CN101498000B - Etching agent composition for copper-containing material - Google Patents
Etching agent composition for copper-containing material Download PDFInfo
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- CN101498000B CN101498000B CN2008101074562A CN200810107456A CN101498000B CN 101498000 B CN101498000 B CN 101498000B CN 2008101074562 A CN2008101074562 A CN 2008101074562A CN 200810107456 A CN200810107456 A CN 200810107456A CN 101498000 B CN101498000 B CN 101498000B
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
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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
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- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The invention provides an etchant composition for copper containing material for producing printed wiring board (or film) for preventing bad form of circuit wiring of fine pattern without short circuit. The composition is characterized that: the composition is composed of (A) 0.1-15 mass % of oxidizer ingredient selected from at least one of copper ion and iron ion, (B) 0.001-5 mass % of glycol ether compound having one hydroxide radical; (C), 0.001-5 mass % of compound obtained by adding at least one of epoxy ethane and propylene oxide into (multivariate) aminated compounds; (D), 0.1-5 mass % of phosphoric acid ingredient selected from at least one of phosphoric acid and phosphate; and (E) 0.1-10 mass % of inorganic acid selected from at least one of hydrochloric acid and sulfuric acid as the necessary ingredients.
Description
Technical field
The present invention relates to a kind of etching agent composition for copper-containing material, particularly a kind ofly can shape carry out etched etching agent composition for copper-containing material to the circuit layout of fine pattern well.
Background technology
The PC board (or film) that the surface is formed with circuit is widely used in installing electronic unit and semiconductor element etc.And, be accompanied by the miniaturized of electronics in recent years and the requirement of multifunction, the slimming of expectation PC board (or film) and the densification of circuit layout.As the method that forms such high-density circuit distribution through wet etching, have to be called the method that deducts (サ Block ト ラ Network テ イ Block) method and false add one-tenth (セ ミ ア デ イ テ イ Block) method.
In order to form the circuit layout of fine pattern, the ideal state is: etching part does not have residual film; The side of the circuit layout of seeing from the top is that the section of straight line (rectilinearity), circuit layout is a rectangle; Demonstrate high etching factor.But, in the reality, can produce the shape defect of circuit layouts such as etching factor that residual film and linear entanglement, side direction etching, end eclipse (ア Application ダ one カ Star ト), distribution upper width cause for a short time is low.Therefore, hope that wet etching can suppress these shape defects.
Reported and multiplely improved the technology of aforesaid circuit layout shape defect through the composition of etching agent composite is worked hard.
For example; A kind of method of utilizing semi-additive process to form circuit pattern is disclosed in the patent documentation 1; Wherein, said semi-additive process used with divalent iron ion, hydrochloric acid, copper-bearing materials etching promotor and copper-bearing materials etching suppressor factor as oxygenant serve as must composition etching agent composite.At this,, for example have: the compound that addition propylene oxide and oxyethane obtain on the active hydrogen base of aminated compounds as copper-bearing materials etching suppressor factor.In addition, disclose in this etching agent composite, the composition as the cleaning effect that makes the copper surface, leveling characteristics improve can cooperate phosphoric acid.
In addition, disclose the etching agent composite of a kind of copper or copper alloy in the patent documentation 2, wherein, said etching agent composite is by the oxygenant that contains copper; With the acid that is selected from hydrochloric acid and the organic acid salt; Constitute with the aqueous solution of polymkeric substance in the multipolymer that is selected from polyalkylene glycol and polyamine and polyalkylene glycol, and can suppress lateral etch, distribution top attenuates.At this,, cupric ion and iron ion have been enumerated as the oxygenant of copper.Have again,, enumerated cupric chloride (II), cupric bromide (II) and verditer (II) as the compound that produces this cupric ion; Have again,, enumerated 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.Further; As the multipolymer of polyamine and polyalkylene glycol, enumerated: the multipolymer of quadrol, NSC 446, Triethylenetetramine (TETA), tetren, penten or N-ethylethylenediamine and polyoxyethylene glycol, W 166 or SYNPERONIC PE/F68.
In addition; A kind of etching agent composite is disclosed in the patent documentation 3; Wherein, Said etching agent composite by contain the oxidative metal ion source and be selected from mineral acid and organic acid at least a acid and only contain nitrogen-atoms as the heteroatomic azole of intra-annular and be selected from glycol and glycol ethers at least a aqueous solution constitute, and can suppress the generation of end eclipse.At this,, cupric ion and iron ion have been enumerated as the oxidative metal ion source.Have again,, enumerated phosphoric acid as acid.Further, as glycol ethers, enumerated: dihydroxypropane single-ether, ethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, dipropylene glycol methyl ether, and diethylene glycol butyl ether.
Patent documentation 1: the spy opens the 2003-138389 communique
Patent documentation 2: the spy opens the 2004-256901 communique
Patent documentation 3: the spy opens the 2005-330572 communique
Summary of the invention
But, when forming the circuit layout of fine pattern, utilize the thin compound of disclosed etching reagent in patent documentation 1 and 2, can not be with copper etching equably, problem such as therefore can produce the shape defect (for example, linear bad) of circuit layout and be short-circuited.In addition, patent documentation 3 disclosed etching agent composites, bad dispersibility, therefore can produce following problem: the fluidity of taking off by fine pattern worsens caused circuit layout shape defect (for example, part end eclipse) and causes circuit to peel off; And cause problem such as be short-circuited from the sludge of the salt of phosphoric acid and copper or iron.
The present invention carries out in order to address the above problem, and its purpose is to provide a kind of etching agent composition for copper-containing material, and it can be made the shape defect of the circuit layout that prevents fine pattern, can not produce the PC board (or film) of short circuit.
The inventor etc. have carried out wholwe-hearted research in order to address the above problem, and the result finds that the etching agent composition for copper-containing material with specific cooperation composition can address the above problem, and accomplishes the present invention thus.
Promptly; Etching agent composition for copper-containing material of the present invention is characterised in that, by be selected from (A) compound 0.001～5 quality %, (D) that obtain at least a oxidizer composition 0.1～15 quality % in cupric ion and the iron ion, glycol ethers compound 0.001～5 quality % that (B) has 1 hydroxyl, (C) active hydrogen with at least a adding to (polynary) aminated compounds in oxyethane and the propylene oxide be selected from phosphoric acid and the phosphoric acid salt at least a kind phosphate compsn 0.1～5 quality % and (E) be selected from least a mineral acid 0.1～10 quality % in hydrochloric acid and the sulfuric acid serve as must composition the aqueous solution constitute.
According to the present invention, a kind of etching agent composition for copper-containing material can be provided, it can be made the shape defect of the circuit layout that prevents fine pattern, not produce the PC board (or film) of short circuit.
Embodiment
Etching agent composition for copper-containing material of the present invention (below be called " etching agent composite ") is to be selected from least a oxidizer composition in cupric ion and the iron ion with (A); (B) has the glycol ethers compound of 1 hydroxyl; (C) compound that obtains on the active hydrogen with at least a adding to (polynary) aminated compounds in oxyethane and the propylene oxide; (D) be selected from least a kind phosphate compsn in phosphoric acid and the phosphoric acid salt; And at least a mineral acid that (E) is selected from hydrochloric acid and the sulfuric acid is the aqueous solution of necessary composition.
(A) oxidizer composition (below be called " (A) composition ") thus having the copper-bearing materials of making oxidation carries out etched effect.As (A) composition, can distinguish independent use cupric ion and iron ion or they are mixed use.Through cooperating copper (II) compound and iron (III) compound respectively, can make and contain these cupric ions and iron ion in the etching agent composite as supply source.
As copper (II) compound, for example can enumerate: cupric chloride (II), cupric bromide (II), copper sulfate (II) and verditer (II) etc.In addition, as iron (III) compound, for example can enumerate: iron(ic)chloride (III), iron bromide (III), ferric iodide (III), ferric sulfate (III), iron nitrate (III) and iron acetate (III) etc.These compounds can use separately, also can mix two or more uses.In addition, in these compounds, from the stability of cost, etching agent composite and the controlled of etching speed, preferred cupric chloride (II), copper sulfate (II) and iron(ic)chloride (III), more preferably copper sulfate (II) and iron(ic)chloride (III).
The concentration of (A) composition in the etching agent composite is scaled 0.1～15 quality % with ion, is preferably 1～10 quality %.At this, so-called ion converts, and when using cupric ion or iron ion separately, is meant that cupric ion converts or iron ion converts; When mix using cupric ion and iron ion, be meant that the two ion of cupric ion and iron ion converts.(A) during the concentration less than 0.1 quality % of composition, etching period is elongated, therefore can produce the problem that resist is aging and productivity reduces.In addition, in the subraction, the etch effect on the Ni at the copper back side, Cr blocking layer reduces, so residual removing property of the film reduction of copper.On the other hand, when (A) concentration of composition surpasses 15 quality %, can not control etching speed, therefore, etching factor reduces.
(B) the glycol ethers compound (below be called " (B) composition ") that has 1 hydroxyl has and improves the infiltrative effect of etching agent composite to the circuit layout pattern, and the effect that reduces the delay of the etching agent composite around the circuit layout.Thus, can make etching agent composite promote etching and homogenizing.
(B) composition is to have 1 hydroxyl, and remaining 1 compound that hydroxyl is obtained by etherificate in the diol compound.As (B) composition, for example can enumerate: 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, DPG monomethyl ether, DPG list ether, DPG monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ether and 3-methyl 3-methoxyl group-low-molecular-weight diol ether compounds such as 3-methoxybutanol; And poly glycol monomethyl ether, polyethyleneglycol ether, and macromolecule diol ether compound such as polyoxyethylene glycol monobutyl ether.These compounds can use separately, also can mix more than 2 kinds and use.In addition, in these compounds, the additive effect of low-molecular-weight diol ether compound is good, and is therefore preferred.
The concentration of (B) composition is 0.001～5 quality % in the etching agent composite, is preferably 0.1～2.5 quality %.(B) during the concentration less than 0.001 quality % of composition, can not obtain through cooperating the desirable effect of (B) composition.On the other hand, when (B) concentration of composition surpassed 5 quality %, it is big that the viscosity of etching agent composite becomes, and therefore can produce to take off that fluidity worsens and rectilinearity is bad.
(C) at least one compound that obtains in addition of ethylene oxide and the propylene oxide (below be called " (C) composition ") on the active hydrogen of (polynary) aminated compounds; Have and improve the infiltrative effect of etching agent composite, and reduce the effect that the etching agent composite around the circuit layout is detained the circuit layout pattern.And it has affinity to copper, therefore also works as the etching suppressor factor.Therefore, can give etching agent composite improves linear effect, suppresses the effect of lateral etch, the effect of inhibition end eclipse, the effect that inhibition distribution upper width reduces etc.
(polynary) aminated compounds as (C) composition is provided for example has: monoethanolamine, diethylolamine, trolamine, monoisopropanolamine, HSDB 338, tri-isopropanolamine, ethanol Yi Bingchunan, di-alcohol Yi Bingchunan, and alkanolamine such as ethanol diisopropanolamine; These alkanolamines are carried out alkyl replace the alkyl alkanolamine that obtains; The compound of formula (1) expression; (polynary) amine of formula (1) expression is carried out alkanol replace the alkanol alkylidene group polyamine that obtains etc.
[changing 1]
In the above-mentioned formula (1), R
1～R
4Be the alkyl of hydrogen or carbonatoms 1～4, and R
1～R
4In at least one be hydrogen; R
5It is the alkylidene group (ア Le カ Application ジ イ Le) of carbonatoms 1～8; N is 0～6 number.
At this, as R
1～R
4Alkyl, for example can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec.-butyl and the tertiary butyl.In addition, as R
5Alkane two bases; For example have: methylene radical, ethylidene, propylidene, methyl ethylidene, butylidene, 1-methyl propylidene, 2-methyl propylidene, 1; 2-dimethyl-propylidene, 1; 3-dimethyl-propylidene, 1-methyl butylidene, 2-methyl butylidene, 3-methyl butylidene, 4-methyl butylidene, 2,4-dimethyl-butylidene, 1,3-dimethyl-butylidene, pentylidene, hexylidene, inferior heptyl and octylene.
When using with oxyethane and propylene oxide that the two adds to the compound that obtains on the active hydrogen of (polynary) aminated compounds, the not special in proper order restriction of the addition to (polynary) aminated compounds of these oxide compounds.In addition, this addition can be the block addition, also can be random addition.In addition, the mol ratio that adds proportional optimization ethylene oxide and propylene oxide of oxyethane and propylene oxide is 95: 5～10: 90.In addition, the addition amount of oxyethane can be 10～80 quality % of the molecular weight of gained addition compound, under the situation of paying attention to control foaming, is preferably 10～50 quality %.
The characteristic of calm etching agent composite easy to control is set out; (C) compound that on the active hydrogen of quadrol, obtains of preferred propylene oxide of composition and ethylene oxide block addition more preferably has the compound that on the propylene oxide adduct of quadrol addition has ethylene oxide structure.
For (C) composition,, can further control the characteristic of etching agent composite through changing molecular weight.Particularly, molecular weight (below, short of exception, the molecular weight in this specification sheets is meant number-average molecular weight) less than 4000 o'clock, the etching restraining effect significantly improved.In addition, molecular weight was greater than 4000 o'clock, and the dispersiveness and the perviousness of etching agent composite uprise, and the delay of the etching agent composite around the circuit layout prevents that effect from significantly improving.But molecular weight was less than 2000 o'clock, and perviousness reduces, and can not obtain the desirable delay of etching agent composite sometimes and prevent function.In addition, molecular weight surpasses at 10000 o'clock, and the etching restraining effect reduces, and circuit layout can produce shape defect sometimes.Therefore, (C) molecular weight of composition is preferably 2000～10000, and more preferably 2500～7000.
Particularly, as far as (C) composition, when the addition amount of control molecular weight and oxyethane, the effect of the shape of the circuit layout that not only can be improved can also obtain to suppress the effect of residual film.In order to obtain such effect, molecular weight is preferably 4000～7000, and in addition, the content of oxyethane is preferably 30～50 quality %.
(C) composition can use separately in one, also can mix more than 2 kinds and use.
The concentration of (C) composition is 0.001～5 quality % in the etching agent composite, is preferably 0.01～2 quality %.(C) during the concentration less than 0.001 quality % of composition, can not obtain through cooperating the desirable effect of (C) composition.On the other hand, when (C) concentration of composition surpassed 5 quality %, the pattern form that the interface caused that etching speed reduces, etching agent composite is penetrated into copper and resist is bad etc., and detrimentally affect became big.
(D) phosphate compsn (below be called " (D) composition ") through and as the ester group reaction of the resin or the softening agent against corrosion of resist composition; Make resist softening, have and to suppress the dysgenic effect that bring at interface that said (C) composition is penetrated into copper and resist.
As (D) composition, can distinguish independent use phosphoric acid and phosphoric acid salt, also can mix and use them.As phosphoric acid salt, for example have: sodium phosphate, potassiumphosphate, calcium phosphate and ammonium phosphate.Have, phosphoric acid salt can be any in acid-salt (monohydric salt, dihydric salt), the neutral salt again.(D) in the composition, the above-mentioned effect of phosphoric acid is very excellent, and is therefore preferred.
The concentration of (D) composition is 0.1～5 quality % in the etching agent composite.(D) during the concentration less than 0.1 quality % of composition, can not fully obtain effect through cooperating (D) composition to bring.On the other hand, when (D) concentration of composition surpassed 5 quality %, the etchant combination deposits yields around wiring closet, the distribution was detained, and can not obtain uniform etching, and, can produce the distribution shape defect that causes by separating out again of copper.
(E) mineral acid (below be called " (E) composition ") not only have the copper sull of removing etched copper-bearing materials surface and copper muriatic effect, stablize oxygenant effect, and improve effect to the leveling characteristics of copper-bearing materials, also have the etched effect of promotion.
As (E) composition, can distinguish independent use hydrochloric acid and sulfuric acid, also can mix them and use.
The concentration of (E) composition is 0.1～10 quality % in the etching agent composite.(E) during the concentration less than 0.1 quality % of composition, can not obtain through cooperating the desirable effect of (E) composition.On the other hand, when (E) concentration of composition surpassed 10 quality %, etching was superfluous, can not control etching speed, thereby circuit layout produces shape defect.
With above-mentioned (A)～(E) is the aqueous solution of essential composition, can easily prepare through above-mentioned (A)～(E) composition being dissolved in the water.As the employed water of this aqueous solution, not special restriction, preferred ion exchanged water, pure water, and water that ionic substance and impurity have been removed such as ultrapure water.
In the etching agent composite of the present invention, in the scope that does not diminish effect of the present invention, except that above-mentioned essential composition, can also contain the known any composition that is useful on this purposes.Any composition as such for example has: polyalkylene glycols compound, tensio-active agent, organic acid, amino acids, azole compounds, pyrimidines, thiourea, aminated compounds, alkyl pyrrolidine ketone compounds, organic complex immunomodulator compounds, SEPIGEL 305 compounds, hydrogen peroxide, persulphate, cuprous ion, and ferrous ion.
When using these any compositions, the concentration of any composition in the etching agent composite is usually in the scope of 0.001 quality %～10 quality %.
As polyalkylene glycol compounds, for example can enumerate: with oxyethane and propylene oxide block or random addition at polyoxyethylene glycol, NHD, terepthaloyl moietie, Ucar 35,1,3-butanols and 1, the polyalkylene glycol that obtains on the glycol such as 4-butanols.
As tensio-active agent, for example can enumerate: fluorine such as fluoroalkyl trimethyl-glycine and fluoroalkyl Soxylat A 25-7 are that the nonionic beyond amphoterics, the above-mentioned polyalkylene glycol compounds is a tensio-active agent.
As organic acid, for example have: 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, Hydrocerol A, oxyacetic acid, lactic acid, thionamic acid, nicotinic acid, xitix, NSC 115936, levulinic acid and β-chloropropionic acid etc.
As amino acids, for example have: amino acid and their an alkali metal salt and ammonium salts etc. such as glycocoll, L-Ala, Xie Ansuan, leucine, Serine, phenylalanine, tryptophane, L-glutamic acid, aspartic acid, Methionin, l-arginine and Histidine.
As azole compounds, for example can enumerate: imidazoles, glyoxal ethyline, 2-undecyl-4-methylimidazole, 2-phenylimidazole, and alkyl imidazole such as 2-tolimidazole; Benzimidazoless such as benzoglyoxaline, 2-tolimidazole, 2-undecyl benzoglyoxaline, 2-Phenylbenzimidazole and 2-mercaptobenzimidazole; 1,2,3-triazoles, 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-two (amino methyl) benzotriazole, 1-methyl-benzotriazole, tolyl-triazole, I-hydroxybenzotriazole, 5-methyl isophthalic acid H-benzotriazole and 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-nitro-benzothiazole, 2-amino-6-methoxyl group benzo thiazole and 2-amino-thiazoless such as 6-chloro benzothiazole etc.
As pyrimidines, for example can enumerate: di-amino-pyrimidine, Triaminopyrimidine, tetraminopyrimidine and mercaptopyrimidine etc.
As thiourea, for example can enumerate: thiocarbamide, ethylene thiourea, thiodiglycol, mercaptan etc.
As aminated compounds, for example have: compound, PAH, polyvinyl pyridine and their hydrochloride etc. of diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethylolamine, trolamine, monoisopropanolamine, HSDB 338, tri-isopropanolamine, ethanol Yi Bingchunan, di-alcohol Yi Bingchunan, ethanol diisopropanolamine, above-mentioned general formula (1) expression.
As the alkyl pyrrolidine ketone compounds, for example can enumerate: 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.
As the organic complex immunomodulator compounds, for example can enumerate: YD 30, diethylene triaminepentaacetic acid(DTPA), TTHA, TPHA tetraethylenepentaamine heptaacetic acid, penten eight acetate, NTA and their an alkali metal salt and ammonium salt etc.
As the SEPIGEL 305 compounds, for example can enumerate: SEPIGEL 305, and tertiary butyl acrylic amide sulfonic acid etc.
As persulphate, for example have: ammonium persulphate, Sodium Persulfate, and Potassium Persulphate.
Compound as cuprous ion is provided for example has: cuprous chloride (I), cuprous bromide (I), cuprous sulfate (I), and cuprous hydroxide (I) etc.In addition, the compound as ferrous ion is provided for example has: iron protochloride (II), ferrous bromide (II), iron iodide (II), ferrous sulfate (II), Iron nitrate (II), and ferrous acetate (II) etc.
Use the etching of the copper-bearing materials that etching agent composite of the present invention carries out to use known method to carry out.At this, as the copper-bearing materials that is etched material, for example can enumerate copper alloy and copper such as yellow gold and aluminum-copper alloy, special preferably copper.In addition, the not special restriction of engraving method and condition can be used batch-type, flowing-type, carry out known variety of ways such as auto-control mode according to the redox potential of etching reagent and proportion, acid concentration.
Use in the etching that etching agent composite of the present invention carries out, in order to recover to add sometimes and replenish liquid owing to the loss of carrying out the etching agent composite that etching causes repeatedly.Particularly in the etching of above-mentioned automatic control type, can be filled in the etching system replenishing liquid in advance, and then add in the etching agent composite.Should replenish liquid be the aqueous solution that for example contains (A) composition, (E) composition and water, (A) composition and (E) concentration of composition be their about 3～20 times of concentration in the etching agent composite.In addition, in this additional liquid, can also add as required in the etching agent composite of the present invention is essential or disposable above-mentioned each composition.
Etching agent composite of the present invention is when forming the circuit layout of fine pattern; Can obtain accurate etch effect; Therefore, except that PC board, can also be preferred for requiring subraction, the semi-additive process of the assembling of minuteness space with substrate, COF and TAB purposes.
Embodiment
Below, the present invention will be described in more detail to use embodiment and comparative example.But the present invention is not limited to following embodiment etc.
(embodiment: etching agent composite No.1～No.23)
With below table 1 and described each composition of cooperation mixed of table 2, preparation etching agent composite No.1～No.23.Have again,, add its 5 hydrates in the reality as copper sulfate.In addition, the concentration of (A) composition in the table 1 is the value that converts and obtain through ion.
Table 1
Table 2
ADEKA Pluronic TR-704 (Asahi Denka Co., Ltd.'s manufacturing): propylene oxide and ethylene oxide block are added to the compound (molecular weight 5000, ethylene oxide content 40 quality %) that obtains on the active hydrogen of quadrol
ADEKA Pluronic TR-504 (Asahi Denka Co., Ltd.'s manufacturing): propylene oxide and ethylene oxide block are added to the compound (molecular weight 3000, ethylene oxide content 40 quality %) that obtains on the active hydrogen of quadrol
ADEKA Pluronic TR-702 (Asahi Denka Co., Ltd.'s manufacturing): propylene oxide and ethylene oxide block are added to the compound (molecular weight 3500, ethylene oxide content 20 quality %) that obtains on the active hydrogen of quadrol
(comparative example: etching agent composite a～n)
Through with each composition of cooperation mixed described in the below table 3, prepare etching agent composite No.a～n.Have, (A) concentration of composition is the value that converts and obtain through ion again.
Table 3
* the composition of drawing glissade is represented to replace the appointment composition among the present invention and the composition that cooperates.
Use the etching agent composite of the foregoing description and comparative example to carry out following etch processes.(158mm * 100mm) goes up application of liquid resist (PMER-P at the COF tape base material of the thick 9 μ m of copper; Tokyo Ying Huashe makes), and carry out drying, utilize exposure apparatus (UFX-2238 afterwards; ウ シ オ motor society makes), the resist pattern of formation spacing 20 μ m.Secondly, use the etching agent composite that obtains by the foregoing description and comparative example,, spray etching under the condition of pressure 0.05MPa 45 ℃ of temperature.Shape to the gained copper circuit is carried out following evaluation.
(1) rectilinearity
The laser microscope that rectilinearity utilizes キ one エ Application ス society to make is observed and is estimated.This evaluation is divided into 5 grades; Be respectively: be evaluated as " 5 " of the irregular equal less than 1 μ m of live width; 1 μ m is above, being evaluated as of less than 1.7 μ m " 4 "; 1.7 μ m is above, being evaluated as of less than 2.4 μ m " 3 ", 2.4 μ m are above, being evaluated as of less than 3 μ m " 2 ", and 3 μ m are above is evaluated as " 1 ".
(2) distribution upper width
The distribution upper width is by the laser microscope determining image.
(3) etching factor
Etching factor uses following formula to calculate.
In the above-mentioned formula, A representes copper thick (μ m), and T representes that top width (μ m), B represent bottom width (μ m).Have, top width and bottom width are by the laser microscope determining image again.
(4) lateral etch
Lateral etch is estimated with the value of (B-T)/2.Top width and bottom width are by the laser microscope determining image.
(5) end eclipse
End eclipse, is estimated with the value of (T-B)/2 by the laser microscope determining image top width and the bottom width in cross section through for the position that produces end eclipse.Have, what lateral etch did not take place is made as 0 again.
(6) residual film
Residual film is estimated through the observation of laser microscope.This is made as 5 with good in estimating, and bad is made as 1, estimates with 5 grades.
The evaluation result of above-mentioned (1)～(6) is shown in below table 4.
Table 4
| No. | Rectilinearity | Distribution upper width (μ m) | Etching factor | Lateral etch (μ m) | End eclipse (μ m) | Residual film |
| 1 | 4 | 6.2 | 4.5 | 1.8 | 0 | 5 |
| 2 | 4 | 6.5 | 4.9 | 1.6 | 0 | 5 |
| 3 | 4 | 6.2 | 4.5 | 1.8 | 0 | 5 |
| 4 | 4 | 6.5 | 4.9 | 1.6 | 0 | 5 |
| 5 | 4 | 6.5 | 5.0 | 1.6 | 0 | 3 |
| 6 | 4 | 6.5 | 5.0 | 1.6 | 0 | 3 |
| 7 | 5 | 7.4 | 8.0 | 1.0 | 0 | 5 |
| 8 | 5 | 7.2 | 7.5 | 1.1 | 0 | 5 |
| 9 | 5 | 6.4 | 4.8 | 1.7 | 0 | 5 |
| 10 | 5 | 6.2 | 4.5 | 1.7 | 0 | 5 |
| 11 | 5 | 7.0 | 5.9 | 1.8 | 0 | 5 |
| 12 | 5 | 7.8 | 8.2 | 1.4 | 0 | 5 |
| 13 | 5 | 8.0 | 9.1 | 0.9 | 0 | 5 |
| 14 | 5 | 8.0 | 9.1 | 0.9 | 0 | 4 |
| 15 | 5 | 8.2 | 10.2 | 0.8 | 0 | 5 |
| 16 | 4 | 6.6 | 5.1 | 1.6 | 0 | 5 |
| 17 | 3 | 7.0 | 5.9 | 1.8 | 0 | 3 |
| 18 | 4 | 6.2 | 4.5 | 1.7 | 0 | 5 |
| 19 | 5 | 6.2 | 4.5 | 1.7 | 0 | 3 |
| 20 | 4 | 7.5 | 7.1 | 1.2 | 0 | 4 |
| 21 | 4 | 6.2 | 75 | 1.1 | 0 | 5 |
| 22 | 5 | 6.3 | 4.6 | 1.7 | 0 | 3 |
| 23 | 3 | 6.5 | 5.0 | 1.6 | 0 | 3 |
| a | 3 | 1.7 | 2.0 | 4.1 | 0 | 4 |
| b | 2 | 1.7 | 2.0 | 4.1 | 0 | 4 |
| c | 1 | 4.6 | 3.1 | 2.6 | 0 | 4 |
| d | 5 | 1.7 | 2.0 | 4.1 | 0 | 4 |
| e | 5 | 4.4 | 3.0 | 2.7 | 0 | 4 |
| f | 4 | 1.7 | 2.0 | 4.1 | 0 | 4 |
| g | 1 | 4.9 | 3.3 | 2.6 | 0 | 4 |
| h | 2 | 6.2 | 4.6 | 1.8 | 0 | 2 |
| i | 2 | 5.4 | 3.7 | 2.2 | 0 | 2 |
| j | 3 | 5.2 | 3.6 | 2.3 | 1.8 | 3 |
| k | 2 | 4.1 | 3.5 | 2.4 | 1.2 | 2 |
| l | 4 | 3.1 | 2.4 | 3.4 | 0 | 2 |
| m | 2 | 5.1 | 3.5 | 2.4 | 0 | 3 |
| n | 2 | 5.4 | 3.0 | 2.7 | 0 | 3 |
As shown in table 4; Relatively use the evaluation result of the shape of the circuit layout of above-mentioned (1)～(5) in the copper circuit that the etching agent composite (No.1～23) of embodiment forms to be well, (it is poor that the evaluation result of the shape of any circuit layout in the copper circuit of the formation of No.a～n) in above-mentioned (1)～(5) is to use the etching agent composite of comparative example.And the evaluation result of the residual film of No.1～4,7～16,18,20 and 21 above-mentioned (6) is also good.
Therefore, etching agent composite of the present invention can be made the circuit layout shape defect that prevents fine pattern, the PC board (or film) that does not produce short circuit.
Claims (5)
1. an etching agent composition for copper-containing material is characterized in that, by with
(A) be selected from least a oxidizer composition 0.1～15 quality % in cupric ion and the iron ion,
(B) have 1 hydroxyl glycol ethers compound 0.001～5 quality %,
(C) with at least a in oxyethane and the propylene oxide add to compound 0.001～5 quality % that obtains on the active hydrogen of aminated compounds,
(D) be selected from phosphoric acid and the phosphoric acid salt at least a kind phosphate compsn 0.1～5 quality % and
(E) be selected from least a mineral acid 0.1～10 quality % in hydrochloric acid and the sulfuric acid
Aqueous solution formation for necessary composition.
2. etching agent composition for copper-containing material according to claim 1 is characterized in that, said aminated compounds is the polyamine compounds.
3. etching agent composition for copper-containing material according to claim 1 and 2 is characterized in that, said (C) composition is with propylene oxide and ethylene oxide block addition or the random compound that obtains on the active hydrogen of quadrol that adds to.
4. etching agent composition for copper-containing material according to claim 1 and 2 is characterized in that, said (C) composition has 2000～10000 number-average molecular weight.
5. etching agent composition for copper-containing material according to claim 3 is characterized in that, said (C) composition has 2000～10000 number-average molecular weight.
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| EP2537960B1 (en) * | 2010-02-15 | 2015-04-01 | Mitsubishi Gas Chemical Company, Inc. | ETCHING SOLUTION and etching method FOR MULTILAYER THIN FILM HAVING COPPER LAYER AND MOLYBDENUM LAYER CONTAINED THEREIN |
| KR101343729B1 (en) | 2010-02-22 | 2013-12-19 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Method of forming circuits upon flexible laminate substrate |
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| JP5531708B2 (en) * | 2010-03-26 | 2014-06-25 | メック株式会社 | Copper etching solution and substrate manufacturing method |
| CN103222349A (en) | 2010-11-12 | 2013-07-24 | 吉坤日矿日石金属株式会社 | Method for forming circuit on flexible laminate substrate |
| JP5535060B2 (en) * | 2010-12-28 | 2014-07-02 | 株式会社Ａｄｅｋａ | Etching composition for copper-containing material and method for etching copper-containing material |
| TW201250059A (en) * | 2011-03-08 | 2012-12-16 | Nagase Chemtex Corp | Etching liquid |
| CN102330098B (en) * | 2011-08-31 | 2014-01-29 | 东莞市富默克化工有限公司 | Surface treating agent for quickly increasing surface roughness and deoxidizing for circuit board |
| JP5933950B2 (en) * | 2011-09-30 | 2016-06-15 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Etching solution for copper or copper alloy |
| CN104160486B (en) * | 2012-03-13 | 2016-11-02 | 株式会社Adeka | The application of etchant and engraving method |
| JP2014036064A (en) * | 2012-08-08 | 2014-02-24 | Ube Ind Ltd | Method of manufacturing printed circuit board |
| EP2754732B1 (en) * | 2013-01-15 | 2015-03-11 | ATOTECH Deutschland GmbH | Aqueous composition for etching of copper and copper alloys |
| JP6078394B2 (en) * | 2013-03-27 | 2017-02-08 | 株式会社Adeka | Etching solution composition and etching method |
| KR102128061B1 (en) * | 2013-04-05 | 2020-06-29 | 해성디에스 주식회사 | Etchant composition for copper-containing metal film and etching method using the same |
| KR102107476B1 (en) * | 2013-04-10 | 2020-05-07 | 해성디에스 주식회사 | Etchant composition for copper-containing metal film and etching method using the same |
| KR101593110B1 (en) * | 2013-11-21 | 2016-02-11 | 주식회사 익스톨 | Etchant composition with stabilizer for touch screen panel |
| JP6164614B2 (en) | 2013-12-06 | 2017-07-19 | メック株式会社 | Etching solution, replenisher, and method for forming copper wiring |
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| KR101571843B1 (en) * | 2015-06-24 | 2015-11-25 | 진정복 | Nano etching composition for improving the surface adhension |
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| WO2020035982A1 (en) | 2018-08-13 | 2020-02-20 | 株式会社Adeka | Composition and etching method |
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| US11268025B2 (en) * | 2019-06-13 | 2022-03-08 | Fujifilm Electronic Materials U.S.A., Inc. | Etching compositions |
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| KR20090078736A (en) | 2009-07-20 |
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