JP2003213463A - Metal anticorrosive and cleaning solution - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal anticorrosive which hardly corrode the low- resistance metallic wiring of a semiconductor device when the semiconductor device is cleaned. <P>SOLUTION: [1] The metal anticorrosive contains at least one kind of compound selected from the group consisting of a triazine derivative, a pterin derivative and a fluoroalkyl acrylate copolymer. [2] The metal anticorrosive described in [1] wherein the pterin derivative consists of 2-amino-4,6-dihydroxy-pterin or folic acid. [3] The cleaning solution contains the metal anticorrosive described in [1] or [2]. [4] In the cleaning method, a semiconductor device having metallic wiring is cleaned with the cleaning solution described in [3]. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal corrosion inhibitor.

[0002]

2. Description of the Related Art In recent years, a wiring using a metal having a lower resistance has been studied for higher integration and higher performance of semiconductor devices.

As a metal wiring having a low resistance, wiring made of copper, copper alloy or the like is known. However, when the wafer surface where the copper wiring is exposed is washed with a known washing liquid, the copper surface after washing is However, there is a problem in that the wiring resistance is increased and the wire is broken due to corrosion due to corrosion.

For example, Japanese Patent Laid-Open No. 2001-148385 discloses benzotriazole, its derivative triazole compounds, and triazine compounds as anticorrosive agents for semiconductor substrates having exposed copper and copper alloy wirings. Even when cleaning is performed using a cleaning solution containing 1,3,5-triazine as an anticorrosion agent, there is a problem that the anticorrosion of the copper wiring is still insufficient.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal corrosion inhibitor which hardly corrodes a metal wiring when cleaning a semiconductor device having a metal wiring having a low resistance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to find a metal corrosion inhibitor which does not have the above-mentioned problems. As a result, the triazine derivative represented by the following formula (I) and the following formula: When a metal corrosion inhibitor containing at least one compound selected from the group consisting of a pterin derivative represented by (II) and a fluoroalkyl acrylate copolymer is used for cleaning a semiconductor device having metal wiring with low resistance, The inventors have found that the metal wiring is less likely to corrode, and have completed the present invention. That is, the present invention provides a triazine derivative represented by the formula (I): ... (I) (R ₁ and R ₂ each independently represent a hydrogen atom, or
A hydroxyl group, an amino group, a carboxyl group, a phenyl group, an alkoxy group, or an optionally substituted alkyl group) A pterin derivative represented by the formula (II), (II) (R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen atom, or a hydroxyl group, an amino group, a carboxyl group, a phenyl group, an alkoxy group, a mercapto group, or Represents an optionally substituted alkyl group, wherein at least one of R _{3 to} R ₆ contains an amino group) and at least one compound selected from the group consisting of fluoroalkyl acrylate copolymers. A metal corrosion inhibitor is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The metal corrosion inhibitor of the present invention is at least selected from the group consisting of a triazine derivative represented by the above formula (I), a pterin derivative represented by the above formula (II), and a fluoroalkyl acrylate copolymer. 1
It comprises a seed compound.

R of the triazine derivative represented by the formula (I)
₁ and R ₂ each independently represent a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, a phenyl group,
It represents an alkoxy group or an optionally substituted alkyl group. Here, the alkyl group has 1 to 20 carbon atoms.
And an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a nonyl group, and a lauryl group. The alkyl group may be substituted, and examples of the substituent include a hydroxyl group, an amino group, an imino group, a carboxyl group, a phenyl group, and an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include alkoxy groups having 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

The triazine derivative represented by the formula (I) is
The position of nitrogen substitution may be 1,3,5 position or 1,2,4 position, and specific examples include 2,4-diamino-6-methyl-1,3,5-triazine and 2,4-diamino. -1,
3,5-triazine, 2-amino-1,3,5-triazine, 2,4-diamino-6-isobutyl-1,3,5
-Triazine, 2,4-diamino-6-xylyl-1,
3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2,4-diamino-6-
Phenyl-1,3,5-triazine, 2-amino-1,
2,4-triazine, 2-amino-4-methoxy-6-
Methyl-1,3,5-triazine, 3-amino-5,6
-Dimethyl-1,2,4-triazine, 2,4,6-triamino-1,3,5-triazine (melamine) and the like can be mentioned. Among these, 2,4-diamino-6-methyl-1,3,5-triazine and 2,4-diamino-6
-Hydroxy-1,3,5-triazine, 2-amino-
1,2,4-triazine, 2,4,6-triamino-
1,3,5-triazine (melamine) is preferred,
4-Diamino-6-methyl-1,3,5-triazine is particularly preferred.

R _{3 of} the pterin derivative represented by the formula (II),
R ₄ , R ₅ , and R ₆ each independently represent a hydrogen atom, or a hydroxyl group, an amino group, a carboxyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a mercapto group,
Alternatively, it represents an optionally substituted alkyl group. R ₃ ~
It is necessary that at least one of R ₆ contains an amino group, and it is preferable that at least one of R _{3 to} R ₆ is an amino group. An optionally substituted alkyl group, having 1 carbon atom
As the alkoxy groups of to 6, the same ones as described above can be exemplified. Examples of the pterin derivative represented by the formula (II) include 2-amino-4-hydroxypterin,
2-amino-4,6-dihydroxypterin (common name:
Xanthopterin), 2-amino-4,7-dihydroxypterin, 2,4-pterindiol, 6-methylpterin, 2,4-diamino-6,7-dimethylpterin, 4-hydroxy-6,7-dimethyl. Examples include pteridine and folic acid. Among these, 2-amino-4-
Hydroxypterin, 2-amino-4,6-dihydroxypterin and folic acid are preferred.

The fluoroalkyl acrylate copolymer is a kind of fluorosurfactant, and is not particularly limited, but contains a polymer unit derived from a fluoroalkyl acrylate monomer represented by the following formula (V). Is preferred. _{CH 2 = CH-COO-R} 6 ··· (V) formula (V), R ₆ represents a fluorinated alkyl group. here,
Examples of the fluorinated alkyl group include fluoromethyl group, fluoroethyl group, fluoropropyl group, fluoroisopropyl group, fluorobutyl group, fluoro-t-butyl group, fluorooctyl group, fluorolauryl group, fluorononyl group, fluorodecyl group. 1 to 20 carbon atoms such as groups
The fluorinated alkyl group of is mentioned.

Examples of the fluoroalkyl acrylate monomer represented by the formula (V) include fluoromethyl acrylate, fluoroethyl acrylate, fluoropropyl acrylate, fluoroisopropyl acrylate, fluorobutyl acrylate, fluoroisobutyl acrylate, fluoro-t-butyl acrylate, Examples thereof include fluorolauryl acrylate, fluoropentadecyl acrylate, fluorocetyl acrylate and fluorostearyl acrylate. Further, the fluoroalkyl acrylate copolymer has the following formulas (VI) to (I
It preferably contains a polymerized unit represented by X). _{C n F 2n + 1 C 2} H 4 OCOCH = CH 2 (n = 5-12) ··· (VI) C n F 2n + 1 CO (C 2 F 4 O) mCF 2 CH 2 OCOCH = CH 2 · ·· (VII) (n = 1-6 , m = 2-20) C 8 F 17 SO 2 n (C 2 H 5) C 2 H 4 OCOCH = CH 2 ··· (VIII) C 8 F 17 SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ OCOCH = CH ₂ (IX)

Other polymer units of the fluoroalkyl acrylate copolymer include, for example, unsaturated hydrocarbons having 1 to 10 carbon atoms such as ethylene, propylene, butene, butadiene, pentadiene and isoprene, and aromatic vinyl such as styrene and methylstyrene. Examples thereof include polymerized units derived from compounds, unsaturated carboxylic acids such as maleic acid, itaconic acid and fumaric acid, and monomers such as methacrylic acid. The degree of polymerization of the fluoroalkyl acrylate copolymer is not particularly limited, but is preferably 1 to 100. Specific examples of the fluoroalkyl acrylate copolymer include Unidyne DS-451 (manufactured by Daikin Industries, Ltd.). The fluoroalkyl acrylate copolymer may be used alone or in combination with other surfactants. Other surfactants include, but are not limited to, nonionic surfactants such as polyoxyethylene phenylphenol ether, ethylenediamine tetrapolyoxyalkylene ether, polyoxyalkylene ether, sorbitan fatty acid ester and the like. is not.

A triazine derivative represented by the formula (I):
The content of at least one compound selected from the group consisting of the pterin derivative represented by (II) and a fluoroalkyl acrylate copolymer is preferably 0.0001 to 10% by weight with respect to the total amount of the metal corrosion inhibitor, and It is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. The mixing ratio when two or more of the above compounds are used in combination is not particularly limited. Two
The total content of the above-mentioned compounds of one or more kinds is preferably 0.0001 to 10% by weight, more preferably 0.001 to 10% by weight, and further preferably 0.001 to 10% by weight based on the total amount of the metal corrosion inhibitor. It is 5% by weight.

The method for producing the triazine derivative represented by the formula (I) is not particularly limited, but, for example, 2,4-diamino-6-methyl-1,3,5-triazine is prepared by adding acetonitrile and dicyandiamide under alkaline conditions. It can be produced by reacting. The method for producing the pterin derivative represented by the formula (II) is not particularly limited, but, for example,
Folic acid can be prepared from dibromopropanol, 2,4,5-triamino-1,6-hydroxypyrimidine and p-aminobenzoylglutamic acid. The production method of the fluoroalkyl acrylate copolymer is not particularly limited, but for example, fluoromethyl acrylate-
The fluorobutyl acrylate copolymer can be produced by anionically polymerizing a fluoromethyl acrylate monomer and a fluorobutyl acrylate monomer in the presence of a base.

The metal corrosion inhibitor of the present invention can be usually mixed with an aqueous solution and used as a cleaning liquid. The compounding method is not particularly limited, and examples thereof include a method in which the metal corrosion inhibitor of the present invention is added to an aqueous solution and stirred to dissolve the metal corrosion inhibitor. The metal corrosion inhibitor of the present invention can be used not only as a cleaning liquid, but also as a resist remover, a chemical mechanical polishing slurry solution, a rinse liquid, and the like.

The concentration of the metal corrosion inhibitor is preferably 0.0001 to 10% by weight, more preferably 0.001 to 10% by weight, still more preferably 0.
001 to 5% by weight. The concentration is 0.0001% by weight
If the concentration is less than 10% by weight, a sufficient corrosion preventing effect tends not to be obtained. On the other hand, if the concentration exceeds 10% by weight, further improvement of the corrosion preventing effect is not observed, and the metal corrosion inhibitor is adsorbed on the semiconductor surface. Management of the semiconductor cleaning process tends to be difficult due to an increase in the amount.

The aqueous solution containing the metal corrosion inhibitor is not particularly limited, and either an alkaline aqueous solution or an acidic aqueous solution can be used. The alkaline aqueous solution is not particularly limited as long as it can be used for a cleaning solution, and an aqueous solution of an inorganic compound such as sodium hydroxide, potassium hydroxide or ammonium hydroxide, an organic compound such as tetramethylammonium hydroxide or choline. And the like. In semiconductor device applications, these compounds are preferably purified in order to remove metal impurities and fine particles. Among them, ammonium hydroxide, tetramethylammonium hydroxide, and a purified aqueous solution of choline are used. Is more preferable, and it is more preferable to use a purified aqueous solution of ammonium hydroxide or tetramethylammonium hydroxide.

The acidic aqueous solution is not particularly limited as long as it can be used as a washing solution, and inorganic acidic aqueous solutions such as hydrochloric acid, hydrofluoric acid, sulfuric acid and nitric acid, oxalic acid, citric acid, malonic acid and apples. An organic acidic aqueous solution of an acid, fumaric acid, maleic acid or the like can be used. In semiconductor device applications, these compounds are preferably purified in order to remove metal impurities and fine particles, and among them, purified aqueous solutions of hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, oxalic acid, and citric acid. Is more preferably used.

The cleaning liquid containing the above-described metal corrosion inhibitor of the present invention further comprises a compound represented by the following formula (IV), a polyhydric alcohol compound having at least two or more hydroxyl groups in the molecule, or these compounds. It may contain a mixture of. (IV) R ₇ and R ₈ of the cyclic urea compound represented by the formula (IV) each independently represent a hydrogen atom, or a hydroxyl group, a carboxyl group or an optionally substituted alkyl group. , Z
Represents an oxygen atom or a sulfur atom. Here, as the optionally substituted alkyl group, the same ones as described above can be exemplified.

Examples of the cyclic urea compound represented by the formula (IV) include 4,5-dihydroxy-2-imidazolidinone and 4,5-dihydroxy-1,3-dimethyl-2-.
Imidazolidinone, 4,5-dihydroxy-1,3-bis (hydroxymethyl) -2-imidazolidinone, 4,
5-dihydroxy-1,3-bis (methoxymethyl)-
2-imidazolidinone etc. are mentioned. Among these, 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone is preferably used.

Examples of the polyhydric alcohol compound having at least two hydroxyl groups in the molecule include glycols such as ethylene glycol, diethylene glycol and triethylene glycol, 1,4 butanediol, 1,6.
Hexanediol, 1,8 octanediol, 1,10
Alcohol compounds such as decanediol, bis (4-hydroxycyclohexyl) methane, trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, arbitol, sorbitol, xylose, alaminose, glucose, galactose, sorbose, fructose, palatinose. , Saccharides such as maltotriose, malezitose and gluconic acid, saponified products of ethylene-vinyl acetate copolymer, organic acids such as polyvinyl alcohol and gluconic acid, polyolefin oligomers having a plurality of hydroxyl groups, ethylene-hydroxyethyl (meth) acrylate A polymer having a plurality of hydroxyl groups in the molecule such as a copolymer, the following formula (X) (R) _a C (CH ₂ OH) _b ... (X) (R is a hydrogen atom, having 1 to 12 carbon atoms) Chain-like residue is a cyclic alkyl group, or A alkyl group, a represents an integer of 0 to 2, b represents an integer of 2 to 4 and is selected so as to satisfy a + b = 4.), A compound represented by the following formula (XI) HO _{-CH 2 CH (OH) CH 2} -O- [CH 2 CH (OH) CH 2 -O] n -H ··· (XI) polyglycerol (n is representing. an integer of 0) represented by A polyoxyalkylene compound having a structure in which ethylene oxide or propylene oxide is added to, or a compound represented by the following formula (XII) R'-COOH ... (XII) (R 'is a chain or cyclic alkyl group having 2 to 25 carbon atoms. , Or an alkyl group), and a polyglycerin ester having two or more hydroxyl groups in the molecule obtained by dehydration condensation of the polyglycerin represented by the formula (XI). Can be mentioned.

Examples of the polyoxyalkylene compound include 1,3-dihydroxypropane, 2,2-dimethyl-1,3-dihydroxypropane, trimethylolethane, 1,1,1-trimethylolpropane, 1 1,1,1-trimethylolhexane, 1,1,1-trimethyloldodecane, 2-cyclohexyl-2-methylol-1,3-dihydroxypropane, 2- (p-methylphenyl) -2-methylol-1,3 -Dihydroxypropane, pentaerythritol, glycerin,
Diglycerin, hexaglycerin, octaglycerin,
Examples thereof include those obtained by adding ethylene oxide or propylene oxide to decaglycerin and the like.

As the polyglycerin ester,
For example, glycerin monostearate, glycerin monooleate, glycerin monolaurate, glycerin monocaprylate, glycerin monohexanoate, glycerin monophenethyl ester, glycerin monopropionate, diglycerin monostearate, diglycerin distearate. , Diglycerin monooleate, diglycerin monohexanoate, diglycerin dioctanoate, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin tetrastearate, tetraglycerin trihexanoate, tetraglycerin monophenethyl Ester, hexaglycerin monostearate, hexaglycerin distearate, hexaglycerin pentastearate, hexaglycerin triolee Door, hexa-glycerin monolaurate, hexa-glycerin penta laurate, decaglycerol monostearate, decaglycerol octa stearate, decaglycerol pentaoleate, decaglycerol dilaurate, penta decaglycerol distearate,
Examples thereof include pentadecaglycerin decaoleate and octadecaglycerin tetrastearate.

The polyhydric alcohol compound having two or more hydroxyl groups in the molecule is preferably one having a melting point of 300 ° C. or lower among the above polyhydric alcohol compounds, more preferably a polyoxyalkylene compound and a saccharide, 1,1-trimethylolpropane and gluconic acid are particularly preferable.

The concentration of the cyclic urea compound, the polyhydric alcohol compound, or a mixture thereof in the cleaning solution is 0.000.
1 to 10% by weight is preferable, more preferably 0.001
~ 1% by weight. If the concentration is less than 0.0001% by weight, the effect of smoothing the metal surface tends not to be obtained, while if the concentration exceeds 10% by weight, the effect of smoothing the metal surface is further improved. Is not observed, and the amount of the cyclic urea compound or polyhydric alcohol compound adsorbed on the semiconductor surface tends to increase, which makes it difficult to control the semiconductor cleaning step.

The above polyhydric alcohol compound, the compound represented by the formula (IV), or a mixture thereof is used in combination with an aqueous ammonium hydroxide solution or an aqueous tetramethylammonium hydroxide solution containing the metal corrosion inhibitor of the present invention. It is preferable from the viewpoint of making the surface condition of the semiconductor after cleaning smoother.

Other chemicals may be added to the cleaning liquid as long as the effects of the present invention are not impaired. As other agents, for example, purified for semiconductor devices,
Examples thereof include hydrogen peroxide water, ammonium fluoride, water-soluble organic solvents and the like.

The organic solvent used in the present invention is preferably a water-soluble organic solvent, and examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol and glycerin. N-methylformamide,
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; lactones such as γ-butyrolactone; esters such as methyl lactate and ethyl lactate; acetone, methyl ethyl ketone, acetylacetone, etc. Ketones; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether; tetrahydrofuran, furaldehyde, tetrahydrofuran Furan compounds such as furyl alcohol, sulfolanes such as sulfolane; dimethyl sulfoxy Like urea compounds such as dimethyl imidazolidinone; sulfoxides such as.

The cleaning liquid containing the metal corrosion inhibitor of the present invention can be suitably used for cleaning semiconductor devices having metal wiring, and particularly cleaning semiconductor devices having copper or copper alloy wiring. Can be suitably used for. Since the wiring pattern on the wafer that constitutes the semiconductor device is extremely fine, it is required to suppress the amount of corrosion of the wiring and to prevent pitting and roughening the surface condition. When the wafer is cleaned with the cleaning liquid containing the metal corrosion inhibitor of the present invention, the adhered metal impurities and fine particles can be removed, and pitting and surface roughness do not occur.

As a method of cleaning a wafer using a cleaning liquid containing the metal corrosion inhibitor of the present invention, ultrasonic irradiation is used in combination with the immersion cleaning method in which the wafer is directly immersed in the cleaning liquid, and the immersion cleaning method. Examples include a method, a brush cleaning method of cleaning with a brush while spraying a cleaning liquid on the wafer surface, and a method of combining brush cleaning and ultrasonic irradiation. In addition, it is possible to heat the cleaning liquid during cleaning, which can improve cleaning efficiency. The heating temperature is not particularly limited, but is usually 20 to 20.
It is about 60 ° C.

[0032]

EXAMPLES The present invention will be described below with reference to examples.
It goes without saying that the present invention is not limited to the examples.

Examples 1 and 2 and Comparative Example 1 0.2% by weight of the corrosion inhibitor shown in Table 1 was added to 0.1% by weight of ammonia water to obtain a cleaning liquid. A silicon wafer on which a Cu film 10000Å was formed by plating was immersed in this cleaning solution as a test piece at room temperature for 10 minutes, the thickness of the Cu film before and after immersion was measured, and the dissolution rate was calculated from the amount of change in film thickness. The corrosion prevention effect was evaluated. The surface before and after the immersion was observed with an electron microscope to observe the state of the Cu film surface. A sheet resistance measuring device manufactured by Napson Corporation was used to measure the film thickness, and a method of converting the film thickness from the sheet resistance value was used. The results are shown in Table 1. It can be seen from Table 1 that the corrosion inhibitor of the present invention is extremely effective in preventing copper corrosion by an alkaline solution.

[0034]

[Table 1] * 1: 2,4-diamino-6-methyl-1,3,5-triazine * 2: 2-butyne-1,4-diol bis (2-hydroxyethyl ether) ◯: No change x: Surface roughness

Examples 3-9 and Comparative Examples 2-6 0.2% by weight of tetramethylammonium hydroxide (TMAH)
0.2% by weight of the corrosion inhibitor shown in Table 2 was added to the aqueous solution to obtain a cleaning liquid. A silicon wafer on which a Cu film 10000Å was formed by plating was immersed in this cleaning solution as a test piece at 40 ° C for 10 minutes, the thickness of the Cu film before and after immersion was measured, and the dissolution rate was calculated from the amount of change in film thickness. Then, the corrosion prevention effect was judged. The surface before and after the immersion was observed with an electron microscope to observe the state of the Cu film surface. A sheet resistance measuring device manufactured by Napson Corporation was used to measure the film thickness, and a method of converting the film thickness from the sheet resistance value was used.
The results are shown in Tables 2 and 3. From Table 2, the corrosion inhibitor of the present invention is extremely effective in preventing copper corrosion by an alkaline solution. From Table 3, when copper corrosion is prevented but the treated copper surface is rough, At least by adding a polyhydric alcohol compound having two or more hydroxyl groups in the molecule and / or a compound represented by the formula (IV),
It was found that the surface condition of copper was improved without affecting the anticorrosion effect.

[0036]

[Table 2] * 3: 6-amino-triazine-2,4-diol * 4: melamine * 5: 1,3,5-triazine * 6: folic acid * 7: xantopterin (2-amino-4,6-dihydroxypterin) * 8: Fluoroalkyl acrylate copolymer (Product name: Unidyne DS-451: Daikin Industries, Ltd.)

[0037]

[Table 3] Compound A: compound represented by the formula (I), 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone * 9: 3-methyl-1-butyn-3-ol ○: no change ×: surface Storm

Example 13 and Comparative Example 7 0.2% by weight of the corrosion inhibitor shown in Table 4 was added to a 1% by weight aqueous hydrochloric acid solution to obtain a cleaning solution. In this cleaning solution,
A silicon wafer with a Cu film of 10000Å formed by plating is immersed as a test piece at room temperature for 10 minutes, the thickness of the Cu film before and after immersion is measured, and the dissolution rate is calculated from the amount of change in film thickness to determine the corrosion prevention effect. It was judged. The surface before and after the immersion was observed with an electron microscope to observe the state of the Cu film surface. A sheet resistance measuring device manufactured by Napson Corporation was used to measure the film thickness, and a method of converting the film thickness from the sheet resistance value was used. The results are shown in Table 4. From Table 4, it was found that the corrosion inhibitor of the present invention is extremely effective in preventing copper corrosion by an acidic solution.

[0039]

[Table 4] * 1: 2,4-diamino-6-methyl-1,3,5-triazine ◯: No change X: surface roughness In the above examples, the copper wiring in the semiconductor device was cleaned. Similar results were obtained with the alloy. Further, if a cleaning liquid is appropriately selected, an excellent anticorrosion effect can be exhibited even for cleaning metals other than copper and metal wiring.

[0040]

According to the present invention, it is possible to provide a metal corrosion inhibitor capable of preparing a cleaning liquid which is less likely to corrode a metal wiring when cleaning a semiconductor device having a metal wiring having a low resistance. .

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C11D 7/32 C11D 7/32 C23F 11/14 101 C23F 11/14 101 H01L 21/304 647 H01L 21/304 647A

Claims (10)

[Claims] 1. A triazine derivative represented by the formula (I): ... (I) (R ₁ and R ₂ each independently represent a hydrogen atom, or
A hydroxyl group, an amino group, a carboxyl group, a phenyl group, an alkoxy group, or an optionally substituted alkyl group) A pterin derivative represented by the formula (II), (II) (R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen atom, or a hydroxyl group, an amino group, a carboxyl group, a phenyl group, an alkoxy group, a mercapto group, or Represents an optionally substituted alkyl group, wherein at least one of R _{3 to} R ₆ contains an amino group) and at least one compound selected from the group consisting of fluoroalkyl acrylate copolymers. Metal corrosion inhibitor. 2. A pterin derivative is 2-amino-4,6-
The metal corrosion inhibitor according to claim 1, which is dihydroxypterin or folic acid represented by the formula (III). ... (III) 3. A cleaning liquid containing the metal corrosion inhibitor according to claim 1 or 2. 4. The cleaning liquid according to claim 3, which is an alkaline aqueous solution. 5. The cleaning liquid according to claim 4, wherein the alkaline aqueous solution is an aqueous ammonia solution and / or an aqueous tetramethylammonium hydroxide solution. 6. The cleaning liquid according to claim 3, which is an acidic aqueous solution. 7. A cyclic urea compound represented by the formula (IV) (R ₇ and R ₈ each independently represent a hydrogen atom,
A hydroxyl group, a carboxyl group or an optionally substituted alkyl group, and Z represents an oxygen atom or a sulfur atom) and / or at least a polyhydric alcohol compound having two or more hydroxyl groups in the molecule. Claim 3 ~
6. The cleaning liquid according to any one of 6. 8. The cleaning liquid according to claim 3, which is for a semiconductor device having metal wiring. 9. The cleaning liquid according to claim 8, wherein the metal is copper or a copper alloy. 10. A cleaning method, which comprises cleaning a semiconductor device having metal wiring with the cleaning liquid according to any one of claims 3 to 9.