WO2004034451A1

WO2004034451A1 - Substrate detergent

Info

Publication number: WO2004034451A1
Application number: PCT/JP2002/010607
Authority: WO
Inventors: Masahiko Kakizawa; Mayumi Kimura; Ichiro Hayashida
Original assignee: Wako Pure Chemical Industries, Ltd.
Priority date: 2002-10-11
Filing date: 2002-10-11
Publication date: 2004-04-22
Also published as: TW583719B; AU2002338176A1

Abstract

A metal corrosion inhibitor; a detergent for substrate surfaces, especially ones having a copper wiring formed thereon, which contains the inhibitor; and a cleaning method. The metal corrosion inhibitor contains either an amino acid having a thiol group in the molecule or a derivative thereof. The treating agent and detergent for substrate surfaces contain the metal corrosion inhibitor. The method of treating and cleaning substrate surfaces employs the metal corrosion inhibitor.

Description

Specification

Substrate cleaning technology

The present invention relates to a metal corrosion inhibitor, and a cleaning agent and a cleaning method for a substrate surface using the same, particularly for a substrate surface having copper wiring on the surface. Technology background

In recent years, the structure of LSIs has been miniaturized as the degree of integration has increased, and it has become a multilayer structure in which metal wiring and the like are superimposed on the semiconductor surface in many stages. Also, the wiring used is changed from conventional aluminum to copper with lower electrical resistance.

A change to (Cu) has been proposed.

In the process of manufacturing a semiconductor having a multilayer structure in which copper wiring is applied over the surface in multiple layers, a so-called chemical-physical polishing technique (which physically polishes and flattens the semiconductor substrate while oxidizing metallic Cu) ( Cu-CMP) is used. On the other hand, the insulating film (silicon oxide) that separates the Cu wiring from each other is exposed on the semiconductor surface after the Cu-CMP process, and the wafer surface after the Cu-CMP process is exposed. Is contaminated by a large amount of metallic impurities.

Metallic impurity contamination is caused by Cu removed by CMP adsorbing on the insulating film and remaining as metal oxide (copper oxide).

If metal oxide (copper oxide) remains on the insulating film, the copper element diffuses into the insulating film due to heat treatment in a later process, and the insulating properties are reduced, thereby deteriorating the characteristics of the device. If the contamination is severe, the isolated wires will be connected, or short-circuited, and the device will be destroyed. Therefore, remove metal oxide (copper oxide) before proceeding to the next step There is a need.

For the above reasons, a cleaning step after the Cu-CMP step is essential to remove the metal impurities as described above.

On the other hand, metallic copper on the surface of a semiconductor has a high activity and is easily corroded by a slight oxidizing power, thereby increasing wiring resistance and causing disconnection. For this reason, in the cleaning process after the Cu-CMP process, a cleaning solution which is conventionally used as a cleaning solution for semiconductors and has a relatively strong oxidizing power and mainly contains an inorganic acid such as hydrochloric acid or hydrofluoric acid is used. If it is used, not only the copper oxide adhering to the insulating film but also the metal copper of the wiring is dissolved, so that the use of the acidic cleaning solution is not preferable.

Detergents mainly composed of organic acids having relatively low oxidizing power, such as oxalic acid and citric acid, also have a copper dissolving effect, although they have a weaker copper dissolving effect than inorganic acids. 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 also decreases, so that it is necessary to clean the semiconductor surface for a long time. It is known that corrosion of metallic copper on a semiconductor surface can be prevented by adding various metal corrosion inhibitors to a cleaning agent in order to solve such a defect.

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 are only effective at high concentrations. However, these compounds have low solubility in water, and it is difficult to add these compounds at a high concentration to ultrapure water, which is generally used as a diluent when using a detergent for semiconductors. Was. In addition, in order to use these compounds at a high concentration, an alkali solubilizing agent such as amine or an alcoholic organic solvent is required. Solvents had a bad effect on the cleaning properties and were difficult to use.

In addition, Japanese Patent Application Laid-Open No. 2000-087268 / Japanese Patent Application Laid-Open No. 2000-280296 discloses cyclic compounds such as mercaptoimidazole and mercaptothiazole. .

However, when these compounds bind to copper on the semiconductor surface, the copper surface becomes hydrophobic, preventing the attack of the detergent and making it difficult to remove these compounds. Thus, if the semiconductor is subjected to a heat treatment in a later process or at the time of device operation while the organic substance such as these compounds remains on the copper surface, the organic substance will burn, explode, etc., and serious defects will occur. There were problems such as the safety of the human body and the environment.

Furthermore, Japanese Patent Application Laid-Open No. 2000-273636 discloses a carbon and hydroxyl group having a mercapto group in a molecule, such as mercaptoethanol and mercaptoglycerol, and having the mercapto group bonded thereto. Discloses an aliphatic alcohol-based compound in which the carbon bonded to is bonded adjacently.

However, the invention disclosed in Japanese Unexamined Patent Publication No. 2000-273663 has a problem of human health and ecosystem compared with the conventional one due to recent problems on the human body and environmental pollution. It is intended to provide a metal corrosion inhibitor that has little risk of harmful effects on steel, but it is highly toxic and still has safety issues. It is not practical because it has an unpleasant odor even when used in an aqueous solution. SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and has an excellent metal corrosion inhibitory action and a highly safe metal corrosion inhibitor. Using the same, a copper wiring is provided on the surface of a substrate, especially on the surface. A method for treating the substrate, which can prevent oxidation and corrosion of the copper wiring on the surface of the substrate, and a method for preventing corrosion and oxidation of the copper wiring on the surface of the substrate; Copper) An object of the present invention is to provide a method for cleaning a substrate which can be effectively removed. Disclosure of the invention

The present invention has the following configurations.

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

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

(3) A method for treating a substrate, comprising treating the substrate with the treatment agent according to (2).

(4) A cleaning agent comprising the metal corrosion inhibitor according to (1).

(5) A method for cleaning a substrate, comprising cleaning the substrate with the cleaning agent according to (4).

(6) After subjecting a semiconductor substrate having a copper coating on its surface to a chemical-physical polishing treatment (CMP), the substrate is treated with the treatment agent described in (2) above. Processing method.

(7) After subjecting a semiconductor substrate having a copper-coated portion to a chemical-physical polishing treatment (CMP), the substrate is treated with the treatment agent described in (2) above, and then the semiconductor substrate is cleaned. Cleaning the substrate with an agent.

(8) Chemical and physical polishing of semiconductor substrate with copper coating on the surface

A method for cleaning a substrate, comprising subjecting the substrate to the cleaning agent according to the above (4) after being subjected to (CMP).

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an amino acid having a thiol group in a molecule or a derivative thereof has a good metal corrosion inhibiting action and high safety, and If the substrate is treated with a cleaning agent containing an amino acid or a derivative thereof, the surface of the substrate, particularly the surface, may have copper. The present inventors have found that metal impurities (copper oxide) on the surface of the substrate on which the wiring has been formed can be effectively removed without causing corrosion or oxidation of the copper wiring, thereby completing the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

The amino acid having a thiol group in the molecule according to the present invention (hereinafter sometimes abbreviated as the amino acid according to the present invention) is a compound having a thiol group, a carboxyl group and an amino group in the molecule. Include compounds represented by the following general formula [1].

HS- R-COOH ^{1 1 J}

(In the formula, R represents a lower alkylene group.) In the general formula [1], examples of the lower alkylene group represented by R include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group. , Hexamethylene, propylene, butylene, methylethylene, methylethylene, methylethylene, methylpropylene, ethylpropylene, pentylene, hexylene, cyclopentylene, cyclohexylene, etc. , Branched or cyclic lower alkylene groups having 1 to 6 carbon atoms. 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 an ethylene group is particularly preferable.

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

More specifically, examples of the compound represented by the general formula [1] include cysteine and homocysteine. These compounds are D-forms, L-forms, DL-forms, and mixtures having a mixing ratio of, respectively. Mixtures of different D- and L-forms can also be used.

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

The N-acyl form of the amino acid according to the present invention is the amino acid according to the present invention in which an amino group has a hydrogen atom introduced into a hydrogen atom of the amino group.

Specifically, as shown in the following general formula [2], an amino group in the above general formula [1] has a hydroxyl group introduced with an acyl group.

NH—— R ¹

I [ ₂ 1

HS- R-CH-COOH

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

The acyl group to be 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. For example, carbon number of formyl group, acetyl group, propionyl group, butyryl group, isopyryl group, valeryl group, isovaleryl group, bivaloyl group, hexanoyl group, cyclopropionylcarbonyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, etc. Those derived from saturated aliphatic monocarboxylic acids having 1 to 6 atoms, for example, those derived from unsaturated aliphatic monocarboxylic acids having 3 to 7 carbon atoms such as acryloyl group, propioloyl group, methyl acryloyl group, crotonyl group, and isocrotonyl group. Substances, for example, benzoyl group, naphthoyl group, pentane carbonyl group, indylene carbonyl group, azulene carbonyl group, heptane carbenyl group, indacene carbonyl group, anthracene carbonyl group, phenanthrene carbonyl group, Aromatic monocarboxylic acid having 7 to 23 carbon atoms, preferably 7 to 12 carbon atoms, such as a triphenylene carbonyl group, a pyrenecarbonyl group, a naphthene sencarbonyl group, a pyrene carbonyl group, a pennecene carbonyl group and the like. Derived from, for example, phenylmethylcarbonyl, phenylethylcarbonyl, Phenylpropylcarbonyl group, phenylisopropylcarbonyl group, phenylbutylcarbonyl group, phenylisobutylcarbonyl group, phenylpentylcarbonyl group, phenylisopentylcarbonyl group, phenylneopentylcarbonyl group, phenylhexyl Carbonyl group, phenylisohexylcarbonyl group, phenylethylpentylcarbonyl group, phenylmethylpentylcarbonyl group, phenyldimethylbutylcarbonyl group, phenylethylbutylcarbonyl group, phenylheptylcarbonyl group, phenylmethylhexylcarbonyl group , Phenyldimethylpentylcarbonyl, phenyloctylcarbonyl, phenylnonylcarbonyl, phenyldecylcarbonyl, phenyldidecylcarbonyl , Phenyldodecylcarbonyl, phenyltridecylcarbonyl, phenylcyclopropylcarbonyl, phenylcyclopentylcarbonyl, phenylcyclohexylcarbonyl, phenylcyclohexylcarbonyl, phenylcycloheptylcarbonyl, phenylcyclone Butylcarbonyl, phenylcyclononylcarbonyl, phenylcyclodecylcarbonyl, phenylcyclounde Number of carbon atoms such as silcarbonyl group, phenylcyclododecylcarbonyl group, phenylcyclotridecylcarbonyl group, etc.? To 20, preferably those derived from aralkylmonocarboxylic acids having 7 to 13 carbon atoms. The aromatic ring of the aromatic monocarboxylic acid-derived acyl group or the aralkyl monocarboxylic acid-derived acyl group has, for example, a lower alkyl group such as a methyl group or an ethyl group as a substituent. You may.

Among the above-mentioned acyl groups, those derived from a saturated aliphatic monocarboxylic acid and those derived from an aralkyl monocarboxylic acid are preferable, and those derived from a saturated aliphatic monocarboxylic acid are more preferable. Is derived from a linear saturated aliphatic monocarboxylic acid. Among the acyl groups derived from linear saturated aliphatic monocarboxylic acids, acetyl groups are particularly preferred. The N-acyl form of the amino acid having a thiol group in the molecule according to the present invention is a commercially available product (eg, (Manufactured by Wako Pure Chemical Industries, Ltd.) or may be appropriately prepared and used according to a method known per se. As the N-acyl form of the amino acid according to the present invention, an N-alkanoyl form 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 (general formula R ^{1 in} [2] is an acyl group derived from a saturated aliphatic monocarboxylic acid) and an N-aralkanoyl derivative having an acetyl group derived from aralkylmonocarboxylic acid (R ^{1 in} general formula [2]) Is preferably an aralkyl monocarboxylic acid-derived acyl group), more preferably an N-alkanoyl compound, and further preferably, a straight-chain hydrogen atom of the amino group of the amino acid according to the present invention. N-linear alkanoyl derivative having an acyl group derived from a saturated aliphatic monocarboxylic acid of the formula (wherein R ¹ in the general formula [2] is an acyl group derived from a linear saturated aliphatic monocarboxylic acid) Also ). Among them, an N-acetate in which an acetyl group is introduced into a hydrogen atom of the amino group of the amino acid according to the present invention. The tyl form (R ¹ in the general formula [2] is an acetyl group) is particularly preferred.

Specific examples of the N-acyl form of the amino acid according to the present invention (compound represented by the general formula [2]) include, for example, N-acetylcysteine, N-butyrylcysteine, N-cyclohexylcarbonylcysteine, Pioloylcis tin, N-crotonylcysteine, N-benzoylcysteine, N-naphthylcysteine, N-phenylmethylcarbonylcysteine, N-phenylbutylcarbonylcysteine, N-phenylcyclohexylcarbonylcysteine , N-acetyl homocysteine, N-butyryl homocysteine, N-cyclohexylcarbonyl homocysteine, N-propioloyl homocysteine, N-crotonyl homocysteine, N-benzoyl homocystin, N-naphthoyl homocysteine, N-phenylmethylcarbonyl homocysteine, N-fenylbuti Lucarponyl homocysteine, N-phenylcyclohexylcarbonyl homocysteine, and the like.These are D-form, L-form, DL-form, and a mixture of D-form and L-form with different mixing ratios. But it can be used. The carboxylic acid ester of the amino acid according to the present invention is the carboxylic acid ester of the amino acid according to the present invention as described above, which is esterified.

More specifically, as shown in the following general formula [2], the hydroxyl group of the carboxyl group in the above general formula [1] has an acyl group introduced.

(In the formula, R ² represents a hydrocarbon residue, and R is the same as described above.) In the general formula [3], the hydrocarbon residue represented by R ² may be any of aliphatic, aromatic, araliphatic, or alicyclic as long as it is a monovalent group. The aliphatic in the aliphatic and araliphatic may be saturated or unsaturated, and may be linear or branched. Representative of these include, for example, linear, branched, or cyclic saturated or unsaturated alkyl, aryl, aralkyl, and alkenyl groups.

Examples of the alkyl group include those having usually 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, and n-propyl. Group, iso-propyl group, n-butyl group, is 0-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, sec-heptyl, n-octyl, iso-octyl, sec-octyl, n-nonyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl , Cycloheptyl, cyclooctyl, cyclodecyl, etc. .

Examples of the aryl group include those having 6 to 14 carbon atoms. Specifically, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2 , 4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,5-xylyl group, naphthyl group, anthryl group and the like.

The aralkyl group usually has 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms, and specifically includes, for example, benzyl, phenethyl, phenylpropyl, phenylbutyl and phenyl. Xyl group, methyl Examples of the aromatic ring of the aryl or aralkyl group include a lower alkyl group such as a methyl group and an ethyl group, a halogen atom, a nitro group, and an amino group. May be included as a substituent.

Examples of the alkenyl group include those having usually 2 to 10 groups. Specifically, for example, a vinyl group, an aryl group, a 1-propenyl group, an iso-propenyl group, a 3-butenyl group, -Butenyl, 1-butenyl, 1,3-butenyl, 4-pentenyl, 3-pentenyl, 2-pentenyl, 1-pentenyl, 1,3-pentenyl, 2, 4-pentenyl 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-methyl 1,3-hexenyl group, 1-heptenyl group, 2-octenyl group, 3-nonenyl group, 4-decenyl group, 2-cyclopentenyl group, 2,4-cyclopentagenenyl group, 1 -Cyclo Hexenyl group, cyclohexenyl group into 2-cyclopropyl, 3-cycloheteroalkyl Wiseniru group, 2-cycloheptenyl, 2-cyclononenyl group, a 3-cyclodecenyl group, and the like.

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 more preferable.

The carboxylic acid ester 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 prepared according to a method known per se. May be.

Examples of the carboxylic acid ester of the amino acid according to the present invention include an alkyl group in which an alkyl group is introduced into a hydroxyl group of the amino acid according to the present invention. Ester (R ² in the general formula [3] is an alkyl group) and aralkyl ester having an aralkyl group introduced therein (R ² in the general formula [3] is an aralkyl group) And more preferably a lower alkyl ester in which an alkyl group having 1 to 6 carbon atoms is introduced into a carboxyl group of the amino acid according to the present invention (wherein R ^{2 in the} general formula [3] is A lower alkyl group of 1 to 6) and a benzyl ester having a benzyl group introduced therein (wherein R ² in the general formula [3] is a benzyl group), and more preferably a lower alkyl group. It is an alkyl ester. Specific examples of the carboxylic acid ester 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 methyl benzyl ester, cysteine vinyl ester, cysteine 3-butenyl ester, cysteine 3-cyclohexenyl ester, homocysteine methyl ester, homo Cystine ethyl ester, homocystine isobutyl ester, homocystine n-hexyl ester, homocystine cyclohexyl ester, homocystine phenyl ester , Homocysteine naphthyl ester, homocysteine benzyl ester, homocysteine methyl benzyl ester, homocysteine vinyl ester, homocysteine 3-butenyl ester, homocysteine 3-cyclohexenyl ester, and the like. It can be used in L-form, DL-form, or a mixture of D-form and L-form with different mixing ratios. An amino acid having a thiol group in the molecule according to the present invention as described above or The derivatives may be used alone or in combination of two or more.

The amount of the amino acid or derivative thereof having a thiol group in the molecule cannot be specified because it varies depending on the type of the amino acid or derivative thereof having a thiol group in the molecule and the surface area of the substrate to be treated. 0.0001-10% by weight, preferably 0.0001-1% by weight, more preferably 0.0001-0.5% by weight. The metal corrosion inhibitor of the present invention comprises the amino acid having a thiol group in the molecule or a derivative thereof according to the present invention as described above. The metal corrosion inhibitor of the present invention is usually in the form 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 of dissolving the amino acid or its derivative according to the present invention in water includes, for example, a method of adding the amino acid or its derivative according to the present invention separately dissolved in water, or a method of directly adding the amino acid or its derivative according to the present invention. A method of adding to water, dissolving and stirring, etc. may be mentioned.

The metal corrosion inhibitor of the present invention thus prepared is preferably subjected to a filtration treatment or the like before use. In addition, the water used here may be any water that has been purified by distillation, ion exchange treatment, or the like, and 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 generally used in this field can be used.

Such reagents include, for example, 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 generally used in this field, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberin and the like. Dicarboxylic acids having 2 to 8 carbon atoms such as acids, 2-n-butylmalonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, phthalic acid, isophtalic acid, terephthalic acid, etc., for example, tricarboxylic 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, and dihydroxydicarboxylic acids having 4 or more carbon atoms, such as tartaric acid, for example, carbon such as citric acid 6 or more monohydroxytricarboxylic acids, such as hydroxytricarboxylic acids, their ammonium salts, etc. Is mentioned.

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, fumaric acid, malic acid, citric acid, and tartaric acid are preferable, and citric acid and oxalic acid are particularly preferable.

These organic acids may be used alone or in combination of two or more.

The amount of the organic acid used varies depending on the type of the organic acid and cannot be specified unconditionally, 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 amine used in the present invention may be any one generally used in this field, and is not particularly limited. Examples thereof include methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, and n-pentylamine. Alkylamines having 1 to 6 carbon atoms such as hexylamine, cyclopentylamine, cyclohexylamine, etc., for example, dimethylamine, methylethylamine Dialkylamines having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as min, getylamine, dipropylamine, etc., for example, carbon atoms such as trimethylamine, dimethylethylamine, methylgetylamine, triethylamine, trippyramine, etc. Trial quilamine having a number of 3 to 18, preferably 3 to 6 carbon atoms, for example, a carbon number of 1 to 18 such as monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, getylethanolamine and the like. Mono- to trihydroxyalkylamines, preferably having 1 to 6 carbon atoms, such as methylenediamine, ethylenediamine, propylenediamine, isopropylenediamine, petylenediamine, methylmethylenediamine, ethylethylenediamine, methylethylene Diamine, methyl Alkylene diamines having 1 to 6 carbon atoms such as pyrylene diamine, ethyl propylene diamine, pentylene diamine, hexylene diamine, cyclopentylene diamine, cyclohexylene diamine, etc., and 2 to 2 carbon atoms such as dimethylenetriamine and diethylenetriamine. 12, preferably a dialkylenetriamine having 2 to 4 carbon atoms, for example, a trialkylenetetramine having 3 to 18 carbon atoms, such as trimethylenetetramine, triethylenetetramine, and the like, preferably a trialkylenetetramine having 3 to 6 carbon atoms, for example, tetramethylammonium Dimethyl hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-pentylammonium hydroxide, tetra-n-hexylammonium hydroxide M hydroxide Tetraalkylammonium hydroxide having 4 to 24 carbon atoms, such as tetracyclopentylammonium hydroxide, tetracyclohexylammonium hydroxide, etc., for example, the following general formula [4]

(Wherein, R ³ represents an alkyl group, R ⁴ and R ⁵ represent an alkylene group, and m and n each represent a positive integer.) And an alkylamine-alkylene oxide adduct represented by the formula: You.

In the general formula [4], the alkyl group represented by R ³ is, for example, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably Are 1 to 4, 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, sec-hexyl, tert-hexyl, n-heptyl, iso-heptyl, sec-heptyl, n-octyl, iso-octyl, sec-octyl , N-nonyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl Heptyl group cycloalkyl, Shikurookuchiru groups include shea Kurodeshiru group. Among them, a cyclohexyl group and the like are particularly preferred.

As the alkylene group represented by R ⁴ and R ⁵ , for example, a linear, branched or cyclic lower alkylene group having 1 to 6 carbon atoms is preferable, for example, a methylene group, an ethylene group, a propylene group, a butylene group, Methyl methylene group, ethyl ethylene group, methyl ethylene group, methyl propylene group, ethyl Examples thereof include a propylene group, a pentylene group, a hexylene group, a cyclopentylene group, a cyclohexylene group, and a methylene group and an ethylene group are particularly preferable.

Further, m and n each represent a positive integer and are usually 1 to 10, preferably 1 to 5.

Examples of the alkylamine-alkylene oxide adduct represented by the general formula [4] 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) (polyoxyethyl propylene), methylamine (polyoxyethyl propylene) (polyoxycyclohexylene), ethylamine di (polyoxymethylene), Luamine di (polyoxyethylene), ethyl amine di (polyoxy propylene), ethyl amine di (polyoxycyclohexylene), ethylamine (polyoxymethylene) (polyoxyethylene), ethylamine (polyoxymethylene) (polyoxyethyl propylene) , Ethylamine (polyoxymethylene) (polyoxycyclohexylene), ethylamine (polyoxyethylene) (polyoxyethylene propylene), ethylamine (polyoxyethylene) (polyoxycyclohexylene), ethylamine (polyoxyethylene propylene) (polyoxycyclo) Hexylene), propylamine di (polyoxymethylene), propylamine di (polyoxyethylene), propylamine di (polyoxyethyl propyle) ), Propylamine di (polio Xycyclohexylene), propylamine (polyoxymethylene) (polyoxyethylene), propylamine (polyoxymethylene) (polyoxyethylene), propylamine (polyoxymethylene) (polyoxycyclohexylene), propylamine (polyoxy Alkylamine di (polyoxyalkylene) such as ethylene) (polyoxyethyl propylene), propylamine (polyoxyethylene) (polyoxycyclohexylene), propylamine (polyoxyethyl propylene) (polyoxycyclohexylene) ), For example, cyclohexylamine di (polyoxymethylene), cyclohexylamine di (polyoxyethylene), cyclohexylamine di (polyoxypropylene), cyclohexylamine di (Polyoxybutylene), cyclohexylamine di (polyoxymethylmethylene), cyclohexylamine di (polyoxyethylethylene), cyclohexylamine di (polyoxyethylpropylene), cyclohexylamine di (polyoxypentylene), cyclohexylamine di ( Polyoxyhexylene), cyclohexylamine di (polyoxycyclohexylene), cyclohexylamine (polyoxymethylene) (polyoxyethylene), cyclohexylamine (polyoxymethylene) (polyoxyethylene propylene), cyclohexylamine (Polyoxymethylene) (polyoxycyclohexylene), cyclohexylamine (polyoxyethylene) (polyoxethyl), cyclohexylamine (poly) (Xoxyethylene) (polyoxysig hexylene), cyclohexylamine (polyoxyethylpropylene) (polyoxycyclohexylene), cyclodecylaminedi (polyoxymethylene), cyclodecylaminedi (polyoxyethylene), cyclodecylaminedi (poly Oxyshetyl propylene), cyclodecylamine (polyoxycyclohexylene), cyclodecylamine (polyoxymethylene) Roxyshethyl propylene), cyclyl decylamine (polyoxymethylene) (polyoxycyclohexylene), cyclodecylamine (polyoxyethylene) (polyoxyethyl propylene), cyclodecylamine (polyoxyethylene) (poly Cycloalkylamine di (polyoxyalkylene) such as oxycyclohexylene) and cyclodecylamine (polyoxyethyl propylene) (polyoxycyclohexylene).

Among the above-mentioned amines, alkylene diamine, dialkylene triamine, trialkylene tetramine, alkylamine-alkylene oxide adduct, and tetraalkylammonium hydroxide are preferred, and among them, alkylene diamine, cycloalkyl Alkylamine di (polyoxyalkylene) is particularly preferred.

Specifically, ethylenediamine, diethylenetriamine, triethylenetetramine, cyclohexylaminedi (polyoxyethylene), cyclohexylamine (polyoxyethylene) (polyoxymethylene), and tetramethylammonium hydroxide are preferred. And cyclohexylamine di (polyoxyethylene) are particularly preferred. These amines may be used alone or in combination of two or more.

The amount of the amine used varies depending on the type of the amine and cannot be specified unconditionally. For example, it is usually 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, and more preferably 0.05 to 10% by weight.

The inorganic compound used in the present invention may be any compound usually used in this field, and is not particularly limited. Examples thereof include hydroxyamine, hydrazine, ammonia, and salts thereof (for example, hydrochloride, sulfate, etc.). And inorganic alkali compounds such as potassium hydroxide and sodium hydroxide. Among them, a nitrogen-containing inorganic alkali compound is preferable, and a nitrogen-containing inorganic alkali compound containing no metal is particularly preferable. Specifically, hydroxylamine, hydrazine and ammonia are preferred, and ammonia is particularly preferred.

These inorganic alkali compounds may be used alone or in an appropriate combination of two or more.

The amount of the inorganic compound used depends on the type of the inorganic compound and cannot be specified unconditionally. For example, it is usually 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, more preferably 0.05 to: 10% by weight. The chelating agent used in the present invention may be any one usually used in this field, and is not particularly limited. 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 A1 can be removed from the substrate surface. it can.

Examples of such chelating agents include EDTA (ethylenediaminetetraacetic acid), EDDA (ethylenediaminediacetic acid), EDTA—OH (hydroxyethylenediaminetriacetic acid), GEDTA (dalicol etherdiaminetetraacetic acid), and DTPA (diethylenetriaminetetraacetic acid). Pentaacetic acid), IDA (iminodiacetic acid), methyl-EDTA (diaminopropanetetraacetic acid), TA (tri-triacetic triacetic acid), TTHA (triethylenetetramine hexaacetic acid), these ammonium salts, and Linear aminopolycarboxylic acids such as complex salts with amines, such as Cy DTA (trans-cyclohexyldiaminotetraacetic acid), ammonium salts thereof, and aminopolycarboxylic acids such as cyclic aminopolycarboxylic acids such as complexes with amines For example, NT PO (ditrilotrismethylene phosphonic acid), HEDPO (hydroxyethylidene di Phosphate)), these Anmoniumu salts, thereof with Amin Polyphosphonic acids such as complex salts with EDDPO (ethylenediaminedi (methylenephosphonic acid)), EDTPO (ethylenediaminetetra (methylenephosphonic acid)), PDTPO (diaminopropanetetra (methylenephosphonic acid)), DETPPO (diethylenetriamine Pennox (methylene phosphonic acid)), TTHPO (triethylenetetraminehexa (methylene phosphonic acid)), their ammonium salts, and phosphonic acids such as aminopolyphosphonic acids such as complex salts of these with amines.

Among them, EDTA, CyDTA, HEDPO, EDTPO, DETPPO, ammonium salts thereof, and complex salts of these with amines are particularly preferred.

In the above, examples of the amine that forms the complex salt include the same amines as described above.

These chelating agents may be used alone or in combination of two or more.

The amount of the chelating agent varies depending on the type of the chelating agent and cannot be specified unconditionally. For example, it is usually 0.0001 to 10% by weight, preferably 0.0001 to 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 generally used in this field. The addition of a surfactant can improve the wettability of the aqueous solution on the substrate surface.

Such surfactants include, for example, nonionic surfactants having a polyoxyalkylene group in the molecule, such as sulfonic acid groups, hydroxyloxyl groups, phosphonic acid groups, sulfoxyl groups, and phosphonoxyl groups in the molecule. Anionic surfactants having a selected group, for example, alkylamines, for example, quaternary ammoniums such as alkyltrimethylammonium, alkyldimethylpentylammonium, for example, alkylpyridinium, Cationic surfactants such as salts thereof (for example, hydrochloride, sulfate, etc.), for example, alkylbetaine derivatives, imidazoliniumbeine derivatives, sulfobeine derivatives, aminocarboxylic acid derivatives, imidazoline derivatives, and aminoxides Examples include, but are not limited to, amphoteric surfactants such as derivatives.

Nonionic surfactants having a polyoxyalkylene group in the molecule include:

For example, polyoxyalkylene alkyl ethers, polyoxyalkylene polyalkylaryl ethers, and the like can be mentioned. More specifically, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, etc. Nonionic surfactants having a oxyethylene group, such as polyoxypropylene alkyl ethers, nonionic surfactants having a polyoxypropylene group in a molecule such as polyoxypropylene alkylphenyl ether, etc., such as polyoxyethylenepolypropylene Nonionic surfactants having a polyoxyethylene group and a polyoxypropylene group in the molecule, such as alkyl ether and polyoxyethylene polyoxypropylene alkylphenyl ether, are exemplified.

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 alkylsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthylenesulfonic acid, and the like. (For example, alkali metal salts such as sodium and potassium, for example, ammonium salts, etc., among which ammonium salts are preferred), etc., and anionic surfactants having a sulfonic acid group in the molecule, for example, alkyl carboxylic acids, Alkyl benzene carboxylic acid, alkyl naphthalene carboxylic acid, and salts thereof (eg, sodium, lithium Anionic surfactants having a carboxyl group in the molecule, such as alkylphosphonic acid, alkylbenzenephosphonic acid, alkylnaphthylenephosphonic acid, etc. Anionic surfactants having a phosphonic acid group in the molecule, such as salts thereof (for example, alkali metal salts such as sodium and potassium, for example, ammonium salts, among which ammonium salts are preferable), such as alkyl sulfates Alkyl benzene sulfate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl benzene sulfate, polyoxyethylene alkyl naphthene sulfate, salts thereof (eg, alkali metal salts such as sodium and potassium, and the like) If Anmoniumu salts, Ru include among others Anmoniumu salts are preferred) Anion-based surfactants having a sulfoxyl group in a molecule, such as and the like.

Among them, nonionic surfactants and anionic surfactants are preferred, and esters are particularly preferred. Examples of the anionic surfactant include those having a sulfonic acid group in a molecule and those having a sulfoxyl group in a molecule. Those are particularly preferred. More specifically, nonionic surfactants having a polyoxyethylene group in a molecule such as a polyoxyethylene alkyl ether, and a polyoxyethylene group and a polyoxygen in a molecule such as a polyoxyethylene polyoxypropylene alkyl ether. Nonionic surfactants having a propylene group, anionic surfactants having a carboxyl group in the molecule such as alkylbenzenesulfonic acid, and anionic surfactants having a sulfoxyl group in the molecule such as polyoxyethylene alkyl sulfate. Activators are particularly preferred.

These surfactants may be used alone or in combination of two or more. They may be used together.

The amount of surfactant used cannot be determined unconditionally because it differs depending on the type of surfactant, but nonionic surfactants only need to be at or above the critical micelle concentration, and if they are thinner, the etching rate will increase. , The effect diminishes. Further, 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 used is different depending on the type of the surfactant and cannot be specified unconditionally. However, it is usually 0.0001 to 1% by weight, preferably 0.0001 to 0.1% by weight, more preferably 0.0001 to 0.05% by weight. The metal corrosion inhibitor of the present invention comprises the amino acid or the derivative thereof according to the present invention as described above, and at least one of the above-described organic acids, amines, inorganic alkali compounds, chelating agents, and surfactants. The one comprising an amino acid or a derivative thereof according to the present invention as described above, a chelating agent or a surfactant is particularly preferred. The metal corrosion inhibitor according to the present invention comprises an amino acid having a thiol group in a molecule or a derivative thereof according to the present invention, which is contained therein and which is adsorbed on a metal surface to form a protective film on the metal surface. It utilizes the property that it can protect the surface and suppress the oxidation and corrosion of metals received from aqueous solutions and air. For example, a substrate having a metal-coated portion on the surface using the metal corrosion inhibitor of the present invention. By treating the surface, oxidation and corrosion of the metal on the substrate surface can be prevented, and furthermore, metal impurities on the substrate surface can be effectively removed. The treating agent of the present invention is a metal corrosion inhibitor of the present invention as described above, Amino acids having a thiol group in the molecule according to the present invention or derivatives thereof, if necessary, for example, reagents usually used in this field, such as organic acids, amines, inorganic alkali compounds, chelating agents, and surfactants as described above. Are contained in the concentration range as 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, oxidation and corrosion of the metal on the substrate surface can be prevented at the same time. Metal impurities (for example, metal oxides such as copper oxide and iron oxide) and particles can be more effectively removed. Among them, those comprising the amino acid or the derivative thereof according to the present invention as described above, a chelating agent or a surfactant are particularly preferable.

Specific examples and preferred embodiments of the reagents as described above are as described above. The treating agent of the present invention is usually in the form of an aqueous solution, and is prepared by adding and dissolving the amino acid or the derivative thereof according to the present invention in water by the same preparation method as the metal corrosion inhibitor of the present invention as described above. Is done.

The treating agent of the present invention thus prepared is preferably subjected to a filtration treatment or the like before use. The treatment method (metal corrosion prevention method) of the present invention comprises contacting the treatment agent (metal corrosion inhibitor) of the present invention as described above with a metal on the surface of a substrate having a metal coating on the surface. May be treated with the treating agent of the present invention (method for preventing metal corrosion).

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

In the present invention, “treatment” refers to bringing the treatment agent of the present invention into contact with the metal on the substrate surface, as described above.

More specifically, examples include, but are not limited to, pretreatment, cleaning treatment, and the like before storage treatment, for example, cleaning treatment. 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, or a pretreatment agent for a substrate having a metal coating on the surface, or having a metal coating on the surface. It can also be used as a processing agent such as a cleaning agent for substrates.

For example, if the treating agent of the present invention is used as a preservative for a substrate having a metal-coated portion on its surface, it is possible to prevent the metal from being oxidized and corroded during storage of the substrate from various atmospheres such as an aqueous solution and air. Further, metal impurities on the substrate surface can be effectively removed. As a method for storing the substrate of the present invention, for example, a method of performing the above-described dip treatment or the like and storing the substrate while immersing the substrate in the processing agent (preservative) of the present invention, or performing the above-described single wafer processing or the like Examples include a method of preserving the treating agent (preservative) of the present invention while sprinkling it on the substrate, or a method of drying and storing the substrate after performing these treatments.

In addition, for example, before treating a substrate having a metal-coated portion on a surface thereof in a cleaning step or the like, the treatment agent of the present invention is used as a pretreatment agent for the substrate to treat the metal on the substrate surface. An aqueous solution of a cleaning agent or the like used in the process can prevent oxidation and corrosion of the metal during the process of the next process from various atmospheres such as air during the next process. By simple operations such as cleaning with pure water, metal impurities on the substrate surface can be effectively removed. Monkey Examples of the pretreatment method of the substrate of the present invention include a method of dipping the substrate in the treatment agent (pretreatment agent) of the present invention by the above-described dip treatment, and a treatment agent of the present invention by the single-wafer processing as described above. A method of sprinkling the (pretreatment agent) on the substrate, or a method of drying the substrate after performing these treatments, and the like.

The substrate thus obtained can be subjected to a cleaning method using a surface treatment agent (cleaning agent) known per se, which is usually performed in this field.

As the surface treatment agent (cleaning agent) used in the above, any one used in this field can be used, and it is not particularly limited. For example, JP-A-5-263275, JP-A-6-112646 JP, JP-A-6-287774, JP-A-7-54169, JP-A-7-79061, JP-A-7-166381, JP-A-7-292483, JP-A-2000-8185 Surface treatment agents (detergents) described in JP-A-10-251867, JP-A-7-267933, JP-A-11-50275, and the like, and the detergent of the present invention described later. . Further, for example, if the treating agent of the present invention is used as a cleaning agent for a substrate having a metal-coated portion on its surface to treat the surface of the substrate having a metal-coated portion on the surface, corrosion and oxidation of the metal on the substrate surface can be achieved. Can be prevented, and metal impurities on the surface can be effectively removed. As described above, the treating agent of the present invention comprises, as described above, an amino acid having a thiol group in a molecule or a derivative thereof, and an organic acid, an amine, an inorganic compound, a chelating agent, and a surfactant as described above. At least one of And more preferably those comprising the amino acid or derivative thereof according to the present invention, a chelating agent or Z and a surfactant, but the treating agent of the present invention is used as a detergent. When used, such a composition is particularly preferable.

The specific examples and preferred embodiments of the above-mentioned organic acid, amine, inorganic alkali compound, chelating agent and surfactant are as described above. The detergent of the present invention is usually in the form of an aqueous solution, and the amino acid or a derivative thereof (or an organic acid, an amine, an inorganic alkali compound, a chelating agent and a surfactant) according to the present invention is used. Is added to and dissolved in water. Examples of the method for dissolving the amino acid or its derivative according to the present invention in water include, for example, the amino acid or its derivative according to the present invention separately dissolved in water (or the separately dissolved organic acid, amine, or inorganic acid). A method of adding an alkali compound, at least one of a chelating agent and a surfactant, and an amino acid or a derivative thereof according to the present invention (or an organic acid, an amine, an inorganic compound, a chelating agent) And at least one of a surfactant and water) and directly dissolving and stirring them in water, or adding the amino acid or derivative thereof according to the present invention dissolved and added in water, and separately in water Stirring and mixing the added and dissolved organic acid, amine, inorganic alkali compound, at least one of a chelating agent and a surfactant, and the like. .

The cleaning agent of the present invention thus prepared is preferably subjected to a filtration treatment or the like before use. Further, the water used here may be any water that has been purified by distillation, ion exchange treatment or the like, but so-called ultrapure water used in this field is more preferable. In the cleaning method of the present invention, the surface of a substrate having a metal coating on the surface may be treated with the cleaning agent of the present invention as described above.

The method of treating the substrate surface having a metal coating on the surface with the cleaning agent of the present invention may be any cleaning method known per se, which is usually performed in this field, and includes, for example, the dip treatment and the single-wafer treatment as described above. And the like. Further, in the present invention, by using physical cleaning at the same time as cleaning, metal impurities (metal oxide equivalent to oxidation, etc.) can be more effectively removed. As a specific method of the combined use, there is a method in which a substrate surface having a metal-coated portion on the surface is subjected to a physical cleaning step in the presence of the cleaning agent of the present invention.

In the above method, as a method for causing the cleaning agent of the present invention to exist, specifically, the physical cleaning step is performed in a state where the cleaning agent of the present invention is present by the above-described dip treatment, single-wafer processing, or the like. And the like. Examples of the physical cleaning (step) include brush scrub cleaning for cleaning the substrate surface using a high-speed rotating polyvinyl alcohol brush or the like, megasonic cleaning using high frequency, and the like.

As a more specific method when physical cleaning is used in combination, for example, after immersing the substrate in the cleaning agent of the present invention, removing the substrate from the cleaning solution and allowing the cleaning agent to exist on the surface of the substrate Physical cleaning after cleaning, a method in which physical cleaning is performed while the substrate is immersed in the cleaning agent of the present invention, and the cleaning agent of the present invention is sprinkled on the surface of the substrate, and the cleaning agent is present on the surface of the substrate. A method in which physical cleaning is performed after the state is performed, or a method in which physical cleaning is performed while the cleaning agent of the present invention is sprinkled on the substrate surface, may be used.

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 the type and purpose of the substrate used The pH is appropriately selected from the pH range usually used in this field.

More specifically, it is preferably weakly acidic to alkaline, and usually has a pH of 2 to 13, preferably 3 to 12, and more preferably 4 to 10. By setting the pH in such a range, the electrical repulsion between the substrate surface and the particles is increased, so that the effect of removing the particles and metal impurities (for example, metal oxides such as copper oxide) is improved. risk of Etsuchin grayed the Si0 ₂ is an interlayer insulating film becomes less. The metal corrosion inhibitor and treatment agent (preservative, pretreatment agent, detergent, etc.) of the present invention can be used, for example, for a substrate having a metal coating on the surface.

Examples of such a substrate include a semiconductor substrate, a printed substrate such as a polyimide resin, a glass substrate used for an LCD, and the like, and are particularly useful for a semiconductor substrate. Still further, the metal coated on the substrate surface may be any metal that reacts with sulfur, such as copper, chromium, silver, and gold, and is particularly useful for metallic copper. Particularly, it is particularly useful for a semiconductor substrate having a copper coating on its surface (with copper wiring). Hereinafter, Examples and Comparative Examples will be described, but the present invention is not limited thereto. The metal Cu deposition layer 18 and the Cu contamination layer used in this example and the comparative example were prepared by the following methods, respectively. The Cu film thickness and the amount of Cu (copper atoms) adsorbed and remaining on the surface of the Cu contamination wafer were measured by the following methods. [Metal Cu deposition @ Ahachi]

A copper deposit was prepared by depositing metallic Cu on the surface of 4-inch silicon wafer by sputtering.

In addition, it was confirmed by the method described below that the thickness of copper on the surface of the metal Cu deposition layer was 100 nm.

CCu contamination 18)

4 inch silicon © E one tooth in which the surface and the Si0 ₂ by thermal oxidation, 1 ppm and aqueous slurry with the addition of Cu ions so (1% silica containing chromatic 0.1% hydrogen peroxide solution) 1 minute 1 L After being immersed, washed with running ultrapure water for 10 minutes, and spin-dried, it was used as a Cu contamination wafer.

In addition, it was confirmed by the method described below that Cu (copper atom) 3 × 10 ¹⁴ atoms Zcm ^{2 was} adsorbed and remained in the Cu contamination layer 8. [Metal Cu film thickness measurement method]

ゥ The wafer was divided in half, the cross section was observed with an electron microscope, and the metal Cu film thickness was measured.

(Cu concentration measurement method)

After the Cu adsorbed on the surface of A-8 was dissolved and recovered with a hydrofluoric acid / nitric acid aqueous solution, the Cu concentration in the recovered solution was measured by an atomic absorption method (graphite furnace atomic absorption spectrometer). Based on the obtained measured values, the adsorption amount of Cu (copper atoms) (residual Cu concentration) was determined. In Examples and Comparative Examples,%, ppm, and ppb all represent weight ratios unless otherwise specified. The water used is all ultrapure water, Copper was used after confirming that it was O.Olppb or less. Example

Examples 1-1 to 14

1 L of each metal corrosion inhibitor (preservative) listed in Table 1 was immersed in the metal Cu deposition wafer prepared by the above method at room temperature for 5 hours. Thereafter, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried.

In order to confirm the presence or absence of oxidation of the metal Cu on the metal Cu deposition wafer treated in this way, the color tone of the Cu film surface on the wafer surface was visually observed, and the presence or absence of corrosion of the metal Cu To confirm this, the film thickness of metallic Cu on the wafer surface was measured. Table 1 shows the results.

table 1

Comparative Examples 1 to 6

Except that the various solutions described in Table 2 were used, metal Cu deposition was treated in the same manner as in Examples 1 to 14, and then the color tone of the Cu film surface on the wafer surface was visually observed. (4) The film thickness of metallic Cu on the surface of the wafer was measured. Table 2 shows the results. One in Table 2 indicates that measurement was not possible. Table 2

As is apparent from Tables 1 and 2, when the metal Cu deposition (A8) was preserved in the metal corrosion inhibitor (preservative) of the present invention (Examples 1 to 14), the Cu film on the surface of the wafer was obtained. It can be seen that there was no change in the color tone of the surface, the metal Cu was not oxidized, and there was almost no change in the Cu film thickness, and the metal Cu was not corroded.

On the other hand, when the metal Cu deposition wafer was stored in the solutions of Comparative Examples 1 and 5, the metal Cu was significantly corroded, and the gloss of the Cu film surface on the wafer surface was lost, and the metal It turns out that 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 metal Cu was not oxidized, the Cu film thickness decreased and the metal Cu corroded. (Dissolved). Furthermore, it can be seen that in Comparative Example 2, metal Cu was oxidized and corroded (dissolved), and particularly in Comparative Example 3, all metal Cu was corroded (dissolved). .

That is, the metal corrosion inhibitor of the present invention can prevent oxidation and corrosion of metal, and preserves a substrate having a metal coating on the surface in a treating agent (preservative) containing the metal inhibitor of the present invention. Then, it can be seen that oxidation and corrosion of the metal can be prevented at the same time, and the substrate having a metal coating on the surface can be stored well in a solution. Examples 15 to 17

The metal Cu deposition 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. Thereafter, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. The wafer was then left in the air for 10 hours.

With respect to the metal Cu deposition wafer thus treated, 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. Table 3 shows the results. Comparative Examples 7 to 10

Except for using the various solutions described in Table 3, the metal Cu deposition wafer was treated in the same manner as in Examples 15 to 17, and the color tone of the Cu film surface on the wafer surface was visually observed. did. The results are shown in Table 3 together with Examples 15 to 17. Table 3

As is clear from Table 3, after treating the metal Cu deposition wafer with the metal corrosion inhibitor of the present invention (preservative) (Examples 15 to 17), the wafer was stored in air. In the figure, there is no change in the color tone of the Cu film surface on the surface of the metal sheet, indicating that the metallic Cu is not oxidized.

In contrast, when the metal Cu deposition wafer was treated with the solutions of Comparative Examples 7 to 10, the gloss of the Cu film surface on the wafer surface disappeared, indicating that the metal Cu was oxidized. .

That is, after treating a substrate having a metal-coated portion on the surface with a treating agent (preservative) containing the metal inhibitor of the present invention and then storing it, oxidation of the metal on the surface of the substrate can be prevented. It can be seen that the substrate having a metal coating on the surface can be stored well in air. Example 18 to 20

500 ml of each metal corrosion inhibitor (preservative) shown in Table 4 was sprinkled on the surface of the metal-Cu-deposited wafer prepared by the above method for 1 minute. Thereafter, the wafer was rinsed with ultrapure water for 10 minutes and spin-dried. Then, the wafer was left in the air for 10 hours.

With respect to the metal Cu deposits thus treated, 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. Table 4 shows the results. Comparative Example 11: 1 to 4

After treating the metal Cu deposition wafer in the same manner as in Examples 18 to 20, except that the various solutions described in Table 4 were used, the color tone of the Cu film surface on the wafer surface was changed. Observed visually. The results are shown in Table 4 together with Examples 18 to 20.

Table 4

As is evident from Table 4, after treating the metal Cu deposition wafer with the metal corrosion inhibitor (preservative) (Examples 18 to 20) of the present invention, the wafer was stored in air. The results show that there was no change in the color tone of the Cu film surface on the wafer surface, and that the metallic Cu was not oxidized.

On the other hand, when the metal Cu deposition wafer was treated with the solutions of Comparative Examples 15 to 17, the gloss of the Cu film surface on the surface of the metal sheet disappeared, and the metal Cu was oxidized. It turns out.

That is, the metal inhibitor of the present invention is contained not only by the so-called dipping treatment as in Examples 15 to 17 but also by the so-called single-wafer treatment as in Examples 18 to 20. After treating a substrate having a metal coating on the surface with a treating agent (preservative), if it is stored, the metal on the substrate surface It can be seen that oxidation can be prevented and the substrate having a metal coating on the surface can be stored well in air. Example 2 1 to 3 4

In 1 L of each metal corrosion inhibitor (pretreatment agent) shown in Table 5, the Cu contamination layer 18 and metal Cu deposition layer produced by the above method were immersed at room temperature for 1 hour. Thereafter, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried.

Next, the PA18 was immersed in 1 L of each cleaning solution described in Table 5 at room temperature for 10 minutes. Thereafter, the AHA was removed, rinsed with ultrapure water for 10 minutes, and spin-dried.

With regard to the Cu contamination layer 18 treated in this way, the residual Cu concentration adsorbed on the wafer surface was measured to evaluate the ability to remove metal impurities. In order to confirm the presence or absence of oxidation of metal Cu, the color tone of the Cu film surface on the wafer surface was visually observed.In addition, the thickness of metal Cu on the wafer surface was measured in order to confirm the presence of corrosion of metal Cu. . Table 5 shows the results. One in Table 5 indicates that measurement was not possible. Comparative Examples 15 to 25

After treating Cu contamination wafers and metal Cu deposition wafers in the same manner as in Examples 21 to 34 except that the various solutions and cleaning agents listed in Table 5 were used, For contamination wafers, the residual Cu concentration adsorbed on the wafer surface was measured.For metal Cu deposition, the color tone of the Cu film surface on the wafer surface was visually observed. Furthermore, the film thickness of metal Cu on the wafer surface was measured. Table 6 shows the results.

In Comparative Examples 15 to 18, the metal corrosion inhibitor (pretreatment agent) was used. Without treatment, immerse the wafer in 1 L of each cleaning solution described in Table 6 at room temperature for 10 minutes, remove the wafer, rinse it with ultrapure water for 10 minutes, and spin dry. · Observed.

Table 5

Table 6

As is clear from the results in Tables 5 and 6, when the pretreatment was performed using the metal corrosion inhibitor (pretreatment agent) of Examples 21, 22, and 27, Cu contamination It can be seen that the residual Cu concentration can be suppressed to the order of 101 ^Q or less, and the oxidation and corrosion of metallic Cu can be prevented. On the other hand, when pretreatment is performed using a conventional metal corrosion inhibitor (surface treatment agent), although the residual Cu concentration can be suppressed to the same extent, oxidation and corrosion of metal Cu occur. Rolling (Comparative Examples 19 and 23), oxidative corrosion of metallic Cu is suppressed However, it can be seen that the residual Cu concentration was high and copper oxide could not be removed effectively (Comparative Examples 20, 24 and 25).

Similarly, in Examples 23 and 30, copper oxide can be effectively removed, and oxidation and corrosion of metal Cu can be prevented, while Comparative Examples 21 and 22 are substrates. It can be seen that the Cu film on the surface is significantly corroded.

Also, from the results of Examples 26, 28, 32, and 34 and Comparative Examples 15 to: I8, if pretreatment was performed using the metal corrosion inhibitor (pretreatment agent) of the present invention, It can be seen that the oxidation and corrosion of metallic Cu during cleaning can be suppressed as compared with the case where this is not performed, and that copper oxide can also be effectively removed.

As is clear from the above, before the substrate having the metal coating on the surface is subjected to the cleaning step, if the substrate is pretreated with the metal corrosion inhibitor (pretreatment agent) of the present invention, the substrate can be cleaned. It can be seen that the metal can be prevented from being oxidized and corroded in the process, and that the metal oxide can also be effectively removed. Example 3 5 to 4 4

The Cu-contaminated wafer prepared by the above method was immersed in 1 L of each cleaning agent (metal corrosion inhibitor) described in Table 7 at room temperature for 10 minutes. Thereafter, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried.

Further, the metal Cu deposition wafer prepared by the above method was immersed in 1 L of each cleaning agent (metal corrosion inhibitor) described in Table 7 at room temperature for 5 hours. Thereafter, the wafer was taken out, rinsed with ultrapure water for 10 minutes, and spin-dried. With regard to the copper contamination treated in this way, the residual Cu concentration adsorbed on the surface of the wafer was measured to evaluate the ability to remove metal impurities. In order to confirm the presence or absence of oxidation, the color tone of the Cu film surface on the wafer surface was visually observed and updated. Next, the thickness of the metal Cu on the wafer surface was measured to confirm the presence or absence of corrosion of the metal Cu. Table 7 shows the results. Comparative Example 26 to 37

After treating Cu contamination and metal Cu deposition wafers in the same manner as in Examples 35 to 44, except that each cleaning agent described in Table 8 was used, the surface of the wafer was treated. The concentration of residual Cu remaining by adsorption was measured, and for metal Cu deposition A8, the color tone of the Cu film surface on the wafer surface was visually observed, and the thickness of metal Cu on the wafer surface was also measured. Table 8 shows the results. One in Table 8 indicates that measurement was not possible.

Table 8

Table 9

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 residual Cu on the wafer surface was reduced. The concentration can be suppressed to the order of less than 101 ^G, the color tone of the Cu film surface does not change, the metal Cu is not oxidized, and the Cu film thickness hardly changes, and the metal Cu is corroded. It turns out that it has not been done.

In contrast, when the cleaning agents of Comparative Examples 27, 30, 30, 31, 33, and 34 were used, the residual Cu concentration could be suppressed to the order of 101 ^Q or less, but the metal Cu Is oxidized and the metal Cu is significantly corroded. When the cleaning agents of Comparative Examples 29 and 35 to 37 were used, the metal Cu on the wafer surface was not oxidized, and the metal Cu was almost corroded. Although not shown, the residual Cu concentration is high, and it can be seen that the copper oxide on the wafer surface cannot be sufficiently removed. Furthermore, when the cleaning agents of Comparative Examples 26 and 32 were used, metal Cu was corroded and oxidized, and the residual Cu concentration was high, and the copper oxide on the surface of the wafer could not be sufficiently removed. I understand. When the cleaning agent of Comparative Example 28 was used, it was found that the metal Cu was significantly corroded, and that the copper oxide on the surface of the coating material could not be sufficiently removed.

That is, by cleaning the surface of the substrate having a metal coating on the surface using the cleaning agent of the present invention, oxidation and corrosion of the metal can be prevented, and metal impurities (copper oxide) on the surface can be effectively removed. It can be seen that it can be removed. Industrial potential

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 substrate surface having copper wiring on the surface. A method of treating the substrate, which can prevent oxidation and corrosion of copper wiring, and a method of preventing corrosion and oxidation of copper wiring on the surface of the substrate, and effectively remove metal impurities (copper oxide) on the surface. The present invention provides a method for cleaning a substrate. The use of the metal corrosion inhibitor of the present invention can solve, for example, various problems in the production of semiconductors.

Claims

The scope of the 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. The metal corrosion inhibitor according to claim 1, wherein the amino acid having a thiol group in the molecule is cysteine or homocystin.

4. The metal corrosion inhibitor according to any one of claims 1 to 3, wherein the amino acid derivative is an N-acyl form of the amino acid or a carboxylic acid ester form of the amino acid.

5. The metal corrosion inhibitor according to claim 4, wherein the N-acyl compound has a carboxylic acid-derived acyl group introduced therein.

6. The metal corrosion inhibitor according to claim 4, wherein the N-acyl form is an N-alkanoyl form or an N-aralkanoyl form.

7. The metal corrosion inhibitor according to claim 4, wherein the N-acyl form is an N-acetyl form. 5. The metal corrosion inhibitor according to claim 4. 5. The metal corrosion inhibitor according to claim 4, wherein:

10. The metal corrosion inhibitor according to any one of claims 1 to 9, 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- to tricarboxylic acid.

12. The metal corrosion inhibitor according to claim 10, wherein the organic acid is a mono- to di-hydroxy di- to tricarboxylic acid.

1 3. The amine is alkylamine, dialkylamine, hydroxyal 10. The metal corrosion inhibitor according to claim 10, wherein the metal corrosion inhibitor is any one of kilamine, alkylenediamine, dialkylenetriamine, trialkylenetetramine, an alkylamine-alkylene oxide adduct, and tetraalkylammonium hydroxide. . 14. The metal corrosion inhibitor according to claim 10, wherein the inorganic alkali compound is a nitrogen-containing inorganic alkali compound.

15. The metal corrosion inhibitor according to claim 14, wherein the nitrogen-containing inorganic alkali 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 amino and phosphonic acids.

17. The metal corrosion inhibitor according to claim 16, wherein the aminopolycarboxylic acids are linear aminopolycarboxylic acids or Z and cyclic aminopolycarboxylic acids.

1 8. Linear aminopolycarboxylic acids are EDTA (ethylenediaminetetraacetic acid), EDDA (ethylenediaminediacetic acid), EDT A-OH (hydroxyethylenediaminetriacetic acid), GEDTA (dalicol etherdiamine). Tetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), IDA (iminodiacetic acid), methyl — EDTA (diaminopropanetetraacetic acid), NTA (tri-triamine triacetic acid), TTHA (triethylenetetramine hexaacetic acid), 18. The metal corrosion inhibitor according to claim 17, which is a complex salt with an ammonium salt or an amine.

19. The metal corrosion inhibitor according to claim 17, wherein the cyclic aminopolycarboxylic acid is CyDTA (trans-hexyldiaminotetraacetic acid), or a complex salt thereof with an ammonium salt or an amine.

20. The phosphonic acids are polyphosphonic acids and / or aminopolyphospho 17. The metal corrosion inhibitor according to claim 16, which is an acid.

21. The method according to claim 20, wherein the polyphosphonic acids are NTPO (ditrilotrismethylene phosphonic acid), HED PO (hydroxyethylidene di (methylene phosphonic acid)), or a complex salt thereof with an ammonium salt or an amine. Metal corrosion inhibitor.

22. Aminopolyphosphonic acids include EDD PO (ethylenediaminedi (methylenephosphonic acid)), EDTPO (ethylenediaminetetra (methylenephosphonic acid)), PDTPO (diaminopropanetetra (methylenephosphonic acid)), DETPPO ( Diethylenetriamine pentoxide (methylenephosphonic acid)), TTHPO (triethylenetetraminehexa (methylenephosphonic acid)) or a complex salt thereof with an ammonium salt or an amine.

20. The metal corrosion inhibitor according to 20.

23. The metal corrosion inhibitor according to claim 10, wherein the surfactant is a nonionic surfactant or an anionic surfactant. 24. The metal corrosion inhibitor according to claim 23, wherein the nonionic surfactant has a polyoxyalkylene group in the molecule.

25. The metal corrosion inhibitor according to claim 23, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether or a polyoxyalkylene polyalkyl aryl ether.

26. The metal corrosion inhibitor according to claim 23, wherein the anionic surfactant has a group selected from the group consisting of a sulfonic acid group, a sulfoxyl group, a phosphonic acid group, and a sulfoxyl group.

2 7. The anionic surfactant is an alkyl sulfonic acid, an alkyl aryl sulfonic acid, an alkyl sulfate, an alkyl aryl sulfate, a polyoxyalkylene alkyl sulfate, a polyoxyalkylene alkyl aryl sulfate, an alkyl carboxylic acid, an alkyl aryl. 27. The metal corrosion inhibitor according to claim 26, which is a carboxylic 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 processing agent according to claim 28, wherein the processing agent is for a substrate having a copper coating on the surface.

30. The processing agent according to claim 29, wherein the substrate is a semiconductor substrate.

31. A method for treating a substrate, comprising treating the substrate with the treatment 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 detergent comprising the metal corrosion inhibitor according to any one of claims 1 to 27.

35. The cleaning agent according to claim 34, wherein the cleaning agent is for a substrate having a copper coating on the surface.

36. The cleaning agent according to claim 34, wherein the substrate is a semiconductor substrate.

37. A method for cleaning a substrate, comprising 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. After subjecting a semiconductor substrate having a copper-coated portion to a chemical-physical polishing treatment (CMP), the substrate is treated with the treatment agent according to claim 28. Processing method.

41. After subjecting a semiconductor substrate having a copper coating on the surface to a chemical and physical polishing treatment (CMP), the substrate is treated with the treatment agent according to claim 28, Next, the substrate is cleaned with a semiconductor substrate cleaning agent.

2. A semiconductor substrate having a copper coating on its surface is subjected to chemical-physical polishing (CMP), and then the substrate is cleaned with the cleaning agent according to claim 34. Method.