JP6514578B2 - Etching composition and method of manufacturing conductive film - Google Patents

Description

  The present invention relates to an etching composition and a method of manufacturing a conductive film using the etching composition.

  The conductive film is a thin film widely used in thin film transistor liquid crystal display devices, plasma display panel display devices, electroluminescent display devices and the like, and in order to form the conductive film in the above flat panel display device, a desired fine pattern An etching process is required to form

  As a transparent electrode film used at that time, an indium tin oxide film, an indium zinc oxide film, and a zinc oxide film are used, and the use of the above indium tin oxide film, an indium zinc oxide film, and a zinc oxide film is on the protective film. An indium tin oxide film, an indium zinc oxide film, and a zinc oxide film are formed thereon, and the photoresist is used as a mask, and then the indium tin oxide film, the indium zinc oxide film, and the zinc oxide film are etched.

  As a conventional conductive film etching solution, hydrochloric acid / nitric acid mixed aqueous solution (aqua regia), hydrochloric acid / acetic acid mixed aqueous solution, phosphoric acid aqueous solution etc. are used, but such a conventional etching solution for conductive film is It has such problems.

  First, although hydrochloric acid / nitric acid mixed aqueous solution (aqua regia) and hydrochloric acid / acetic acid mixed aqueous solution have a high etching rate and are stable, the fluctuation of the component amount of the etching solution composition is severe because hydrochloric acid and nitric acid are volatilized. Therefore, the generation of fumes is apt to contaminate the working environment and to infringe the copper or copper alloy mainly used as an electrode material in the thin film transistor manufacturing process of the thin film transistor liquid crystal display.

  Secondly, the phosphoric acid aqueous solution has a disadvantage that it infringes a copper film, a copper alloy film or the like mainly used as an electrode material and interferes with the etching of the indium tin oxide film in the conductive film.

  The conductive film etching composition for solving the above problems, particularly the phenomenon of invading copper film, copper alloy film and the like mainly used as an electrode material of thin film transistors, comprises a corrosion inhibitor of a predetermined composition and a temporal change inhibitor An aqueous solution has been proposed (e.g., Patent Document 1).

Japanese Patent Application Publication No. 2012-508965

  However, even with the conductive film etching composition as described in Patent Document 1, the elimination of the invasion phenomenon to copper etc. is insufficient.

  The present invention has been made in view of such conventional circumstances, and an etching composition capable of suppressing corrosion of copper and the like on the substrate surface, and a method of manufacturing a conductive film using the etching composition. Intended to be provided.

  The present inventors include a saturated fatty acid or saturated fatty acid ester of a specific structure in which a predetermined position is substituted with an aromatic group of a predetermined structure and an imidazolyl group which may have a substituent. The inventors have found that the above-mentioned problems can be solved by etching a conductive film on a substrate having copper or the like such as an electrode and a wiring on the surface using an etching composition, and the present invention has been completed. Specifically, the present invention provides the following.

（式中、Ｒはそれぞれ独立に水素原子又は１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^４はそれぞれ独立にハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。上記Ｒは他方のＲ又はＲ^２と結合して環状構造を形成してもよい。） A first aspect of the present invention is an etching composition containing an oxidizing agent, water, and a corrosion inhibitor represented by the following general formula (1a).

(Wherein, R each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ⁴ each independently represents a halogen atom, a hydroxyl group or a mercapto group Represents a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n represents an integer of 0 to 3. R is the other R Or may combine with R ² to form a cyclic structure)

  A second aspect of the present invention is a method of producing a conductive film, comprising the step of etching a conductive film on a substrate using the etching composition of the first aspect of the present invention.

  According to the present invention, it is possible to provide an etching composition capable of suppressing corrosion of copper and the like on the surface of a substrate, and a method of manufacturing a conductive film using the etching composition.

«Etching composition»
The etching composition which is the first aspect of the present invention contains an oxidizing agent, water, and a corrosion inhibitor represented by the following general formula (1a).

<Corrosion Inhibitor Represented by Formula (1a)>
The corrosion inhibitor used in the present invention is an imidazole compound represented by the formula (1a) (hereinafter sometimes abbreviated as "imidazole compound"). The etching composition of the present invention contains the imidazole compound, thereby forming a wiring comprising a metal such as copper or copper alloy on at least a part of the surface and a surface of the substrate from metal such as copper or copper alloy. , Corrosion of the metal on the surface of the substrate having electrodes and the like (which may be collectively referred to as "substrate surface" in this specification) can be prevented. Although the mechanism of action is not clear, when the imidazole compound is brought into contact with a metal such as copper or copper alloy, the imidazole compound reacts with metal ions to form a chemical conversion film on the surface of the metal. It is considered that the conversion coating suppresses the corrosion of metal.

（式中、Ｒはそれぞれ独立に水素原子又は１価の有機基を表し、Ｒ^２は置換基を有してもよい芳香族基を表し、Ｒ^４はそれぞれ独立にハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を表し、ｎは０〜３の整数を表す。上記Ｒは他方のＲ又はＲ^２と結合して環状構造を形成してもよい。）

(Wherein, R each independently represents a hydrogen atom or a monovalent organic group, R ² represents an aromatic group which may have a substituent, and R ⁴ each independently represents a halogen atom, a hydroxyl group or a mercapto group Represents a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, and n represents an integer of 0 to 3. R is the other R Or may combine with R ² to form a cyclic structure)

In formula (1a), R is a monovalent organic group. The monovalent organic group is not particularly limited, and may be, for example, an alkyl group which may have a substituent or an aromatic group which may have a substituent. May have an ester bond or the like. The alkyl group may be, for example, the same as R ¹ and the like in the formula (1) described later, but its carbon number is preferably 1 to 40, more preferably 1 to 30, still more preferably 1 to 20, 10 is even more preferred. The substituent which the alkyl group may have may be, for example, the same as the substituent which the alkylene group which is R ³ in Formula (1) described below may have. The aromatic group which may have a substituent is the same as R ² in formula (1) described later, preferably an aryl group, more preferably a phenyl group. The aromatic group which may have a substituent as R may be the same as or different from R ² . In formula (1a), one R is preferably a hydrogen atom, and one R is a hydrogen atom, and the other R may have a substituted alkyl group or a substituted aromatic group. It is more preferable that it is a group group. In the formula (1a), R may combine with the other R or R ² to form a cyclic structure, for example, when at least one R is an alkyl group which may have a substituent, R May be bonded to the other R or R ² to form a cyclic structure.

  The imidazole compound represented by Formula (1a) may be a compound represented by the following Formula (1).

（式（１）中、Ｒ^２、Ｒ^４、及びｎは、式（１ａ）と同様であり、Ｒ^１は水素原子又はアルキル基であり、Ｒ^３は置換基を有してもよいアルキレン基である。Ｒ^３はＲ^２と結合して環状構造を形成してもよい。）

(In formula (1), R ² , R ⁴ and n are the same as in formula (1a), R ¹ is a hydrogen atom or an alkyl group, and R ³ is an alkylene group which may have a substituent R ³ may combine with R ² to form a cyclic structure.)

In formula (1), R ¹ is a hydrogen atom or an alkyl group. When R ¹ is an alkyl group, the alkyl group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

Specific examples of the alkyl group suitable as R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl group, Isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Groups, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group.

In formula (1), R ² is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent, or may be an aromatic heterocyclic group which may have a substituent.

  The type of aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, or may be formed by condensation of two or more aromatic hydrocarbon groups, or two or more aromatic hydrocarbon groups. May be formed by bonding by a single bond. The aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group or a phenanthrenyl group.

  The type of aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. The aromatic heterocyclic group is preferably a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group and a benzoimidazolyl group.

  As a substituent which a phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group And sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group and organic group. When the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

  When the substituent that the aromatic group has is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when forming a cyclic structure.

  When the aromatic group has a substituent on the adjacent carbon atom, two substituents bonded on the adjacent carbon atom may combine to form a cyclic structure. The cyclic structure includes an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

  When the substituent which the aromatic group has is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group is an oxygen atom, a nitrogen atom, a silicon atom, etc. And a bond containing the hetero atom of Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond and the like.

  As a bond containing a hetero atom which the organic group may have, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, from the viewpoint of the heat resistance of the imidazole compound represented by Formula (1a) or Formula (1) , Ester bond, amide bond, amino bond (-NR-: R represents a hydrogen atom or a monovalent organic group) urethane bond, imino bond (-N = C (-R)-, -C (= NR)- R is preferably a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond or a sulfinyl bond.

  When the organic group is a substituent other than a hydrocarbon group, the type of the substituent other than a hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a silyl group, a silanol group and an alkoxy group. , Alkoxycarbonyl group, amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino Groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphonato groups, alkyl ether groups, alkenyl ether groups, alkyl thioether groups, alkenyl thioether groups, aryl ether groups, aryl thioether groups and the like. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. The hydrocarbon group contained in the above-mentioned substituent may be linear, branched or cyclic.

  As a substituent which a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms And the aryloxy group having 1 to 12 carbon atoms, the arylamino group having 1 to 12 carbon atoms, and a halogen atom are preferable.

As R ² , an imidazole compound represented by Formula (1a) or Formula (1) can be easily and inexpensively synthesized, and since the solubility of the imidazole compound in water or an organic solvent is good, each has a substituent. Preferred is a phenyl group, a furyl group or a thienyl group.

In formula (1), R ³ is an alkylene group which may have a substituent. The substituent which the alkylene group may have is not particularly limited as long as the object of the present invention is not impaired. A hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom etc. are mentioned as a specific example of the substituent which the alkylene group may have. The alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferable. Although the carbon atom number of an alkylene group is not specifically limited, 1-20 are preferable, 1-10 are preferable and 1-5 are more preferable. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent bonded to the alkylene group.

  The alkoxy group as a substituent bonded to an alkylene group may be a linear alkoxy group or a branched alkoxy group. Although the carbon atom number of the alkoxy group as a substituent is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.

  The amino group as a substituent bonded to an alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a linear alkyl group or a branched alkyl group. Although the carbon atom number of the alkyl group contained in a monoalkyl amino group or a dialkylamino group is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.

Specific examples of the alkylene group suitable as R ³ include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, n-butane -1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl group Group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group , N-octadecane-1,18-diyl group, n And -nonadecane-1,19-diyl group and n-icosan-1,20-diyl group.

R ⁴ is a halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, or organic group, and n is 0 to 3 Is an integer of When n is an integer of 2 to 3, a plurality of R ⁴ may be the same or different.

When R ⁴ is an organic group, the organic group is the same as the organic group which the aromatic group may have as a substituent for R ² .

When R ⁴ is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, or an aromatic heterocyclic group. As an alkyl group, a C1-C8 linear or branched alkyl group is preferable, and a methyl group, an ethyl group, n-propyl group, and an isopropyl group are more preferable. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group and a phenanthrenyl group are preferable, a phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable. As the aromatic heterocyclic group, pyridyl group, furyl group, thienyl group, imidazolyl group, pyrazolyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, benzoxazolyl group, benzothiazolyl group, and benzimidazolyl group are preferable, Furyl and thienyl are more preferred.

When R ⁴ is an alkyl group, the bonding position of the alkyl group on the imidazole ring is preferably any of 2-, 4- and 5-positions, and more preferably 2-position. When R ⁴ is an aromatic hydrocarbon group or an aromatic heterocyclic group, the bonding position of these groups on imidazole is preferably at the 2-position.

  Among the imidazole compounds represented by the above formula (1a), compounds represented by the following formula (1-1a) are preferable from the viewpoint of being inexpensive and easily synthesizable and having excellent solubility in water.

（式（１−１ａ）中、Ｒ、Ｒ^４及びｎは、式（１ａ）と同じであり、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基であり、但し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９のうち少なくとも１つは水素原子以外の基である。Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９のうち少なくとも２つが結合して環状構造を形成してもよい。ＲはＲ^７と結合して環状構造を形成してもよい。）

(In formula (1-1a), R, R ⁴ and n are the same as in formula (1a), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, Or an organic group, provided that at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is a group other than a hydrogen atom R ⁵ , R ⁶ , R ⁷ , R ⁸ and At least two of R ⁹ may combine to form a cyclic structure, and R may combine with R ⁷ to form a cyclic structure.)

R < ⁵ >, R < ⁶ >, R <^7> , R < ⁸ > and R < ⁹ > are the same as the below-mentioned Formula (1-1). In the formula (1-1a), R may be bonded to R ⁷ to form a cyclic structure. For example, when R is an alkyl group which may have a substituent, R is bonded to R ⁷ It may form a ring structure.

Among the imidazole compounds represented by the above formula (1) or formula (1-1a), it is possible to synthesize inexpensively and easily, and is represented by the following formula (1-1) from the viewpoint of excellent solubility in water. is preferably a compound that is represented by the formula (1-1), R ³ is a methylene group is more preferable.

（式（１−１）中、Ｒ^１、Ｒ^３、Ｒ^４、及びｎは、式（１）と同様であり、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９は、式（１−１ａ）と同様である。Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、及びＲ^９のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^３はＲ^７と結合して環状構造を形成してもよい。）

(In Formula (1-1), R ¹ , R ³ , R ⁴ , and n are the same as in Formula (1), and R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are And at least two of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be combined to form a cyclic structure, and R ³ is combined with R ^7. It may form an annular structure.)

When R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ are organic groups, the organic groups are the same as the organic groups that R ² in formula (1) has as a substituent. R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms in terms of the solubility of the imidazole compound in the solvent.

Among them, at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably the following substituent, and it is particularly preferable that R ⁹ is the following substituent. When R ⁹ is the following substituent, R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably hydrogen atoms.
-O-R ¹⁰
(R ¹⁰ is a hydrogen atom or an organic group)

When R ¹⁰ is an organic group, the organic group is the same as the organic group that R ² in Formula (1) has as a substituent. As R ¹⁰ , an alkyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is particularly preferable, and a methyl group is most preferable.

（式（１−１−１）において、Ｒ^１、Ｒ^４、及びｎは、式（１）と同様であり、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５は、それぞれ独立に、水素原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基であり、ただし、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、及びＲ^１５のうち少なくとも１つは水素原子以外の基である。） Among the compounds represented by the above formula (1-1), a compound represented by the following formula (1-1-1) is preferable.

(In Formula (1-1-1), R ¹ , R ⁴ , and n are the same as in Formula (1), and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are each independently) Hydrogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group Or an organic group, provided that at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a group other than a hydrogen atom.

Among the compounds represented by the formula (1-1-1), at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is a group represented by the above-described —O—R ¹⁰ preferably ^there, the a ^{group R 15} is represented by ^{-O-R 10} is particularly preferred. When R ¹⁵ is a group represented by —O—R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms.

The synthesis method of the imidazole compound represented by the above formula (1a) is not particularly limited. For example, a halide represented by R ² CR (Hal) R (R ² and R are the same as in formula (1a) and Hal is a halogen atom), and a halide represented by formula (II) described below The imidazole compound represented by the said Formula (1a) can be synthesize | combined by making it react with an imidazole compound according to a conventional method, and performing imidazolylation.

  The synthesis method of the imidazole compound represented by the above formula (1) is not particularly limited. For example, the above-mentioned formula (1) can be obtained by reacting a halogen-containing carboxylic acid derivative represented by the following formula (I) with an imidazole compound represented by the following formula (II) according to a conventional method to carry out imidazolylation. The imidazole compound represented by these can be synthesize | combined.

（式（Ｉ）及び式（ＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びｎは、式（１）と同様である。式（Ｉ）において、Ｈａｌはハロゲン原子である。）

(In Formula (I) and Formula (II), R ¹ , R ² , R ³ , R ⁴ and n are the same as in Formula (1). In Formula (I), Hal is a halogen atom)

When the imidazole compound is a compound represented by the formula (1) and R ³ is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (1-1), The imidazole compound can also be synthesized by the method described by the Michael addition reaction.

（式（１−２）中、Ｒ^１、Ｒ^２、Ｒ^４及びｎは、式（１）と同様である。）

(In Formula (1-2), R ¹ , R ² , R ⁴ and n are the same as in Formula (1).)

  Specifically, for example, a 3-substituted acrylic acid derivative represented by the following formula (III) and an imidazole compound represented by the above formula (II) are mixed in a solvent to cause a Michael addition reaction. Thus, an imidazole compound represented by the above formula (1-2) is obtained.

（式（ＩＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^４及びｎは、式（１）と同様である。）

(In formula (III), R ¹ , R ² , R ⁴ and n are the same as in formula (1).)

  Moreover, the imidazole compound represented by a following formula (1-3) is obtained by adding the 3-substituted acrylic acid derivative containing an imidazolyl group represented by a following formula (IV) in the solvent containing water .

（式（ＩＶ）及び式（１−３）中、Ｒ^２、Ｒ^４及びｎは、式（１）と同様である。）

(In Formula (IV) and Formula (1-3), R ² , R ⁴ and n are the same as in Formula (1).)

  In this case, the imidazole compound represented by the above formula (II) and the 3-substituted acrylic acid represented by the following formula (V) by hydrolysis of the 3-substituted acrylic acid derivative represented by the above formula (IV) And generate. Then, a Michael addition reaction occurs between the 3-substituted acrylic acid represented by the following formula (V) and the imidazole compound represented by the above formula (II), and is represented by the above formula (1-3) An imidazole compound is formed.

（式（Ｖ）中、Ｒ^２は、式（１）と同様である。）

(In Formula (V), R ² is the same as Formula (1).)

Preferable specific examples of the imidazole compound represented by the formula (1a) include the following.

  The content of the corrosion inhibitor represented by the formula (1a) is, for example, 0.1% by mass, preferably 0.5% by mass, and more preferably 0.1% by mass as a lower limit based on the mass of the etching composition of the present invention. The upper limit is, for example, 10% by mass, preferably 7% by mass, and more preferably 5% by mass. Within this range, corrosion of metals such as copper and copper alloy on the surface of the substrate can be suppressed while maintaining an appropriate etching rate.

<Oxidizing agent>
The oxidizing agent contained in the etching composition of the present invention is not particularly limited as long as it etches the etching target or promotes the etching, but generally, it is roughly classified into halogen-containing compounds, auxiliary oxidizing agents, and etching regulators. Be done.

[Halogen-containing compounds]
The halogen-containing compound contained in the etching composition of the present invention functions as a main oxidizing agent for etching an etching object such as a conductive film. The halogen-containing compound is not particularly limited, but a compound capable of being dissociated into a halogen ion or a polyatomic halogen ion in the etching composition can be preferably used, and specifically, it is represented by the following general formula (2) Compounds can be mentioned.

（式中、Ａは水素イオン（Ｈ^＋）、アンモニウムイオン（ＮＨ^４＋）、鉄イオン（Ｆｅ^２＋、Ｆｅ^３＋）、アルミニウムイオン（Ａｌ^３＋）又は酸化数が１〜３価であるアルキル金属イオンであり、Ｘはハロゲン元素であり、ｍはＡの酸化数である。）

(Wherein, A is hydrogen ion (H ⁺ ), ammonium ion (NH ^{4 +} ), iron ion (Fe ²⁺ , Fe ³⁺ ), aluminum ion (Al ³⁺ ) or alkyl metal ion having an oxidation number of 1 to ³ ) X is a halogen element, m is the oxidation number of A.)

Specific examples of the halogen-containing compound include hydrogen halide, ammonium halide, iron halide or alkali halide, and more specifically hydrogen chloride (HCl), aluminum chloride (AlCl ₃ ), ammonium fluoride It is preferably at least one selected from the group consisting of (NH ₄ F), potassium iodide (KI), potassium chloride (KCl) and ammonium chloride (NH ₄ Cl).

  The lower limit of the content of the halogen-containing compound is, for example, 0.05% by mass, preferably 2% by mass, more preferably 4% by mass, and the upper limit is, for example, 15% by mass, preferably Is 12% by mass, more preferably 10% by mass. Within this range, it is possible to suppress the corrosion of metals such as copper and copper alloy on the surface of the substrate and to exhibit the etching action while maintaining the etching rate appropriately.

[Auxiliary oxidant]
The auxiliary oxidizing agent contained in the etching composition of the present invention functions to support etching. As the auxiliary oxidizing agent, a compound which dissociates into nitrate ion (NO ₃ ⁻ ) in the etching composition can be preferably used, and specifically, ammonium nitrate (NH ₄ NO ₃ ), potassium nitrate (KNO ₃ ), nitric acid (HNO) ₃ ) At least one selected from the group consisting of copper nitrate (CuNO ₃ ) and sodium nitrate (NaNO ₃ ).

  The lower limit value of the auxiliary oxidizing agent is, for example, 0.1% by mass, preferably 3% by mass, more preferably 5% by mass, and the upper limit value is, for example, 20% by mass, preferably, based on the mass of the etching composition of the present invention Is 18% by mass, more preferably 15% by mass. Within this range, corrosion of metals such as copper on the substrate surface can be suppressed, and the etching rate can be kept moderate.

[Etching modifier]
As an etching regulator contained in the etching composition of the present invention, for example, sulfuric acid and a sulfate compound can be used, and more specifically, sulfuric acid (H ₂ SO ₄ ), ammonium sulfate ((NH ₄ ) ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), potassium sulfate (K ₂ SO ₄ ), ammonium bisulfate (NH ₄ SO ₄ H), sodium bisulfate (NaSO ₄ H), potassium bisulfate (KSO ₄ H), At least one selected from the group consisting of ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), sodium persulfate (Na ₂ S ₂ O ₈ ) and potassium persulfate (K ₂ S ₂ O ₈ ) Is preferred. Compounds that dissociate into sulfate ions (SO ₄ ⁻ ) in the etching composition can be preferably used.

  The etching regulator has a lower limit of, for example, 0.05% by mass, preferably 3% by mass, more preferably 5% by mass, based on the mass of the etching composition of the present invention, and an upper limit of 15% by mass, preferably Is 14% by mass. Within this range, corrosion of metals such as copper on the substrate surface can be suppressed, and the etching rate can be kept moderate.

<Other ingredients>
The etching composition of the present invention may also contain, for example, other components as described below, as necessary, in addition to the corrosion inhibitor and the oxidizing agent represented by the above-mentioned general formula (1a) Good.

[Temperature change inhibitor]
The aging inhibitor which may be contained in the etching composition of the present invention reduces the evaporation of the etching composition to reduce the fluctuation of the amount of components of the etching composition, thereby reducing the amount of fume generation. can do. The temporal change inhibitor is not particularly limited, but is preferably at least one selected from the group consisting of ethylene glycol, tetraethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
The aging inhibitor is preferably 0 to 50% by mass with respect to the mass of the etching composition of the present invention. When the content of the aging inhibitor is too large, a phenomenon may occur in which the etching rate of the conductive film is reduced.

（式中、Ｂは水素イオン（Ｈ^＋）、アンモニウムイオン（ＮＨ^４＋）、鉄イオン（Ｆｅ^２＋、Ｆｅ^３＋）、アルミニウムイオン（Ａｌ^３＋）又は酸化数が１〜３価であるアルキル金属イオンであり、ｎはＢの酸化数である。） Residue inhibitor
The residue inhibitor which may be contained in the etching composition of the present invention can improve the wettability of the etching composition to facilitate etching and suppress the residue. As a residue inhibitor, a compound having a water-soluble acetic acid group can be preferably used, and specifically, it can have a structure of the following general formula (3).

(Wherein, B is hydrogen ion (H ⁺ ), ammonium ion (NH ^{4 +} ), iron ion (Fe ²⁺ , Fe ³⁺ ), aluminum ion (Al ³⁺ ) or alkyl metal ion having an oxidation number of 1 to ³ ) Yes, n is the oxidation number of B.)

In the above general formula (3), n is preferably an integer of 1 to 3.
The residue inhibitor is not particularly limited, but is preferably at least one selected from the group consisting of acetic acid, potassium acetate, ammonium acetate, sodium acetate, magnesium acetate, manganese acetate and zinc acetate.
The residue inhibitor is preferably 0.1 to 15% by weight based on the weight of the etching composition of the present invention. If it is in this range, the residue is suppressed, and a remnant is not generated even after using the etching composition, and the change with time can be suppressed.

  The etching composition of the present invention does not need to contain any other corrosion inhibitor, as long as it contains the imidazole compound represented by the above-mentioned general formula (1a). May also be contained. Such other corrosion inhibitors are not particularly limited, and, for example, benzotriazole, aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1- (1-naphthyl) tetrazole, 1-methyl-5-one In addition to nitrogen-containing heterocyclic compounds such as aminotetrazole, 1,5-diaminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine and pyrroline, secondary amine compounds, amino acid compounds and the like can be mentioned. .

<Water>
The etching composition of the present invention contains water in addition to the oxidant and the corrosion inhibitor represented by the above general formula (1a). That is, the etching composition of the present invention contains at least the above-mentioned oxidizing agent and the corrosion inhibitor represented by the general formula (1a), optionally contains the above-mentioned other components, and the balance is water. .

<Method of Preparing Etching Composition>
The etching composition of the present invention contains at least the above-mentioned oxidizing agent and the corrosion inhibitor represented by the general formula (1a), and, if necessary, the above-mentioned other components, and the balance is water. The components can be prepared by mixing and homogenizing them in any order so as to achieve the above-mentioned content so that the total amount is 100% by mass.

<Application of Etching Composition>
Although the etching composition according to the present invention is not particularly limited, it can be suitably used for etching a conductive film, and can be used, for example, to form a transparent electrode for flat panel display. At this time, as the transparent electrode film used, an indium tin oxide film, an indium zinc oxide film, a zinc oxide film, etc. can be used, and the use of the above indium tin oxide film, an indium zinc oxide film, a zinc oxide film is protection After an indium tin oxide film, an indium zinc oxide film, and a zinc oxide film are formed on the film and coated using a photoresist as a mask, the indium tin oxide film, the indium zinc oxide film, and the zinc oxide film can be etched.
Also, the etching composition according to the present invention may be used to etch a non-transparent conductive film. Examples of the non-transparent conductive film include a copper oxide film and an aluminum copper film.

«Method of manufacturing conductive film»
A method of manufacturing a conductive film according to a second aspect of the present invention includes the step of etching a conductive film on a substrate using the etching composition of the first aspect of the present invention.

The type of substrate is not particularly limited, and for example, a substrate generally used for the production of a conductive film, such as an inorganic substrate such as silicon, SiO ₂ or SiN, a coated inorganic substrate such as SOG, etc. can be used. The etching composition according to the first aspect of the present invention is a substrate having a metal such as copper or copper alloy on at least a part of its surface, a wiring made of a metal such as copper or copper alloy on the surface of the substrate, an electrode or the like The substrate having the above can be particularly preferably used. Examples of the metal constituting the substrate, the wiring and the like include copper, gold, nickel, palladium and the like, which may be an alloy containing these, but the viewpoint and the height at which the object of the present invention is achieved particularly effectively From the viewpoint of versatility, in particular, copper and copper alloys can be suitably used.

  The substrate supporting the metal wiring is usually an insulating substrate. As the insulating substrate, an organic substrate, a ceramic substrate, a silicon substrate, a glass substrate, and the like can be given. The material of the organic substrate is not particularly limited, and thermosetting resins such as phenol resin, urea resin, melamine resin, and alkyd resin epoxy resin, and thermal resins such as polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, liquid crystal polymer, etc. A plastic resin can be used. A material obtained by impregnating a thermosetting resin with a woven or non-woven fabric such as glass fiber, aramid fiber, aromatic polyamide fiber or the like and then curing it is also suitably used as a substrate.

  The method of etching using the etching composition according to the first aspect of the present invention is not particularly limited, and any conventional method can be used. For example, a conductive film formed on a substrate using photolithography or the like The etching composition of the present invention is exposed to a pattern by a spray method, an immersion method, a spin coat method, a slit coat method, a roller coat method or the like to maintain an etching composition at, for example, 10 to 80 ° C, preferably 20 to 40 ° C. For example, it can be carried out by contacting for 0.5 to 10 minutes, preferably for 1 to 5 minutes. After etching, it is usually washed with running pure water or the like.

  The etching composition of the present invention and the method for producing a conductive film using the etching composition make it possible to etch while effectively suppressing the corrosion of metals, particularly copper and copper alloys, on the substrate surface. For example, while etching an etching target such as an indium tin oxide film, even if there is a metal film such as a copper film or a copper alloy film below the etching target, the corrosion (infection) of the metal film is suppressed. It is possible to protect the substrate surface below the etching target without adversely affecting the etching due to metal elution, and to contribute also to cost reduction and process yield improvement. it can. Such inventive etching compositions are particularly suitable for the preparation of conductive films and allow selective pattern etching of conductive films.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example, Comparative Example
<Corrosion inhibitor>
As a corrosion inhibitor, a compound 1, a comparative compound 1, a comparative compound 2 and a benzotriazole of the following structure were used as a comparative compound 3.

Synthesis Example 1
Among the above-mentioned corrosion inhibitors, the above-mentioned compound 1 was synthesized by the following method.
First, 30 g of a cinnamic acid derivative having a structure of the following formula was dissolved in 200 g of methanol, and 7 g of potassium hydroxide was added to the methanol. The methanol solution was then stirred at 40 ° C. The methanol is distilled off and the residue is suspended in 200 g of water. The resulting suspension was mixed with 200 g of tetrahydrofuran, stirred, and the aqueous phase was separated. Under ice-cooling, 4 g of hydrochloric acid was added and stirred, and then 100 g of ethyl acetate was mixed and stirred. After the mixture was allowed to stand, the oil phase was separated. The target product was crystallized from the oil phase, and the precipitate was collected to obtain an imidazole compound (compound 1) of the above structure.

The measurement result of < ¹ > H-NMR of the imidazole compound (compound 1) of the said structure is as follows.
¹ H-NMR (DMSO): 11.724 (s, 1 H), 7. 838 (s, 1 H), 7. 340 (d, 2 H, J = 4.3 Hz), 7. 321 (d, 1 H, J = 7.2 Hz), 6.893 (d, 2 H, J = 4.3 Hz), 6.876 (d, 1 H, J = 6.1 Hz), 5.695 (dd, 1 H, J = 4.3 J, 3.2 J), 3.720 (s, 3 H), 3. 250 (m, 2 H)

<Preparation Example of Etching Composition>
Each component of the type and content shown in Table 1 was mixed, and the balance was constituted with water to prepare an etching composition such that the total mass of the entire composition was 100% by weight. In Table 1, NH 4 _Ac represents ammonium acetate, EG represents ethylene glycol, also the unit of numerical value representing the content of each component is mass%.

<Evaluation of copper corrosion inhibition>
An indium tin oxide film / copper film / molybdenum titanium alloy film was formed on a glass substrate (100 mm × 100 mm) by vapor deposition so as to have a film thickness of 400 Å / 3000 Å / 300 Å, respectively, and patterned to obtain samples of etching films. This sample is immersed in 500 ml of each etching composition obtained according to the preparation example, maintained at 40 ° C., and after 48 hours, the solution is collected, and eluted copper ion using ICP-MS (Inductively coupled plasma mass spectroscopy). The concentration was measured. The results are shown in Table 1.
<Evaluation criteria>
◎: Cu elution less than 20 ppm ○: Cu elution not less than 20 ppm, less than 30 ppm ×: Cu elution not less than 30 ppm

From Table 1, when it etches using the etching composition of Examples 1-4 containing the compound 1, since elution of copper is suppressed, corrosion (infection) of the copper film by etching is prevented. all right.
On the other hand, in the etching compositions of Comparative Examples 1 and 2 containing Comparative Compound 1 and Comparative Compound 2 and Comparative Compound 3 having an imidazole ring but not included in General Formula (1a), copper is eluted by etching. It was found that the copper film was corroded (corrupted) by the etching.
From the above results, it is considered that the etching composition of the present invention can suppress not only copper but also corrosion of a copper alloy, and is expected to similarly suppress corrosion of other metals. .

  Further, among them, although the composition of Comparative Example 4 slightly suppresses the elution of copper, Example 4, Comparative Example 8 and Comparative Example 12 in which the composition of Comparative Example 4 and the composition other than the imidazole compound are the same. When comparative example 4 is compared, it turned out that only example 4 using compound 1 instead of comparative compounds 1 to 3 as an imidazole compound is excellent in the suppression effect of copper elution.

Claims (5)

An etching composition used for etching a conductive film comprising a transparent electrode film or a copper oxide film,
The etching composition containing an oxidizing agent, water, and the corrosion inhibitor represented by following General formula (1) .

(Wherein R ² represents an aromatic group which may have a substituent, and R ⁴ each independently represents a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, Represents a sulfonato group, a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, n represents an integer of 0 to 3, R ¹ represents a hydrogen atom or an alkyl group, and R ³ may have a substituent Represents an alkylene group, and R ³ may combine with R ² to form a cyclic structure) The etching composition according to claim 1 , further comprising an aging inhibitor. Further, containing residual渣抑suppressant, etching composition according to claim 1 or 2.   The etching composition according to any one of claims 1 to 3, wherein the transparent electrode film comprises an oxide of indium, tin and / or zinc. The manufacturing method of a conductive film including the process of etching the said conductive film on a board | substrate using the etching composition of any one of Claims 1-4 .