TW202142681A - Cleaning solution, method for cleaning semiconductor substrate - Google Patents

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 25 DEG C is 9.0 or more.

Description

Cleaning solution, cleaning method of semiconductor substrate

The present invention relates to a cleaning solution for semiconductor substrates and a method for cleaning semiconductor substrates.

In the manufacture of semiconductor devices, chemical mechanical polishing (CMP: Chemical Mechanical Polishing) is sometimes performed, which uses a polishing slurry containing abrasive particles (for example, silicon dioxide, aluminum oxide, etc.) to have a metal wiring film The surface of the substrate such as barrier metal and insulating film is flattened. In the CMP process, metal components derived from the abrasive particles used in the CMP process, the polished wiring metal film, and/or barrier metal are likely to remain on the surface of the polished semiconductor substrate. These residues can short-circuit between wirings and affect the electrical characteristics of the semiconductor. Therefore, a cleaning step of removing these residues from the surface of the semiconductor substrate is usually performed.

For example, Patent Document 1 describes a cleaning treatment agent for the surface of a semiconductor substrate, which contains an organic acid having at least one carboxyl group and a complexing agent. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 10-072594

[The problem to be solved by the invention] The inventors studied the cleaning solution for semiconductor substrates after CMP with reference to Patent Document 1, and found that when the semiconductor substrate after CMP contains tungsten and cobalt, the cleaning performance is And at least one of the corrosion prevention performance for tungsten and/or cobalt is poor. That is, it has been found that there is room for further improvement regarding the coexistence of cleaning performance and corrosion prevention performance in a cleaning solution for a semiconductor substrate containing tungsten and cobalt after CMP.

The subject of the present invention is to provide a cleaning solution which is a cleaning solution for a semiconductor substrate after performing CMP and has excellent cleaning performance and excellent corrosion prevention performance for both tungsten and cobalt. In addition, the subject of the present invention is to provide a method for cleaning a semiconductor substrate after performing CMP.

[Means to solve the problem] The inventors found that the problem can be solved by the following structure.

[1] A cleaning solution, which is a cleaning solution for semiconductor substrates subjected to a chemical mechanical polishing treatment, and the cleaning solution contains a compound represented by the formula (1) described later, an alkanolamine, and water to clean The pH of the liquid at 25°C is 9.0 or more. [2] The cleaning solution as described in [1], wherein the ClogP value of the compound represented by formula (1) is -3.50 to -1.45. [3] The cleaning solution according to claim 1 or claim 2, wherein the hydrogen bond term of the Hansen solubility parameter of the compound represented by formula (1) is 31.0 or less (MPa) ^0.5 , The term is 17.0 (MPa) ^0.5 to 18.0 (MPa) ^0.5 , and the term between dipoles 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 in the compound represented by formula (1) is 2 above. [5] The cleaning liquid according to any one of [1] to [4], wherein the content of the compound represented by formula (1) is 0.5% by mass or more with respect to the total mass of the cleaning liquid. [6] The cleaning solution according to any one of [1] to [5], wherein the compound represented by 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 formula (a-1) described later. [8] The cleaning solution as described in any one of [1] to [7], wherein the alkanolamine comprises 2-amino-2-methyl-1-propanol, 2-amino-2 -At least one of the group consisting of methylpropanediol and trihydroxymethylaminomethane. [9] The cleaning solution according to any one of [1] to [8], wherein the mass ratio of the content of the compound represented by the formula (1) to the content of the alkanolamine has a value of 0.1-10. [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, including the step of using the cleaning solution as described in any one of [1] to [11] to clean the semiconductor substrate after the chemical mechanical polishing treatment.

[Effects of the invention] According to the present invention, it is possible to provide a cleaning solution which is a cleaning solution for a semiconductor substrate after performing CMP and has excellent cleaning performance and excellent corrosion prevention performance for tungsten and cobalt. In addition, according to the present invention, a method for cleaning a semiconductor substrate after CMP can be provided.

Hereinafter, an example of a form for implementing the present invention will be described. In this specification, the numerical range indicated by "～" means a range that includes the numerical values described before and after "～" as the lower limit and the upper limit.

In this specification, when there are two or more types of a certain component, the "content" of the component refers to the total content of the two or more components. In this manual, "ppm" means "parts-per-million (10 ^-6 )" and "ppb" means "parts-per-billion (10 ^-9) )”. The compounds described in this specification may also include isomers (compounds with the same number of atoms but different structures), optical isomers, and isotopes, unless they are particularly limited. In addition, isomers and isotopes may include only one type, or may include multiple types.

In this specification, the so-called ClogP value refers to the value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. As for the methods and software used in the calculation of ClogP values, well-known methods and software can be used. As long as there is no special description, the present invention uses Cambridgesoft's ChemBioDrawUltra 12.0. ClogP program entered. In this manual, the so-called psi refers to pound-force per square inch (pound-force per square inch), which means 1 psi=6894.76 Pa.

The cleaning solution of the present invention (hereinafter, also simply referred to as "cleaning solution") is a cleaning solution for semiconductor substrates subjected to chemical mechanical polishing (CMP) treatment, and includes the following expression (1) The cleaning solution of compound, alkanolamine, and water has a pH of 9.0 or more at 25°C.

The inventors obtained the following knowledge and completed the present invention: By using the cleaning solution in the cleaning step after CMP on a semiconductor substrate containing tungsten and cobalt, the cleaning performance and the effect on tungsten and cobalt Corrosion prevention performance is improved.

The detailed mechanism by which the effect of the present invention is obtained by such a cleaning solution is not clear, but the present invention is estimated as follows. The functional groups such as the carboxyl group of the compound represented by formula (1) and the amine group of the alkanolamine interact with metal particles attached or adsorbed on the surface of the semiconductor substrate after the CMP is performed by complex formation, etc., It is considered that the dispersibility of metal particles and the like is improved, whereby high cleaning performance can be obtained. In addition, it is presumed that the corrosion of cobalt is prevented by setting the pH value to 9.0 or higher. On the other hand, the compound represented by formula (1) forms a protective film on the surface of tungsten by interaction to prevent the corrosion of tungsten. As a result, the corrosion prevention performance of both cobalt and tungsten is excellent.

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

[Compound represented by formula (1)] The cleaning solution contains the compound represented by formula (1) (hereinafter also referred to as "compound (1)").

[化1]

In the formula (1), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 6 carbons which may have a group selected from the group consisting of a hydroxyl group and a carboxyl group. R ^{a1 is} preferably an alkyl group having 1 to 6 carbons which may have a group selected from the group consisting of a hydroxyl group and a carboxyl group, and more preferably may have a group selected from the group consisting of a hydroxyl group and a carboxyl group The alkyl group having 1 to 3 carbons. In addition, as ^Ra1 , an alkyl group having 1 to 6 carbon atoms having a hydroxyl group is preferred, and an alkyl group having 1 to 3 carbon atoms having a hydroxyl group is more preferred. The alkyl group represented by R ^a1 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. In addition, the alkyl group may be linear or branched. The said alkyl group may further have substituents other than a hydroxyl group and a carboxyl group. As a substituent, a halogen atom and an amino group are mentioned, for example. The number of hydroxyl groups of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 to 4. The number of carboxyl groups of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and still 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> In terms of at least excellent cleaning performance and corrosion prevention performance of the cleaning solution (hereinafter, also simply referred to as "the aspect with more excellent effects of the present invention"), it is preferably The hydrogen bonding term of the Hansen solubility parameter of compound (1) (hereinafter also referred to as "δh") is 31.0 or less (MPa) ^0.5 , and the dispersed phase (hereinafter also referred to as "δd") is 17.0 (MPa) ^0.5 to 18.0 ( MPa) ^0.5 , and the dipole term (hereinafter also referred to as "δp") is 13.0 or less (MPa) ^0.5 .

The so-called Hansen Solubility Parameters refers to "Hansen Solubility Parameters: A Users Handbook, Second Edition" (Page 1-Page 310, published by CRC, published in 2007) Hansen solubility parameters described in et al. That is, it can be considered that the Hansen solubility parameter represents solubility by a multi-dimensional vector (δh, δd, and δp), and these three parameters are the coordinates of points in a three-dimensional space called the Hansen space. The δh, δd, and δp of the Hansen solubility parameter of the compound (1) can be calculated, for example, using HsPIP (Hansen Solubility Parameters in Practice, Hansen Solubility Parameters in Practice).

＜ClogP value＞ In terms of more excellent effects of the present invention, the ClogP value of the compound (1) is preferably -3.50 to -1.45, more preferably -3.20 to -2.00.

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

If the number of hydroxyl groups that the compound (1) has is 2 or more, it is not particularly limited, and it may be 3 or more. The upper limit is not particularly limited, and it is preferably 10 or less, more preferably 8 or less, and still more preferably 5 or less. Among them, in terms of more excellent effects of the present invention, the number of hydroxyl groups is preferably from 1 to 5, more preferably from 2 to 5, and still more preferably from 3 to 5. If the number of carboxyl groups that the compound (1) has is one or more, there is no particular limitation, and it may be two or more. The upper limit is not particularly limited, but is preferably 10 or less, and more preferably 5 or less. Among them, the number of carboxyl groups is preferably one in terms of more excellent effects of the present invention.

Examples of the compound (1) include gluconic acid, mucic acid, glyceric acid, and heptonic acid. Among them, in terms of the more excellent effect of the present invention, as the compound (1), at least one selected from the group consisting of gluconic acid, mucic acid, and glyceric acid is preferred, and gluconic acid or Mucic acid, more preferably gluconic acid.

As the compound (1), optical isomers can also be used. In addition, one type of optical isomer may be used alone, or two or more types may be used in combination. In the case of mainly using one optical isomer, its optical purity 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 solution is not particularly limited. It is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more relative to the total mass of the cleaning solution. Furthermore, it is preferably 1% by mass or more, particularly preferably 3% by mass or more, and most preferably 4% by mass or more. The upper limit is not particularly limited. With respect to the total mass of the cleaning liquid, it is preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, and particularly preferably 5% by mass or less.

〔Alkanolamine〕 The cleaning liquid contains alkanolamine. The so-called alkanolamine refers to an aliphatic compound having one or more amine groups and one or more hydroxyl groups in the molecule. The alkanolamine may have any one of a primary amino group to a tertiary amino group, and preferably has a primary amino group.

As an alkanolamine, the compound represented by formula (a-1) is mentioned, for example, Preferably it is a compound represented by formula (a-2).

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 hetero atom. The ^{alkylene group represented by La1} is preferably an alkylene group having 1 to 10 carbon atoms which may have an oxygen atom, more preferably an alkylene group having 1 to 6 carbon atoms which may have an oxygen atom, and more preferably not Substituted alkylene having 1 to 6 carbon atoms. The hydrogen atom in the alkylene group may be further substituted by a substituent. As a substituent, a hydroxyl group, an alkyl group, an amino group, and these combinations are mentioned. Among them, a hydroxyl group is preferred. In addition, the alkylene group may be linear or branched. ^{The number of hydroxyl groups of the alkylene group represented by La1} is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3. In addition, the compound represented by the formula (a-1) may be an inorganic acid salt or an organic acid salt.

[化2]

In the formula (a-2), ^La2 represents a single bond or an alkylene group having 1 to 6 carbon atoms which may have a hetero atom. Among them, as ^La2 , a single bond is preferred. As the alkylene represented by L ^a2, preferably having a carbon number of oxygen atoms alkylene group having 1 to 6 carbon atoms, more preferably having a hydroxy alkylene group having 1 to 6, more preferably is unsubstituted An alkylene having 1 to 6 carbon atoms. The hydrogen atom in the alkylene group may be further substituted with a substituent. Examples of the substituent include an alkyl group, a hydroxyl group, an amino group, and a combination of these. In addition, the alkylene group may be linear or branched.

R ^a2 to R ^a5 each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 2 carbons. Among them, in terms of more excellent effects of the present invention, as ^Ra2 and ^Ra3 , a hydrogen atom is preferred. In addition, as R ^a4 and R ^a5 , a methyl group is preferred. The alkyl group represented by R ^a2 to R ^a5 may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group, an amino group, and a halogen atom. Among them, a hydroxyl group is preferred. ^{The alkyl group represented by Ra2} to ^Ra5 is preferably a methyl group or an ethyl group which may have a hydroxyl group, and more preferably an unsubstituted methyl group or an ethyl group. In addition, the compound represented by formula (a-2) may be an inorganic acid salt or an organic acid salt.

Examples of alkanolamines include 2-amino-2-methyl-1-propanol (AMP) and trishydroxymethylamino methane ( Tris), 2-amino-2-methyl propanediol (AMPD), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA) ), diethylene glycolamine (DEGA), 2-(methylamino)-2-methyl-1-propanol (2-(methylamino)-2-methyl-1-propanol, N-MAMP ), 2-(aminoethoxy)ethanol (AEE), 2-(2-aminoethylamino)ethanol (AAE), and 2-(2-Aminoethoxy)ethanol. Among them, it is preferably at least one selected from the group consisting of AMP, Tris, and AMPD, more preferably at least one selected from the group consisting of AMP and Tris, and still more preferably AMP. In addition, in terms of excellent cleaning performance (especially cleaning performance for a metal film containing W), MEA, DEA, AEE, or AAE is preferred.

Alkanolamine may be used alone or in combination of two or more. The content of the alkanolamine in the cleaning liquid is not particularly limited, but it is preferably 10% by mass or less, and more preferably 5 mass% or less with respect to the total mass of the cleaning liquid. The lower limit is not particularly limited. With respect to the total mass of the cleaning solution, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 3% by mass or more.

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

〔water〕 The cleaning liquid contains water as a solvent. The type of water used in the cleaning solution is not particularly limited as long as it does not adversely affect the semiconductor substrate. Distilled water, deionized water, and pure water (ultra-pure water) can be used. In terms of containing almost no impurities and having less influence on the semiconductor substrate in the manufacturing step of the semiconductor substrate, pure water (ultra-pure water) is preferred. The content of water in the cleaning solution may be the remainder of the compound (1), alkanolamine, and optional components described later. The content of water is not particularly limited. It is preferably 1% by mass or more, more preferably 30% by mass or more, still more preferably 60% by mass or more, and particularly preferably 85% by mass or more relative to the total mass of the cleaning liquid. The upper limit is not particularly limited, but it is preferably 99% by mass or less, and more preferably 98% by mass or less with respect to the total mass of the cleaning liquid.

〔PH〕 The pH of the cleaning solution of the present invention is 9.0 or more at 25°C. In terms of more excellent effects of the present invention, the pH of the cleaning solution at 25°C is preferably 10.0 or higher, more preferably 11.0 or higher. In addition, in terms of better corrosion prevention performance (especially corrosion prevention performance for semiconductor substrates containing W or Cu), the pH of the cleaning solution at 25°C is preferably 13.0 or less, more preferably 12.0 or less , And more preferably 11.5 or less. The pH of the cleaning solution can be determined by using the pH adjuster described later, as well as compound (1), alkanolamine, second amine compound, quaternary ammonium compound, corrosion inhibitor, organic acid, anionic surfactant, etc. It can be adjusted by the ingredients with the function of pH adjustment. In addition, the pH of the cleaning solution can be measured by a method based on Japanese Industrial Standards (JIS) Z8802-1984 using a known pH meter.

〔Arbitrary ingredients〕 In addition to the above-mentioned components, the cleaning liquid may also include other optional components. Examples of optional components include: second amine compounds, surfactants, pH adjusters, corrosion inhibitors, organic acids, reducing agents, and chelating agents whose ligands are nitrogen-containing groups (hereinafter also referred to as "specific chelating agents" "), 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, a corrosion inhibitor, an organic acid, and a polymer. Any component may be used alone or in combination of two or more.

Hereinafter, the optional components will be described.

＜Second amine compound＞ The cleaning liquid may also contain a second amine compound. The second amine compound is an amine compound different from the alkanolamine. As the second amine compound, an amine compound containing at least one selected from the group consisting of an alicyclic amine compound, an aliphatic monoamine compound, an aliphatic polyamine compound, and an amino acid can be cited. Among them, in terms of more excellent effects of the present invention, at least one selected from the group consisting of alicyclic amine compounds and amino acids is preferred.

(Alicyclic amine compound) The alicyclic amine compound is not particularly limited as long as it is a compound having a non-aromatic heterocyclic ring in which at least one of the atoms constituting the ring is a nitrogen atom. As an alicyclic amine compound, a piperazine compound and a cyclic amidine compound are mentioned, for example.

-Piperazine compound- The piperazine compound is a compound having a hetero six-membered ring (piperazine ring) in which the opposing -CH- group of the cyclohexane ring is substituted 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 carbons which may have a hydroxyl group, and an aryl group having 6 to 10 carbons.

Examples of piperazine compounds include piperazine, 1-methyl piperazine (NMPZ), 1-ethyl piperazine, 1-propyl piperazine, 1-butyl piperazine, 2- Methylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2- Hydroxymethylpiperazine, 1-(2-hydroxyethyl)piperazine (1-(2-hydroxyethyl)piperazine, HEP), N-(2-aminoethyl)piperazine (N-(2-aminoethyl) piperazine, AEP), 1,4-bis(2-hydroxyethyl)piperazine (1,4-Bis(2-hydroxyethyl)piperazine, BHEP), 1,4-bis(2-aminoethyl)piperazine (1,4-Bis(2-aminoethyl)piperazine, BAEP), and 1,4-bis(3-aminopropyl)piperazine (1,4-Bis(3-aminopropyl)piperazine, BAPP), preferably It is piperazine, NMPZ, HEP, AEP, BHEP, BAEP, or BAPP, more preferably piperazine or NMPZ.

As the alicyclic amine compound, in addition to the above, for example, 1,3-dimethyl-2-imidazolidinone, and imidazolidinethione (imidazolidinethione), etc., contain heteropentane members that are not aromatic Ring compounds, and compounds having a seven-membered ring containing a nitrogen atom.

-Cyclic Amidine Compounds- The cyclic amidine compound is a compound having a heterocyclic ring containing an amidine structure (>N-C=N-) in the ring. The number of ring members of the heterocyclic ring contained in the cyclic amidine compound is not particularly limited, and is preferably 5 or 6, and more preferably 6.

As the cyclic amidine compound, for example, diazabicycloundecene (1,8-diazabicyclo[5.4.0] undec-7-ene: DBU (1,8-Diazabicyclo[5.4. 0]undec-7-ene)), diazabicyclononene (1,5-diazabicyclo[4.3.0]non-5-ene: DBN(1,5-diazabicyclo[4.3.0]non- 5-ene)), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimido[1.2-a]azocine, 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-octahydropyrimido[1.2-a]azidine, and creatinine, preferably DBU.

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

(Aliphatic monoamine compound) As an aliphatic monoamine compound other than an alkanolamine and an alicyclic amine compound, the compound represented by following formula (a) (it also describes as "compound (a)" below) is mentioned, for example.

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 0-2. As the C1-C3 alkyl group, a methyl group, an ethyl group, a n-propyl group, and an isopropyl group are mentioned, Preferably it is an ethyl group or a n-propyl group.

Examples of the compound (a) include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, and triethylamine, and ethylamine is preferred, Propylamine, diethylamine, or triethylamine.

Examples of aliphatic monoamine compounds other than the compound (a) include n-butylamine, 3-methoxypropylamine, tertiary butylamine, n-hexylamine, cyclohexylamine, n-octylamine, 2-Ethylhexylamine, morpholine, and 4-(2-aminoethyl)morpholine (AEM).

(Aliphatic polyamine compound) As the aliphatic polyamine compound, for example, ethylenediamine (EDA), 1,3-propane diamine (1,3-propane diamine, PDA), 1,2-propane diamine, 1,3- Butanediamine, and 1,4-butanediamine and other alkylene diamines, as well as diethylenetriamine (DETA), triethylenetetramine (triethylenetetramine, TETA), bis(aminopropyl) ethyl Polyalkyl polyamines such as bis(aminopropyl)ethylenediamine (BAPEDA) and ethylenepentamine are preferably EDA.

(Amino acid) Amino acids are compounds having 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, tyrosine, valine, histidine, histidine derivatives, asparagine, glutamine, proline Amino acid (proline), phenylalanine, the compound described in paragraph [0021] to paragraph [0023] of JP 2016-086094 A, and their salts. In addition, as histidine derivatives, the compounds described in JP 2015-165561 A, JP 2015-165562 and the like can be cited, and these contents are incorporated in this specification. In addition, examples of the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, carbonate, and acetate. Among them, arginine or a sulfur-containing amino acid containing a sulfur atom is preferred. Examples of the sulfur-containing amino acid include cystine, cysteine, ethionine, and methionine, and cystine or cysteine is preferred.

One kind of the second amine compound may be used alone, or two or more kinds may be used in combination. The content of the second amine compound in the cleaning solution is not particularly limited. Relative to the total mass of the cleaning solution, it is preferably 0.03% by mass to 30% by mass, more preferably 0.05% by mass to 15% by mass, and still more preferably 0.05% by mass to 5% by mass, particularly preferably 0.05% by mass to 3% by mass.

＜Surface active agent＞ The cleaning liquid may also contain a surfactant. The surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group (oleophilic group) in the molecule. Examples include anionic surfactants, cationic surfactants, and nonionic surfactants. Agent, and amphoteric surfactant.

Surfactants often have a hydrophobic group selected from aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and combinations of these. The hydrophobic group possessed by the surfactant is not particularly limited. Among them, when the hydrophobic group contains an aromatic hydrocarbon group, the carbon number of the aromatic hydrocarbon group is preferably 6 or more, and more preferably the carbon number of the aromatic hydrocarbon group is 10 or more. The upper limit of the carbon number of the aromatic hydrocarbon group is not particularly limited, but it is preferably 20 or less, and more preferably 18 or less. In addition, when the hydrophobic group does not contain an aromatic hydrocarbon group but is composed only of an aliphatic hydrocarbon group, the aliphatic hydrocarbon group preferably has 10 or more carbon atoms, more preferably the aliphatic hydrocarbon group has 12 or more carbon atoms, and more preferably The carbon number which is an aliphatic hydrocarbon group is 16 or more. The upper limit of the carbon number of the aliphatic hydrocarbon group is not particularly limited, but it is preferably 20 or less, and more preferably 18 or less.

(Anionic surfactant) Examples of the anionic surfactant contained in the cleaning solution include: phosphate-based surfactants having a phosphate group as a hydrophilic group (acid group), and phosphines having a phosphonic acid group as a hydrophilic group (acid group). Acid-based surfactants, sulfonic acid-based surfactants having a sulfo group as a hydrophilic group (acid group), carboxylic acid-based surfactants having a carboxyl group as a hydrophilic group (acid group), and a sulfate ester group as a hydrophilic group ( Acid base) sulfate-based surfactants. In terms of more excellent effects of the present invention, the cleaning liquid preferably contains an anionic surfactant.

-Phosphate ester surfactants- As a phosphate-based surfactant, a phosphate (alkyl ether phosphate), a polyoxyalkylene ether phosphate, and these salts are mentioned, for example. Phosphoric acid ester and polyoxyalkylene ether phosphoric acid generally include both monoester and diester, and monoester or diester can be used alone. Examples of the salt of the phosphate-based surfactant include sodium salt, potassium salt, ammonium salt, and organic amine salt. The alkyl group possessed by the phosphoric acid ester and polyoxyalkylene ether phosphate ester is not particularly limited, and is preferably an alkyl group having 2 to 24 carbon atoms, more preferably an alkyl group having 6 to 18 carbon atoms, and still more preferably a carbon number 12-18 alkyl group. The alkylene group possessed by the polyoxyalkylene ether phosphate ester is not particularly limited, but it is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an ethylene group or 1,2-propanediyl group. In addition, the number of repetitions of the oxyalkylene group in the polyoxyalkylene ether phosphate is preferably 1-12, more preferably 3-10.

As the phosphate-based surfactant, octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, and polyoxyethylene phosphate are preferred. Octyl ether phosphate, polyoxyethylene lauryl ether phosphate, or polyoxyethylene tridecyl ether phosphate.

As a phosphate-based surfactant, the compound described in paragraph [0012] to paragraph [0019] of JP-A-2011-040502 can also be cited, and these contents are incorporated in this specification.

-Phosphonic acid surfactants- Examples of phosphonic acid-based surfactants include alkylphosphonic acid and polyvinylphosphonic acid. In addition, for example, aminomethylphosphonic acid described in JP 2012-057108 A and the like can also be cited.

-Sulfuric acid-based surfactants- Examples of sulfonic acid-based surfactants include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, and sulfosuccinate Acid diesters, polyoxyalkylene alkyl ether sulfonic acids, and their salts.

The alkyl group possessed by the sulfonic acid-based surfactant is not particularly limited, and it is preferably an alkyl group with a carbon number of 10 or more, and more preferably an alkyl group with a carbon number of 12 or more. The upper limit of the carbon number of the alkyl group is not particularly limited, but it is preferably 24 or less. In addition, the alkylene group possessed by the polyoxyalkylene alkyl ether sulfonic acid is not particularly limited, but it is preferably an ethylene group or 1,2-propanediyl group. In addition, the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfonic acid is preferably 1-12, more preferably 1-6.

Specific examples of sulfonic acid-based surfactants include: hexane sulfonic acid, octane sulfonic acid, decane sulfonic acid, dodecane sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, and octyl benzene sulfonic acid , Dodecyl benzene sulfonic acid (DBSA), dinitro benzene sulfonic acid (DNBSA), and lauryl dodecyl phenyl ether disulfonic acid (lauryl dodecyl phenyl ether disulfonic acid) disulfonic acid, LDPEDSA). Among them, a sulfonic acid-based surfactant having an alkyl group with a carbon number of 10 or more is preferable, a sulfonic acid-based surfactant having an alkyl group with a carbon number of 12 or more is more preferable, and DBSA is still more preferable.

-Carboxylic acid surfactants- Examples of carboxylic acid-based surfactants include alkyl carboxylic acids, alkyl benzene carboxylic acids, polyoxyalkylene alkyl ether carboxylic acids, and salts of these. The alkyl group possessed by the carboxylic acid-based surfactant is not particularly limited, but is preferably an alkyl group having 7 to 25 carbon atoms, and more preferably an alkyl group having 11 to 17 carbon atoms. In addition, the alkylene group possessed by the polyoxyalkylene alkyl ether carboxylic acid is not particularly limited, but it is preferably an ethylene group or 1,2-propanediyl group. In addition, the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether carboxylic acid is preferably 1-12, more preferably 1-6.

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

-Sulfuric acid ester surfactants- As a sulfate-type surfactant, a sulfate (alkyl ether sulfate), a polyoxyalkylene ether sulfate, and these salts are mentioned, for example. The alkyl group possessed by the sulfate ester and polyoxyalkylene ether sulfate ester is not particularly limited, but is preferably an alkyl group having 2 to 24 carbon atoms, and more preferably an alkyl group having 6 to 18 carbon atoms. The alkylene group contained in the polyoxyalkylene ether sulfate is not particularly limited, and it is more preferably an ethylene group or a 1,2-propanediyl group. In addition, the number of repetitions of the oxyalkylene group in the polyoxyalkylene ether sulfate is preferably 1-12, more preferably 1-6. Specific examples of sulfate-based surfactants include lauryl sulfuric acid, myristyl sulfuric acid, and polyoxyethylene lauryl ether sulfuric acid.

The anionic surfactant is preferably selected from phosphate ester surfactants, sulfonic acid surfactants (more preferably sulfonic acid surfactants having an alkyl group with 12 or more carbon atoms), and phosphonic acid surfactants. At least one of the group consisting of the active agent and the carboxylic acid-based surfactant is more preferably a phosphate ester-based surfactant or a sulfonic acid-based surfactant having an alkyl group with 12 or more carbon atoms.

Anionic surfactants may be used alone or in combination of two or more. In terms of better corrosion prevention performance (especially corrosion prevention performance for semiconductor substrates containing Cu and/or Co), the cleaning solution preferably contains two or more anionic surfactants.

In the case where the cleaning liquid contains an anionic surfactant, the content of the anionic surfactant relative to the total mass of the cleaning liquid is preferably 0.01% by mass to 5.0% by mass, more preferably 0.05% by mass to 2.0% by mass %. In addition, as these anionic surfactants, what is necessary is just to use a commercially available anionic surfactant.

(Cationic surfactant) Examples of cationic surfactants include: primary alkyl amine salt to tertiary alkyl amine salt (for example, monostearyl ammonium chloride, distearyl ammonium chloride, and tristearyl ammonium chloride Etc.), and modified aliphatic polyamines (for example, polyethylene polyamines, etc.).

(Non-ionic surfactant) Examples of nonionic surfactants include polyoxyalkylene alkyl ethers (for example, polyoxyethylene stearyl ether, etc.), polyoxyalkylene alkenyl ethers (for example, polyoxyethylene Base oleyl ether, etc.), polyoxyethylene alkyl phenyl ether (for example, polyoxyethylene nonyl phenyl ether, etc.), polyoxyalkylene glycol (for example, polyoxyethylene propylene poly Oxyethylene glycol, etc.), polyoxyethylene monoalkylate (monoalkyl fatty acid ester polyoxyalkylene) (for example, polyoxyethylene monostearate, and polyoxyethylene Base monooleate and other polyoxyethylene monoalkylate), polyoxyalkylene dialkylate (dialkyl fatty acid ester polyoxyalkylene) (for example, polyoxyethylene distearate) Acid ester, and polyoxyethylene dialkylate such as polyoxyethylene dioleate), dipolyoxyethylene alkyl amide (for example, dipolyoxyethylene stearyl amide, etc.) ), sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene oxypropylene block copolymer, Acetylene glycol-based surfactants, and acetylene-based polyoxyethylene oxide.

(Amphoteric surfactant) As an amphoteric surfactant, for example, carboxybetaine (for example, alkyl-N,N-dimethylaminoacetic acid betaine and alkyl-N,N-dihydroxyethylaminoacetic acid betaine, etc.) , Sultaine (e.g., alkyl-N,N-dimethylsulfoethylammonium betaine, etc.), and imidazolium betaine (e.g., 2-alkyl-N-carboxymethyl-N-hydroxyl Ethyl imidazolium betaine, etc.).

As the surfactant, paragraph [0092] to paragraph [0096] of Japanese Patent Laid-Open No. 2015-158662, paragraph [0045] to paragraph [0046] of Japanese Patent Laid-Open No. 2012-151273, and Japan The compounds described in paragraph [0014] to paragraph [0020] of Japanese Patent Laid-Open No. 2009-147389 are incorporated into this specification.

Surfactants can be used alone or in combination of two or more. When the cleaning solution contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.05% to 2.0% by mass relative to the total mass of the cleaning solution.

＜pH adjuster＞ The cleaning liquid may also contain a pH adjusting agent. Examples of the pH adjuster include components other than the above-mentioned components, for example, 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 obtained by substituting four hydrocarbon groups (preferably an alkyl group) with a nitrogen atom or a salt thereof. Examples of quaternary ammonium compounds include quaternary ammonium hydroxide, quaternary ammonium fluoride, quaternary ammonium bromide, quaternary ammonium iodide, acetate of quaternary ammonium, and carbonate of quaternary ammonium.

The quaternary ammonium compound is preferably a quaternary ammonium hydroxide represented by the following formula (4).

_{^{(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 be the same or different from each other.

The alkyl group represented by R ⁸ is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. The alkyl group which may have a hydroxyl group or a phenyl group represented by R ⁸ is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, or a benzyl group, and more preferably a methyl group, an ethyl group, Propyl, butyl, or 2-hydroxyethyl, more preferably methyl, ethyl, or 2-hydroxyethyl.

Examples of quaternary ammonium compounds include 2-hydroxyethyl trimethylammonium hydroxide (choline), tetramethylammonium hydroxide (TMAH), and trimethylethylammonium hydroxide (trimethylethylammonium hydroxide). , TMEAH), diethyldimethylammonium hydroxide (DEDMAH), methyltriethylammonium hydroxide (MTEAH), tetraethylammonium hydroxide (TEAH), tetraethylammonium hydroxide Tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), bis(2-hydroxyethyl)dimethylammonium hydroxide, tris(2-hydroxyethyl)methyl hydrogen Ammonium oxide, tetrakis (2-hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and cetyltrimethylammonium hydroxide. As a quaternary ammonium compound other than the above-mentioned specific examples, for example, the compound described in paragraph [0021] of JP 2018-107353 A can be cited, and the content can be incorporated in this specification.

The quaternary ammonium compound used in the cleaning solution is preferably choline, TMAH, TMEAH, DEDMAH, MTEAH, TEAH, TPAH, TBAH, or bis(2-hydroxyethyl)dimethylammonium hydroxide, more preferably For choline.

In addition, in terms of excellent corrosion prevention performance, the cleaning liquid preferably contains a quaternary ammonium compound having an asymmetric structure. The so-called quaternary ammonium compound "has an asymmetric structure" means that the four hydrocarbon groups substituted for the nitrogen atom are all different. In other words, it means that at least one of the four hydrocarbon groups substituted with a nitrogen atom is a different kind 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 preferred.

One kind of quaternary ammonium compound may be used alone, or two or more kinds may be used in combination.

In the case where the cleaning liquid contains a pH adjusting agent, in terms of better cleaning performance, the content of the pH adjusting agent is preferably 0.05% by mass or more relative to the total mass of the cleaning liquid, and more preferably 0.1% by mass or more, more preferably 0.2% by mass or more. The upper limit of the content of the pH adjuster is not particularly limited. In terms of suppressing the reduction in cleaning performance due to aggregation of residue particles and/or resorption of residues in the cleaning step, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

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

＜Corrosion inhibitor＞ The cleaning solution may also contain an anti-corrosion agent. The cleaning solution may also contain an anti-corrosion agent. Furthermore, as the corrosion inhibitor, a component different from the above-mentioned component is preferable. Examples of the corrosion inhibitor include heterocyclic compounds having a heterocyclic structure and other corrosion inhibitors.

(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 a corrosion inhibitor that improves the corrosion prevention performance of the cleaning solution. Therefore, the cleaning liquid preferably contains a nitrogen-containing heteroaromatic compound. Examples of nitrogen-containing heteroaromatic compounds include azole compounds, pyridine compounds, pyrazine compounds, and pyrimidine compounds.

The azole compound is a compound containing at least one nitrogen atom and having a hetero five-membered ring having aromaticity. The number of nitrogen atoms contained in the hetero five-membered ring contained in the azole compound is not particularly limited, and it is preferably 2 to 4, more preferably 3 or 4. In addition, the azole compound may have a substituent on the hetero five-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 triazole compounds, imidazole compounds, pyrazole compounds, thiazole compounds, and tetrazole compounds.

As the triazole compound, for example, 1,2,4-triazole, 1-bis(2-hydroxyethyl)aminomethyl-5-methyl-1H benzotriazole, 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-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropyl benzotriazole, 2,3- Dicarboxypropyl benzotriazole, 4-hydroxybenzotriazole, 4-carboxybenzotriazole, and 5-methylbenzotriazole. Among them, it is preferably selected from 1,2,4-triazole, 1-bis(2-hydroxyethyl)aminomethyl-5-methyl-1H benzotriazole, and 1-bis(2-hydroxyl Ethyl) at least one of the group consisting of aminomethyl-4-methyl-1H-benzotriazole.

As the imidazole compound, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl- 2-Mercaptoimidazole, 4-hydroxyimidazole, 2,2'-biimidazole, 4-imidazole carboxylic acid, histamine, benzimidazole, 2-aminobenzimidazole, and adenine.

As the pyrazole compound, for example, pyrazole, 4-pyrazole carboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-amino-5 -Methylpyrazole, 3-aminopyrazole, and 4-aminopyrazole.

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

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

The azole compound is preferably an imidazole compound or a pyrazole compound, preferably selected from 1,2,4-triazole, 1-bis(2-hydroxyethyl)aminomethyl-5-methyl-1H At least one of benzotriazole and 1-bis(2-hydroxyethyl)aminomethyl-4-methyl-1H-benzotriazole.

The pyridine compound is a compound containing a hetero six-membered ring (pyridine ring) that contains one nitrogen atom and is aromatic. Examples of pyridine compounds include pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 2-cyanopyridine, 2-carboxypyridine, And 4-carboxypyridine.

A pyrazine compound is a compound containing an aromatic six-membered ring (pyrazine ring) containing two nitrogen atoms in the para position, and a pyrimidine compound is a compound containing aromaticity and two nitrogen atoms in the meta position. The hetero six-membered ring (pyrimidine ring) compound. Examples of pyrazine compounds include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetra Methylpyrazine, 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 preferred.

The nitrogen-containing heteroaromatic compound is preferably an azole compound or a pyrazine compound, more preferably an azole compound, and still more preferably a triazole compound.

The nitrogen-containing heteroaromatic compound may be used alone or in combination of two or more kinds. In the case where the cleaning liquid contains nitrogen-containing heteroaromatic compounds, the content of the nitrogen-containing heteroaromatic compounds in the cleaning liquid is not particularly limited, and is preferably 0.01% by mass to 10% relative to the total mass of the cleaning liquid % By mass, more preferably 0.05% by mass to 5% by mass.

(Other corrosion inhibitors) Other corrosion inhibitors include, for example, sugars 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 of these, and polyhydric alcohols such as Vinylpyrrolidone, cyanuric acid, barbituric acid and its derivatives, glucuronic acid, squaric acid, α-keto acid, adenosine and Its derivatives, purine compounds and their derivatives, phenanthroline, resorcinol, hydroquinone, nicotinamide and its derivatives, flavonol and its derivatives, anthocyanins ( anthocyanin) and its derivatives, and combinations of these.

＜Organic acid＞ The cleaning liquid may also contain organic acids. Organic acids are organic compounds that have acidic functional groups and exhibit acidity (pH value less than 7.0) in an aqueous solution. As an acidic functional group, a carboxyl group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a mercapto group are mentioned, for example. In addition, in this specification, the compound which functions as the said compound (1), an amino acid, and an anionic surfactant is not included in an organic acid.

The organic acid is not particularly limited. Examples include carboxylic acid (carboxylic acid) having a carboxyl group in the molecule, phosphonic acid (phosphonic acid) having a phosphonic acid group in the molecule, and sulfonic acid (sulfonic acid) having a sulfo group in the molecule. Preferably it is carboxylic acid or phosphonic acid.

The number of acidic functional groups possessed by the organic acid is not particularly limited, and is preferably from 1 to 4, and more preferably from 1 to 3. In addition, in terms of more excellent cleaning performance, the organic acid is preferably a compound that has a function of chelating with the metal contained in the residue, and more preferably has two or more metal ions in the molecule. Compounds that coordinately bond functional groups (ligands). As the ligand, the acidic functional group may be mentioned, 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. In terms of more excellent cleaning performance, a polycarboxylic acid having two or more carboxyl groups (more preferably two to four, and still more preferably two or three) carboxyl groups is preferred.

Examples of carboxylic acids include amino polycarboxylic acids, hydroxycarboxylic acids, and aliphatic carboxylic acids.

-Amino polycarboxylic acid- The amino polycarboxylic acid is a compound having one or more amino groups and two or more carboxyl groups as ligands in the molecule. Examples of amino polycarboxylic acids include aspartic acid, glutamic acid, butanediaminetetraacetic acid, diethylenetriamine pentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, and tertiary acid. Ethylenetetraaminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediamine tetraacetic acid (EDTA) , Trans-1,2-diamino cyclohexane tetraacetic acid (trans-1,2-diamino cyclohexane tetraacetic acid, CyDTA), ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexaethylene Methyl-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1 ,4,7,10-Tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid, (hydroxyethyl)ethylenediaminetriacetic acid, and imino diacetic acid (IDA) . Among them, DTPA, EDTA, CyDTA or IDA is preferred.

-Hydroxycarboxylic acid- The hydroxycarboxylic acid is a compound having one or more hydroxyl groups and one or more carboxyl groups in the molecule. In terms of maintaining the corrosion prevention performance of the cleaning solution and further improving the cleaning performance, the cleaning solution preferably contains hydroxycarboxylic acid. Examples of hydroxycarboxylic acids include malic acid, citric acid, glycolic acid, tartaric acid, and lactic acid. Glycolic acid, malic acid, tartaric acid, or citric acid is preferred, and citric acid is more preferred.

-Aliphatic carboxylic acid- Examples of aliphatic carboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, and maleic acid, preferably succinic acid or adipic acid . Especially by using adipic acid, compared with other chelating agents, the performance of the cleaning solution (cleaning performance and corrosion prevention) can be greatly improved. Regarding this specific effect of adipic acid, the detailed mechanism is not clear. When the complex is formed, a stable ring structure is formed.

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

The carboxylic acid is preferably hydroxycarboxylic acid or aliphatic carboxylic acid, more preferably cystine, cysteine, gluconic acid, glycolic acid, malic acid, tartaric acid, citric acid, succinic acid, or adipic acid , More preferably cysteine, gluconic acid, citric acid, succinic acid, or adipic acid.

One kind of carboxylic acid may be used alone, or two or more kinds may be used in combination. The content of the carboxylic acid in the cleaning liquid is not particularly limited, and it is preferably 10% by mass or less, and more preferably 5 mass% or less with respect to the total mass of the cleaning liquid. The lower limit is not particularly limited, and it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more with respect to the total mass of the cleaning liquid.

(Phosphonic acid) The phosphonic acid may be a monophosphonic acid having one phosphonic acid, or a polyphosphonic acid having two or more phosphonic acid groups. In terms of more excellent cleaning performance, a polyphosphonic acid having two or more phosphonic acid groups is preferred.

As polyphosphonic acid, the compound represented by formula (P1), the compound represented by formula (P2), and the compound represented by formula (P3) are mentioned, for example.

[化3]

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 C 1-10 alkyl group represented by R 11} in the formula (P1) may be any of linear, branched, and 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 addition, in the specific examples of the alkyl group described in this specification, n- represents a normal (normal-) body. As X in the formula (P1), a hydroxyl group is preferred.

As the polyphosphonic acid represented by the formula (P1), ethylene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (1-hydroxyethylidene-1,1'-diphosphonic acid, HEDPO), 1-hydroxypropylene-1,1'-diphosphonic acid, or 1-hydroxybutylene-1,1'-diphosphonic acid.

[化4]

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 the following formula (P4) The base represented.

[化5]

Wherein, in the same Q and R ¹³ in the formula (P2) Q and R ^13.

^{Examples of the alkylene group represented by R 12 in} the formula (P2) include linear or branched alkylene groups having 1 to 12 carbon atoms. The ^{alkylene represented by R 12} is preferably a linear or branched alkylene having 1 to 6 carbons, and more preferably a linear or branched alkylene having 1 to 4 carbons. The group is more preferably an ethylene group. ^{As the alkylene group represented by R 13 in} the formula (P2) and formula (P4), a straight-chain or branched-chain alkylene having 1 to 10 carbon atoms is mentioned, and a straight or branched alkylene group having 1 to 4 carbon atoms is preferred. The chain or branched alkylene group is more preferably a methylene group or an ethylene group, and still more preferably a methylene group. As Q in formula (P2) and formula (P4), -R ¹³ -PO ₃ H _{2 is} preferable. As Y in the formula (P2), the ^{group represented by -R 13} -PO ₃ H ₂ or the formula (P4) is preferable, and the group represented by the formula (P4) is more preferable.

The compound represented by the formula (P2) is preferably ethylamino bis(methylene phosphonic acid), dodecylamino bis(methylene phosphonic acid), nitrilotri(methylene phosphonic acid) Acid) (nitrilotris(methylene phosphonic acid), NTPO), ethylenediamine bis(methylene phosphonic acid) (EDDPO), 1,3-propanediamine bis(methylene phosphonic acid) ), ethylenediamine tetra(methylene phosphonic acid) (EDTPO), ethylenediamine tetra(methylene phosphonic acid), 1,3-propanediamine tetra(methylene phosphonic acid) Acid) (1,3-propylenediamine tetra (methylene phosphonic acid), PDTMP), 1,2-diaminopropane tetra (methylene phosphonic acid), or 1,6-hexamethylene diamine tetra (methylene phosphonic acid) Phosphonic acid).

[化6]

In the formula, R ¹⁴ and R ¹⁵ each independently represent an alkylene group having 1 to 4 carbon atoms, n represents an integer of ^{1 to 4,} and at least four of Z 1 to Z 4 and n Z ⁵ represent phosphonic acid groups. The alkyl group, the remainder represents the alkyl group.

The alkylene 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 methylene, ethylene, propylene, trimethylene, ethylmethylene, tetramethylene,} 2-methylethylene propylene, 2-methyltrimethylene, and ethyl ethylene, preferably ethylene. As n in 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 linear or branched chain alkyl groups having 1 to 4 carbon atoms. Preferably it is methyl. 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.} Examples of the alkyl groups having phosphonic acid groups represented by Z ¹ to Z ⁵ include linear or branched alkyl groups having 1 to 4 carbon atoms and having one or two phosphonic acid groups, preferably It is (mono)phosphinylmethyl or (mono)phosphinylethyl, more preferably (mono)phosphinylmethyl. ^{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 alkyl group having a phosphonic acid group.

The compound represented by the formula (P3) is preferably diethylenetriamine penta(methylene phosphonic acid) (DEPPO), diethylenetriamine penta(methylene phosphonic acid), and diethylenetriamine penta(methylene phosphonic acid). ), ethylenetetramine hexa (methylene phosphonic acid), or ethylene tetramine hexa (ethylene phosphonic acid).

As the polyphosphonic acid used in the cleaning solution, not only the compound represented by the formula (P1), the compound represented by the formula (P2), and the compound represented by the formula (P3) can be used, but also the International Publication No. The compound described in paragraph [0026] to paragraph [0036] of Specification No. 2018/020878 and the compound ((co)polymer) described in paragraph [0031] to paragraph [0046] of Specification No. 2018/030006, Incorporate these contents into this manual.

The number of phosphonic acid groups possessed by the phosphonic acid is preferably from 2 to 5, more preferably from 2 to 4, and still more preferably 2 or 3. In addition, the carbon number of the phosphonic acid is preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. The lower limit is not particularly limited, but it is preferably 1 or more. The phosphonic acid is preferably a compound exemplified as a preferable specific example among the compound represented by the formula (P1), the compound represented by the formula (P2), and the compound represented by the formula (P3) , More preferably HEDP.

Phosphonic acid can be used alone or in combination of two or more. The content of the phosphonic acid in the cleaning liquid is not particularly limited, and it is preferably 2% by mass or less, and more preferably 1% by mass or less with respect to the total mass of the cleaning liquid. The lower limit is not particularly limited, and it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more with respect to the total mass of the cleaning liquid.

The organic acid is preferably a carboxylic acid, more preferably an aliphatic carboxylic acid, and still more preferably adipic acid.

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

One kind of organic acid may be used alone, or two or more kinds may be used in combination. In terms of excellent cleaning performance (especially cleaning performance for semiconductor substrates containing W), the cleaning solution preferably contains two or more organic acids. The content of the organic acid in the cleaning liquid is not particularly limited, but it is preferably 10% by mass or less, and more preferably 5 mass% or less with respect to the total mass of the cleaning liquid. The lower limit is not particularly limited, and it is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more with respect to the total mass of the cleaning liquid.

<Reducing agent> The cleaning liquid may contain a reducing agent. ^{The reducing agent is a compound that has an oxidizing effect and has a function of oxidizing OH-} ions or dissolved oxygen contained in the cleaning solution, and is also called a deoxidizer. In terms of more excellent corrosion prevention performance of the cleaning liquid, the cleaning liquid preferably contains a reducing agent. The reducing agent used in the cleaning solution is not particularly limited, and examples thereof include ascorbic acid compounds, catechol compounds, hydroxylamine compounds, hydrazine compounds, and reducing sulfur compounds.

-Ascorbic acid compound- The ascorbic acid compound refers to at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives, and salts of these. Examples of ascorbic acid derivatives include ascorbic acid phosphate and ascorbic acid sulfate. As the ascorbic acid compound, ascorbic acid, ascorbic acid phosphate, or ascorbic acid sulfate is preferred, and ascorbic acid is more preferred.

-Catechol compounds- The catechol compound refers to at least one selected from the group consisting of pyrocatechol (benzene-1,2-diphenol) and catechol derivatives. The so-called catechol derivative refers to a compound in which at least one substituent in catechol is substituted. Examples of the substituents possessed by the catechol derivatives include hydroxyl groups, carboxyl groups, carboxylate groups, sulfo groups, sulfonate groups, and alkyl groups (preferably carbon number 1 to 6, more preferably carbon number 1. ~4), and aryl (preferably phenyl). The carboxyl group and sulfo group which the catechol derivative has as a substituent may be a salt with a cation. In addition, the alkyl group and the aryl group that the catechol derivative has as a substituent may further have a substituent. Examples of catechol compounds include catechol, 4-tert-butylcatechol, gallic acid, gallic acid, methyl gallate, 1,2,4-benzenetriol, And tiron.

—Hydroxyamine Compound— The hydroxylamine compound refers to at least one selected from the group consisting of hydroxylamine (NH ₂ OH), hydroxylamine derivatives, and salts of these. In addition, the term “hydroxyamine derivative” refers to a compound in which at least one organic group _{in hydroxylamine (NH 2 OH) is substituted.} It is preferably a compound different from the alkanolamine. The salt of hydroxylamine or hydroxylamine derivative may be an inorganic acid salt or an organic acid salt of hydroxylamine or hydroxylamine derivative. The salt of hydroxylamine or hydroxylamine derivative is preferably a salt with an inorganic acid, the inorganic acid being at least one non-metal selected from the group consisting of Cl, S, N and P to bond with hydrogen It is more preferably hydrochloride, sulfate, or nitrate.

As a hydroxylamine compound, the compound represented by following formula (3) or its salt is mentioned, for example.

[化7]

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 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear, branched, and cyclic. In addition, ^{at least one of R 5} and R ⁶ is preferably an organic group (more preferably, an alkyl group having 1 to 6 carbons). The alkyl group having 1 to 6 carbon atoms is preferably ethyl or n-propyl, and more preferably ethyl.

As the hydroxylamine compound, for example, hydroxylamine, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethyl Hydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethyl Hydroxylamine, and N,N-disulfoethylhydroxylamine. Among them, N-ethyl hydroxylamine, N, N-diethyl hydroxylamine (DEHA) or N-n-propyl hydroxylamine are preferred, and DEHA is more preferred.

-Hydrazine compound- The hydrazine compound refers to a compound in which the hydroxyl group of an acid is _{substituted with a hydrazine group (-NH-NH 2} ), and derivatives thereof (a compound in which at least one substituent in the hydrazine group is substituted). The hydrazine compound may have two or more hydrazine groups. Examples of the hydrazine compound include hydrazine carboxylate and hydrazine sulfonate, and carbohydrazide (CHZ) is preferred.

-Reducing sulfur compounds- The reducing sulfur compound is not particularly limited as long as it contains a sulfur atom and has a function as a reducing agent. Examples include mercaptosuccinic acid, dithiodiglycerol, and bis(2,3-dihydroxyl Propylthio) ethylene, 3-(2,3-dihydroxypropylthio)-2-methyl-propyl sulfonate, 1-thioglycerol, 3-mercapto-1-propanesulfonate sodium, 2- Mercaptoethanol, thioglycolic acid, and 3-mercapto-1-propanol. Among them, a compound having an SH group (mercapto compound) is preferred, and 1-thioglycerol, sodium 3-mercapto-1-propanesulfonate, 2-mercaptoethanol, 3-mercapto-1-propanol, or Thioglycolic acid.

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

One type of reducing agent may be used alone, or two or more types may be used in combination. In terms of better corrosion prevention performance (especially corrosion prevention performance for semiconductor substrates containing W), the cleaning solution preferably contains two or more reducing agents. In the case where the cleaning liquid contains a reducing agent, the content of the reducing agent is not particularly limited. Relative to the total mass of the cleaning liquid, it is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 5% by mass . In addition, commercially available reducing agents may be used for these reducing agents, or a reducing agent synthesized in accordance with a known method may be used.

＜Specific chelating agent＞ The cleaning liquid may also contain a specific chelating agent. The cleaning liquid may also contain a specific chelating agent having a nitrogen-containing group in the ligand. The specific chelating agent has two or more nitrogen-containing groups in one molecule as ligands for coordinate bonding with metal ions. Examples of the nitrogen-containing group as the ligand include an amino group.

As the specific chelating agent, for example, a compound having a biguanide group or a biguanide compound as a salt thereof can be cited. The number of biguanide groups that the biguanide compound has is not particularly limited, and it may have a plurality of biguanide groups. Examples of the biguanide compound include the compounds described in paragraph [0034] to paragraph [0055] of JP 2017-504190 A, and this content is incorporated in this specification.

As the compound having a biguanide group, ethylenedibiguanide, propylenedibiguanide, tetramethylenebibiguanide, pentamethylenebibiguanide, hexamethylenebibiguanide, heptamethylenebibiguanide, Octamethylene bisbiguanide, 1,1'-hexamethylene bis(5-(p-chlorophenyl)biguanide) (chlorhexidine), 2-(benzyloxymethyl)pentane -1,5-bis(5-hexyl biguanide), 2-(phenylthiomethyl)pentane-1,5-bis(5-phenethyl biguanide), 3-(phenylthio)hexane-1 ,6-bis(5-hexyl biguanide), 3-(phenylthio)hexane-1,6-bis(5-cyclohexyl biguanide), 3-(benzylthio)hexane-1,6-bis( 5-hexyl biguanide) or 3-(benzylthio)hexane-1,6-bis(5-cyclohexyl biguanide), more preferably loxidine. The salt of the compound having a biguanide group is preferably hydrochloride, acetate, or gluconate, and more preferably gluconate. As the specific chelating agent, Chlorhexidine Gluconate (CHG) is preferred.

The specific chelating agent may be used alone or in combination of two or more. In the case where the cleaning liquid contains a specific chelating agent, the content of the specific chelating agent in the cleaning liquid is not particularly limited. Relative to the total mass of the cleaning liquid, it is preferably 0.01% by mass to 10% by mass, more preferably 0.05% to 5% by mass.

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

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

(Oxidant) In addition to the above-mentioned components, the cleaning liquid may also include an oxidizing agent. Examples of the oxidizing agent include periodic acid or its salt, ammonium persulfate, potassium persulfate, hydrogen peroxide, ferric nitrate, diammonium cerium nitrate, ferric sulfate, hypochlorous acid, ozone, and peracetic acid. Periodic acid or its salt.

The oxidizing agent can be used alone or in combination of two or more. In the case where the cleaning liquid contains an oxidizing agent, relative to the total mass of the cleaning liquid, the content of the oxidizing agent is preferably 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 20% by mass, and still more preferably 5% by mass ～15% by mass.

(polymer) The cleaning liquid may also contain polymers. The polymer is a component different from the respective components. The weight average molecular weight of the polymer is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more. The upper limit is not particularly limited, but it 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 1,000 or more, more preferably 1,500 or more, and still more preferably 3,000 or more. The upper limit of the weight average molecular weight of the water-soluble polymer is not limited, for example, it is 1,500,000 or less, preferably 1,200,000 or less, more preferably 1,000,000 or less, and still more preferably 10,000 or less. In addition, the "weight average molecular weight" in this specification refers to the weight average molecular weight in terms of polyethylene glycol measured by Gel Permeation Chromatography (GPC). The polymer preferably contains a repeating unit having a carboxyl group (a repeating unit derived from (meth)acrylic acid, etc.). The content of the repeating unit having a carboxyl group relative to the total mass of the polymer is preferably 30% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and still more preferably 85% by mass to 100% by mass.

The polymer is also preferably a water-soluble polymer. Furthermore, the so-called "water-soluble polymer" refers to a compound in which two or more repeating units are connected in a linear or network shape via covalent bonds, and the mass dissolved in 100 g of water at 20°C is 0.1 g The above compound.

Examples of water-soluble polymers include: polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and their salts; styrene; , Copolymers of monomers such as α-methylstyrene, and/or 4-methylstyrene and acid monomers such as (meth)acrylic acid and/or maleic acid, and their salts; using formalin Polymers containing repeating units having aromatic hydrocarbon groups formed by condensation of benzenesulfonic acid, and/or naphthalenesulfonic acid, etc., and their salts; polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, Vinyl synthetic polymers such as polyvinyl pyridine, polypropylene amide, polyvinyl formamide, polyethylene imine, polyvinyl oxazoline, polyvinyl imidazole, and polyallylamine; hydroxyl ethyl Modified products of natural polysaccharides such as cellulose, carboxymethyl cellulose, and processed starch.

The water-soluble polymer may be a homopolymer or a copolymer obtained by copolymerizing two or more 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 an amine group. Monomers of, and monomers in the group consisting of monomers with heterocycles. The water-soluble polymer is also preferably a polymer consisting essentially of only structural units derived from a monomer selected from the group. The so-called polymer is essentially composed of only structural units derived from the monomers selected from the group, for example, relative to the mass of the polymer, the structural units derived from the monomers selected from the group The content of is preferably 95% by mass to 100% by mass, more preferably 99% by mass to 100% by mass.

As the polymer, for example, polyacrylic acid (Mw=700,000) (manufactured by Toagosei Co., Ltd., trade name "Jurymer AC-10H"), polyacrylic acid (Mw=55,000) (Toagosei Co., Ltd.) Manufactured by the company, brand name "Jurymer (Jurymer) AC-10L"), polyacrylic acid (Mw=6,000) (manufactured by Toagosei Co., Ltd., brand name "Aron (Aron) A-10SL"), styrene- Maleic acid copolymer (manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name "DKS discoat N-10") (Mw=3,200), styrene-maleic acid half ester copolymer (No. Manufactured by First Industrial Pharmaceutical Co., Ltd., trade name "DKS discoat N-14" (Mw=3,600), Na salt of formalin naphthalenesulfonate condensate (manufactured by First Industrial Pharmaceutical Co., Ltd., Trade name "Lavelin (Lavelin) FD-40", (Mw=2,700)), and polymaleic acid (MW=2,000) (manufactured by NOF Corporation, trade name "Nonpol (Nonpol) PWA-50W" ").

In addition, as the polymer, the water-soluble polymer described in paragraph [0043] to paragraph [0047] of JP 2016-171294 A can also be cited, and this content is incorporated in this specification.

One type of polymer may be used alone, or two or more types may be used in combination. When the cleaning liquid contains a polymer, the content of the polymer is preferably 0.001% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more relative to 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 still more preferably 5% by mass or less. If the content of the polymer is within the above range, the polymer is appropriately adsorbed on the surface of the substrate, which can help improve the corrosion prevention performance of the cleaning solution, and can also increase the viscosity and/or cleaning performance of the cleaning solution. The balance is good.

(Polyhydroxy compounds with a molecular weight of 500 or more) The cleaning liquid may also contain a polyhydroxy compound having a molecular weight of 500 or more. The polyhydroxy compound is a component different from the respective 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 (in the case of a molecular weight distribution, the weight average molecular weight) is 500 or more, preferably 500-3000.

As the polyhydroxy compound, for example, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; manninotriose, cellulose three Oligosaccharides such as cellotriose, gentianose, raffinose, melicitose, cellotetrose, and stachyose; starch, glycogen , Cellulose, xylose, chitin, and chitosan and other polysaccharides and their hydrolysates.

In addition, the polyhydroxy compound is also preferably cyclodextrin. Cyclodextrin is a type of cyclic oligosaccharide in which multiple D-glucoses are bonded by glucosidic bonds to obtain a cyclic structure. There are known compounds to which 5 or more (for example, 6 to 8) glucoses are bonded. Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and among them, γ-cyclodextrin is preferred.

The said polyhydroxy compound may be used individually by 1 type, and may use 2 or more types. In the case where the washing liquid contains the polyhydroxy compound, the content of the polyhydroxy compound relative to the total mass of the washing liquid is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, More preferably, it is 0.1% by mass to 3% by mass.

(Other pH adjusters) In order to adjust and maintain the pH of the cleaning solution, the cleaning solution may include a pH adjusting agent in addition to the above-mentioned components. Examples of the pH adjuster include basic compounds and acidic compounds other than the above-mentioned components.

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

Commercially available compounds can be used for these basic compounds, or compounds suitably synthesized by a known method can also be used.

As an acidic compound, an inorganic acid is mentioned, for example. Examples of inorganic acids include hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, boric acid, and hexafluorophosphoric acid. In addition, salts of inorganic acids can also be used, such as ammonium salts of inorganic acids, more specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, ammonium borate , And ammonium hexafluorophosphate. As the inorganic acid, phosphoric acid or phosphate is preferred, and phosphoric acid is more preferred.

As an acidic compound, if it is a compound which becomes an acid or an acid radical ion (anion) in an aqueous solution, the salt of an acidic compound can also be used. As the acidic compound, a commercially available compound may be used, or a compound appropriately synthesized by a known method may be used.

One kind of pH adjusting agent may be used alone, or two or more kinds may be used in combination. When the cleaning liquid contains a pH adjuster, its content can be selected according to the types and amounts of other ingredients and the pH value of the target cleaning liquid. Relative to the total mass of the cleaning liquid, it is preferably 0.01% by mass ~3% by mass, more preferably 0.05% by mass to 1% by mass.

(Fluorine compound) As the fluorine compound, the compound described in paragraph [0013] to paragraph [0015] of JP 2005-150236 A can be cited, and this content is incorporated in this specification.

(Organic solvents) As the organic solvent, any of known organic solvents can be used, and hydrophilic organic solvents such as alcohols and ketones are preferred. The organic solvent can be used alone or in combination of two or more.

(Other chelating agents) The cleaning liquid may also contain chelating agents other than the organic acid having a chelating function and the specific chelating agent. Examples of other chelating agents include inorganic acid-based chelating agents such as condensed phosphoric acid and salts thereof. As condensed phosphoric acid and its salt, pyrophosphoric acid and its salt, metaphosphoric acid and its salt, tripolyphosphoric acid and its salt, and hexametaphosphoric acid and its salt are mentioned, for example. The use amount of other corrosion inhibitors, other chelating agents, polymers, fluorine compounds, and organic solvents is not particularly limited, as long as they are appropriately set within a range that does not hinder the effects of the present invention.

Furthermore, the content of each component in the cleaning solution can be determined by gas chromatography-mass spectrometry (GC-MS: Gas Chromatography-Mass Spectrometry), liquid chromatography-mass spectrometry (LC-MS: Liquid Chromatography). -Mass Spectrometry) method, and ion-exchange chromatography (IC: Ion-exchange Chromatography) method and other well-known methods for measurement.

〔Physical properties of detergent〕 ＜Metal content＞ In the cleaning solution, the content of metals (Fe, Co, Na, K, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag metal elements) contained as impurities in the liquid ( Measured as ion concentration) are preferably 5 ppm by mass or less, and more preferably 1 ppm by mass or less. Since it is assumed that a cleaner with higher purity is required in the manufacture of the most advanced semiconductor elements, the metal content is further preferably less than 1 mass ppm, that is, the mass ppb level or less, and particularly preferably 100 mass ppb or less , The best is less than 10 quality ppb. The lower limit is not particularly limited, but 0 is preferred.

Examples of methods for reducing the metal content include: distillation, filtration using ion exchange resins or filters, etc. Refined treatment. As another method of reducing the metal content, for example, the use of a container with less elution of impurities described later as a container for accommodating the raw material or the manufactured cleaning solution can be cited. In addition, it may also be exemplified that a fluorine-based resin lining is applied to the inner wall of the pipe so that the metal component does not elute from the pipe or the like during the production of the cleaning solution.

＜Coarse particles＞ The cleaning solution may also contain coarse particles, but its content is preferably low. Here, the so-called coarse particles refer to particles having a diameter (particle diameter) of 0.4 μm or more when the shape of the particle is regarded as a sphere. As the content of coarse particles in the cleaning solution, the content of particles having a particle diameter of 0.4 μm or more is preferably 1,000 or less per 1 mL of the cleaning solution, and more preferably 500 or less. The lower limit is not particularly limited, and 0 can be cited. In addition, it is more preferable that the content of particles having a particle diameter 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 correspond to the following substances: particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw materials, and as contaminants in the preparation of the cleaning liquid Particles such as dust, dust, organic solids, and inorganic solids that are brought in, and are ultimately in the form of particles that do not dissolve in the cleaning solution. The content of the coarse particles present in the cleaning solution can be measured in a liquid phase using a commercially available measuring device of a light scattering type particle in liquid measuring method using a laser as a light source. As a method of removing coarse particles, for example, purification treatments such as filtering described later can be cited.

The cleaning liquid can also be made into a set that divides its raw materials into multiple parts.

〔Manufacturing of washing liquid〕 The cleaning liquid can be produced by a known method. Hereinafter, the manufacturing method of the cleaning liquid will be described in detail.

＜Adjusting steps＞ The method of adjusting the cleaning solution is not particularly limited. For example, the cleaning solution can be produced by mixing the components. The order and/or timing of mixing the components are not particularly limited. For example, the following method may be mentioned: the compound (1) and the alkanolamine, and optional components are sequentially added to a container containing purified water After that, stirring and mixing are performed, and a pH adjusting agent is added to adjust the pH of the mixed solution, thereby preparing. In addition, when adding water and each component to a container, they may be added together, or may be divided into multiple times and added.

The stirring device and stirring method used in the liquid adjustment of the cleaning liquid are not particularly limited, and as the stirring machine or the dispersing machine, a known device may be used. As a stirrer, an industrial mixer, a mobile stirrer, a mechanical stirrer (mechanical stirrer), and a magnetic stirrer (magnetic stirrer) are mentioned, for example. Examples of the disperser include industrial dispersers, homogenizers, ultrasonic dispersers, and bead mills.

The mixing of the components in the liquid conditioning step of the cleaning solution, the purification treatment described later, and the storage of the produced cleaning solution are preferably performed at 40°C or lower, and more preferably at 30°C or lower. In addition, it is preferably 5°C or higher, and more preferably 10°C or higher. By performing liquid conditioning, treatment, and/or storage of the cleaning solution within the above-mentioned temperature range, the performance can be stably maintained for a long period of time.

(Refined processing) It is preferable to preliminarily subject any one or more of the raw materials used for the preparation of the cleaning solution to a refining treatment. 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 preferably purified until the purity of the raw material reaches 99% by mass or more, and more preferably until the purity of the original solution reaches 99.9% by mass or more.

As a specific method of the purification treatment, 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 a refining treatment, a plurality of the refining methods described above can also be combined and implemented. For example, the raw material may be subjected to primary purification through the RO membrane, and then secondary purification through the purification device containing cation exchange resin, anion exchange resin, or mixed bed ion exchange resin. In addition, the refining treatment can also be carried out multiple times.

(Filtering) As a filter used in filtering, there are no particular restrictions if it is convenient for users in filtering purposes from before. For example, fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinylether copolymer (PFA), polyamide resins such as nylon, and A filter of at least one resin in the group consisting of polyolefin resins (including high-density or ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these materials, it is preferably selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide resin (including nylon). At least one material, more preferably a fluororesin filter. By using a filter formed of these materials to filter the raw material, it is possible to effectively remove foreign matter with high polarity that is likely to cause defects.

The critical surface tension of the filter is preferably 70 mN/m to 95 mN/m, more preferably 75 mN/m to 85 mN/m. Furthermore, the value of the critical surface tension of the filter is the nominal value of the manufacturer. By using a filter with a critical surface tension in the above-mentioned range, it is possible to effectively remove foreign matter with high polarity that is likely to cause defects.

The pore size of the filter is preferably 2 nm to 20 nm, more preferably 2 nm to 15 nm. By setting it in this range, it is possible to reliably remove fine foreign matter such as impurities and aggregates contained in the raw material while suppressing clogging of the filter. The pore size here can refer to the nominal value of the filter manufacturer.

Filtering can be performed only once or more than twice. In the case of performing filtering more than twice, the filters used may be the same or different.

In addition, filtering is preferably performed at room temperature (25°C) or lower, more preferably 23°C or lower, and still more preferably 20°C or lower. In addition, it is preferably 0°C or higher, more preferably 5°C or higher, and still more preferably 10°C or higher. By filtering within the 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 removed efficiently.

(container) As long as the corrosivity and the like are not a problem, the cleaning solution (in the form of the kit or the diluent described later) can be filled into any container for storage, transportation, and use.

The container is preferably a container for semiconductor applications, in which the cleanliness of the container is high, and the elution of impurities from the inner wall of the container of the container to each liquid is suppressed. Examples of such a container include various containers commercially available as containers for semiconductor cleaning liquids. For example, the "clean bottle" series manufactured by Aicello Chemical Co., Ltd., and Kodama ( Kodama) "pure bottle" manufactured by the resin industry, etc., but not subject to these restrictions. In addition, as a container for accommodating the cleaning liquid, it is preferable that the inner wall of the accommodating part and other liquid contact parts that come into contact with each liquid are made of fluorine-based resin (perfluororesin), or after rust prevention and metal elution prevention treatments are applied. Metal container. The inner wall of the container is preferably made of at least one resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from the resin, or stainless steel, Heshi Special alloy (Hastelloy), Inconel (Inconel), and Monel (Monel) and other metal formation after rust prevention and metal elution prevention treatment.

As the different resin, a fluorine-based resin (perfluororesin) is preferred. In this way, by using a container whose inner wall is a fluorine-based resin, compared with a container whose inner wall is a polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, the elution of ethylene or propylene oligomers can be suppressed. The occurrence of a bad situation. As a specific example of such a container whose inner wall is a fluorine-based resin, for example, a FluoroPure PFA composite cylinder manufactured by Entegris, etc. can be cited. In addition, page 4 of Japanese Patent Publication No. Hei 3-502677, page 3 of International Publication No. 2004/016526, and pages 9 and 16 of International Publication No. 99/46309 may also be used. The container described in.

In addition, for the inner wall of the container, in addition to the fluorine-based resin, quartz and electrolytically polished metal materials (that is, electrolytically polished metal materials) can also be preferably used. The metal material used in the manufacture of the electrolytically ground metal material preferably contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel exceeds the total mass of the metal material. The 25% by mass metal material includes, for example, stainless steel, nickel-chromium alloy, and the like. 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. In addition, the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but it is usually preferably 90% by mass or less.

The method of electrolytic polishing of a metal material is not specifically limited, A well-known method can be used. For example, the method described in paragraph [0011]-paragraph [0014] of Japanese Patent Laid-Open No. 2015-227501 and paragraph [0036]-paragraph [0042] of Japanese Patent Laid-Open No. 2008-264929 can be used. .

It is preferable to clean the inside of these containers before filling the cleaning liquid. The liquid used in washing preferably has a reduced amount of metal impurities in the liquid. The cleaning liquid can be bottling into a gallon bottle or coated bottle after manufacture for transportation and storage.

For the purpose of preventing changes in the composition of the cleaning solution in storage, the inside of the container can also be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or more. Particularly preferred is a gas with a low moisture content. In addition, during transportation and storage, the temperature may be normal, and in order to prevent deterioration, the temperature may be controlled within the range of -20°C to 20°C.

(Clean room) It is preferable that all operations, processing analysis, and measurement including the manufacturing of the cleaning solution, the opening of the container, the cleaning, and the filling of the cleaning solution, are performed in a clean room. The clean room preferably meets the 14644-1 clean room standard. Preferably, it satisfies any of ISO (International Standardization Organization) level 1, ISO level 2, ISO level 3, and ISO level 4, more preferably satisfies ISO level 1 or ISO level 2, and more preferably satisfies ISO class 1.

＜Dilution step＞ The cleaning solution is preferably used for cleaning the semiconductor substrate after a dilution step of diluting with a diluent such as water.

The dilution rate of the cleaning solution in the dilution step may be appropriately adjusted according to the type and content of each component, and the semiconductor substrate to be cleaned. The ratio of the diluted cleaning solution to the cleaning solution before dilution is The volume ratio is preferably 10 times to 10000 times, more preferably 20 times to 3000 times, and still more preferably 50 times to 1000 times. In addition, in terms of more excellent effects of the present invention, the cleaning solution is preferably diluted with water.

The specific method of the dilution step of diluting the cleaning liquid is not particularly limited, as long as it is performed according to the liquid adjustment step of the cleaning liquid. In addition, the stirring device and the stirring method used in the dilution step are also not particularly limited, as long as they are used for the well-known stirring device listed in the liquid adjustment step of the cleaning solution.

It is preferable to refine the water used in the dilution step in advance. In addition, it is preferable to perform a purification treatment on the diluted washing liquid obtained in the dilution step. The purification treatment is not particularly limited. Examples of the purification treatment for the cleaning liquid include ion component reduction treatment using ion exchange resins or RO membranes, and foreign matter removal using filtering. , It is preferable to perform any of these treatments.

[Purpose of cleaning liquid] The cleaning solution is used in the cleaning step of cleaning the semiconductor substrate after the chemical mechanical polishing (CMP) process. In addition, the cleaning solution can also be used for cleaning the semiconductor substrate in the manufacturing process of the semiconductor substrate. As described above, in the cleaning of the semiconductor substrate, a diluted cleaning solution obtained by diluting the cleaning solution can also be used.

〔Object to be cleaned〕 As the object to be cleaned by the cleaning solution, for example, a semiconductor substrate having a metal-containing material can be cited. In addition, the term "on the semiconductor substrate" in this specification includes, for example, any of the front and back sides, side surfaces, and the inside of the groove of the semiconductor substrate. In addition, the so-called metal-containing material on the semiconductor substrate includes not only the case where the metal-containing material is directly present on the surface of the semiconductor substrate, but also the case where the metal-containing material is interposed by another layer on the semiconductor substrate. The metal content on the semiconductor substrate preferably contains cobalt and tungsten. That is, a semiconductor substrate containing cobalt and tungsten is preferable.

Examples of metals contained in the metal content include: selected from Cu (copper), Co (cobalt), W (tungsten), Ti (titanium), Ta (tantalum), Ru (ruthenium), Cr (chromium), and Hf (Hafnium), Os (osmium), Pt (platinum), Ni (nickel), Mn (manganese), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium) Of at least one metal M.

The metal-containing substance may be a substance containing a metal (metal atom), and examples thereof include a simple substance of metal M, an alloy containing metal M, an oxide of metal M, a nitride of metal M, and an oxynitride of metal M. In addition, the metal-containing material may be a mixture containing two or more of these compounds. Furthermore, the oxides, nitrides, and oxynitrides may also be composite oxides, composite nitrides, and composite oxynitrides containing metals. The content of metal atoms in the metal-containing material is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more with respect to the total mass of the metal-containing material. Since the metal-containing material may be the metal itself, the upper limit is 100% by mass or less.

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

The semiconductor substrate that is the object to be cleaned by the cleaning solution is not particularly limited. For example, a substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of a wafer constituting the semiconductor substrate is exemplified.

Specific examples of the wafers constituting the semiconductor substrate include silicon (Si) wafers, silicon carbide (SiC) wafers, and silicon-containing resin-based wafers (glass epoxy wafers) that contain silicon-based materials. Wafers, gallium phosphate (GaP) wafers, gallium arsenic (GaAs) wafers, and indium phosphorus (InP) wafers. As a silicon wafer, it can be an n-type silicon wafer formed by doping a silicon wafer with pentavalent atoms (for example, phosphorus (P), arsenic (As), and antimony (Sb), etc.), and a silicon wafer A p-type silicon wafer doped with trivalent atoms (for example, boron (B), gallium (Ga), etc.). The silicon used as the silicon wafer may be any of amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon (polysilicon), for example. Among them, the cleaning solution is useful for wafers containing silicon-based materials, such as silicon wafers, silicon carbide wafers, and silicon-containing resin-based wafers (glass epoxy wafers).

The semiconductor substrate may also have an insulating film on the wafer. As a specific example of the insulating film, a silicon oxide film (for example, a silicon dioxide (SiO ₂ ) film, and a _{tetraethyl orthosilicate (Si(OC 2} H ₅ ) ₄ ) film (TEOS (tetra Ethyl ester, tetraethyl orthosilicate film), etc.), silicon nitride film (for example, silicon nitride (Si ₃ N ₄ ), and silicon carbonitride (SiNC), etc.), and low dielectric constant (Low-k) film (For example, a silicon oxide (SiOC) film doped with carbon, and a silicon carbide (SiC) film, etc.).

As the metal film of the semiconductor substrate, a metal film containing at least one metal selected from the group consisting of copper (Cu), cobalt (Co), and tungsten (W), for example, mainly copper Component film (copper-containing film), cobalt-based film (cobalt-containing film), tungsten-based film (tungsten-containing film), and a group consisting of Cu, Co, and W A metal film composed of at least one alloy in the group. The semiconductor substrate preferably has Co and W. That is, the semiconductor substrate particularly preferably has at least a metal containing material containing Co (preferably a cobalt containing film) and a metal containing material containing W (preferably a tungsten containing film).

Examples of the copper-containing film include a wiring film (copper wiring film) containing only metallic copper, and a wiring film (copper alloy wiring film) made of an alloy containing metallic copper and other metals. As a specific example of the copper alloy wiring film, one or more metals selected from aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), tantalum (Ta), and tungsten (W) can be cited , Wiring film made of an alloy with copper. More specifically, include: copper-aluminum alloy wiring film (CuAl alloy wiring film), copper-titanium alloy wiring film (CuTi alloy wiring film), copper-chromium alloy wiring film (CuCr alloy wiring film), copper-manganese Alloy wiring film (CuMn alloy wiring film), copper-tantalum alloy wiring film (CuTa alloy wiring film), copper-tungsten alloy wiring film (CuW alloy wiring film), etc.

Examples of the cobalt-containing film (a metal film containing cobalt as a main component) include: a metal film containing only metallic cobalt (cobalt metal film), and a metal film containing an alloy of metallic cobalt and other metals (cobalt alloy metal film) ). As a specific example of a cobalt alloy metal film, it may be selected from titanium (Ti), chromium (Cr), iron (Fe), nickel (Ni), molybdenum (Mo), palladium (Pd), tantalum (Ta), and A metal film made of an alloy of at least one metal in the group consisting of tungsten (W) and cobalt. More specifically, they include: 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-tantalum alloy metal film (CoTa alloy metal film), and cobalt -Tungsten alloy metal film (CoW alloy metal film), etc. The cleaning solution is useful for a substrate having a cobalt-containing film. Among the cobalt-containing films, the cobalt metal film is mostly used as a wiring film, and the cobalt alloy metal film is mostly used as a barrier metal.

In addition, it is sometimes preferable to use a cleaning solution to clean a substrate that has at least a copper-containing wiring film on the upper part of the wafer constituting the semiconductor substrate, and is composed of only metal cobalt and serves as a copper-containing wiring The barrier metal of the film is a metal film (cobalt barrier metal), and the copper-containing wiring film is in contact with the cobalt barrier metal on the surface of the substrate.

As a tungsten-containing film (a metal film containing tungsten as a main component), for example, a metal film containing only tungsten (tungsten metal film), and a metal film containing an alloy of tungsten and other metals (tungsten alloy metal film) can be cited. Specific examples of the tungsten alloy metal film include, for example, 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.

The method of 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 generally performed in this field. As a method of forming an insulating film, for example, the following method can be cited: the wafer constituting the semiconductor substrate is heat-treated in the presence of oxygen to form a silicon oxide film, and then gaseous silane and ammonia are flowed in, and chemical vapor vaporization is used. The silicon nitride film is formed by the CVD (Chemical Vapor Deposition) method. As a method of forming a copper-containing wiring film, a cobalt-containing film, and a tungsten-containing film, for example, the following method can be cited: a circuit is formed on a wafer with the insulating film using a known method such as a resist, and then gold plating is used And CVD method and other methods to form a copper-containing wiring film, a cobalt-containing film, and a tungsten-containing film.

＜CMP treatment＞ CMP treatment is, for example, a treatment to flatten the surface of a substrate having metal wiring films, barrier metals, and insulating films by using a chemical action of a polishing slurry containing abrasive particles (abrasive grains) and a combined action of mechanical polishing. . On the surface of the semiconductor substrate after the CMP process, there may be leftovers derived from the abrasive grains used in the CMP process (for example, silicon dioxide and aluminum oxide, etc.), polished metal wiring films, and barrier metals. Impurities such as metal impurities (metal residues). These impurities, for example, may short-circuit between wirings and degrade the electrical characteristics of the semiconductor substrate. Therefore, the semiconductor substrate subjected to the CMP process is subjected to a cleaning process for removing these impurities from the surface. As a specific example of a semiconductor substrate subjected to CMP treatment, there can be cited the CMP treatment described in "Journal of the Japan Society of Precision Engineering" (Vol. 84, No. 3, 2018). Substrate, but it is not limited by this.

〔Method for cleaning semiconductor substrate〕 The cleaning method of the semiconductor substrate is not particularly limited as long as it includes a cleaning step of cleaning the semiconductor substrate after the CMP process using the cleaning solution. The cleaning method of the semiconductor substrate preferably includes a step of applying the diluted cleaning solution obtained in the dilution step to the semiconductor substrate after the CMP process is performed to perform cleaning.

The cleaning step for cleaning the semiconductor substrate with the cleaning solution is not particularly limited if it is a well-known method performed on the semiconductor substrate after the CMP process, and the following method generally performed in this field can be suitably adopted: The substrate is supplied with a cleaning solution, and the cleaning member such as a brush is brought into physical contact with the surface of the semiconductor substrate to remove residues. The immersion type of the semiconductor substrate is immersed in the cleaning solution; while the semiconductor The rotating (dripping) method in which the cleaning liquid is dropped while the substrate is rotating; and the spray (spray) method in which the cleaning liquid is sprayed. In the immersion cleaning, it is preferable to perform ultrasonic treatment on the cleaning solution impregnated with the semiconductor substrate in terms of further reducing the impurities remaining on the surface of the semiconductor substrate. The washing step may be performed only once, or may be performed more than twice. When washing is performed twice or more, the same method may be repeated repeatedly, or different methods may be combined.

As a method for cleaning the semiconductor substrate, either a piece-by-piece method or a batch method can be used. The piece-by-piece method is usually a method of processing semiconductor substrates one by one, and the batch method is usually a method of processing multiple semiconductor substrates at the same time.

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

The cleaning time in the cleaning of the semiconductor substrate depends on the type and content of the components contained in the cleaning solution, and therefore cannot be generalized. From a practical point of view, it is preferably 10 seconds to 2 minutes, more preferably 20 seconds ~1 minute and 30 seconds, more preferably 30 seconds to 1 minute.

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

In the cleaning of the semiconductor substrate, in order to further improve the cleaning ability of the cleaning solution, a mechanical stirring method may also be used. As a mechanical stirring method, for example, a method of circulating a cleaning solution on a semiconductor substrate, a method of flowing a cleaning solution or spraying a cleaning solution on a semiconductor substrate, and a method of using ultrasonic or megasonic (megasonic) ) The method of stirring the cleaning liquid, etc.

After the semiconductor substrate is cleaned, a step of rinsing the semiconductor substrate with a solvent to clean it (hereinafter referred to as a “rinsing step”) may also be performed. The rinsing step is preferably performed continuously after the cleaning step of the semiconductor substrate, and is a step of rinsing with a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes. The rinsing step can also be carried out using the mechanical stirring method.

Examples of the rinsing solvent include: water (preferably DI: De Ionize), methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl Sulfide, ethyl lactate, and propylene glycol monomethyl ether acetate. In addition, an aqueous rinse with a pH of over 8 (diluted aqueous ammonium hydroxide, etc.) can also be used. As a method of bringing the rinsing solvent into contact with the semiconductor substrate, the method of bringing the cleaning solution into contact with the semiconductor substrate can be similarly applied.

In addition, a drying step of drying the semiconductor substrate may be performed after the rinsing step. The drying method is not particularly limited, and examples include: spin drying, a method of flowing dry gas on a semiconductor substrate, a method of heating the substrate by a heating plate or an infrared lamp-like heating mechanism, and Marangoni (Marangoni) ) Drying method, Rotagoni drying method, IPA (isopropyl alcohol) drying method, and any combination of these. [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, and the like 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 present invention is not limitedly interpreted by the examples shown below.

In the following examples, the pH value of the cleaning solution was measured at 25°C using a pH meter (manufactured by Horiba Manufacturing Co., Ltd., model "F-74") and based on JIS Z8802-1984. In addition, when manufacturing the cleaning solutions of the Examples and Comparative Examples, the handling of the container, the adjustment, filling, storage, and analysis of the cleaning solution were all performed in a clean room that satisfies ISO Class 2 or lower.

[Materials of the cleaning solution] The following compounds are used in order to produce the cleaning solution. In addition, the various components used in the examples are all components classified as semiconductor grades or components classified as high-purity grades based on this.

[Compound (1)] ·Gluconic acid: ClogP value is -3.17, Hansen solubility parameter δh is 30.3 (MPa) ^0.5 , δd is 17.3 (MPa) ^0.5 , δp is 12.7 (MPa) ^0.5 , Fujifilm and Ko Pure Chemical (Stock) Manufacturing·Mucic acid: ClogP value is -1.46, δh of Hansen solubility parameter is 31.0 (MPa) ^0.5 , δd is 17.3 (MPa) ^0.5 , δp is 14.2 (MPa) ^0.5 , Fujifilm and Ko Pure Chemical (stock ) Manufacturing·Glyceric acid: ClogP value is -1.92, Hansen solubility parameter δh is 27.5 (MPa) ^0.5 , δd is 18.1 (MPa) ^0.5 , δp is 13.4 (MPa) ^0.5 , manufactured by Fujifilm and Ko Pure Chemical [Alkanolamine] ·2-Amino-2-methyl-1-propanol (AMP): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ·2-amino-2-methylpropanediol (AMPD): Fujifilm Wako Pure Chemical Industries, Ltd. · Tris: Tris: Fujifilm Wako Pure Chemical Industries, Ltd. [Second Amine Compound] · Piperazine: Fujifilm Wako Pure Chemical Industries, Ltd. · Ethylenediamine: Fujifilm Wako Pure Chemical Industries, Ltd. · Morpholine: Fujifilm Wako Pure Chemical Industries, Ltd. · N-methylpiperazine (NMPZ): Fujifilm Wako Pure Chemical Industries, Ltd. · Arginine (L-arginine): manufactured by Tokyo Chemical Industry Co., Ltd. · Diazabicycloundecene (DBU): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. [corrosion inhibitor] ･azole compound 1: 2, 2' -{[(5-Methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol·1,2,4-triazole: Fuji Film Wako Pure Chemical Industries (stock) manufacturing [additives ] · alkyl (EO) ₃ phosphate _{(alkyl (EO) 3 phosphate ester} ): Takemoto oil & fat Co., Ltd. · periodic acid: Japan Sigma-Aldrich (Sigma-Aldrich Japan) · adipic: tokyo Chemical industry Co. Co., Ltd. · Succinic acid: Tokyo Chemical Industry Co., Ltd. · Histidine: Fuji Film Wako Pure Chemical Industries Co., Ltd. · Polyacrylic acid (Mw=700,000): Toa Gosei Co., Ltd., brand name "Jurymer (Jurymer) )AC-10H" ·Polyacrylic acid (Mw=55,000): manufactured by Toagosei Co., Ltd., trade name "Jurymer AC-10L" ·Polyacrylic acid (Mw=6,000): manufactured by Toagosei Co., Ltd., Trade name "Aron (Aron) A-10SL" · Polymaleic acid (Mw=2,000): manufactured by NOF Corporation, trade name "Nonpol (Nonpol) PWA-50W" · Styrene-maleic acid copolymer Material: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name "DKS Discourt (DKS Discoat N-10" · Styrene-maleic acid half ester copolymer: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name "DKS Discoat N-14" · Condensation of formalin naphthalenesulfonate Substance Na salt: manufactured by Daiichi Industrial Pharmaceutical Co., Ltd., trade name "Lavelin (Lavelin) FD-40" · γ-cyclodextrin: manufactured by Cyclochem Co., Ltd. [pH adjuster 〕 ·2-Hydroxyethyl trimethylammonium hydroxide (choline): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

In addition, in the manufacturing steps of the cleaning solution in this embodiment _{, any one of choline, potassium hydroxide (KOH), and sulfuric acid (H 2} SO ₄ ), and commercially available ultrapure water ( Fujifilm Wako Pure Chemical Industries, Ltd. is used as a pH adjuster.

[Manufacturing of washing liquid] Next, using Example 1 as an example, the method of manufacturing the cleaning solution will be described. After adding gluconic acid, AMP, and piperazine to the ultrapure water in an amount to become the content described in Table 1, respectively, 2.3% by mass of DBU was added so that the pH of the prepared cleaning solution became 11.0. The obtained mixed liquid was sufficiently stirred with a stirrer to obtain the washing liquid of Example 1.

According to the manufacturing method of Example 1, washing liquids of Examples 2 to 42 and Comparative Examples 1 to 5 having the compositions shown in Table 1 were respectively manufactured. Furthermore, each item of the Hansen solubility parameter or ClogP value is determined by the method described above.

[Evaluation of Cleaning Performance] The cleaning performance (residue removal performance) when the metal film after chemical mechanical polishing was cleaned using the cleaning solution produced by the above method was evaluated. Using FREX300S-II (polishing device, manufactured by Ebara Seisakusho Co., Ltd.), a wafer (8 inches in diameter) with a metal film containing copper, tungsten, or cobalt on the surface was polished. For wafers with a metal film containing copper on the surface, CSL9044C and BSL8176C (trade names, both manufactured by FUJIFILM Planar Solutions) were used as polishing liquids for polishing. This suppresses variation in the cleaning performance evaluation caused by the polishing liquid. Similarly, for wafers having a metal film containing cobalt on the surface, CSL5340C and CSL5250C (trade names, both manufactured by FUJIFILM Planar Solutions) are used as polishing liquids for polishing. For wafers with a metal film containing tungsten on the surface, only W-2000 (trade name, manufactured by Cabot) was used for polishing. The grinding pressure is 2.0 psi, and the supply rate of the grinding liquid is 0.28 mL/(min·cm ² ). The grinding time is 60 seconds. After that, using each cleaning solution adjusted to room temperature (23° C.), each polished wafer was cleaned for 30 seconds, and then dried.

Using a defect inspection device (manufactured by AMAT, ComPlus-II), the number of signal strengths corresponding to defects with a length of 0.1 μm or more on the polished surface of the obtained wafer was measured, and the cleaning solution’s performance was evaluated according to the following evaluation criteria Washing performance. The evaluation results are shown in Table 1. The smaller the number of defects due to residues detected on the polished surface of the wafer, the better the cleaning performance can be evaluated. "A": The number of defects per wafer is less than 50 "B": The number of defects per wafer is more than 50 and less than 200 "C": The number of defects per wafer is more than 200 and less than 500 "D": The number of defects per wafer is more than 500

[Evaluation of corrosion prevention performance] Die the wafer (12 inches in diameter) with a metal film containing copper, tungsten, or cobalt on the surface, and prepare a coupon of 2 cm in length x 2 cm in width. The thickness of each metal film was set to 200 nm. The wafer test piece was immersed in the cleaning solution (temperature: 23° C.) manufactured by the method described above, and the immersion treatment was performed for 3 minutes at 250 rpm of the stirring revolution. For each metal film, the content of copper, tungsten, or cobalt in each cleaning solution was measured before and after the immersion treatment. Calculate the corrosion rate per unit time (unit: Å/min) based on the obtained measurement results. The corrosion prevention performance of the cleaning solution was evaluated according to the following evaluation criteria. The results of these are shown in Table 1. Furthermore, the lower the corrosion rate, the better the corrosion prevention performance of the cleaning solution. (Evaluation criteria of W and Co) "A": Corrosion rate is less than 1.0 Å/min "B": The corrosion rate is 1.0 Å/min or more and less than 2.0 Å/min "C": The corrosion rate is 2.0 Å/min or more and less than 3.0 Å/min "D": The corrosion rate is 3.0 Å/min or more (Evaluation Criteria of Cu) "A": Corrosion rate is less than 0.5 Å/min "B": The corrosion rate is 0.5 Å/min or more and less than 1.0 Å/min "C": The corrosion rate is 1.0 Å/min or more and less than 2.0 Å/min "D": The corrosion rate is 2.0 Å/min or more

In the table, the "amount (%)" column indicates the content (unit: mass %) of each component relative to the total mass of the cleaning liquid. The "*1" in the "pH adjuster" column means that choline, H ₂ SO ₄ and Any one of KOH. Furthermore, in Example 25, choline was used to adjust the pH. The "remaining part" in the "water" column refers to the remaining part composed of water other than the components listed in Table 1 in the cleaning liquid. The "number of COOH groups" column indicates the number of carboxyl groups in compound (1), and the number of OH groups indicates the number of hydroxyl groups in compound (1). The column of "OH group/COOH group" shows the value of the ratio [number of hydroxyl groups/number of carboxyl groups] of the number of hydroxyl groups contained in compound (1) to the number of carboxyl groups. The column "(A)/(B)" represents the value of the mass ratio of the content of the compound (1) to the content of the alkanolamine [the content of the compound (1)/the content of the alkanolamine]. The value in the "pH value" column indicates the pH value of the washing liquid at 25°C measured by the pH meter.

[Table 1] Table 1 (Part 1) Composition of detergent pH value Washing performance Corrosion prevention performance Compound (1) (A) Alkanolamine (B) (A)/(B) Second amine compound Second amine compound Corrosion inhibitor other pH adjuster water Object metal Object metal type Number of COOH groups Number of OH groups OH group / COOH group quality(%) type quality(%) ratio type quality(%) type quality(%) type quality(%) type quality(%) quality(%) Cu W Co Cu W Co Comparative example 1 - - - - - AMP 4 - Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 D D D B D B Comparative example 2 Gluconate - - - 4 - - - Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A B D C Comparative example 3 tartaric acid - - - 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 B A B B D B Comparative example 4 Gluconate - - - 1 AMP 1 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 8.5 B A B B D B Comparative example 5 Gluconate - - - 4 AMP 1 4 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 8.5 A A A B D B Example 1 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A A A Example 2 Mucic Acid 2 4 2 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A B A B A Example 3 Glyceric acid 1 2 2 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A B A B A Example 4 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 B A C A C A Example 5 Gluconate 1 5 5 0.9 AMP 2 0.45 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 B A B A B A Example 6 Gluconate 1 5 5 2 AMP 2 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A B A B A Example 7 Gluconate 1 5 5 4 AMP 2 2 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A B A Example 8 Gluconate 1 5 5 4 AMP 0.4 10 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A B B Example 9 Gluconate 1 5 5 4 AMP 0.2 20 Piperazine 0.1 DBU 2.3 - - - *1 The remaining part 11.0 A A A B C B Example 10 Gluconate 1 5 5 4 AMPD 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A B A Example 11 Gluconate 1 5 5 4 Tris 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A B A Example 12 Mucic Acid 2 4 2 4 Tris 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 B A B A B A Example 13 Glyceric acid 1 2 2 4 Tris 4 1 Piperazine 0.1 DBU 2.3 - - - *1 The remaining part 11.0 B A B A B A Example 14 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 9.0 A A B A A B Example 15 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 10.0 A A A A A B Example 16 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 12.0 A A A A B A Example 17 Gluconate 1 5 5 4 AMP 4 1 - - DBU 2.3 - - - - *1 The remaining part 11.0 B A B A A A Example 18 Gluconate 1 5 5 4 AMP 4 1 Ethylene Diamine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 B A B A A A Example 19 Gluconate 1 5 5 4 AMP 4 1 Morpholine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 B A B A A A Example 20 Gluconate 1 5 5 4 AMP 4 1 NMPZ 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A A A Example 21 Gluconate 1 5 5 4 AMP 4 1 Arginine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A A A

[Table 2] Table 1 (Part 2) Composition of detergent pH value Washing performance Corrosion prevention performance Compound (1) (A) Alkanolamine (B) (A)/ (B) Second amine compound Second amine compound Corrosion inhibitor other pH adjuster water Object metal Object metal type Number of COOH groups Number of OH groups OH group / COOH group quality(%) type quality(%) ratio type quality(%) type quality(%) type quality(%) type quality(%) quality(%) Cu W Co Cu W Co Example 22 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 Azole compound 1 0.5 - - *1 The remaining part 11.0 B A C A A A Example 23 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 DBU 2.3 Azole compound 1 0.5 - - *1 The remaining part 11.0 A A A A A A Example 24 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 DBU 2.3 1,2,4-triazole 0.5 - - *1 The remaining part 11.0 A A A A A A Example 25 Gluconate 1 5 5 4 AMP 4 1 Piperazine 0.1 - - - - - - *1 The remaining part 11.0 B A B A A A Example 26 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Alkyl (EO) ₃ phosphate 0.5 *1 The remaining part 11.0 A A A A C A Example 27 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Periodic acid 10 *1 The remaining part 11.0 A A A A C A Example 28 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Adipic acid 1 *1 The remaining part 11.0 A A A A C A Example 29 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Succinic acid 1 *1 The remaining part 11.0 A A A A C A Example 30 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Histidine 1 *1 The remaining part 11.0 A A A A C A Example 31 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Jurymer AC-10H 0.01 *1 The remaining part 11.0 A A A A C A Example 32 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Jurymer AC-10L 0.01 *1 The remaining part 11.0 A A A A C A Example 33 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Aron A-10SL 0.01 *1 The remaining part 11.0 A A A A C A Example 34 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Concentrated (Nonpol) PWA-50W 0.01 *1 The remaining part 11.0 A A A A C A Example 35 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - DKS discoat N-10 0.01 *1 The remaining part 11.0 A A A A C A Example 36 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - DKS discoat N-14 0.01 *1 The remaining part 11.0 A A A A C A Example 37 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - Lavelin FD-40 0.01 *1 The remaining part 11.0 A A A A C A Example 38 Gluconate 1 5 5 0.1 AMP 2 0.05 Piperazine 0.1 DBU 2.3 - - γ-Cyclodextrin 0.2 *1 The remaining part 11.0 A A A A C A Example 39 Gluconate 1 5 5 4 AMP 4 1 - - DBU 2.3 - - - - *1 The remaining part 9.0 A A B A A B Example 40 Gluconate 1 5 5 4 AMP 4 1 - - DBU 2.3 - - - - *1 The remaining part 10.0 A A A A A B Example 41 Gluconate 1 5 5 4 AMP 4 1 - - DBU 2.3 - - - - *1 The remaining part 12.0 A A A A B A Example 42 Gluconate 1 5 5 2 AMP 4 1 Piperazine 0.1 DBU 2.3 - - - - *1 The remaining part 11.0 A A A A A A Glyceric acid 1 2 2 2

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

It was confirmed that 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) relative to the total mass of the cleaning solution, the effect is more excellent (implementation Comparison of Example 4 to Example 7). It was confirmed that when the compound (1) is gluconic acid, the effect is more excellent (comparison of Examples 1 to 3). It was confirmed that the effect is more excellent when the value of the mass ratio of the content of the compound (1) to the content of the alkanolamine is 0.1 to 10 (comparison of Example 1 and Examples 4 to 9). It was confirmed that when the cleaning solution further includes a surfactant, the effect is more excellent (comparison of Example 4 and Example 26).

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Claims (12)

A cleaning solution, which is a cleaning solution for semiconductor substrates subjected to chemical mechanical polishing treatment, and the cleaning solution contains a compound represented by the following formula (1), an alkanolamine, and water. The pH of the clean liquid at 25°C is above 9.0,

In the formula (1), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 6 carbons 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 cleaning liquid according to claim 1 or claim 2, wherein the hydrogen bond term of the Hansen solubility parameter of the compound represented by the formula (1) is 31.0 or less (MPa) ^0.5 , and the dispersion term is 17.0 (MPa) ^0.5 ~ 18.0 (MPa) ^0.5 , and the dipole term is 13.0 or less (MPa) ^0.5 . The cleaning solution according to claim 1 or 2, wherein the value of the ratio of the number of hydroxyl groups to the number of carboxyl groups in the compound represented by the formula (1) is 2 or more. The cleaning liquid according to claim 1 or 2, 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 liquid. The cleaning solution according to claim 1 or 2, wherein the compound represented by the formula (1) is gluconic acid. The cleaning solution according to claim 1 or claim 2, wherein the alkanolamine is a compound represented by the following formula (a-1), HO-L ^a1 -NH ₂ (a-1): In -1), ^La1 represents an alkylene group having 1 to 14 carbon atoms which may have a hetero atom. The cleaning liquid according to claim 1 or claim 2, wherein the alkanolamine contains two amino acids selected from the group consisting of 2-amino-2-methyl-1-propanol, 2-amino-2-methylpropane At least one of the group consisting of alcohol and trihydroxymethylaminomethane. The cleaning liquid according to claim 1 or 2, wherein the mass ratio of the content of the compound represented by the formula (1) to the content of the alkanolamine has a value of 0.1-10. The cleaning liquid according to claim 1 or 2, wherein the cleaning liquid further contains a second amine compound different from the alkanolamine. The cleaning liquid according to claim 1 or 2, wherein the cleaning liquid further contains a surfactant. A method for cleaning a semiconductor substrate includes the step of using the cleaning solution as described in any one of claim 1 to claim 11 to clean a semiconductor substrate after a chemical mechanical polishing process.