CN101949013A - Etchant composition for and etching method of materials containing copper - Google Patents

Etchant composition for and etching method of materials containing copper Download PDF

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Publication number
CN101949013A
CN101949013A CN201010218563XA CN201010218563A CN101949013A CN 101949013 A CN101949013 A CN 101949013A CN 201010218563X A CN201010218563X A CN 201010218563XA CN 201010218563 A CN201010218563 A CN 201010218563A CN 101949013 A CN101949013 A CN 101949013A
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China
Prior art keywords
copper
etching
acid
composition
etching agent
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CN201010218563XA
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Chinese (zh)
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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Priority to CN201510670357.5A priority Critical patent/CN105386055B/en
Publication of CN101949013A publication Critical patent/CN101949013A/en
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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 provides an etchant composition for materials containing copper capable of forming micro circuit patterns without bad shapes and an etching method of materials containing copper. The etchant composition for materials containing copper is composed of aqueous solution which comprises (A) at least one 0.1-15% by mass oxidant component selected from copper ion and iron ion, (B) 0.1-20% by mass hydrogen chloride, and (C) 0.001-5% by mass non-ionic surfactant which is shown in the following formula (1) and has 1,500-3,000 number-average molar mass. In the formula (1), R represents alkyl having 8-18 carbon atoms; X represents polypropylene alkyl which is formed by the irregular polymerization or block polymerization of ethylene oxide unit and propylene epoxide. The formula (1) is R-O-X-H.

Description

The engraving method of etching agent composition for copper-containing material and copper-bearing materials
Technical field
The present invention relates to the engraving method of etching agent composition for copper-containing material and copper-bearing materials, relate in detail and can form the etching agent composition for copper-containing material that do not have the fine circuits of shape defect pattern (wiring) and the engraving method of copper-bearing materials.
Background technology
The printed-wiring board (PWB) (or film) that is formed with wiring from the teeth outwards is widely used in installing electronic component and semiconductor element etc.And, follow the miniaturization of electronics and the requirement of multifunction in recent years, also expect its densification and slimming for the wiring of printed-wiring board (PWB) (or film).
As the method for making highdensity wiring is known the method that is called as subraction (サ Block ト ラ Network テ ィ Block method) and semi-additive process (セ ミ ア デ ィ テ ィ Block method) arranged.Because general subraction is the method that forms circuit with wet etching, so operation is few, cost is low, but is 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 of seeing from top is straight line (rectilinearity); The section of wiring is a rectangle; And demonstrate high etching factor (difference of the upper width of wiring and the lower width of wiring is little).But the upper width that in fact can produce residual film, linear mixed and disorderly, side etching, undercutting (ア Application ダ one カ ッ ト) and wiring carefully waits shape defect.Therefore, wish in wet etching, can keep productivity, and suppress these shape defects.
Reported multiple by the composition of etching agent composite being tried every possible means the technology that the shape defect of aforesaid wiring is improved.
For example, disclose the etching solution of a kind of copper or copper alloy in patent documentation 1, wherein said etching solution is made of the aqueous solution, and the described aqueous solution contains: the oxygenant of copper; The acid of from the group of hydrochloric acid and organic acid salt formation, selecting; And at least a polymkeric substance of from the group of polyalkylene glycol and polyamines and polyalkylene glycol multipolymer formation, selecting, the etching solution of described copper or copper alloy can suppress side etching and wiring top attenuates.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 that produces 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 that produces iron ion.In addition, as polyalkylene glycol polyoxyethylene glycol, polypropylene glycol, PEP-101 are disclosed.Polyoxyethylene glycol, polypropylene glycol, the PEP-101 of quadrol, diethylenetriamine, Triethylenetetramine (TETA), tetren, penten, N-ethylethylenediamine etc. are disclosed as polyamines and polyalkylene glycol multipolymer.
In addition, disclose a kind of etching reagent that can suppress undercutting in patent documentation 2, this etching reagent is made of the aqueous solution, and the described aqueous solution contains: the oxidative metal ion source; The acid of from mineral acid or organic acid, selecting; The azole that only contains nitrogen-atoms as the intra-annular heteroatoms; And from two pure and mild glycol ethers, select at least a.At this, cupric ion and iron ion are disclosed as the oxidative metal ion source, hydrochloric acid is disclosed as acid.In addition, disclose as the tensio-active agent that in etching reagent, adds: anion surfactants such as soap, alkyl sulfuric ester salt and alkyl phosphate salt; The nonionic surface active agent such as block polymer of Voranol EP 2001, polyoxypropylene alkyl oxide and polyoxyethylene and polyoxypropylene; And amphotericses such as trimethyl-glycine, aminocarboxylic acid such as lauryl betaine and lauryl hydroxyl sulfo betaine.
Patent documentation 1: Japanese Patent open communique spy open 2004-256901 number
Patent documentation 2: Japanese Patent open communique spy open 2005-330572 number
, the problem that exists of patent documentation 1 and 2 disclosed etching agent composites is: can not obtain can with the abundant corresponding etching performance of fine circuits.Particularly under the situation of the narrow pattern (for example 10 μ m～60 μ m) of the etching space (distance between centers of tracks, gap) that forms removed copper, will produce the shape defect of circuit pattern.
Summary of the invention
In order to address the above problem, to the purpose of this invention is to provide and a kind ofly can form the etching agent composition for copper-containing material of the fine pattern that does not have shape defect and the engraving method of copper-bearing materials.
In order to address the above problem, the inventor etc. have carried out wholwe-hearted research repeatedly, its formation that found that the composition of etching agent composite and fine circuits pattern is closely related, utilization has the etching agent composite of specific composition and uses this etching agent composite to carry out etching, can address the above problem, thereby realize 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 of the aqueous solution, the described aqueous solution contains: (A) at least a oxidizer composition of selecting from cupric ion and iron ion of 0.1～15 quality %; (B) hydrogenchloride of 0.1～20 quality %; And (C) the following general formula of usefulness (1) expression of 0.001～5 quality %, and number-average molecular weight is 500～1,500 nonionic surface active agent;
R-O-X-H (1)
In described general formula (1), R represents that carbonatoms is 8～18 alkyl, 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, is that 10～40 μ m and etching space are the pattern of the copper-bearing materials of 10～60 μ m for forming thickness, uses 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 that does not have 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 of the aqueous solution, and the described aqueous solution contains: (A) at least a oxidizer composition of selecting from cupric ion and iron ion (hereinafter referred to as (A) composition); (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 the copper-bearing materials of making oxidation and carries out etched function, can use the mixture of cupric ion, iron ion or cupric ion and iron ion.They can be allocated copper, copper (II) compound and/or iron (III) compound usually as supply source.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 use separately, also can mix two or more uses.Wherein, from the stability of cost, etching agent composite and the controlled aspect of etching speed, preferably copper, cupric chloride, copper sulfate and iron(ic) chloride, more preferably iron(ic) chloride.
The content of (A) composition is scaled 0.1～15 quality % with cupric ion and/or iron ion in the etching agent composite, preferably 1～10 quality %.If (A) content of composition is less than 0.1 quality %, then cause etching period elongated, resist is aging, productivity reduces thereby cause.In addition, in subraction, because Ni-Cr substrate layer (シ one De at the copper back side
Figure BSA00000172057000041
) etch effect reduce, so remove the mis-behave of the residual film of copper.On the other hand, if (A) content of composition is greater than 15 quality %, then becomes and can not control etching speed, etching factor worsens.
In addition, if cupric ion uses with iron ion, then can control redox potential, proportion, acid concentration and the copper concentration etc. of etching agent composite, thereby can control the etch capabilities of etching agent composite automatically.Content of copper ion in this case is scaled 0.5～10 quality % with cupric ion, preferably 1～10 quality %.If content of copper ion then often can not obtain enough results of use less than 0.5 quality %.On the other hand, if content of copper ion greater than 10 quality %, then often produces sludge in etching agent composite.
(B) function that has of composition is: remove the copper oxide film on etched copper-bearing materials surface and copper muriate, make oxygenant stable and improve levelling property (レ ベ リ Application グ) to copper-bearing materials, (B) composition is to promote etched composition.
(B) component content in the etching agent composite is 0.1～20 quality %, preferably 0.5～10 quality %.If (B) component content then can not obtain enough results of use less than 0.1 quality %.On the other hand, if (B) component content is greater than 20 quality %, then etching is excessive, becomes and can not control etching speed, and wiring can produce shape defect.
(C) composition passes through to improve 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 over-drastic affinities such as the complexing action of copper-bearing materials or coordinations, so can not cause etching speed to reduce the deterioration of isoproductivity.
(C) composition is represented with following general formula (1).
R-O-X-H (1)
In the above-mentioned general formula (1), R represents that carbonatoms is 8～18 alkyl, promptly can be straight chain, also can have side chain.In addition, X is ethylene oxide unit (CH 2-CH 2-O-) with propylene oxide units (CR 1H-CR 2H-O-(R 1And R 2In one be hydrogen atom, another is a methyl) the polyalkylene oxide base that becomes of random polymerization or block polymerization.Wherein, the quantity of the propylene oxide units in the polyalkylene oxide base and ethylene oxide unit is than preferably 0.1～1.If this odds ratio 1 is big, then often can not obtain enough rectilinearity and etching factor.On the other hand, if this odds ratio 0.1 is little, then often can not obtain enough etching factors.This ratio preferred range is 0.25～0.5, if in this scope, it is remarkable then to suppress the effect that the wiring upper width attenuates, and can carry out making the little etching of difference of wiring upper width and wiring lower width.
(C) nonionic surface active agent of composition can be that raw material is made with natural or synthol, oxyethane and propylene oxide usually.R in the above-mentioned general formula (1) is from base natural or that synthol imports.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 one 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 uses.
(C) manufacture method of the nonionic surface active agent of composition is known in this technical field, can also can use the commodity of selling on market by the known method manufacturing.
(C) number-average molecular weight of composition is 500～1,500, if number-average molecular weight less than 500, then can not obtain enough rectilinearity and etching factor.On the other hand, if number-average molecular weight greater than 1,500, then can not obtain enough etching factors.The number-average molecular weight preferred range is 700～1,000, and in this scope, the effect that inhibition wiring top attenuates is remarkable, and the little etching of difference of wiring upper width and wiring lower width can be provided.
If increase the content of (C) composition in etching agent composite, then owing to can improve etching factor and rectilinearity, so have the tendency that circuitry shapes improves, etching speed reduces, the tendency of productivity reduction but can exist on the contrary.Therefore, (C) component content in the 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 effect that circuitry shapes is improved, and the shortcoming that productivity reduces becomes big.On the other hand, if (C) component content then can not obtain enough results of use less than 0.001 quality %.
In etching agent composite of the present invention, in the scope that does not hinder effect of the present invention, except the necessary composition (A)～(C) of above-mentioned explanation, can allocate the known any composition that is used for this purposes into.As having that any composition can exemplify: (B) 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 the ferrous ion beyond the mineral acid beyond the composition, organic acid, glycol ethers compound, (C) composition.Under the situation of using these any compositions, the concentration of these any compositions is generally in the scope of 0.001 quality %～10 quality %.
For example can enumerate as the mineral acid beyond (B) composition: sulfuric acid, nitric acid, phosphoric acid and polyphosphoric acid etc.They can use separately, also can mix two or more uses.
As organic acid, what can exemplify has: carboxylic-acids such as formic acid, acetate, 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 organic sulfonic acid classes such as methylsulfonic acid, ethyl sulfonic acid, 2-ethylenehydrinsulfonic acid, propanesulfonic acid, Phenylsulfonic acid and toluenesulphonic acids.They can use separately, also can mix two or more uses.
As the glycol ethers compound, what can exemplify has: 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, triglycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ether and 3-methyl-low-molecular-weight diol ether compounds such as 3-methoxybutanol; And poly glycol monomethyl ether, polyethyleneglycol ether and the contour molecule glycol ethers of polyoxyethylene glycol monobutyl ether compound.They can use separately, also can mix two or more uses.
As the tensio-active agent beyond (C) composition, what can exemplify has: anion surfactant, with nonionic surface active agent nonionic surface active agent, cats product and the amphoterics etc. in addition of above-mentioned general formula (1) expression.
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; sulfation soap; the alpha-sulfonated fatty hydrochlorate; phosphate ester salt; the sulfuric acid of fatty acid ester; the glyceryl ester sulfuric acid; the sulfonate of fatty acid ester; α-Huang Jizhifangsuanjiazhiyan; the polyoxyalkylene alkyl sulfuric acid; polyoxyalkylene alkyl phenyl ether sulfuric acid; the 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; the polyoxyalkylene sulfosuccinate; the salt of N-acyl group-N methyl taurine; N-acyl glutamic acid or its salt; the acyloxy ethyl sulfonate; alkoxyethyl sulfonate; N-acyl group-Beta-alanine or its salt; N-acyl group-N-propyloic taurine or its salt; N-acyl group-N-carboxymethyl glycine or its salt; acyl-lactate; the mixture of one or more of N-acyl sarcosinate and alkyl or alkenyl aminocarboxylic ylmethyl vitriol etc.
As nonionic surface active agent, what can exemplify has: polyoxyalkylene alkyl, the polyoxyalkylene alkene ether, polyoxyethylene polyoxy-propylene (the addition mode of oxyethane and propylene oxide can be random addition, also can be the block addition), the polyoxyethylene glycol propylene oxide adduct, the polypropylene glycol ethylene oxide adduct, random or the block affixture of the oxyethane of alkylene diamine and propylene oxide, 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-long chain alkyl dimethyl amine oxide etc.
As cats product, what can exemplify has: alkyl (thiazolinyl) leptodactyline, dialkyl group (thiazolinyl) dimethyl ammonium, alkyl (thiazolinyl) quarternary ammonium salt, contain ether, the list of ester group or amide group or dialkyl group (thiazolinyl) quarternary ammonium salt, alkyl (thiazolinyl) pyridinium salt, alkyl (thiazolinyl) dimethyl benzene methyl 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 ゥ ム salt), polyoxypropylene alkyl (thiazolinyl) amine, alkyl (thiazolinyl) amine salt, the polyamines derivative of fatty acid, the 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 ィ Application), amidoamino acid and imidazolinium betaine class tensio-active agent etc.
Above-mentioned tensio-active agent can use separately, also can mix two or more uses.
As amino acids, what can exemplify has: 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 use separately, also can mix two or more uses.
As azole compounds, what can exemplify has: alkyl imidazoles such as imidazoles, glyoxal ethyline, 2-undecyl-4-methylimidazole and 2-phenylimidazole; 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, 1,2, triazole species such as 3-benzotriazole, the amino benzotriazole of 1-, the amino benzotriazole of 4-, 1-diamino Methylbenzotriazole, 1-methyl-benzotriazole, tolyl-triazole, I-hydroxybenzotriazole, 5-methyl isophthalic acid H-benzotriazole, 5-chlorobenzotriazole; 1H-tetrazolium, 5-amino-1H-tetrazolium, 5-methyl isophthalic acid H-tetrazolium, 5-phenyl-1H-tetrazolium, 5-sulfydryl-1H-tetrazolium, 1-phenyl-5-sulfydryl-1H-tetrazolium, 1-cyclohexyl-5-sulfydryl-1H-tetrazolium and 5,5 '-two-tetrazolium classes such as 1H-tetrazolium; And benzothiazole, 2-mercaptobenzothiazole, 2-phenyl thiazole, 2-aminobenzothiazole, 2-amino-6-nitrobenzene thiazole, 2-amino-6-methoxyl group benzo thiazole and 2-amino-thiazoless such as 6-chloro benzothiazole.They can use separately, also can mix two or more uses.
As pyrimidines, what can exemplify has: di-amino-pyrimidine, Triaminopyrimidine, tetraminopyrimidine and mercaptopyrimidine etc.They can use separately, also can mix two or more uses.
As thiourea, what can exemplify has: thiocarbamide, ethylene thiourea, thiodiglycol and mercaptan etc.They can use separately, also can mix two or more uses.
As aminated compounds, what can exemplify has: diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, trolamine, monoisopropanolamine, diisopropanolamine (DIPA), tri-isopropanolamine, ethanol Yi Bingchunan, di-alcohol Yi Bingchunan, ethanol diisopropanolamine, PAH, polyvinylpyridine and their hydrochloride etc.They can use separately, also can mix two or more uses.
As the alkyl pyrrolidine ketone compounds, what can exemplify has: N-N-methyl-2-2-pyrrolidone N-, 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 use separately, also can mix two or more uses.
As organic chelated immunomodulator compounds, what can exemplify has: ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentacetic acid (DTPA), triethylenetetramine hexaacetic acid, tetraethylene pentamine seven acetate, five ethene hexamines, eight acetate, nitrilotriacetic acid(NTA) and their an alkali metal salt and ammonium salt etc.They can use separately, also can mix two or more uses.
As the polyacrylamide compounds, what can exemplify has: polyacrylamide and tertiary butyl acrylamide sulfonic acid etc.They can use separately, also can mix two or more uses.
As persalt, what can exemplify has: ammonium persulphate, Sodium Persulfate, Potassium Persulphate, ammoniumper chlorate, sodium perchlorate and potassium perchlorate etc.They can use separately, also can mix two or more uses.
As inorganic salt, what can exemplify has: sodium-chlor, Repone K, ammonium chloride, bicarbonate of ammonia, sodium bicarbonate, saleratus, volatile salt, yellow soda ash, salt of wormwood, ammonium sulfate, sodium sulfate, vitriolate of tartar, SODIUMNITRATE, saltpetre, ammonium nitrate, ammonium chlorate, sodium chlorate and Potcrate etc.They can use separately, also can mix two or more uses.
As the compound that cuprous ion is provided, what can exemplify has: cuprous chloride (I), cuprous bromide (I), cuprous sulfate (I) and cuprous hydroxide (I) etc.In addition, as the compound that ferrous ion is provided, 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 use separately, also can mix two or more uses.
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, can use known mixing device to mix.
The proportion of the etching agent composite of the present invention that obtains so preferably 1.050～1.200.If proportion less than 1.050, then often can not obtain enough etching speeds.On the other hand, if proportion 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 effect of inhibition shape defect and the viewpoint of etching speed, the pattern that is fit to the copper-bearing materials of formation thickness 5～40 μ m and etching space 4～60 μ m, the pattern of the copper-bearing materials of the most suitable formation thickness 10～40 μ m and etching space 10～60 μ m.
Use the etching of the copper-bearing materials that etching agent composite of the present invention carries out to adopt known usual method to carry out.As the copper-bearing materials of etched material, what can exemplify has: copper alloy and copper such as yellow gold, aluminum-copper alloy, special preferably copper.In addition, there is no particular limitation for engraving method, can use pickling process or gunite etc., for etching condition, as long as suitably adjust according to the etching agent composite and the engraving method that use.In addition, can use batch-type, flowing-type and carry out known various modes such as auto-control mode according to redox potential, proportion and the acid concentration of etching reagent.
Use in gunite under the situation of etching agent composite of the present invention, preferably: treatment temp is that 30～50 ℃, processing pressure are that 0.05～0.2MPa, treatment time are 20～300 seconds.
In addition, in using the engraving method of etching agent composite of the present invention, in order to recover also can to add additional liquid because of carrying out the liquid properties of the reduction that etching causes repeatedly.Particularly in the engraving method of above-mentioned automatic control mode, can be placed on additional liquid in the etching system in advance, add in the etching agent composite in the stage that liquid properties reduces.Should replenish liquid for example be (A) composition, (B) composition and water, (A) composition and (B) concentration of composition be their about 1～20 times of concentration in the etching agent composite.In addition, in this additional liquid, also can add (C) composition or any composition of etching agent composite of the present invention as required.
Etching agent composite of the present invention is owing to forming the fine pattern that does not have shape defect, so except printed-wiring board (PWB), can also be applicable to the subraction of the base plate for packaging, COF and the TAB purposes that require minuteness space.
Embodiment
Below, the present invention is described in detail by embodiment and comparative example, and still, the present invention is not limited to following embodiment etc.
The nonionic surface active agent that uses in following embodiment and comparative example is illustrated in table 1 and the table 2.
Table 1
Figure BSA00000172057000111
Table 2
Figure BSA00000172057000112
Embodiment 1 and comparative example 1
Nonionic surface active agent shown in table 1 and the table 2, iron(ic) chloride (iron ion), hydrogenchloride, copper (cupric ion) and the water composition according to table 3 is mixed, obtain etching agent composite.In addition, the remainder of the amount of table 3 is a water.
Table 3
Embodiment 2 and comparative example 2
For the test substrate that on the resin matrix of Copper Foil, is formed with dry film photoresist with live width 100 μ m and regulation distance between centers of tracks (etching space) pattern with thickness 20 μ m, the etching agent composite that use obtains in the foregoing description and comparative example sprays etching to described test substrate under defined terms.After this, dipping is 1 minute in the aqueous sodium hydroxide solution (50 ℃) of 5 quality %, removes dry film photoresist.Shape to the copper circuit that obtains is carried out following evaluation.
(1) wiring upper width (top width)
Utilize opticmicroscope that transverse section (observation section) measured.Unit is μ m.
(2) wiring lower width (bottom width)
Utilize opticmicroscope that transverse section (observation section) measured.Unit is μ m.
(3) bottom width and top width is poor
Utilize following formula to obtain.Unit is μ m.
The observed value of the observed value-top width of the poor=bottom width of bottom width and top width
(4) residual film
Observe with the laser microscope that Keyemce company (キ one エ Application ス society) makes, residually have the example of etching part to be decided to be " having ", residually have the example of etching part to be decided to be " nothing " not observing observing.
The result of the above-mentioned evaluation of expression in table 4 and table 5.
Table 4
Figure BSA00000172057000141
Shown in the result of table 4 and table 5, the etching agent composite of numbering 1～10 that use contains the nonionic surface active agent of regulation carries out etched embodiment 2-1～embodiment 2-20, carrying out etched comparative example 2-1～comparative example 2-9 with the etching agent composite of the numbering 11～14 of using the nonionic surface active agent that does not contain regulation compares, can keep top width well, and the difference of bottom width and top width is also little.Particularly carry out among etched embodiment 2-7～embodiment 2-12 at the etching agent composite that uses numbering 4～6, described effect is remarkable.
Embodiment 3 and comparative example 3
Nonionic surface active agent shown in table 1 and the table 2, iron(ic) chloride, hydrogenchloride, copper and the water composition according to table 6 is mixed, obtain etching agent composite.In addition, the remainder of the amount of table 6 is a water.
Table 6
Figure BSA00000172057000151
Embodiment 4 and comparative example 4
Except using the etching agent composite in the foregoing description 3 and comparative example 3, obtain to spray to be etched with, obtained copper circuit by the method identical with embodiment 2 and comparative example 2, at the shape of this copper circuit, carried out the evaluation of above-mentioned (1)～(4).It the results are shown in table 7.
Figure BSA00000172057000161
Shown in the result of table 7, the etching agent composite of numbering 15～18 that use contains the nonionic surface active agent of regulation carries out etched embodiment 4-1～embodiment 4-9, carrying out etched comparative example 4-1～comparative example 4-3 with the etching agent composite of the numbering 19～21 of using the nonionic surface active agent that does not contain regulation compares, 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, the etching agent composition for copper-containing material that can form the fine pattern that does not have shape defect and the engraving method of copper-bearing materials can be provided.

Claims (3)

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