WO2021230127A1

WO2021230127A1 - Cleaning liquid and method for cleaning semiconductor substrate

Info

Publication number: WO2021230127A1
Application number: PCT/JP2021/017353
Authority: WO
Inventors: 浩平林
Original assignee: 富士フイルムエレクトロニクスマテリアルズ株式会社
Priority date: 2020-05-12
Filing date: 2021-05-06
Publication date: 2021-11-18
Also published as: TW202142681A; JPWO2021230127A1

Abstract

The present invention provides a cleaning liquid for a semiconductor substrate that has been subjected to chemical mechanical polishing (CMP). The cleaning liquid exhibits excellent cleaning performance and excellent corrosion prevention performance against both tungsten and cobalt. The present invention also provides a method for cleaning a semiconductor substrate that has been subjected to CMP. This cleaning liquid is for a semiconductor substrate that has been subjected to chemical mechanical polishing. The cleaning liquid contains a compound represented by formula (1), an alkanolamine and water. The pH of the cleaning liquid at 25ºC is 9.0 or more.

Description

Cleaning liquid, cleaning method of semiconductor substrate

The present invention relates to a cleaning liquid for a semiconductor substrate and a method for cleaning the semiconductor substrate.

In the manufacture of semiconductor elements, chemical mechanical polishing (CMP) is used to flatten the surface of a substrate having a metal wiring film, barrier metal, insulating film, etc. using a polishing slurry containing polishing fine particles (for example, silica, alumina, etc.). Mechanical Polishing) processing may be performed. In the CMP treatment, metal components derived from the polished fine particles used in the CMP treatment, the polished wiring metal film, and / or the barrier metal and the like tend to remain on the surface of the semiconductor substrate after polishing.
Since these residues can short-circuit the wiring and affect the electrical characteristics of the semiconductor, a cleaning step of removing these residues from the surface of the semiconductor substrate is generally performed.

For example, Patent Document 1 describes a cleaning agent for the surface of a semiconductor substrate, which comprises an organic acid having at least one carboxyl group and a complexing agent.

Japanese Unexamined Patent Publication No. 10-072594

The present inventor has examined a cleaning liquid for a semiconductor substrate to which CMP has been applied with reference to Patent Document 1 and the like. When the semiconductor substrate to which CMP has been applied contains tungsten and cobalt, the cleaning performance and tungsten have been investigated. And / or at least one of the corrosion protection against cobalt was found to be inferior.
That is, it was found that there is room for further improvement in both cleaning performance and corrosion prevention performance in the cleaning liquid for a semiconductor substrate containing tungsten and cobalt to which CMP has been applied.

An object of the present invention is to provide a cleaning liquid for a semiconductor substrate to which CMP has been applied, which has excellent cleaning performance and excellent corrosion prevention performance against both tungsten and cobalt.
Another object of the present invention is to provide a method for cleaning a semiconductor substrate to which CMP has been applied.

The present inventor has found that the above problem can be solved by the following configuration.

[1]
A cleaning liquid for semiconductor substrates that has been subjected to chemical mechanical polishing treatment.
A cleaning solution containing a compound represented by the formula (1) described later, an alkanolamine, and water, and having a pH value of the cleaning solution at 25 ° C. of 9.0 or more.
[2]
The cleaning solution according to [1], wherein the ClogP value of the compound represented by the formula (1) is -3.50 to -1.45.
[3]
The Hansen solubility parameter of the compound represented by the formula (1) has a hydrogen bond term of 31.0 or less (MPa) ^0.5 , a dispersion term of 17.0 to 18.0 (MPa) ^0.5 , and between dipoles. The cleaning solution according to claim 1 or 2, wherein the item is 13.0 or less (MPa) ^0.5.
[4]
The cleaning solution according to any one of [1] to [3], wherein the value of the ratio of the number of hydroxyl groups to the number of carboxyl groups of the compound represented by the formula (1) is 2 or more.
[5]
The cleaning solution according to any one of [1] to [4], wherein the content of the compound represented by the formula (1) is 0.5% by mass or more with respect to the total mass of the cleaning solution.
[6]
The cleaning solution according to any one of [1] to [5], wherein the compound represented by the formula (1) is gluconic acid.
[7]
The cleaning solution according to any one of [1] to [6], wherein the alkanolamine is a compound represented by the formula (a-1) described later.
[8]
The alkanolamine comprises at least one selected from the group consisting of 2-amino-2-methyl-1-propanol, 2-amino-2-methylpropanediol, and trishydroxymethylaminomethane [1]. The cleaning solution according to any one of [7].
[9]
The cleaning solution according to any one of [1] to [8], wherein the value of the mass ratio of the content of the compound represented by the formula (1) to the content of alkanolamine is 0.1 to 10.
[10]
The cleaning solution according to any one of [1] to [9], wherein the cleaning solution further contains a second amine compound different from the alkanolamine.
[11]
The cleaning solution according to any one of [1] to [10], wherein the cleaning solution further contains a surfactant.
[12]
A method for cleaning a semiconductor substrate, which comprises a step of cleaning the semiconductor substrate subjected to chemical mechanical polishing treatment using the cleaning liquid according to any one of [1] to [11].

According to the present invention, it is possible to provide a cleaning liquid for a semiconductor substrate to which CMP has been applied, which has excellent cleaning performance and excellent corrosion prevention performance against tungsten and cobalt.
Further, according to the present invention, it is possible to provide a method for cleaning a semiconductor substrate to which CMP has been applied.

Hereinafter, an example of a mode for carrying out the present invention will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.

In the present specification, when a certain component is present in two or more kinds, the "content" of the component means the total content of the two or more kinds of components.
As used herein, "ppm" means "parts-per-million ( ^10-6 )" and "ppb" means "parts-per-billion ( ^10-9 )".
The compounds described herein may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes, if not particularly limited. Further, only one kind of isomer and isotope may be contained, or a plurality of kinds may be contained.

In the present specification, the LogP value is a value obtained by calculation of the common logarithm logP of 1-octanol and the partition coefficient P to water. Known methods and software can be used for calculating the ClogP value, but unless otherwise specified, the ClogP program incorporated in ChemBioDrowUltra12.0 of Cambridgebest is used in the present invention.
As used herein, psi is intended for pound-force per squaree inch; 1 psi = 6894.76 Pa, intended for pound-force per square inch.

The cleaning liquid of the present invention (hereinafter, also simply referred to as “cleaning liquid”) is a cleaning liquid for a semiconductor substrate subjected to chemical mechanical polishing (CMP) treatment, and is a compound represented by the formula (1) described later. , A cleaning solution containing alkanolamine and water, and the pH value of the cleaning solution at 25 ° C. is 9.0 or more.

The present inventor has determined that by using this cleaning liquid in the cleaning step after CMP is applied to a semiconductor substrate containing tungsten and cobalt, the cleaning performance and the corrosion prevention performance for tungsten and cobalt are improved. We found out and completed the present invention.

Although the detailed mechanism by which the effect of the present invention is obtained by such a cleaning solution is unknown, the present invention is presumed as follows.
The carboxyl group of the compound represented by the formula (1) and the functional group such as the amino group of the alkanolamine adhere to or adsorbed on the surface of the semiconductor substrate after CMP was applied to the metal particles and the like. It is considered that high cleaning performance can be obtained by causing interactions such as complex formation and improving the dispersibility of metal particles and the like. Further, by setting the pH to 9.0 or higher, corrosion of cobalt is prevented, while the compound represented by the formula (1) interacts to form a protective film on the surface of tungsten to prevent corrosion of tungsten. It is presumed that by preventing it, the corrosion prevention performance of both cobalt and tungsten is excellent.

[Cleaning liquid]
The cleaning solution of the present invention contains a compound represented by the following formula (1), alkanolamine, and water, and the pH value of the cleaning solution at 25 ° C. is 9.0 or more.
Hereinafter, each component contained in the cleaning liquid will be described.

[Compound represented by the formula (1)]
The cleaning liquid contains a compound represented by the formula (1) (hereinafter, also referred to as “compound (1)”).

In formula (1), ^Ra1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a group selected from the group consisting of a hydroxyl group and a carboxyl group.
As ^Ra1 , an alkyl group having 1 to 6 carbon atoms which may have a group selected from the group consisting of a hydroxyl group and a carboxyl group is preferable, and a group selected from the group consisting of a hydroxyl group and a carboxyl group is preferable. Alkyl groups having 1 to 3 carbon atoms which may be possessed are more preferable. Also. As ^Ra1 , an alkyl group having a hydroxyl group and having 1 to 6 carbon atoms is preferable, and an alkyl group having a hydroxyl group and having 1 to 3 carbon atoms is more preferable.
The ^{alkyl group represented by Ra1} may have a group selected from the group consisting of a hydroxyl group and a carboxyl group. The alkyl group may have both a hydroxyl group and a carboxyl group.
Further, the alkyl group may be linear or branched. The alkyl group may further have a substituent other than the hydroxyl group and the carboxyl group. Examples of the substituent include a halogen atom and an amino group.
The number of hydroxyl groups contained in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 4.
The number of carboxyl groups contained in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.
The compound (1) may be an inorganic salt or an organic salt, and preferably does not form a salt.

<Hansen solubility parameter>
The hydrogen bond term of the Hansen solubility parameter of compound (1) is that at least one of the cleaning performance and the corrosion prevention performance of the cleaning liquid is excellent (hereinafter, also simply referred to as “the effect of the present invention is more excellent”). (Hereinafter also referred to as “δh”) is 31.0 or less (MPa) ^0.5 , and the dispersion term (hereinafter also referred to as “δd”) is 17.0 to 18.0 (MPa) ^0.5 . It is preferable that the bipolar term (hereinafter, also referred to as “δp”) is 13.0 or less (MPa) ^0.5.

The Hansen solubility parameter means the Hansen solubility parameter described in "Hansen Solubility Parameter: A Users Handbook, Second Edition" (page 1-310, CRC Press, 2007) and the like. That is, the Hansen solubility parameter represents solubility as a multidimensional vector (δh, δd, and δp), and these three parameters can be considered as the coordinates of points in a three-dimensional space called Hansen space.
The Hansen solubility parameters δh, δd, and δp of compound (1) can be calculated using, for example, HsPIP (Hansen Solubility Parameters in Practice).

<LogP value>
The ClogP value of compound (1) is preferably -3.50 to -1.45, more preferably -3.20 to -2.00, in that the effect of the present invention is more excellent.

<Number of hydroxyl groups relative to the number of carboxyl groups>
The value of the ratio of the number of hydroxyl groups to the number of carboxyl groups [number of hydroxyl groups / number of carboxyl groups] of the compound (1) is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more. The upper limit is not particularly limited, but 10 or less is preferable, 8 or less is more preferable, and 6 or less is further preferable.

The number of hydroxyl groups contained in the compound (1) is not particularly limited as long as it is 2 or more, and may be 3 or more. The upper limit is not particularly limited, but 10 or less is preferable, 8 or less is more preferable, and 5 or less is further preferable. Among them, the number of hydroxyl groups is preferably 1 to 5, more preferably 2 to 5, and even more preferably 3 to 5, in that the effect of the present invention is more excellent.
The number of carboxyl groups contained in the compound (1) is not particularly limited as long as it is 1 or more, and may be 2 or more. The upper limit is not particularly limited, but 10 or less is preferable, and 5 or less is more preferable. Among them, the number of carboxyl groups is preferably one because the effect of the present invention is more excellent.

Examples of the compound (1) include gluconic acid, mucinic acid, glyceric acid, and heptonic acid. Among them, at least one selected from the group consisting of gluconic acid, mucinic acid, and glyceric acid is preferable as the compound (1), and gluconic acid or mucinic acid is more preferable, because the effect of the present invention is more excellent. , Gluconic acid is more preferred.

As the compound (1), an optical isomer may be used. Further, one type of optical isomer may be used alone, or two or more types may be used in combination. When one kind of optical isomer is mainly used, the optical purity thereof is preferably 90% or more, more preferably 95% or more.

Compound (1) may be used alone or in combination of two or more.

The content of the compound (1) in the cleaning liquid is not particularly limited, but is often 0.01% by mass or more, preferably 0.1% by mass or more, and 0.5% by mass or more with respect to the total mass of the cleaning liquid. Is more preferable, 1% by mass or more is further preferable, 3% by mass or more is particularly preferable, and 4% by mass or more is most preferable. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 5% by mass or less, based on the total mass of the cleaning liquid.

[Alkanolamine]
The cleaning solution contains an alkanolamine.
The alkanolamine means an aliphatic compound having one or more amino groups and one or more hydroxyl groups in the molecule.
The alkanolamine may have any of a primary to tertiary amino group, but preferably has a primary amino group.

Examples of the alkanolamine include a compound represented by the formula (a-1), and a compound represented by the formula (a-2) is preferable.

HO-L ^a1- NH ₂ (a-1)

In the formula (a-1), ^La1 represents an alkylene group having 1 to 14 carbon atoms which may have a heteroatom.
As the ^{alkylene group represented by La1} , an alkylene group having 1 to 10 carbon atoms which may have an oxygen atom is preferable, and an alkylene group having 1 to 6 carbon atoms which may have an oxygen atom is more preferable. Preferably, an unsubstituted alkylene group having 1 to 6 carbon atoms is more preferable.
The hydrogen atom in the alkylene group may be further substituted with a substituent. Substituents include hydroxyl groups, alkyl groups, amino groups, and combinations thereof. Of these, a hydroxyl group is preferable. Further, the alkylene group may be linear or branched.
The number of hydroxyl groups of the alkylene group represented by L ^a1 is preferably 1 to 10, more preferably 1 to 5, 1 to 3 is more preferred.
Further, the compound represented by the formula (a-1) may be an inorganic acid salt or an organic acid salt.

In formula (a-2), ^La2 represents an alkylene group having 1 to 6 carbon atoms which may have a single bond or a heteroatom. Among them, a single bond is preferable as ^La2.
As the ^{alkylene group represented by La2} , an alkylene group having 1 to 6 carbon atoms having an oxygen atom is preferable, an alkylene group having 1 to 6 carbon atoms having a hydroxyl group is more preferable, and an unsubstituted alkylene group having 1 to 6 carbon atoms is preferable. The alkylene group of is more preferred. The hydrogen atom in the alkylene group may be further substituted with a substituent. Substituents include alkyl groups, hydroxyl groups, amino groups, and combinations thereof. Further, the alkylene group may be linear or branched.

R ^a2 to R ^a5 each independently represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may have a substituent. Among them, a hydrogen atom is preferable as ^Ra2 and ^{Ra3 in} that the effect of the present invention is more excellent. Further, as R ^a4 and R ^a5 , a methyl group is preferable.
The ^{alkyl group represented by R a2} to R ^a5 may have a substituent or may be unsubstituted. Substituents include, for example, hydroxyl groups, amino groups, and halogen atoms. Of these, a hydroxyl group is preferable.
As the ^{alkyl group represented by R a2} to R ^a5 , a methyl group or an ethyl group which may have a hydroxyl group is preferable, and an unsubstituted methyl group or an ethyl group is more preferable.
Further, the compound represented by the formula (a-2) may be an inorganic acid salt or an organic acid salt.

Examples of the alkanolamine include 2-amino-2-methyl-1-propanol (AMP), trishydroxymethylaminomethane (Tris), 2-amino-2-methylpropanediol (AMPD), and monoethanolamine (AMPD). MEA), Diethanolamine (DEA), Triethanolamine (TEA), Diethylene Glycolamine (DEGA), 2- (Methylamino) -2-Methyl-1-propanol (N-MAMP), 2- (Aminoethoxy) Ethanol (AEE) ), 2- (2-Aminoethylamino) ethanol (AAE), and 2- (2-aminoethoxy) ethanol.
Among them, at least one selected from the group consisting of AMP, Tris, and AMPD is preferable, at least one selected from the group consisting of AMP and Tris is more preferable, and AMP is further preferable. Further, MEA, DEA, AEE, or AAE is preferable in terms of excellent cleaning performance (particularly cleaning performance for a metal film containing W).

One type of alkanolamine may be used alone, or two or more types may be used in combination.
The content of alkanolamine in the cleaning liquid is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the cleaning liquid. The lower limit is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and 0.5% by mass or more with respect to the total mass of the cleaning liquid. Is particularly preferable, and 3% by mass or more is most preferable.

The value of the mass ratio of the content of the compound (1) to the content of the alkanolamine [content of the compound (1) / content of the alkanolamine] is preferably 0.01 to 20, more preferably 0.1 to 10. It is preferable, 0.3 to 5 is more preferable, 0.4 to 3 is particularly preferable, and 0.4 to 1.5 is most preferable.

〔water〕
The cleaning liquid contains water as a solvent.
The type of water used for the cleaning liquid is not particularly limited as long as it does not adversely affect the semiconductor substrate, and distilled water, deionized 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 in the manufacturing process of the semiconductor substrate.
The water content in the cleaning solution may be the balance of compound (1), alkanolamine, and any component described later. The content of water is not particularly limited, but is preferably 1% by mass or more, more preferably 30% by mass or more, further preferably 60% by mass or more, and particularly preferably 85% by mass or more, based on the total mass of the cleaning liquid. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 98% by mass or less, based on the total mass of the cleaning liquid.

[PH value]
The pH value of the cleaning solution of the present invention is 9.0 or more at 25 ° C.
The pH value of the cleaning liquid is preferably 10.0 or more, more preferably 11.0 or more at 25 ° C. in that the effect of the present invention is more excellent. Further, the pH value of the cleaning liquid is preferably 13.0 or less, more preferably 12.0 or less, and more preferably 12.0 or less at 25 ° C. in that it is excellent in corrosion prevention performance (particularly, corrosion prevention performance for semiconductor substrates containing W or Cu). It is more preferably 5.5 or less.
The pH value of the cleaning solution is determined by the pH adjusting agent described later, and the pH adjusting function of compound (1), alkanolamine, secondary amine compound, quaternary ammonium compound, anticorrosion agent, organic acid, anionic surfactant and the like. It can be adjusted by using a component having.
The pH value of the cleaning solution can be measured by a method based on JIS Z8802-1984 using a known pH meter.

[Arbitrary component]
The cleaning liquid may contain other optional components in addition to the above-mentioned components. As optional components, for example, a secondary amine compound, a surfactant, a pH adjuster, an anticorrosion agent, an organic acid, a reducing agent, and a chelating agent whose coordinating group is a nitrogen-containing group (hereinafter, also referred to as “specific chelating agent”). ), And various additives.

The cleaning liquid preferably contains at least one selected from the group consisting of a second amine compound, a surfactant, a pH adjuster, an anticorrosive agent, an organic acid, and a polymer.
As the optional component, one kind may be used alone, or two or more kinds may be used in combination.

The optional components will be described below.

<Second amine compound>
The cleaning liquid may contain a second amine compound.
The second amine compound is an amine compound different from the above-mentioned alkanolamine. Examples of the second amine compound include an alicyclic amine compound, an aliphatic monoamine compound, an aliphatic polyamine compound, and an amine compound containing at least one selected from the group consisting of amino acids.
Among them, at least one selected from the group consisting of an alicyclic amine compound and an amino acid is preferable because the effect of the present invention is more excellent.

(Alicyclic amine compound)
The alicyclic amine compound is not particularly limited as long as it is a compound having a non-aromatic heterocycle in which at least one of the atoms constituting the ring is a nitrogen atom.
Examples of the alicyclic amine compound include a piperazine compound and a cyclic amidine compound.

-Piperazine compound-
The piperazine compound is a compound having a hetero 6-membered ring (piperazine ring) in which the opposite -CH- group of the cyclohexane ring is replaced with a nitrogen atom.
The piperazine compound may have a substituent on the piperazine ring. Examples of such a substituent include a hydroxyl group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and an aryl group having 6 to 10 carbon atoms.

Examples of the piperazine compound include piperazine, 1-methylpiperazine (NMPZ), 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 2-methylpiperazine, 1,4-dimethylpiperazine and 2,5-dimethylpiperazine. , 2,6-dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2-hydroxymethylpiperazine, 1- (2-hydroxyethyl) piperazine (HEP), N- (2-aminoethyl) piperazine (AEP), 1,4-Bis (2-hydroxyethyl) piperazine (BHEP), 1,4-bis (2-aminoethyl) piperazine (BAEP), and 1,4-bis (3-aminopropyl) piperazine (BAPP). Piperazine, NMPZ, HEP, AEP, BHEP, BAEP, or BAPP is preferable, and piperazine or NMPZ is more preferable.

In addition to the above, the alicyclic amine compound includes, for example, 1,3-dimethyl-2-imidazolidinone, a compound having a hetero5-membered ring having no aromaticity such as imidazolidinethione, and a nitrogen atom. Examples include compounds having a 7-membered ring.

-Cyclic amidine compound-
The cyclic amidine compound is a compound having a heterocycle containing an amidine structure (> NC = N—) in the ring.
The number of ring members of the above heterocycle contained in the cyclic amidine compound is not particularly limited, but is preferably 5 or 6, and more preferably 6.

Examples of the cyclic amidine compound include diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-en: DBU) and diazabicyclononene (1,5-diazabicyclo [4.3. 0] Nona-5-en: DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimid [1.2-a] azocin, 3,4,6,7,8 , 9-Hexahydro-2H-pyrido [1.2-a] pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo [1.2-a] imidazole, 3-ethyl-2,3,4,6 , 7,8,9,10-octahydropyrimid [1.2-a] azepine, and creatinine, with DBU being preferred.

The cyclic amidine compound may be used alone or in combination of two or more.

(Aliphatic monoamine compound)
Examples of the aliphatic monoamine compound other than the alkanolamine and the alicyclic amine compound include a compound represented by the following formula (a) (hereinafter, also referred to as “compound (a)”).

NH _x R _(3-x) (a)

In the formula, R represents an alkyl group having 1 to 3 carbon atoms, and x represents an integer of 0 to 2.
Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group and an isopropyl group, and an ethyl group or an n-propyl group is preferable.

Examples of the compound (a) include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine, and ethylamine, propylamine, diethylamine, and triethylamine are preferable.

Examples of the aliphatic monoamine compound other than the compound (a) include n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, morpholin, and the like. 4- (2-Aminoethyl) morpholine (AEM) can be mentioned.

(Aliphatic polyamine compound)
Examples of the aliphatic polyamine compound include alkylenediamines such as ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, and 1,4-butanediamine. Further, polyalkylpolyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), bis (aminopropyl) ethylenediamine (BAPEDA), and tetraethylenepentamine are mentioned, and EDA is preferable.

(amino acid)
Amino acids are compounds that have one carboxyl group and one or more amino groups in the molecule.

Examples of amino acids include arginine, glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), lysine, leucine, isoleucine, cysteine, methionine, ethionine, threonine, tryptophan, and the like. Examples thereof include tyrosine, valine, histidine, histidine derivative, asparagine, glutamine, proline, phenylalanine, the compounds described in paragraphs [0021] to [0023] of JP-A-2016-086094, and salts thereof. As the histidine derivative, the compounds described in JP-A-2015-165561, JP-A-2015-165562 and the like can be incorporated, and the contents thereof are incorporated in the present specification. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, carbonate, and acetate. Of these, arginine or a sulfur-containing amino acid containing a sulfur atom is preferable. Examples of the sulfur-containing amino acid include cystine, cysteine, ethionine and methionine, and cystine or cysteine is preferable.

The second amine compound may be used alone or in combination of two or more.
The content of the second amine compound in the cleaning liquid is not particularly limited, but is preferably 0.03 to 30% by mass, more preferably 0.05 to 15% by mass, and 0.05 to 5% by mass with respect to the total mass of the cleaning liquid. The mass% is more preferable, and 0.05 to 3% by mass is particularly preferable.

<Surfactant>
The cleaning liquid may contain a surfactant.
The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in the molecule, and for example, an anionic surfactant, a cationic surfactant, and a nonionic surfactant. , And amphoteric surfactants.

Surfactants often have an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a hydrophobic group selected from combinations thereof. The hydrophobic group of the surfactant is not particularly limited. Among them, when the hydrophobic group contains an aromatic hydrocarbon group, the aromatic hydrocarbon group preferably has 6 or more carbon atoms, and more preferably 10 or more carbon atoms of the aromatic hydrocarbon group. The upper limit of the number of carbon atoms of the aromatic hydrocarbon group is not particularly limited, but is preferably 20 or less, and more preferably 18 or less.
When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, the aliphatic hydrocarbon group preferably has 10 or more carbon atoms, and the aliphatic hydrocarbon group has 12 carbon atoms. The above is more preferable, and the carbon number of the aliphatic hydrocarbon group is further preferably 16 or more. The upper limit of the number of carbon atoms of the aliphatic hydrocarbon group is not particularly limited, but is preferably 20 or less, and more preferably 18 or less.

(Anionic surfactant)
Examples of the anionic surfactant contained in the cleaning liquid include, as a hydrophilic group (acid group), a phosphate ester-based surfactant having a phosphate ester group, a phosphonic acid-based surfactant having a phosphonic acid group, and the like. Examples thereof include a sulfonic acid-based surfactant having a sulfo group, a carboxylic acid-based surfactant having a carboxyl group, and a sulfate ester-based surfactant having a sulfate ester group.
It is preferable that the cleaning liquid contains an anionic surfactant because the effect of the present invention is more excellent.

-Phosphoric acid ester-based surfactant-
Examples of the phosphoric acid ester-based surfactant include a phosphoric acid ester (alkyl ether phosphoric acid ester), a polyoxyalkylene ether phosphoric acid ester, and salts thereof. Phosphoric acid ester and polyoxyalkylene ether phosphoric acid usually contain both monoester and diester, but monoester or diester can be used alone.
Examples of the salt of the phosphoric acid ester-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt.
The alkyl group contained in the phosphoric acid ester and the polyoxyalkylene ether phosphoric acid ester is not particularly limited, but an alkyl group having 2 to 24 carbon atoms is preferable, an alkyl group having 6 to 18 carbon atoms is more preferable, and an alkyl group having 12 to 12 carbon atoms is more preferable. Eighteen alkyl groups are even more preferred.
The alkylene group contained in the polyoxyalkylene ether phosphoric acid ester is not particularly limited, but an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a 1,2-propanediyl group is more preferable. The number of repetitions of the oxyalkylene group in the polyoxyalkylene ether phosphoric acid ester is preferably 1 to 12, more preferably 3 to 10.

Examples of the phosphoric acid ester-based surfactant include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene. Lauryl ether phosphate ester or polyoxyethylene tridecyl ether phosphate ester is preferred.

As the phosphoric acid ester-based surfactant, the compounds described in paragraphs [0012] to [0019] of JP2011-040502A can also be incorporated, and these contents are incorporated in the present specification.

-Phosphonate-based surfactant-
Examples of the phosphonic acid-based surfactant include alkylphosphonic acid and polyvinylphosphonic acid. Further, for example, aminomethylphosphonic acid and the like described in Japanese Patent Application Laid-Open No. 2012-057108 and the like can also be mentioned.

-Sulfonic acid-based surfactant-
Examples of the sulfonic acid-based surfactant include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof. Can be mentioned.

The alkyl group contained in the above-mentioned sulfonic acid-based surfactant is not particularly limited, but an alkyl group having 10 or more carbon atoms is preferable, and an alkyl group having 12 or more carbon atoms is more preferable. The upper limit of the number of carbon atoms of the alkyl group is not particularly limited, but is preferably 24 or less.
The alkylene group contained in the polyoxyalkylene alkyl ether sulfonic acid is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable. The number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfonic acid is preferably 1 to 12, more preferably 1 to 6.

Specific examples of the sulfonic acid-based surfactant include hexanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid (DBSA), and di. Examples thereof include nitrobenzene sulfonic acid (DNBSA) and laurildodecylphenyl ether disulfonic acid (LDPEDSA).
Among them, a sulfonic acid-based surfactant having an alkyl group having 10 or more carbon atoms is preferable, a sulfonic acid-based surfactant having an alkyl group having 12 or more carbon atoms is more preferable, and DBSA is further preferable.

-Carboxylic acid-based surfactant-
Examples of the carboxylic acid-based surfactant include alkylcarboxylic acids, alkylbenzenecarboxylic acids, polyoxyalkylene alkyl ether carboxylic acids, and salts thereof.
The alkyl group contained in the above-mentioned carboxylic acid-based surfactant is not particularly limited, but an alkyl group having 7 to 25 carbon atoms is preferable, and an alkyl group having 11 to 17 carbon atoms is more preferable.
The alkylene group contained in the polyoxyalkylene alkyl ether carboxylic acid is not particularly limited, but an ethylene group or a 1,2-propanediyl group is preferable. The number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether carboxylic acid is preferably 1 to 12, more preferably 1 to 6.

Specific examples of the carboxylic acid-based surfactant include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.

-Sulfuric acid ester-based surfactant-
Examples of the sulfate ester-based surfactant include a sulfate ester (alkyl ether sulfate ester), a polyoxyalkylene ether sulfate ester, and salts thereof.
The alkyl group contained in the sulfate ester and the polyoxyalkylene ether sulfate ester is not particularly limited, but an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
The alkylene group contained in the polyoxyalkylene ether sulfate ester is not particularly limited, but an ethylene group or a 1,2-propanediyl group is more preferable. The number of repetitions of the oxyalkylene group in the polyoxyalkylene ether sulfate ester is preferably 1 to 12, more preferably 1 to 6.
Specific examples of the sulfate ester-based surfactant include lauryl sulfate, myristyl sulfuric acid, and polyoxyethylene lauryl ether sulfate.

Examples of the anionic surfactant include a phosphate ester-based surfactant, a sulfonic acid-based surfactant (more preferably, a sulfonic acid-based surfactant having an alkyl group having 12 or more carbon atoms), a phosphonic acid-based surfactant, and the like. And at least one selected from the group consisting of carboxylic acid-based surfactants are preferable, and phosphoric acid ester-based surfactants or sulfonic acid-based surfactants having an alkyl group having 12 or more carbon atoms are more preferable.

The anionic surfactant may be used alone or in combination of two or more. The cleaning liquid preferably contains two or more kinds of anionic surfactants in that it is excellent in corrosion prevention performance (particularly, corrosion prevention performance for semiconductor substrates containing Cu and / or Co).

When the cleaning liquid contains an anionic surfactant, the content thereof is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total mass of the cleaning liquid.
As these anionic surfactants, commercially available ones may be used.

(Cationic surfactant)
Examples of the cationic surfactant include primary to tertiary alkylamine salts (eg, monostearylammonium chloride, distearylammonium chloride, tristearylammonium chloride, etc.), and modified aliphatic polyamines (eg, for example. (Polyethylene polyamine, etc.) can be mentioned.

(Nonionic surfactant)
Examples of the nonionic surfactant include polyoxyalkylene alkyl ether (for example, polyoxyethylene stearyl ether and the like), polyoxyalkylene alkenyl ether (for example, polyoxyethylene oleyl ether and the like), and polyoxyethylene alkyl phenyl ether (for example). , Polyoxyethylene nonylphenyl ether, etc.), Polyoxyalkylene glycol (eg, polyoxypropylene polyoxyethylene glycol, etc.), Polyoxyalkylene monoalkhet (monoalkyl fatty acid ester polyoxyalkylene) (eg, polyoxyethylene monosteer) Rates, and polyoxyethylene monoalchelates such as polyoxyethylene monoolates), polyoxyalkylene dialchelates (dialkyl fatty acid ester polyoxyalkylenes) (eg, polyoxyethylene distearates, and polys such as polyoxyethylene diolates). Oxyethylene dial chelate), bispolyoxyalkylene alkylamide (eg, bispolyoxyethylene stearylamide, etc.), sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block Examples thereof include copolymers, acetylene glycol-based surfactants, and acetylene-based polyoxyethylene oxides.

(Amphoteric surfactant)
Examples of the amphoteric tenside include carboxybetaine (eg, alkyl-N, N-dimethylaminoacetic acid betaine and alkyl-N, N-dihydroxyethylaminoacetic acid betaine, etc.) and sulfobetaine (eg, alkyl-N, N-). Dimethylsulfoethyleneammonium betaine and the like), and imidazolinium betaine (eg, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine and the like).

Examples of the surfactant include paragraphs [0092] to [0090] of JP-A-2015-158662, paragraphs [0045]-[0046] of JP-A-2012-151273, and paragraphs of JP-A-2009-147389. The compounds described in [0014] to [0020] can also be incorporated, and the contents thereof are incorporated in the present specification.

As the surfactant, one type may be used alone, or two or more types may be used in combination. When the cleaning liquid contains a surfactant, the content thereof is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total mass of the cleaning liquid.

<pH adjuster>
The cleaning solution may contain a pH adjuster.
Examples of the pH adjuster include components other than those described above, and examples thereof include quaternary ammonium compounds.

(Quaternary ammonium compound)
The quaternary ammonium compound is not particularly limited as long as it is a compound having a quaternary ammonium cation in which a nitrogen atom is substituted with four hydrocarbon groups (preferably an alkyl group) or a salt thereof. Examples of the quaternary ammonium compound include a quaternary ammonium hydroxide, a quaternary ammonium fluoride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium acetate, and a quaternary ammonium compound. Examples include ammonium carbonate.

As the quaternary ammonium compound, a quaternary ammonium hydroxide represented by the following formula (4) is preferable.

^{_{^{^{(R 8) 4 N + OH}}}} - (4)

In the formula, R ⁸ represents an alkyl group which may have a hydroxyl group or a phenyl group. The four R ⁸ may being the same or different.

As the ^{alkyl group represented by R 8} , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is preferable.
As the alkyl group which may have a hydroxyl group or a phenyl group represented by R ^8, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, or a benzyl group preferably a methyl group, An ethyl group, a propyl group, a butyl group, or a 2-hydroxyethyl group is more preferable, and a methyl group, an ethyl group, or a 2-hydroxyethyl group is further preferable.

Examples of the quaternary ammonium compound include 2-hydroxyethyltrimethylammonium hydroxide (choline), tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), diethyldimethylammonium hydroxide (DEDH), and methyl. Triethylammonium Hydroxide (MTEAH), Tetraethylammonium Hydroxide (TEAH), Tetrapropylammonium Hydroxide (TPAH), Tetrabutylammonium Hydroxide (TBAH), Bis (2-Hydroxyethyl) Dimethylammonium Hydroxide, Tri (2-) Examples thereof include hydroxyethyl) methylammonium hydroxide, tetra (2-hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and cetyltrimethylammonium hydroxide.
As the quaternary ammonium compound other than the above specific examples, for example, the compound described in paragraph [0021] of JP-A-2018-107353 can be incorporated, and the content thereof is incorporated in the present specification.

As the quaternary ammonium compound used in the washing liquid, choline, TMAH, TMEAH, DEDMAH, MTEAH, TEAH, TPAH, TBAH, or bis (2-hydroxyethyl) dimethylammonium hydroxide is preferable, and choline is more preferable.

Further, from the viewpoint of excellent corrosion prevention performance, the cleaning liquid preferably contains a quaternary ammonium compound having an asymmetric structure. When a quaternary ammonium compound "has an asymmetric structure", it means that none of the four hydrocarbon groups substituted with nitrogen atoms are the same. In other words, at least one of the four hydrocarbon groups that replace the nitrogen atom is a different type of hydrocarbon group.
Examples of the quaternary ammonium compound having an asymmetric structure include choline, TMEAH, DEDMAH, MTEAH, and bis (2-hydroxyethyl) dimethylammonium hydroxide, and choline is preferable.

The quaternary ammonium compound may be used alone or in combination of two or more.

When the cleaning liquid contains a pH adjuster, the content thereof is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 0. 2% by mass or more is more preferable. The upper limit of the content of the pH adjuster is not particularly limited, but is preferably 10% by mass or less, preferably 5% by mass, in terms of suppressing deterioration of cleaning performance due to aggregation of residue particles and / or readsorption of the residue in the cleaning step. % Or less is more preferable, and 3% by mass or less is further preferable.

The mass ratio of the alkanolamine content to the pH adjuster content in the cleaning solution [alkanolamine content / pH adjuster content] is preferably 0.01 to 20, more preferably 0.05 to 15. It is preferable, 0.1 to 10 is more preferable.

<Corrosion inhibitor>
The cleaning liquid may contain an anticorrosive agent.
The cleaning liquid may contain an anticorrosive agent. As the anticorrosive agent, a component different from the above-mentioned component is preferable.
Examples of the anticorrosive agent include heterocyclic compounds having a heterocyclic structure and other anticorrosive agents.

(Nitrogen-containing heteroaromatic compound)
The nitrogen-containing heteroaromatic compound is not particularly limited as long as it is a compound having a heteroaromatic ring (nitrogen-containing heteroaromatic ring) in which at least one of the atoms constituting the ring is a nitrogen atom. The nitrogen-containing heteroaromatic compound functions as an anticorrosive agent for improving the corrosion prevention performance of the cleaning liquid. Therefore, it is preferable that the cleaning liquid contains a nitrogen-containing heteroaromatic compound.
Examples of the nitrogen-containing heteroaromatic compound include an azole compound, a pyridine compound, a pyrazine compound, and a pyrimidine compound.

The azole compound is a compound having at least one nitrogen atom and having an aromatic 5-membered ring. The number of nitrogen atoms contained in the hetero 5-membered ring of the azole compound is not particularly limited, and is preferably 2 to 4, more preferably 3 or 4.
Further, the azole compound may have a substituent on the hetero 5-membered ring. Examples of such a substituent include a hydroxyl group, a carboxyl group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group.
Examples of the azole compound include a triazole compound, an imidazole compound, a pyrazole compound, a thiazole compound, and a tetrazole compound.

Examples of the triazole compound include 1,2,4-triazole, 1-bis (2-hydroxyethyl) aminomethyl-5-methyl-1H benzotriazole, and 1-bis (2-hydroxyethyl) aminomethyl-4. -Methyl-1H-benzotriazole, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole, 1,2,3-triazole, 1-methyl-1, 2,3-Triazol, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, and 5-methyl Examples include benzotriazole. Among them, 1,2,4-triazol, 1-bis (2-hydroxyethyl) aminomethyl-5-methyl-1H benzotriazole, and 1-bis (2-hydroxyethyl) aminomethyl-4-methyl- At least one selected from the group consisting of 1H-benzotriazole is preferred.

Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole and 4-hydroxy. Examples include imidazole, 2,2'-biimidazole, 4-imidazole carboxylic acid, histamine, benzoimidazole, 2-aminobenzoimidazole, and adenine.

Examples of the pyrazole compound include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-amino-5-methylpyrazole, 3-aminopyrazole, and 4 -Aminopyrazole can be mentioned.

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

Examples of the tetrazole compound include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole and 5-amino-1,2,3. Examples thereof include 4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1- (2-dimethylaminoethyl) -5-mercaptotetrazole.

As the azole compound, an imidazole compound or a pyrazole compound is preferable, 1,2,4-triazole, 1-bis (2-hydroxyethyl) aminomethyl-5-methyl-1Hbenzotriazole, and 1-bis (2). -Hydroxyethyl) At least one selected from the group consisting of aminomethyl-4-methyl-1H-benzotriazole is preferable.

The pyridine compound is a compound having a hetero 6-membered ring (pyridine ring) containing one nitrogen atom and having aromaticity.
Examples of the pyridine compound include pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 2-cyanopyridine, 2-carboxypyridine, and 4-carboxypyridine. Can be mentioned.

The pyrazine compound has aromaticity and has a hetero 6-membered ring (pyrazine ring) containing two nitrogen atoms located at the para position, and the pyrimidine compound has aromaticity and is at the meta position. It is a compound having a hetero 6-membered ring (pyrimidine ring) containing two located nitrogen atoms.
Examples of the pyrazine compound include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine and 2-ethyl-3-methylpyrazine. , And 2-amino-5-methylpyrazine.
Examples of the pyrimidine compound include pyrimidine, 2-methylpyrimidine, 2-aminopyrimidine, and 4,6-dimethylpyrimidine, and 2-aminopyrimidine is preferable.

As the nitrogen-containing heteroaromatic compound, an azole compound or a pyrazine compound is preferable, an azole compound is more preferable, and a triazole compound is further preferable.

The nitrogen-containing heteroaromatic compound may be used alone or in combination of two or more.
When the cleaning liquid contains a nitrogen-containing heteroaromatic compound, the content of the nitrogen-containing heteroaromatic compound in the cleaning liquid is not particularly limited, but is preferably 0.01 to 10% by mass with respect to the total mass of the cleaning liquid. More preferably, 0.05 to 5% by mass.

(Other anticorrosive agents)
Examples of other anticorrosive agents include saccharides such as fructose, glucose and ribose, polyols such as ethylene glycol, propylene glycol and glycerin, polyacrylic acid, polymaleic acid, and polycarboxylic acids such as copolymers thereof. Polyvinylpyrrolidone, cyanuric acid, barbituric acid and its derivatives, glucuronic acid, squalic acid, α-ketoic acid, adenosine and its derivatives, purine compounds and their derivatives, phenanthroline, resorcinol, hydroquinone, nicotine amide and its derivatives, flavonol And derivatives thereof, anthocyanins and derivatives thereof, and combinations thereof.

<Organic acid>
The cleaning liquid may contain an organic acid.
The organic acid is an organic compound having an acidic functional group and showing acidity (pH is less than 7.0) in an aqueous solution. Examples of the acidic functional group include a carboxyl group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a mercapto group.
In this specification, the above-mentioned compound (1), amino acids, and compounds that function as anionic surfactants are not included in the organic acid.

The organic acid is not particularly limited, but is a carboxylic acid having a carboxyl group in the molecule (carboxylic acid), a phosphonic acid having a phosphonic acid group in the molecule (phosphonic acid), and a sulfonic acid having a sulfo group in the molecule (the sulfonic acid). Sulfuric acid), preferably carboxylic acid or phosphonic acid.

The number of acidic functional groups contained in the organic acid is not particularly limited, but 1 to 4 is preferable, and 1 to 3 is more preferable.
Further, the organic acid is preferably a compound having a function of chelating with the metal contained in the residue in that it is excellent in cleaning performance, and is a functional group (coordinating group) that coordinates with a metal ion in the molecule. A compound having two or more of the above is more preferable. Examples of the coordinating group include the above acidic functional groups, and a carboxylic acid group or a phosphonic acid group is preferable.

(carboxylic acid)
The carboxylic acid may be a monocarboxylic acid having one carboxyl group or a polycarboxylic acid having two or more carboxyl groups. A polycarboxylic acid having 2 or more (more preferably 2 to 4, more preferably 2 or 3) carboxyl groups is preferable because it is more excellent in cleaning performance.

Examples of the carboxylic acid include aminopolycarboxylic acid, hydroxycarboxylic acid, and aliphatic carboxylic acid.

-Aminopolycarboxylic acid-
Aminopolycarboxylic acid is a compound having one or more amino groups and two or more carboxyl groups as coordinating groups in the molecule.
Examples of the aminopolycarboxylic acid include asparagic acid, glutamic acid, butylenediamine tetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N', N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (CyDTA), ethylenediaminediaminetetraacetic acid, ethylenediaminediaminedipropionic acid, 1,6- Hexylenediamine-diamine-N, N, N', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetate, diaminopropanetetraacetic acid, 1,4,7,10 -Tetraazacyclododecane-tetraacetic acid, diaminopropanol tetraacetic acid, (hydroxyethyl) ethylenediaminetriacetic acid, and iminodiacetic acid (IDA) can be mentioned.
Of these, DTPA, EDTA, CyDTA or IDA are preferable.

-Hydroxycarboxylic acid-
A hydroxycarboxylic acid is a compound having one or more hydroxyl groups and one or more carboxyl groups in the molecule.
The cleaning liquid preferably contains a hydroxycarboxylic acid in that the cleaning performance can be further improved while maintaining the corrosion prevention performance of the cleaning liquid.
Examples of the hydroxycarboxylic acid include malic acid, citric acid, glycolic acid, tartaric acid and lactic acid, preferably glycolic acid, malic acid, tartaric acid or citric acid, and more preferably citric acid.

-Alphatic carboxylic acid-
Examples of the aliphatic carboxylic acid include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, and maleic acid, and succinic acid or adipic acid is preferable. In particular, the use of adipic acid can significantly improve the performance of the cleaning liquid (cleaning performance and corrosion resistance) as compared with other chelating agents. Although the detailed mechanism of such a specific effect of adipic acid is unknown, the number of carbon chains of the alkylene group is particularly excellent in the relationship with the two carboxyl groups, and it is particularly excellent in hydrophilicity and hydrophobicity, and during complex formation with a metal. It is expected to be derived from the formation of a stable ring structure.

Examples of the carboxylic acid other than the above aminopolycarboxylic acid, amino acid, hydroxycarboxylic acid, and aliphatic carboxylic acid include monocarboxylic acid.
Examples of the monocarboxylic acid include lower (1 to 4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid.

As the carboxylic acid, hydroxycarboxylic acid or aliphatic carboxylic acid is preferable, and cystine, cysteine, gluconic acid, glycolic acid, malic acid, tartrate acid, citric acid, succinic acid, or adipic acid is more preferable, and cysteine, gluconic acid, Citrate, succinic acid, or adipic acid is more preferred.

The carboxylic acid may be used alone or in combination of two or more.
The content of the carboxylic acid in the cleaning liquid is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the cleaning liquid. The lower limit is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the cleaning liquid.

(Phosphonate)
The phosphonic acid may be a monophosphonic acid having one phosphonic acid or a polyphosphonic acid having two or more phosphonic acid groups. Polyphosphonic acid having two or more phosphonic acid groups is preferable because it is superior in cleaning performance.

Examples of the polyphosphonic acid include a compound represented by the formula (P1), a compound represented by the formula (P2), and a compound represented by the formula (P3).

In the formula, X represents a hydrogen atom or a hydroxyl group, and R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

The alkyl group having 1 to 10 carbon atoms represented by ^{R 11} in the formula (P1) may be linear, branched or cyclic.
^{As R 11} in the formula (P1), an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable.
In the specific examples of the alkyl group described in the present specification, n- represents a normal-form.
As X in the formula (P1), a hydroxyl group is preferable.

Examples of the polyphosphonic acid represented by the formula (P1) include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropyridene-1,1'-diphosphonic acid, or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.

In the formula, Q represents a hydrogen atom or R ^13- PO ₃ H ₂ , R ¹² and R ¹³ each independently represent an alkylene group, and Y represents a hydrogen atom, -R ^13- PO ₃ H _2. , Or a group represented by the following formula (P4).

In the formula, Q and R ¹³ are the same as ^{Q and R 13} in the formula (P2).

^{Examples of the alkylene group represented by R 12} in the formula (P2) include a linear or branched alkylene group having 1 to 12 carbon atoms.
As the ^{alkylene group represented by R 12} , a linear or branched alkylene group having 1 to 6 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 4 carbon atoms is more preferable. Ethylene groups are more preferred.
The alkylene group represented by R ¹³ in formula (P2) and (P4), for example, linear or branched alkylene group having 1 to 10 carbon atoms, having 1 to 4 linear or carbon A branched alkylene group is preferable, a methylene group or an ethylene group is more preferable, and a methylene group is further preferable.
As Q in the formulas (P2) and (P4), -R ^13- PO ₃ H ₂ is preferable.
As Y in the formula (P2) ^{, a group represented by -R 13-} PO ₃ H ₂ or the formula (P4) is preferable, and a group represented by the formula (P4) is more preferable.

Examples of the compound represented by the formula (P2) include ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), and ethylenediaminebis (methylenephosphonic acid) (EDDPO). ), 1,3-propylene diaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP), 1,2-Diaminopropanetetra (methylenephosphonic acid) or 1,6-hexamethylenediaminetetra (methylenephosphonic acid) is preferable.

^{Wherein, R 14} and ^{R 15} each independently represents an alkylene group having 1 to 4 carbon atoms, n represents an integer of ^1-4, Z 1 ~ ^{Z 4} and at least 4 of the n ^{Z 5} One represents an alkyl group having a phosphonic acid group, and the rest represents an alkyl group.

The alkylene group having 1 to 4 carbon atoms represented by ^{R 14} and R ¹⁵ in the formula (P3) may be either linear or branched. Examples of the alkylene group having 1 to 4 carbon atoms represented by R ¹⁴ and R ¹⁵ include a methylene group, an ethylene group, a propylene group, a trimethylene group, an ethylmethylene group, a tetramethylene group, a 2-methylpropylene group and 2-. Examples thereof include a methyltrimethylene group and an ethylethylene group, and an ethylene group is preferable.
As n in the formula (P3), 1 or 2 is preferable.

^{Examples of the alkyl group in the alkyl group represented by Z 1} to Z ⁵ in the formula (P3) and the alkyl group having a phosphonic acid group include a linear or branched alkyl group having 1 to 4 carbon atoms. The methyl group is preferred.
The number of phosphonic acid groups in the alkyl group having a phosphonic acid group represented by Z ¹ to Z ^{5 is preferably one or two, and more preferably one.}
The ^{alkyl group having a phosphonic acid group represented by Z 1} to Z ⁵ is, for example, a linear or branched alkyl group having 1 to 4 carbon atoms and having one or two phosphonic acid groups. , (Mono) phosphonomethyl group or (mono) phosphonoethyl group is preferable, and (mono) phosphonomethyl group is more preferable.
^{As Z 1} to Z ⁵ in the formula (P3), it is preferable that all of Z ¹ to Z ⁴ and n Z ⁵ are the above-mentioned alkyl groups having a phosphonic acid group.

Examples of the compound represented by the formula (P3) include diethylenetriaminepenta (methylenephosphonic acid) (DEPPO), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), and triethylenetetraminehexa (ethylenephosphonic acid). ) Is preferable.

The polyphosphonic acid used in the washing liquid includes not only the compound represented by the above formula (P1), the compound represented by the formula (P2), and the compound represented by the formula (P3), but also International Publication No. 2018 /. The compounds described in paragraphs [0026] to [0036] of the specification of 020878 and the compounds ((co) polymers) described in paragraphs [0031] to [0046] of International Publication No. 2018/030006 can be incorporated. , These contents are incorporated herein.

The number of phosphonic acid groups contained in the phosphonic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 or 3.
The carbon number of the phosphonic acid is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. The lower limit is not particularly limited, and 1 or more is preferable.
As the phosphonic acid, the compounds listed as suitable specific examples in each of the above-mentioned compound represented by the formula (P1), the compound represented by the formula (P2), and the compound represented by the formula (P3) are preferable. , HEDP is more preferred.

One type of phosphonic acid may be used alone, or two or more types may be used in combination.
The content of phosphonic acid in the washing liquid is not particularly limited, but is preferably 2% by mass or less, more preferably 1% by mass or less, based on the total mass of the washing liquid. The lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the cleaning liquid.

As the organic acid, a carboxylic acid is preferable, an aliphatic carboxylic acid is more preferable, and adipic acid is further preferable.

The organic acid preferably has a low molecular weight. Specifically, the molecular weight of the organic acid is preferably 600 or less, more preferably 450 or less, still more preferably 300 or less. The lower limit is not particularly limited, but 85 or more is preferable.
The carbon number of the organic acid is preferably 15 or less, more preferably 12 or less, and even more preferably 8 or less. The lower limit is not particularly limited, but 2 or more is preferable.

The organic acid may be used alone or in combination of two or more. The cleaning liquid preferably contains two or more kinds of organic acids in that it is excellent in cleaning performance (particularly, cleaning performance for a semiconductor substrate containing W).
The content of the organic acid in the cleaning liquid is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the cleaning liquid. The lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total mass of the cleaning liquid.

<Reducing agent>
The cleaning liquid may contain a reducing agent.
The reducing agent is a compound having an oxidizing action and having ^{a function of oxidizing OH-} ions or dissolved oxygen contained in the cleaning liquid, and is also called a deoxidizing agent. The cleaning liquid preferably contains a reducing agent because it is more excellent in the corrosion prevention performance of the cleaning liquid.
The reducing agent used in the cleaning liquid is not particularly limited, and examples thereof include ascorbic acid compounds, catechol compounds, hydroxylamine compounds, hydrazide compounds, and reducing sulfur compounds.

-Ascorbic acid compound-
The ascorbic acid compound means at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives, and salts thereof.
Examples of the ascorbic acid derivative include ascorbic acid phosphate ester and ascorbic acid sulfate ester.
As the ascorbic acid compound, ascorbic acid, ascorbic acid phosphate ester, or ascorbic acid sulfate ester is preferable, and ascorbic acid is more preferable.

-Catechol compound-
The catechol compound means at least one selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives.
The catechol derivative means a compound in which at least one substituent is substituted with pyrocatechol. As the substituent contained in the catechol derivative, a hydroxyl group, a carboxyl group, a carboxylic acid ester group, a sulfo group, a sulfonic acid ester group, an alkyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms), and Examples include an aryl group (preferably a phenyl group). The carboxyl group and sulfo group of the catechol derivative as substituents may be salts with cations. Further, the alkyl group and the aryl group that the catechol derivative has as a substituent may further have a substituent.
Examples of the catechol compound include pyrocatechol, 4-tert-butylcatechol, pyrogallol, gallate, methyl gallate, 1,2,4-benzenetriol, and tyron.

-Hydroxylamine compound-
Hydroxylamine compound means at least one selected from the group consisting of hydroxylamine _{(NH 2 OH), hydroxylamine derivatives, and salts thereof.} Further, the hydroxylamine derivative means a compound in which at least one organic group is substituted with _{hydroxylamine (NH 2 OH).} Compounds different from alkanolamines are preferred.
The salt of the hydroxylamine or the hydroxylamine derivative may be an inorganic acid salt or an organic acid salt of the hydroxylamine or the hydroxylamine derivative. As the salt of the hydroxylamine or the hydroxylamine derivative, a salt with an inorganic acid in which at least one non-metal selected from the group consisting of Cl, S, N and P is bonded to hydrogen is preferable, and a salt salt and a sulfate are used. Salts or nitrates are more preferred.

Examples of the hydroxylamine compound include a compound represented by the following formula (3) or a salt thereof.

In formula (3), R ⁵ and R ⁶ each independently represent a hydrogen atom or an organic group.

The organic group represented by R ⁵ and R ^6, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic.
Further, ^{it is preferable that at least one of R 5} and R ⁶ is an organic group (more preferably, an alkyl group having 1 to 6 carbon atoms).
As the alkyl group having 1 to 6 carbon atoms, an ethyl group or an n-propyl group is preferable, and an ethyl group is more preferable.

Examples of the hydroxylamine compound include hydroxylamine, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine and N-ethylhydroxylamine. , N, N-diethyl hydroxylamine, N, O-diethylhydroxylamine, O, N, N-trimethylhydroxylamine, N, N-dicarboxyethyl hydroxylamine, and N, N-disulfoethyl hydroxylamine. Will be.
Of these, N-ethylhydroxylamine, N, N-diethylhydroxylamine (DEHA) or Nn-propylhydroxylamine are preferable, and DEHA is more preferable.

-Hydrazide compound-
The hydrazide compound means a compound in which the hydroxyl group of an acid is _{substituted with a hydrazino group (-NH-NH 2} ), and a derivative thereof (a compound in which at least one substituent is substituted with a hydrazino group).
The hydrazide compound may have two or more hydrazino groups.
Examples of the hydrazide compound include carboxylic acid hydrazide and sulfonic acid hydrazide, and carbohydrazide (CHZ) is preferable.

-Reducing sulfur compounds-
The reducing sulfur compound is not particularly limited as long as it is a compound containing a sulfur atom and having a function as a reducing agent, and for example, mercaptosuccinic acid, dithiodiglycerol, bis (2,3-dihydroxypropylthio) ethylene, etc. 3- (2,3-Dihydroxypropylthio) -2-methyl-propyl sulfonate sodium, 1-thioglycerol, 3-mercapto-1-propanesulfonate sodium, 2-mercaptoethanol, thioglycolic acid, and 3-mercapto -1-Propanol can be mentioned.
Among them, a compound having an SH group (mercapto compound) is preferable, and 1-thioglycerol, 3-mercapto-1-propanesulfonate sodium, 2-mercaptoethanol, 3-mercapto-1-propanol, or thioglycolic acid is more preferable. preferable.

As the reducing agent, an ascorbic acid compound or a hydroxylamine compound is preferable, and a hydroxylamine compound is more preferable.

As the reducing agent, one type may be used alone, or two or more types may be used in combination. The cleaning liquid preferably contains two or more kinds of reducing agents in that it is excellent in corrosion prevention performance (particularly, corrosion prevention performance for semiconductor substrates containing W).
When the cleaning liquid contains a reducing agent, the content of the reducing agent is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the cleaning liquid.
As these reducing agents, commercially available ones may be used, or those synthesized according to a known method may be used.

<Specific chelating agent>
The cleaning solution may contain a specific chelating agent.
The cleaning solution may contain a specific chelating agent whose coordination group has a nitrogen-containing group. The specific chelating agent has two or more nitrogen-containing groups as coordination groups that coordinate with metal ions in one molecule. Examples of the nitrogen-containing group as a coordination group include an amino group.

Examples of the specific chelating agent include a compound having a biguanide group or a biguanide compound which is a salt thereof. The number of biguanide groups contained in the biguanide compound is not particularly limited, and may have a plurality of biguanide groups.
Examples of the biguanide compound include the compounds described in paragraphs [0034] to [0055] of JP-A-2017-504190, the contents of which are incorporated in the present specification.

Examples of the compound having a biguanide group include ethylene diviguanide, propylene diviguanide, tetramethylene diviguanide, pentamethylene diviguanide, hexamethylene diviguanide, heptamethylene diviguanide, octamethylene diviguanide, and 1,1'-hexamethylenebis ( 5- (p-chlorophenyl) biguanide) (chlorhexidine), 2- (benzyloxymethyl) pentane-1,5-bis (5-hexylbiguanide), 2- (phenylthiomethyl) pentane-1,5-bis (5) -Phenetyl biguanide), 3- (phenylthio) hexane-1,6-bis (5-hexylbiguanide), 3- (phenylthio) hexane-1,6-bis (5-cyclohexylbiguanide), 3- (benzylthio) hexane- 1,6-bis (5-hexylbiguanide) or 3- (benzylthio) hexane-1,6-bis (5-cyclohexylbiguanide) is preferred, and chlorhexidine is more preferred.
As the salt of the compound having a biguanide group, hydrochloride, acetate or gluconate is preferable, and gluconate is more preferable.
As the specific chelating agent, chlorhexidine gluconate (CHG) is preferable.

The specific chelating agent may be used alone or in combination of two or more.
When the cleaning liquid contains a specific chelating agent, the content of the specific chelating agent in the cleaning liquid is not particularly limited, but is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total mass of the cleaning liquid. More preferred.

The cleaning liquid preferably contains both a nitrogen-containing heteroaromatic compound and a specific chelating agent because it is excellent in cleaning performance (particularly, cleaning performance for a metal film containing W).
When the cleaning solution contains both a nitrogen-containing heteroaromatic compound and a specific chelating agent, the mass ratio of the content of the specific chelating agent to the content of the nitrogen-containing heteroaromatic compound in the cleaning solution [content of the specific chelating agent / content of the specific chelating agent] The value of the nitrogen chelate aromatic compound] is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

<Additives>
The cleaning liquid may contain additives other than the above-mentioned components.
Examples of additives other than the above components include oxidizing agents, polymers, other pH adjusters, other anticorrosive agents, fluorine compounds, organic solvents and the like.

(Oxidant)
The cleaning liquid may contain an oxidizing agent in addition to the above components.
Examples of the oxidizing agent include periodic acid or a salt thereof, ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, diammonium cerium nitrate, iron sulfate, hypochlorite, ozone, and peracetic acid. Therefore, periodic acid or a salt thereof is preferable.

As the oxidizing agent, one type may be used alone, or two or more types may be used in combination.
When the cleaning liquid contains an oxidizing agent, the content thereof is preferably 0.01 to 30% by mass, more preferably 0.05 to 20% by mass, still more preferably 5 to 15% by mass, based on the total mass of the cleaning liquid. ..

(Polymer)
The cleaning liquid may contain a polymer.
The polymer is a component different from each of the above components.
The weight average molecular weight of the polymer is preferably 500 or more, more preferably 1000 or more, still more preferably 2000 or more. The upper limit is not particularly limited, but is preferably 1,000,000 or less, and more preferably 500,000 or less.
Among them, when the polymer is a water-soluble polymer described later, the weight average molecular weight of the water-soluble polymer is preferably 1000 or more, more preferably 1500 or more, still more preferably 3000 or more. The upper limit of the weight average molecular weight of the water-soluble polymer is not limited, and is, for example, 1500,000 or less, preferably 120,000 or less, more preferably 1,000,000 or less, still more preferably 10,000 or less.
The "weight average molecular weight" in the present specification refers to the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).
The polymer preferably has a repeating unit having a carboxy group (such as a repeating unit derived from (meth) acrylic acid). The content of the repeating unit having a carboxy group is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, based on the total mass of the polymer.

The polymer is also preferably a water-soluble polymer.
The "water-soluble polymer" is a compound in which two or more repeating units are linearly or reticulated via covalent bonds, and the mass dissolved in 100 g of water at 20 ° C. is 0.1 g or more. Intended for a compound.

Examples of the water-soluble polymer include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and salts thereof; styrene, α-methylstyrene, and / or. Polymers of monomers such as 4-methylstyrene and acid monomers such as (meth) acrylic acid and / or maleic acid, and salts thereof; benzenesulfonic acid and / or naphthalenesulfonic acid and the like. Polymers with repeating units having aromatic hydrocarbon groups condensed with formarin, and salts thereof; polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylformamide, polyethyleneimine, polyvinyloxazoline, Vinyl-based synthetic polymers such as polyvinylimidazole and polyallylamine; modified natural polysaccharides such as hydroxyethyl cellulose, carboxymethyl cellulose, and processed starch can be mentioned.

The water-soluble polymer may be a homopolymer or a copolymer obtained by copolymerizing two or more kinds of monomers. Examples of such a monomer include a monomer having a carboxyl group, a monomer having a sulfonic acid group, a monomer having a hydroxyl group, a monomer having a polyethylene oxide chain, and a simpler having an amino group. Examples thereof include a monomer selected from the group consisting of a monomer having a metric and a heterocycle.
It is also preferable that the water-soluble polymer is substantially composed of only structural units derived from the monomers selected from the above group. The fact that the polymer is substantially only the structural unit derived from the monomer selected from the above group means that, for example, the structural unit derived from the monomer selected from the above group with respect to the mass of the polymer is used. The content of the above is preferably 95 to 100% by mass, more preferably 99 to 100% by mass.

Examples of the polymer include polyacrylic acid (Mw = 700,000) (manufactured by Toagosei Co., Ltd., trade name “Julimer AC-10H”) and polyacrylic acid (Mw = 55,000) (manufactured by Toagosei Co., Ltd.). , Product name "Julimer AC-10L"), Polyacrylic acid (Mw = 6,000) (manufactured by Toagosei Co., Ltd., Product name "Aron A-10SL"), Styrene-maleic acid copolymer (Daiichi Kogyo Seiyaku Co., Ltd.) Made by Co., Ltd., trade name "DKS Discoat N-10") (Mw = 3,200), styrene-maleic acid half ester copolymer (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "DKS Disccoat N-14" (Mw = 3,600)), Naphthalene sulfonic acid formarin condensate Na salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "Laberin FD-40", (Mw = 2,700)), and polymeric acid (Mw). = 2,000) (manufactured by Nichiyu Co., Ltd., trade name "Non-Pole PWA-50W").

Further, as the polymer, other water-soluble polymers described in paragraphs [0043] to [0047] of JP-A-2016-171294 are also mentioned, and the contents thereof are incorporated in the present specification.

As the polymer, one kind may be used alone, or two or more kinds may be used in combination.
When the cleaning liquid contains a polymer, the content thereof is preferably 0.001% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, based on the total mass of the cleaning liquid. The upper limit is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
When the content of the polymer is within the above range, the polymer is appropriately adsorbed on the surface of the substrate and can contribute to the improvement of the corrosion prevention performance of the cleaning liquid, and the viscosity and / or the cleaning performance of the cleaning liquid is well balanced. Can be done.

(Polyhydroxy compound having a molecular weight of 500 or more)
The cleaning liquid may contain a polyhydroxy compound having a molecular weight of 500 or more.
The polyhydroxy compound is a component different from each of the above-mentioned components.
The polyhydroxy compound is an organic compound having two or more (for example, 2 to 200) alcoholic hydroxyl groups in one molecule.
The molecular weight of the polyhydroxy compound (weight average molecular weight when having a molecular weight distribution) is 500 or more, preferably 500 to 3000.

Examples of the polyhydroxy compound include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; mannitriose, cellotriose, gentianose, raffinose, meletitos, cellotetholose, and stachyose. Oligosaccharides; polysaccharides such as starch, glycogen, cellulose, xylose, chitin, and chitosan and their hydrolyzates.

Further, as the polyhydroxy compound, cyclodextrin is also preferable. Cyclodextrin is a kind of cyclic oligosaccharide having a cyclic structure in which a plurality of D-glucoses are bound by a glucosidic bond. Compounds to which 5 or more (for example, 6 to 8) glucose are bound are known.
Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and among them, γ-cyclodextrin is preferable.

The polyhydroxy compound may be used alone or in combination of two or more.
When the cleaning liquid contains the above polyhydroxy compound, the content thereof is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and 0.1 to 3% by mass with respect to the total mass of the cleaning liquid. % Is more preferable.

(Other pH regulators)
In addition to the above components, the cleaning liquid may contain a pH adjusting agent for adjusting and maintaining the pH of the cleaning liquid. Examples of the pH adjuster include basic compounds and acidic compounds other than the above components.

Examples of the basic compound include a basic organic compound and a basic inorganic compound.
The basic organic compound is a basic organic compound different from the above-mentioned components. Examples of the basic organic compound include amine oxides, nitros, nitroso, oximes, ketooximes, aldoximes, lactams, isocyanides, and ureas.
Examples of the basic inorganic compound include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.

As these basic compounds, commercially available ones may be used, or those appropriately synthesized by a known method may be used.

Examples of the acidic compound include inorganic acids.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, sulfite, nitric acid, nitrite, phosphoric acid, boric acid, and hexafluorophosphate. In addition, salts of inorganic acids may be used, and examples thereof include ammonium salts of inorganic acids, and more specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, and ammonium borate. , And ammonium hexafluoride phosphate.
As the inorganic acid, phosphoric acid or phosphate is preferable, and phosphoric acid is more preferable.

As the acidic compound, a salt of the acidic compound may be used as long as it becomes an acid or an acid ion (anion) in an aqueous solution.
As the acidic compound, a commercially available compound may be used, or a compound appropriately synthesized by a known method may be used.

As the pH adjuster, one type may be used alone, or two or more types may be used in combination.
When the cleaning solution contains a pH adjuster, the content thereof is selected according to the type and amount of other components and the pH of the target cleaning solution, but is 0.01 to 3 with respect to the total mass of the cleaning solution. The mass% is preferable, and 0.05 to 1% by mass is more preferable.

(Fluorine compound)
Examples of the fluorine compound include the compounds described in paragraphs [0013] to [0015] of JP-A-2005-150236, the contents of which are incorporated in the present specification.

(Organic solvent)
As the organic solvent, any known organic solvent can be used, but hydrophilic organic solvents such as alcohol and ketone are preferable. The organic solvent may be used alone or in combination of two or more.

(Other chelating agents)
The cleaning liquid may contain an organic acid having a chelating function and other chelating agents other than the specific chelating agent. Examples of other chelating agents include inorganic acid-based chelating agents such as condensed phosphoric acid and salts thereof.
Examples of the condensed phosphoric acid and its salt include pyrophosphoric acid and its salt, metaphosphoric acid and its salt, tripolyphosphoric acid and its salt, and hexametaphosphoric acid and its salt.
The amount of other anticorrosive agent, other chelating agent, polymer, fluorine compound, and organic solvent used is not particularly limited and may be appropriately set as long as the effect of the present invention is not impaired.

The content of each of the above components in the washing solution is determined by a gas chromatography-mass spectrometry (GC-MS) method or a liquid chromatography-mass spectrometry (LC-MS) method. , And a known method such as an ion-exchange chromatography (IC) method.

[Physical characteristics of cleaning liquid]
<Metal content>
In the cleaning liquid, the content (ion concentration) of metals (metal elements of Fe, Co, Na, K, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) contained as impurities in the liquid. (Measured as) is preferably 5 mass ppm or less, and more preferably 1 mass ppm or less. Since it is assumed that a cleaning liquid having higher purity is required in the manufacture of the most advanced semiconductor element, the metal content thereof should be lower than 1 mass ppm, that is, the mass ppb order or less. It is particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit is not particularly limited, but 0 is preferable.

As a method for reducing the metal content, for example, distillation and purification treatment such as filtration using an ion exchange resin or a filter are performed at the stage of the raw material used in the production of the cleaning liquid or the stage after the production of the cleaning liquid. Can be mentioned.
As another method for reducing the metal content, for example, as a container for accommodating a raw material or a manufactured cleaning liquid, a container with less elution of impurities, which will be described later, may be used. Further, it is also possible to lining the inner wall of the pipe with a fluororesin so that the metal component does not elute from the pipe or the like during the production of the cleaning liquid.

<Coarse particles>
The cleaning liquid may contain coarse particles, but the content thereof is preferably low. Here, the coarse particles mean particles having a diameter (particle size) of 0.4 μm or more when the shape of the particles is regarded as a sphere.
As for the content of coarse particles in the cleaning liquid, the content of particles having a particle size of 0.4 μm or more is preferably 1000 or less per 1 mL of the cleaning liquid, and more preferably 500 or less. The lower limit is not particularly limited, but 0 is mentioned. Further, it is more preferable that the content of particles having a particle size of 0.4 μm or more measured by the following measuring method is not more than the detection limit value.
The coarse particles contained in the cleaning liquid include particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw materials, and dust, dust, organic solids, and dust, dust, organic solids, which are brought in as contaminants during the preparation of the cleaning liquid. Particles such as inorganic solids that finally exist as particles without being dissolved in the cleaning solution fall under this category.
The content of coarse particles present in the cleaning liquid can be measured in the liquid phase by using a commercially available measuring device in a light scattering type liquid particle measuring method using a laser as a light source.
Examples of the method for removing coarse particles include purification treatment such as filtering described later.

The cleaning liquid may be a kit in which the raw material is divided into a plurality of parts.

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

<Liquid preparation process>
The method for preparing the cleaning liquid is not particularly limited, and for example, the cleaning liquid can be produced by mixing the above-mentioned components. The order and / or timing of mixing each of the above-mentioned components is not particularly limited. For example, compound (1), an alkanolamine, and an optional component are sequentially added to a container containing purified pure water, and then stirred. A method of preparing the mixture by adding a pH adjuster to adjust the pH of the mixed solution can be mentioned. Further, when water and each component are added to the container, they may be added all at once or divided into a plurality of times.

The stirring device and stirring method used for preparing the cleaning liquid are not particularly limited, and a known device as a stirring machine or a disperser may be used. Examples of the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer. Dispersers include, for example, industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

The mixing of each component in the liquid preparation step of the cleaning liquid, the purification treatment described later, and the storage of the produced cleaning liquid are preferably performed at 40 ° C. or lower, more preferably 30 ° C. or lower. Further, 5 ° C. or higher is preferable, and 10 ° C. or higher is more preferable. By preparing, treating and / or storing the cleaning liquid in the above temperature range, stable performance can be maintained for a long period of time.

(Refining process)
It is preferable to perform a purification treatment in advance on any one or more of the raw materials for preparing the cleaning liquid. Examples of the purification treatment include known methods such as distillation, ion exchange, and filtration.
The degree of purification is not particularly limited, but it is preferable to purify until the purity of the raw material is 99% by mass or more, and it is more preferable to purify until the purity of the stock solution is 99.9% by mass or more.

Specific methods of the purification treatment include, for example, a method of passing a raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering described later.
As the purification treatment, a plurality of the above-mentioned purification methods may be combined and carried out. For example, the raw material is subjected to primary purification by passing it through an RO membrane, and then passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin. May be.
Moreover, the purification treatment may be carried out a plurality of times.

(filtering)
The filter used for filtering is not particularly limited as long as it is conventionally used for filtration purposes and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (high density). Or at least one filter selected from the group consisting of (including ultrahigh molecular weight). Among these materials, at least one material selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide-based resin (including nylon) is preferable. , Fluororesin filters are more preferred. By filtering the raw materials using a filter formed of these materials, it is possible to effectively remove highly polar foreign substances that are likely to cause defects.

The critical surface tension of the filter is preferably 70 to 95 mN / m, more preferably 75 to 85 mN / m. The value of the critical surface tension of the filter is the nominal value of the manufacturer. By using a filter having a critical surface tension in the above range, it is possible to effectively remove highly polar foreign substances that are likely to cause defects.

The pore diameter of the filter is preferably 2 to 20 nm, more preferably 2 to 15 nm. Within this range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the raw material while suppressing filtration clogging. For the hole diameter here, the nominal value of the filter manufacturer can be referred to.

Filtering may be performed only once or twice or more. When filtering is performed twice or more, the filters used may be the same or different.

Further, the filtering is preferably performed at room temperature (25 ° C.) or lower, more preferably 23 ° C. or lower, and even more preferably 20 ° C. or lower. Further, 0 ° C. or higher is preferable, 5 ° C. or higher is more preferable, and 10 ° C. or higher is even more preferable. By filtering in the above temperature range, the amount of particulate foreign matter and impurities dissolved in the raw material can be reduced, and the foreign matter and impurities can be efficiently removed.

(container)
The cleaning liquid (including the form of the kit or the diluted liquid described later) can be filled in any container and stored, transported, and used as long as corrosiveness is not a problem.

As the container, a container having a high degree of cleanliness inside the container and suppressing elution of impurities from the inner wall of the container's accommodating portion into each liquid is preferable for semiconductor applications. Examples of such containers include various containers commercially available as containers for semiconductor cleaning liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Corporation and the "Pure Bottle" manufactured by Kodama Resin Industry. However, it is not limited to these.
Further, as a container for accommodating the cleaning liquid, the wetted portion with each liquid such as the inner wall of the accommodating portion is formed of a fluororesin (perfluororesin) or a metal subjected to rust prevention and metal elution prevention treatment. The rusted container is preferred.
The inner wall of the container is made of at least one resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from this, or rustproofing of stainless steel, hasteroi, inconel, monel, and the like. It is preferably formed from a metal that has been subjected to a metal elution prevention treatment.

As the above-mentioned different resins, a fluororesin (perfluororesin) is preferable. In this way, by using a container whose inner wall is a fluororesin, a problem of elution of ethylene or propylene oligomer occurs as compared with a container whose inner wall is polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin. Can be suppressed.
Specific examples of such a container whose inner wall is a fluororesin include a FluoroPure PFA composite drum manufactured by Entegris. In addition, it is described on page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004/016526, and pages 9 and 16 of International Publication No. 99/46309. Containers can also be used.

Further, in addition to the above-mentioned fluororesin, quartz and an electropolished metal material (that is, an electropolished metal material) are also preferably used for the inner wall of the container.
The metal material used for producing the electrolytically polished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is 25 mass with respect to the total mass of the metal material. The metal material is preferably more than%, and examples thereof include stainless steel and nickel-chromium alloys.
The total content of chromium and nickel in the metal material is more preferably 30% by mass or more with respect to the total mass of the metal material.
The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.

The method for electrolytically polishing a metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs [0011]-[0014] of JP-A-2015-227501 and paragraphs [0036]-[0042] of JP-A-2008-264929 can be used.

It is preferable that the inside of these containers is cleaned before filling with the cleaning liquid. The liquid used for cleaning preferably has a reduced amount of metal impurities in the liquid. The cleaning liquid may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production.

The inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) having a purity of 99.99995% by volume or more for the purpose of preventing changes in the components in the cleaning liquid during storage. In particular, a gas having a low water content is preferable. Further, during transportation and storage, the temperature may be normal temperature, but in order to prevent deterioration, the temperature may be controlled in the range of −20 ° C. to 20 ° C.

(Clean room)
It is preferable that the manufacturing of the cleaning liquid, the opening of the container, the cleaning, the handling including the filling of the cleaning liquid, the processing analysis, and the measurement are all performed in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably to satisfy ISO class 1 or ISO class 2, and to satisfy ISO class 1. Is more preferable.

<Dilution step>
It is preferable that the above-mentioned cleaning liquid is used for cleaning the semiconductor substrate after undergoing a dilution step of diluting with a diluent such as water.

The dilution ratio of the cleaning liquid in the dilution step may be appropriately adjusted according to the type and content of each component, the semiconductor substrate to be cleaned, etc., but the ratio of the diluted cleaning liquid to the cleaning liquid before dilution is a volume ratio. It is preferably 10 to 10000 times, more preferably 20 to 3000 times, still more preferably 50 to 1000 times.
Further, the cleaning liquid is preferably diluted with water because the effect of the present invention is more excellent.

The specific method of the dilution step of diluting the cleaning liquid is not particularly limited, and may be performed according to the above-mentioned liquid preparation step of the cleaning liquid. The stirring device and the stirring method used in the dilution step are also not particularly limited, and the known stirring device mentioned in the above-mentioned cleaning liquid preparation step may be used.

It is preferable to purify the water used in the dilution step in advance. Further, it is preferable to carry out a purification treatment on the diluted washing liquid obtained by the dilution step.
The purification treatment is not particularly limited, and examples thereof include an ion component reduction treatment using an ion exchange resin or an RO membrane and foreign matter removal using filtering described as the purification treatment for the cleaning liquid described above. It is preferable to perform the above processing.

[Use of cleaning liquid]
The cleaning liquid is used in a cleaning process for cleaning a semiconductor substrate that has been subjected to chemical mechanical polishing (CMP) treatment. The cleaning liquid can also be used for cleaning the semiconductor substrate in the semiconductor substrate manufacturing process.
As described above, a diluted cleaning solution obtained by diluting the cleaning solution may be used for cleaning the semiconductor substrate.

[Items to be cleaned]
Examples of the object to be cleaned by the cleaning liquid include a semiconductor substrate having a metal-containing substance.
The term "on the semiconductor substrate" as used herein includes, for example, any of the front and back surfaces, the side surfaces, the inside of the groove, and the like of the semiconductor substrate. Further, the metal-containing material on the semiconductor substrate includes not only the case where the metal-containing material is directly on the surface of the semiconductor substrate but also the case where the metal-containing material is present on the semiconductor substrate via another layer.
The metal content on the semiconductor substrate preferably contains cobalt and tungsten. That is, a semiconductor substrate containing cobalt and tungsten is preferable.

The metal contained in the metal-containing substance is, for example, Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium). , Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lantern), and Ir (iridium). Seed metal M is mentioned.

The metal-containing substance may be a substance containing a metal (metal atom), and may be, for example, a simple substance of the metal M, an alloy containing the metal M, an oxide of the metal M, a nitride of the metal M, and an acid nitride of the metal M. Can be mentioned.
Further, the metal-containing substance may be a mixture containing two or more of these compounds.
The oxide, the nitride, and the oxynitride may be a composite oxide, a composite nitride, and a composite oxynitride containing a metal.
The content of the metal atom in the metal-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, based on the total mass of the metal-containing material. The upper limit is 100% by mass or less because the metal-containing substance may be the metal itself.

The semiconductor substrate preferably has a metal M-containing material containing a metal M, and preferably has a metal-containing material containing at least one metal selected from the group consisting of Cu, Co, W, Ti, Ta, and Ru. Is more preferable, and it is further preferable to have a metal-containing material containing at least one metal selected from the group consisting of Cu, Co, Ti, Ta, Ru, and W.

The semiconductor substrate to be cleaned by the cleaning liquid is not particularly limited, and examples thereof include a substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of a wafer constituting the semiconductor substrate.

Specific examples of the wafer constituting the semiconductor substrate include a silicon (Si) wafer, a silicon carbide (SiC) wafer, a wafer made of a silicon-based material such as a resin-based wafer containing silicon (glass epoxy wafer), and gallium phosphorus (GaP). ) Wafers, gallium arsenic (GaAs) wafers, and indium phosphorus (InP) wafers.
Examples of the silicon wafer include an n-type silicon wafer in which a silicon wafer is doped with a pentavalent atom (for example, phosphorus (P), arsenic (As), antimony (Sb), etc.), and a silicon wafer having a trivalent atom (for example,). , Boron (B), gallium (Ga), etc.) may be doped in a p-type silicon wafer. The silicon of the silicon wafer may be, for example, amorphous silicon, single crystal silicon, polycrystalline silicon, or polysilicon.
In particular, the cleaning liquid is useful for wafers made of silicon-based materials such as silicon wafers, silicon carbide wafers, and resin-based wafers (glass epoxy wafers) containing silicon.

The semiconductor substrate may have an insulating film on the above-mentioned wafer.
Specific examples of the insulating film include a silicon oxide film (for example, a silicon dioxide (SiO ₂ ) film, a tetraethyl orthosilicate (Si (OC ₂ H ₅ ) ₄ ) film (TEOS film), etc.), and a silicon nitride film (for example, a silicon nitride film). silicon nitride _(Si _{3 N} 4), and silicon carbonitride (SiNC), etc.), as well as low dielectric constant (low-k) film (e.g., carbon-doped silicon oxide (SiOC) film, and a silicon carbide (SiC) film or the like ).

The metal film contained in the semiconductor substrate is a metal film containing at least one metal selected from the group consisting of copper (Cu), cobalt (Co), and tungsten (W), for example, a film containing copper as a main component. (Copper-containing film), cobalt-based film (cobalt-containing film), tungsten-based film (tungsten-containing film), and at least one selected from the group consisting of Cu, Co, and W. Examples thereof include a metal film composed of a containing alloy.
The semiconductor substrate preferably has Co and W. That is, it is particularly preferable that the semiconductor substrate has at least a metal-containing substance containing Co (preferably a cobalt-containing film) and a metal-containing substance containing W (preferably a tungsten-containing film).

Examples of the copper-containing film include a wiring film made of only metallic copper (copper wiring film) and a wiring film made of an alloy of metallic copper and another metal (copper alloy wiring film).
Specific examples of the copper alloy wiring film include one or more metals selected from aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), tantalum (Ta), and tungsten (W). An example is a wiring film made of an alloy made of copper. More specifically, copper-aluminum alloy wiring film (CuAl alloy wiring film), copper-titanium alloy wiring film (CuTi alloy wiring film), copper-chrome alloy wiring film (CuCr alloy wiring film), copper-manganese alloy wiring. Examples thereof include a film (CuMn alloy wiring film), a copper-tantal alloy wiring film (CuTa alloy wiring film), and a copper-tungsten alloy wiring film (CuW alloy wiring film).

Examples of the cobalt-containing film (metal film containing cobalt as a main component) include a metal film made of only metallic cobalt (cobalt metal film) and a metal film made of an alloy of metallic cobalt and other metals (cobalt alloy metal). Membrane).
Specific examples of the cobalt alloy metal film include titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), molybdenum (Mo), palladium (Pd), tantalum (Ta), and tungsten (W). Examples thereof include a metal film made of an alloy composed of at least one metal and cobalt selected from the group consisting of. More specifically, cobalt-titanium alloy metal film (CoTi alloy metal film), cobalt-chromium alloy metal film (CoCr alloy metal film), cobalt-iron alloy metal film (CoFe alloy metal film), cobalt-nickel alloy metal. Film (CoNi alloy metal film), cobalt-molybdenum alloy metal film (CoMo alloy metal film), cobalt-palladium alloy metal film (CoPd alloy metal film), cobalt-tantal alloy metal film (CoTa alloy metal film), and cobalt- Examples thereof include a tungsten alloy metal film (CoW alloy metal film).
The cleaning solution is useful for substrates having a cobalt-containing film. Of the cobalt-containing films, cobalt metal films are often used as wiring films, and cobalt alloy metal films are often used as barrier metals.

Further, the cleaning liquid has at least a copper-containing wiring film and a metal film (cobalt barrier metal) which is composed of only metallic cobalt and is a barrier metal of the copper-containing wiring film on the upper part of the wafer constituting the semiconductor substrate. It may be preferable to use it for cleaning a substrate in which a copper-containing wiring film and a cobalt barrier metal are in contact with each other on the surface of the substrate.

Examples of the tungsten-containing film (metal film containing tungsten as a main component) include a metal film made of only tungsten (tungsten metal film) and a metal film made of an alloy of tungsten and other metals (tungsten alloy metal film). Can be mentioned.
Specific examples of the tungsten alloy metal film include a tungsten-titanium alloy metal film (WTi alloy metal film), a tungsten-cobalt alloy metal film (WCo alloy metal film), and the like.
Tungsten-containing films are often used as barrier metals in general.

The method for forming the insulating film, the copper-containing wiring film, the cobalt-containing film, and the tungsten-containing film on the wafer constituting the semiconductor substrate is not particularly limited as long as it is a method usually performed in this field.
As a method for forming the insulating film, for example, a silicon oxide film is formed by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen gas, and then silane and ammonia gas are introduced to form a chemical vapor deposition. Examples thereof include a method of forming a silicon nitride film by a vapor deposition (CVD) method.
As a method for forming a copper-containing wiring film, a cobalt-containing film, and a tungsten-containing film, for example, a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as a resist, and then plating and a CVD method or the like are used. A method for forming a copper-containing wiring film, a cobalt-containing film, and a tungsten-containing film can be mentioned.

<CMP processing>
The CMP treatment is, for example, a treatment for flattening the surface of a substrate having a metal wiring film, a barrier metal, and an insulating film by a combined action of chemical action using a polishing slurry containing polishing fine particles (abrasive grains) and mechanical polishing. be.
On the surface of the semiconductor substrate subjected to the CMP treatment, abrasive grains (for example, silica and alumina) used in the CMP treatment, a polished metal wiring film, and metal impurities (metal residues) derived from the barrier metal are present. Impurities may remain. Since these impurities may cause a short circuit between wirings and deteriorate the electrical characteristics of the semiconductor substrate, for example, the semiconductor substrate subjected to the CMP treatment is used for cleaning treatment for removing these impurities from the surface. Served.
Specific examples of the semiconductor substrate subjected to the CMP treatment include the Journal of Precision Engineering Vol. 84, No. 3. The substrate subjected to the CMP treatment according to 2018 is mentioned, but is not limited thereto.

[How to clean the semiconductor substrate]
The method for cleaning the semiconductor substrate is not particularly limited as long as it includes a cleaning step of cleaning the semiconductor substrate subjected to the CMP treatment using the above-mentioned cleaning liquid. It is preferable that the method for cleaning the semiconductor substrate includes a step of applying the diluted cleaning liquid obtained in the above dilution step to the semiconductor substrate subjected to the CMP treatment for cleaning.

The cleaning step of cleaning the semiconductor substrate with the cleaning liquid is not particularly limited as long as it is a known method performed on the semiconductor substrate treated with CMP, and the cleaning member such as a brush is used as a semiconductor while supplying the cleaning liquid to the semiconductor substrate. Brush scrub cleaning that physically contacts the surface of the substrate to remove residues, immersion type that immerses the semiconductor substrate in the cleaning liquid, spin (drop) type that drops the cleaning liquid while rotating the semiconductor substrate, and spraying the cleaning liquid. A mode usually used in this field, such as a spraying method, may be appropriately adopted. In the immersion type cleaning, it is preferable to perform ultrasonic treatment on the cleaning liquid in which the semiconductor substrate is immersed because impurities remaining on the surface of the semiconductor substrate can be further reduced.
The cleaning step may be performed only once or twice or more. When washing twice or more, the same method may be repeated, or different methods may be combined.

As a method for cleaning the semiconductor substrate, either a single-wafer method or a batch method may be adopted. The single-wafer method is generally a method of processing semiconductor substrates one by one, and the batch method is a method of processing a plurality of semiconductor substrates at the same time.

The temperature of the cleaning liquid used for cleaning the semiconductor substrate is not particularly limited as long as it is a temperature usually used in this field. Generally, cleaning is performed at room temperature (25 ° C.), but the temperature can be arbitrarily selected in order to improve the cleaning property and suppress the damage resistance to the member. The temperature of the cleaning liquid is preferably 10 to 60 ° C, more preferably 15 to 50 ° C.

The cleaning time in cleaning a semiconductor substrate cannot be unequivocally determined because it depends on the type and content of the components contained in the cleaning liquid, but practically, it is preferably 10 seconds to 2 minutes, preferably 20 seconds to 1 minute. 30 seconds is more preferable, and 30 seconds to 1 minute is even more preferable.

The supply amount (supply rate) of the cleaning liquid in the cleaning step of the semiconductor substrate is not particularly limited, but is preferably 50 to 5000 mL / min, more preferably 500 to 2000 mL / min.

In cleaning the semiconductor substrate, a mechanical stirring method may be used in order to further enhance the cleaning ability of the cleaning liquid.
Examples of the mechanical stirring method include a method of circulating the cleaning liquid on the semiconductor substrate, a method of flowing or spraying the cleaning liquid on the semiconductor substrate, a method of stirring the cleaning liquid by ultrasonic waves or megasonic, and the like.

After cleaning the semiconductor substrate, a step of rinsing the semiconductor substrate with a solvent to clean it (hereinafter referred to as "rinsing step") may be performed.
The rinsing step is continuously performed after the cleaning step of the semiconductor substrate, and is preferably a rinsing step using a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes. The rinsing step may be performed by using the above-mentioned mechanical stirring method.

Examples of the rinsing solvent include water (preferably De Ionize water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Can be mentioned. Further, an aqueous rinsing solution having a pH of more than 8 (diluted aqueous ammonium hydroxide or the like) may be used.
As a method of contacting the rinsing solvent with the semiconductor substrate, the above-mentioned method of contacting the cleaning liquid with the semiconductor substrate can be similarly applied.

Further, after the rinsing step, a drying step of drying the semiconductor substrate may be performed.
The drying method is not particularly limited, and is not particularly limited, for example, a spin drying method, a method of flowing a dry gas over a semiconductor substrate, a method of heating the substrate by a heating means such as a hot plate or an infrared lamp, a malangoni drying method, and rotagoni. Drying methods, IPA (isopropyl alcohol) drying methods, and any combination thereof can be mentioned.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, proportions, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention is not limitedly construed by the examples shown below.

In the following examples, the pH of the cleaning solution was measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model “F-74”) in accordance with JIS Z8802-1984.
Further, in the production of the cleaning liquids of Examples and Comparative Examples, the handling of the container, the preparation, filling, storage, and analysis measurement of the cleaning liquid were all performed in a clean room at a level satisfying ISO class 2 or less.

[Raw material for cleaning liquid]
The following compounds were used to produce the cleaning solution. As the various components used in the examples, those classified into semiconductor grade or those classified into high-purity grade equivalent thereto were used.

[Compound (1)]
Gluconic acid: ClogP value-3.17, Hansen solubility parameter δh30.3 (MPa) ^0.5 , δd17.3 (MPa) ^0.5 , δp12.7 (MPa) ^0.5 , Fujifilm Wako Pure Chemical Industries, Ltd. Made by Mutinic Acid Co., Ltd .: ClogP value-1.46, Hansen solubility parameter δh31.0 (MPa) ^0.5 , δd17.3 (MPa) ^0.5 , δp14.2 (MPa) ^0.5 , Fuji Wako Pure Chemical Industries, Ltd. Glyceric acid: ClogP value -1.92, Hansen solubility parameter δh27.5 (MPa) ^0.5 , δd18.1 (MPa) ^0.5 , δp13.4 (MPa) ^{0 .5} , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [Arcanolamine]
・ 2-Amino-2-methyl-1-propanol (AMP): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ 2-Amino-2-methylpropandiol (AMPD): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. -Tris hydroxymethylaminomethane (Tris): manufactured by Wako Pure Chemical Industries, Ltd. [second amine compound]
・ Piperazine: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Ethylene diamine: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Morholin: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ N-methylpiperazine (NMPZ): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Manufactured by Arginin Co., Ltd. (L-arginine): Manufactured by Tokyo Chemical Industry Co., Ltd.
・ Azole compound 1: 2,2'-{[(5-methyl-1H-benzotriazole-1-yl) methyl] imino} diethanol ・ 1,2,4-triazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [ Additive〕
・ Alkyl (EO) ₃ phosphate ester: Takemoto Oil & Fat Co., Ltd. ・ Periodic acid: Sigma-Aldrich Japan ・ Adipic acid: Tokyo Chemical Industry Co., Ltd. ・ Kohaku acid: Tokyo Chemical Industry Co., Ltd. ・ Histidin: Fujifilm Wako Pure Chemical Industries, Ltd. ) Made of polyacrylic acid (Mw = 700,000): manufactured by Toa Synthetic Co., Ltd., trade name "Julimer AC-10H"
-Polyacrylic acid (Mw = 55,000): manufactured by Toagosei Co., Ltd., product name "Julimer AC-10L"
-Polyacrylic acid (Mw = 6,000): manufactured by Toagosei Co., Ltd., product name "Aron A-10SL"
Polymaleic acid (Mw = 2,000): manufactured by NOF CORPORATION, product name "Non-Pole PWA-50W"
-Styrene-maleic acid copolymer: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "DKS Disccoat N-10"
-Styrene-maleic acid half ester copolymer: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "DKS Disccoat N-14"
-Naphthalene sulfonic acid formalin condensate Na salt: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Laberin FD-40"
-Γ-Cyclodextrin: manufactured by Cyclochem Co., Ltd. [pH adjuster]
-2-Hydroxyethyltrimethylammonium hydroxide (choline): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

Further, in the manufacturing process of the cleaning liquid in this embodiment, if necessary, as a pH adjusting agent, choline, either potassium hydroxide (KOH), and sulfuric acid (H 2 _SO _4), as well as, commercially available ultra pure water (Fuji Film Wako Pure Chemical Industries, Ltd.) was used.

[Manufacturing of cleaning liquid]
Next, a method for producing a cleaning liquid will be described by taking Example 1 as an example.
After adding gluconic acid, AMP, and piperazine to ultrapure water in the amounts shown in Table 1, 2.3 mass of DBU is added so that the pH of the prepared cleaning solution becomes 11.0. % Was added. The cleaning liquid of Example 1 was obtained by sufficiently stirring the obtained mixed liquid with a stirrer.

The cleaning solutions of Examples 2 to 42 and Comparative Examples 1 to 5 having the compositions shown in Table 1 were produced according to the production method of Example 1, respectively.
Each item of the Hansen solubility parameter or the ClogP value was measured by the method described above.

[Evaluation of cleaning performance]
The cleaning performance (residue removal performance) when the metal film subjected to chemical mechanical polishing was cleaned using the cleaning liquid produced by the above method was evaluated.
A wafer (8 inches in diameter) having a metal film made of copper, tungsten, or cobalt on the surface was polished using a FREX300S-II (polishing device, manufactured by Ebara Corporation). Wafers having a metal film made of copper on the surface were polished using CSL9044C and BSL8176C (trade names, both manufactured by FUJIFILM Planar Solutions) as polishing liquids. As a result, variations in the cleaning performance evaluation due to the polishing liquid were suppressed. Similarly, a wafer having a metal film made of cobalt on the surface was polished using CSL5340C and CSL5250C (trade names, both manufactured by FUJIFILM Planar Solutions) as polishing liquids. Wafers having a metal film made of tungsten on the surface were polished using only W-2000 (trade name, manufactured by Cabot Corporation). The polishing pressure was 2.0 psi, and the supply rate of the polishing liquid was 0.28 mL / (minute · cm ² ). The polishing time was 60 seconds.
Then, each of the polished wafers was washed over 30 seconds with each cleaning solution adjusted to room temperature (23 ° C.), and then dried.

Using a defect detection device (ComPlus-II manufactured by AMAT), the number of detected signal strengths corresponding to defects having a length of 0.1 μm or more on the polished surface of the obtained wafer was measured and evaluated as follows. The cleaning performance of the cleaning liquid was evaluated according to the standard. The evaluation results are shown in Table 1. It can be evaluated that the smaller the number of defects due to the residue detected on the polished surface of the wafer, the better the cleaning performance.
"A": Number of defects per wafer is less than 50 "B": Number of defects per wafer is 50 or more and less than 200 "C": Number of defects per wafer is 200 or more and less than 500 "D": Wafer More than 500 defects per

[Evaluation of corrosion prevention performance]
Wafers (12 inches in diameter) having a metal film made of copper, tungsten, or cobalt on the surface were cut, and wafer coupons having a length of 2 cm and a width of 2 cm were prepared. The thickness of each metal film was 200 nm. The wafer coupon was immersed in the cleaning liquid (temperature: 23 ° C.) produced by the above method, and the immersion treatment was performed for 3 minutes at a stirring rotation speed of 250 rpm. For each metal film, the content of copper, tungsten, or cobalt in each cleaning solution was measured before and after the dipping treatment. From the obtained measurement results, the corrosion rate per unit time (unit: Å / min) was calculated. The corrosion prevention performance of the cleaning liquid was evaluated according to the following evaluation criteria. The results are shown in Table 1.
The lower the corrosion rate, the better the corrosion prevention performance of the cleaning liquid.
(Evaluation criteria for W and Co)
"A": Corrosion rate is less than 1.0 Å / min "B": Corrosion rate is 1.0 Å / min or more, less than 2.0 Å / min "C": Corrosion rate is 2.0 Å / min or more, 3.0 Å Less than / min "D": Corrosion rate is 3.0 Å / min or more (Cu evaluation standard)
"A": Corrosion rate is less than 0.5 Å / min "B": Corrosion rate is 0.5 Å / min or more, less than 1.0 Å / min "C": Corrosion rate is 1.0 Å / min or more, 2.0 Å Less than / min "D": Corrosion rate is 2.0 Å / min or more

In the table, the "Amount (%)" column indicates the content (unit: mass%) of each component with respect to the total mass of the cleaning liquid. "* 1" in the "pH adjusting agent" column, if necessary, choline, that one of H ₂ SO ₄ and KOH, pH of the cleaning solution to be prepared was added in an amount to a number of "pH" column Means. In Example 25, the pH was adjusted using choline.
The “remaining portion” in the “water” column means that water constitutes the rest of the cleaning liquid other than each component shown in Table 1.
The column of "number of COOH groups" indicates the number of carboxyl groups possessed by the compound (1), and the number of OH groups indicates the number of hydroxyl groups possessed by the compound (1).
The "OH group / COOH group" column shows the value of the ratio of the number of hydroxyl groups to the number of carboxyl groups [number of hydroxyl groups / number of carboxyl groups] of the compound (1).
The column "(A) / (B)" shows the value of the mass ratio of the content of the compound (1) to the content of the alkanolamine [content of compound (1) / content of alkanolamine].
The numerical value in the "pH" column indicates the pH of the cleaning solution measured by the above pH meter at 25 ° C.

[result]
As is clear from Table 1, it was confirmed that the cleaning solution of the present invention showed a predetermined effect.

It was confirmed that the effect is more excellent when the content of the compound (1) is 0.5% by mass or more (preferably 1% by mass or more, more preferably 3% by mass or more) with respect to the total mass of the cleaning liquid. (Comparison of Examples 4 to 7).
It was confirmed that when the compound (1) was gluconic acid, the effect was more excellent (comparison of Examples 1 to 3).
It was confirmed that the effect was more excellent when the value of the mass ratio of the content of the compound (1) to the content of the alkanolamine was 0.1 to 10 (comparison of Examples 1 and 4 to 9).
It was confirmed that the cleaning liquid was more effective when it further contained a surfactant (comparison of Examples 4 and 26).

Claims

A cleaning liquid for semiconductor substrates that has been subjected to chemical mechanical polishing treatment.
A cleaning solution containing a compound represented by the following formula (1), alkanolamine, and water, and having a pH value of the cleaning solution at 25 ° C. of 9.0 or more.

In formula (1), Ra1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a group selected from the group consisting of a hydroxyl group and a carboxyl group.
The cleaning solution according to claim 1, wherein the ClogP value of the compound represented by the formula (1) is -3.50 to -1.45.
The Hansen solubility parameter of the compound represented by the formula (1) has a hydrogen bond term of 31.0 or less (MPa) 0.5 , a dispersion term of 17.0 to 18.0 (MPa) 0.5 , and a dipole. The cleaning solution according to claim 1 or 2, wherein the interim item is 13.0 or less (MPa) 0.5.
The cleaning solution according to any one of claims 1 to 3, wherein the value of the ratio of the number of hydroxyl groups to the number of carboxyl groups of the compound represented by the formula (1) is 2 or more.
The cleaning solution according to any one of claims 1 to 4, wherein the content of the compound represented by the formula (1) is 0.5% by mass or more with respect to the total mass of the cleaning solution.
The cleaning solution according to any one of claims 1 to 5, wherein the compound represented by the formula (1) is gluconic acid.
The cleaning solution according to any one of claims 1 to 6, wherein the alkanolamine is a compound represented by the following formula (a-1).
HO-L a1- NH 2 (a-1)
In the formula (a-1), La1 represents an alkylene group having 1 to 14 carbon atoms which may have a heteroatom.
Claimed that the alkanolamine comprises at least one selected from the group consisting of 2-amino-2-methyl-1-propanol, 2-amino-2-methylpropanediol, and trishydroxymethylaminomethane. The cleaning solution according to any one of 1 to 7.
The cleaning solution according to any one of claims 1 to 8, wherein the value of the mass ratio of the content of the compound represented by the formula (1) to the content of the alkanolamine is 0.1 to 10.
The cleaning solution according to any one of claims 1 to 9, wherein the cleaning solution further contains a second amine compound different from the alkanolamine.
The cleaning solution according to any one of claims 1 to 10, wherein the cleaning solution further contains a surfactant.
A method for cleaning a semiconductor substrate, which comprises a step of cleaning the semiconductor substrate that has been subjected to chemical mechanical polishing treatment by using the cleaning liquid according to any one of claims 1 to 11.