JP2011017053A - Etchant composition for copper-containing material and method for etching copper-containing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an etchant composition for a copper-containing material, which can form a fine pattern without causing a failure in the shape.SOLUTION: The etchant composition for the copper-containing material is formed of an aqueous solution which includes: (A) 0.1-15 mass% of at least one oxidizing agent component selected from a cupric ion and a ferric ion; (B) 0.1-20 mass% of hydrogen chloride; and (C) 0.001-5 mass% of a nonionic surface active agent which is expressed by formula (1): R-O-X-H (wherein R represents a 8-18 C alkyl group; and X represents a polyalkylene oxide group in which an ethylene oxide unit and a propylene oxide unit are polymerized in a random or block form), and has a number average molecular weight of 500-1,500.

Description

  The present invention relates to an etchant composition for copper-containing material and a method for etching a copper-containing material, and more specifically, an etchant composition for copper-containing material and copper that can form a fine circuit pattern (circuit wiring) without a defective shape. The present invention relates to a method for etching a contained material.

A printed wiring board (or film) having circuit wiring formed on the surface is widely used for mounting electronic components, semiconductor elements, and the like. With recent demands for downsizing and higher functionality of electronic devices, it is desired to increase the density and thickness of printed circuit boards (or films) as well.
As a method for manufacturing a high-density circuit wiring, methods called a subtractive method and a semi-additive method are known. In general, the subtractive method is a circuit forming method by wet etching, and thus has a small number of steps and is low in cost. However, it is said that the subtractive method is not suitable for forming a fine circuit pattern.

  In order to form fine circuit wiring, there is no residual film in the etched part, the side surface of the wiring viewed from above is straight (linearity), the circuit wiring has a rectangular cross section, and a high etching factor. It is ideal to show (the difference between the upper width of the circuit wiring and the lower width of the wiring is small), but in reality, shape defects such as residual film, disorder of linearity, side etching, undercut, and narrowing of the upper width of the wiring Happens. For this reason, in wet etching, it is desired to suppress these shape defects while maintaining productivity.

Various techniques for improving the shape defects of the circuit wiring as described above by devising the components of the etchant composition have been reported.
For example, Patent Document 1 discloses at least one acid selected from the group consisting of an acid selected from the group consisting of copper oxidants, hydrochloric acid, and organic acid salts, a polyalkylene glycol, and a copolymer of polyamine and polyalkylene glycol. A copper or copper alloy etching solution is disclosed which is made of an aqueous solution containing a polymer and suppresses side etching and thinning of circuit wiring upper portions. Here, cupric ions and ferric ions are disclosed as copper oxidizing agents, and copper (II) chloride, copper (II) bromide and copper hydroxide are the compounds that generate cupric ions. (II), compounds that generate ferric ions include iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate and iron acetate (III ) Is disclosed. Polyalkylene glycols include polyethylene glycol, polypropylene glycol, and ethylene oxide / propylene oxide copolymers. Polyethylene and polyalkylene glycol copolymers include ethylene diamine, diethylene triamine, triethylene tetramine, tetra Polyethylene glycol, polypropylene glycol, and ethylene oxide / propylene oxide copolymers of ethylene pentamine, pentaethylene hexamine, and N-ethylethylenediamine are disclosed.

  Patent Document 2 contains at least one selected from an oxidizing metal ion source, an acid selected from inorganic acids or organic acids, an azole having only a nitrogen atom as a hetero atom in the ring, glycol and glycol ether. The etching agent which consists of the aqueous solution which suppresses undercut is disclosed. Here, cupric ions and ferric ions are disclosed as the oxidizing metal ion source, and hydrochloric acid is disclosed as the acid. In addition, as surfactants that can be added to the etching agent, anionic surfactants such as fatty acid salts, alkyl sulfate ester salts and alkyl phosphate ester salts, polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, and polyoxyethylene Nonionic surfactants such as block polymers with polyoxypropylene, betaines such as lauryldimethylaminoacetic acid betaine and laurylhydroxysulfobetaine, and amphoteric surfactants such as aminocarboxylic acids are disclosed.

JP 2004-256901 A JP-A-2005-330572

  However, the etching agent compositions disclosed in Patent Documents 1 and 2 have a problem that an etching performance that can sufficiently cope with a fine circuit pattern cannot be obtained. In particular, when a pattern (for example, 10 μm to 60 μm) with a narrow etching space (line-to-line, gap) of copper to be removed is formed, a circuit pattern shape defect occurs.

  The present invention has been made to solve the above-described problems, and provides an etching composition for contained materials and a method for etching a copper-containing material capable of forming a fine pattern without a shape defect. Objective.

  As a result of intensive studies to solve the above problems, the present inventors have found that the composition of the etching agent composition is closely related to the formation of a fine circuit pattern, and the etching agent composition having a specific composition and The inventors have found that the above problem can be solved by etching using this, and have reached the present invention.

That is, the present invention comprises (A) at least one oxidant component selected from cupric ions and ferric ions in an amount of 0.1 to 15% by mass, (B) 0.1 to 20% by mass of hydrogen chloride, and (C) The following general formula:
R—O—X—H (1)
(Wherein R represents an alkyl group having 8 to 18 carbon atoms, X represents a polyalkylene oxide group in which ethylene oxide units and propylene oxide units are randomly or block-polymerized), and the number average molecular weight is It is an etching agent composition for copper containing materials characterized by consisting of the aqueous solution containing 0.001-5 mass% of nonionic surfactant which is 500-1,500.
Moreover, this invention is an etching method of the copper containing material characterized by using said etching agent composition in patterning of the copper containing material of thickness 10-40 micrometers and etching space 10-60 micrometers.

  ADVANTAGE OF THE INVENTION According to this invention, the etching method for containing materials which can form a fine pattern without shape defect and the etching method of a copper containing material can be provided.

The etchant composition for copper-containing material of the present invention (hereinafter referred to as an etchant composition) comprises (A) at least one oxidant component (hereinafter referred to as (A)) selected from cupric ions and ferric ions. Component), (B) hydrogen chloride (hereinafter referred to as component (B)), and (C) an aqueous solution containing a specific nonionic surfactant (hereinafter referred to as component (C)).
(A) A component is a component which has a function which oxidizes a copper containing material, and performs an etching, and using the mixture of a cupric ion, a ferric ion, or a cupric ion and a ferric ion is used. it can. These can usually be blended using copper, a copper (II) compound and / or an iron (III) compound as a supply source. Examples of the copper (II) compound include cupric chloride, cupric bromide, cupric sulfate, cupric hydroxide and cupric acetate. Examples of the iron (III) compound include ferric chloride. , Ferric bromide, ferric iodide, ferric sulfate, ferric nitrate, and ferric acetate. These may be used alone or in combination of two or more. Among these, copper, cupric chloride, cupric sulfate and ferric chloride are preferable, and ferric chloride is more preferable in terms of cost, stability of the etching composition, and controllability of the etching rate.

  Content of (A) component in an etching agent composition is 0.1-15 mass% in conversion of a cupric ion and / or ferric ion, Preferably it is 1-10 mass%. When the content of the component (A) is less than 0.1% by mass, the etching time becomes long, the resist deteriorates, and the productivity decreases. Moreover, in the subtractive method, the etching effect of the Ni—Cr seed layer on the copper back surface is lowered, so that the copper residual film removability is deteriorated. On the other hand, when the content of the component (A) is more than 15% by mass, the etching rate cannot be controlled and the etching factor is deteriorated.

  Moreover, if cupric ions are used together with ferric ions, the oxidation-reduction potential, specific gravity, acid concentration, copper concentration, etc. of the etching composition can be controlled, and the etching ability of the etching composition can be automatically controlled. . In this case, the content of cupric ions is 0.5 to 10% by mass, preferably 1 to 10% by mass in terms of copper ions. If the content of cupric ions is less than 0.5% by mass, sufficient use effects may not be obtained. On the other hand, when the content of cupric ions is more than 10% by mass, sludge may be generated in the etching agent composition.

The component (B) has a function of removing the copper oxide film and copper chloride on the surface of the copper-containing material to be etched, a function of stabilizing the oxidizing agent, and a function of improving the leveling property for the copper-containing material. It is a component that promotes.
Content of (B) component in an etching agent composition is 0.1-20 mass%, Preferably it is 0.5-10 mass%. When the content of the component (B) is less than 0.1% by mass, a sufficient use effect cannot be obtained. On the other hand, when the content of the component (B) is more than 20% by mass, the etching becomes excessive, and the etching rate cannot be controlled, or the circuit wiring has a defective shape.

  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. is there. In addition, the component (C) does not exhibit excessive affinity such as complexation or coordination with the copper-containing material, so that productivity does not deteriorate such as a decrease in etching speed.

The component (C) is represented by the following general formula (1).
R—O—X—H (1)
In said formula (1), R is a C8-C18 alkyl group, may be linear and may have a branched chain. X represents an ethylene oxide unit (—CH ₂ —CH ₂ —O—) and a propylene oxide unit (—CR ¹ H—CR ² H—O— ( ^one of R ¹ and R ² is a hydrogen atom and the other is The methyl group)) is a polyalkylene oxide group polymerized in a random or block form. Here, the ratio of the number of propylene oxide units to the ethylene oxide units in the polyalkylene oxide group is preferably 0.1-1. If the ratio is greater than 1, sufficient linearity and etching factor may not be obtained. On the other hand, if the ratio is less than 0.1, a sufficient etching factor may not be obtained. A preferable range of the ratio is 0.25 to 0.5, and if it is within this range, the effect of suppressing the narrowing of the upper width of the wiring becomes remarkable, and etching with a small difference between the upper width of the wiring and the lower width of the wiring is given. Can do.

Component (C), a nonionic surfactant, can usually be produced using natural or synthetic alcohols, ethylene oxide, and propylene oxide as raw materials. R in the above formula (1) is a group introduced from a natural or synthetic alcohol. Examples of the alcohol include octanol, 2-ethylhexanol, secondary octanol, isooctanol, tertiary octanol, nonanol, isononanol, secondary nonanol, decanol, secondary decanol, undecanol, secondary undecanol, dodecanol, secondary dodecanol, tridecanol. , Isotridecanol, secondary tridecanol, tetradecanol, secondary tetradecanol, hexadecanol, secondary hexadecanol, stearyl alcohol, and isostearyl alcohol. One type of R may be used, or two or more types may be mixed and used.
(C) The manufacturing method of the nonionic surfactant of a component is well-known in the said technical field, can be manufactured according to a well-known method, and a commercially available thing may be used.

  (C) The number average molecular weight of a component is 500-1,500. When the number average molecular weight is less than 500, sufficient linearity and etching factor cannot be obtained. On the other hand, if the number average molecular weight is more than 1,500, a sufficient etching factor cannot be obtained. The preferable range of the number average molecular weight is 700 to 1,000, and if it is within this range, the effect of suppressing the narrowing of the upper part width of the wiring becomes remarkable, and etching with a small difference between the upper width of the wiring and the lower width of the wiring is given. Can do.

  The component (C) tends to improve the circuit shape by improving the etching factor, improving the linearity, etc. if the content in the etching agent composition is increased, but the etching rate is lowered and the productivity is reduced. It tends to decrease. Therefore, content of (C) component in an etching agent composition is 0.001-5 mass%, Preferably it is 0.01-2 mass%, More preferably, it is 0.05-1 mass%. When the content of the component (C) is more than 5% by mass, a significant improvement in the circuit shape cannot be obtained, and the disadvantage of a decrease in productivity increases. On the other hand, when the content of the component (C) is less than 0.001% by mass, a sufficient use effect cannot be obtained.

  In addition to the essential components (A) to (C) described above, the etching composition of the present invention is blended with known optional components used for the application within a range that does not hinder the effects of the present invention. can do. As optional components, inorganic acids other than component (B), organic acids, glycol ether compounds, surfactants other than component (C), amino acids compounds, azole compounds, pyrimidine compounds, thioureas compounds, amines Compound, alkylpyrrolidone compound, organic chelating compound, polyacrylamide compound, hydrogen peroxide, peracid salt, inorganic salt, cuprous ion, and ferrous ion. The concentration in the case of using these optional components is generally in the range of 0.001% by mass to 10% by mass.

  (B) As inorganic acids other than a component, a sulfuric acid, nitric acid, phosphoric acid, polyphosphoric acid etc. are mentioned, for example. These can be used individually or in mixture of 2 or more types.

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

  Examples of the glycol ether compound 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 mono Ethyl 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 glycol monobutyl ether, tripropylene group Low molecular glycol ether compounds such as coal monomethyl ether, tripropylene glycol monoethyl ether, and 3-methyl-3-methoxy-3-methoxybutanol, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, and polyethylene glycol monobutyl ether A high molecular glycol ether compound is mentioned. These can be used individually or in mixture of 2 or more types.

Examples of the surfactant other than the component (C) include an anionic surfactant, a nonionic surfactant other than the nonionic surfactant represented by the general formula (1), a cationic surfactant, and Examples include amphoteric surfactants.
Examples of the anionic surfactant include higher fatty acid salts, higher alcohol sulfate esters, sulfurized olefin salts, higher alkyl sulfonates, α-olefin sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, and phosphate esters. Salt, sulfate ester of fatty acid ester, glyceride sulfate ester salt, sulfonate salt of fatty acid ester, α-sulfo fatty acid methyl ester salt, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxy Alkylene alkyl ether carboxylates, acylated peptides, sulfate esters of fatty acid alkanolamides or alkylene oxide adducts thereof, sulfosuccinates, alkylbenzene sulfonates, alkyl naphthalene sulfones Acid salt, alkylbenzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N-acyl-N-methyltaurine salt, N-acyl glutamic acid or a salt thereof, acyloxyethane sulfonate, alkoxyethane sulfonate, N- Acyl-β-alanine or its salt, N-acyl-N-carboxyethyltaurine or its salt, N-acyl-N-carboxymethylglycine or its salt, acyl lactate, N-acyl sarcosine salt, and alkyl or alkenylamino One kind or a mixture of two or more kinds such as carboxymethyl sulfate can be exemplified.

  Nonionic surfactants include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene polyoxypropylene alkyl ether (addition form of ethylene oxide and propylene oxide may be random or block) ), Polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, random or block adduct of alkylenediamine with ethylene oxide and propylene oxide, glycerin fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxyethylene sorbitan Fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or ethylene oxide addition , Fatty acid-N-methyl monoethanolamide or its ethylene oxide adduct, fatty acid diethanolamide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl (poly) glycerin ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl Examples thereof include ester ethoxylate and N-long chain alkyldimethylamine oxide.

Examples of the cationic surfactant include alkyl (alkenyl) trimethyl ammonium salt, dialkyl (alkenyl) dimethyl ammonium salt, alkyl (alkenyl) quaternary ammonium salt, mono- or dialkyl (ether group, ester group or amide group). Alkenyl) quaternary ammonium salt, alkyl (alkenyl) pyridinium salt, alkyl (alkenyl) dimethylbenzyl ammonium salt, alkyl (alkenyl) isoquinolinium salt, dialkyl (alkenyl) morphonium salt, polyoxyethylene alkyl (alkenyl) amine, alkyl (alkenyl) Examples thereof include 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, amide amino acid, and imidazolinium betaine surfactant.
Said surfactant 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.

  Examples of the azole compounds include alkyl imidazoles such as imidazole, 2-methylimidazole, 2-undecyl-4-methylimidazole, 2-phenylimidazole, and 2-methylbenzimidazole; benzimidazole, 2-methylbenzimidazole, 2 -Benzimidazoles such as undecylbenzimidazole, 2-phenylbenzimidazole, 2-mercaptobenzimidazole; 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, tri Triazoles such as triazole, 1-hydroxybenzotriazole, 5-methyl-1H-benzotriazole, 5-chlorobenzotriazole; 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl Tetrazole such as -1H-tetrazole, 5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-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-amino-6-chlorobenzo Thiazo Thiazoles such as Le like. 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 the thiourea compound include thiourea, ethylenethiourea, thiodiglycol, and mercaptan. These can be used individually or in mixture of 2 or more types.

  Examples of amine compounds include diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethanolisopropanolamine, diethanolisopropanolamine, ethanol Examples thereof include diisopropanolamine, polyallylamine, polyvinylpyridine, and hydrochlorides thereof. 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, N-amyl-2-pyrrolidone, N -Hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone and the like. These can be used individually or in mixture of 2 or more types.

  Examples of the organic chelating agent compound include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetraethylenepentaminepentaacetic acid, pentaethylenehexamineoctacetic acid, nitrilotriacetic acid, and alkali metal salts and ammonium salts thereof. Is mentioned. These can be used individually or in mixture of 2 or more types.

  Examples of the polyacrylamide compounds include polyacrylamide and t-butylacrylamide sulfonic acid. These can be used individually or in mixture of 2 or more types.

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

  Examples of the inorganic salt include sodium chloride, potassium chloride, ammonium chloride, ammonium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium carbonate, sodium carbonate, potassium carbonate, ammonium sulfate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, Examples thereof include ammonium nitrate, ammonium chlorate, sodium chlorate, and potassium chlorate. These can be used individually or in mixture of 2 or more types.

  Examples of the compound that provides cuprous ions include copper (I) chloride, copper (I) bromide, copper (I) sulfate, and copper hydroxide (I). Examples of compounds that give ferrous ions include iron (II) chloride, iron (II) bromide, iron (II) iodide, iron (II) sulfate, iron (II) nitrate, and iron acetate ( II) and the like. These can be used individually or in mixture of 2 or more types.

The etching agent composition of this invention can be prepared by mixing said component and water. The mixing method is not particularly limited, and mixing may be performed using a known mixing device.
The specific gravity of the thus obtained etching composition of the present invention is preferably 1.050 to 1.200. If the specific gravity is less than 1.050, a sufficient etching rate may not be obtained. On the other hand, if the specific gravity is larger than 1.200, the linearity may be lowered.

  The etchant composition of the present invention can form a fine pattern in a copper-containing material, but in particular, copper having a thickness of 5 to 40 μm and an etching space of 4 to 60 μm from the viewpoint of shape defect suppression effect and etching rate. It is suitable for patterning of contained materials, and is most suitable for patterning of copper-containing materials having a thickness of 10 to 40 μm and an etching space of 10 to 60 μm.

  Etching of the copper-containing material using the etching agent composition of the present invention can be performed by a well-known general method. Examples of the copper-containing material that is the material to be etched include copper alloys such as silver-copper alloys and aluminum-copper alloys, and copper, with copper being particularly preferred. Further, the etching method is not particularly limited, and an immersion method, a spray method, or the like can be used. The etching conditions may be appropriately adjusted according to the etching agent composition to be used and the etching method. In addition, various known methods such as a batch method, a flow method, an oxidation-reduction potential or specific gravity of an etchant, and an auto-control method based on an acid concentration may be used.

When the etching agent composition of the present invention is used in a spray method, the processing temperature is preferably 30 to 50 ° C., the processing pressure is 0.05 to 0.2 MPa, and the processing time is preferably 20 to 300 seconds.
Further, in the etching method using the etching agent composition of the present invention, a replenishing solution may be added in order to recover the deterioration of the solution due to repeated etching. In particular, in the above-described auto-control type etching method, the replenisher is set in advance in the etching apparatus, and is added to the etching agent composition when the liquid has deteriorated. The replenisher is, for example, a component (A), a component (B), and water, and the concentration of the component (A) and (B) is about 1 to 20 times that of the etching agent composition. Moreover, you may add the (C) component or arbitrary component of the etching agent composition of this invention to the said replenishing liquid as needed.

  Since the etching composition of the present invention can form a fine pattern without a defective shape, it can be suitably used for printed circuit boards, package substrates that require fine pitch, and subtractive methods for COF and TAB applications. can do.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited by these.
Nonionic surfactants used in the following Examples and Comparative Examples are shown in Tables 1 and 2.

(Example 1 and Comparative Example 1)
The nonionic surfactant, ferric chloride (ferric ion), hydrogen chloride, copper (cupric ion) and water shown in Table 1 and Table 2 are mixed in the composition shown in Table 3 to produce an etchant composition. Got. In addition, the balance of content of Table 3 is water.

(Example 2 and Comparative Example 2)
Etching obtained in the above examples and comparative examples on a test substrate in which a dry film resist having a line width of 100 μm and a pattern between predetermined lines (etching spaces) was formed on a resin substrate having a copper foil having a thickness of 20 μm Using the agent composition, spray etching was performed under predetermined conditions. Then, it was immersed in 5 mass% sodium hydroxide aqueous solution (50 degreeC) for 1 minute, and the dry film resist was removed. The following evaluation was performed about the shape of the obtained copper circuit.
(1) Wiring top width (top width)
It was measured by a cross section (cross-sectional observation) using an optical microscope. The unit is μm.
(2) Wiring bottom width (bottom width)
It was measured by a cross section (cross-sectional observation) using an optical microscope. The unit is μm.
(3) Difference between bottom width and top width It was determined by the following equation. The unit is μm.
Difference between bottom width and top width = measured value of bottom width−measured value of top width (4) Residual film “Yes” indicates that the remainder of the etched portion was observed by observation using a Keyence laser microscope. What was not observed was defined as “none”.
The results of the evaluation are shown in Tables 4-5.

  As shown in the results of Tables 4 and 5, an etching composition No. containing a predetermined nonionic surfactant was used. In Examples 2-1 to 2-20 in which etching was performed using 1 to 10, etching composition No. 1 containing no predetermined nonionic surfactant was used. Compared to Comparative Examples 2-1 to 2-9 in which etching was performed using 11 to 14, the top width was excellent, and the difference between the top width and the bottom width was small. In particular, the etching composition No. In Examples 2-7 to 2-12 in which etching was performed using 4 to 6, the effect was remarkable.

(Example 3 and Comparative Example 3)
The nonionic surfactant shown in Table 1 and Table 2, ferric chloride, hydrogen chloride, copper and water were mixed in the composition shown in Table 6 to obtain an etchant composition. In addition, the remainder of content of Table 6 is water.

(Example 4 and Comparative Example 4)
The shape of the copper circuit obtained in the same manner as in Example 2 and Comparative Example 2 except that spray etching was performed using the etching agent composition obtained in Example 3 and Comparative Example 3 above. (1) to (4) were evaluated. The results are shown in Table 7.

  As shown in the results of Table 7, the etching composition No. containing a predetermined nonionic surfactant was used. In Examples 4-1 to 4 to 9 where etching was performed using 15 to 18, the etching composition No. 1 containing no predetermined nonionic surfactant was used. Compared to Comparative Examples 4-1 to 4-3 in which etching was performed using 19 to 21, the top width was excellent and the difference between the top width and the bottom width was small.

  As can be seen from the above results, according to the present invention, it is possible to provide an etching composition for contained material and a method for etching a copper-containing material capable of forming a fine pattern without a shape defect.

Claims (3)

(A) 0.1 to 15% by mass of at least one oxidant component selected from cupric ions and ferric ions,
(B) 0.1-20% by mass of hydrogen chloride, and (C) the following general formula:
R—O—X—H (1)
(Wherein R represents an alkyl group having 8 to 18 carbon atoms, X represents a polyalkylene oxide group in which ethylene oxide units and propylene oxide units are randomly or block-polymerized), and the number average molecular weight is Nonionic surfactant which is 500-1,500 0.001-5 mass%
An etching composition for copper-containing materials, comprising an aqueous solution containing   2. The ratio of the number of propylene oxide units to the ethylene oxide units in the polyalkylene oxide group represented by X in the general formula (1) is 0.25 to 0.5. Etching composition for copper-containing material.   A method for etching a copper-containing material, comprising using the etching agent composition according to claim 1 or 2 in patterning a copper-containing material having a thickness of 10 to 40 µm and an etching space of 10 to 60 µm.