboxylic acid, cobalt dissolution could be further suppressed.

[0153] REFERENCE SIGNS LIST 1 substrate 2 metal layer 3 etching stop layer 4 insulating film 5 metal hard mask 6 hole 10 stacked body 11 inner wall 11a cross-sectional wall 11b bottom wall 12 dry etching residue

Claims

1. A semiconductor processing solution containing water, an organic solvent, a corrosion inhibitor, a chelating agent, and a basic compound, and not containing any of hydroxylamine and its salts, wherein the basic compound is a basic inorganic compound or -NH ２ , -NHR Ｎ , -NR Ｎ ２ , and -N ＋ R Ｎ ３ X － and a content of the organic solvent is 0.1 to 9.5 mass % based on the total mass of the semiconductor processing solution. Ｎ each independently represents a hydrocarbon group; X － represents a monovalent anion.

2. The semiconductor processing solution of claim 1, further comprising an oxidizing agent.

3. The semiconductor processing solution according to claim 1 or 2, wherein the water content is 90.0 mass % or more based on the total mass of the semiconductor processing solution.

4. The semiconductor processing solution according to claim 1 or 2, wherein the organic solvent comprises a glycol ether solvent.

5. The semiconductor processing solution according to claim 1 or 2, wherein the organic solvent comprises 2-butoxyethanol.

6. The semiconductor processing solution according to claim 1 or 2, wherein the anticorrosive agent comprises a compound having an azole structure.

7. The semiconductor processing solution according to claim 1 or 2, wherein the corrosion inhibitor comprises a substituted benzotriazole.

8. The semiconductor processing solution according to claim 1 or 2, wherein the corrosion inhibitor comprises 5-methylbenzotriazole.

9. The semiconductor processing solution according to claim 1 or 2, wherein the content of the anticorrosive agent is 0.12 to 0.21 mass % based on the total mass of the semiconductor processing solution.

10. The semiconductor processing solution according to claim 1 or 2, wherein the chelating agent comprises a compound having a carboxylic acid group.

11. The semiconductor processing solution according to claim 1 or 2, wherein the chelating agent comprises a polyaminocarboxylic acid.

12. The semiconductor processing solution of claim 1 or 2, wherein the chelating agent comprises diethylenetriaminepentaacetic acid.

13. The semiconductor processing solution according to claim 1 or 2, wherein the content of the chelating agent is 0.3 to 0.8 mass % based on the total mass of the semiconductor processing solution.

14. The semiconductor processing solution according to claim 1 or 2, wherein the basic compound comprises ammonia.

15. The semiconductor processing solution according to claim 1 or 2, wherein the content of the basic compound is 0.01 to 0.2 mass % based on the total mass of the semiconductor processing solution.

16. The semiconductor processing solution according to claim 1 or 2, further comprising an aminocarboxylic acid having a cyano group.

17. The semiconductor processing solution according to claim 16, wherein the aminocarboxylic acid having a cyano group includes a compound represented by the following formula (1): In formula (1), each R is independently a hydrogen atom, —CH ２ —COOH or —CH ２ -CN, provided that at least one of the five R's is -CH ２ -COOH, and at least one is -CH ２ - represents CN.

18. The semiconductor processing solution according to claim 1 or 2, which is used for processing a semiconductor substrate containing at least one element selected from the group consisting of cobalt and tungsten.

19. A method for manufacturing a semiconductor device, comprising a step of treating a semiconductor substrate with the semiconductor treatment solution according to claim 1 or 2.

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