KR20110005206A

KR20110005206A - Etching agent compositions for copper-containing materials and methods for etching copper-containing materials

Info

Publication number: KR20110005206A
Application number: KR1020100058468A
Authority: KR
Inventors: 유스케 나카무라; 유이치로 키시
Original assignee: 가부시키가이샤 아데카
Priority date: 2009-07-09
Filing date: 2010-06-21
Publication date: 2011-01-17
Also published as: TWI358465B; JP2011017054A; CN101949014A; CN101949014B; JP4685180B2; TW201124562A; KR101032204B1

Abstract

PURPOSE: An etching agent composition for a copper-containing material and a method for etching a copper-containing material are provided to prevent distortion by adding one or more phosphoric acid components. CONSTITUTION: An etching agent composition for a copper-containing material is composed of one or more oxidizing agents 0.1~15 weight%, polymer polyesterdiol 0.001~3 weight%, polyol 0.001~3 weight%, phosphoric acid component 0.1~5 weight%, and one or more inorganic acid components 0.05~10 weight%. The one or more oxidizing agents are selected from cupric ion and ferric ion. The polymer polyesterdiol has ethylene oxide base and propylene oxide base. One or more phosphoric acid components are selected from phosphate and phosphoric acid. The inorganic acid components are selected from hydrogen chloride and sulfuric acid.

Description

Etching agent compositions for copper-containing materials and methods for etching copper-containing materials

The present invention relates to an etchant composition for copper-containing materials and an etching method for the copper-containing material, and in particular, an etchant composition and copper-containing material for copper-containing materials capable of forming a fine circuit pattern (circuit wiring) without shape defects. The etching method of this invention is related.

BACKGROUND OF THE INVENTION A printed wiring board (or film) having circuit wiring formed on its surface is widely used for mounting electronic components, semiconductor devices, and the like. In recent years, in accordance with the demand for miniaturization and high functionalization of electronic devices, high density and thinning of circuit wiring of printed wiring boards (or films) are desired.

As a method of manufacturing a high-density circuit wiring, the methods called subtractive method and the semiadditive method are known, and wet etching is performed by these methods.

In order to form fine circuit wiring, there should be no residual film at the bottom of the etching, the side of the wiring viewed from the top should be straight (straight), the cross section of the circuit wiring should be rectangular, and the high etching factor is ideal. In reality, however, shape defects such as residual film, linear dizziness, side etching, undercut, and lowering of the etching factor due to narrowing of the wiring upper width (hereinafter also referred to as "top width") j occur. For this reason, in wet etching, controlling these shape defects is desired.

As for the shape defect of the circuit wiring as described above, a technique for improving by studying the components of the etchant composition is often reported.

For example, Patent Document 1 discloses a circuit pattern forming method by a semiadditive method using an etchant composition containing a ferric ions, hydrochloric acid, hydrochloric acid, a copper-containing material etching accelerator, and a copper-containing material etching inhibitor as essential components. Here, as a copper-containing material etching inhibitor, the compound which added propylene oxide and ethylene oxide to the active hydrogen group of an amine compound is disclosed, and also using phosphoric acid as a component which improves the cleaning effect and leveling property of copper surface is disclosed.

In addition, Patent Document 2 consists of an aqueous solution containing a polymer selected from the group consisting of acid, polyalkylene glycol and copolymer of polyamine and polyalkylene glycol selected from the group consisting of copper oxidant, hydrochloric acid and organic acid salt, The etchant composition of the copper or copper alloy which suppressed narrowing of etch and a circuit wiring upper part is disclosed. Here, copper ions and ferric ions are disclosed as copper oxidizing agents, and copper (II) chloride, copper bromide (II) and copper hydroxide (II), and ferric ions include copper ions. Examples of the compound to be produced include iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate and iron (III) acetate. Moreover, as a polyalkylene glycol, polyethyleneglycol, polypropylene glycol, an ethylene oxide propylene oxide copolymer are disclosed, As a copolymer of a polyamine and a polyalkylene glycol, ethylene diamine, diethylene triamine, triethylene tetramine, tetra Copolymers of ethylenediamine, such as ethylenepentamine, pentaethylenehexamine, and N-ethylethylenediamine, with polyethylene glycol, polypropylene glycol, and ethylene oxide / propylene oxide copolymers are disclosed.

Patent Literature 3 also discloses an etchant comprising an aqueous solution containing an azole containing only nitrogen atoms as an acid selected from an oxidizing metal ion source, an inorganic acid or an organic acid, and other atoms in the ring, and suppressing undercutting. Here, as copper oxide, ferric ions are disclosed as an oxidizing metal ion source, and hydrochloric acid is disclosed as an acid. It is also disclosed to use nonionic surfactants, such as block polymers of polyoxyethylene and polyoxypropylene, to provide etching with a uniform surface shape.

Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-138389

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-256901

Patent Document 3: Japanese Patent Application Laid-Open No. 2005-330572

However, the etching agent compositions disclosed in Patent Literatures 1 and 2 cannot uniformly etch fine circuit patterns, and as a result, there is a problem that a circuit shape defect (poor linearity), a short, or the like occurs. In addition, the etchant composition disclosed in Patent Document 3 is low in dispersibility and poor in liquid drainage with respect to a fine circuit pattern, so that circuit peeling due to poor circuit shape (partial undercut), phosphoric acid and copper or iron There arises a problem such as short generation due to the generation of sludge derived from salt.

The present invention has been made to solve the above problems, and an object thereof is to provide an etchant composition for a copper-containing material and a etching method for the same-containing material which can form a fine pattern without a shape defect.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said problem, the composition of an etchant composition is closely related to formation of a fine circuit pattern, and is etching by using the etchant composition which has a specific composition, and this, It has been found that the above problem can be solved and the present invention has been reached.

That is, this invention is 0.1-15 mass% of at least 1 oxidizing agent component chosen from (A) copper ions and ferric ions, (B) the number average molecular weight is 1,500-3,000, and content of ethylene oxide group 0.001-3 mass% of polymer polyetherdiol which has the ethylene oxide group and the propylene oxide group which are 15-50 mass%, (C) 0.001-3 mass% of polyol represented by following General formula (1)

(Wherein R ¹ represents an alkylene group having 2 to 6 carbon atoms, X ¹ to X ³ represent a group represented by the following general formula (2), and X ⁴ represents a hydrogen atom or a group represented by the following general formula (2)) N represents a number from 1 to 5)

(Wherein R ² And R ³ Represents an ethylene group or a propylene group, and R ³ is a propylene group when R ² is an ethylene group, R ² is and R ³ is an ethylene group if a propylene group, p and q is the number average molecular weight of polyol 200 ~ 10,000 And (D) 0.1-5 mass% of at least one phosphoric acid component selected from (D) phosphoric acid and phosphate, and (E) at least selected from hydrogen chloride and sulfuric acid. It consists of aqueous solution containing 0.05-10 mass% of one inorganic acid component, The etching agent composition for copper containing materials characterized by the above-mentioned.

Moreover, this invention uses the said etchant composition in the patterning of the copper containing material of thickness 1-10 micrometers and etching space 1-10 micrometers, The etching method of the copper containing material characterized by the above-mentioned.

According to this invention, the etching agent composition for copper containing materials and the etching method of the same containing material which can form a fine pattern without a shape defect can be provided.

The etchant composition for copper-containing materials of the present invention (hereinafter referred to as an etchant composition) is at least one oxidant component selected from (A) copper ions and ferric ions (hereinafter referred to as component (A)). (B) predetermined polymer polyetherdiol (hereinafter referred to as component (B)), (C) predetermined polyol (hereinafter referred to as component (C)), (D) predetermined phosphoric acid component (hereinafter referred to as (D) Component), and (E) an aqueous solution containing a predetermined inorganic acid component (hereinafter referred to as component (E)).

Component (A) is a component having a function of oxidizing the copper-containing material to perform etching, and a mixture of cupric ions, ferric ions or cupric ions and ferric ions can be used. These can normally mix | blend a copper, a copper (II) compound, and / or an iron (III) compound as a source. Examples of copper (II) compounds include cupric chloride, cuprobromide, cupric sulfate, cupric hydroxide and cupric acetate. Examples of the iron (III) compound are ferric chloride and ferric bromide. And ferric iodide, ferric sulfate, ferric nitrate and ferric acetate. These may be used independently and may mix and use 2 or more types. Among these, copper, cupric chloride, cupric sulfate, and ferric chloride are preferable in view of cost, stability of the etching agent composition, and controllability of the etching rate, and more preferably ferric chloride.

The content of the component (A) in the etchant composition is 0.1 to 15% by mass, preferably 1 to 10% by mass, in terms of cupric ions and / or ferric ions. When content of (A) component is less than 0.1 mass%, etching time becomes long, a resist may deteriorate, and productivity falls. Moreover, in the subtractive method, since the etching effect of the Ni-Cr seed layer of copper back surface falls, the residual film removal property of copper worsens. On the other hand, when content of (A) component is more than 15 mass%, an etching rate cannot be controlled and an etching factor will deteriorate.

When the copper ions are used together with the ferric ions, the redox potential, specific gravity, acid concentration, copper concentration, etc. of the etchant composition can be controlled to automatically control the etching ability of the etchant composition. The content of the second copper ion in this case is 0.5 to 10% by mass, preferably 1 to 10% by mass, in terms of copper ions. If the content of the copper ions is less than 0.5% by mass, the desired use effect may not be obtained. On the other hand, when content of a 2nd copper ion is more than 10 mass%, sludge may generate | occur | produce in an etching agent composition.

Component (B) is a component that improves the permeability of the etchant composition into the circuit pattern to provide uniform etching, and is a polymer polyetherdiol having ethylene oxide groups and propylene oxide groups. Although it does not restrict | limit especially as this polymeric polyetherdiol, For example, Polyethylene, such as ethylene oxide and alkylene oxide adduct of alkylene glycol, such as ethylene glycol, propylene glycol, and butylene glycol, polyethyleneglycol, polypropylene glycol, and polybutylene glycol Ethylene oxide and alkylene oxide adducts of alkylene glycols. Polymeric polyetherdiol may be used individually by 1 type, and 2 or more types may be mixed and used for it.

The number average molecular weight of polymeric polyetherdiol is 1,500-3,000. If the number average molecular weight is less than 1,500, the linearity of the circuit shape is lowered, and a desired circuit pattern cannot be obtained. On the other hand, when the number average molecular weight is larger than 3,000, the etching rate is slow, and the etching efficiency is lowered.

In addition, the content of ethylene oxide groups in the polymer polyetherdiol is 15 to 50% by mass. When content of an ethylene oxide group is less than 15 mass%, the compatibility of an etching agent composition will fall and a short etc. will arise. On the other hand, if the content of ethylene oxide groups is more than 50 mass%, the etching factor does not improve and a desired circuit pattern cannot be obtained.

Ethylene oxide groups and propylene oxide groups may be distributed in block form or may be distributed in random form. It is preferable to distribute in block shape from a viewpoint of reducing the foamability of an etching agent composition.

Among the polymer polyether diols, the compound represented by the following general formula (3) is particularly preferable because a better circuit shape can be obtained.

In said formula (3), R and R 'represent an ethylene group or a propylene group, R' is a propylene group when R is an ethylene group, R 'is an ethylene group when R is a propylene group, a, b, and c The number average molecular weight is 1,500-3,000, and shows the number whose content of an ethylene oxide group is 15-50 mass%.

The content of the component (B) in the etchant composition is 0.001 to 3 mass%, preferably 0.05 to 2 mass%. When content of (B) component is less than 0.001 mass%, sufficient use effect cannot be acquired. On the other hand, when content of (B) component is more than 3 mass%, the viscosity of an etching agent composition will become high, liquid drainage property will fall, and circuit linearity will worsen.

The component (C) is a component having an effect of imparting a good circuit shape by improving the permeability of the etchant composition into the circuit pattern and reducing the retention of the etchant composition around the circuit pattern. In addition, the component (C) does not exhibit excessive affinity such as complexing or coordination with the copper-containing material, and thus acts as an appropriate etching inhibitor. By mix | blending this (C) component, it becomes an etching agent composition which provides effects, such as improvement of linearity, suppression of side etching, suppression of undercut, and reduction of the width of a circuit wiring upper width.

(C) component which exhibits the above effects is a polyol represented by following General formula (1). This polyol may be used individually by 1 type, and may mix and use 2 or more types.

In said formula (1), R <^1> represents a C2-C6 alkylene group, X <^1> -X <^3> represents group represented by following General formula (2), X <^4> is a hydrogen atom or following General formula (2) The group represented by is represented, and n represents the number of 1-5.

In the formula ^(2), R 2 And R ³ Represents an ethylene group or a propylene group, and R ³ is a propylene group when R ² is an ethylene group, R ² is and R ³ is an ethylene group if a propylene group, p and q is the number average molecular weight of polyol 200 ~ 10,000 Moreover, the number by which content of an ethylene oxide group becomes 50 mass% or less is shown.

Examples of the alkylene group having 2 to 6 carbon atoms represented by R ¹ include ethylene group, propylene group, butylene group, pentylene group, hexylene group, and the like, and these groups may be bonded at any position and branched. Also good. R ² And the propylene group represented by R ³ is -CY ¹ H-CY ² H- (Y ¹ And Y ² may be hydrogen, and the other may be a methylene group), or may be -CH ₂ -CH ₂ -CH _2- .

Among the polyols represented by the general formula (1), polyols in which R ¹ is ethylene, n is 1, and X ¹ to X ⁴ are represented by the general formula (2) are easily available and have an effect of preventing shape defects. It is preferable because it is excellent.

The number average molecular weight of the polyol is 200 to 10,000, preferably 200 to 1,500. When the number average molecular weight of a polyol is less than 200, the effect of improving a circuit shape is not enough. On the other hand, if the number average molecular weight of the polyol is greater than 10,000, a sufficient etching rate cannot be obtained.

The content of ethylene oxide groups in the polyol is also at most 50 mass%, preferably at 15 to 50 mass%. If the content of ethylene oxide groups is more than 50% by mass, the etching factor is lowered, and a desired circuit pattern cannot be obtained. In addition, when the content of ethylene oxide groups is less than 15% by mass, sufficient etching effects cannot be obtained.

Content of (C) component in an etching composition is 0.001-3 mass%, Preferably it is 0.05-2 mass%. When content of (C) component is less than 0.001 mass%, sufficient use effect cannot be acquired. On the other hand, when content of (C) component is more than 3 mass%, the defect of a circuit shape arises by penetration into a resist interface.

Component (D) is a component that reacts with a resin, which is a resist component, or an ester group, which is a resist plasticizer, to soften the resist, and inhibits the polyol from penetrating the interface between copper and the resist. In addition, the component (D) also has an effect of promoting etching of the Ni—Cr seed layer on the copper back surface.

The component (D) is at least one selected from phosphoric acid and phosphate. Examples of the phosphate include sodium phosphate, potassium phosphate, calcium phosphate, aluminum phosphate and the like. The phosphate may be any of acid salts (monohydrogen salts, dihydrogen salts) and neutral salts. Especially, phosphoric acid is preferable because the effect of preventing shape defects is remarkable.

Content of (D) component in an etching composition is 0.1-5 mass%. When content of (D) component is less than 0.1 mass%, sufficient use effect cannot be acquired. On the other hand, when the content of the component (D) is more than 5% by mass, retention of the etchant composition between the wirings and the wirings occurs, so that uniform etching cannot be performed, resulting in poor shape of the circuit wiring due to copper reprecipitation. .

Component (E) is a component that promotes etching having a function of removing a copper oxide film or copper chloride on the surface of a copper-containing material to be etched, a function of stabilizing an oxidizing agent, and a leveling property for the copper-containing material.

The component (E) is at least one selected from hydrogen chloride and sulfuric acid.

Content of (E) component in an etching composition is 0.05-10 mass%. When content of (E) component is less than 0.05 mass%, sufficient use effect cannot be acquired. On the other hand, when content of (E) component is more than 10 mass%, etching becomes excess and it becomes impossible to control etching rate. As a result, a shape defect of a circuit wiring occurs.

The well-known arbitrary components used for the said use can be mix | blended with the etchant composition of this invention in addition to the essential components (A)-(E) demonstrated above in the range which does not impair the effect of this invention. Optional components include glycol ether compounds, surfactants other than the components (B) and (C), inorganic acids, organic acids, amino acid compounds, azole compounds, pyrimidine compounds, and thiourea other than the components (D) and (E). The compound, an amine compound, an alkylpyrrolidone compound, an organic chelating compound, a polyacrylamide compound, hydrogen peroxide, a persulfate, an inorganic salt, a cuprous ion, and a ferrous ion are mentioned. The concentration in the case of using these arbitrary components is generally 0.001 mass%-10 mass%.

Examples of the glycol ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene Low molecular glycol ether compounds such as glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and 3-methyl-3-methoxy-3-methoxybutanol, polyethylene glycol monomethyl ether, polyethylene glycol There may be mentioned a high molecular compound such as a glycol ether call monoethyl ether, and polyethylene glycol monobutyl ether. You may use these individually or in mixture of 2 or more types.

As surfactant, anionic surfactant, nonionic surfactant other than (B) and (C) component, cationic surfactant, amphoteric surfactant, etc. are mentioned, for example.

Anionic surfactants include, for example, higher fatty acid salts, higher alcohol sulfate salts, sulfide olefin salts, higher alkyl sulfonates, α-olefin sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, phosphoric acid ester salts, and sulfuric acid esters of fatty acid esters. Salts, glyceride sulfate ester salts, sulfonates of fatty acid esters, α-sulfofatty acid methyl ester salts, polyoxyalkylene alkylether sulfate ester salts, polyoxyalkylene alkylphenylether sulfate ester salts, polyoxyalkylene alkylether carboxy Sulfuric acid ester salts of acid salts, acylated peptides, fatty acid alkanolamides or alkylene oxide adducts thereof, sulfosuccinic esters, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylbenzoimidazolesulfonates, polyoxyalkylenesulfosuccinates, Salts of N-acyl-N-methyltaurine, N-acylglutamic acid or salts thereof, acyloxy Sulfonates, alkoxyethanesulfonates, N-acyl-β-alanine or salts thereof, N-acyl-N-carboxyethyltaurine or salts thereof, N-acyl-N-carboxymethylglycine or salts thereof, acyl lactates, N- Acyl sarcosine salt, alkyl, or alkenylamino carboxymethyl sulfate, etc. are mentioned.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, and polyoxyethylene polyoxypropylene alkyl ethers (additional forms of ethylene oxide and propylene oxide may be random or block). Glycol propylene oxide adducts, polypropylene glycol ethylene oxide adducts, random or block adducts of ethylene oxide and propylene oxide of alkylenediamine, glycerin fatty acid esters or ethylene oxide adducts thereof, sorbitan fatty acid esters, polyoxyethylene sorbents Non-fatty acid esters, alkylpolyglucosides, fatty acid monoethanol amides or ethylene oxide adducts thereof, fatty acid-N-methylmonoethanolamides or ethylene oxide adducts thereof, fatty acid diethanolamides or ethylene oxides thereof Adducts, sucrose fatty acid esters, alkyl (poly) glycerin ethers, polyglycerin fatty acid esters, polyethylene glycol fatty acid esters, fatty acid methyl ester ethoxylates, and N-long chain alkyldimethylamine oxides.

Cationic surfactants include, for example, alkyl (alkenyl) trimethylammonium salts, dialkyl (alkenyl) dimethylammonium salts, alkyl (alkenyl) quaternary ammonium salts, mono or dialkyl (alkenyl) containing ether groups or ester groups or amide groups Quaternary ammonium salt, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzyl ammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (alkenyl) Amines, alkyl (alkenyl) amine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride.

Examples of the amphoteric surfactant include carboxybetaine, sulfobetaine, phosphobetaine, amideamino acid, and imidazolinium betaine-based surfactant.

Said surfactant can be used individually or in mixture of 2 or more types.

Examples of the inorganic acid include nitric acid and polyphosphoric acid. These can be used individually or in mixture of 2 or more types.

As organic acids, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeline acid, maleic acid, fumaric acid, oxalic acid, malic acid Carboxylic acids such as tartaric acid, citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid, levulinic acid and β-chloropropionic acid, methanesulfonic acid, ethanesulfonic acid, 2-hydroxy Organic sulfonic acids such as ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid. These can be used individually or in mixture of 2 or more types.

Examples of amino acid compounds include amino acids such as glycine, alanine, valine, leucine, serine, phenylalanine, tryptophan, glutamic acid, aspartic acid, lysine, arginine and histidine, and alkali metal salts and ammonium salts thereof. These can be used individually or in mixture of 2 or more types.

As an azole compound, Alkyl imidazole, such as imidazole, 2-methylimidazole, 2-undecyl-4-methylimidazole, 2-phenylimidazole, 2-methylbenzoimidazole; Benzoimidazoles such as benzoimidazole, 2-methylbenzoimidazole, 2-undecylbenzoimidazole, 2-phenylbenzoimidazole, and 2-mercaptobenzoimidazole; 1,2,3-triazole, 1,2,4-triazole, 5-phenyl-1,2,4-triazole, 5-amino-1,2,4-triazole, 1,2,3- Benzotriazole, 1-aminobenzotriazole, 4-aminobenzotriazole, 1-bisaminomethylbenzotriazole, 1-methyl-benzotriazole, tolyltriazole, 1-hydroxybenzotriazole, 5-methyl Triazoles such as -1H-benzotriazole and 5-chlorobenzotriazole; 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto Tetrazole such as -1H-tetrazole, 1-cyclohexyl-5-mercapto-1H-tetrazole, 5,5'-bis-1H-tetrazole; Benzothiazole, 2-mercaptobenzothiazole, 2-phenylthiazole, 2-aminobenzothiazole, 2-amino-6-nitrobenzothiazole, 2-amino-6-methoxybenzothiazole, 2- And thiazoles such as amino-6-chlorobenzothiazole. These can be used individually or in mixture of 2 or more types.

Examples of the pyrimidine compounds include diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, mercaptopyrimidine and the like. These can be used individually or in mixture of 2 or more types.

Examples of thiourea compounds include thiourea, ethylene thiourea, thiodiglycol, mercaptan and the like. These can be used individually or in mixture of 2 or more types.

As the amine compound, for example, diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethanol isopropanolamine, diethanol isopropanol Amines, ethanol diisopropanolamine, polyarylamines, polyvinylpyridine, hydrochlorides thereof and the like. These can be used individually or in mixture of 2 or more types.

Examples of the alkylpyrrolidone compounds include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone and N-amyl 2-pyrrolidone, N-hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Examples of the organic chelating compound include ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, triethylenetetramine hexaacetic acid, tetraethylenepentamine citric acid, pentaethylenehexamine palmacetic acid, nitrilo triacetic acid, and alkali metal salts thereof, and Ammonium salt etc. are mentioned. These can be used individually or in mixture of 2 or more types.

As a polyacrylamide compound, polyacrylamide, t-butyl acrylamide sulfonic acid, etc. are mentioned, for example. These can be used individually or in mixture of 2 or more types.

Examples of the persulfate include ammonium persulfate, sodium persulfate and potassium persulfate. These can be used individually or in mixture of 2 or more types.

As inorganic salts, for example, sodium chloride, potassium chloride, ammonium chloride, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate, sodium carbonate, potassium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, ammonium nitrate, ammonium chlorate , Sodium chlorate, potassium chlorate and the like. These can be used individually or in mixture of 2 or more types.

As a compound which provides a primary copper ion, copper chloride (I), copper bromide (I), copper sulfate (I), copper hydroxide (I), etc. are mentioned, for example. Moreover, as a compound which provides a ferrous ion, iron (II) chloride, iron bromide (II), iron iodide (II), iron sulfate (II), iron nitrate (II), iron acetate (II), etc. are mentioned, for example. have. These can be used individually or in mixture of 2 or more types.

Among the above-mentioned optional components, the components which are particularly preferably blended are ferrous ions. Ferrous ions are used in the case of employing an auto control based on redox potential, specific gravity, acid concentration, copper concentration or the like with respect to the etching ability of the etchant composition. When ferrous ion is used, its content in a coating composition is 0.1-5 mass% in conversion of ferrous ion. If the content of ferrous ions is less than 0.1% by mass, sufficient use effects cannot be obtained. On the other hand, when content of ferrous ion is more than 5 mass%, etching capability etc. will fall.

The etchant composition of this invention can be manufactured by mixing the said component and water. Although the mixing method is not specifically limited, What is necessary is just to mix using a well-known mixing apparatus.

It is preferable that the specific gravity of the etchant composition of this invention obtained in this way is 1.10-1.30. If the specific gravity is less than 1.10, a sufficient etching rate may not be obtained, and the etching factor may decrease. On the other hand, if the specific gravity is greater than 1.30, the etching factor may be lowered.

Although the etchant composition of this invention can form a fine pattern from the copper containing material, especially the patterning of the copper containing material whose thickness is 1-10 micrometers and an etching space is 1-10 micrometers from a viewpoint of a shape defect suppression effect and an etching rate. Suitable for Moreover, it can use also in the patterning of the copper containing material whose thickness exceeds 10 micrometers and 25 micrometers or less and an etching space exceeds 10 micrometers and 40 micrometers or less.

Etching of the copper-containing material using the etchant composition of this invention can be performed by a well-known general method. As copper-containing material which is a material to be etched, copper alloys, such as silver copper alloy and aluminum copper alloy, and copper are mentioned, and copper is especially suitable. The etching method is not particularly limited either, but an immersion method, a spray method, or the like may be used, and the etching method may be appropriately adjusted depending on the etching agent composition and the etching method to be used. In addition, various well-known methods, such as a batch type, a blow type, the redox potential of a etchant, specific gravity, and the auto-control type based on acid concentration, may be used.

When using the etching agent composition of this invention by a spray method, it is preferable that processing temperature is 30-50 degreeC, processing pressure is 0.03-0.2 MPa, and processing time is 20-300 second.

In addition, in the etching method using the etchant composition of the present invention, a replenishment liquid may be added to recover the deterioration of the liquid by repeating the etching. In particular, in the above-described auto-control etching method, the replenishment liquid is set in advance in the etching apparatus, and the liquid is added to the etchant composition in the step of deteriorating the liquid. This replenishment liquid is (A) component, (E) component, and water, for example, and the density | concentration of (A) component and (E) is about 1-20 times of an etching agent composition. Moreover, you may add (B)-(D) component or arbitrary components of the etching agent composition of this invention to this replenishment liquid as needed.

Since the etching agent composition of this invention can form a fine pattern without a shape defect, it can be used suitably for the subtractive method of the packaging substrate, COF, and TAB use which require fine etching other than a printed wiring board.

Example

Although an Example and a comparative example demonstrate this invention in detail, this invention is not restrict | limited by these.

The nonionic surfactants used in the following examples and comparative examples are shown in Tables 1 and 2.

High molecular polyether
Dior Kinds Number average molecular weight Content of Ethylene Oxide Groups (mass%) a-1 Of polypropylene glycol
Ethylene oxide adduct 2,200 40 a-2 ＂ 2,500 20 a-3 ＂ 4,200 40 a-4 Polyethylene glycol 2,000 100

Polyol Kinds Number average molecular weight Content of Ethylene Oxide Groups (mass%) b-1 Block Adducts of Propylene Oxide Groups and Ethylene Oxide Groups of Ethylenediamine
In formula (1), R ¹ = ethylene group, n = 1, R ² = propylene group, R ³ = ethylene group, X ⁴ ≠ hydrogen 280 40 b-2 ＂ 580 40 b-3 ＂ 1,300 40 b-4 Propylene Oxide Adducts of Ethylenediamine
In formula (1), R ¹ = ethylene group, n = 1, q = 0, R ² = propylene group, X ⁴ ≠ hydrogen 300 0 b-5 Block Adducts of Propylene Oxide Groups and Ethylene Oxide Groups of Ethylenediamine
In formula (1), R ¹ = ethylene group, n = 1, R ² = propylene group, R ³ = ethylene group, X ⁴ ≠ hydrogen 3,500 20 b-6 ＂ 5,000 40

(Example 1)

Etching agent compositions No. 1 to 2 were prepared by mixing the polymer polyetherdiol and polyol shown in Tables 1 and 2, ferric chloride (4.9 mass%), cupric chloride (6.6 mass%), phosphoric acid and hydrogen chloride in the compositions shown in Table 3. 11 was obtained. In Table 3, the content of ferric chloride was expressed in terms of ferric ion conversion, and the content of cupric chloride was expressed in cupric ion conversion. In addition, remainder of content is water.

(Comparative Example 1)

In the same manner as in Example 1, each component was mixed in the composition shown in Table 3 to obtain etchant composition Nos. 12 to 19.

(Example 2)

After coating and drying a resist (PMER-P; manufactured by Tokyo Oka Co., Ltd.) on a COF tape substrate (158 mm x 100 mm) having a thickness of 8 µm, exposure was performed using an exposure apparatus (UFX-2458B; manufactured by Ushio Electric Co., Ltd.). Then, by developing and rinsing, a resist pattern having a pitch of 20 μm and a space of 6 μm was formed.

Subsequently, using the etchant composition Nos. 1 to 11 with respect to the COF tape base material on which the resist pattern was formed, for a number of seconds (60 to 100 seconds) to be just etched under the conditions of treatment temperature 45 ° C. and treatment pressure 0.05 MPa. Wet etching was performed by spraying. And the resist pattern was removed using the resist remover (acetone), and the copper circuit pattern was obtained. The following evaluation was performed about the shape of the obtained copper circuit pattern.

(1) linearity

The shape of the copper circuit pattern was observed using a laser microscope manufactured by Keyens Co., Ltd., and "3" for the wave width of the line width was 1 µm, "4" for 1 µm or more and less than 1.7 µm, and "3" for 1.7 µm or more and less than 2.4 µm. , 5-step evaluation which made "2" the thing of 2.4 micrometers or more and less than 3 micrometers "1" was performed.

(2) Wiring Upper Width (Top Width)

It was measured by a laser microscope. In addition, the unit is micrometer.

(3) etching factor

It calculated by the following formula.

Etch Factor = Copper Thickness (μm) / {(B-T) / 2}

In formula, T is top width (micrometer), B is bottom width (micrometer).

(4) remaining film

The remainder of the etching part was observed by observation using the laser microscope manufactured by Keyence Corporation. Five-step evaluation was performed by making "5" that there is no remainder of an etching part and "1" that having many of the remainder of an etching part.

(5) etching rate

The wet etching process was performed for 30 second with respect to the tape base material, and the mass difference (eluted copper) of the tape base material was calculated | required before and after the said etching process, and it computed from the following formula. In addition, the unit is micrometer / min.

Etch rate = (weight of tape substrate before etching (g)-weight of tape substrate after etching (g) / (treatment area (cm ² ) x 8.93 (g / cm ³ )) x 10000 x 60/30

The evaluation results are shown in Table 4.

(Comparative Example 2)

Except having used etchant composition numbers 12-19, it carried out wet etching similarly to Example 2, and obtained the copper circuit pattern.

The said evaluation (1)-(4) was performed about the shape of the obtained copper circuit pattern. The evaluation results are shown in Table 4.

As shown in the results of Table 4, the etchant compositions Nos. 1 to 11 of the present invention all provided good circuit shapes.

On the other hand, the etchant composition number 12 which does not contain a polymer polyetherdiol and a polyol, the etchant composition number 13 which does not contain a polyol, the etchant composition numbers 14-17 which do not contain a polymer polyetherdiol, and a predetermined polymer polyether All etchant composition nos. 19 without diols did not provide good circuit shape. Moreover, as can be seen from the result of etchant composition No. 18, when the number average molecular weight of the polymer polyetherdiol was too large, linearity fell and there were many residual films.

In addition, as can be seen from the comparison between the etchant composition No. 2 and the etchant composition No. 11, the higher the content of ethylene oxide was, the better the top width and the etching factor were provided.

As can be seen from the above results, according to the present invention, it is possible to provide an etchant composition for a copper-containing material and a etching method for the same-containing material which can form a fine circuit pattern without a shape defect.

Claims

(A) 0.1 to 15 mass% of at least one oxidant component selected from cupric ions and ferric ions,
(B) 0.001 to 3 mass% of a polymer polyetherdiol having an ethylene oxide group and a propylene oxide group having a number average molecular weight of 1,500 to 3,000 and a content of ethylene oxide groups of 15 to 50% by mass,
(C) 0.001 to 3 mass% of polyols represented by the following general formula (1)

(Wherein R ² And R ³ Represents an ethylene group or a propylene group, and R ³ is a propylene group when R ² is an ethylene group, R ² is and R ³ is an ethylene group if a propylene group, p and q is the number average molecular weight of polyol 200 ~ 10,000 And a number such that the content of ethylene oxide groups is 50% by mass or less),
(D) 0.1-5 mass% of at least one phosphoric acid component selected from phosphoric acid and phosphate salts, and
(E) An etchant composition for copper-containing materials, comprising an aqueous solution containing 0.05 to 10 mass% of at least one inorganic acid component selected from hydrogen chloride and sulfuric acid.

According to claim 1, wherein the (B) polymer polyetherdiol is represented by the general formula (3)

(Wherein R and R 'represent an ethylene group or a propylene group, R' is a propylene group when R is an ethylene group, R 'is an ethylene group when R is a propylene group, and a, b and c are number average molecular weights) The number is 1,500-3,000, and the content of ethylene oxide group is 15-50 mass%), and is represented by the etching agent composition for copper-containing materials characterized by the above-mentioned.

The number average molecular weight of the said (C) polyol is 200-1,500, The etchant composition for copper containing materials of Claim 1 or 2 characterized by the above-mentioned.

The etchant composition for copper-containing materials according to any one of claims 1 to 3, wherein R ² in General Formula (2) is a propylene group.

In the patterning of the copper-containing material having a thickness of 1 to 10 µm and an etching space of 1 to 10 µm, the etching agent composition according to any one of claims 1 to 4 is used. .