CN105386055A - Etchant composition for copper-containing material and method for etching copper-containing material - Google Patents

Etchant composition for copper-containing material and method for etching copper-containing material Download PDF

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Publication number
CN105386055A
CN105386055A CN201510670357.5A CN201510670357A CN105386055A CN 105386055 A CN105386055 A CN 105386055A CN 201510670357 A CN201510670357 A CN 201510670357A CN 105386055 A CN105386055 A CN 105386055A
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Prior art keywords
copper
etching
acid
containing material
etching agent
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CN201510670357.5A
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CN105386055B (en
Inventor
正元祐次
下泽正和
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Adeka Corp
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Asahi Denka Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/061—Etching masks
    • H05K3/062—Etching masks consisting of metals or alloys or metallic inorganic compounds

Abstract

The invention relates to an etching agent composition for a copper-containing material and etching method for a copper-containing material, providing an etching agent composition for a copper-containing material capable of forming micro-circuit patterns without shape defect. The etching agent composition for the copper-containing material according to this invention is composed of an aqueous solution containing the following components: (A) 0.1 to 0.15 mass% of at least one oxidant component selected from a divalent copper ion and a trivalent ferric ion; (B) 0.1 to 20 mass% of hydrogen chloride; and (C) 0.001 to 5 mass% of a nonionic surfactant represented by the following formula (1) and has an average arithmetic molecular weight of 500 to 1,500 : Formula (1): R-O-X-H (in the formula (1), R represents an alkyl group having carbon numbers of 8 to 18, X represents a polyalkylene oxide group in which the ethylene oxide group unit and an propylene oxide group unit are polymerized in a random form or a block form).

Description

The engraving method of etching agent composition for copper-containing material and copper-bearing materials
The application number that the application is the applying date is on July 6th, 2010, denomination of invention is " engraving method of etching agent composition for copper-containing material and copper-bearing materials " is the divisional application of 201010218563.X patent application.
Technical field
The present invention relates to the engraving method of etching agent composition for copper-containing material and copper-bearing materials, relate to the etching agent composition for copper-containing material of fine circuit pattern (wiring) and the engraving method of copper-bearing materials that can be formed and there is no shape defect in detail.
Background technology
The printed-wiring board (PWB) (or film) being formed with wiring is from the teeth outwards widely used in mounting electronic parts and semiconductor element etc.And in recent years with the miniaturization of electronics and the requirement of multifunction, the wiring for printed-wiring board (PWB) (or film) also expects its densification and slimming.
As manufacturing the method for highdensity wiring there are known be called as the method for subraction (サ Block ト ラ Network テ ィ Block method) and semi-additive process (セ ミ ア デ ィ テ ィ Block method).Because general subraction is the method forming circuit with wet etching, so operation is few, cost is low, but be considered to be not suitable for forming fine circuit pattern.
In order to form fine wiring, it is desirable to: etching part does not have residual film; The wiring side seen from top is straight line (rectilinearity); The section of wiring is rectangle; And demonstrate high etching factor (difference of the upper width of wiring and the lower width of wiring is little).But, in fact can produce the upper width shape defect such as carefully of residual film, linear mixed and disorderly, side etching, undercutting (ア ン ダ ー カ ッ ト) and wiring.Therefore, wish in wet etching, can productivity be kept, and suppress these shape defects.
Report the multiple technology by trying every possible means to improve the shape defect of wiring as above to the composition of etching agent composite.
Such as, Patent Document 1 discloses the etching solution of a kind of copper or copper alloy, wherein said etching solution is made up of the aqueous solution, and the described aqueous solution contains: the oxygenant of copper; The acid selected from the group that hydrochloric acid and organic acid salt are formed; And at least one polymkeric substance selected from the group that polyalkylene glycol and polyamines and polyalkylene glycol copolymers are formed, the etching solution of described copper or copper alloy can suppress side etching and wiring top to attenuate.At this, oxygenant as copper discloses cupric ion and iron ion, disclose cupric chloride (II), cupric bromide (II) and copper hydroxide (II) as the compound producing cupric ion, disclose iron(ic) chloride (III), iron bromide (III), ferric iodide (III), ferric sulfate (III), iron nitrate (III) and iron acetate (III) as the compound producing iron ion.In addition, polyoxyethylene glycol, polypropylene glycol, PEP-101 is disclosed as polyalkylene glycol.Polyoxyethylene glycol, polypropylene glycol, the PEP-101 of quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, NEED etc. is disclosed as polyamines and polyalkylene glycol copolymers.
In addition, Patent Document 2 discloses a kind of etching reagent that can suppress undercutting, this etching reagent is made up of the aqueous solution, and the described aqueous solution contains: oxidative metal ion source; The acid selected from mineral acid or organic acid; As the azole of the heteroatoms in ring only containing nitrogen-atoms; And at least one selected from glycol and glycol ethers.At this, disclose cupric ion and iron ion as oxidative metal ion source, disclose hydrochloric acid as acid.In addition, disclose as the tensio-active agent added in etching reagent: the anion surfactants such as soap, alkyl sulfuric ester salt and alkyl phosphate salt; The nonionic surface active agent such as the block polymer of Voranol EP 2001, polyoxypropylene alkyl ether and polyoxyethylene and polyoxypropylene; And the amphoterics such as trimethyl-glycine, aminocarboxylic acid such as lauryl betaine and lauryl hydroxyl sulfo betaine.
Patent documentation 1: No. 2004-256901, Japanese Laid-Open Patent Publication
Patent documentation 2: No. 2005-330572, Japanese Laid-Open Patent Publication
, disclosed in patent documentation 1 and 2, etching agent composite Problems existing is: can not obtain can corresponding etching performance abundant with fine circuits.Particularly when pattern (such as 10 μm ~ 60 μm) that the etching space (distance between centers of tracks, gap) forming removed copper is narrow, the shape defect of circuit pattern will be produced.
Summary of the invention
In order to solve the problem, the object of this invention is to provide and a kind ofly can form the etching agent composition for copper-containing material of the fine pattern not having shape defect and the engraving method of copper-bearing materials.
In order to solve the problem, the present inventor etc. have carried out wholwe-hearted research repeatedly, it found that the formation of the composition of etching agent composite and fine circuit pattern is closely related, utilization has the etching agent composite of specific composition and uses this etching agent composite to etch, can solve the problem, thus achieve the present invention.
That is, the invention provides a kind of etching agent composition for copper-containing material, it is characterized in that, be made up of the aqueous solution, the described aqueous solution contains: (A) 0.1 ~ 15 at least one oxidizer composition selected from cupric ion and iron ion of quality %; (B) hydrogenchloride of 0.1 ~ 20 quality %; And (C) 0.001 ~ 5 the representing with following general formula (1) of quality %, and number-average molecular weight is the nonionic surface active agent of 500 ~ 1,500;
R-O-X-H(1)
In described general formula (1), R represents that carbonatoms is the alkyl of 8 ~ 18, the polyalkylene oxide base of X representative ring oxirane unit and propylene oxide units random polymerization or block polymerization.
In addition, the invention provides a kind of engraving method of copper-bearing materials, it is characterized in that, be the pattern of the copper-bearing materials of 10 ~ 60 μm for form thickness be 10 ~ 40 μm and etching space, use above-mentioned etching agent composite.
According to the present invention, can provide a kind of and can form the etching agent composition for copper-containing material of the fine pattern not having shape defect and the engraving method of copper-bearing materials.
Embodiment
Etching agent composition for copper-containing material of the present invention (hereinafter referred to as etching agent composite) is made up of the aqueous solution, and the described aqueous solution contains: at least one oxidizer composition (hereinafter referred to as (A) composition) that (A) selects from cupric ion and iron ion; (B) hydrogenchloride (hereinafter referred to as (B) composition); And (C) specially appointed nonionic surface active agent (hereinafter referred to as (C) composition).
(A) composition has and copper-bearing materials is oxidized carry out the function that etches, can use the mixture of cupric ion, iron ion or cupric ion and iron ion.They supply source can be allocated copper, copper (II) compound and/or iron (III) compound usually.As copper (II) compound, what can exemplify has: cupric chloride, cupric bromide, copper sulfate, copper hydroxide and neutralized verdigris etc.As iron (III) compound, what can exemplify has: iron(ic) chloride, iron bromide, ferric iodide, ferric sulfate, iron nitrate and iron acetate etc.They can be used alone, and also can mix two or more use.Wherein, from the stability of cost, etching agent composite and the controlling aspect of etching speed, preferably copper, cupric chloride, copper sulfate and iron(ic) chloride, more preferably iron(ic) chloride.
In etching agent composite, the content cupric ion of (A) composition and/or iron ion are scaled 0.1 ~ 15 quality %, preferably 1 ~ 10 quality %.If (A) content of composition is less than 0.1 quality %, then cause etching period elongated, thus cause that resist is aging, productivity reduces.In addition, in subraction, the Ni-Cr substrate layer (シ ー De Layer due to the copper back side) etch effect reduce, so remove the penalty of the residual film of copper.On the other hand, if the content of (A) composition is greater than 15 quality %, then becomes and can not control etching speed, etching factor worsens.
In addition, if cupric ion uses together with iron ion, then can control the redox potential of etching agent composite, proportion, acid concentration and copper concentration etc., thus automatically can control the etch capabilities of etching agent composite.In this case content of copper ion cupric ion is scaled 0.5 ~ 10 quality %, preferably 1 ~ 10 quality %.If content of copper ion is less than 0.5 quality %, then often can not obtain enough results of use.On the other hand, if content of copper ion is greater than 10 quality %, then often in etching agent composite, sludge is produced.
(B) function that composition has is: remove the muriate of the copper oxide film on etched copper-bearing materials surface and copper, oxygenant is stablized and improves the levelling property (レ ベ リ Application グ) to copper-bearing materials, and (B) composition is the composition promoting etching.
(B) component content in etching agent composite is 0.1 ~ 20 quality %, preferably 0.5 ~ 10 quality %.If (B) component content is less than 0.1 quality %, then can not obtain enough results of use.On the other hand, if (B) component content is greater than 20 quality %, then it is excessive to etch, and becomes and can not control etching speed, and wiring can produce shape defect.
(C) composition is by improving the perviousness of etching agent composite to circuit pattern, and reduces the delay of etching agent composite around circuit pattern, has the effect of giving good circuitry shapes.In addition, because (C) composition does not show the excessive affinity such as the complexing action of copper-bearing materials or coordination, so etching speed can not be caused to reduce the deterioration of isoproductivity.
(C) composition following general formula (1) represents.
R-O-X-H(1)
In above-mentioned general formula (1), R represents that carbonatoms is the alkyl of 8 ~ 18, namely can be straight chain, also can have side chain.In addition, X is ethylene oxide unit (-CH 2-CH 2-O-) and propylene oxide units (-CR 1h-CR 2h-O-(R 1and R 2in one be hydrogen atom, another is methyl) the polyalkylene oxide base that becomes of random polymerization or block polymerization.Wherein, the propylene oxide units in polyalkylene oxide base and the number ratio of ethylene oxide unit preferably 0.1 ~ 1.If this odds ratio 1 is large, then often can not obtain enough rectilinearity and etching factor.On the other hand, if this odds ratio 0.1 is little, then often enough etching factors can not be obtained.The preferred scope of this ratio is 0.25 ~ 0.5, if within the scope of this, then the Be very effective suppressing wiring upper width to attenuate, can carry out the etching that the difference of wiring upper width and wiring lower width can be made little.
(C) nonionic surface active agent of composition usually can with natural or synthol, oxyethane and propylene oxide for raw material manufactures.R in above-mentioned general formula (1) is the base imported from natural or synthol.As this alcohol, what can exemplify has: octanol, 2-Ethylhexyl Alcohol, secondary octanol, isooctyl alcohol, three grades of octanols (the 3rd オ Network タ ノ ー Le), nonyl alcohol, isononyl alcohol, secondary nonyl alcohol, decyl alcohol, secondary decyl alcohol, hendecanol, secondary hendecanol, dodecanol, secondary dodecanol, tridecyl alcohol, different tridecyl alcohol, secondary tridecyl alcohol, tetradecanol, secondary tetradecanol, cetyl alcohol, secondary cetyl alcohol, stearyl alcohol and isooctadecanol etc.R can be a kind of, also can mix two or more use.
(C) manufacture method of the nonionic surface active agent of composition is known in this technical field, can manufacture, also can use the commodity commercially sold by known method.
(C) number-average molecular weight of composition is 500 ~ 1,500, if number-average molecular weight is less than 500, then can not obtain enough rectilinearity and etching factor.On the other hand, if number-average molecular weight is greater than 1,500, then can not obtain enough etching factors.The preferred scope of number-average molecular weight is 700 ~ 1,000, and within the scope of this, the Be very effective suppressing wiring top to attenuate, can provide the etching that the difference of wiring upper width and wiring lower width is little.
If increase the content of (C) composition in etching agent composite, then due to etching factor and rectilinearity can be improved, so have the tendency that circuitry shapes improves, but the tendency that etching speed reduces, productivity reduces can be there is on the contrary.Therefore, (C) component content in etching agent composite is 0.001 ~ 5 quality %, preferably 0.01 ~ 2 quality %, more preferably 0.05 ~ 1 quality %.If (C) component content is greater than 5 quality %, then can not obtain the effect making circuitry shapes improve significantly, and the shortcoming that productivity reduces becomes large.On the other hand, if (C) component content is less than 0.001 quality %, then enough results of use can not be obtained.
In etching agent composite of the present invention, in the scope not hindering effect of the present invention, except necessary composition (A) ~ (C) of above-mentioned explanation, the known any composition for this purposes can be allocated into.What can exemplify as any composition has: tensio-active agent, amino acids, azole compounds, pyrimidines, thiourea, aminated compounds, alkyl pyrrolidine ketone compounds, organic chelated immunomodulator compounds, polyacrylamide compounds, hydrogen peroxide, persalt, inorganic salt, cuprous ion and ferrous ion beyond the mineral acid beyond (B) composition, organic acid, glycol ethers compound, (C) composition.When using these any compositions, the concentration of these any compositions is generally in the scope of 0.001 quality % ~ 10 quality %.
Such as can enumerate as the mineral acid beyond (B) composition: sulfuric acid, nitric acid, phosphoric acid and polyphosphoric acid etc.They can be used alone, and also can mix two or more use.
As organic acid, what can exemplify has: the carboxylic-acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, vinylformic acid, butenoic acid, methylacrylic acid, oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, toxilic acid, fumaric acid, oxysuccinic acid, tartrate, citric acid, oxyacetic acid, lactic acid, thionamic acid, nicotinic acid, xitix, hydroxypivalic acid, levulinic acid and β-chloropropionic acid; And the organic sulfonic acid class such as methylsulfonic acid, ethyl sulfonic acid, 2-ethylenehydrinsulfonic acid, propanesulfonic acid, Phenylsulfonic acid and toluenesulphonic acids.They can be used alone, and also can mix two or more use.
As glycol ethers compound, what can exemplify has: the low-molecular-weight diol ether compounds such as 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, triglycol list ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, Dipropylene glycol mono-n-butyl Ether, Tripropylene glycol monomethyl Ether, tripropylene glycol list ether and 3-methyl-3-methoxybutanol; And the contour molecule glycol ether compound of poly glycol monomethyl ether, polyethyleneglycol ether and polyoxyethylene glycol monobutyl ether.They can be used alone, and also can mix two or more use.
As the tensio-active agent beyond (C) composition, what can exemplify has: nonionic surface active agent, cats product and amphoterics etc. beyond anion surfactant, the nonionic surface active agent that represents with above-mentioned general formula (1).
As anion surfactant, what can exemplify has: higher fatty acid salt, higher alcohol sulfate salt, olefine sulfide salt (sulfuration オ レ Off ィ ン salt), senior alkyl sulfonate, sulfonated α-olefin, sulfate fatty hydrochlorate, alpha-sulfonated fatty hydrochlorate, phosphate ester salt, the sulfuric acid of fatty acid ester, glyceryl ester sulfuric acid, the sulfonate of fatty acid ester, α-sulfofattyacidmethylestersalt, polyoxyalkylene alkyl sulfuric acid, polyoxyalkylene alkyl phenyl ether sulfuric acid, polyoxyalkylene alkyl carboxylate salt, acylated peptide, the sulfuric acid of fatty acid alkyl amide or its oxirane affixture, sulfosuccinic ester, alkylbenzene sulfonate, sulfonated alkyl naphathalene, alkyl benzimidazole sulfonate, polyoxyalkylene sulfosuccinate, the salt of N-acyl-N-methyl taurine, N-acyl glutamic acid or its salt, trimethylammonium sulfonate, alkoxyethyl sulfonate, N-acyl-beta-L-Ala or its salt, N-acyl group-N-propyloic taurine or its salt, N-acyl group-N-carboxymethyl glycine or its salt, acyl-lactate, one or more mixture of N-acyl sarcosinate and alkyl or alkenyl aminocarboxylic ium methosulfate etc.
As nonionic surface active agent, what can exemplify has: polyoxyalkylene alkyl, polyoxyalkylene alkenyl ether, (the addition mode of oxyethane and propylene oxide can be random addition to polyoxyethylene polyoxy-propylene, also can be block addition), polyoxyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, the oxyethane of alkylene diamine and the random of propylene oxide or block affixture, glycerol fatty acid ester or its ethylene oxide adduct, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, alkyl poly glucoside, fatty monoethanol amide or its ethylene oxide adduct, lipid acid-N-methyl single ethanol amide or its ethylene oxide adduct, fatty diglycollic amide or its ethylene oxide adduct, sucrose fatty ester, alkyl (gathering) glyceryl ether, polyglycerol fatty acid ester, cithrol, fatty acid methyl ester ethoxylate and N-alkyl dimethyl amine oxides etc.
As cats product, what can exemplify has: alkyl (thiazolinyl) leptodactyline, dialkyl group (thiazolinyl) dimethyl ammonium, alkyl (thiazolinyl) quarternary ammonium salt, containing ether, the list of ester group or amide group or dialkyl group (thiazolinyl) quarternary ammonium salt, alkyl (thiazolinyl) pyridinium salt, alkyl (thiazolinyl) dimethyl benzyl ammonium salt, alkyl (thiazolinyl) isoquinoline 99.9 salt, dialkyl group (thiazolinyl) alkylbenzyldimethylasaltsum saltsum (ジ ア Le キ Le (ア Le ケ ニ Le) モ Le ホ ニ ウ ム salt), polyoxypropylene alkyl (thiazolinyl) amine, alkyl (thiazolinyl) amine salt, polyamines derivative of fatty acid, amylalcohol derivative of fatty acid, benzalkonium chloride and benzethonium chloride etc.
As amphoterics, what can exemplify has: carboxybetaine, sultaine, phosphoric acid ester trimethyl-glycine (ホ ス ホ ベ タ イ Application), amidoamino acid and imidazolinium betaine class tensio-active agent etc.
Above-mentioned tensio-active agent can be used alone, and also can mix two or more use.
As amino acids, what can exemplify has: the amino acid such as glycine, L-Ala, Valerian propylhomoserin, leucine, Serine, phenylalanine, tryptophane, L-glutamic acid, aspartic acid, Methionin, arginine and Histidine; And their an alkali metal salt and ammonium salt etc.They can be used alone, and also can mix two or more use.
As azole compounds, what can exemplify has: the alkyl imidazoles such as imidazoles, glyoxal ethyline, 2-undecyl-4-methylimidazole and 2-phenylimidazole; The benzimidazoless such as benzoglyoxaline, 2-tolimidazole, 2-undecyl benzoglyoxaline, 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, the triazole species such as the amino benzotriazole of 2,3-benzotriazole, 1-, 4-amino benzotriazole, 1-bis aminomethyl benzotriazole, 1-methyl-benzotriazole, tolyl-triazole, I-hydroxybenzotriazole, 5-methyl isophthalic acid H-benzotriazole, 5-chlorobenzotriazole; Four azoles such as 1H-TETRAZOLE, 5-amino-1H-TETRAZOLE, 5-methyl isophthalic acid H-tetrazolium, 5-phenyl-1H-TETRAZOLE, 5-sulfydryl-1H-TETRAZOLE, 1-phenyl-5-sulfydryl-1H-TETRAZOLE, 1-cyclohexyl-5-sulfydryl-1H-TETRAZOLE and 5,5 '-bis--1H-TETRAZOLE; And the thiazoles such as benzothiazole, 2-mercaptobenzothiazole, 2-phenyl thiazole, 2-aminobenzothiazole, 2-amino-6-nitrobenzothiazole, 2-amino-6-methoxybenzothiazole and 2-amino-6-chloro benzothiazole.They can be used alone, and also can mix two or more use.
As pyrimidines, what can exemplify has: di-amino-pyrimidine, Triaminopyrimidine, tetraminopyrimidine and mercaptopyrimidine etc.They can be used alone, and also can mix two or more use.
As thiourea, what can exemplify has: thiocarbamide, ethylene thiourea, thiodiglycol and mercaptan etc.They can be used alone, and also can mix two or more use.
As aminated compounds, what can exemplify has: diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, Ethanol Isopropanol amine, diethanol-isopropanolamine, ethanol diisopropanolamine, PAH, polyvinylpyridine and their hydrochloride etc.They can be used alone, and also can mix two or more use.
As alkyl pyrrolidine ketone compounds, what can exemplify has: METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-propyl group-2-Pyrrolidone, N-butyl-2-Pyrrolidone, N-amyl group-2-Pyrrolidone, N-hexyl-2-Pyrrolidone, N-heptyl-2-Pyrrolidone and N-octyl group-2-Pyrrolidone etc.They can be used alone, and also can mix two or more use.
As organic chelated immunomodulator compounds, what can exemplify has: ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), triethylenetetramine hexaacetic acid, tetraethylene pentamine seven acetic acid, five ethene hexamine eight acetic acid, nitrilotriacetic acid(NTA) and their an alkali metal salt and ammonium salt etc.They can be used alone, and also can mix two or more use.
As polyacrylamide compounds, what can exemplify has: polyacrylamide and tert-butyl acrylamide sulfonate etc.They can be used alone, and also can mix two or more use.
As persalt, what can exemplify has: ammonium persulphate, Sodium Persulfate, Potassium Persulphate, ammoniumper chlorate, sodium perchlorate and potassium perchlorate etc.They can be used alone, and also can mix two or more use.
As inorganic salt, what can exemplify has: sodium-chlor, Repone K, ammonium chloride, bicarbonate of ammonia, sodium bicarbonate, saleratus, volatile salt, sodium carbonate, salt of wormwood, ammonium sulfate, sodium sulfate, potassium sulfate, SODIUMNITRATE, saltpetre, ammonium nitrate, ammonium chlorate, sodium chlorate and Potcrate etc.They can be used alone, and also can mix two or more use.
As the compound providing cuprous ion, what can exemplify has: cuprous chloride (I), cuprous bromide (I), cuprous sulfate (I) and cuprous hydroxide (I) etc.In addition, as the compound providing ferrous ion, what can exemplify has: iron protochloride (II), ferrous bromide (II), iron iodide (II), ferrous sulfate (II), Iron nitrate (II) and ferrous acetate (II) etc.They can be used alone, and also can mix two or more use.
Etching agent composite of the present invention can be prepared by mentioned component is mixed with water.There is no particular limitation for blending means, and known mixing device can be used to mix.
The proportion of the etching agent composite of the present invention obtained so preferably 1.050 ~ 1.200.If proportion is less than 1.050, then often can not obtain enough etching speeds.On the other hand, if proportion is greater than 1.200, then often rectilinearity reduces.
Etching agent composite of the present invention can form fine pattern on copper-bearing materials, particularly from the view point of the effect and the etching speed that suppress shape defect, be applicable to the pattern of the copper-bearing materials forming thickness 5 ~ 40 μm and etching space 4 ~ 60 μm, the pattern of the copper-bearing materials of the most applicable formation thickness 10 ~ 40 μm and etching space 10 ~ 60 μm.
The etching of the copper-bearing materials using etching agent composite of the present invention to carry out can adopt known usual method to carry out.As by the copper-bearing materials of etching material, what can exemplify has: the copper alloy such as yellow gold, aluminum-copper alloy and copper, particularly preferably copper.In addition, for engraving method, there is no particular limitation, can use pickling process or gunite etc., for etching condition, as long as suitably adjust according to the etching agent composite used and engraving method.In addition, batch-type, flowing-type can be used and carry out the known various modes such as the mode that automatically controls according to the redox potential of etching reagent, proportion and acid concentration.
When using etching agent composite of the present invention in gunite, preferably: treatment temp is 30 ~ 50 DEG C, processing pressure is 0.05 ~ 0.2MPa, the treatment time is 20 ~ 300 seconds.
In addition, in the engraving method using etching agent composite of the present invention, in order to recover the liquid properties because repeatedly carrying out etching the reduction caused, also replenisher can be added.Particularly in the engraving method of above-mentioned automatic control mode, can in advance replenisher be placed in etching system, add in etching agent composite in the stage that liquid properties reduces.This replenisher is such as (A) composition, (B) composition and water, and the concentration of (A) composition and (B) composition is their about 1 ~ 20 times of concentration in etching agent composite.In addition, in this replenisher, also can add (C) composition of etching agent composite of the present invention or any composition as required.
Etching agent composite of the present invention does not have the fine pattern of shape defect owing to being formed, so except printed-wiring board (PWB), can also be applicable to require the base plate for packaging of minuteness space, the subraction of COF and TAB purposes.
embodiment
Below, by embodiment and comparative example, the present invention is described in detail, but the present invention is not limited to following embodiment etc.
The nonionic surface active agent used in following embodiment and comparative example represents in table 1 and table 2.
Table 1
Table 2
embodiment 1 and comparative example 1
Nonionic surface active agent shown in table 1 and table 2, iron(ic) chloride (iron ion), hydrogenchloride, copper (cupric ion) and water are mixed according to the composition of table 3, obtains etching agent composite.In addition, the remainder of the amount of table 3 is water.
Table 3
embodiment 2 and comparative example 2
For the test substrate being formed with the dry film photoresist with live width 100 μm and regulation distance between centers of tracks (etching space) pattern on the resin matrix of Copper Foil with thickness 20 μm, be used in the etching agent composite obtained in above-described embodiment and comparative example, under defined terms, injection etching carried out to described test substrate.After this, dipping 1 minute in the aqueous sodium hydroxide solution (50 DEG C) of 5 quality %, removing dry film photoresist.Following evaluation is carried out to the shape of the copper circuit obtained.
(1) connect up upper width (top width)
Opticmicroscope is utilized to measure transverse section (observation section).Unit is μm.
(2) connect up lower width (bottom width)
Opticmicroscope is utilized to measure transverse section (observation section).Unit is μm.
(3) difference of bottom width and top width
Following formula is utilized to obtain.Unit is μm.
The observed value of the observed value-top width of the difference=bottom width of bottom width and top width
(4) residual film
With Keyemce company (キ ー エ Application ス society) laser microscope that manufactures observes, being decided to be " having ", being decided to be "None" not observing the example remaining etching part observing the example remaining etching part.
The result of above-mentioned evaluation is represented in table 4 and table 5.
Table 4
As shown in the result of table 4 and table 5, the etching agent composite of the numbering 1 ~ 10 of the nonionic surface active agent containing regulation is used to carry out the embodiment 2-1 ~ embodiment 2-20 etched, compared with the comparative example 2-1 ~ comparative example 2-9 using the etching agent composite of the numbering 11 ~ 14 not containing the nonionic surface active agent specified to carry out etching, can keep top width well, and the difference of bottom width and top width is also little.Particularly the etching agent composite of numbering 4 ~ 6 is being used to carry out in the embodiment 2-7 ~ embodiment 2-12 etched, described Be very effective.
embodiment 3 and comparative example 3
Nonionic surface active agent shown in table 1 and table 2, iron(ic) chloride, hydrogenchloride, copper and the water composition according to table 6 is mixed, obtains etching agent composite.In addition, the remainder of the amount of table 6 is water.
Table 6
embodiment 4 and comparative example 4
Except being used in the etching agent composite obtained in above-described embodiment 3 and comparative example 3 and carrying out injection and be etched with, copper circuit is obtained by the method identical with comparative example 2 with embodiment 2, for the shape of this copper circuit, carry out the evaluation of above-mentioned (1) ~ (4).The results are shown in table 7.
As shown in the result of table 7, the etching agent composite of the numbering 15 ~ 18 of the nonionic surface active agent containing regulation is used to carry out the embodiment 4-1 ~ embodiment 4-9 etched, compared with the comparative example 4-1 ~ comparative example 4-3 using the etching agent composite of the numbering 19 ~ 21 not containing the nonionic surface active agent specified to carry out etching, can keep top width well, and the difference of bottom width and top width is also little.
Be appreciated that according to the present invention from above result, can provide and can form the etching agent composition for copper-containing material of the fine pattern not having shape defect and the engraving method of copper-bearing materials.

Claims (3)

1. an etching agent composition for copper-containing material, is characterized in that,
Be made up of the aqueous solution, the described aqueous solution contains:
(A) at least one oxidizer composition selected from cupric ion and iron ion of 0.1 ~ 15 quality %;
(B) hydrogenchloride of 0.1 ~ 20 quality %; And
(C) the representing with following general formula (1) of 0.001 ~ 5 quality %, and number-average molecular weight is the nonionic surface active agent of 500 ~ 1,500;
R-O-X-H(1)
In described general formula (1), R represents that carbonatoms is the alkyl of 8 ~ 18, the polyalkylene oxide base of X representative ring oxirane unit and propylene oxide units random polymerization or block polymerization,
The proportion of described etching agent composite is 1.050 ~ 1.200.
2. etching agent composition for copper-containing material according to claim 1, is characterized in that, the propylene oxide units in the polyalkylene oxide base represented with X in described general formula (1) and the number ratio of ethylene oxide unit are 0.25 ~ 0.5.
3. an engraving method for copper-bearing materials, is characterized in that, is the pattern of the copper-bearing materials of 10 ~ 60 μm, uses the etching agent composite described in claim 1 or 2 for form thickness be 10 ~ 40 μm and etching space.
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