JP2024045009A - Processing liquid, method for processing object to be processed and method for manufacturing semiconductor device - Google Patents

Abstract

To provide a processing liquid with excellent Cu corrosion inhibition and organic residue removal properties.SOLUTION: A processing liquid contains a reducing agent and at least one specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalocrotonic acid, and 3,4,5-trioxocyclohexane-1-carboxylic acid.SELECTED DRAWING: None

Description

The present invention relates to a processing liquid, a method of processing a target object, and a method of manufacturing a semiconductor device.

Semiconductor elements are manufactured by forming a resist film on a laminate having a metal film, which serves as the wiring material on a substrate, an etching stop layer, and an interlayer insulating layer, and then carrying out a photolithography process. In the photolithography process, a method is widely known in which etching or removing foreign matter from the substrate surface is carried out using a treatment liquid that dissolves metals and/or organic substances.

In the manufacture of semiconductor devices, a chemical mechanical polishing (CMP) process may be performed to planarize a semiconductor substrate surface having a metal wiring film, a barrier metal, an insulating film, and the like, using a polishing slurry containing abrasive particles (e.g., silica, alumina, and the like).
In the CMP process, the abrasive particles and various organic components used in the CMP process, as well as metal components derived from the polished wiring metal film and/or barrier metal, etc., tend to remain on the polished semiconductor substrate surface. For this reason, after the CMP process, a step of removing these residues using a treatment liquid is generally carried out.

As mentioned above, during the semiconductor manufacturing process, the processing liquid is used for processes such as removing unwanted metal inclusions, resist, and residues on the substrate.

As an example of such a treatment liquid, Patent Document 1 discloses a substrate treatment liquid for semiconductor devices having a pH of 8 or more and containing a specific compound represented by histidine and histidine derivatives, ascorbic acid, gallic acid, and water, in which the concentration of ascorbic acid in the treatment liquid is 0.01% by mass or more and the concentration of gallic acid in the treatment liquid is 0.01% by mass or more.

JP 2019-125810 A

When the present inventors studied the treatment liquid described in Patent Document 1, they found that it was difficult to achieve both Cu corrosion inhibition and organic residue removal properties, and further improvement was required.

Therefore, an object of the present invention is to provide a treatment liquid that is excellent in inhibiting corrosion of Cu and also excellent in removing organic residues.
Another object of the present invention is to provide a method for treating an object using the treatment liquid, and a method for manufacturing a semiconductor device.

As a result of intensive studies to solve the above problems, the present inventors found that the problems could be solved by the following configuration.

[1] Reducing agent and
and at least one specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalocrotonic acid, and 3,4,5-trioxocyclohexane-1-carboxylic acid. , treatment liquid.
[2] The treatment liquid according to [1], wherein the reducing agent contains at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives or salts thereof, and polyphenol compounds.
[3] The reducing agent according to [1] or [2], wherein the reducing agent contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or salts thereof, and gallic acid and gallic acid derivatives. processing liquid.
[4] The treatment liquid according to any one of [1] to [3], wherein the mass ratio of the content of the specific compound to the content of the reducing agent is 0.01 to 199.
[5] The treatment liquid according to any one of [1] to [4], further comprising a quaternary ammonium compound represented by formula (B) described below.
[6] The treatment liquid according to [5], wherein the mass ratio of the content of the quaternary ammonium compound to the content of the specific compound is 0.01 to 100.0.
[7] The treatment liquid according to any one of [1] to [6], which has a pH of 8.0 to 13.0.
[8] The treatment liquid according to any one of [1] to [7], further comprising a chelating agent.
[9] The treatment liquid according to [8], wherein the chelating agent contains an organic acid.
[10] The treatment liquid according to [9], wherein the organic acid includes at least one selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, and phosphonic acids.
[11] The organic acid is at least selected from the group consisting of citric acid, formic acid, oxalic acid, tartaric acid, lactic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and ethylenediaminetetra (methylenephosphonic acid). The treatment liquid according to [9], containing one type.
[12] The treatment liquid according to any one of [8] to [11], wherein the mass ratio of the content of the reducing agent to the content of the chelating agent is 0.005 to 5.0.
[13] The treatment liquid according to any one of [1] to [12], further comprising an amine compound.
[14] The treatment liquid according to [13], wherein the amine compound includes a compound represented by formula (C1) described below.
[15] The treatment liquid according to [14], wherein the group represented by R ⁹ in the above formula (C1) has 2 to 4 carbon atoms.
[16] The treatment liquid according to any one of [1] to [15], further comprising an anticorrosive agent.
[17] The treatment liquid according to any one of [1] to [16], further comprising water, and the water content is 60% by mass or more based on the total mass of the treatment liquid. .
[18] The treatment liquid according to any one of [1] to [17], which is used for cleaning an object containing Cu that has been subjected to a chemical mechanical polishing treatment.
[19] Treatment of a target object, which comprises a step of bringing the target object containing Cu, which has been subjected to a chemical mechanical polishing treatment, into contact with the treatment liquid according to any one of [1] to [18]. Method.
[20] A method for manufacturing a semiconductor device, comprising the method for cleaning an object according to [19].

According to the present invention, it is possible to provide a treatment liquid that is excellent in inhibiting corrosion of Cu and is also excellent in removing organic residues.
Further, according to the present invention, a method for treating a target object and a method for manufacturing a semiconductor device using the above-mentioned treatment liquid can also be provided.

The present invention will be described in detail below.
The following description of the configuration may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

The following describes the meaning of each description in this specification.
In this specification, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.
In addition, in this specification, when two or more types of a component are present, the "content" of the component means the total content of those two or more components.
In this specification, "the total mass of components in the treatment liquid excluding the solvent" means the total content of all components contained in the treatment liquid other than the solvent, such as water and organic solvent.

In this specification, when there are multiple substituents, linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when multiple substituents, etc. are specified at the same time, each substituent, etc. This means that they may be the same or different from each other. This also applies to the definition of the number of substituents, etc.
In the compounds described in this specification, unless otherwise specified, isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes may be included. Moreover, only one type of isomer and isotope may be included, or multiple types may be included.
In this specification, the bonding direction of the divalent group (for example, -COO-) is not limited unless otherwise specified. For example, when Y in a compound represented by the formula "X-Y-Z" is -COO-, the above compound may be "X-O-CO-Z", and "X-CO -O-Z".

As used herein, "psi" means pound-force per square inch; 1 psi = 6894.76 Pa.
As used herein, "ppm" means "parts-per-million (10 ^-6 )" and "ppb" means "parts-per-billion (10 ^-9 )".
In this specification, 1 Å (angstrom) corresponds to 0.1 nm.

As used herein, "weight average molecular weight" means a weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).

[Processing solution]
Each component contained in the processing liquid of the present invention will be described in detail below.
The treatment liquid of the present invention (hereinafter, also simply referred to as "treatment liquid") contains a reducing agent and a specific compound described below.

The reason why the treatment liquid having the above structure can solve the problems of the present invention is not necessarily clear, but due to the cooperative action of the reducing agent and the specific compound, the treatment liquid has excellent corrosion inhibition properties for Cu, and It is assumed that it is also excellent in removing organic residues.
For example, the reducing agent contained in the treatment liquid lowers the oxidation-reduction potential of Cu contained in the target object, thereby suppressing corrosion of Cu. Furthermore, the reducing agent and the specific compound improve the solubility of organic residues (for example, organic residues derived from polishing liquid), thereby facilitating the removal of organic residues. As a result, the treatment liquid is considered to be excellent in both Cu corrosion inhibition and organic residue removal properties.
Note that the above speculation does not limit the mechanism by which the effect is obtained. In other words, even cases where effects are obtained by mechanisms other than those described above are included within the scope of the present invention.
Hereinafter, the fact that at least one of Cu's corrosion inhibition property and organic residue removal property is better is also referred to as "the effect of the present invention is better".

[Reducing Agent]
The processing liquid contains a reducing agent.
The reducing agent is a compound having a reducing function, and examples thereof include ascorbic acid and ascorbic acid derivatives or their salts, polyphenol compounds, reducing sulfur compounds, hydrogen peroxide, hydrazine derivatives, and sugars. Note that the reducing agent does not include the specific compounds described below.
Among these, the reducing agent is preferably ascorbic acid, an ascorbic acid derivative, or a salt thereof, or a polyphenol compound.

<Ascorbic acid and ascorbic acid derivatives or salts thereof>
Ascorbic acid includes L-ascorbic acid, D-ascorbic acid, and isoascorbic acid.
Examples of the ascorbic acid derivative include alkylglyceryl ascorbic acid, glycerol ascorbic acid, ascorbic acid alkyl ether, ascorbic acid alkyl ester, ascorbic acid sulfate, and ascorbic acid phosphate.
Salts of ascorbic acid and ascorbic acid derivatives can also be suitably used. Examples of the salt include alkali metal salts such as sodium ascorbate.
Preferably, the reducing agent includes ascorbic acid.

<Polyphenol compound>
A polyphenol compound is a compound having at least two phenolic hydroxy groups.
Examples of polyphenol compounds include catechol, resorcinol, hydroquinone, and derivatives thereof.

The polyphenol compound is preferably a compound represented by formula (A).

R ^A represents a hydrogen atom or a monovalent organic group. The plurality of ^RAs may be the same or different.
Examples of the monovalent organic group include, but are not particularly limited to, a carboxy group, an aldehyde group, and a hydrocarbon group that may have a heteroatom.
Hydrocarbon groups having heteroatoms include -O-, -CO-, -COO-, -NR ^N -, -CONR ^N -, -S-, A group having at least one divalent linking group selected from the group consisting of and -SO ₂ -. Note that ^RN represents a hydrogen atom or an alkyl group.
The number of carbon atoms in the hydrocarbon group is preferably 1 to 25, more preferably 1 to 15, even more preferably 1 to 10.
The hydrocarbon group may be linear, branched, or cyclic.
When the hydrocarbon group has a ring structure, the ring may be monocyclic or polycyclic.
The above hydrocarbon group may further have a substituent.
Examples of substituents that the hydrocarbon group may further have include halogen atoms such as chlorine atoms, hydroxy groups, alkoxy groups, acyl groups, alkyl groups, carboxy groups, thiol groups, cyano groups, and nitro groups. A hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or a carboxy group is preferable, and a hydroxy group or a carboxy group is more preferable.
As the hydrocarbon group, an alkyl group, an alkenyl group, or an aryl group is preferable.
The hydrocarbon group having a hetero atom is preferably an acyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylamido group, or a heteroaryl group, and more preferably an alkoxy group.
R ^A is preferably a hydrogen atom, a carboxy group, an alkyl group, an alkenyl group, an acyl group, an alkoxy group, an alkyloxycarbonyl group, or a heteroaryl group; More preferred is a hydrogen atom, a methyl group, a methoxy group, or a carboxy group.

A plurality of R ^A may be bonded to each other to form a ring.
The ring formed by bonding a plurality of R ^A to each other may further have a substituent. Examples of the substituent include substituents that the above-mentioned hydrocarbon group may have, and a hydroxy group or a carboxy group is preferable.
Examples of the ring structure formed by bonding a plurality of R ^A to each other include a benzene skeleton, a naphthalene skeleton, a cyclohexanedione skeleton, and an anthracene skeleton.

k is an integer from 2 to 4, preferably 2 or 3, and more preferably 3.
When k is 2 or more, it is preferable that at least two hydroxy groups in formula (A) are adjacent to each other. That is, the compound represented by formula (A) is preferably catechol or a catechol derivative.
Examples of catechol derivatives include pyrogallol, hydroxyquinol, gallic acid, gallic acid derivatives, 4-tert-butylcatechol, 3-methylcatechol, catechol-4-acetic acid, urushiol, caffeic acid, 1,2-dihydroxynaphthalene, Examples include 2,3-dihydroxynaphthalene, alizarin, quercetin, and catechin.

Among these, gallic acid or gallic acid derivatives are preferred as the compound represented by formula (A). Examples of gallic acid derivatives include alkyl gallates such as methyl gallate, ethyl gallate, propyl gallate, octyl gallate, and lauryl gallate, and gallic acid amide.

As the compound represented by formula (A), flavonoids such as flavonols, anthocyanidins, and flavanols are also preferred. For example, flavonols are compounds in which one of R ^A is a chroman derivative.

Examples of polyphenol compounds include catechol, hydroquinone, resorcinol, pyrogallol, hydroxyquinol, phloroglucinol, gallic acid, alkyl gallate, gallic acid amide, 4-tert-butylcatechol, 3-methylcatechol, and catechol-4-acetic acid. , urushiol, caffeic acid, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, naphresorcinol, alizarin, endocrocin, emodin, quercetin, catechin, and anthocyanin.

<Reducing sulfur compound>
The reducing sulfur compound is not particularly limited as long as it contains a sulfur atom and has a function as a reducing agent, but examples include mercaptosuccinic acid, dithiodiglycerol, bis(2,3-dihydroxypropylthio)ethylene, Sodium -(2,3-dihydroxypropylthio)-2-methyl-propylsulfonate, 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, thioglycolic acid, and 3-mercapto -1-propanol is mentioned.
Among these, compounds having an SH group (mercapto compounds) are preferred, and 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, 3-mercapto-1-propanol, or thioglycolic acid are preferred. More preferred is 1-thioglycerol or thioglycolic acid.

<Other reducing agents>
The reducing agent may include other reducing agents in addition to those mentioned above.
Other reducing agents include, for example, hydrogen peroxide; hydrazine derivatives such as hydrazine and hydrazide compounds; sugars such as fructose, glucose, and ribose; polyvinylpyrrolidone; and phenanthroline.

The reducing agent preferably contains at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or salts thereof, polyphenol compounds, hydrogen peroxide, and hydrazine; It is more preferable to include at least one selected from the group consisting of salts and polyphenol compounds, and at least one selected from the group consisting of ascorbic acid and ascorbic acid derivatives or salts thereof, and gallic acid and gallic acid derivatives. It is more preferable to include one type.
Among them, the reducing agents include ascorbic acid, 3-O-ethylglyceryl ascorbic acid, sodium ascorbate, gallic acid, alkyl gallate, pyrogallol, hydroxyquinol, catechol, resorcinol, hydroquinone, caffeic acid, alizarin, endocrocin, and emodin. , quercetin, catechin, hydrogen peroxide, and hydrazine, preferably contains at least one selected from the group consisting of ascorbic acid, ethylglyceryl ascorbic acid, sodium ascorbate, gallic acid, alkyl gallate, pyrogallol, hydroxy It is more preferable to contain at least one selected from the group consisting of quinol, catechol, resorcinol, hydroquinone, caffeic acid, alizarin, endocrocin, emodin, quercetin, and catechin, including ascorbic acid, ethylglyceryl ascorbic acid, and ascorbic acid. It is more preferable to contain at least one selected from the group consisting of sodium, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, hydroxyquinol, pyrogallol, and catechol.

One type of reducing agent may be used alone, or two or more types may be used in combination.
In order to achieve better effects of the present invention, the content of the reducing agent is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and 0.02% by mass based on the total mass of the treatment liquid. The above is more preferable, and 0.03% by mass or more is particularly preferable. The upper limit is not particularly limited, but in terms of reducing the amount used while maintaining the effects of the present invention, it is preferably 10.0% by mass or less, more preferably 6.0% by mass or less, and 0.5% by mass or less. More preferred.
In order to achieve better effects of the present invention, the content of the reducing agent is preferably 0.5% by mass or more, more preferably 2.0% by mass or more, based on the total mass of the components of the treatment liquid excluding the solvent. , more preferably 8.0% by mass or more. The upper limit is preferably 95.0% by mass or less, more preferably 60.0% by mass or less, even more preferably 45.0% by mass or less, and particularly 35.0% by mass from the viewpoint of maintaining the effects of the present invention. preferable.

[Specific compound]
The treatment liquid contains at least one specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalocrotonic acid, and 3,4,5-trioxocyclohexane-1-carboxylic acid. including.

The specific compounds may be used alone or in combination of two kinds.
In order to obtain better effects of the present invention, the content of the specific compound is preferably 0.001 to 15.0 mass %, more preferably 0.005 to 10.0 mass %, even more preferably 0.02 to 3.0 mass %, and particularly preferably 0.03 to 0.3 mass %, relative to the total mass of the treatment liquid.
In order to obtain better effects of the present invention, the content of the specific compound is preferably 0.1 to 97.0 mass %, more preferably 2.0 to 90.0 mass %, even more preferably 7.0 to 60.0 mass %, and particularly preferably 10.0 to 55.0 mass %, based on the total mass of the components excluding the solvent in the treatment liquid.
In order to obtain better effects of the present invention, the mass ratio of the content of the specific compound to the content of the reducing agent is preferably 0.001 to 200, more preferably 0.01 to 199, even more preferably 0.1 to 50, and particularly preferably 0.1 to 5.

The treatment liquid may contain other components than the above-mentioned components (reducing agent and specific compound).
The other components will be explained in detail below.

[Quaternary ammonium compound represented by formula (B)]
The treatment liquid may contain a quaternary ammonium compound represented by formula (B) (hereinafter, also referred to as a "specific quaternary ammonium compound"). When the treatment liquid contains the specific quaternary ammonium compound, the organic residue removability is more excellent.

R ¹ to R ⁴ each independently represent an alkyl group which may have a substituent and which may have a linking group represented by —O—.
The alkyl group may be linear, branched, or cyclic.
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
The total number of carbon atoms in the groups represented by R ¹ to R ⁴ is 5 or more, preferably 5 to 22, more preferably 5 to 16, and even more preferably 5 to 12.
When the groups represented by R ¹ to R ⁴ are alkyl groups having a substituent, the total number of carbon atoms of the substituent and the alkyl group is within the above range. When the groups represented by R ¹ to R ⁴ are alkyl groups having no substituent, the total number of carbon atoms of the alkyl group is within the above range.
Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom; an alkoxy group; a hydroxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group; an acyl group such as an acetyl group, a propionyl group, and a benzoyl group; a cyano group; and a nitro group, with a hydroxy group being preferred.
The alkyl group is preferably a methyl group, an ethyl group, a 2-hydroxyethyl group, a propyl group, or a butyl group, and more preferably an ethyl group or a butyl group.
A plurality of R ¹ to R ⁴ may be bonded to each other to form a ring.

X ⁻ represents an anion.
Examples of the anion include acid anions such as a carboxylate ion, a phosphate ion, a phosphonate ion, and a nitrate ion, as well as a hydroxide ion, with the hydroxide ion being preferred.

Examples of specific quaternary ammonium compounds include tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH), dimethylbis(2-hydroxyethyl)ammonium hydroxide, ethyltrimethylammonium hydroxide (ETMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), tetrapropylammonium hydroxide (TPAH), 2-hydroxyethyltrimethylammonium hydroxide (choline), bis(2-hydroxyethyl)dimethylammonium hydroxide, tri(2-hydroxyethyl)methylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, and cetyltrimethylammonium hydroxide. THEMAH, ETMAH, choline, TBAH, or TEAH are preferred, and TEAH or TBAH are more preferred.

The specific quaternary ammonium compounds may be used alone or in combination of two or more.
From the viewpoint of obtaining a more excellent effect of the present invention, the content of the specific quaternary ammonium compound is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass, based on the total mass of the treatment liquid. The upper limit is not particularly limited, but from the viewpoint of reducing the amount used while maintaining the effect of the present invention, it is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, even more preferably 5.0% by mass or less, and particularly preferably 1.0% by mass or less.
In order to obtain better effects of the present invention, the content of the specific quaternary ammonium compound is preferably 1.0 to 90.0 mass%, more preferably 10.0 to 80.0 mass%, and even more preferably 20.0 to 70.0 mass%, based on the total mass of the components excluding the solvent in the treatment liquid.
In order to obtain better effects of the present invention, the mass ratio of the content of the specific quaternary ammonium compound to the content of the specific compound is preferably 0.01 to 150.0, more preferably 0.01 to 100.0, even more preferably 0.1 to 50.0, and particularly preferably 0.5 to 30.0.

[Chelating agent]
The treatment liquid may contain a chelating agent.
A chelating agent is a compound having a functional group (coordination group) that can function as a ligand for a residue and/or a target object in a treatment step. Note that the chelating agent does not contain any of the above-mentioned compounds (reducing agent, specific compound, and specific quaternary ammonium compound) that may be included in the treatment liquid.

The coordination group that the chelating agent has includes an acid group.
Examples of the acid group include a carboxy group, a phosphonic acid group, a sulfo group, and a phenolic hydroxy group.
The chelating agent preferably has a carboxy group or a phosphonic acid group as a coordinating group, and more preferably has a carboxy group.

Chelating agents include organic chelating agents and inorganic chelating agents.
The organic chelating agent is a chelating agent made of an organic compound, and includes, for example, a carboxylic acid-based chelating agent having a carboxy group as a coordinating group, a phosphonic acid-based chelating agent having a phosphonic acid group as a coordinating group, and a coordinating group. Examples include sulfonic acid-based chelating agents having a sulfo group.
Examples of inorganic chelating agents include condensed phosphoric acid and salts thereof.

As the chelating agent, an organic chelating agent is preferable, and it is also preferable that the chelating agent has an acid group as a coordinating group. That is, the chelating agent is preferably an organic acid.

<Organic acid>
An organic acid is an organic compound having at least one acid group.
Examples of the organic acid include carboxylic acid, phosphonic acid, and sulfonic acid, with carboxylic acid or phosphonic acid being preferred, and carboxylic acid being more preferred.
The number of acid groups that the organic acid has is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

Preferably, the organic acid has a low molecular weight.
Specifically, the molecular weight of the organic acid is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less. The lower limit is preferably 50 or more, more preferably 100 or more.
The number of carbon atoms in the organic acid is preferably 1 to 15, more preferably 2 to 15.

Carboxylic acids include, for example, polycarboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids.
Examples of polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, maleic acid, and adipic acid, with oxalic acid, malonic acid, or succinic acid being preferred.
Examples of hydroxycarboxylic acids include citric acid, malic acid, glycolic acid, gluconic acid, heptonic acid, tartaric acid, lactic acid, phenyllactic acid, hydroxyphenyllactic acid, and phenylsuccinic acid, with citric acid, tartaric acid, or lactic acid being preferred.
Examples of aminocarboxylic acids include histidine or a derivative thereof, alanine (2-aminopropionic acid or 3-aminopropionic acid), arginine, asparagine, aspartic acid, cystine, cysteine, glutamine, glutamic acid, glycine or a derivative thereof, isoleucine, leucine, lysine, methionine, phenylalanine, serine, ethionine, threonine, tyrosine, valine, tryptophan, 2-amino-3-aminopropanoic acid, and proline, with histidine or a derivative thereof being preferred.
An example of a carboxylic acid other than the above is formic acid.
Examples of the aminocarboxylic acid include the compounds described in paragraphs [0021] to [0023] of JP2016-086094A.
Examples of histidine derivatives include the compounds described in JP-A-2015-165561 and JP-A-2015-165562. Examples of glycine derivatives include N,N-di(2-hydroxyethyl)glycine.

Examples of phosphonic acids include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDT PO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylenetetraminehexa(ethylenephosphonic acid), with HEDPO or EDTPO being preferred.

Examples of phosphonic acids include 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, the contents of which are incorporated herein by reference.

The chelating agent preferably contains an organic acid, more preferably contains at least one selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, and phosphonic acids, and even more preferably contains at least one selected from the group consisting of polycarboxylic acids and hydroxycarboxylic acids.
In particular, the chelating agent preferably contains at least one selected from the group consisting of citric acid, formic acid, oxalic acid, tartaric acid, lactic acid, HEDPO, EDTPO, and histidine, and more preferably contains at least one selected from the group consisting of oxalic acid, tartaric acid, and citric acid.

One type of chelating agent may be used alone, or two or more types may be used in combination.
In order to achieve better effects of the present invention, the content of the chelating agent is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total mass of the treatment liquid. , 0.01 to 2.0% by mass is more preferable.
In order to obtain better effects of the present invention, the content of the chelating agent is preferably from 0.1 to 97.0% by mass, and from 1.0 to 95% by mass, based on the total mass of the components of the treatment liquid excluding the solvent. 0% by mass is more preferred, 3.0 to 80.0% by mass is even more preferred, and 5.0 to 30.0% by mass is particularly preferred.
In order to obtain better effects of the present invention, the mass ratio of the reducing agent content to the chelating agent content is preferably 0.001 to 300.0, more preferably 0.005 to 5.0, and 0.001 to 300.0, more preferably 0.005 to 5.0. 02 to 5.0 is more preferable, and 0.1 to 3.5 is particularly preferable.
In order to obtain better effects of the present invention, the mass ratio of the content of the chelating agent to the content of the specific compound is preferably 0.001 to 500, more preferably 0.003 to 100, and 0.01 to 15. 0 is more preferable.

[Amine compound]
The treatment liquid may contain an amine compound.
An amine compound is a compound in which at least one hydrogen atom of ammonia is replaced with another substituent. For example, a primary amine compound having a primary amino group (-NH ₂ ) in the molecule, Examples include secondary amine compounds having a secondary amino group (>NH) and tertiary amine compounds having a tertiary amino group (>N-) in the molecule. In addition, when it has an amino group of a different series, it is classified into the amine compound with the highest series.
The amine compound does not contain any of the above-mentioned compounds (reducing agent, chelating agent, specific quaternary ammonium compound, etc.) that may be contained in the treatment liquid, and the nitrogen-containing heterocyclic compound.
The treatment liquid preferably contains an amine compound from the viewpoint of excellent organic residue removal properties.

The amine compound preferably has two or more amino groups in that the effects of the present invention are more excellent.
In addition, it is also preferable that the compound has a hydroxy group as a substituent, in that the effects of the present invention are more excellent.

The pKa of the amine compound is preferably 5.0 to 20.0, more preferably 7.5 to 15.0, even more preferably 9.0 to 14.5.
For the above pKa, the value described in SC-Database can be used. Further, values measured using known methods such as neutralization titration, spectrophotometry, and capillary electrophoresis can also be used.

As the amine compound, a compound represented by formula (C1) is preferred.

R ⁵ to R ⁸ each independently represent a hydrogen atom or an alkyl group which may have a substituent or a linking group represented by -O-.
The alkyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 6, and particularly preferably 1 to 4.
Examples of the substituent include substituents that can be taken by the groups represented by R ¹ to R ⁴ in formula (B), and a hydroxy group or an alkoxy group is preferable.
When the alkyl group has a linking group represented by -O-, the number of linking groups represented by -O- in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and 1 to 3. is even more preferable.
Among these, R ⁵ to R ⁸ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, or an isopropyl group. , methyl group or ethyl group are more preferred.
A plurality of R ⁵ to R ⁸ may be bonded to each other to form a ring.

R ⁹ represents an alkylene group having 2 or more carbon atoms which may have a substituent and which may have a linking group represented by —O— or —NR ^N —, where R ^N represents a hydrogen atom or an alkyl group.
The alkylene group has 2 or more carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the substituent include those which may be taken by the groups represented by R ¹ to R ⁴ in formula (B), and a hydroxy group or an alkoxy group is preferred.
When the alkylene group has a linking group represented by -O-, the number of linking groups represented by -O- on the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
When the alkylene group has a linking group represented by -NR ^N -, the alkylene group preferably has 1 to 5 linking groups represented by -NR ^N -, more preferably 1 to 3, and even more preferably 1 or 2.
R ^{1 N} represents a hydrogen atom or an alkyl group.
The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
Among these, R ⁹ is preferably an ethylene group, a propylene group, a butylene group, or a hexylene group, and more preferably an ethylene group, a propylene group, or a butylene group.

Compounds represented by formula (C1) include 1,2-diaminopropane, N-methyl-1,3-diaminopropane, 1,2-diaminoethane, 1,3-diaminopropane, 2-methyl-1,3-diaminopropane, 1,4-diaminobutane, 1,3-diaminobutane, 1,3-bis(dimethylamino)butane, 2-(2-aminoethylamino)ethanol (AAE), 1-(2-hydroxyethyl)piperazine, N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,2-bis These include diamine compounds such as (2-aminoethoxy)ethane, 1,6-diaminohexane, tetramethylethylenediamine, and tetramethyl-1,4-butanediamine, as well as polyalkylpolyamines such as diethylenetriamine (DETA), N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA), and tetraethylenepentamine.

As amine compounds other than the amine compound represented by formula (C1), monoamine compounds having a hydroxy group are also preferred.
As the monoamine compound having a hydroxy group, a compound represented by formula (C2) is preferable.

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group which may have a substituent.
The alkyl group may be linear, branched, or cyclic.
The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 6, and particularly preferably 1 to 4.
Examples of the substituent include substituents that can be taken by the groups represented by R ¹ to R ⁴ in formula (B), and a hydroxy group is preferred.
R ¹⁰ and R ¹¹ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxy group, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group. or a 2-hydroxyethyl group is more preferred, and a hydrogen atom, a methyl group, or an ethyl group is even more preferred.
R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.

R ¹² represents an alkylene group which may have a substituent.
The alkylene group may be linear, branched, or cyclic.
The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.
Examples of the substituent include those which the groups represented by R ¹ to R ⁴ in formula (B) may have, and a hydroxy group is preferred.
R ¹² is preferably a methylene group, an ethylene group, a propylene group, a methylethylene group, an ethylethylene group, a 1-methylpropylene group, a 1,1-dimethylethylene group, or a 1,2-dimethylethylene group, and more preferably an ethylene group, a methylethylene group, or a propylene group.

Examples of the compound represented by formula (C2) include ethanolamine, propanolamine, isopropanolamine, trishydroxymethylaminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), 2-dimethyl Amino-2-methyl-1-propanol (DMAMP), 2-amino-2-methyl-1,3-propanediol (AMPDO), 2-amino-2-ethyl-1,3-propanediol (AEPDO), 2 -Amino-1,3-propanediol (2-APDO), 3-amino-1,2-propanediol (3-APDO), 3-methylamino-1,2-propanediol (MAPDO), 2-(methyl Amino)-2-methyl-1-propanediol (N-MAMP), 2-(aminoethoxy)ethanol (AEE), diethanolamine (DEA), triethanolamine (TEA), N-methylethanolamine, N-butylethanol amine, N-cyclohexylethanolamine, 2-(ethylamino)ethanol, propylaminoethanol, diethylene glycolamine (DEGA), N-tert-butyldiethanolamine, N-butyldiethanolamine, N-methyldiethanolamine, and 1-piperidineethanol. Can be mentioned.

Other amine compounds besides those mentioned above include, for example, aliphatic monoamine compounds such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, n-butylamine, tert-butylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, 3-methoxypropylamine, trimethylamine, and triethylamine.

The amine compound preferably contains at least one selected from the group consisting of a compound represented by formula (C1) and a compound represented by formula (C2), and the compound represented by formula (C1) It is more preferable to include at least one selected from the group consisting of:
Among these, amine compounds include methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, , N-diethylethanolamine, N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, N-ethylethanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanol Amine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2-methyl-1,3-diaminopropane, and N-methyl-1,3 - Diaminopropane, preferably at least one selected from the group consisting of ethanolamine, propanolamine, 1,2-diaminopropane, and N-methyl-1,3-diaminopropane. It is more preferable to include at least one kind of.

The amine compounds may be used alone or in combination of two or more.
In order to obtain superior effects of the present invention, the content of the amine compound is preferably from 0.01 to 20.0 mass %, more preferably from 0.03 to 15.0 mass %, and even more preferably from 0.05 to 5.0 mass %, based on the total mass of the treatment liquid.
In order to obtain better effects of the present invention, the content of the amine compound is preferably from 0.01 to 99.0 mass%, more preferably from 3.0 to 50.0 mass%, even more preferably from 15.0 to 40.0 mass%, and particularly preferably from 15.0 to 35.0 mass%, based on the total mass of the components excluding the solvent in the treatment liquid.

[Anti-corrosion agent]
The treatment liquid may contain an anticorrosive agent.
The anticorrosive agent is a compound that has the function of preventing corrosion of a metal component (for example, a metal layer containing Cu or a Cu alloy) contained in a target object. Note that the anticorrosive agent does not contain any of the above-mentioned compounds (reducing agent, specific compound, specific quaternary ammonium compound, chelating agent, and amine compound) that may be included in the treatment liquid.

The anticorrosive agent is not particularly limited, but a heterocyclic compound is preferred.
Examples of the heterocyclic compound include an azole compound, a pyrrole compound, a pyridine compound, a pyrazine compound, a pyrimidine compound, an indole compound, an indolizine compound, an indazole compound, a quinoline compound, and an oxazole compound. An azole compound or a pyrrole compound is preferable.

Examples of azole compounds include imidazole compounds in which one of the atoms constituting the azole ring is a nitrogen atom, pyrazole compounds in which two of the atoms constituting the azole ring are nitrogen atoms, and one of the atoms constituting the azole ring Thiazole compounds in which one is a nitrogen atom and the other is a sulfur atom, triazole compounds in which three of the atoms constituting the azole ring are nitrogen atoms, and four of the atoms constituting the azole ring are nitrogen atoms. Examples include tetrazole compounds.

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 pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole, and 4-aminopyrazole.

Examples of thiazole compounds include 2,4-dimethylthiazole, benzothiazole and 2-mercaptobenzothiazole.

Examples of triazole compounds include benzotriazole compounds in which two adjacent substituents on a triazole ring are bonded to each other to form a benzene ring.
Examples of benzotriazole compounds include benzotriazole, 5-methyl-1H-benzotriazole (CAS registration number: 136-85-6), tolyltriazole (CAS registration number: 29385-43-1), and 5-aminobenzotriazole. , 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 5,6-dimethylbenzotriazole, 1-[N,N-bis(hydroxyethyl)aminoethyl]benzotriazole, 1-(1,2-dicarboxyethyl) ) benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-{[ Examples include (methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol and carboxybenzotriazole.
Examples of triazole compounds other than benzotriazole compounds include 1,2,3-triazole, 1,2,4-triazole, 3-methyl-1,2,4-triazole, and 3-amino-triazole. Examples include 1,2,4-triazole and 1-methyl-1,2,3-triazole.

Tetrazole compounds include, for example, 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1-(2-dimethylaminoethyl)-5-mercaptotetrazole.

The azole compound is preferably a triazole compound or a tetrazole compound.
The anticorrosive agent is preferably a triazole compound, a tetrazole compound, or a pyrrole compound, and more preferably triazole, tetrazole, or pyrrole.
In this specification, the above azole compounds include their tautomers.

The anticorrosive agent may be used alone or in combination of two or more kinds.
In order to obtain a more excellent effect of the present invention, the content of the anticorrosive agent is preferably 0.005 to 20.0 mass %, more preferably 0.01 to 10.0 mass %, and even more preferably 0.03 to 1.0 mass %, based on the total mass of the treatment liquid.
In order to obtain a more excellent effect of the present invention, the content of the corrosion inhibitor is preferably 0.01 to 50.0 mass%, more preferably 1.0 to 40.0 mass%, and even more preferably 10.0 to 30.0 mass%, based on the total mass of the components excluding the solvent of the treatment liquid.

〔water〕
The treatment liquid may contain water as a solvent.
The type of water used in the processing liquid may be any water that does not adversely affect the semiconductor substrate, and distilled water, deionized (DI) water, and pure water (ultrapure water) can be used. Pure water (ultrapure water) is preferable because it contains almost no impurities and has less influence on the semiconductor substrate during the manufacturing process of the semiconductor substrate.
The content of water is preferably 60.0% by mass or more, more preferably 80.0% by mass or more, and even more preferably 90.0% by mass or more, based on the total mass of the treatment liquid. The upper limit is preferably 99.99% by mass or less, more preferably 99.90% by mass or less, and even more preferably 99.50% by mass or less, based on the total mass of the treatment liquid.

[Other ingredients]
In addition to the above compounds, the treatment liquid may contain at least one component selected from the group consisting of a surfactant, a pH adjuster, an organic solvent, a polymer, and a polyhydroxy compound having a molecular weight of 500 or more.
The other ingredients will be described below.

<Surfactant>
Surfactants are compounds that have a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule, such as nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Examples include surfactants.
Note that the surfactant is a compound different from the above-mentioned compounds that may be included in the treatment liquid.

Surfactants often have at least one hydrophobic group selected from the group consisting of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
When the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms in the hydrophobic group contained in the surfactant is preferably 6 or more, more preferably 10 or more. The total carbon number of the surfactant is preferably 16 to 100.

Examples of the nonionic surfactant include ester type nonionic surfactants, ether type nonionic surfactants, and ester ether type nonionic surfactants, with ether type nonionic surfactants being preferred.

Examples of nonionic surfactants include polyethylene glycol, alkyl polyglucoside (Triton BG-10 and Triton CG-110 surfactants manufactured by Dow Chemical Company), and octylphenol ethoxylate (Triton X- manufactured by Dow Chemical Company). 114), silane polyalkylene oxide (copolymer) (Y-17112-SGS sample manufactured by Momentive Performance Materials), nonylphenol ethoxylate (Tergitol NP-12 manufactured by Dow Chemical Company, and Triton (registered Trademark) X-102 , X-100, X-45, -20), polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkylaryl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene of glycerin ester Ether, polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester, BRIJ (registered trademark) 56 (C ₁₆ H ₃₃ (OCH) ₂ CH ₂ ) ₁₀ OH), BRIJ (registered trademark) 58 (C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂₀ OH), BRIJ (registered trademark) 35 (C ₁₂ H ₂₅ (OCH ₂ CH ₂ ) ₂₃ OH), etc. Alcohol ethoxylates, alcohol (primary and secondary) ethoxylates, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), cetyl alcohol, stearyl alcohol, cetostearyl alcohol (cetyl and stearyl alcohol), oleyl alcohol , octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol alkyl ether, decyl glucoside, lauryl glucoside, octyl glucoside, polyoxyethylene glycol octyl phenol ether, nonoxynol-9, glycerol alkyl ester, glyceryl laurate, Included are block copolymers of polyoxyethylene glycol sorbitan alkyl ester, polysorbate, sorbitan alkyl ester, and polypropylene glycol, and mixtures thereof.

As surfactants, for example, the compounds exemplified in paragraph [0126] of WO 2022/044893 can also be used, the contents of which are incorporated herein by reference.

The surfactant may be used alone or in combination of two or more kinds.
In view of excellent performance of the treatment liquid, the content of the surfactant is preferably from 0.001 to 8.0 mass %, more preferably from 0.005 to 5.0 mass %, and even more preferably from 0.01 to 3.0 mass %, based on the total mass of the treatment liquid.
In view of excellent performance of the treatment liquid, the content of the surfactant is preferably 0.01 to 50.0 mass %, more preferably 0.1 to 45.0 mass %, and even more preferably 1.0 to 20.0 mass %, based on the total mass of the components in the treatment liquid excluding the solvent.

<pH Adjuster>
The treatment solution may contain a pH adjuster to adjust and maintain the pH of the treatment solution.
The pH adjuster is a basic compound or an acidic compound different from the above-mentioned compounds that may be contained in the treatment liquid, however, it is permissible to adjust the pH of the treatment liquid by adjusting the amount of each of the above-mentioned components added.

A basic compound is a compound that exhibits alkaline properties (pH greater than 7.0) in an aqueous solution.
The basic compound includes basic inorganic compounds, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides.

An acidic compound is a compound that exhibits acidity (pH less than 7.0) in an aqueous solution.
Acidic compounds include inorganic acids, such as hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and boric acid.

As the acidic compound, a salt of an acidic compound may be used as long as it becomes an acid or an acid ion (anion) in an aqueous solution.

The pH adjusters may be used alone or in combination of two or more.
The content of the pH adjuster can be selected depending on the type and amount of other components and the intended pH of the treatment liquid. For example, the content of the pH adjuster is preferably 0.01 to 10 mass %, more preferably 0.1 to 8 mass %, based on the total mass of the treatment liquid.
The content of the pH adjuster is preferably from 0.01 to 80% by mass, and more preferably from 0.1 to 60% by mass, based on the total mass of the components in the treatment liquid excluding the solvent.

<Organic solvent>
Examples of the organic solvent include known organic solvents, such as alcohol solvents, glycol solvents, glycol ether solvents, and ketone solvents.
The organic solvent is preferably miscible with water in any ratio.

As the organic solvent, for example, compounds exemplified in paragraphs [0135] to [140] of International Publication No. 2022/044893 can be used, the contents of which are incorporated herein.

<Polymer>
It is also preferable that the treatment liquid contains a polymer, since the effects of the present invention are more excellent.
As the polymer, for example, the water-soluble polymers described in paragraphs [0043] to [0047] of JP-A-2016-171294 can be used, and the contents thereof are incorporated herein.
The polymer is preferably a water-soluble polymer, and specifically, for example, polyvinyl alcohol, hydroxyethyl cellulose, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polymethacrylamide, and these. Examples include copolymers. Note that the water-soluble polymer is intended to mean a polymer that dissolves in 100 g of water at 20° C. in a mass of 0.1 g or more.
The weight average molecular weight (Mw) of the water-soluble polymer is preferably 10,000 to 1,500,000, more preferably 40,000 to 1,200,000. Note that the weight average molecular weight (Mw) of the water-soluble polymer refers to the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).

The polymers may be used alone or in combination of two or more.
The content of the polymer is preferably from 0.01 to 5.0% by mass, and more preferably from 0.05 to 0.5% by mass, based on the total mass of the treatment liquid.
The content of the polymer is preferably from 0.1 to 10.0% by mass, and more preferably from 0.5 to 5.0% by mass, based on the total mass of the components excluding the solvent in the treatment liquid.

<Polyhydroxy Compound with Molecular Weight of 500 or More>
The polyhydroxy compound having a molecular weight of 500 or more is a compound different from the above-mentioned compounds that may be contained in the treatment liquid.
The polyhydroxy compound is an organic compound having two or more (eg, 2 to 200) alcoholic hydroxy groups in one molecule.
The molecular weight of the polyhydroxy compound (weight average molecular weight when the compound has a molecular weight distribution) is 500 or more, preferably 500 to 100,000, and more preferably 500 to 3,000.

As the polyhydroxy compound, compounds exemplified in paragraphs [0101] and [0102] of International Publication No. 2022/014287 can also be cited, and the contents of these are incorporated herein.

[Physical properties of processing solution]
<pH>
The treatment liquid may be either alkaline or acidic.
In order to obtain a more excellent effect of the present invention, the pH of the treatment liquid is preferably from 4.0 to 14.0, more preferably from 8.0 to 14.0, even more preferably from 8.0 to 13.0, and particularly preferably from 10.5 to 13.0.
In particular, when the treatment liquid is used to treat an object containing at least one selected from the group consisting of Cu, Co, and Ru, the pH of the treatment liquid is preferably 8.0 to 14.0, more preferably 8.0 to 13.0, and even more preferably 10.5 to 13.0, in order to have better corrosion inhibition properties for Cu, Co, and Ru.
Furthermore, when the treatment liquid is used to treat a workpiece containing W, the pH of the treatment liquid is preferably 4.0 to 13.0, more preferably 5.0 to 9.0, and even more preferably 5.0 to 7.0, in order to obtain better corrosion inhibition properties for W.
The pH of the treatment solution can be measured by a method conforming to JIS Z8802-1984 using a known pH meter. The pH is measured at a temperature of 25°C.

<Metal content>
The content (measured as ion concentration) of metals (e.g., Fe, Co, Na, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag metal elements) contained as impurities in the treatment liquid is preferably 5 mass ppm or less, more preferably 1 mass ppm or less. Since it is expected that a treatment liquid with even higher purity will be required in the manufacture of cutting-edge semiconductor devices, it is more preferable that the content of the above metals is lower than 1 mass ppm, that is, on the order of ppb or less, particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit is preferably 0.

Methods for reducing metal content include, for example, purification treatments such as distillation and filtration using ion exchange resins or filters at the stage of raw materials used when manufacturing the treatment liquid or at the stage after the manufacture of the treatment liquid. One example is to do the following.
Another method for reducing the metal content is to use a container that contains less impurities, which will be described later, as a container for storing raw materials or manufactured processing liquids. Another possibility is to line the inner walls of the pipes with fluororesin to prevent metal components from eluting from the pipes during production of the processing liquid.

<Insoluble particles>
It is preferred that the treatment liquid be substantially free of insoluble particles.
The above-mentioned "insoluble particles" refer to particles of inorganic solids and organic solids, etc., which do not dissolve and ultimately exist as particles in the treatment liquid.
The above-mentioned "substantially free of insoluble particles" means that the treatment liquid is diluted 10,000 times with a solvent contained in the treatment liquid to prepare a composition for measurement, and the number of particles having a particle size of 50 nm or more contained in 1 mL of the composition for measurement is 40,000 or less. The number of particles contained in the composition for measurement can be measured in the liquid phase using a commercially available particle counter.
Commercially available particle counter devices include those manufactured by Rion and PMS. A representative device of the former is the KS-19F, and a representative device of the latter is the Chem20. Devices such as the KS-42 series and LiQuilaz II S series can be used to measure larger coarse particles.
Examples of insoluble particles include particles of inorganic solids such as silica (including colloidal silica and fumed silica), alumina, zirconia, ceria, titania, germania, manganese oxide, and silicon carbide; and particles of organic solids such as polystyrene, polyacrylic resin, and polyvinyl chloride.
Methods for removing insoluble particles from the treatment liquid include, for example, purification treatments such as filtering.

<Coarse particles>
The treatment liquid may contain coarse particles, but it is preferable that the content of coarse particles is low.
The term "coarse particles" refers to particles whose diameter (particle size) when considered as a sphere is 1 μm or more.
The coarse particles contained in the treatment liquid include particles such as dust, dirt, organic solids, and inorganic solids that are contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids that are brought in as contaminants during the preparation of the treatment liquid, and which ultimately exist as particles in the treatment liquid without dissolving.

Regarding the content of coarse particles in the treatment liquid, the content of particles having a particle diameter of 1 μm or more per 1 mL of the treatment liquid is preferably 100 or less, more preferably 50 or less. The lower limit is preferably 0 or more, more preferably 0.01 or more per 1 mL of the treatment liquid.
The content of coarse particles present in the treatment liquid 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.
Examples of a method for removing coarse particles include a purification process such as filtering, which will be described later.

[Production method]
The treatment liquid can be produced by a known method. The method for producing the treatment liquid will be described in detail below.

[Liquid preparation process]
The treatment liquid can be produced, for example, by mixing the above components.
As a method for preparing the treatment liquid, for example, a reducing agent, a specific compound, and optional components as needed are sequentially added to a container containing purified pure water, and then the mixture is stirred and mixed. An example of this method is to prepare the treatment liquid by adding a pH adjuster accordingly to adjust the pH of the mixed liquid. Furthermore, when adding each component to the container, it may be added all at once, or may be added in multiple portions.

The stirring device and stirring method used to prepare the treatment liquid may be a device known as a stirrer or disperser. Examples of stirrers include industrial mixers, portable stirrers, mechanical stirrers, and magnetic stirrers. Examples of dispersers include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

The mixing of each component in the process of preparing the treatment liquid, the purification treatment described below, and the storage of the manufactured treatment liquid are preferably carried out at 40°C or lower, more preferably at 30°C or lower. Moreover, as a lower limit, 5 degreeC or more is preferable, and 10 degreeC or more is more preferable. By preparing, treating and/or storing the treatment liquid within the above temperature range, performance can be maintained stably for a long period of time.

<Refinification>
It is preferable to perform a purification treatment in advance on one or more of the raw materials for preparing the treatment liquid. Examples of the purification treatment include known methods such as distillation, ion exchange, and filtration.
The degree of purification is preferably such that the purity of the raw material is 99% by mass or more, and more preferably such that the purity of the undiluted solution is 99.9% by mass or more. The upper limit is preferably 99.9999% by mass or less.

Examples of the purification method include passing the raw material through an ion exchange resin or a reverse osmosis membrane (RO membrane), distilling the raw material, and filtering.
The purification process may be a combination of the above purification methods. For example, the raw material may be subjected to a primary purification process in which the raw material is passed through an RO membrane, and then a secondary purification process in which the raw material is passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed-bed ion exchange resin.
The purification process may be carried out multiple times.

The filter used for filtering is not particularly limited as long as it has been conventionally used for filtration purposes. For example, fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyallylsulfone (PAS), and polyethylene and polypropylene (PP). Examples include filters made of polyolefin resins (including high-density or ultra-high molecular weight) such as. 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; is more preferable. By filtering raw materials using filters made of these materials, highly polar foreign substances that tend to cause defects can be effectively removed.

<Container>
The treatment liquid (including the diluted treatment liquid described below) can be filled into any container for storage, transport and use, so long as corrosiveness and other issues do not pose a problem.

The container is preferably one that is highly clean for semiconductor applications and that suppresses the elution of impurities from the inner wall of the container into each liquid. Examples of such containers include various containers that are commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited thereto.
In addition, the containers exemplified in paragraphs [0121] to [0124] of WO 2022/004217 can also be used, the contents of which are incorporated herein by reference.

The inside of these containers is preferably cleaned before being filled with the processing liquid. The liquid used for cleaning preferably has a reduced amount of metal impurities in the liquid. After production, the treatment liquid may be bottled in a container such as a gallon bottle or a coated bottle, and then transported and stored.

To prevent changes in the components of the treatment liquid during storage, the inside of the container may be replaced with an inert gas (such as nitrogen or argon) with a purity of 99.99995% by volume or more. Gases with a low moisture content are particularly preferred. In addition, the treatment liquid may be stored and transported at room temperature, or the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

<Clean room>
It is preferable that all of the manufacturing of the treatment liquid, handling including opening and cleaning of containers, filling of the treatment liquid, treatment analysis, and measurement are 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 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.

[Dilution process]
The treatment liquid may be subjected to a dilution step in which the treatment liquid is diluted with a diluent such as water, and then used as the diluted treatment liquid (diluted treatment liquid) for treatment of an object.
Incidentally, the diluted processing solution is also one form of the processing solution of the present invention so long as it satisfies the requirements of the present invention.

It is preferable to perform a purification treatment beforehand for the dilution liquid used in the dilution step. It is more preferable to perform a purification treatment on the diluted liquid obtained in the dilution step.
Examples of the purification treatment include the ion component reduction treatment using an ion exchange resin or an RO membrane, etc., and the removal of foreign matter using filtering, which are described above as purification treatments for the treatment liquid, and it is preferable to perform any one of these treatments.

The dilution rate of the treatment liquid in the dilution step may be appropriately adjusted depending on the type and content of each component, and the object to be treated. The ratio of the diluted treatment liquid to the treatment liquid before dilution (dilution ratio) is preferably 10 to 10,000 times, more preferably 20 to 3,000 times, and even more preferably 50 to 1,000 times, in terms of mass ratio or volume ratio (volume ratio at 23° C.).
In addition, in terms of superior residue removal properties, the treatment liquid is preferably diluted with water.

The change in pH before and after dilution (the difference between the pH of the treatment liquid before dilution and the pH of the diluted treatment liquid) is preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.5 or less.
The pH of the treatment liquid before dilution and the pH of the diluted treatment liquid are preferably in the above-mentioned preferred embodiments.

A specific method for diluting the treatment liquid may be carried out in accordance with the process of preparing the treatment liquid described above. As for the stirring device and stirring method used in the dilution step, the known stirring device mentioned in the above-mentioned treatment liquid preparation step may be used.

[Use applications]
The treatment liquid of the present invention can be used for various materials used in semiconductor manufacturing. Hereinafter, the object to be treated with the treatment liquid of the present invention will be described in detail.

The above-mentioned processing liquid can be used, for example, to remove an insulating film, resist, antireflection film, etching residue, ashing residue, etc. existing on the substrate. It is more preferable that the processing liquid is used in a CMP process or a cleaning process for cleaning a buffed object (particularly a semiconductor substrate).
As described above, when using the treatment liquid, it may be used as a diluted treatment liquid obtained by diluting the treatment liquid.

[Target object]
The object to be treated with the treatment liquid may be, for example, an object containing a metal, and is preferably a semiconductor substrate containing a metal.
When the semiconductor substrate contains a metal, the metal may be present on any of the front and back surfaces, side surfaces, and inside the grooves of the semiconductor substrate, for example. When the semiconductor substrate contains a metal, the metal may be present not only directly on the surface of the semiconductor substrate, but also on the semiconductor substrate via another layer.

Examples of metals include at least one metal M selected from the group consisting of copper (Cu), cobalt (Co), ruthenium (Ru), aluminum (Al), tungsten (W), titanium (Ti), tantalum (Ta), chromium (Cr), hafnium (Hf), osmium (Os), platinum (Pt), nickel (Ni), manganese (Mn), iron (Fe), zirconium (Zr), molybdenum (Mo), palladium (Pd), lanthanum (La), and iridium (Ir). Cu, Co, Ru, Mo, or W is preferred, Cu, Co, or Ru is more preferred, and Cu is even more preferred. In other words, the target object is preferably an object containing Cu. Also, the target object is preferably an object containing W.

The metal may be any substance that contains a metal (metal atom), and examples include metal M alone and alloys that contain metal M.

The object to be treated with the treatment liquid may include, for example, a semiconductor substrate, a metal wiring film, a barrier metal, and an insulating film.

Wafers constituting the semiconductor substrate include, for example, silicon (Si) wafers, silicon carbide (SiC) wafers, wafers made of silicon-based materials such as silicon-containing resin wafers (glass epoxy wafers), and gallium phosphide (GaP) wafers. ) wafers, gallium arsenide (GaAs) wafers, and indium phosphide (InP) wafers.
Examples of silicon wafers include n-type silicon wafers doped with pentavalent atoms (e.g., phosphorus (P), arsenic (As), and antimony (Sb), etc.), and silicon wafers doped with trivalent atoms. Examples include p-type silicon wafers doped with atoms (eg, boron (B), gallium (Ga), etc.). Examples of the silicon of the silicon wafer include amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon.
Among these, wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and resin-based wafers containing silicon (glass epoxy wafers) are preferred.

Examples of the insulating film include silicon oxide films (e.g., silicon dioxide (SiO ₂ ) films, tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) films (TEOS films), etc.), silicon nitride films (e.g., silicon nitride films), etc. (Si ₃ N ₄ ) and silicon nitride carbide (SiNC)), and low-k films (such as carbon-doped silicon oxide (SiOC) films, BD (black diamond) films, and silicon carbide (Si 3 N 4 ), silicon nitride carbide (SiNC), etc.); (SiC) film, etc.), and a low dielectric constant (Low-k) film is preferred.

As the metal wiring film, a copper-containing film, a cobalt-containing film, and a ruthenium-containing film are preferable.
Examples of the copper-containing film include a wiring film made only of metallic copper (copper wiring film) and a wiring film made of an alloy made of metallic copper and another metal (copper alloy wiring film).
Examples of the copper alloy wiring film include a wiring film made of an alloy made of copper and one or more metals selected from Al, Ti, Cr, Mn, Ta, and W. More specifically, copper-aluminum alloy wiring film (CuAl alloy wiring film), copper-titanium alloy wiring film (CuTi alloy wiring film), copper-chromium alloy wiring film (CuCr alloy wiring film), copper-manganese alloy wiring film (CuMn alloy wiring film), copper-tantalum alloy wiring film (CuTa alloy wiring film), and copper-tungsten alloy wiring film (CuW alloy wiring film).

Examples of the cobalt-containing film include a metal film made only of metallic cobalt (cobalt metal film) and a metal film made of an alloy made of metallic cobalt and another metal (cobalt alloy metal film).
Examples of the cobalt alloy metal film include metal films made of an alloy of cobalt and one or more metals selected from Ti, Cr, Fe, Ni, Mo, Pd, Ta, and W. More specifically, examples of the cobalt alloy metal film include a cobalt-titanium alloy metal film (CoTi alloy metal film), a cobalt-chromium alloy metal film (CoCr alloy metal film), a cobalt-iron alloy metal film (CoFe alloy metal film), a cobalt-nickel alloy metal film (CoNi alloy metal film), a cobalt-molybdenum alloy metal film (CoMo alloy metal film), a cobalt-palladium alloy metal film (CoPd alloy metal film), a cobalt-tantalum alloy metal film (CoTa alloy metal film), and a cobalt-tungsten alloy metal film (CoW alloy metal film).

Examples of ruthenium-containing films include metal films consisting only of metallic ruthenium (ruthenium metal film) and metal films made of alloys consisting of metallic ruthenium and other metals (ruthenium alloy metal film).

There are no particular limitations on the method of forming the above-mentioned insulating film, copper-containing film, cobalt-containing film, and ruthenium-containing film on the wafer constituting the semiconductor substrate, as long as it is a method normally performed in this field.
As a method for forming an insulating film, for example, a silicon oxide film is formed by performing heat treatment on a wafer constituting a semiconductor substrate in the presence of oxygen gas, and then chemical treatment is performed by flowing silane and ammonia gas. A method of forming a silicon nitride film by a chemical vapor deposition (CVD) method is exemplified.
As a method for forming a copper-containing film, a cobalt-containing film, and a ruthenium-containing film, for example, a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as resist, and then plating and CVD are performed. Examples include a method of forming a copper-containing film, a cobalt-containing film, and a ruthenium-containing film.

<Object subjected to CMP treatment>
The target object when using the treatment liquid for cleaning is preferably a CMP-treated target (especially a semiconductor substrate), and more preferably a CMP-treated target containing Cu. .
CMP processing, for example, processes the surface of a semiconductor substrate having a metal wiring film, a barrier metal, and an insulating film by a combined action of chemical action and mechanical polishing using a polishing slurry containing polishing fine particles (abrasive grains). This is a flattening process.

On the surface of the object that has been subjected to the CMP treatment, residues such as abrasive grains (e.g., silica and alumina) used in the CMP treatment, polished metal wiring film, and metal impurities derived from the barrier metal may remain. In addition, organic matter derived from the CMP treatment liquid used in the CMP treatment may remain as residue. These residues may, for example, cause short circuits between wirings and deteriorate the electrical properties of the semiconductor substrate, so the semiconductor substrate that has been subjected to the CMP treatment is subjected to a cleaning treatment to remove these residues from the surface.
A specific example of the object to be treated by CMP is a substrate to which CMP has been applied, as described in Journal of the Japan Society for Precision Engineering, Vol. 84, No. 3, 2018, but is not limited thereto.

<Object that has been buffed>
The surface of the object may be subjected to a buffing process after the CMP process.
Buffing is a process for reducing residues on the surface of an object using a polishing pad. Specifically, the surface of an object that has been subjected to CMP is brought into contact with the polishing pad, and the object and the polishing pad are slid relative to each other while a buffing composition is supplied to the contact portion. As a result, the residues on the surface of the object are removed by the frictional force of the polishing pad and the chemical action of the buffing composition.

As the buffing composition, any known buffing composition can be used as appropriate depending on the type of object and the type and amount of the residue to be removed. Components contained in the buffing composition are not particularly limited, but include, for example, water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid.
The polishing device and polishing conditions used in the buffing process can be appropriately selected from known devices and conditions depending on the type of object and the type of residue. Examples of the buffing treatment include the treatments described in paragraphs [0085] to [0088] of International Publication No. 2017/169539, the contents of which are incorporated herein.

As an embodiment of the buffing process, it is also preferable to use the above-mentioned treatment liquid as a buffing composition to perform buffing on an object. In other words, it is also preferable to use the treatment liquid for buffing an object that has residues after CMP processing.

[how to use]
The processing solution can be used in a known manner, and the method of using the processing solution will be described in detail below.

[Treatment process]
Examples of methods for using the treatment liquid include a method for treating an object including a step of contacting the object with the treatment liquid. Hereinafter, the step of contacting the object with the treatment liquid is also referred to as a "contact step."
The method for contacting the object with the treatment liquid is not particularly limited, and examples thereof include a method of immersing the object in the treatment liquid contained in a tank, a method of spraying the treatment liquid on the object, a method of pouring the treatment liquid on the object, and a combination of these. The above method may be appropriately selected depending on the purpose.
The above method may be appropriately adopted from the methods usually used in this field. For example, it may be a scrub cleaning method in which a cleaning member such as a brush is brought into physical contact with the surface of the object while supplying the processing liquid to remove residues, or a spin (drop) method in which the processing liquid is dropped onto the object while rotating the object. In the immersion method, it is preferable to perform ultrasonic treatment on the object immersed in the processing liquid, since impurities remaining on the surface of the object can be further reduced.

The contact between the object and the treatment liquid in the contact step may be carried out only once, or may be carried out two or more times. When making contact two or more times, the same method may be repeated or different methods may be combined.

The contact step may be carried out by either a single wafer method or a batch method.
The single-wafer method generally refers to a method in which objects are processed one by one, while the batch method generally refers to a method in which a plurality of objects are processed simultaneously.

There are no particular limitations on the temperature of the processing liquid, so long as it is a temperature that is normally used in this field. Generally, cleaning is performed at room temperature (approximately 25°C), but the temperature can be selected as desired to improve residue removal and minimize damage to components. For example, the temperature of the processing liquid is preferably 10 to 60°C, and more preferably 15 to 50°C.

The contact time between the object and the treatment liquid can be changed as appropriate depending on the type and content of each component contained in the treatment liquid, and the object and purpose of the treatment liquid. Practically, the time is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

The supply amount (supply rate) of the treatment liquid is preferably 50 to 5000 mL/min, more preferably 500 to 2000 mL/min.

In the contact step, a mechanical stirring method may be used to further improve the treating capacity of the treating solution.
Examples of the mechanical stirring method include a method of circulating the treatment liquid above the object, a method of passing or spraying the treatment liquid above the object, and a method of stirring the treatment liquid by ultrasonic or megasonic means.

Further, after the contacting step, a step of bringing the object into contact with a rinsing liquid (hereinafter also referred to as a "rinsing step") may be performed. By performing the rinsing step, the object obtained in the contacting step can be washed with a rinsing liquid and residues can be efficiently removed.
The rinsing step is preferably performed continuously after the object treatment step, and is a step of rinsing the object using a rinsing liquid. The rinsing step may be performed using the mechanical stirring method described above.

Examples of rinsing solutions include water (preferably DI water), methanol, ethanol, isopropyl alcohol (IPA), N-methylpyrrolidinone, gamma-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. In addition, an aqueous rinsing solution having a pH greater than 8.0 (such as diluted aqueous ammonium hydroxide) may be used.

As a method of bringing the rinsing liquid into contact with the object, the method of bringing the treatment liquid into contact with the object can be similarly applied.
The contact time between the object and the rinsing liquid can be changed as appropriate depending on the type and content of each component contained in the treatment liquid, and the object and purpose of the treatment liquid. Practically, the time is preferably 10 to 120 seconds, more preferably 20 to 90 seconds, and even more preferably 30 to 60 seconds.

After the rinsing step, a drying step for drying the object may be performed.
Drying methods include, for example, spin drying, flowing a dry gas over the object, heating the substrate with a heating means such as a hot plate or an infrared lamp, Marangoni drying, Rotagoni drying, IPA (isopropyl alcohol) drying, and any combination of these.

[Method for manufacturing semiconductor devices]
The method for treating the object described above can be suitably applied to a method for manufacturing semiconductor devices.
The above processing methods may be performed in combination before or after other steps performed on the substrate. The above treatment method may be incorporated into other steps while implementing the above treatment method, or may be implemented by incorporating the above treatment method into other steps.
Other processes include, for example, processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and nonmagnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and metamorphosis, etc.), a resist formation process, an exposure process and a removal process, a heat treatment process, a cleaning process, and an inspection process.

The above processing method can be performed at any stage of the back end process (BEOL: Back end of the line), middle process (MOL: Middle of the line), or front end process (FEOL: Front end of the line). It is preferable to perform this in a front-end process or a middle process.

The present invention will be explained in more detail below based on Examples.
The materials, amounts used, proportions, processing details, processing procedures, etc. 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 Examples shown below.

In the following examples, the pH of the treatment solution was measured at 25° C. using a pH meter (manufactured by Horiba, Ltd., model "F-74") in accordance with JIS Z8802-1984.
In addition, in producing the treatment solutions of the Examples and Comparative Examples, handling of containers, preparation, filling, storage and analysis of the treatment solutions were all carried out in a clean room of a level satisfying ISO class 2 or lower.

[Raw materials for processing liquid]
A treatment liquid was manufactured using the compounds listed in the table below. All of the components used to produce the treatment liquid were classified as semiconductor grade or equivalent high purity grade.

[Reducing Agent]
・Ascorbic acid ・Caffeic acid (polyphenol compound)
・Alizarin (polyphenol compound)
・Endocrinol (polyphenol compound)
・Urushiol (a polyphenol compound)
・Resorcinol (a polyphenol compound)
・Hydroquinone (polyphenol compound)
・Emodin (a polyphenol compound)
・Quercetin (a polyphenol compound)
・Catechin (polyphenol compound)
・Hydrogen peroxide ・Hydrazine ・Gallic acid (polyphenol compound)
3-O-Ethylglyceryl Ascorbic Acid (Ascorbic Acid Derivative)
・Sodium ascorbate (ascorbate salt)
・Catechol (polyphenol compound)
・Hydroxyquinol (polyphenol compound)
・Methyl gallate (polyphenol compound, gallic acid derivative)
・Ethyl gallate (polyphenol compound, gallic acid derivative)
・Propyl gallate (polyphenol compound, gallic acid derivative)
・Octyl gallate (polyphenol compound, gallic acid derivative)
・Pyrogallol (polyphenol compound)

[Specific Compound]
Dehydroascorbic acid 2,3-diketogulonic acid 4-oxalocrotonic acid Compound X: 3,4,5-trioxocyclohexane-1-carboxylic acid

[Other compounds]
TEAH: Tetraethylammonium hydroxide (a specific quaternary ammonium compound)
TBAH: Tetrabutylammonium hydroxide (specific quaternary ammonium compound)
ETMAH: Ethyltrimethylammonium hydroxide (a specific quaternary ammonium compound)
Choline: 2-hydroxyethyltrimethylammonium hydroxide (a specific quaternary ammonium compound)
・1,2-diaminopropane (amine compound)
N-methyl-1,3-diaminopropane (amine compound)
・Ethanolamine (amine compound)
・Propanolamine (amine compound)
・Citric acid (chelating agent)
・Formic acid (chelating agent)
・Oxalic acid (chelating agent)
・Tartaric acid (chelating agent)
・Lactic acid (chelating agent)
HEDPO: 1-hydroxyethylidene-1,1'-diphosphonic acid (chelating agent)
EDTPO: Ethylenediaminetetra(methylenephosphonic acid) (chelating agent)
・Histidine (chelating agent)
・Triazole (corrosion inhibitor)
・Tetrazole (corrosion inhibitor)
・Pyrrole (anticorrosive agent)
Polyacrylic acid (Mw=2,000, polymer)
Polyethylene glycol (Mw=500, surfactant)

The pH of the treatment solution was adjusted using sulfuric acid and/or potassium hydroxide as a pH adjuster, if necessary.
In the treatment liquid, the components specified as components of the treatment liquid in the table and the remaining components (remainder) excluding the pH adjuster are ultrapure water.

[Preparation of Processing Solution]
The method for producing the treatment liquid will be described using Example 1 as an example.
Ascorbic acid, dehydroascorbic acid, and TEAH were added to ultrapure water in amounts such that the final treatment solution would have the composition shown in the table below. The resulting mixture was thoroughly stirred to obtain the treatment solution of Example 1.

According to the manufacturing method of Example 1, treatment liquids of each Example or each Comparative Example having the compositions shown in the table below were manufactured.

[Evaluation of Processing Solution]
The resulting treatment solution was evaluated for its ability to inhibit corrosion of Cu and its ability to remove organic residues. The evaluation methods are described below.

[Evaluation of Cu corrosion inhibition]
The treatment solution produced by the above method was used to evaluate its corrosion inhibition ability against Cu.
A 2.0 cm x 2.0 cm Cu wafer was placed in 150 mL of the treatment solution of each Example or Comparative Example, and immersed for 10 minutes at room temperature (25° C.). The thickness of the wafer before and after the immersion treatment was measured using a CR300DE (resistance measuring device, manufactured by Kokusai Electric Semiconductor Services Co., Ltd.), and the etching rate (ER-A) (Å/min) was calculated from the difference in thickness before and after the immersion treatment.
The etching rate (ER-B) (Å/min) was measured in the same manner using DIW as the processing liquid.

The ratio (ER-A/ER-B) of the etching rate (ER-A) when the treatment liquid of the Example or Comparative Example was used to the etching rate (ER-B) obtained when DIW was used as the treatment liquid was evaluated according to the following evaluation criteria. The smaller the ER-A/ER-B, the better the corrosion inhibition of Cu.
7: ER-A/ER-B≦0.3
6: 0.3<ER-A/ER-B≦0.5
5: 0.5<ER-A/ER-B≦0.9
4: 0.9<ER-A/ER-B≦1.1
3: 1.1<ER-A/ER-B≦1.5
2: 1.5<ER-A/ER-B≦2.0
1:2.0<ER-A/ER-B

[Evaluation of organic residue removal]
The treating solution produced by the above method was used to clean a semiconductor substrate that had been subjected to chemical mechanical polishing, and the removability of organic residues was evaluated.
Using a FREX300S-II (polishing device, manufactured by Ebara Corporation), a 12-inch diameter wafer having a TEOS film (Low-k film) on its surface was polished using polishing liquid 1 as the polishing liquid under conditions of an in-plane average polishing pressure of 105 hPa, a polishing liquid supply rate of 200 mL/min, and a polishing time of 30 seconds. Next, using polishing liquid 2 as the polishing liquid, the wafer that had been subjected to the above polishing treatment was polished under conditions of an in-plane average polishing pressure of 70 hPa, a polishing liquid supply rate of 200 mL/min, and a polishing time of 60 seconds.
The resulting CMP-treated wafer was scrubbed for 60 seconds using a sample of the treatment liquid of each Example or Comparative Example adjusted to room temperature (23° C.), and then dried.
The compositions of the polishing solutions 1 and 2 are as follows:
Polishing solution 1 (pH 7.0)
Colloidal silica (PL3, manufactured by Fuso Chemical Co., Ltd.) 0.1% by mass
Glycine 1.0% by mass
0.2% by mass of 3-amino-1,2,4-triazole
Benzotriazole (BTA) 30 ppm by mass
Hydrogen peroxide 1.0% by mass
・pH adjusters (ammonia and nitric acid)
Water Remainder Polishing solution 2 (pH 10.5)
Colloidal silica (PL3, manufactured by Fuso Chemical Co., Ltd.) 6.0% by mass
Citric acid 1.0% by mass
Alkyl alkoxylate surfactant 100 ppm by mass
BTA 0.2% by mass
Hydrogen peroxide 1.0% by mass
・pH adjuster (potassium hydroxide and nitric acid)
Water Remainder

Thereafter, the polished surface of the obtained wafer was observed using an S-4800 (Scanning Electron Microscope, SEM, manufactured by Hitachi High-Tech Corporation), and, if necessary, the constituent elements were analyzed using an energy dispersive X-ray spectroscopy (EDX) to identify the target.
In this way, the number of defects due to organic residues (residues mainly composed of organic matter) present within a unit area of 2 cm x 2 cm was counted.

The organic residue removability of the treatment liquid was evaluated according to the following evaluation criteria: The fewer the number of organic residues detected per unit area on the polished surface of the wafer, the better the organic residue removability.
7: The number of organic residues per unit area is less than 2 6: The number of organic residues per unit area is 2 or more but less than 3 5: The number of organic residues per unit area is 3 or more but less than 5 4: The number of organic residues per unit area is 5 or more but less than 10 3: The number of organic residues per unit area is 10 or more but less than 20 2: The number of organic residues per unit area is 20 or more but less than 30 1: The number of organic residues per unit area is 30 or more

[result]
In the table, the "Content (mass %)" column indicates the content (mass %) of each component relative to the total mass of the treatment liquid.
In the table, "quaternary ammonium compound" indicates a specific quaternary ammonium compound represented by formula (B).
In the table, the numerical value in the "B/A" column is the mass ratio of the specific compound content (B) to the reducing agent content (A) (specific compound content (B)/reducing agent content (A). )).
In the table, the numerical value in the "C/B" column is the mass ratio of the content (C) of the specific quaternary ammonium compound to the content (B) of the specific compound (content (C) of the specific quaternary ammonium compound). / content (B)) of the specific compound.
In the table, the numerical value in the "A/D" column is the mass ratio of the reducing agent content (A) to the chelating agent content (D) (reducing agent content (A)/chelating agent content (D) )).
In the table, the numerical values in the pH column indicate the pH of the treatment solution at 25° C. before and after dilution, as measured by the above-mentioned pH meter.
In the table, the "Cu corrosion protection" column shows the evaluation results of the corrosion inhibition properties of Cu.
Table 2 is a continuation of Table 1, Table 4 is a continuation of Table 3, and Table 6 is a continuation of Table 5. For example, the treatment liquid of Example 28 listed in Tables 1 and 2 contains 0.06% by mass of ascorbic acid, 0.01% by mass of dehydroascorbic acid, 0.126% by mass of TEAH, and 0.02% by mass of citric acid. % and 0.106% by mass of 1,2-diaminopropane, and has a pH of 11.0.

From the above table, it was confirmed that the treatment liquid of the present invention has excellent Cu corrosion inhibition properties (corrosion prevention properties) and is also excellent in organic residue removal properties.
From the results of Examples 1 to 6, it was confirmed that the effects of the present invention were more excellent when the content of the reducing agent was 0.02% by mass or more based on the total mass of the treatment liquid.
From the results of Examples 6 to 8, it was confirmed that the effects of the present invention were more excellent when the content of the specific compound was 0.02% by mass or more based on the total mass of the treatment liquid.
From the results of Examples 61 to 65, when the content of the specific compound is 3.0% by mass or less based on the total mass of the treatment liquid, the corrosion resistance is better, and when the content is 0.3% by mass or less, the corrosion resistance is better. It was confirmed that the effect of the treatment was even better.
From the results of Examples 61 to 65, when the mass ratio (B/A) of the specific compound content (B) to the reducing agent content (A) is 50 or less, the corrosion protection is better; It was confirmed that the corrosion resistance was even better when
From the results of Examples 61 to 65, when the mass ratio (C/B) of the content (C) of the specific quaternary ammonium compound to the content (B) of the specific compound is 0.1 or more, corrosion resistance It was confirmed that the corrosion resistance was even more excellent when the value was 0.5 or more.
From the results of Examples 9 to 20 and 45 to 56, when the reducing agent is at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives or salts thereof, and polyphenol compounds, the effects of the present invention are obtained. was confirmed to be superior.
From the results of Examples 25 to 27, it was confirmed that the effects of the present invention were more excellent when the content of the chelating agent was 0.01% by mass or more.
From the results of Examples 25 to 27, the effect of the present invention is more effective when the mass ratio (A/D) of the reducing agent content (A) to the chelating agent content (D) is 0.02 or more. It was confirmed that the effect of the present invention is even more excellent when it is 0.1 or more.
From the results of Examples 1 and 28 to 32, it was confirmed that the effects of the present invention are more excellent when the treatment liquid contains an amine compound.
From the results of Examples 39 to 40 and 42 to 43, it was confirmed that when the content of the amine compound was 5.0% by mass or less based on the total mass of the treatment liquid, the corrosion resistance was more excellent.
From the results of Examples 2 and 36 to 38, it was confirmed that the effects of the present invention are more excellent when the treatment liquid contains an anticorrosive agent.
From the results of Examples 66 to 70, it was confirmed that the effects of the present invention were more excellent when the pH of the treatment liquid was 10.5 to 13.0.
From the results of Examples 28 and 35, it was confirmed that the effects of the present invention are excellent even when the concentrations of the treatment liquids are different.

[Evaluation of W corrosion inhibition]
The treatment solutions of Examples 83 to 90 and Comparative Examples 1 and 2 prepared by the above method were used to evaluate the corrosion inhibition ability of W (tungsten).
A 2.0 cm x 2.0 cm W wafer was placed in a container filled with the treatment solution of each Example or Comparative Example, and immersion treatment was performed for 30 minutes at room temperature (25° C.). Thereafter, the film thickness of the obtained wafer was measured using a resistivity meter (VR250, manufactured by Kokusai Electric Semiconductor Services Co., Ltd.), and the etching rate (Å/min) was calculated from the difference in film thickness before and after the immersion treatment.

The corrosion inhibitory properties of the treatment solution for W were evaluated according to the following evaluation criteria: The lower the etching rate, the better the corrosion inhibitory properties.
7: Less than 1.5 Å/min 6: 1.5 Å/min or more, less than 1.8 Å/min 5: 1.8 Å/min or more, less than 2.1 Å/min 4: 2.1 Å/min or more, less than 2.4 Å/min 3: 2.4 Å/min or more, less than 2.7 Å/min 2: 2.7 Å/min or more, less than 3.0 Å/min 1: 3.0 Å/min or more

Table 7 shows the evaluation results of the corrosion inhibiting properties of W. The compositions of the treatment liquids of each Example and Comparative Example are shown in Tables 5 and 6.

As shown in Table 7, it was confirmed that the treatment liquid of the present invention is also excellent in inhibiting W corrosion.
From a comparison of Examples 83 to 90, it was confirmed that when the pH of the treatment liquid was 5.0 to 7.0, the organic residue removal property and W corrosion inhibition property were superior.

Claims (20)

A reducing agent;
and at least one specific compound selected from the group consisting of dehydroascorbic acid, 2,3-diketogulonic acid, 4-oxalocrotonic acid, and 3,4,5-trioxocyclohexane-1-carboxylic acid. The treatment solution according to claim 1, wherein the reducing agent contains at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives or salts thereof, and polyphenol compounds. The treatment solution according to claim 1, wherein the reducing agent comprises at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives or salts thereof, and gallic acid and gallic acid derivatives. The treatment liquid according to claim 1, wherein the mass ratio of the content of the specific compound to the content of the reducing agent is 0.01 to 199. The treatment liquid according to claim 1 , further comprising a quaternary ammonium compound represented by formula (B):

In formula (B), R ¹ to R ⁴ each independently represent an alkyl group which may have a substituent and which may have a linking group represented by -O-. A plurality of R ¹ to R ⁴ may be bonded to each other to form a ring. The total number of carbon atoms in the groups represented by R ¹ to R ⁴ is 5 or more.
X ⁻ represents an anion. The processing liquid according to claim 5, wherein a mass ratio of the content of the quaternary ammonium compound to the content of the specific compound is 0.01 to 100.0. The treatment liquid according to claim 1, having a pH of 8.0 to 13.0. The treatment solution according to claim 1, further comprising a chelating agent. The treatment solution according to claim 8, wherein the chelating agent comprises an organic acid. The treatment liquid according to claim 9, wherein the organic acid includes at least one selected from the group consisting of polycarboxylic acids, hydroxycarboxylic acids, and phosphonic acids. The organic acid contains at least one selected from the group consisting of citric acid, formic acid, oxalic acid, tartaric acid, lactic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and ethylenediaminetetra (methylenephosphonic acid). The processing liquid according to claim 9, comprising: The processing liquid according to claim 8, wherein a mass ratio of the content of the reducing agent to the content of the chelating agent is 0.005 to 5.0. The treatment solution according to claim 1, further comprising an amine compound. The treatment liquid according to claim 13 , wherein the amine compound comprises a compound represented by formula (C1):

In formula (C1), R ⁵ to R ⁸ each independently represent a hydrogen atom or an alkyl group which may have a substituent and which may have a linking group represented by -O-. A plurality of R ⁵ to R ⁸ may be bonded to each other to form a ring.
In formula (C1), R ⁹ represents an alkylene group having 2 or more carbon atoms which may have a substituent and which may contain a linking group represented by —O— or —NR ^N —, where R ^N represents a hydrogen atom or an alkyl group. The treatment liquid according to claim 14, wherein the group represented by R ⁹ in formula (C1) has 2 to 4 carbon atoms. The treatment liquid according to claim 1, further comprising an anticorrosive agent. The treatment solution according to claim 1, further comprising water, the water content being 60% by mass or more based on the total mass of the treatment solution. The processing liquid according to claim 1, which is used for cleaning an object containing Cu that has been subjected to a chemical mechanical polishing process. A method for treating an object, the method comprising the step of contacting an object containing Cu that has been subjected to a chemical mechanical polishing treatment with the treatment liquid according to any one of claims 1 to 18. A method for manufacturing a semiconductor device, comprising the method for cleaning an object according to claim 19.