JP7288511B2 - detergent composition - Google Patents

Description

The present invention relates to cleaning compositions. In particular, it relates to a cleaning composition that can be suitably used for manufacturing semiconductor devices.

Semiconductor devices such as CCDs (Charge-Coupled Devices) and memories are manufactured by forming fine electronic circuit patterns on substrates using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography process and a dry etching process (e.g., plasma etching process) are performed. A semiconductor device is manufactured by carrying out.

The substrate that has undergone the dry etching process is optionally subjected to a resist stripping process for stripping the resist film mainly composed of organic substances by a stripping means such as a dry ashing process (for example, plasma ashing). will be
After the dry etching process and the resist stripping process, the wiring film and/or the interlayer insulating film of the substrate have residue containing a large amount of organic components derived from the resist film. In order to avoid this, treatment is often performed to remove the residue using a cleaning composition.

For example, in Patent Document 1, a redox agent, a first chelating agent that is a polyaminopolycarboxylic acid, a second chelating agent that contains at least two nitrogen-containing groups, a metal corrosion inhibitor that is benzotriazole, an organic solvent, A cleaning composition is disclosed comprising water and a desired pH adjusting agent.

Japanese Patent Publication No. 2017-504190

Based on the description of Patent Document 1, the present inventors investigated a cleaning composition used in the manufacturing process of semiconductor devices, and found that the performance of removing organic residue after storing the cleaning composition over time was further investigated. We have found that there is room for improvement.

In addition, the cleaning composition suppresses corrosion of wiring metals (e.g., one or more metals selected from the group consisting of Cu, W and Co) forming metal layers of semiconductor devices to be cleaned. (corrosion prevention) is required.

Accordingly, it is an object of the present invention to provide a cleaning composition for use in semiconductor devices, which exhibits excellent long-term stability in removing organic residue and is also excellent in preventing corrosion of metal layers. is the subject.

As a result of intensive studies aimed at achieving the above object, the inventors of the present invention have found that the above object can be solved by the following configuration.

[1] A cleaning composition for semiconductor devices, comprising at least one hydroxylamine compound selected from the group consisting of hydroxylamine and hydroxylamine salts, a carboxylic acid-based chelating agent other than polyaminocarboxylic acid, and phosphonic acid A detergent composition comprising one or more chelating agents selected from the group consisting of acid chelating agents and a benzotriazole compound.
[2] The detergent composition of [1], wherein the chelating agent contains a phosphonic acid-based chelating agent.
[3] The detergent composition of [2], wherein the phosphonic acid-based chelating agent contains one or more compounds selected from the group consisting of hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds. thing.
[4] The detergent composition of [2] or [3], wherein the phosphonic acid-based chelating agent contains an aminophosphonic acid compound.
[5] The cleaning composition of [1], wherein the chelating agent contains a carboxylic acid-based chelating agent.
[6] The carboxylic acid-based chelating agent of [5], which contains one or more compounds selected from the group consisting of hydroxy acid compounds, polycarboxylic acid compounds, and aromatic polycarboxylic acid compounds. cleaning composition.
[7] The detergent composition of [5] or [6], wherein the carboxylic acid-based chelating agent contains a hydroxy acid compound.
[8] the hydroxylamine compound is hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate, and N,N-diethylhydroxylamine sulfate; The cleaning composition according to any one of [1] to [7], containing one or more selected from the group consisting of:
[9] The cleaning composition according to any one of [1] to [8], wherein the benzotriazole compound contains a compound represented by formula (A) described below.
[10] The cleaning composition according to any one of [1] to [9], wherein the mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound is 1-1000.
[11] The detergent composition according to any one of [1] to [10], wherein the mass ratio of the content of the hydroxylamine compound to the content of the chelating agent is 0.1-100.
[12] The cleaning composition according to any one of [1] to [11], which is used for cleaning a substrate having a metal layer containing one or more selected from the group consisting of copper, tungsten and cobalt.

ADVANTAGE OF THE INVENTION According to this invention, it is a cleaning composition for semiconductor devices, and can provide the cleaning composition which is excellent in the time-dependent stability of the removal performance of an organic substance residue, and was excellent also in corrosion prevention with respect to a metal layer.

1 is a schematic cross-sectional view showing an example of a laminate that can be applied to a cleaning method using a cleaning composition; FIG.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
In addition, the term "preparation" used in this specification includes not only synthesizing or preparing specific materials, but also procuring predetermined items through purchase.
Also, in this specification, "ppm" means "parts-per-million (10 ^-6 )", "ppb" means "parts-per-billion (10 ^-9 )", and "ppt" means "parts-per-trillion (10 ^-12 )".
Also, in this specification, 1 Å (angstrom) corresponds to 0.1 nm.
In addition, in the notation of a group (atom group) in the present specification, a notation that does not describe substituted or unsubstituted includes not having a substituent as well as one having a substituent within a range that does not impair the effect of the present invention. It also includes For example, the term "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). . This is also the same for each compound.
In the present specification, the pH of the detergent composition is a value measured at room temperature (25° C.) using F-51 (trade name) manufactured by Horiba, Ltd.
In addition, the term “radiation” as used herein means the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, or electron beams. Moreover, in this specification, light means actinic rays or radiation. Unless otherwise specified, the term "exposure" in the present invention means not only exposure by far ultraviolet rays represented by mercury lamps and excimer lasers, X-rays or EUV light, but also drawing by particle beams such as electron beams or ion beams. Include in exposure.

[Cleaning composition]
The cleaning composition of the present invention is a cleaning composition for semiconductor devices, comprising at least one hydroxylamine compound selected from the group consisting of hydroxylamine and hydroxylamine salts, a carboxylic acid (with the proviso that polyaminocarboxylic acid) and phosphonic acid (hereinafter also referred to as “specific chelating agent”), and a benzotriazole compound.

The present inventors have surprisingly found that by containing a hydroxylamine compound, a specific chelating agent, and a benzotriazole compound, the organic residue removal performance is excellent in stability over time, and corrosion prevention for metal layers It has been found that a detergent composition which is also excellent in is obtained.
In this specification, the term "organic residue" means a residue mainly composed of an organic substance, which is generated in the manufacturing process of semiconductor devices. In this case, "mainly composed of" an organic substance means that the content of the organic substance is 50% by mass or more relative to the total amount of the residue. In addition, in this specification, the removal performance of organic residue is also simply referred to as “removal performance”.

Each component contained in the detergent composition will be described below.

〔component〕
<Hydroxylamine compound>
The detergent composition of the present invention contains one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and hydroxylamine salts. A hydroxylamine compound has the function of promoting the decomposition and solubilization of organic residue.

Here, "hydroxylamine" related to the hydroxylamine compound refers to a broadly defined hydroxylamine including substituted or unsubstituted alkylhydroxylamine. , excellent corrosion protection and can be obtained.
The hydroxylamine compound is not particularly limited, but preferred embodiments include unsubstituted hydroxylamine, hydroxylamine derivatives, and salts thereof.

Examples of hydroxylamine derivatives include, but are not limited to, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, N-ethyl hydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine, and N,N-disulfoethylhydroxylamine is mentioned.

Salts of unsubstituted hydroxylamine or hydroxylamine derivatives are preferably inorganic acid salts or organic acid salts of the above-mentioned unsubstituted hydroxylamine or hydroxylamine derivatives. is more preferably a salt with an inorganic acid in which is bound, and a salt with any one of hydrochloric acid, sulfuric acid and nitric acid is even more preferable. Among them, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate, or mixtures thereof are preferred.
Organic acid salts of unsubstituted hydroxylamine or hydroxylamine derivatives described above can also be used. Organic acid salts include, for example, hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium fluoride.

The hydroxylamine compound is preferably hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate, or N,N-diethylhydroxylamine sulfate. Hydroxylamine or hydroxylamine sulfate is more preferred from the viewpoint of better removal performance, and hydroxylamine is even more preferred from the viewpoint of better corrosion prevention.
One type of hydroxylamine compound may be used alone, or two or more types may be used. It is preferable to use two or more hydroxylamine compounds from the viewpoint of better corrosion prevention.

The content of the hydroxylamine compound is, for example, 0.1 to 30% by mass with respect to the total mass of the detergent composition.
Among them, the content of the hydroxylamine compound is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the cleaning composition, from the viewpoint of better removal performance.
Moreover, the content of the hydroxylamine compound is preferably 20% by mass or less, more preferably 15% by mass or less, relative to the total mass of the cleaning composition, from the viewpoint of more excellent corrosion prevention.
A hydroxylamine compound may be used individually by 1 type, and may be used 2 or more types. When two or more are used, the total content thereof is preferably within the above range.

<Specific chelating agent>
The detergent composition of the present invention contains, as a specific chelating agent, one or more compounds selected from the group consisting of carboxylic acids other than polyaminocarboxylic acids and phosphonic acid-based chelating agents.
In addition, in this specification, polyaminocarboxylic acid means a compound having a plurality of amino groups and one or more carboxyl groups.

The specific chelating agent contained in the cleaning composition has the function of chelating metal in the cleaning step included in the semiconductor device manufacturing process. Among them, a compound having two or more functional groups (coordination groups) that coordinately bond with metal ions in one molecule is preferable.
Although the number of coordinating groups possessed by the specific chelating agent is not particularly limited, it is preferably 2-6, more preferably 2-4, and even more preferably 2 or 3.

(Phosphonic acid-based chelating agent)
Phosphonic chelating agents are compounds that have one or more phosphonic acid groups and chelate metals.
Phosphonic acid-based chelating agents include, for example, hydroxyphosphonic acid compounds, polyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds.
Among them, a hydroxyphosphonic acid compound, an aminophosphonic acid compound, or a phosphonocarboxylic acid compound is preferred, and an aminophosphonic acid compound is more preferred.

A hydroxyphosphonic acid compound is a compound having one or more phosphonic acid groups and one or more hydroxyl groups in the molecule.
A polyphosphonic acid compound is a compound having two or more phosphonic acid groups in the molecule. A compound having any one of a hydroxyl group, an amino group and a carboxyl group in the molecule is not included in the polyphosphonic acid compound.

Examples of hydroxyphosphonic acid compounds and polyphosphonic acid compounds include compounds represented by the following formula (1).

In the formula, X represents a hydroxy group and ^R1 represents a hydrogen atom or an alkyl group.

The alkyl group represented by R ¹ in formula (1) may be linear, branched or cyclic, preferably linear or branched.
The number of carbon atoms in the alkyl group represented by R ¹ is not particularly limited, but is preferably 1-10, more preferably 1-6, and even more preferably 1-4. The alkyl group represented by R ¹ is preferably an ethyl group, an n-propyl group or an isopropyl group.
In specific examples of alkyl groups described in this specification, n- represents normal-form.

Compounds represented by formula (1) include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid, and 1-hydroxybutane-1,1-diphosphonic acid. be done.
Hydroxyphosphonic acid compounds other than the compound represented by formula (1) include 2-hydroxyethane-1,1-diphosphonic acid, 3-hydroxypropane-1,1-diphosphonic acid, glycerol 3-phosphate, and ethanehydroxy-1,1,2-triphosphonic acid.
Preferred hydroxyphosphonic acid compounds are 1-hydroxyethane-1,1-diphosphonic acid and glycerol 3-phosphate. Among them, 1-hydroxyethane-1,1-diphosphonic acid is more preferable from the viewpoint of better removal performance and corrosion prevention, and glycerol 3-phosphate is more preferable from the viewpoint of better stability of removal performance over time.

An aminophosphonic acid compound is a compound having one or more phosphonic acid groups and one or more amino groups in the molecule. A compound having a carboxyl group in the molecule is not included in the aminophosphonic acid compound.
Examples of aminophosphonic acid compounds include compounds represented by the following formula (2) and compounds represented by the following formula (3).

In the formula, Q represents a hydrogen atom or —R ³ —PO ₃ H ₂ , R ² and R ³ each independently represent an alkylene group, Y is a hydrogen atom, —PO ₃ H ₂ , Or represents a group represented by the following formula (4).

In formula (4), Q and ^R3 are the same as Q and ^R3 in formula (2).

The alkylene group represented by R ² in formula (2) may be linear or branched. The alkylene group represented by R ² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably a methylene group or an ethylene group.
Y in formula (2) is preferably —PO ₃ H ₂ or a group represented by formula (4), more preferably —PO ₃ H ₂ .
The combination of R ² and Y in formula (2) includes a combination in which R ² is a methylene group and Y is —PO ₃ H ₂ , or a combination in which R ² is an ethylene group and Y is a formula (4 ) is preferred.

Q in formulas (2) and (4) is preferably -R ³ -PO ₃ H ₂ .
The alkylene group represented by R ³ in formulas (2) and (4) may be linear or branched. The alkylene group represented by R ³ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, still more preferably a methylene group or an ethylene group, and particularly preferably a methylene group.

Examples of aminophosphonic acid compounds represented by formula (2) include ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylene phosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) ) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), and 1,6-hexamethylenediaminetetra(methylenephosphonic acid).

In the formula, R ⁴ and R ⁵ each independently represent an alkylene group having 1 to 4 carbon atoms, n represents an integer of 1 to 4, and at least 4 of Z ¹ to Z ⁴ and n Z ⁵ One represents an alkyl group having a phosphonic acid group and the rest represent alkyl groups.

The C 1-4 alkylene group represented by R ⁴ and R ⁵ in formula (3) may be linear or branched. The alkylene group having 1 to 4 carbon atoms represented by R ⁴ and R ⁵ is preferably an ethylene group.
As n in Formula (3), 1 or 2 is preferable.

The alkyl group in the alkyl group and the alkyl group having a phosphonic acid group represented by Z ¹ to Z ⁵ in formula (3) may be either a straight-chain alkyl group or a branched-chain alkyl group. An alkyl group of numbers 1 to 4 is preferred, and a methyl group is more preferred.
The number of phosphonic acid groups in the alkyl group having a phosphonic acid group represented by Z ¹ to Z ⁵ is preferably 1 or 2, more preferably 1.
The alkyl group having a phosphonic acid group represented by Z ¹ to Z ⁵ is preferably a monophosphonomethyl group or a monophosphonoethyl group, more preferably a monophosphonomethyl group.

Z ¹ to Z ⁵ in formula (3) are preferably all of Z ¹ to Z ⁴ and n Z ⁵ are alkyl groups having a phosphonic acid group.

Examples of aminophosphonic acid compounds represented by formula (3) include diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylene Tetramine hexa(ethylene phosphonic acid) can be mentioned.

Aminophosphonic acid compounds include ethylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), ethylenediaminetetra(methylenephosphonic acid) (EDTPO), ethylenediamine Tetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), or diethylenetriaminepenta(methylenephosphonic acid) (DEPPO) are preferred, and NTPO or EDDPO are more preferred.

A phosphonocarboxylic acid compound is a compound having one or more carboxyl groups and one or more phosphonic acid groups in the molecule.
Examples of phosphonocarboxylic acid compounds include compounds represented by the following formula (5).
R ⁶ (-COOH) _i (-PO ₃ H ₂ ) _j (5)
In formula (5), R ⁶ represents an (i+j)-valent aliphatic hydrocarbon group, i represents an integer of 1-4, and j represents an integer of 1-4.

The aliphatic hydrocarbon group represented by ^R6 may be linear, branched or cyclic, preferably linear or branched. The aliphatic hydrocarbon group represented by ^R6 may be either saturated hydrocarbon or unsaturated hydrocarbon, but saturated hydrocarbon is preferred.
The aliphatic hydrocarbon group represented by R ⁶ may have a linking group containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, an oxygen atom or a nitrogen atom or preferably does not have a heteroatom-containing linking group, and from the viewpoint of better stability of removal performance over time, it is more preferable not to have a heteroatom-containing linking group. .
The number of carbon atoms in the aliphatic hydrocarbon group represented by R ⁶ is not particularly limited, but is preferably 1-8, more preferably 2-6, and even more preferably 3-5.

i in formula (5) is preferably an integer of 1-3.
j in formula (5) is preferably an integer of 1 to 3, more preferably 1 or 2.
The sum (i+j) of i and j in formula (5) is preferably an integer of 2-6, more preferably an integer of 2-4.

Hydroxyphosphonic acid compounds include, for example, 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobutyric acid, and glycine-N,N-bis(methylenephosphonic acid), 2-phosphonobutane-1, 2,4-tricarboxylic acid, 4-phosphonobutyric acid, or glycine-N,N-bis(methylenephosphonic acid) are preferred.
Among them, 2-phosphonobutane-1,2,4-tricarboxylic acid or 4-phosphonobutyric acid is more preferable from the viewpoint of better stability of removal performance over time, and from the viewpoint of excellent residue removal performance and corrosion prevention, 2 -phosphonobutane-1,2,4-tricarboxylic acid or glycine-N,N-bis(methylenephosphonic acid) are more preferred. As the hydroxyphosphonic acid compound, 2-phosphonobutane-1,2,4-tricarboxylic acid is more preferable.

A polyphosphonic acid compound is a compound having two or more phosphonic acid groups in the molecule. The hydroxyphosphonic acid compound, aminophosphonic acid compound, and phosphonocarboxylic acid compound described above are not included in the polyphosphonic acid compound.

Examples of polyphosphonic acid compounds include compounds represented by the following formula (6).
^R7 _{( -PO3H2} ) _k (6)
In formula (6), R ⁷ represents a k-valent aliphatic hydrocarbon group, and k represents an integer of 2-6.
The aliphatic hydrocarbon group represented by ^R7 may be linear, branched or cyclic, preferably linear or branched. The aliphatic hydrocarbon group represented by ^R7 may be either a saturated hydrocarbon or an unsaturated hydrocarbon, preferably a saturated hydrocarbon.
The number of carbon atoms in the aliphatic hydrocarbon group represented by R ⁷ is not particularly limited, but is preferably 1-10, more preferably 2-6.
k is preferably an integer of 2 to 4, more preferably 2 or 3.

Polyphosphonic acid compounds include, for example, ethylidenebisphosphonic acid, propylidenebisphosphonic acid, butylidenebisphosphonic acid, and isopropylidenebisphosphonic acid.
The polyphosphonic acid compound also includes compounds ((co)polymers) described in paragraphs [0031] to [0046] of International Publication No. 2018/030006, the contents of which are incorporated herein. .

(Carboxylic acid-based chelating agent)
Carboxylic acid-based chelating agents are compounds that have one or more carboxyl groups and chelate with metals. Hereinafter, carboxylic acid-based chelating agents other than polyaminocarboxylic acids are simply referred to as "carboxylic acid-based chelating agents" unless otherwise specified. A compound having both a carboxyl group and a phosphonic acid group is not included in the carboxylic acid-based chelating agent, but is included in the phosphonic acid-based chelating agent.

Carboxylic acid-based chelating agents include, for example, polycarboxylic acid compounds, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds.
Among them, polycarboxylic acid compounds, hydroxy acid compounds, or aromatic carboxylic acid compounds are preferred, and hydroxy acid compounds are more preferred.

A polycarboxylic acid compound is a compound having two or more carboxyl groups in the molecule. However, hydroxy acid compounds, aromatic carboxylic acid compounds, and amino acid compounds, which will be described later, are not included in the polycarboxylic acid compounds.

Examples of polycarboxylic acid compounds include compounds represented by the following formula (7).
R ⁸ (-COOH) _p (7)
In formula (7), R ⁸ represents a p-valent aliphatic hydrocarbon group, and p represents an integer of 2-6.
The aliphatic hydrocarbon group represented by R ⁸ may be linear, branched or cyclic, preferably linear or branched. The aliphatic hydrocarbon group represented by ^R8 may be either saturated hydrocarbon or unsaturated hydrocarbon, but saturated hydrocarbon is preferred.
The aliphatic hydrocarbon group represented by R ⁸ may have a linking group containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, and contains a heteroatom. It is preferred not to have a linking group.
The number of carbon atoms in the aliphatic hydrocarbon group represented by R ⁸ is not particularly limited, but is preferably 1 to 10, more preferably 2 to 6, and 2 to 4 from the viewpoint of excellent stability of removal performance over time. More preferred.
p is preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.

Examples of polycarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, sebacic acid, maleic acid, and 1,3,5-pentanetricarboxylic acid. Among them, succinic acid, glutaric acid, adipic acid, pimelic acid, 3-methyladipic acid, or 1,3,5-pentanetricarboxylic acid are preferable, and succinic acid and glutaric acid are preferable from the viewpoint of excellent stability of removal performance over time. Or adipic acid is more preferable. In terms of removal performance, 1,3,5-pentanetricarboxylic acid is more preferable.

A hydroxy acid compound is a compound having one or more carboxyl groups and one or more hydroxy groups in the molecule. However, a compound having an aromatic ring in its molecule is not included in the hydroxy acid compound.

Examples of hydroxy acid compounds include compounds represented by the following formula (8).
R ⁹ (-COOH) _m (-OH) _n (8)
In formula (8), R ⁹ represents an (m+n)-valent aliphatic hydrocarbon group, m represents an integer of 1-4, and n represents an integer of 1-4.
The aliphatic hydrocarbon group represented by R ⁹ may be linear, branched or cyclic, preferably linear or branched. The aliphatic hydrocarbon group represented by ^R9 may be either saturated hydrocarbon or unsaturated hydrocarbon, but saturated hydrocarbon is preferred.
The aliphatic hydrocarbon group represented by R ⁹ may have a linking group containing one or more heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, an oxygen atom or a nitrogen atom or no linking group containing a heteroatom.
The number of carbon atoms in the aliphatic hydrocarbon group represented by R ⁹ is not particularly limited, but is preferably 1 to 8, more preferably 2 to 6, and even more preferably 3 to 5 from the viewpoint of excellent corrosion prevention.

1 or 2 is preferable and, as for m in Formula (8), 1 is more preferable.
n in formula (8) is preferably an integer of 1 to 3, more preferably 1 or 2.
The sum (m+n) of m and n in formula (8) is preferably an integer of 2 to 4, more preferably 2 or 3.

Examples of hydroxy acid compounds include malic acid, citric acid, glycolic acid, tartaric acid, lactic acid, and diethanolglycine. Malic acid, citric acid, or diethanolglycine is preferred, and citric acid is preferred because of its excellent anti-corrosion properties. Or diethanolglycine is more preferred.

An aromatic carboxylic acid compound is a compound having one or more carboxyl groups and an aromatic ring in the molecule.
Examples of aromatic carboxylic acid compounds include compounds represented by the following formula (9).
Ar(-COOH) _q (9)
In formula (9), Ar represents a q-valent aromatic hydrocarbon group which may have a substituent, and q represents an integer of 1-6. However, when q represents 1, the aromatic hydrocarbon group represented by Ar further has a coordinating group other than the carboxyl group and the phosphonic acid group.
Substituents that the aromatic hydrocarbon group represented by Ar may have include, for example, one or more coordinating groups selected from the group consisting of a hydroxyl group, an amino group, and a sulfo group, and the above may have a coordinating group (preferably an alkyl group having 1 to 4 carbon atoms). In addition, the aliphatic hydrocarbon group which Ar has may have the carboxy group in Formula (9).
The number of carbon atoms in the aromatic hydrocarbon group represented by Ar is not particularly limited, but is preferably 6-14, more preferably 6-10.
q is preferably an integer of 1 to 3, more preferably 1 or 2.
As the aromatic hydrocarbon group represented by Ar, a benzene ring optionally having a hydroxy group is preferred.

Examples of the aromatic carboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid. Isophthalic acid or salicylic acid is preferable, and isophthalic acid is more preferable from the viewpoint of excellent corrosion resistance.

An amino acid compound is a compound having one or more carboxyl groups and one or more amino groups as coordinating groups in the molecule. However, the hydroxy acid compounds and aromatic carboxylic acid compounds described above are not included in the amino acid compounds.
Examples of amino acid compounds include glycine, serine, α-alanine (2-aminopropionic acid), β-alanine (3-aminopropionic acid), leucine, isoleucine, cysteine, ethionine, threonine, aspartic acid, glutamic acid, proline, Methionine, phenylalanine, and salts thereof.
Salts include alkali metal salts such as sodium and potassium salts, ammonium salts, carbonates, and acetates.

The specific chelating agent is preferably a hydroxyphosphonic acid compound, an aminophosphonic acid compound, a phosphonocarboxylic acid compound, a polycarboxylic acid compound, a hydroxy acid compound, or an aromatic carboxylic acid compound. An aminophosphonic acid compound or a hydroxy acid compound is more preferable because of their superiority.

One type of specific chelating agent may be used alone, or two or more types may be used.
The content of the specific chelating agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.1% by mass or more, based on the total mass of the cleaning composition, from the viewpoint of excellent removal performance stability over time. 0.5% by mass or more is more preferable.
Although the upper limit is not particularly limited, it is preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably less than 2% by mass, based on the total mass of the cleaning composition, from the viewpoint of better corrosion prevention. .

In the cleaning composition, the mass ratio of the content of the hydroxylamine compound to the content of the specific chelating agent (content of the hydroxylamine compound/content of the specific chelating agent) is 0.1 from the viewpoint of superior corrosion prevention. 1 or more is preferable, and 1 or more is more preferable.
In addition, the mass ratio is preferably 100 or less, more preferably 10 or less, from the viewpoint of superior stability of removal performance over time.

<Benzotriazole compound>
The cleaning composition of the present invention contains a benzotriazole compound.
The benzotriazole compound is not particularly limited as long as it is a compound having a benzotriazole structure, and examples thereof include compounds represented by the following formula (A).

In formula (A), R ¹¹ represents a substituent.
^R12 represents a hydrogen atom or a substituent.
n represents an integer of 0 to 4, and when n is 2 or more, n R ¹¹ may be the same or different.

Examples of the substituent represented by R ¹¹ in formula (A) include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and the following formula (B). and a hydroxyl group, a mercapto group, a carboxy group, and an alkoxycarbonyl group having 1 to 12 carbon atoms.
Moreover, the substituent represented by R ¹¹ may further have one or more substituents selected from the group consisting of a hydroxyl group and a carboxy group.

In formula (B), R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group.
R ¹⁵ represents a single bond or an alkylene group having 1 to 6 carbon atoms.
* represents a binding site.

R ¹³ and R ¹⁴ in formula (B) are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and having a hydroxyl group, more preferably a hydrogen atom or a 2-hydroxyethyl group.
R ¹⁵ in formula (B) is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably a single bond or an ethylene group.
The group represented by formula (B) is preferably an amino group or an N,N-bis(hydroxyethyl)aminoethyl group.

R ¹¹ in formula (A) is preferably a carboxyl group, an amino group, or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
n in formula (A) is preferably an integer of 0 to 2, more preferably 0 or 1.

Examples of the substituent represented by R ¹² include an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a group represented by the above formula (B). , a hydroxyl group, a mercapto group, and an alkoxycarbonyl group having 1 to 12 carbon atoms.
Moreover, the substituent represented by R ¹² may further have one or more substituents selected from the group consisting of a hydroxyl group and a carboxy group.
R ¹² in formula (A) is preferably a hydrogen atom, a hydroxyl group, a group represented by formula (B) above, or an alkyl group having 1 to 6 carbon atoms which may have a carboxyl group, and is preferably a hydrogen atom. , or hydroxyl groups are more preferred.

Benzotriazole compounds include benzotriazole, 5-methyl-1H-benzotriazole, 5-aminobenzotriazole, 1-hydroxybenzotriazole, 4-carboxybenzotriazole, 5,6-dimethylbenzotriazole, 1-[N, N-bis(hydroxyethyl)aminoethyl]benzotriazole, 1-(1,2-dicarboxyethyl)benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N , N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, or 2,2′-{[(methyl-1H-benzotriazol-1-yl)methyl]imino}bisethanol is preferred, and benzotriazole, 5- Methyl-1H-benzotriazole or 1-hydroxybenzotriazole are more preferred.

A benzotriazole compound may be used individually by 1 type, and may be used 2 or more types.
The content of the benzotriazole compound is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, relative to the total mass of the cleaning composition, from the viewpoint of better corrosion prevention.
Although the upper limit is not particularly limited, it is preferably 10% by mass or less, more preferably 3% by mass or less, and 0.5% by mass or less, based on the total mass of the cleaning composition, from the viewpoint of excellent residue removal performance. More preferred.

In the cleaning composition, the mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound (content of the hydroxylamine compound/content of the benzotriazole compound) should be 1 or more from the viewpoint of superior residue removal performance. Preferably, 10 or more is more preferable.
Moreover, the mass ratio is preferably 1,000 or less, more preferably 100 or less, from the viewpoint of better corrosion prevention.

<Solvent>
The chemical solution may contain a solvent.
Solvents include water and organic solvents, with water being preferred.

(water)
The cleaning composition preferably contains water.
The type of water used in the cleaning composition is not particularly limited as long as it does not adversely affect the semiconductor substrate. ). Pure water is preferable because it contains almost no impurities and has less influence on the semiconductor substrate in the semiconductor device manufacturing process.
The content of water in the cleaning composition is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 85% by mass or more, relative to the total mass of the cleaning composition. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 95% by mass or less.

(Organic solvent)
The cleaning composition may contain an organic solvent.
The organic solvent is preferably a water-soluble organic solvent, more preferably an alcohol-based solvent, a ketone-based solvent, or an amide-based solvent, and still more preferably an alcohol-based solvent.

Examples of alcohol solvents include alkanediols, alkylene glycols, alkoxy alcohols, saturated or unsaturated aliphatic alcohols, and trihydric or higher alcohols.

Examples of alkanediols include glycol, 2-methyl-1,3-propanediol, 1,2-propanediol, 1,3-propanediol (1,3-dihydroxypropane), 2-methyl-2,4- Pentanediol, 2,2-dimethyl-1,3-hexanediol, 1,4-butanediol (1,4-dihydroxybutane), 1,3-butanediol, 1,2-butanediol, 2,3-butane Diols, 2,5-dihydroxy-2,5-dimethylhexane, pinacols and alkylene glycols.

Alkylene glycols include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and tetraethylene glycol.

Alkoxy alcohols include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.
Alkylene glycol monoalkyl ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol. monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy- 1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, and 1-Methoxy-2-butanol can be mentioned.
Examples of alkylene glycol dialkyl ethers include diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene. Glycol dimethyl ether is mentioned.
The number of carbon atoms in the alkylene glycol monoalkyl ether and alkylene glycol dialkyl ether used in the detergent composition is preferably 3-16, more preferably 4-12, and even more preferably 6-10.

Saturated or unsaturated aliphatic alcohols include, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, t-pentyl alcohol. , 1-hexanol, allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.

Trihydric or higher alcohols include, for example, glycerin.

Alkoxy alcohol is preferable as the alcohol solvent. As the alkoxy group, for example, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is preferable.

Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

The organic solvent is preferably alkylene glycol monoalkyl ether, more preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, or ethylene glycol monobutyl ether, and still more preferably ethylene glycol monobutyl ether.

An organic solvent may be used individually by 1 type, and may be used 2 or more types.
When the cleaning composition contains an organic solvent, the content of the organic solvent is preferably 0.001 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the cleaning composition.

<pH adjuster>
The cleaning composition may contain a pH adjuster to adjust the pH of the cleaning composition.
Examples of pH adjusters include inorganic acids, organic acids (excluding specific chelating agents), organic bases, and inorganic bases.

Inorganic acids include sulfuric acid, acetic acid, nitric acid, phosphoric acid, and hydrofluoric acid. Organic acids include lower (1 to 4 carbon atoms) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid. Further, the carboxylic acid-based chelating agent described above may also be used as a pH adjuster for lowering the pH of the cleaning composition.

Organic bases include, for example, quaternary ammonium salt compounds, nitrogen-containing heterocyclic compounds, and water-soluble amines.

As the quaternary ammonium salt compound, a quaternary ammonium hydroxide is preferable, and a compound represented by the following formula (10) is more preferable.

In formula (10), R ^4A to R ^4D are each independently an alkyl group having 1 to 6 carbon atoms (preferably a methyl group, an ethyl group, a propyl group or a butyl group), a hydroxyalkyl group having 1 to 6 carbon atoms (preferably a hydroxymethyl group, a hydroxyethyl group or a hydroxybutyl group), a benzyl group, or an aryl group (preferably a phenyl group, a naphthyl group or a naphthalene group). Among them, an alkyl group having 1 to 6 carbon atoms, a hydroxyethyl group having 1 to 6 carbon atoms, or a benzyl group is preferable.

Examples of compounds represented by formula (10) include tetramethylammonium hydroxide (TMAH), ethyltrimethylammonium hydroxide (ETMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide ( TBAH), dimethyldipropylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methyltri(hydroxyethyl)ammonium hydroxide, tetra(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, bishydroxyethyldimethyl Ammonium hydroxide and choline. Among them, TMAH, ETMAH, TEAH, or TBAH is preferable.

As used herein, the nitrogen-containing heterocyclic compound means a compound having a heterocyclic ring in which at least one of the atoms constituting the ring is a nitrogen atom, and is not included in the benzotriazole compounds described above.
Examples of nitrogen-containing heterocyclic compounds include azole compounds other than benzotriazole compounds, pyridine compounds, pyrazine compounds, pyrimidine compounds, piperazine compounds, and cyclic amidine compounds, with cyclic amidine compounds being preferred.

A cyclic amidine compound is a compound having a heterocyclic ring containing an amidine structure (>NC=N-) in the ring.
Cyclic amidine compounds include, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) and 1,5-diazabicyclo[4.3.0]nonene-5 (DBN).

As used herein, water-soluble amines are intended to be amines that can dissolve 50 g or more in 1 L of water. The pKa of the water-soluble amine is not particularly limited, but preferably 7.5 to 13.0. In addition, the water-soluble amine does not contain the above-mentioned hydroxylamine compound and ammonia.

Examples of water-soluble amines having a pKa of 7.5 to 13.0 include diglycolamine (DGA) (pKa = 9.80), methylamine (pKa = 10.6), ethylamine (pKa = 10.6 ), propylamine (pKa=10.6), butylamine (pKa=10.6), pentylamine (pKa=10.0), monoethanolamine (pKa=9.3), monopropanolamine (pKa=9. 3), monobutanolamine (pKa = 9.3), methoxyethylamine (pKa = 10.0), methoxypropylamine (pKa = 10.0), dimethylamine (pKa = 10.8), diethylamine (pKa = 10 .9), dipropylamine (pKa=10.8), trimethylamine (pKa=9.80), and triethylamine (pKa=10.72).

Inorganic bases include, for example, alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
Alkali metal hydroxides include, for example, lithium hydroxide, sodium hydroxide, and potassium hydroxide. Alkaline earth metal hydroxides include, for example, calcium hydroxide, strontium hydroxide, and barium hydroxide.

The pH adjuster for lowering the pH of the cleaning composition is preferably a quaternary ammonium hydroxide, a nitrogen-containing heterocyclic compound, a water-soluble amine, or ammonia, represented by the above formula (10). Quaternary ammonium hydroxides, cyclic amidine compounds, or water-soluble amines are more preferred.

A pH adjuster may be used individually by 1 type, and may use 2 or more types.
With regard to the type and content of the pH adjuster, the type of pH adjuster to be used may be appropriately selected and the content adjusted so that the pH of the cleaning composition falls within the preferred range described below. However, when an inorganic base is used as the pH adjuster, the content of the inorganic base is preferably 0.1% by mass or less with respect to the total mass of the detergent composition.

<Additive>
The detergent composition may contain additives other than the above-mentioned components, if necessary.
Such additives include, for example, surfactants, reducing agents, defoamers, rust inhibitors, and preservatives.

The cleaning composition may contain a surfactant.
The type of surfactant is not particularly limited, and examples thereof include ionic surfactants (anionic surfactants, cationic surfactants, and amphoteric surfactants) and nonionic surfactants.
When the cleaning composition contains a surfactant, the content of the surfactant is preferably 1 mass ppm or more and 3 mass% or less with respect to the total mass of the cleaning composition.

The cleaning composition may contain other ingredients than those mentioned above as long as the effects of the present invention and the functions of each ingredient are not impaired.

The content of the above components contained in the cleaning composition is determined by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). method, and ion-exchange chromatography (IC: (Ion-exchange Chromatography) method.

[pH]
The pH of the cleaning composition is not particularly limited, but is preferably greater than 7, more preferably 8 or more, from the viewpoint of superior stability of removal performance over time and superior corrosion resistance.
Although the upper limit of the pH is not particularly limited, it is preferably 14 or less, more preferably 12 or less.
The pH of the cleaning composition may be adjusted using the pH adjuster described above.
In the present specification, the pH of the detergent composition is obtained by measuring at 25° C. using a pH meter (F-51 (trade name) manufactured by Horiba, Ltd.).

〔Production method〕
The method for producing the cleaning composition is not particularly limited, and the composition can be produced, for example, by mixing the components described above. The order and/or timing of mixing the components described above is not particularly limited.
For example, a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and optional components are sequentially added to a mixer such as a mixing mixer filled with purified pure water, and then sufficiently stirred to mix each component. , a method of manufacturing a detergent composition.

It is preferable to use raw materials that are classified as semiconductor grades or those that are classified as high-purity grades corresponding thereto for each raw material used in the preparation of the detergent composition.
Moreover, any one or more of the raw materials for producing the cleaning composition may be purified in advance by distillation, ion exchange, or filtration.

The purification method is not particularly limited, but includes a method of passing through an ion exchange resin or RO membrane (Reverse Osmosis Membrane), distillation, and filtering. More specifically, after primary purification is performed by passing through a reverse osmosis membrane, secondary purification is performed by passing through a purification device comprising a cation exchange resin, an anion exchange resin, or a mixed bed ion exchange resin. methods of implementation.

<Kit and concentrate>
The cleaning composition may be a kit in which the raw material is divided into a plurality of parts.
Although not particularly limited, as a specific method of using the cleaning composition as a kit, for example, a liquid composition containing a hydroxylamine compound, a specific chelating agent and a benzotriazole compound is prepared as the first liquid, and An aspect of preparing a liquid composition containing other components is exemplified.
The cleaning composition may also be prepared using a concentrate. When preparing a concentrated solution of the detergent composition, the concentration ratio is appropriately determined depending on the composition, but is preferably 5 to 2000 times. That is, the detergent composition is used by diluting the concentrated solution 5- to 2000-fold. In order to further improve the stability of the removal performance over time, it is preferable to use a composition containing a large amount of an alcohol-based solvent while reducing water, which causes decomposition of the hydroxylamine compound, as much as possible.

<Container (container)>
The cleaning composition (regardless of whether it is a kit or a concentrate) can be stored, transported, and used in any container as long as no problem such as corrosiveness occurs. As for the container, it is preferable that the container has a high degree of cleanliness in the container and little elution of impurities for use in semiconductors. Usable containers include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry.

The container is preferably a container whose inside has been cleaned before being filled with the cleaning composition. It is preferable that the liquid used for cleaning has a reduced amount of metal impurities in the liquid. After production, the cleaning composition may be bottled in a container such as a gallon bottle or a coated bottle, transported, and stored.

<Clean room>
The manufacturing of the cleaning composition, the opening and/or cleaning of the storage container, the handling including the filling of the cleaning composition, processing analysis, and measurement are all preferably performed in a clean room. The clean room preferably meets 14644-1 clean room standards, more preferably ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, ISO Class 4, ISO Class 1 or ISO Class 2 is more preferred, and ISO Class 1 is particularly preferred.

[Washing method]
Examples of the cleaning method using the cleaning composition include a cleaning step (hereinafter also referred to as “cleaning step B”) of cleaning a semiconductor substrate having a metal layer using the cleaning composition. be done. In addition, the cleaning method may have a cleaning composition preparation step (hereinafter also referred to as “cleaning composition preparation step A”) for preparing the cleaning composition before the cleaning step B.
In the following description of the cleaning method, the case where the cleaning composition preparation step A is performed before the cleaning step B is shown as an example, but the cleaning method is not limited to this. It may be performed using an object.

<Items to be washed>
The object to be cleaned is not particularly limited as long as it is used in the manufacturing process of semiconductor devices, and examples thereof include a semiconductor substrate having a metal layer formed using a metal wiring material. Examples of metal wiring materials include Cu (copper), W (tungsten), and Co (cobalt).
A more specific object to be cleaned is, for example, a laminate having at least the metal layer, the interlayer insulating layer, and the metal hard mask on the substrate in this order. The laminate further has a hole formed from the surface (opening) of the metal hard mask toward the substrate so as to expose the surface of the metal layer through a dry etching process.

The method for manufacturing a laminate having a hole as described above is not particularly limited, but for example, for a pre-treatment laminate having a substrate, a metal layer, an interlayer insulating layer, and a metal hard mask in this order, A dry etching process is performed using the metal hard mask as a mask to etch the interlayer insulating layer so that the surface of the metal layer is exposed, thereby providing a hole penetrating through the metal hard mask and the interlayer insulating layer. mentioned.
The method of manufacturing the metal hard mask is not particularly limited. A method of manufacturing a metal hard mask (that is, a film in which a metal film is patterned) is exemplified by etching a metal film using the film as a mask.
After manufacturing the metal hard mask, a resist stripping step is performed to strip the resist film by dry ashing such as plasma ashing.
Residues containing organic components originating from the resist film are attached to the metal layer and/or the interlayer insulating layer of the substrate that has undergone the dry etching process and the resist stripping process. These adhering residues are removed from the laminate using the cleaning composition described above.
The laminate may have layers other than those mentioned above, including, for example, etch stop layers and antireflective layers.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate, which is an object to be cleaned in a cleaning method using the cleaning composition.
A laminate 10 shown in FIG. 1 includes a metal layer 2, an etching stop layer 3, an interlayer insulating layer 4, and a metal hard mask 5 on a substrate 1 in this order. A hole 6 through which 2 is exposed is formed. That is, the laminate 10 shown in FIG. is a laminate provided with a hole 6 penetrating from its surface to the surface of the metal layer 2 at the position of . Moreover, the resist film is removed in the laminate 10 shown in FIG. 1 by the resist stripping process.
The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a composed of the etching stop layer 3, the interlayer insulating layer 4 and the metal hard mask 5, and a bottom wall 11b composed of the exposed metal layer 2, and the residue 12 is adhered. ing.

The cleaning method can be suitably used for cleaning for the purpose of removing these residues 12 . In other words, the cleaning agent composition is excellent in removing the residue 12 and is excellent in preventing corrosion of the inner wall 11 (for example, the metal layer 2, etc.) of the object to be cleaned.
Each layer constituent material of the laminate described above will be described below.

(metal hard mask)
The metal hard mask preferably contains at least one component selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx and TaOx. Here, x and y are numbers represented by x=1 to 3 and y=1 to 2, respectively.
Examples of materials for the metal hard mask include TiN, _WO2 and _ZrO2 .

(Interlayer insulating layer)
Materials for the interlayer insulating layer are not particularly limited, and examples thereof include those having a dielectric constant k of preferably 3.0 or less, more preferably 2.6 or less.
Specific examples of materials for the interlayer insulating layer include SiO ₂ , SiOC-based materials, and organic polymers such as polyimide.

(Etching stop layer)
The material of the etching stop layer is not particularly limited. Specific materials for the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.

(metal layer)
The wiring material forming the metal layer is not particularly limited, and examples thereof include metals containing one or more selected from the group consisting of Cu (copper), W (tungsten), and Co (cobalt). The wiring material may be a metal consisting only of Cu, W or Co, or may be an alloy of Cu, W or Co and another metal. Among them, a metal containing W or Co is preferable, and a metal containing Co is more preferable.
Also, the wiring material may further contain metals other than Cu, W and Co, metal nitrides or alloys, such as titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxides, and It may further contain one or more selected from the group consisting of aluminum.

(substrate)
The "substrate" used herein includes, for example, a single-layer semiconductor substrate and a multi-layer semiconductor substrate.
The material constituting the single-layer semiconductor substrate is not particularly limited, and is preferably composed of silicon, silicon germanium, a group III-V compound such as GaAs, or any combination thereof.
In the case of a multi-layered semiconductor substrate, its configuration is not particularly limited. It may have a circuit structure. Metals and alloys used in interconnect structures include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. not a thing The semiconductor substrate may also have layers such as interlevel dielectric layers, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide.

<Processing process>
The cleaning composition preparation step A and the cleaning step B will be described in detail below.

(Detergent composition preparation step A)
The cleaning composition preparation step A is a step of preparing the cleaning composition. Each component used in this step is as described above.
The procedure of this step is not particularly limited, and for example, a method of preparing a detergent composition by adding a hydroxylamine compound, a specific chelating agent, a benzotriazole compound, and other optional components and stirring and mixing. is mentioned. In addition, when each component is added, it may be added all at once, or may be added in portions over a plurality of times.
In addition, each component contained in the detergent composition is preferably classified as a semiconductor grade or classified as a high-purity grade corresponding thereto. It is preferable to use one whose ionic components have been reduced by an exchange resin. Moreover, after mixing the raw material components, it is preferable to further remove foreign matter by filtering and/or reduce ion components by an ion exchange resin.

Further, when a concentrated liquid of the cleaning composition is prepared, the concentrated liquid is diluted to obtain a diluted liquid before performing the cleaning step B, and then the cleaning step B is performed using this diluted liquid. implement. At this time, the dilution is preferably performed using a diluent containing water.

(Washing step B)
Examples of the object to be cleaned in the cleaning process B include the laminate described above, and as described above, the laminate 10 in which holes are formed by the dry etching process and the dry ashing process is exemplified (Fig. 1). A residue 12 adheres to the inside of the hole 6 of the laminate 10 .

<Washing method>
The method of contacting the object to be cleaned with the cleaning composition is not particularly limited, but examples include a method of immersing the object to be cleaned in the cleaning composition in a container, and spraying the cleaning composition onto the object to be cleaned. Methods, methods of flowing a cleaning composition onto an object to be cleaned, and combinations thereof. From the viewpoint of removal performance, the method of immersing the object to be cleaned in the cleaning composition is preferred.

The temperature of the detergent composition is preferably 90°C or less, more preferably 25 to 80°C, even more preferably 30 to 75°C, and particularly preferably 40 to 70°C.

The cleaning time can be adjusted according to the cleaning method used and the temperature of the cleaning composition.
When washing by an immersion batch method (a batch method in which a plurality of objects to be washed are immersed and treated in a treatment tank), the washing time is, for example, within 60 minutes, preferably 1 to 60 minutes, and 3 to 3 to 60 minutes. 20 minutes is more preferred, and 4 to 15 minutes is even more preferred.

In the case of single wafer cleaning, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, more preferably 15 seconds to 3 minutes, and even more preferably 20 seconds to 2 minutes.

Further, a mechanical agitation method may be used to further enhance the cleaning ability of the cleaning composition.
Examples of mechanical stirring methods include a method of circulating the detergent composition over the object to be cleaned, a method of flowing or spraying the detergent composition over the object to be cleaned, and ultrasonic or megasonic cleaning. and a method of stirring the agent composition.

(Rinse step B2)
The method for cleaning a substrate using the cleaning composition may further include a step of cleaning the object to be cleaned by rinsing it with a solvent (hereinafter referred to as "rinsing step B2") after the cleaning step.
The rinsing step B2 is preferably performed following the washing step, and is preferably a step of rinsing with a rinsing solvent (rinsing liquid) for 5 seconds to 5 minutes. The rinsing step B2 may be performed using the mechanical agitation method described above.

The rinse solvent is not particularly limited, and examples thereof include deionized (DI) water, methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, γ-butyrolactone, dimethylsulfoxide, ethyl lactate and propylene glycol monomethyl ether acetate. be done. Aqueous rinses with a pH greater than 8 (such as dilute aqueous ammonium hydroxide) may also be utilized.
The rinse solvent is preferably an aqueous ammonium hydroxide solution, DI water, methanol, ethanol, or isopropyl alcohol, more preferably an aqueous ammonium hydroxide solution, DI water, or isopropyl alcohol, and even more preferably an aqueous ammonium hydroxide solution or DI water.
As the method of bringing the rinse solvent into contact with the object to be cleaned, the above-described method of bringing the cleaning composition into contact with the object to be cleaned can be similarly applied.
The temperature of the rinse solvent in the rinse step B2 is preferably 16-27°C.

(Drying step B3)
The substrate cleaning method using the cleaning composition may have a drying step of drying the cleaning object after the rinsing step.
The drying method is not particularly limited, and examples thereof include a spin drying method, a method of flowing a dry gas over the surface of the object to be cleaned, a method of heating the substrate with a heating means such as a hot plate or an infrared lamp, and a Marangoni drying method. , Rotagoni drying, IPA (isopropyl alcohol) drying, and combinations thereof.
The drying time varies depending on the drying method, but is preferably 30 seconds to several minutes.

The object to be cleaned in the method for cleaning a substrate using the cleaning composition is not limited to the laminate having at least a metal layer, an interlayer insulating layer and a metal hard mask on the substrate in this order as described above. For example, it can also be used to remove residue derived from a photoresist film adhering to a laminate comprising at least a metal layer, an interlayer insulating layer and a photoresist film on a substrate in this order.

The present invention will be described in more detail based on examples below. Materials, usage amounts, ratios, processing details, and processing procedures shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below. In addition, "%" intends "mass %" unless otherwise indicated.

[Preparation of detergent composition]
A cleaning composition was prepared according to the following procedure. In addition, in each detergent composition, the contents of various components used (all based on mass) are as described in the table.

〔material〕
Each raw material used for preparation of the detergent composition is shown below. All of the compounds used in the preparation of the detergent composition were those classified as semiconductor grades or those classified as high-purity grades corresponding thereto.

<Hydroxylamine compound (or redox agent)>
HA: hydroxylamine HAS: hydroxylamine sulfate DEHA: N,N-diethylhydroxylamine H ₂ O ₂ : hydrogen peroxide (not hydroxylamine compound)

<Specific chelating agent>
(Aminophosphonic acid compound)
1-a: Nitrilotris (methylene phosphonic acid)
1-b: ethylenediaminetetra(methylenephosphonic acid)
(Hydroxy acid compound)
2-a: diethanolglycine 2-b: citric acid 2-c: malic acid (phosphonocarboxylic acid compound)
3-a: 2-phosphonobutane-1,2,4-tricarboxylic acid 3-b: 4-phosphonobutyric acid 3-c: glycine-N,N-bis (methylene phosphonic acid)
(Aromatic carboxylic acid compound)
4-a: isophthalic acid 4-b: salicylic acid (polycarboxylic acid compound)
5-a: glutaric acid 5-b: 1,3,5-pentanetricarboxylic acid 5-c: 3-methyladipic acid 5-d: N,N'-di(2-hydroxybenzyl)ethylenediamine-N,N' - diacetic acid monohydrochloride hydrate (not included in specified chelating agents)
(Hydroxyphosphonic acid compound)
6-a: 1-hydroxyethane-1,1-diphosphonic acid 6-b: glycerol 3-phosphate

<pH adjuster>
DBU: 1,8-diazabicyclo[5.4.0]undecene-7
MEA: monoethanolamine TMAH: tetramethylammonium hydroxide

<Organic solvent>
EGBE: ethylene glycol monobutyl ether EGME: ethylene glycol monomethyl ether

<Water>
Water: DI water

〔evaluation〕
Various evaluations shown below were performed for each cleaning composition prepared above.

<Removal performance of organic residue>
A multi-layer substrate was prepared in which a resist film, a metal hard mask (TiN layer), an etching stop layer (Al ₂ O ₃ layer), a Co layer and an interlayer dielectric layer (ILD) were laminated in this order on the surface of the substrate. . This multilayer substrate is subjected to patterning processing by lithography, etching processing using a plasma etching apparatus for metal, and removal processing of the resist film by oxygen plasma ashing, and a multilayer substrate for evaluation test (hereinafter referred to as "test (also referred to as "piece") was produced. The obtained test piece was washed using the cleaning composition of each example and each comparative example.

200 mL of the cleaning composition was filled into a glass beaker with a volume of 500 mL. The temperature of the cleaning composition was raised to 65° C. while stirring using a stirrer. Then, while stirring, the test piece prepared above was immersed in the detergent composition at a liquid temperature of 65°C for 5 minutes to wash the test piece. While the specimen was immersed in the cleaning composition, the specimen was held with the photoresist-removed side of the specimen facing the stirrer using 4-inch long plastic locking tweezers.
After the cleaning time had elapsed, the specimen was immediately removed from the detergent composition and placed in 400 mL of gently stirred DI water (17° C. water temperature) filled in a 500 mL capacity plastic beaker. After immersing the specimen in DI water for 30 seconds, the specimen was immediately removed and rinsed under DI water flow at 17°C for 30 seconds.

Subsequently, the test piece was exposed to a stream of nitrogen gas to blow off droplets adhering to the surface of the test piece and dry the surface of the test piece.
After this nitrogen drying step, the test piece was removed from the holding portion of the plastic tweezers, and placed in a lidded plastic storage box with the element side up for storage.

The surface of the obtained test piece was subjected to composition analysis by X-ray Photoelectron Spectroscopy (XPS). The surface of the obtained test piece was measured using an XPS device (manufactured by Ulvac-PHI, trade name QuanteraSXM). Regarding the amount of fluorine atoms contained in the organic residue of the measured test piece, the reduction rate before and after the treatment was calculated and defined as the residue removal rate. The organic residue removal performance was evaluated according to the following evaluation criteria.
5: Removal rate is 95% or more 4: Removal rate is 80% or more and less than 95% 3: Removal rate is 75% or more and less than 80% 2: Removal rate is 50% or more and less than 75% 1: Removal rate is less than 50%

<Stability of removal performance over time>
Next, a storage test was performed using the cleaning composition of each example and each comparative example as a test solution, and the stability of the removal performance of each cleaning composition over time was evaluated.
A container made of high-density polyethylene having a capacity of 250 mL was filled with 200 mL of each test liquid prepared by the above method and sealed. The container filled with the test liquid was stored in an environment of 60°C for 24 hours.
Except for using the cleaning composition after the storage test, the removal performance evaluation test was performed according to the above-described removal performance evaluation method, and the stability over time of each cleaning composition was evaluated.

<Corrosion prevention>
A substrate (a substrate having a metal layer formed thereon) was prepared by forming a layer of Co (a Co layer) on one surface of a substrate (silicon wafer (diameter: 12 inches)) by a CVD (Chemical Vapor Deposition) method. Then, the substrate with the Co layer formed thereon was immersed in the cleaning compositions (65° C.) of Examples and Comparative Examples for 5 minutes.
The etching rate (Å/min) of the Co layer of the cleaning composition was calculated from the difference in the thickness of the Co layer before and after immersion in the cleaning composition. The lower the etching rate (ER) for Co measured in this test, the better the corrosion prevention for Co.
From the measured ER, the corrosion inhibitory property against Co was evaluated according to the following criteria.
A: ER<0.1 Å/min B: 0.1 Å/min≦ER<0.5 Å/min C: 0.5 Å/min≦ER<2.0 Å/min D: 2.0 Å/min≦ER<5 .0 Å/min E: 5.0 Å/min ≤ ER

〔result〕
The composition and evaluation results of each detergent composition are shown in Tables 1 to 7 below.
In the table, "HA compound" means "hydroxylamine compound" and "BTA compound" means "benzotriazole compound".
The notation "Yes" in the "pH adjuster" column indicates the pH adjuster contained in each cleaning composition. The content of the pH adjuster in each cleaning composition is such that the finally obtained cleaning composition has a pH value shown in the "pH" column in the table.
The description of "remainder" shown as the content of water means that the finally obtained cleaning composition contains the components excluding the pH adjuster of the content shown in the table and the pH of the amount that becomes the pH shown in the table. and a modifier, and the remaining component is water.

In the table, the "Ratio 1" column indicates the ratio (mass ratio) of the content of the hydroxylamine compound (or redox agent) to the content of the chelating agent, and the "Ratio 2" column indicates the content of the benzotetrazole compound. The content ratio (mass ratio) of the hydroxylamine compound (or redox agent) is shown.

In the table, the "removal performance" column shows the evaluation results of the organic residue removal performance using the cleaning composition of each example and each comparative example. The column "After preparation" of "Removal performance" shows the evaluation results of the removal performance performed immediately after preparing each cleaning composition, and the "After storage" column of "Removal performance" shows the results of each cleaning after the storage test. The results of evaluating the removal performance of the agent composition are shown.

From the results shown in the table, it was confirmed that the problems of the present invention can be solved by using the cleaning composition of the present invention.

From the results shown in the table, when the content of the specific chelating agent is 0.1% by mass or more with respect to the total mass of the cleaning composition, the removal performance is more stable over time, and when it is 0.5% by mass or more, In some cases, it was confirmed that the stability of the removal performance over time was even better (comparison of Examples 1 to 3, comparison of Examples 23, 24 and 27).
Moreover, it was confirmed that when the content of the specific chelating agent was 10% by mass or less with respect to the total mass of the cleaning composition, the anticorrosiveness was more excellent (comparison of Examples 4 and 5).

When the content of the specific chelating agent is 0.1% by mass or more with respect to the total mass of the cleaning composition, the stability of the removal performance over time is excellent, and when it is 0.5% by mass or more, the retention of the removal performance over time Further excellent stability was confirmed (comparison of Examples 1 to 3, comparison of Examples 24, 25 and 27).
Moreover, it was confirmed that when the content of the specific chelating agent was 10% by mass or less with respect to the total mass of the cleaning composition, the anticorrosiveness was more excellent (comparison of Examples 4 and 5).

In the cleaning composition, when the ratio 1 (mass ratio of the content of the hydroxylamine compound to the content of the specific chelating agent) is 100 or less, the removal performance is more stable over time, and when the ratio 1 is 10 or less. , It was confirmed that the stability of the removal performance over time was further excellent (comparison of Examples 1 to 3, comparison of Examples 24, 25 and 27).
In addition, it was confirmed that when the ratio 1 is 0.1 or more, the corrosion prevention property is excellent, and when the ratio 1 is 1 or more, the corrosion prevention property is further excellent (comparison of Examples 2, 4 and 5, (compare Examples 28 and 35).

It was confirmed that when the content of the benzotriazole compound was 0.5% by mass or less with respect to the total mass of the cleaning composition, the residue removal performance was superior (comparison between Examples 2 and 8).

It was confirmed that when the ratio 2 (mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound) in the cleaning composition was 1000 or less, the corrosion prevention was more excellent (Examples 7 and 12 comparison).
Moreover, it was confirmed that when the ratio 2 was 10 or more, the residue removal performance was superior (comparison between Examples 2 and 8).

From the results in Table 2, it was confirmed that among hydroxylamine compounds, when hydroxylamine or hydroxylamine sulfate was used, the removal performance was superior (comparison of Examples 24, 39 and 40).
In addition, it was confirmed that when two or more hydroxylamine compounds were used, corrosion prevention was superior to when a hydroxylamine compound was used alone (comparison of Examples 24, 39 and 41).

From the results of Tables 1 to 6, it was confirmed that among the specific chelating agents, when an aminophosphonic acid compound or a hydroxy acid compound was used, the removal performance and the stability of the removal performance over time were superior (Example 2, 16, 24, 35, 36, 45, 47, 48, 50, 52, 54, 56, 57, 59 and 61).

From the results in Table 3, it was confirmed that, among the phosphonocarboxylic acid compounds, when 2-phosphonobutane-1,2,4-tricarboxylic acid or 4-phosphonobutyric acid was used, the stability of removal performance over time was superior ( Comparison of Examples 45, 47 and 48), 2-phosphonobutane-1,2,4-tricarboxylic acid, or glycine-N,N-bis(methylenephosphonic acid) was confirmed to be more excellent in residue removal performance. (compare Examples 45, 47 and 48).

From the results in Table 5, it was confirmed that when glutaric acid was used among the polycarboxylic acid compounds, the stability of the removal performance over time was superior (comparison of Examples 54, 56 and 57). It was confirmed that the removal performance was superior when pentanetricarboxylic acid was used (comparison of Examples 54, 56 and 57).

From the results in Table 6, it was confirmed that when 1-hydroxyethane-1,1-diphosphonic acid was used among the hydroxyphosphonic acid compounds, it was superior in removal performance and corrosion prevention (comparison of Examples 59 and 61). , glycerol 3-phosphate, it was confirmed that the stability of the removal performance over time was superior (comparison of Examples 59 and 61).

REFERENCE SIGNS LIST 1 substrate 2 metal layer 3 etching stop layer 4 interlayer insulating layer 5 metal hard mask 6 hole 10 laminate 11 inner wall 11a cross-sectional wall 11b bottom wall 12 residue

Claims (12)

A cleaning composition for semiconductor devices, comprising:
one or more hydroxylamine compounds selected from the group consisting of hydroxylamine and hydroxylamine salts;
one or more chelating agents selected from the group consisting of carboxylic acid-based chelating agents other than polyaminocarboxylic acids, and phosphonic acid-based chelating agents;
a benzotriazole compound;
The content of the benzotriazole compound is 0.5% by mass or less with respect to the total mass of the cleaning composition.
cleaning composition. The cleaning composition according to claim 1, wherein said chelating agent comprises said phosphonic acid-based chelating agent. The cleaning composition according to claim 2, wherein the phosphonic acid-based chelating agent comprises one or more compounds selected from the group consisting of hydroxyphosphonic acid compounds, aminophosphonic acid compounds, and phosphonocarboxylic acid compounds. The cleaning composition according to claim 2 or 3, wherein the phosphonic acid-based chelating agent contains an aminophosphonic acid compound. The cleaning composition according to claim 1, wherein the chelating agent comprises the carboxylic acid-based chelating agent. The cleaning composition according to claim 5 , wherein the carboxylic acid-based chelating agent contains one or more compounds selected from the group consisting of hydroxy acid compounds, polycarboxylic acid compounds, and aromatic polycarboxylic acid compounds. The cleaning composition according to claim 5 or 6, wherein the carboxylic acid-based chelating agent contains a hydroxy acid compound. The hydroxylamine compound is the group consisting of hydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, hydroxylamine sulfate, N,N-dimethylhydroxylamine sulfate, and N,N-diethylhydroxylamine sulfate. The cleaning composition according to any one of claims 1 to 7, comprising one or more selected from. The cleaning composition according to any one of claims 1 to 8, wherein the benzotriazole compound contains a compound represented by the following formula (A).

In formula (A), R ¹¹ represents a carboxyl group, an amino group, or an alkyl group having 1 to 6 carbon atoms.
n represents an integer of 0 to 2;
^R12 represents a hydrogen atom or a hydroxyl group. The cleaning composition according to any one of claims 1 to 9, wherein the mass ratio of the content of the hydroxylamine compound to the content of the benzotriazole compound is 1-1000. The cleaning composition according to any one of claims 1 to 10, wherein the mass ratio of the content of the hydroxylamine compound to the content of the chelating agent is 0.1-100. The cleaning composition according to any one of claims 1 to 11, which is used for cleaning a substrate having a metal layer containing one or more selected from the group consisting of copper, tungsten and cobalt.

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