JP2003013266A - Substrate cleaning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal corrosion inhibitor, which is added to a cleaning agent particularly for the substrate surface having a copper electric wiring thereon, and can effectively remove metal impurities (copper oxide) on the surface, without causing corrosion and oxidation of the copper electric wiring. SOLUTION: The metal corrosion inhibitor includes amino acid having a thiol group in a molecular, like cysteine; or amino acid derivatives which include an N-acyl compound of amino acid like N-acetylcysteine, and a carboxylic acid ester of amino acid like a cysteine methyl ester. The substrate cleaning agent includes the above metal corrosion inhibitor.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal corrosion inhibitor,
The present invention also relates to a cleaning agent and a cleaning method for a substrate surface using the same, especially for a substrate surface having copper wiring on the surface.

[0002]

2. Description of the Related Art In recent years, the structure of LSI has been miniaturized along with higher integration, and has a multi-layer structure in which metal wiring and the like are superposed on the surface of a semiconductor. Also, it has been proposed that the wiring used is changed from conventional aluminum to copper (Cu) having a lower electric resistance.

In the process of manufacturing a semiconductor having a multi-layered structure in which copper wiring is provided in multiple layers on the surface, a so-called chemical-physical method in which a semiconductor substrate is physically polished and planarized while oxidizing metal Cu. Polishing technology (Cu-CMP) is used.

On the other hand, on the surface of the semiconductor after the Cu-CMP process, Cu is
The insulating film (silicon oxide) that separates the wiring and each Cu wiring is exposed, and the wafer surface after the Cu-CMP process is contaminated with a large amount of metallic impurities. Contamination of metal impurities is due to the fact that Cu scraped off by CMP is adsorbed on the insulating film and remains as metal oxide (copper oxide).

When the metal oxide (copper oxide) remains on the insulating film as described above, the copper element diffuses into the insulating film by the heat treatment in the subsequent step, and the insulating property is deteriorated to deteriorate the device characteristics. When the contamination is remarkable, the isolated wirings are connected to each other, that is, a short circuit occurs, and the device is destroyed. Therefore, it is necessary to remove the metal oxide (copper oxide) before proceeding to the next step.

For the above reasons, the cleaning process after the Cu-CMP process is indispensable for removing the metal impurities as described above.

On the other hand, the metallic copper on the surface of the semiconductor has a high activity, and is easily corroded by a slight oxidizing force to increase the wiring resistance or cause a disconnection. For this reason,
In the cleaning process after the Cu-CMP process, a cleaning liquid having a relatively strong oxidizing power, which is conventionally used as a cleaning liquid for semiconductors, and whose main component is an inorganic acid such as hydrochloric acid or hydrofluoric acid is used. The use of the acidic cleaning liquid is not preferable because not only the copper oxide adhered on the insulating film but also the metal copper of the wiring is dissolved. Further, a cleaning agent mainly composed of an organic acid having a relatively weak oxidizing power such as oxalic acid or citric acid has a weak copper dissolving action as compared with an inorganic acid, but since it has a copper dissolving action, it is as much as possible. It was necessary to use low concentrations of organic acids. For this reason, when the organic acid is used at a low concentration, the dissolving power of the metal oxide is also reduced, and it is necessary to clean the semiconductor surface for a long time.

In order to solve such a drawback, it is known that the corrosion of metallic copper on the semiconductor surface can be prevented by adding various metal corrosion inhibitors to the cleaning agent.

For example, Japanese Patent Application Laid-Open No. 7-79061 discloses aromatic compounds represented by benzotriazoles and imidazoles. However, these compounds have a low copper corrosion inhibitory effect, and the inhibitory effect is observed only at a high concentration. However, the compounds have low solubility in water, and it was difficult to add these compounds at a high concentration to ultrapure water that is generally used as a diluting solution when using a cleaning agent for semiconductors. Further, in order to use these compounds at a high concentration, an alkali solubilizing agent such as an amine or an alcoholic organic solvent is required, but since these solubilizing agents and organic solvents adversely affect the cleaning characteristics, It was difficult to use.

Further, JP-A-2000-87268 and JP-A-2000-282096 disclose cyclic compounds such as mercaptoimidazole and mercaptothiazole. However, when these compounds bind to the copper on the semiconductor surface, the copper surface becomes hydrophobic and prevents the attack of the cleaning agent, making it difficult to remove these compounds. As described above, when the semiconductor is subjected to heat treatment in a later process or device operation while the organic substances such as these compounds remain on the copper surface, the organic substances are burned or exploded, and serious defects are caused. There are problems such as the occurrence of the problem, strong toxicity, and safety for the human body and the environment.

Further, in Japanese Patent Laid-Open No. 2000-273663, carbon having a mercapto group in the molecule and having a mercapto group bonded thereto and a carbon having a hydroxyl group bonded thereto, such as mercaptoethanol and mercaptoglycerol. Disclosed are aliphatic alcohol-based compounds in which are bound adjacently. However, Japanese Patent Laid-Open No. 2000-27366
The invention disclosed in Japanese Patent Publication No. 3 discloses a metal corrosion inhibitor which is less likely to have a harmful effect on human health and an ecosystem as compared with the conventional one, because of problems relating to the human body and environmental pollution in recent years. Although it was made for the purpose of providing it, it is highly toxic and still has a problem in safety.Moreover, these compounds have a relatively low vapor pressure, and they have an unpleasant odor even when they are used by being added to an aqueous solution. However, it is not practical.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and a metal corrosion inhibitor having a good metal corrosion prevention action and high safety, and a substrate using the same. Surface, in particular, a method of treating the substrate that can prevent oxidation and corrosion of copper wiring on the surface of the substrate having copper wiring on the surface, and can prevent corrosion and oxidation of copper wiring on the surface of the substrate, In addition, the present invention provides a method for cleaning a substrate that can effectively remove metal impurities (copper oxide) on the surface.

[0013]

The present invention has the following constitution.

(1) A metal corrosion inhibitor containing an amino acid having a thiol group in the molecule or a derivative thereof.

(2) A treating agent containing the metal corrosion inhibitor according to (1) above.

(3) A method of treating a substrate, which comprises treating the substrate with the treatment agent described in (2) above.

(4) A detergent containing the metal corrosion inhibitor according to (1) above.

(5) A method of cleaning a substrate, which comprises cleaning the substrate with the cleaning agent described in (4) above.

(6) A semiconductor substrate having a copper coating on the surface is subjected to chemical physical polishing (CMP), and then the substrate is treated with the treating agent described in (2) above. A method for treating the substrate.

(7) After subjecting a semiconductor substrate having a copper coating on the surface to chemical physical polishing (CMP), the substrate is treated with the treatment agent described in (2) above, and then the substrate is treated. A method for treating a substrate, which comprises cleaning with a semiconductor substrate cleaning agent.

(8) A semiconductor substrate having a copper coating on the surface is subjected to chemical physical polishing (CMP), and then the substrate is washed with the cleaning agent described in (4) above. A method for cleaning the substrate.

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, an amino acid having a thiol group in the molecule or a derivative thereof has a good effect of preventing metal corrosion and is highly safe. And if the substrate is treated with a cleaning agent containing the amino acid or its derivative, the substrate surface, particularly the substrate surface having copper wiring on the surface, does not cause corrosion or oxidation of the copper wiring, The inventors have found that metal impurities (copper oxide) can be effectively removed, and have completed the present invention.

The amino acid having a thiol group in the molecule of the present invention (hereinafter sometimes abbreviated as the amino acid of the present invention) has a thiol group, a carboxyl group and an amino group in the molecule, Specific examples thereof include compounds represented by the following general formula [1].

[0024]

[Chemical 1]

(In the formula, R represents a lower alkylene group.)

In the general formula [1], examples of the lower alkylene group represented by R include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, propylene group, butylene group,
Number of linear, branched or cyclic carbon atoms such as methylmethylene group, ethylethylene group, methylethylene group, methylpropylene group, ethylpropylene group, pentylene group, hexylene group, cyclopentylene group and cyclohexylene group 1
~ 6 lower alkylene groups. Among them, a linear alkylene group having 1 to 6 carbon atoms (methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group) is preferable, and a methylene group or ethylene group is particularly preferable.

The amino acid having a thiol group in the molecule according to the present invention may be a commercially available product (for example, manufactured by Wako Pure Chemical Industries, Ltd.), or may be appropriately prepared according to a method known per se and used. Good.

More specific examples of the compound represented by the above general formula [1] include cysteine and homocysteine, which are in the D form, the L form, the DL form, and the mixing ratio thereof, respectively. It is also possible to use a mixture of a D-form and an L-form having different values.

As described above, the derivative of the amino acid having a thiol group in the molecule of the present invention is not particularly limited as long as it has a metal corrosion inhibiting action. For example, N-acyl of the amino acid of the present invention can be used. Or a carboxylic acid ester of the amino acid according to the present invention.

The N-acyl derivative of the amino acid according to the present invention is
The acyl group is introduced into the hydrogen atom of the amino group of the amino acid according to the present invention as described above. Specifically, as shown in the following general formula [2], the above general formula [1]
In the above, an acyl group is introduced into the hydroxyl group of the amino group.

[0031]

[Chemical 2]

(In the formula, R ¹ represents an acyl group, and R is as defined above.)

The acyl group introduced into the hydrogen atom of the amino group of the amino acid according to the present invention or the acyl group represented by R ¹ in the general formula [2] may be linear, branched or cyclic. Well, for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group,
C1-C1 such as cyclopropionylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group
6 derived from saturated aliphatic monocarboxylic acid, for example, derived from unsaturated aliphatic monocarboxylic acid having 3 to 7 carbon atoms such as acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, for example, benzoyl group, Naphthoyl group, pentalene carbonyl group, indene carbonyl group, azulene carbonyl group, heptalene carbonyl group, indacene carbonyl group, anthracene carbonyl group, phenanthrene carbonyl group, triphenylene carbonyl group, pyrene carbonyl group, naphthacene carbonyl group, pyrylene Carbon number such as carbonyl group, pentacene carbonyl group and the like, preferably 7 to 12 carbon atoms
Derived from an aromatic monocarboxylic acid such as phenylmethylcarbonyl group, phenylethylcarbonyl group, phenylpropylcarbonyl group, phenylisopropylcarbonyl group, phenylbutylcarbonyl group, phenylisobutylcarbonyl group, phenylpentylcarbonyl group,
Phenylisopentylcarbonyl group, phenylneopentylcarbonyl group, phenylhexylcarbonyl group, phenylisohexylcarbonyl group, phenylethylpentylcarbonyl group, phenylmethylpentylcarbonyl group, phenyldimethylbutylcarbonyl group, phenylethylbutylcarbonyl group, phenylheptylcarbonyl group Group, phenylmethylhexylcarbonyl group, phenyldimethylpentylcarbonyl group, phenyloctylcarbonyl group, phenylnonylcarbonyl group, phenyldecylcarbonyl group, phenylundecylcarbonyl group, phenyldodecylcarbonyl group, phenyltridecylcarbonyl group, phenylcyclopropylcarbonyl group Group, phenylcyclopentylcarbonyl group, phenylcyclohexylcarbonyl group, Phenylcyclohexylcarbonyl group, phenylcycloheptylcarbonyl group, phenylcyclooctylcarbonyl group, phenylcyclononylcarbonyl group, phenylcyclodecylcarbonyl group, phenylcycloundecylcarbonyl group, phenylcyclododecylcarbonyl group, phenylcyclotridecylcarbonyl group, etc. And those derived from aralkyl monocarboxylic acid having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms.
The aromatic ring of an acyl group derived from an aromatic monocarboxylic acid or an acyl group derived from an aralkyl monocarboxylic acid as described above may have a lower alkyl group such as a methyl group or an ethyl group as a substituent. Good. Among the acyl groups as described above, those derived from saturated aliphatic monocarboxylic acid and those derived from aralkyl monocarboxylic acid are preferable, more preferably those derived from saturated aliphatic monocarboxylic acid, and further preferably linear It is derived from the saturated aliphatic monocarboxylic acid. Among the linear saturated acyl monocarboxylic acid-derived acyl groups, an acetyl group is particularly preferable.

The N-acyl derivative of an amino acid having a thiol group in the molecule according to the present invention may be a commercially available product (for example, manufactured by Wako Pure Chemical Industries, Ltd.) or may be prepared by a method known per se. It may be appropriately prepared and used.

The N-acyl derivative of the amino acid according to the present invention is an N-alkanoyl derivative in which an acyl group derived from a saturated aliphatic monocarboxylic acid is introduced into the hydrogen atom of the amino group of the amino acid according to the present invention (generally, R ^{1 in the} formula [2] is an acyl group derived from a saturated aliphatic monocarboxylic acid) and an N-aralkanoyl compound into which an acyl group derived from an aralkyl monocarboxylic acid is introduced (in the general formula [2] R ¹ is an acyl group derived from aralkyl monocarboxylic acid), more preferably an N-alkanoyl derivative, and even more preferably a linear group at the hydrogen atom of the amino group of the amino acid according to the present invention. Saturated aliphatic monocarboxylic acid-derived acyl group-introduced N-linear alkanoyl compound (R ¹ in the general formula [2] is a linear saturated aliphatic monocarboxylic acid-derived acyl group) Something). Of these, an N-acetyl derivative in which an acetyl group is introduced into the hydrogen atom of the amino group of the amino acid according to the present invention (R ¹ in the general formula [2] is an acetyl group) is particularly preferable. Specific examples of the N-acyl derivative of the amino acid according to the present invention (compound represented by the general formula [2]) include, for example, N-acetyl cysteine, N-butyryl cysteine, N-cyclohexylcarbonyl cysteine, N-propioroyl. Cysteine, N-crotonoyl cysteine, N-benzoyl cysteine, N-naphthoyl cysteine, N-phenylmethyl carbonyl cysteine, N-phenylbutyl carbonyl cysteine, N-phenyl cyclohexyl carbonyl cysteine, N-acetyl homocysteine, N-butyryl Homocysteine, N-cyclohexylcarbonyl homocysteine, N-propioroyl homocysteine, N-crotonoyl homocysteine, N-benzoyl homocysteine, N-naphthoyl homocysteine, N-phenylmethylcarbonyl homocysteine, N-phenylbutyl Carbonyl homozy Stain, N-phenyl cyclohexyl carbonyl homocysteine and the like,
These can be used in the D-form, the L-form, the DL-form, or the mixture of the D-form and the L-form having different mixing ratios.

The carboxylic acid ester of the amino acid according to the present invention is an ester of the carboxyl group of the amino acid according to the present invention as described above. Specifically, as shown in the following general formula [2], an acyl group is introduced into the hydroxyl group of the carboxyl group in the general formula [1].

[0037]

[Chemical 3]

(In the formula, R ² represents a hydrocarbon residue, and R is the same as above.)

In the general formula [3], the hydrocarbon residue represented by R ² may be aliphatic, aromatic, araliphatic or alicyclic as long as it is a monovalent group. ,Also,
The aliphatic aliphatic and araliphatic may be saturated or unsaturated, and may be linear or branched. Typical examples thereof include linear, branched, or cyclic saturated or unsaturated alkyl groups, aryl groups, aralkyl groups, alkenyl groups, and the like. Examples of the alkyl group include those having 1 to 10 carbon atoms, preferably those having 1 to 6 carbon atoms, and more preferably those having 1 to 4 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group. , Iso-propyl group, n-butyl group, iso-butyl group,
sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, iso-hexyl group, 3-methylpentyl group, 2 -Methylpentyl group, 1,2-dimethylbutyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, iso-heptyl group, sec-heptyl group, n-octyl group,
Examples thereof include iso-octyl group, sec-octyl group, n-nonyl group, n-decyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclodecyl group. Examples of the aryl group include those having 6 to 14 carbon atoms, specifically, for example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2, 4-xylyl group, 2,5
-Xylyl group, 2,6-xylyl group, 3,5-xylyl group, naphthyl group, anthryl group and the like. Examples of the aralkyl group include those having 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms, and specific examples thereof include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylhexyl group and methyl. Examples thereof include a benzyl group, a methylphenethyl group and an ethylbenzyl group.
The aromatic ring of the aryl group or aralkyl group as described above may have a lower alkyl group such as a methyl group or an ethyl group, a halogen atom, a nitro group, an amino group or the like as a substituent. The alkenyl group is usually 2
10 are mentioned, and specifically, for example, vinyl group,
Allyl group, 1-propenyl group, iso-propenyl group, 3-butenyl group, 2-butenyl group, 1-butenyl group, 1,3-butadienyl group, 4-pentenyl group, 3-pentenyl group, 2-pentenyl group, 1-pentenyl group, 1,3-pentadienyl group, 2,4-pentadienyl group, 1,1-dimethyl-2-propenyl group, 1-ethyl-2-propenyl group, 1,2-dimethyl-1-propenyl group, 1-
Methyl-1-butenyl group, 5-hexenyl group, 4-hexenyl group, 2-hexenyl group, 1-hexenyl group, 1-methyl-1-hexenyl group, 2-methyl-2-hexenyl group, 3-methyl1, 3-
Hexadienyl group, 1-heptanyl group, 2-octenyl group,
3-nonenyl group, 4-decenyl group, 2-cyclopentenyl group,
2,4-cyclopentadienyl group, 1-cyclohexenyl group,
Examples thereof include a 2-cyclohexenyl group, a 3-cyclohexenyl group, a 2-cycloheptenyl group, a 2-cyclononenyl group and a 3-cyclodecenyl group. Of these, an alkyl group and an aralkyl group are preferable, a lower alkyl group having 1 to 6 carbon atoms and a benzyl group are more preferable, and a lower alkyl group having 1 to 6 carbon atoms is still more preferable.

The carboxylic acid ester form of an amino acid having a thiol group in the molecule according to the present invention may be a commercially available product (for example, manufactured by Wako Pure Chemical Industries, Ltd.) or may be appropriately used according to a method known per se. You may prepare and use it.

The carboxylic acid ester form of the amino acid according to the present invention is an alkyl ester form in which an alkyl group is introduced into the carboxyl group of the amino acid according to the present invention (R ^{2 in the} general formula [3] is an alkyl group). That is)
And an aralkyl ester body in which an aralkyl group is introduced (wherein R ² in the general formula [3] is an aralkyl group) are preferable, and more preferably, the carboxyl group of the amino acid according to the present invention has 1 to 6 carbon atoms. A lower alkyl ester body in which the alkyl group of (in the general formula [3]
In which R ² in the formula is a lower alkyl group having 1 to 6 carbon atoms) and a benzyl ester into which a benzyl group has been introduced (in which R ² in the general formula [3] is a benzyl group)
And more preferably a lower alkyl ester form. Specific examples of the carboxylic acid ester form of the amino acid according to the present invention (compound represented by the general formula [3]) include, for example, cysteine methyl ester, cysteine ethyl ester, cysteine isobutyl ester, cysteine n-hexyl ester, cysteine cyclohexyl ester, Cysteine phenyl ester, cysteine naphthyl ester, cysteine benzyl ester, cysteine methylbenzyl ester, cysteine vinyl ester, cysteine 3-butenyl ester, cysteine 3-cyclohexenyl ester, homocysteine methyl ester, homocysteine ethyl ester, homocysteine isobutyl ester, Homocysteine n-hexyl ester, homocysteine cyclohexyl ester, homocysteine phenyl ester, homocysteine Examples include futyl ester, homocysteine benzyl ester, homocysteine methylbenzyl ester, homocysteine vinyl ester, homocysteine 3-butenyl ester, homocysteine 3-cyclohexenyl ester, and the like. These are D-form, L-form, DL-form. However, it is also possible to use a mixture of D-form and L-form with different mixing ratios.

The amino acid having a thiol group in the molecule or its derivative according to the present invention as described above may be used alone or in combination of two or more kinds.

The amount of the amino acid having a thiol group in the molecule or its derivative used cannot be generally stated because it depends on the type of the amino acid having a thiol group in the molecule or its derivative and the surface area of the substrate to be treated. Eg normal
The amount is 0.0001 to 10% by weight, preferably 0.0001 to 1% by weight, and more preferably 0.0001 to 0.5% by weight.

The metal corrosion inhibitor of the present invention comprises the amino acid having a thiol group in the molecule or its derivative as described above according to the present invention. The metal corrosion inhibitor of the present invention is usually in the state of an aqueous solution, and is prepared by adding and dissolving the amino acid or its derivative according to the present invention in water.

The method for dissolving the amino acid or its derivative according to the present invention in water is, for example, the method of adding the amino acid or its derivative according to the present invention separately dissolved in water, or the amino acid or its derivative according to the present invention. Examples of the method include adding directly to water, dissolving and stirring.

The metal corrosion inhibitor of the present invention thus prepared is preferably filtered before use. Further, the water used here may be water purified by distillation, ion exchange treatment, etc., but so-called ultrapure water used in this field is more preferable.

Further, in the metal corrosion inhibitor according to the present invention,
In addition to the amino acid or its derivative according to the present invention as described above, reagents usually used in this field can be used. Examples of such reagents include organic acids, amines, inorganic alkali compounds, chelating agents, surfactants and the like.

The organic acid used in the present invention is not particularly limited as long as it is usually used in this field, and for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid. , Suberic acid, 2-n-butylmalonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, phthalic acid, isophthalic acid, terephthalic acid and the like, dicarboxylic acids having 2 to 8 carbon atoms, such as tricarballylic acid, benzenetricarboxylic acid Tricarboxylic acids having 6 or more carbon atoms such as acids, for example, monohydroxydicarboxylic acids having 3 or more carbon atoms such as tartronic acid and malic acid, dihydroxydicarboxylic acids having 4 or more carbon atoms such as tartaric acid,
Examples thereof include monohydroxytricarboxylic acids having 6 or more carbon atoms such as citric acid, for example hydroxytricarboxylic acid, ammonium salts thereof, and the like. Among them, dicarboxylic acid, monohydroxydicarboxylic acid, monohydroxytricarboxylic acid and dihydroxydicarboxylic acid are preferable, and dicarboxylic acid and monohydroxytricarboxylic acid are particularly preferable. More specifically, oxalic acid, malonic acid,
Phthalic acid, malic acid, citric acid and tartaric acid are preferable, and citric acid and oxalic acid are particularly preferable. Moreover, these organic acids may be used alone or in combination of two or more kinds. The amount of the organic acid used cannot be generally specified because it varies depending on the type of the organic acid, but is usually 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, and more preferably 0.0.
It is 5 to 10% by weight.

The amine used in the present invention is not particularly limited as long as it is usually used in this field, and examples thereof include methylamine and ethylamine.
C1-C6 alkylamines such as n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, cyclopentylamine, cyclohexylamine, etc., such as dimethylamine, methylethylamine, diethylamine, dipropylamine, etc. A dialkylamine having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, for example, a trialkylamine having 3 to 18 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylamine, dimethylethylamine, methyldiethylamine, triethylamine and tripropylamine. For example, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine and the like having 1 to 18 carbon atoms, preferably 1 to 6 carbon mono- or trihydroxyalkylamines, such as methylenediamine. Min, ethylenediamine, propylenediamine, isopropylenediamine, butylenediamine, methylmethylenediamine, ethylethylenediamine, methylethylenediamine, methylpropylenediamine, ethylpropylenediamine, pentylenediamine, hexylenediamine, cyclopentylenediamine, cyclohexylenediamine, etc. C1-C6 alkylenediamine, for example dimethylenetriamine, diethylenetriamine, etc., having 2-12 carbon atoms, preferably C2-C4 dialkylenetriamine, for example, trimethylenetetramine, triethylenetetramine, etc.
18, preferably a C 3-6 trialkylenetetramine, such as tetramethylammonium hydroxide,
Tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-pentylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetracyclopentylammonium hydroxide, tetracyclohexylammonium Tetraalkylammonium hydroxide having 4 to 24 carbon atoms such as hydroxide, for example, the following general formula [4]

[0050]

[Chemical 4]

(In the formula, R ³ is an alkyl group, R ⁴ and R
⁵ represents an alkylene group, and m and n represent a positive integer. ) And an alkylamine-alkylene oxide adduct. In the general formula [4], R ³
Examples of the alkyl group represented by include linear, branched or cyclic ones having 1 to 10 carbon atoms, preferably those having 1 to 6 carbon atoms, more preferably those having 1 to 4 carbon atoms. Include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, se
c-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, iso-hexyl group, 3-methylpentyl group, 2 -Methylpentyl group, 1,2-dimethylbutyl group,
sec-hexyl group, tert-hexyl group, n-heptyl group, iso
-Heptyl group, sec-heptyl group, n-octyl group, iso-octyl group, sec-octyl group, n-nonyl group, n-decyl group,
Examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a cyclodecyl group. Of these, a cyclohexyl group and the like are particularly preferable. Examples of the alkylene group represented by R ⁴ and R ⁵ include linear, branched or cyclic carbon atoms of 1 to
6 is preferably a lower alkylene group such as methylene group,
Ethylene group, propylene group, butylene group, methylmethylene group, ethylethylene group, methylethylene group, methylpropylene group, ethylpropylene group, pentylene group, hexylene group, cyclopentylene group, cyclohexylene group and the like, Of these, a methylene group and an ethylene group are particularly preferable. In addition, m and n are positive integers, and usually 1 to
10, preferably 1-5. Specific examples of the alkylamine-alkylene oxide adduct represented by the general formula [4] as described above include, for example, methylamine di (polyoxymethylene), methylamine di (polyoxyethylene), methylamine di (polyoxyethyl propylene), methylamine di (Polyoxycyclohexylene), Methylamine (Polyoxymethylene) (Polyoxyethylene), Methylamine (Polyoxymethylene)
(Polyoxyethylpropylene), methylamine (polyoxymethylene) (polyoxycyclohexylene), methylamine (polyoxyethylene) (polyoxyethylpropylene), methylamine (polyoxyethylene)
(Polyoxycyclohexylene), methylamine (polyoxyethylpropylene) (polyoxycyclohexylene), ethylamine di (polyoxymethylene), ethylamine di (polyoxyethylene), ethylamine di (polyoxyethylpropylene), ethylamine di ( Polyoxycyclohexylene), ethylamine (polyoxymethylene) (polyoxyethylene), ethylamine (polyoxymethylene) (polyoxyethylpropylene), ethylamine (polyoxymethylene) (polyoxycyclohexylene), ethylamine (polyoxyethylene)
(Polyoxyethylpropylene), ethylamine (polyoxyethylene) (polyoxycyclohexylene), ethylamine (polyoxyethylpropylene) (polyoxycyclohexylene), propylaminedi (polyoxymethylene), propylaminedi (polyoxyethylene) ), Propylaminedi (polyoxyethylpropylene), propylaminedi (polyoxycyclohexylene), propylamine (polyoxymethylene) (polyoxyethylene), propylamine (polyoxymethylene) (polyoxyethylpropylene), propyl Amine (polyoxymethylene) (polyoxycyclohexylene), propylamine (polyoxyethylene) (polyoxyethylpropylene), propylamine (polyoxyethylene) (polyoxycyclo Xylene), propylamine (polyoxyethylpropylene) (polyoxycyclohexylene), and other alkylamine di (polyoxyalkylenes) such as cyclohexylamine di (polyoxymethylene), cyclohexylamine di (polyoxyethylene), cyclohexylamine di (Polyoxypropylene), cyclohexylamine di (polyoxybutylene), cyclohexylamine di (polyoxymethylmethylene), cyclohexylamine di (polyoxyethylethylene), cyclohexylamine di (polyoxyethylpropylene), cyclohexylamine di (poly Oxypentylene), cyclohexylamine di (polyoxyhexylene), cyclohexylamine di (polyoxycyclohexylene), cyclohexylamine (polyoxymethene) Ren) (polyoxyethylene), cyclohexylamine (polyoxymethylene) (polyoxyethylated propylene), cyclohexylamine (polyoxymethylene)
(Polyoxycyclohexylene), cyclohexylamine (polyoxyethylene) (polyoxyethylpropylene), cyclohexylamine (polyoxyethylene)
(Polyoxycyclohexylene), cyclohexylamine (polyoxyethylpropylene) (polyoxycyclohexylene), cyclodecylamine di (polyoxymethylene), cyclodecylamine di (polyoxyethylene), cyclodecylamine di (polyoxyethyl) Propylene), cyclodecylamine di (polyoxycyclohexylene), cyclodecylamine (polyoxymethylene)
(Polyoxyethylene), cyclodecylamine (polyoxymethylene) (polyoxyethylpropylene), cyclodecylamine (polyoxymethylene) (polyoxycyclohexylene), cyclodecylamine (polyoxyethylene) (polyoxyethylpropylene) , Cyclodecylamine (polyoxyethylene) (polyoxycyclohexylene), cyclodecylamine (polyoxyethylpropylene) (polyoxycyclohexylene), and other cycloalkylamine di (polyoxyalkylene).

Among the above-mentioned amines, alkylenediamine, dialkylenetriamine, trialkylenetetramine, alkylamine-alkyleneoxide adduct and tetraalkylammonium hydroxide are preferable, and among them, alkylenediamine, cycloalkylaminedi (polyoxy). Alkylene) is particularly preferred. Specifically, ethylenediamine, diethylenetriamine, triethylenetetramine, cyclohexylaminedi (polyoxyethylene), cyclohexylamine (polyoxyethylene) (polyoxymethylene), and tetramethylammonium hydroxide are preferable, and among them, ethylenediamine and cyclohexylaminediamine are preferable. (Polyoxyethylene) is particularly preferred. These amines may be used alone or in combination of two or more kinds. The amount of amine used varies depending on the type of amine and cannot be generally stated, but is usually 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, more preferably 0.05 to 10% by weight.
Is.

The inorganic alkaline compound used in the present invention is not particularly limited as long as it is one usually used in this field, and for example, hydroxyamine,
Hydrazine, ammonia, their salts (eg hydrochloride,
Nitrogen-containing inorganic alkali compounds such as sulfates), for example, inorganic alkalis such as potassium hydroxide and sodium hydroxide, and the like. Among these, nitrogen-containing inorganic alkali compounds are preferable, and nitrogen-containing inorganic alkali compounds containing no metal are particularly preferable. Specifically, hydroxylamine, hydrazine and ammonia are preferable, and ammonia is particularly preferable. These inorganic alkaline compounds may be used alone or in combination of two or more kinds. The amount of the inorganic alkali compound used varies depending on the type of the inorganic alkali compound and cannot be generally specified, but is, for example, usually 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, and more preferably 0.05 to 10% by weight.

The chelating agent used in the present invention is not particularly limited as long as it is usually used in this field. By adding a chelating agent, metal oxides such as copper oxide dispersed in the liquid can be solubilized and re-adsorption can be suppressed, and impurities such as Fe and Al can be removed from the substrate surface. . Examples of such chelating agents include EDTA (ethylenediaminetetraacetic acid),
EDDA (Ethylenediaminediacetic acid), EDTA-OH
(Hydroxyethylenediaminetriacetic acid), GEDTA
(Glycol ether diamine tetraacetic acid), DTPA (diethylenetriamine pentaacetic acid), IDA (iminodiacetic acid), methyl-EDTA (diaminopropane tetraacetic acid), NTA (nitrilotriacetic acid), TTHA (triethylenetetramine hexaacetic acid), ammonium thereof. Amino acids such as salts, linear aminopolycarboxylic acids such as complex salts of these with amines such as CyDTA (trans-cyclohexyldiaminotetraacetic acid), ammonium salts thereof, cyclic aminopolycarboxylic acids such as complex salts of these with amines, and the like. Polycarboxylic acids such as NTPO (nitrilotrismethylenephosphonic acid), HEDPO (hydroxyethylidene di (methylenephosphonic acid)), ammonium salts thereof, and complex salts of these with amines such as EDDPO (ethylene chloride). Jiaminji (methylene phosphonic acid)), EDTPO (ethylene diamine tetra (methylene phosphonic acid)), PDTPO (diaminopropane tetra (methylenephosphonic acid)), DETPPO (diethylene triamine penta (methylene phosphonic acid)), TT
Examples thereof include HPO (triethylenetetramine hexa (methylenephosphonic acid)), ammonium salts thereof, phosphonic acids such as aminopolyphosphonic acids such as complex salts of these with amines, and the like. Among them, EDTA, CyDTA, H
Particularly preferred are EDPO, EDTPO, DETPPO, ammonium salts thereof, and complex salts of these with amines. In addition, in the above, as the amine forming the complex salt, the same amines as mentioned above can be mentioned. Also,
These chelating agents may be used alone or in combination of two or more kinds. The amount of the chelating agent used varies depending on the type of the chelating agent and cannot be generally stated, but is usually 0.0001 to 10% by weight, preferably 0.0001 to
It is 1% by weight, more preferably 0.0001 to 0.5% by weight.

The surfactant used in the present invention is not particularly limited as long as it is usually used in this field. The addition of a surfactant may improve the wettability of the aqueous solution with respect to the substrate surface. Examples of such a surfactant include a nonionic surfactant having a polyoxyalkylene group in the molecule, for example, a group selected from a sulfonic acid group, a carboxyl group, a phosphonic acid group, a sulfoxyl group and a phosphonoxyl group in the molecule. Anionic surfactants having, for example, alkylamines, for example, quaternary ammoniums such as alkyltrimethylammonium, alkyldimethylbenzylammonium, for example, alkylpyridinium, salts thereof (for example, hydrochloride,
(Sulfate, etc.), etc., and cationic surfactants such as alkylbetaine derivatives, imidazolinium betaine derivatives, sulfobetaine derivatives, aminocarboxylic acid derivatives, imidazoline derivatives, amine oxide derivatives, and other amphoteric surfactants. It is not limited to these. Examples of the nonionic surfactant having a polyoxyalkylene group in the molecule include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene polyalkylaryl ether and the like, and more specifically, for example, polyoxyethylene alkyl ether and polyoxyethylene alkyl ether. Nonionic surfactants having a polyoxyethylene group in the molecule such as oxyethylene alkylphenyl ether, for example, nonionic surfactants having a polyoxypropylene group in the molecule such as polyoxypropylene alkyl ether and polyoxypropylene alkylphenyl ether Agents such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl phenyl ether, etc. Nonionic surfactants having a group. Examples of the anionic surfactant having a group selected from a sulfonic acid group, a carboxyl group, a phosphonic acid group, a sulfoxyl group and a phosphonoxyl group in the molecule include, for example, alkylsulfonic acid, alkylbenzenesulfonic acid,
An anionic surfactant having a sulfonic acid group in the molecule such as alkylnaphthalene sulfonic acid, a salt thereof (for example, an alkali metal salt such as sodium and potassium, for example, an ammonium salt, among which an ammonium salt is preferable),
For example, alkyl carboxylic acid, alkyl benzene carboxylic acid, alkyl naphthalene carboxylic acid, and salts thereof (for example, alkali metal salts such as sodium and potassium, for example, ammonium salt, and among others, ammonium salt is preferable).
Anionic surfactants having a carboxyl group in the molecule such as, for example, alkylphosphonic acid, alkylbenzenephosphonic acid, alkylnaphthalenephosphonic acid, salts thereof (for example, alkali metal salts such as sodium and potassium, for example, ammonium salt, etc., among others) (An ammonium salt is preferred) and the like, an anionic surfactant having a phosphonic acid group in the molecule, for example, alkyl sulfate, alkylbenzene sulfate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylbenzene sulfate, polyoxyethylene alkylnaphthalene sulfate. Anionic compounds having a sulfoxyl group in the molecule, such as esters and their salts (for example, alkali metal salts such as sodium and potassium, for example, ammonium salts, among which ammonium salts are preferred) Surface active agents, and the like. Of these, nonionic surfactants and anionic surfactants are preferable. Further, polyoxyalkylene alkyl ether is particularly preferable as the nonionic surfactant, and those having a sulfonic acid group in the molecule and those having a sulfoxyl group in the molecule are particularly preferable as the anionic surfactant. More specifically, a nonionic surfactant having a polyoxyethylene group in the molecule such as polyoxyethylene alkyl ether, a polyoxyethylene group and a polyoxypropylene group in the molecule such as polyoxyethylene polyoxypropylene alkyl ether Particularly preferred are nonionic surfactants, anionic surfactants having a carboxyl group in the molecule such as alkylbenzene sulfonic acid, and anionic surfactants having a sulfoxyl group in the molecule such as polyoxyethylene alkyl sulfate.
These surfactants may be used alone or in combination of two or more kinds. The amount of surfactant used varies depending on the type of surfactant, so it cannot be generally stated, but nonionic surfactants need only have a critical micelle concentration or higher, and if they are thinner, the etching rate will be faster. , The effect fades. Further, the amount of the surfactant other than the nonionic surfactant may be an amount that can reduce the surface tension of the substrate surface treatment agent. The specific amount to be used depends on the type of surfactant and cannot be generally stated, but is usually 0.0001 to 1% by weight, preferably 0.0001 to 0.1% by weight,
It is more preferably 0.0001 to 0.05% by weight.

The metal corrosion inhibitor of the present invention comprises the above-described amino acid or derivative thereof of the present invention and at least one of the above-mentioned organic acids, amines, inorganic alkali compounds, chelating agents and surfactants. Those containing the amino acid or the derivative thereof according to the present invention as described above and the chelating agent and / or the surfactant are particularly preferable.

The metal corrosion inhibitor of the present invention is adsorbed on a metal surface of an amino acid having a thiol group in the molecule or a derivative thereof according to the present invention contained therein to form a protective film on the surface. , Utilizing the property of protecting the metal surface and suppressing the oxidation and corrosion of the metal received from the aqueous solution or air, and using the metal corrosion inhibitor of the present invention, for example, having a metal coating portion on the surface By treating the surface of the substrate, it is possible to prevent the metal on the surface of the substrate from being oxidized or corroded, and further it is possible to effectively remove metal impurities on the surface of the substrate.

The treating agent of the present invention is the metal corrosion inhibitor of the present invention as described above, that is, an amino acid having a thiol group in the molecule of the present invention or a derivative thereof, if necessary, for example, an organic acid as described above. , Amines, inorganic alkali compounds,
It comprises reagents usually used in this field such as chelating agents and surfactants within the concentration range described above. When at least one of the reagents usually used in this field as described above is contained in the treatment agent of the present invention, the metal on the surface of the substrate is prevented from being oxidized or corroded, and at the same time, metal impurities are prevented. (For example, metal oxides such as copper oxide and iron oxide) and particles can be removed more effectively. Among these, those containing the amino acid or derivative thereof according to the present invention as described above and a chelating agent and / or a surfactant are particularly preferable. Specific examples of the reagents as described above, preferable embodiments, and the like are as described above.

The treating agent of the present invention is usually in the state of an aqueous solution, and the amino acid or its derivative according to the present invention is added to and dissolved in water by the same preparation method as that for the metal corrosion inhibitor of the present invention as described above. It is prepared by

The treating agent of the present invention thus prepared is
It is preferable to perform a filtration treatment or the like before use.

Treatment method of the present invention (metal corrosion prevention method)
Is the treating agent of the present invention (metal corrosion inhibitor) as described above.
And the metal on the surface of the substrate having a metal coating portion on the surface are brought into contact with each other, and the surface of the substrate may be treated with the treatment agent (metal corrosion prevention method) of the present invention.

The method for treating the surface of a substrate having a metal coating on its surface with the treatment agent (metal corrosion preventing method) of the present invention may be any method known per se in this field, and specifically, Examples of the method include dipping treatment in which the substrate is simply immersed in a treatment agent (metal corrosion inhibitor), single-wafer treatment in which the treatment agent is sprinkled on the substrate in a shower shape, and the like.

In the present invention, "treatment" means bringing the treating agent of the present invention into contact with the metal on the surface of the substrate, as described above. More specifically, examples thereof include preserving treatment, pretreatment before subjecting to washing treatment, and washing treatment, but are not limited thereto.

That is, the metal corrosion inhibitor of the present invention is, for example, a preservative for a substrate having a metal coating on the surface, a pretreatment agent for a substrate having a metal coating on the surface, or a metal coating on the surface. It can also be used as a treating agent such as a cleaning agent for the substrate.

For example, when the treating agent of the present invention is used as a preservative for a substrate having a metal coating on its surface, the metal is prevented from being oxidized or corroded during storage of the substrate from various atmospheres such as an aqueous solution or air. Further, the metal impurities on the substrate surface can be effectively removed. As the method for storing the substrate of the present invention, for example, a method of performing the dip treatment as described above and storing the substrate while being immersed in the treatment agent (preservative) of the present invention, or performing the single-wafer treatment as described above Examples thereof include a method of storing the treatment agent (preservative) of the present invention while sprinkling it on the substrate, or a method of performing the treatments and then drying and storing the substrate.

If the treatment agent of the present invention is used as a pretreatment agent for the substrate, for example, before the substrate having a metal coating on the surface is subjected to a cleaning process, the metal on the substrate surface is treated. It is possible to prevent oxidation and corrosion of the metal during the process of the next step from an aqueous solution such as a cleaning agent used in the next step and various atmospheres such as air during the next step. Metal impurities on the substrate surface can be effectively removed by a simple operation such as washing with pure water. The substrate pretreatment method of the present invention includes, for example, the treatment agent (pretreatment agent) of the present invention by the dip treatment as described above.
A method of immersing the substrate therein, a method of sprinkling the treatment agent (pretreatment agent) of the present invention on the substrate by the single-wafer treatment as described above,
Alternatively, a method of drying the substrate after performing these treatments may be used.

The substrate thus obtained can be subjected to a cleaning method which is generally used in this field and which uses a surface treatment agent (cleaning agent) known per se. As the surface treatment agent (cleaning agent) used in the above, it is possible to use all those used in this field, is not particularly limited, for example, JP-A-5-263275, JP-A-6-112646 JP, 6-287774, JP 7-54169, JP 7-79061, JP 7166381, JP 7-2
92483, JP 2000-8185, JP 10-251867
Examples thereof include surface treatment agents (cleaning agents) described in JP-A Nos. 7-267933 and 11-50275, and the cleaning agent of the present invention described below.

Further, for example, by using the treating agent of the present invention as a cleaning agent for a substrate having a metal coating portion on the surface,
By treating the surface of the substrate having the metal coating portion on the surface, it is possible to prevent the metal on the surface of the substrate from being corroded or oxidized, and to effectively remove the metal impurities on the surface.

As described above, the treating agent of the present invention comprises an amino acid having a thiol group in the molecule thereof according to the present invention or a derivative thereof, an organic acid, an amine, an inorganic alkali compound, a chelating agent and a surface active agent as described above. Those containing at least one of the agents are preferable, and those containing the amino acid or its derivative according to the present invention and a chelating agent and / or a surfactant are more preferable, but the treating agent of the present invention is When used as a cleaning agent, it is particularly preferable to have such a composition. The specific examples and preferable embodiments of the organic acids, amines, inorganic alkali compounds, chelating agents and surfactants as described above are as described above.

The cleaning agent of the present invention is usually in the state of an aqueous solution, and contains the amino acid or its derivative according to the present invention (or the amino acid, amine, inorganic alkali compound, chelating agent and surfactant among these). And at least one) are added to and dissolved in water. As a method of dissolving the amino acid or its derivative according to the present invention in water,
For example, the separately dissolved amino acid of the present invention or its derivative (or at least one of the separately dissolved organic acid, amine, inorganic alkali compound, chelating agent and surfactant) is added to water. A method or an amino acid or a derivative thereof according to the present invention (or at least one of an organic acid, an amine, an inorganic alkali compound, a chelating agent and a surfactant) is directly added to water to dissolve it,
A method of stirring, or added to water, the amino acid or derivative thereof according to the present invention dissolved and added separately to water,
Examples include a method of stirring and mixing the dissolved at least one of an organic acid, an amine, an inorganic alkali compound, a chelating agent, and a surfactant.

The cleaning agent of the present invention thus prepared is preferably filtered before use. Further, the water used here may be one purified by distillation, ion exchange treatment or the like, but is used in this field,
So-called ultrapure water is more preferable.

In the cleaning method of the present invention, the surface of the substrate having the metal coating portion on the surface may be treated with the cleaning agent of the present invention as described above.

The method for treating the surface of the substrate having the metal coating on the surface with the cleaning agent of the present invention may be any of the washing methods known per se in this field, for example, the dipping treatment as described above Examples of the method include leaf treatment.

Further, in the present invention, the metal impurities (such as metal oxides equivalent to oxidation) can be removed more effectively by using physical washing together with the washing.
Specific examples of the combined use include subjecting the surface of the substrate having a metal coating portion to a physical cleaning step in the presence of the cleaning agent of the present invention.

In the above method, the method of causing the cleaning agent of the present invention to exist is, specifically, by physically dipping or cleaning the above-described cleaning agent of the present invention. Examples include a method of applying the washing step.
Examples of the physical cleaning (process) include brush scrub cleaning for cleaning the substrate surface using a high-speed rotating brush made of polyvinyl alcohol, megasonic cleaning using high frequency, and the like.

As a more specific method in the case of using physical cleaning in combination, for example, after the substrate is immersed in the cleaning agent of the present invention, it is taken out from the cleaning solution and the cleaning agent is allowed to exist on the substrate surface. A method of performing physical cleaning after
A method of performing a physical cleaning while the substrate is immersed in the cleaning agent of the present invention, and a physical cleaning is performed after the cleaning agent of the present invention is sprinkled on the substrate surface so that the cleaning agent is present on the substrate surface. Examples thereof include a method or a method of performing physical cleaning while sprinkling the cleaning agent of the present invention on the surface of the substrate.

The liquid properties of the metal corrosion inhibitor and the treating agent (preservative, pretreatment agent, cleaning agent, etc.) of the present invention as described above are not particularly limited, and are usually in this field depending on the kind of the substrate used and the purpose of use. Is appropriately selected from the pH range used in.
More specifically, it is preferably weakly acidic to alkaline, usually pH 2 to 13, preferably pH 3 to 12, and more preferably pH 4.
Is ~ 10. With such a pH range, the electrical repulsion between the substrate surface and the particles increases, so the effect of removing particles and metal impurities (such as metal oxides such as copper oxide) improves, and further Insulating film Si
There is less risk of etching O ₂ .

The metal corrosion inhibitor and treatment agent (preservative, pretreatment agent, cleaning agent, etc.) of the present invention can be used, for example, for a substrate having a metal coating on the surface. As such a substrate,
For example, semiconductor substrate, printed circuit board such as polyimide resin,
Examples thereof include glass substrates used for LCDs and the like, and are particularly useful as semiconductor substrates. The metal coated on the surface of the substrate may be any metal that reacts with sulfur, and examples thereof include copper, chromium, silver, and gold, and are particularly useful for metallic copper. Among them, it is particularly useful for a semiconductor substrate having a copper coating on the surface (provided with copper wiring).

Examples and comparative examples will be given below, but the present invention is not limited to these.

The metal Cu-deposited wafer and the Cu-contaminated wafer used in this example and the comparative example were prepared by the following methods, respectively. The amount of Cu (copper atoms) adsorbed and remaining on the surface of the Cu-contaminated wafer (remaining Cu concentration) was measured by the following methods.

[Metallic Cu-Deposited Wafer] A 4-inch silicon wafer having metallic Cu deposited on the surface by a sputtering method was used as a copper-deposited wafer. The thickness of copper on the surface of the metal Cu-deposited wafer was confirmed to be 1000 nm by the method described below.

[Cu-contaminated wafer] The surface was cleaned by a thermal oxidation method.
SiO₂4inch silicon wafer is 1ppm
Slurry solution (1% silica
0.1% hydrogen peroxide solution) contained in 1L for 1 minute
After washing with running water for 10 minutes, spin-dry it with Cu
It was a contaminated wafer. In addition, according to the method shown below,
Cu (copper atom) is 3 × 10 in Cu contaminated wafer. ¹⁴Atom / cm
²It was confirmed that adsorption remained.

[Metal Cu Film Thickness Measuring Method] The wafer was divided into halves and the cross section was observed with an electron microscope to measure the metal Cu film thickness.

[Cu Concentration Measuring Method] Cu adsorbed and remaining on the wafer surface was dissolved and recovered in a hydrofluoric acid-nitric acid aqueous solution, and the Cu concentration in the recovered solution was measured by an atomic absorption method (graphite furnace atomic absorption spectrophotometer). It was measured by. Cu based on the obtained measurements
The amount of adsorption of (copper atoms) (residual Cu concentration) was determined.

In the examples and comparative examples, unless otherwise specified,%, ppm and ppb, which represent the concentration, all represent weight ratios. In addition, the water used is all ultrapure water, and copper is 0.01
It was used after confirming that it was below ppb.

[0086]

[Examples] Examples 1 to 14 A metal Cu-deposited wafer prepared by the above method was immersed in 1 L of each metal corrosion inhibitor (preservative) shown in Table 1 at room temperature for 5 hours. Then, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. Regarding the metal Cu deposited wafer treated in this way, in order to confirm the presence or absence of oxidation of the metal Cu, visually observe the color tone of the Cu film surface of the wafer surface, and to confirm the presence or absence of corrosion of the metal Cu, the wafer The film thickness of metallic Cu on the surface was measured. The results are shown in Table 1.

[0087]

[Table 1]

Comparative Examples 1 to 6 Examples 1 to 14 except that various solutions shown in Table 2 were used.
After treating the metal Cu-deposited wafer in the same manner as in 1., the color tone of the Cu film surface on the wafer surface was visually observed, and the film thickness of the metal Cu on the wafer surface was measured. The results are shown in Table 2. In addition, -in Table 2 indicates that measurement is impossible.

[0089]

[Table 2]

As is clear from Tables 1 and 2, when metal Cu-deposited wafers were stored in the metal corrosion inhibitor (preservative) of the present invention (Examples 1 to 14),
It can be seen that there is no change in the color tone of the Cu film surface, the metallic Cu is not oxidized, and there is almost no change in the Cu film thickness, and the metallic Cu is not corroded. On the other hand, when the metal Cu-deposited wafers were stored in the solutions of Comparative Examples 1 and 5,
Is significantly corroded, the luster of the Cu film surface on the wafer surface disappears, and it is understood that the metallic Cu is oxidized. Also,
When stored in the solutions of Comparative Examples 4 and 6, there was no change in the color tone of the Cu film surface on the wafer surface, and although the Cu metal was not oxidized, the Cu film thickness decreased and the Cu metal was corroded ( It is understood that it has been dissolved). Furthermore, in Comparative Example 2, the metal Cu was oxidized and corroded (dissolved),
Especially in Comparative Example 3, it is found that all the metallic Cu is corroded (dissolved). That is, the metal corrosion inhibitor of the present invention can prevent metal oxidation and corrosion, and can be used for preserving a substrate having a metal coating portion on the surface in a treatment agent (preservative) containing the metal inhibitor of the present invention. For example, it can be seen that the oxidation and corrosion of the metal can be prevented at the same time, and the substrate having the metal coating on the surface can be well preserved in the solution.

Examples 15 to 17 The metal Cu-deposited wafer prepared by the above method was immersed in 1 L of each metal corrosion inhibitor (preservative) shown in Table 3 at room temperature for 1 minute. Then, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. The wafer was then left in air for 10 hours. Regarding the metal Cu-deposited wafer treated in this way, the color tone of the Cu film surface on the wafer surface was visually observed in order to confirm the presence or absence of oxidation of the metal Cu.
The results are shown in Table 3.

Comparative Examples 7 to 10 Examples 15 to 1 except that various solutions shown in Table 3 were used.
After treating the metal Cu-deposited wafer in the same manner as in No. 7, the color tone of the Cu film surface on the wafer surface was visually observed. The results are shown in Table 3 together with Examples 15 to 17.

[0093]

[Table 3]

As is clear from Table 3, when the metal Cu-deposited wafer was treated with the metal corrosion inhibitor (preservative) of the present invention (Examples 15 to 17) and the wafer was stored in air, It can be seen that there is no change in the color tone of the Cu film surface on the wafer surface and the metallic Cu is not oxidized. On the other hand, when the metal Cu-deposited wafers were treated with the solutions of Comparative Examples 7 to 10, it was found that the gloss of the Cu film surface on the wafer surface disappeared and the metal Cu was oxidized. That is, by treating a substrate having a metal coating portion on its surface with a treating agent (preservative) containing the metal inhibitor of the present invention and then storing it, oxidation of the metal on the substrate surface can be prevented. It can be seen that a substrate having a metal coating on the surface can be well stored in air.

Examples 18 to 20 500 ml of each metal corrosion inhibitor (preservative) shown in Table 4 was added.
The surface of the metal Cu-deposited wafer produced by the above method was sprinkled for 1 minute. Then, the wafer was rinsed with ultrapure water for 10 minutes and spin dried. The wafer was then left in air for 10 hours. Regarding the metal Cu-deposited wafer treated in this way, the color tone of the Cu film surface on the wafer surface was visually observed in order to confirm the presence or absence of oxidation of the metal Cu.
The results are shown in Table 4.

Comparative Examples 11-14 Examples 18-2 except that various solutions shown in Table 4 were used.
After treating the metal Cu-deposited wafer in the same manner as in No. 0, the color tone of the Cu film surface on the wafer surface was visually observed. The results are shown in Table 4 together with Examples 18 to 20.

[0097]

[Table 4]

As is clear from Table 4, when the metal Cu-deposited wafer was treated with the metal corrosion inhibitor (preservative) of the present invention (Examples 18 to 20) and the wafer was stored in air, It can be seen that there is no change in the color tone of the Cu film surface on the wafer surface and the metallic Cu is not oxidized. On the other hand, when the metal Cu-deposited wafers were treated with the solutions of Comparative Examples 15 to 17, it was found that the gloss of the Cu film surface on the wafer surface disappeared and the metal Cu was oxidized. That is, not only by the so-called dip treatment as performed in Examples 15 to 17 but also by the so-called single-wafer treatment as performed in Examples 18 to 20, a treating agent (preservative agent) containing the metal inhibitor of the present invention. ), After treating the substrate having a metal coating on the surface and then storing it, the metal on the surface of the substrate can be prevented from being oxidized, and the substrate having a metal coating on the surface can be well stored in air. I know you will get it.

Examples 21 to 34 In 1 L of each metal corrosion inhibitor (pretreatment agent) shown in Table 5, the Cu-contaminated wafer and the metal Cu-deposited wafer produced by the above method were immersed at room temperature for 1 hour. Then, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried.
Then, the wafer was immersed in 1 L of each cleaning solution shown in Table 5 at room temperature for 10 minutes. Then, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. For Cu-contaminated wafers treated in this way, in order to evaluate the ability to remove metal impurities, the residual Cu concentration adsorbed and remaining on the wafer surface was measured, and for metal Cu-deposited wafers, the presence or absence of metal Cu oxidation In order to confirm, the color tone of the Cu film surface on the wafer surface is visually observed, and
In order to confirm the corrosion of Cu, metal Cu on the wafer surface
Was measured. The results are shown in Table 5. In addition, in Table 5
Indicates that measurement is impossible.

Comparative Examples 15 to 25 Cu-contaminated wafers and metals were prepared in the same manner as in Examples 21 to 34, except that the various solutions and cleaning agents shown in Table 6 were used.
After processing Cu-deposited wafers, for Cu-contaminated wafers, measure the residual Cu concentration adsorbed and remaining on the wafer surface, and for metallic Cu-deposited wafers, visually observe the color tone of the Cu film surface on the wafer surface. Then, the film thickness of metal Cu on the wafer surface was measured. The results are shown in Table 6. still,
In Comparative Examples 15 to 18, the treatment with the metal corrosion inhibitor (pretreatment agent) was not performed, and 1 L of each cleaning liquid described in Table 6 was added.
After immersing the wafer at room temperature for 10 minutes, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried, and then measured and observed.

[0101]

[Table 5]

[0102]

[Table 6]

As is clear from the results of Tables 5 and 6,
When pretreatment is performed using the metal corrosion inhibitor (pretreatment agent) of Examples 21, 22 and 27, the residual Cu concentration on the surface of the Cu-contaminated wafer can be suppressed to 10 ¹⁰ order or less, and It is understood that oxidation and corrosion can be prevented. On the other hand, when the pretreatment is performed using the conventional metal corrosion inhibitor (surface treatment agent), the residual Cu concentration can be suppressed to the same level, but the metal Cu may be oxidized or corroded. (Comparative Examples 19 and 23), it can be seen that although the oxidative corrosion of metallic Cu is suppressed, the residual Cu concentration is high and copper oxide cannot be effectively removed (Comparative Examples 20, 24 and 25). Similarly, in Examples 23 and 30, copper oxide can be effectively removed, and oxidation and corrosion of metallic Cu can be prevented, while Comparative Examples 21 and 22 are Cu films on the substrate surface. It can be seen that is corroded significantly. In addition, Examples 26, 28,
From the results of 32 and 34 and Comparative Examples 15 to 18, when the pretreatment was performed using the metal corrosion inhibitor (pretreatment agent) of the present invention, the metal Cu in the cleaning was compared with the case where it was not performed.
It is also understood that the oxidation and corrosion of the copper oxide can be suppressed, and further the copper oxide can be effectively removed. As is clear from the above, if the substrate having the metal coating portion on the surface is subjected to the cleaning step and the substrate is pretreated with the metal corrosion inhibitor (pretreatment agent) of the present invention, the cleaning step is performed. It can be seen that the metal can be prevented from being oxidized and corroded, and further the metal oxide can be effectively removed.

Examples 35 to 44 The Cu-contaminated wafer produced by the above method was immersed in 1 L of each cleaning agent (metal corrosion inhibitor) shown in Table 7 at room temperature for 10 minutes. Then, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. Further, the metal Cu-deposited wafer manufactured by the above method was immersed in 1 L of each cleaning agent (metal corrosion inhibitor) shown in Table 7 at room temperature for 5 hours. afterwards,
The wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. For Cu-contaminated wafers treated in this way, in order to evaluate the ability to remove metal impurities, the residual Cu concentration adsorbed and remaining on the wafer surface was measured, and for metal Cu-deposited wafers, the presence or absence of metal Cu oxidation In order to confirm the above, the color tone of the Cu film surface on the wafer surface was visually observed, and further, in order to confirm the presence or absence of corrosion of the metal Cu, the film thickness of the metal Cu on the wafer surface was measured. The results are shown in Table 7.

Comparative Examples 26 to 37 Examples 35 to 4 except that the cleaning agents shown in Table 8 were used.
After treating Cu-contaminated wafers and metal-Cu-deposited wafers in the same way as in No. 4, remains adsorbed on the wafer surface
The Cu concentration was measured, and for the metal Cu-deposited wafer, the color tone of the Cu film surface on the wafer surface was visually observed, and the film thickness of the metal Cu on the wafer surface was measured. The results are shown in Table 8. In addition, -in Table 8 indicates that measurement is impossible.

[0106]

[Table 7]

[0107]

[Table 8]

As is clear from Tables 7 and 8, when the wafer was cleaned using the cleaning agent (metal corrosion inhibitor) of the present invention (Examples 35 to 44), the wafer surface remained.
The Cu concentration can be suppressed to 10 ¹⁰ order or less, the color tone of the Cu film surface does not change, and the metallic Cu is not oxidized.
Moreover, it can be seen that there is almost no change in the Cu film thickness and that the metallic Cu is not corroded. In contrast, Comparative Examples 27, 30, 3
When the cleaning agents 1, 33 and 34 are used, the residual Cu concentration can be suppressed to 10 ¹⁰ order or less, but metallic Cu
It can be seen that the Cu is oxidized and the metallic Cu is significantly corroded. Further, when the cleaning agents of Comparative Examples 29 and 35 to 37 were used, although the metal Cu on the wafer surface was not oxidized and the metal Cu was hardly corroded,
It can be seen that the residual Cu concentration is high and the copper oxide on the wafer surface cannot be sufficiently removed. Furthermore, when the cleaning agents of Comparative Examples 26 and 32 were used, it was found that the metal Cu was corroded and oxidized, and the residual Cu concentration was high, so that the copper oxide on the wafer surface could not be sufficiently removed. It can be seen that when the cleaning agent of Comparative Example 28 was used, the metallic Cu was significantly corroded, and the copper oxide on the wafer surface could not be sufficiently removed. That is, if the surface of a substrate having a metal coating on the surface is washed with the cleaning agent of the present invention, the oxidation and corrosion of the metal can be prevented, and the metal impurities (copper oxide) on the surface can be effectively removed. I know you will get it.

[0109]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a metal corrosion inhibitor having a good metal corrosion inhibiting action and high safety, and a substrate surface using the same, particularly a copper wiring on the surface. A method for treating a substrate capable of preventing the oxidation and corrosion of copper wiring on the surface of the substrate, and a method of preventing corrosion and oxidation of the copper wiring on the surface of the substrate, and effectively using metal impurities (copper oxide) on the surface. The present invention provides a method of cleaning a substrate that can be removed, and by using the metal corrosion inhibitor of the present invention, various problems at the time of manufacturing a semiconductor can be solved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 21/304 H01L 21/304 647B F term (reference) 4H003 AB03 AB14 AB18 AB19 AB27 AB31 AC08 DA09 DA15 EA21 EA23 EB08 EB13 EB14 EB15 EB16 EB24 ED02 FA07 FA15 4K053 PA06 QA01 RA45 RA51 RA54 RA63 YA03 YA07 4K062 AA01 AA03 BB16 BB21 CA05 FA09 FA16 GA10

Claims (42)

[Claims] 1. A metal corrosion inhibitor comprising an amino acid having a thiol group in the molecule or a derivative thereof. 2. The metal corrosion inhibitor according to claim 1, which is an aqueous solution. 3. An amino acid having a thiol group in the molecule,
The metal corrosion inhibitor according to claim 1, which is cysteine or homocysteine. 4. The amino acid derivative is an N-acyl form of an amino acid or a carboxylic acid ester form of an amino acid.
The metal corrosion inhibitor according to any one of 1. 5. The metal corrosion inhibitor according to claim 4, wherein the N-acyl derivative has an acyl group derived from a carboxylic acid introduced therein. 6. The metal corrosion inhibitor according to claim 4, wherein the N-acyl derivative is an N-alkanoyl derivative or an N-aralkanoyl derivative. 7. The N-acyl derivative is an N-acetyl derivative.
The metal corrosion inhibitor according to. 8. The metal corrosion inhibitor according to claim 4, wherein the ester form is an alkyl ester form or an aralkyl ester form. 9. The metal corrosion inhibitor according to claim 4, wherein the ester is a lower alkyl ester or a benzyl ester. 10. The metal corrosion inhibitor according to claim 1, further comprising at least one of an organic acid, an amine, an inorganic alkali compound, a chelating agent and a surfactant. 11. The metal corrosion inhibitor according to claim 10, wherein the organic acid is a di- or tricarboxylic acid. 12. The metal corrosion inhibitor according to claim 10, wherein the organic acid is a mono- or dihydroxydi- or tricarboxylic acid. 13. The amine is any one of alkylamine, dialkylamine, hydroxyalkylamine, alkylenediamine, dialkylenetriamine, trialkylenetetramine, alkylamine-alkylene oxide adduct, and tetraalkylammonium hydroxide. The metal corrosion inhibitor according to. 14. The metal corrosion inhibitor according to claim 10, wherein the inorganic alkaline compound is a nitrogen-containing inorganic alkaline compound. 15. The metal corrosion inhibitor according to claim 14, wherein the nitrogen-containing inorganic alkaline compound is selected from the group consisting of hydroxylamine, hydrazine, ammonia, and salts thereof. 16. The metal corrosion inhibitor according to claim 10, wherein the chelating agent is an aminopolycarboxylic acid or / and a phosphonic acid. 17. The metal corrosion inhibitor according to claim 16, wherein the aminopolycarboxylic acids are linear aminopolycarboxylic acids and / or cyclic aminopolycarboxylic acids. 18. A linear aminopolycarboxylic acid is ED
TA (ethylenediaminetetraacetic acid), EDDA (ethylenediaminediacetic acid), EDTA-OH (hydroxyethylenediaminetriacetic acid), GEDTA (glycol etherdiaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), IDA (iminodiacetic acid), methyl-ED
TA (diaminopropane tetraacetic acid), NTA (nitrilotriacetic acid), TTHA (triethylenetetramine hexaacetic acid),
The metal corrosion inhibitor according to claim 17, which is also an ammonium salt or a complex salt with an amine. 19. A cyclic aminopolycarboxylic acid is CyD.
TA (trans-cyclohexyldiaminotetraacetic acid),
The metal corrosion inhibitor according to claim 17, which is also an ammonium salt or a complex salt with an amine. 20. The metal corrosion inhibitor according to claim 16, wherein the phosphonic acids are polyphosphonic acids and / or aminopolyphosphonic acids. 21. The polyphosphonic acid is NTPO (nitrilotrismethylenephosphonic acid), HEDPO (hydroxyethylidene di (methylenephosphonic acid)), or its ammonium salt or a complex salt with an amine.
The metal corrosion inhibitor according to 0. 22. Aminopolyphosphonic acids are EDDPO
(Ethylenediaminedi (methylenephosphonic acid)), ED
TPO (ethylenediaminetetra (methylenephosphonic acid)), PDTPO (diaminopropanetetra (methylenephosphonic acid)), DETPPO (diethylenetriaminepenta (methylenephosphonic acid)), TTHPO (triethylenetetraminehexa (methylenephosphonic acid)) or its ammonium salt Alternatively, the metal corrosion inhibitor according to claim 20, which is a complex salt with an amine. 23. The metal corrosion inhibitor according to claim 10, wherein the surfactant is a nonionic surfactant or an anionic surfactant. 24. The nonionic surfactant is a nonionic surfactant having a polyoxyalkylene group in the molecule.
The metal corrosion inhibitor according to 3. 25. The metal corrosion inhibitor according to claim 23, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether or a polyoxyalkylene polyalkylaryl ether. 26. The anionic surfactant has a group selected from the group consisting of a sulfonic acid group, a carboxyl group, a phosphonic acid group and a sulfoxyl group.
The metal corrosion inhibitor according to 3. 27. An anionic surfactant is an alkyl sulfonic acid, an alkyl aryl sulfonic acid, an alkyl sulfuric acid ester, an alkyl aryl sulfuric acid ester, a polyoxyalkylene alkyl sulfuric acid ester, a polyoxyalkylene alkyl aryl sulfuric acid ester, an alkyl carboxylic acid,
27. The metal corrosion inhibitor according to claim 26, which is an alkylarylcarboxylic acid or a salt thereof. 28. A treating agent comprising the metal corrosion inhibitor according to any one of claims 1 to 27. 29. The treating agent according to claim 28, which is for a substrate having a copper coating on the surface. 30. The treating agent according to claim 29, wherein the substrate is a semiconductor substrate. 31. A method of treating a substrate, which comprises treating the substrate with the treating agent according to claim 28. 32. The processing method according to claim 31, wherein the substrate has a copper coating on the surface. 33. The processing method according to claim 32, wherein the substrate is a semiconductor substrate. 34. A cleaning agent comprising the metal corrosion inhibitor according to claim 1. 35. The cleaning agent according to claim 34, which is for a substrate having a copper coating on its surface. 36. The cleaning agent according to claim 34, wherein the substrate is a semiconductor substrate. 37. A method of cleaning a substrate, which comprises cleaning the substrate with the cleaning agent according to claim 34. 38. The cleaning method according to claim 37, wherein the substrate is a semiconductor substrate having a copper coating on the surface. 39. The cleaning method according to claim 38, wherein the substrate is a semiconductor substrate. 40. A semiconductor substrate having a copper coating on its surface is subjected to chemical physical polishing (CMP) and then treated with the treating agent according to claim 28. Processing method. 41. A semiconductor substrate having a copper coating on its surface is subjected to a chemical physical polishing treatment (CMP), the substrate is treated with the treating agent according to claim 28, and then the semiconductor substrate is treated. A method of treating the substrate, which comprises cleaning with a cleaning agent. 42. A semiconductor substrate having a copper coating on its surface is subjected to chemical physical polishing (CMP), and then washed with the cleaning agent according to claim 34. Cleaning method.