CN105386055B - The engraving method of etching agent composition for copper-containing material and copper-bearing materials - Google Patents
The engraving method of etching agent composition for copper-containing material and copper-bearing materials Download PDFInfo
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- CN105386055B CN105386055B CN201510670357.5A CN201510670357A CN105386055B CN 105386055 B CN105386055 B CN 105386055B CN 201510670357 A CN201510670357 A CN 201510670357A CN 105386055 B CN105386055 B CN 105386055B
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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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
The present invention provides the engraving method of a kind of etching agent composition for copper-containing material and copper-bearing materials, can form the fine pattern of no shape defect.The etching agent composition for copper-containing material of the present invention is made of aqueous solution, which contains：(A) at least one oxidizer composition selected in the slave copper ion and iron ion of 0.1~15 mass %；(B) hydrogen chloride of 0.1~20 mass %；And use the following general formula (1) of (C) 0.001~5 mass % represents, and number-average molecular weight is 500~1,500 nonionic surface active agent, in the general formula (1), R represents the alkyl that carbon atom number is 8~18, and X represents ethylene oxide unit and propylene oxide units atactic polymerization or the polyalkylene oxide base of block polymerization.R‑O‑X‑H(1).
Description
It is on July 6th, 2010, entitled " etching agent composition for copper-containing material and cupric the applying date that the application, which is,
The divisional application application No. is 201010218563.X patent applications of the engraving method of material ".
Technical field
The present invention relates to etching agent composition for copper-containing material and the engraving method of copper-bearing materials, being related in detail can be with
Form the etching agent composition for copper-containing material and copper-bearing materials of the fine circuit pattern (wiring) of no shape defect
Engraving method.
Background technology
The printed wiring board (or film) for being formed with wiring on the surface is widely used in installing electronic component and partly lead
Volume elements part etc..Moreover, in recent years with the miniaturization of electronic equipment and the requirement of multifunction, for printed wiring board (or film)
Wiring be also contemplated that its densification and slimming.
It is referred to as subraction (サ Block ト ラ Network テ ィ Block method) as having well known to the method for manufacturing highdensity wiring
And the method for semi-additive process (セ ミ ア デ ィ テ ィ Block method).Since general subraction is with the method for wet etching formation circuit, institute
It is few, at low cost with process, but be considered being not suitable for forming fine circuit pattern.
In order to form fine wiring, it is generally desirable to：Etching part does not have residual film；The wiring side being viewed from above
It is straight line (linearity)；The section of wiring is rectangle；And show the high etching factor (upper width of wiring
And the difference of the lower width of wiring is small).But it can actually generate residual film, linear mixed and disorderly, side etching, undercutting (ア Application
ダ ー カ ッ ト) and wiring upper width carefully wait shape defects.Therefore, it is intended that in wet etching, productivity can be kept,
And inhibit these shape defects.
It has been reported that a variety of ingredients by etching agent composite are tried every possible means come to wiring as described above
The technology that shape defect is improved.
For example, Patent Document 1 discloses the etching solution of a kind of copper or copper alloy, wherein the etching solution is by aqueous solution
It forms, the aqueous solution contains：The oxidant of copper；The acid selected in the group formed from hydrochloric acid and acylate；And from poly- Asia
At least one polymer selected in the group that alkyl diol and polyamines are formed with polyalkylene glycol copolymers, the copper or
The etching solution of copper alloy can inhibit side etching and wiring top to attenuate.Here, the oxidant as copper discloses copper
Ion and iron ion disclose copper chloride (II), copper bromide (II) and Kocide SD (II) as the compound for generating copper ion,
As generate iron ion compound disclose iron chloride (III), ferric bromide (III), ferric iodide (III), ferric sulfate (III),
Ferric nitrate (III) and ferric acetate (III).In addition, disclose polyethylene glycol, polypropylene glycol, epoxy second as polyalkylene glycol
Alkane-epoxy propane copolymer.Ethylenediamine, diethylenetriamines, Sanya are disclosed as polyamines and polyalkylene glycol copolymers
The polyethylene glycol of tetramine, tetren, penten, n-ethylethylenediamine etc., polypropylene glycol, epoxy second
Alkane-epoxy propane copolymer.
In addition, Patent Document 2 discloses a kind of etchant that can inhibit undercutting, the etchant is by aqueous solution structure
Into the aqueous solution contains：Oxidative metal ion source；The acid selected from inorganic acid or organic acid；As the miscellaneous original in ring
The son only azole containing nitrogen-atoms；And at least one selected from glycol and glycol ethers.Here, as oxidisability metal from
Component discloses copper ion and iron ion, and hydrochloric acid is disclosed as acid.In addition, as the surfactant added in etchant
It discloses：The anion surfactants such as fatty acid salt, alkyl sulfate salt and alkyl phosphate salt；Polyoxyethylene alkyl ether,
The nonionic surface active agent such as the block polymer of polyoxypropylene alkyl ether and polyoxyethylene and polyoxypropylene；And bay
The amphoteric surfactantes such as the glycine betaines such as base glycine betaine and lauryl hydroxyl sulfo betaine, amino carboxylic acid.
Patent document 1：Japanese Laid-Open Patent Publication 2004-256901
Patent document 2：Japanese Laid-Open Patent Publication 2005-330572
But etching agent composite disclosed in patent document 1 and 2 the problem is that：Cannot obtain can be with fine electricity
The fully corresponding etching performance in road.Particularly forming the narrow pattern (example of the etching space (line spacing, gap) of copper that is removed
Such as 10 μm~60 μm) in the case of, will generation circuit pattern shape defect.
Invention content
To solve the above-mentioned problems, the object of the present invention is to provide a kind of fine patterns that can form no shape defect
Etching agent composition for copper-containing material and copper-bearing materials engraving method.
To solve the above-mentioned problems, wholwe-hearted research has been repeated in the inventors of the present invention, as a result, it has been found that etchant combination
The formation of the composition and fine circuit pattern of object is closely related, should using the etching agent composite with specific composition and use
Etching agent composite is etched, and can be solved the above problems, it is achieved thereby that of the invention.
That is, the present invention provides a kind of etching agent composition for copper-containing material, which is characterized in that it is made of aqueous solution, it is described
Aqueous solution contains：(A) at least one oxidizer composition selected in the slave copper ion and iron ion of 0.1~15 mass %；(B)
The hydrogen chloride of 0.1~20 mass %；And use the following general formula (1) of (C) 0.001~5 mass % represents, and number-average molecular weight
For 500~1,500 nonionic surface active agent；
R-O-X-H (1)
In the general formula (1), R represents the alkyl that carbon atom number is 8~18, and X represents ethylene oxide unit and epoxy third
Alkane unit atactic polymerization or the polyalkylene oxide base of block polymerization.
In addition, the present invention provides a kind of engraving method of copper-bearing materials, which is characterized in that is 10~40 for forming thickness
μm and etching space be 10~60 μm copper-bearing materials pattern, use above-mentioned etching agent composite.
According to the present invention, a kind of copper-bearing materials etching of fine pattern that can form no shape defect can be provided
The engraving method of agent composition and copper-bearing materials.
Specific embodiment
The etching agent composition for copper-containing material (hereinafter referred to as etching agent composite) of the present invention is made of aqueous solution, described
Aqueous solution contains：(A) at least one oxidizer composition (hereinafter referred to as (A) ingredient) selected from copper ion and iron ion；(B)
Hydrogen chloride (hereinafter referred to as (B) ingredient)；And (C) specially appointed nonionic surface active agent (hereinafter referred to as (C) ingredient).
(A) ingredient has the function of to be etched copper-bearing materials oxidation, can use copper ion, iron ion or copper
The mixture of ion and iron ion.They usually can be using copper, copper (II) compound and/or iron (III) compound as supply
Source is allocated.As copper (II) compound, what can be enumerated has：Copper chloride, copper bromide, copper sulphate, Kocide SD and vinegar
Sour copper etc..As iron (III) compound, what can be enumerated has：Iron chloride, ferric bromide, ferric iodide, ferric sulfate, ferric nitrate and vinegar
Sour iron etc..They may be used singly or in combination of two or more.Wherein, from cost, the stabilization of etching agent composite
Property and etching speed controlling in terms of set out, preferably copper, copper chloride, copper sulphate and iron chloride, more preferably chlorine
Change iron.
The content copper ion of (A) ingredient and/or iron ion are scaled 0.1~15 mass % in etching agent composite, excellent
Choosing is 1~10 mass %.If the content of (A) ingredient is less than 0.1 mass %, cause etching period elongated, so as to cause
Resist aging, productivity reduce.In addition, in subraction, due to the Ni-Cr substrate layer (シ ー De Layer at the copper back side) etching
Effect reduces, so removing the penalty of the residual film of copper removal.On the other hand, if the content of (A) ingredient is more than 15 mass %,
Become unable to control etching speed, etching factor deteriorates.
In addition, if copper ion is used together with iron ion, then can control etching agent composite oxidation-reduction potential,
Proportion, acid concentration and copper concentration etc., so as to automatically control the etch capabilities of etching agent composite.In this case copper
Ion concentration is scaled 0.5~10 mass %, preferably 1~10 mass % with copper ion.If content of copper ion is less than 0.5
Quality % then tends not to obtain enough using effects.On the other hand, it is past if content of copper ion is more than 10 mass %
Toward generating sludge in etching agent composite.
(B) function that ingredient has is：It removes the copper oxidation film on the copper-bearing materials surface being etched and the chloride of copper, make
Oxidant is stable and raising is to the levelability (レ ベ リ Application グ) of copper-bearing materials, and (B) ingredient is the ingredient for promoting etching.
(B) component content in etching agent composite is 0.1~20 mass %, preferably 0.5~10 mass %.If
(B) component content is less than 0.1 mass %, then cannot obtain enough using effects.On the other hand, if (B) component content is big
In 20 mass %, then excess is etched, become unable to control etching speed, wiring can generate shape defect.
(C) ingredient is existed by improving etching agent composite to the permeability of circuit pattern and reduction etching agent composite
Delay around circuit pattern has the effect for assigning good circuitry shapes.Further, since (C) ingredient is not shown to cupric
The excessive compatibility such as the complexing of material or coordination, so the evil of the productivities such as etching speed reduction will not be caused
Change.
(C) ingredient is represented with the following general formula (1).
R-O-X-H (1)
In above-mentioned general formula (1), R represents the alkyl that carbon atom number is 8~18, you can be straight chain, it is possible to have branch.
In addition, X is ethylene oxide unit (- CH2-CH2- O-) and propylene oxide units (- CR1H-CR2H-O-(R1And R2In one be hydrogen
Atom, the other is methyl) atactic polymerization or block polymerization into polyalkylene oxide base.Wherein, the epoxy third in polyalkylene oxide base
The quantity of alkane unit and ethylene oxide unit is than preferably 0.1~1.If the odds ratio 1 is big, tend not to obtain enough
Linearity and etching factor.On the other hand, it if the odds ratio 0.1 is small, tends not to obtain enough etching factors.It should
Ratio preferably ranging from 0.25~0.5, can if in the range, inhibiting to connect up the significant effect that upper width attenuates
To carry out the etching that the difference of wiring upper width and wiring lower width can be made small.
(C) nonionic surface active agent of ingredient usually can be with natural or synthetic alcohol, ethylene oxide and propylene oxide
It is manufactured for raw material.R in above-mentioned general formula (1) is the base imported from natural or synthetic alcohol.As the alcohol, what can be enumerated has：
Octanol, 2-Ethylhexyl Alcohol, two level octanol, isooctanol, three-level octanol (the 3rd オ Network タ ノ ー Le), nonyl alcohol, isononyl alcohol, two level nonyl
Alcohol, decyl alcohol, two level decyl alcohol, tip-nip, two level tip-nip, dodecanol, two level dodecanol, tridecanol, different 13
Alkanol, two level tridecanol, tetradecanol, two level tetradecanol, hexadecanol, two level hexadecanol, stearyl alcohol and different tristearin
Alcohol etc..R can be a kind of, can also mix two or more uses.
(C) manufacturing method of the nonionic surface active agent of ingredient is well known in the technical field, can be by known
Method manufacture, the commodity sold on the market can also be used.
(C) number-average molecular weight of ingredient is 500~1,500, if number-average molecular weight is less than 500, cannot be obtained enough
Linearity and etching factor.On the other hand, if number-average molecular weight is more than 1,500, then enough etching factors cannot be obtained.
The preferred range of number-average molecular weight is 700~1,000, in the range, the significant effect that wiring top is inhibited to attenuate, Ke Yiti
For the small etching of the difference of wiring upper width and wiring lower width.
If increasing content of (C) ingredient in etching agent composite, since etching factor and linearity can be improved,
So with the tendency that circuitry shapes improve, but can be reduced on the contrary there are etching speed, the tendency that productivity reduces.Therefore, it loses
(C) component content in agent composition is carved as 0.001~5 mass %, preferably 0.01~2 mass %, more preferably
0.05~1 mass %.If (C) component content is more than 5 mass %, the effect that circuitry shapes is significantly made to improve cannot be obtained
Fruit, and become larger the shortcomings that productivity reduction.On the other hand, it if (C) component content is less than 0.001 mass %, cannot obtain
Enough to using effect.
In the etching agent composite of the present invention, in the range of the effect for not interfering the present invention, in addition to above description
Other than necessary ingredient (A)~(C), the well known any ingredient for the purposes can be incorporated.It can example as any ingredient
That lifts has：(B) surfactant other than the inorganic acid other than ingredient, organic acid, glycol ethers compound, (C) ingredient, amino
Acid compounds, azole compounds, pyrimidines, thiourea, aminated compounds, alkyl pyrrolidine ketone chemical combination
Object, organic chelated immunomodulator compounds, polyacrylamide compound, hydrogen peroxide, persalt, inorganic salts, cuprous ion and Asia
Iron ion.In the case where using these any ingredients, the concentration of these any ingredients is generally in the matter of 0.001 mass %~10
In the range of amount %.
As the inorganic acid other than (B) ingredient for example,：Sulfuric acid, nitric acid, phosphoric acid and polyphosphoric acid etc..They can
To be used alone, two or more uses can also be mixed.
As organic acid, what can be enumerated has：Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, butenoic acid,
Methacrylate, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, malic acid, tartaric acid,
The carboxylic acids such as citric acid, glycolic, lactic acid, sulfamic acid, niacin, ascorbic acid, 3-hydroxypivalic acid, levulic acid and β-chloropropionic acid
Class；And the organic sulfonic acids class such as methanesulfonic acid, ethanesulfonic acid, 2- ethylenehydrinsulfonic acids, propane sulfonic acid, benzene sulfonic acid and toluenesulfonic acid.They can
To be used alone, two or more uses can also be mixed.
As glycol ethers compound, what can be enumerated has：Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol only son
Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol list ether, triethylene glycol list
Butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, two
The low-molecular-weight diols ethers such as propylene glycol monobutyl ether, Tripropylene glycol monomethyl Ether, tripropylene glycol list ether and 3- methyl -3- methoxybutanols
Compound；And poly glycol monomethyl ether, polyethyleneglycol ether and polyethylene glycol monobutyl ether grade height molecule glycol ether compound.
They may be used singly or in combination of two or more.
As the surfactant other than (C) ingredient, what can be enumerated has：Anion surfactant, with above-mentioned general formula
(1) nonionic surface active agent, cationic surfactant and the both sexes other than the nonionic surface active agent represented
Surfactant etc..
As anion surfactant, what can be enumerated has：Higher fatty acid salt, fatty alcohol sulfate salt, vulcanization alkene
Hydrocarbon salt (vulcanization オ レ Off ィ Application salt), senior alkyl sulfonate, alpha-alkene sulfonate, sulfate fatty hydrochlorate, alpha-sulfonated fatty acid
Salt, phosphate ester salt, the sulfuric acid of aliphatic ester, glyceride sulfuric acid, the sulfonate of aliphatic ester, alpha-sulfo-fatty acid first
Ester salt, polyoxyalkylene alkyl sulfuric acid, polyoxyalkylene alkyl phenyl ether sulfuric acid, polyoxyalkylene alkyl carboxylate,
Acylated peptide, the sulfuric acid of fatty acid alkanol amides or its alkylene oxide addition product, sulfosuccinate, alkylbenzenesulfonate,
Alkylnaphthalene sulfonate, alkyl benzimidazole sulfonate, polyoxyalkylene sulfosuccinate, N- acyl-N-methyl taurines salt,
N- acyl glutamic acids or its salt, trimethylammonium sulfonate, alkoxyethyl sulfonate, N- acyl-betas-alanine or it
Salt, N- acyl groups-N- carboxyethyls taurine or its salt, N- acyl groups-N- carboxymethyls glycine or its salt, acyl-lactate, N-
One or more kinds of mixtures of acyl sarcosinates and alkyl or alkenyl aminocarboxylic ium methosulfate etc..
As nonionic surface active agent, what can be enumerated has：Polyoxyalkylene alkyl, is gathered polyoxyalkylene alkenyl ether
(the addition mode of ethylene oxide and propylene oxide can be random addition or block to ethylene oxide polyoxypropylene alkyl ether
Addition), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, alkylene diamine ethylene oxide and epoxy
Random or block addition product, fatty acid glyceride or its ethylene oxide adduct of propane, sorbitan fatty acid esters,
Polyoxyethylene sorbitan fatty acid esters, alkyl poly glucoside, fatty monoethanol amide or its ethylene oxide add
Into object, aliphatic acid-N- methyl single ethanol amide or its ethylene oxide adduct, fatty diglycollic amide or its epoxy second
Alkane addition product, sucrose fatty ester, alkyl (poly-) glycerin ether, polyglyceryl fatty acid ester, cithrol, fatty acid methyl
Ester ethoxylate and N- alkyl dimethyl amine oxides etc..
As cationic surfactant, what can be enumerated has：Alkyl (alkenyl) leptodactyline, dialkyl group (alkenyl) two
Methyl ammonium salt, alkyl (alkenyl) quarternary ammonium salt, the list containing ether, ester group or amide groups or dialkyl group (alkenyl) quarternary ammonium salt,
Alkyl (alkenyl) pyridiniujm, alkyl (alkenyl) dimethyl benzyl ammonium salt, alkyl (alkenyl) isoquinolin salt, dialkyl group (alkenyl)
Quinoline salt (ジ ア Le キ Le (ア Le ケ ニ Le) モ Le ホ ニ ウ ム salt), polyoxypropylene alkyl (alkenyl) amine, alkyl (alkenyl) amine
Salt, polyamines derivative of fatty acid, amylalcohol derivative of fatty acid, benzalkonium chloride and benzethonium chloride etc..
As amphoteric surfactant, what can be enumerated has：Carboxybetaine, sulfobetaines, phosphate glycine betaine (ホ
ス ホ ベ タ イ Application), amidoamino acid and imidazolinium betaine class surfactant etc..
Above-mentioned surfactant may be used singly or in combination of two or more.
As amino acids, what can be enumerated has：Glycine, alanine, Valerian propylhomoserins, leucine, serine, benzene
The amino acid such as base alanine, tryptophan, glutamic acid, aspartic acid, lysine, arginine and histidine；And their alkali gold
Belong to salt and ammonium salt etc..They may be used singly or in combination of two or more.
As azole compounds, what can be enumerated has：Imidazoles, 2-methylimidazole, 2- undecyls -4-methylimidazole and 2-
The alkyl imidazoles such as phenylimidazole；Benzimidazole, 2- tolimidazoles, 2- undecyls benzimidazole, 2- phenyl benzo miaows
The benzimidazoles such as azoles, 2-mercaptobenzimidazole；1,2,3- triazoles, 1,2,4- triazoles, 5- phenyl -1,2,4- triazoles, 5- amino -
1,2,4- triazoles, l, 2,3 triazole, 1- amino benzotriazole, 4- amino benzotriazole, 1- bis aminomethyls benzotriazole,
1- methyl-benzotriazole, tolyl-triazole, I-hydroxybenzotriazole, 5- methyl-1 H- benzotriazole, 5- chlorobenzotriazoles etc. three
Azole；1H-TETRAZOLE, 5- amino -1H-TETRAZOLE, 5- methyl-1 H- tetrazoliums, 5- phenyl -1H-TETRAZOLE, 5- sulfydryls -1H-TETRAZOLE, 1- benzene
Base -5- sulfydryls -1H-TETRAZOLE, 1- cyclohexyl -5- sulfydryls-four azoles such as 1H-TETRAZOLE and 5,5 '-bis- -1H-TETRAZOLE；And benzo thiophene
Azoles, 2-mercaptobenzothiazole, 2- phenyl thiazoles, 2- aminobenzothiazoles, 2- amino-6-nitrobenzothiazoles, 2- amino -6- first
The thiazoles such as oxygroup benzothiazole and 2- amino -6- chloro benzothiazoles.They can be used alone, and can also mix two or more
It uses.
As pyrimidines, what can be enumerated has：Di-amino-pyrimidine, Triaminopyrimidine, tetraminopyrimidine and mercapto
Yl pyrimidines etc..They may be used singly or in combination of two or more.
As thiourea, what can be enumerated has：Thiocarbamide, ethylene thiourea, thiodiglycol and mercaptan etc..They
It may be used singly or in combination of two or more.
As aminated compounds, what can be enumerated has：Diamylamine, dibutyl amine, triethylamine, triamylamine, monoethanolamine, diethyl
Hydramine, triethanolamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, Ethanol Isopropanol amine, diethanol-isopropanolamine, second
Alcohol diisopropanolamine (DIPA), polyallylamine, polyvinylpyridine and their hydrochloride etc..They can be used alone, and also may be used
To mix two or more uses.
As alkyl pyrrolidine ketone compound, what can be enumerated has：N-methyl-2-pyrrolidone, N- ethyl -2- pyrroles
Alkanone, N- propyl -2-Pyrrolidone, N- butyl -2-Pyrrolidone, N- amyls -2-Pyrrolidone, N- hexyls -2-Pyrrolidone,
N- heptyl -2-Pyrrolidone and N- octyl groups -2-Pyrrolidone etc..They can be used alone, and can also mix two or more
It uses.
As organic chelated immunomodulator compounds, what can be enumerated has：Ethylenediamine tetra-acetic acid, diethylene triamine pentacetic acid (DTPA), three second
Four hexaacetic acid of alkene, seven acetic acid of tetraethylenepentamine, eight acetic acid of pentaethylene hexamine, nitrilotriacetic acid and their alkali metal salt
With ammonium salt etc..They may be used singly or in combination of two or more.
As polyacrylamide compound, what can be enumerated has：Polyacrylamide and tert-butyl acrylamide sulfonate
Deng.They may be used singly or in combination of two or more.
As persalt, what can be enumerated has：Ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, ammonium perchlorate, sodium perchlorate
And potassium hyperchlorate etc..They may be used singly or in combination of two or more.
As inorganic salts, what can be enumerated has：Sodium chloride, potassium chloride, ammonium chloride, ammonium hydrogen carbonate, sodium bicarbonate, bicarbonate
Potassium, ammonium carbonate, sodium carbonate, potassium carbonate, ammonium sulfate, sodium sulphate, potassium sulfate, sodium nitrate, potassium nitrate, ammonium nitrate, ammonium chlorate, chloric acid
Sodium and potassium chlorate etc..They may be used singly or in combination of two or more.
As the compound for providing cuprous ion, what can be enumerated has：Stannous chloride (I), cuprous bromide (I), sulfuric acid are sub-
Copper (I) and cuprous hydroxide (I) etc..In addition, as the compound for providing ferrous ion, what can be enumerated has：Frerrous chloride
(II), ferrous bromide (II), iron iodide (II), ferrous sulfate (II), ferrous nitrate (II) and ferrous acetate (II) etc..It
May be used singly or in combination of two or more.
The etching agent composite of the present invention can be by with water mixing mentioned component to prepare.Mixed method is not special
Restriction, can be mixed using well known mixing arrangement.
The proportion of the etching agent composite of the present invention obtained in this way is preferably 1.050~1.200.If proportion is less than
1.050, then it tends not to obtain enough etching speeds.On the other hand, if proportion is more than 1.200, often linearity drops
It is low.
The etching agent composite of the present invention can form fine pattern on copper-bearing materials, particularly from inhibition shape not
From the perspective of good effect and etching speed, the copper-bearing materials of 4~60 μm of 5~40 μm of thickness and etching space are suitably formed
Pattern is most suitable for being formed the pattern of the copper-bearing materials of 10~60 μm of 10~40 μm of thickness and etching space.
Using the present invention etching agent composite carry out copper-bearing materials etching may be used well known usual method into
Row.As the copper-bearing materials of etched material, what can be enumerated has：The copper alloys such as yellow gold, aluminium copper and copper, especially
It is preferred that copper.In addition, for engraving method, there is no particular limitation, can use infusion process or gunite etc., for etching condition,
As long as according to the etching agent composite and engraving method used suitably adjust.In addition it is possible to use batch-type, flowing
It is various each well known to mode that the formula and oxidation-reduction potential according to etchant, proportion and acid concentration carry out automatically controlling etc.
The mode of sample.
In the case of using the etching agent composite of the present invention in gunite, preferably：Treatment temperature is 30~50
DEG C, processing pressure be 0.05~0.2MPa, processing time is 20~300 seconds.
In addition, in the engraving method of etching agent composite of the present invention is used, in order to restore to make because etching is repeated
Into reduction liquid properties, replenisher can also be added.It, can particularly in the engraving method of above-mentioned automatic control mode
Replenisher is placed in Etaching device in advance, it is added in etching agent composite in the stage that liquid properties reduce.The benefit
They is dense in a concentration of etching agent composite of filling liquid e.g. (A) ingredient, (B) ingredient and water, (A) ingredient and (B) ingredient
1~20 times or so of degree.In addition, can also be added as needed in the replenisher (C) of etching agent composite of the present invention into
Point or any ingredient.
Fine pattern of the etching agent composite of the present invention since no shape defect can be formed, so in addition to track
Other than the plate of road, can be applicable to require the package substrate of fine pitch, COF and TAB purposes subraction.
Embodiment
In the following, by embodiment and comparative example, the present invention is described in detail, and still, the present invention is not limited to following
Embodiment etc..
The nonionic surface active agent used in following embodiments and comparative example is represented in Tables 1 and 2.
Table 1
Table 2
Embodiment 1 and comparative example 1
Shown in Tables 1 and 2 nonionic surface active agent, iron chloride (iron ion), hydrogen chloride, copper (copper ion) with
And water is 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 being formed on the resin matrix of the copper foil with 20 μm of thickness with 100 μm of line width and regulation line spacing
The experiment substrate of the dry film photoresist of (etching space) pattern uses the etchant group obtained in above-described embodiment and comparative example
Object is closed, injection etching is carried out to the experiment substrate under the defined conditions.Hereafter, in the sodium hydrate aqueous solution of 5 mass %
Dipping 1 minute in (50 DEG C), removes dry film photoresist.Following evaluations are carried out to the obtained shape of copper circuit.
(1) wiring upper width (top width)
Cross section (observation section) is measured using light microscope.Unit is μm.
(2) wiring lower width (bottom width)
Cross section (observation section) is measured using light microscope.Unit is μm.
(3) difference of bottom width and top width
It is obtained using following formula.Unit is μm.
The measured value of measured value-top width of bottom width and difference=bottom width of top width
(4) residual film
With (キ ー エ Application ス societies of Keyemce company) laser microscope that manufactures observed, remain etching observing
Partial example is set to " having ", is set to "None" the example that remains etching part is not observed.
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 erosion of the number 1~10 containing defined nonionic surface active agent is used
Embodiment 2-1~embodiment 2-20 that agent composition is etched is carved, defined non-ionic surfactant is not contained with using
Comparative example 2-1~comparative example 2-9 that the etching agent composite of the number 11~14 of agent is etched is compared, and can be kept well
Top width, and the difference of bottom width and top width is also small.Particularly the etching agent composite for using number 4~6 into
In embodiment 2-7~embodiment 2-12 of row etching, the significant effect.
Embodiment 3 and comparative example 3
Nonionic surface active agent, iron chloride, hydrogen chloride, copper and the water shown in Tables 1 and 2 according to the composition of table 6
Mixing, obtains etching agent composite.In addition, the remainder of the amount of table 6 is water.
Table 6
Embodiment 4 and comparative example 4
Other than the etching agent composite obtained in above-described embodiment 3 and comparative example 3 is used to carry out injection etching, lead to
Cross the method identical with embodiment 2 and comparative example 2 and obtained copper circuit, for the shape of the copper circuit, carried out above-mentioned (1)~
(4) evaluation.The results are shown in tables 7.
As shown in the result of table 7, the etchant of the number 15~18 containing defined nonionic surface active agent is used
Embodiment 4-1~embodiment 4-9 that composition is etched does not contain the volume of defined nonionic surface active agent with using
Comparative example 4-1~comparative example 4-3 that numbers 19~21 etching agent composite is etched is compared, and can keep top wide well
Degree, and the difference of bottom width and top width is also small.
It is appreciated that from above result, it is proposed, according to the invention, can provide can form the fine figure of no shape defect
The etching agent composition for copper-containing material of case and the engraving method of copper-bearing materials.
Claims (3)
1. a kind of etching agent composition for copper-containing material, which is characterized in that
It is made of aqueous solution, the aqueous solution contains：
(A) at least one oxidizer composition selected in the slave copper ion and iron ion of 0.1~15 mass %；
(B) hydrogen chloride of 0.1~20 mass %；And
(C) 0.001~5 mass % use the following general formula (1) represent, and number-average molecular weight be 500~1,500 it is non-ionic
Surfactant；
R-O-X-H(1)
In the general formula (1), R represents the alkyl that carbon atom number is 8~18, and X represents ethylene oxide unit and propylene oxide list
First atactic polymerization or the polyalkylene oxide base of block polymerization, wherein, propylene oxide units and ethylene oxide list in polyalkylene oxide base
The quantity ratio of member is 0.1~1,
The proportion of the etching agent composite is 1.050~1.200.
2. etching agent composition for copper-containing material according to claim 1, which is characterized in that X tables are used in the general formula (1)
The quantity ratio of propylene oxide units and ethylene oxide unit in the polyalkylene oxide base shown is 0.25~0.5.
3. a kind of engraving method of copper-bearing materials, which is characterized in that thickness is 10~40 μm and etching space is 10 for being formed
The pattern of~60 μm of copper-bearing materials uses the etching agent composite described in claims 1 or 22.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009162717A JP5443863B2 (en) | 2009-07-09 | 2009-07-09 | Etching composition for copper-containing material and method for etching copper-containing material |
| JP2009-162717 | 2009-07-09 | ||
| CN201010218563XA CN101949013A (en) | 2009-07-09 | 2010-07-06 | Etchant composition for and etching method of materials containing copper |
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| CN201010218563XA Division CN101949013A (en) | 2009-07-09 | 2010-07-06 | Etchant composition for and etching method of materials containing copper |
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| CN201010218563XA Pending CN101949013A (en) | 2009-07-09 | 2010-07-06 | Etchant composition for and etching method of materials containing copper |
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| TW201250059A (en) * | 2011-03-08 | 2012-12-16 | Nagase Chemtex Corp | Etching liquid |
| JP5971246B2 (en) * | 2011-07-04 | 2016-08-17 | 三菱瓦斯化学株式会社 | Etching solution of copper or copper-based compound |
| CN102291952B (en) * | 2011-08-05 | 2013-04-24 | 奥士康精密电路（惠州）有限公司 | Method for preparing multi-layer PCB (printed circuit board) |
| WO2013136624A1 (en) * | 2012-03-13 | 2013-09-19 | 株式会社Adeka | Etching solution composition and etching method |
| SG11201408660QA (en) * | 2012-09-28 | 2015-01-29 | Mec Co Ltd | Microetching agent for copper, supplementary liquid for same, and manufacturing method for circuit board |
| KR102079658B1 (en) * | 2013-04-05 | 2020-02-20 | 해성디에스 주식회사 | Etchant composition for copper-containing metal film and etching method using the same |
| CN105143515B (en) * | 2013-04-16 | 2019-03-08 | Mec股份有限公司 | Etching solution and circuit forming method |
| CN104805441B (en) * | 2013-04-27 | 2017-11-24 | 苏州诺菲纳米科技有限公司 | Etching paste, the application of etching paste and the method using etching paste etching of nano silver conductive material |
| CN104278273A (en) * | 2014-06-13 | 2015-01-14 | 叶涛 | Circuit board low-acid high-efficiency acidic cupric chloride etching solution |
| KR102204210B1 (en) * | 2014-06-27 | 2021-01-18 | 동우 화인켐 주식회사 | Etching solution composition for metal layer and manufacturing method of an array substrate for Liquid crystal display using the same |
| JP6333455B1 (en) * | 2017-08-23 | 2018-05-30 | メック株式会社 | Copper microetching agent and method of manufacturing wiring board |
| CN107460464B (en) * | 2017-08-28 | 2019-11-01 | 厦门大学 | A kind of surface treatment method of copper-bearing materials |
| CN109862706B (en) * | 2019-01-24 | 2020-08-14 | 绍兴市微益电器有限公司 | Circuit board printing process |
| WO2020261995A1 (en) * | 2019-06-28 | 2020-12-30 | 株式会社Adeka | Composition and etching method |
| JP7507041B2 (en) | 2020-08-25 | 2024-06-27 | 株式会社Adeka | Composition, etching method, and method for forming circuit pattern |
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| JP2001181868A (en) * | 1999-12-20 | 2001-07-03 | Asahi Denka Kogyo Kk | Microetching agent for copper and copper alloy |
| JP2001181867A (en) * | 1999-12-20 | 2001-07-03 | Asahi Denka Kogyo Kk | Microetching agent |
| JP4350364B2 (en) * | 2002-12-12 | 2009-10-21 | 昭和電工株式会社 | Cleaning composition, semiconductor wafer cleaning method and manufacturing method |
| JP4055595B2 (en) * | 2003-02-05 | 2008-03-05 | 凸版印刷株式会社 | Etching liquid for metal material and etching method |
| JP4018559B2 (en) * | 2003-02-27 | 2007-12-05 | メック株式会社 | Manufacturing method of electronic substrate |
| TWI282377B (en) * | 2003-07-25 | 2007-06-11 | Mec Co Ltd | Etchant, replenishment solution and method for producing copper wiring using the same |
| JP2007180172A (en) * | 2005-12-27 | 2007-07-12 | Mec Kk | Manufacturing method of board |
| ATE445031T1 (en) * | 2006-02-17 | 2009-10-15 | Atotech Deutschland Gmbh | COMPOSITION AND METHOD FOR TREATING THE SURFACES OF COPPER ALLOYS TO IMPROVE THE ADHESION BETWEEN THE METAL SURFACE AND THE BONDED POLYMERIC MATERIAL |
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| KR20110005207A (en) | 2011-01-17 |
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| KR20160076496A (en) | 2016-06-30 |
| CN105386055A (en) | 2016-03-09 |
| TW201120247A (en) | 2011-06-16 |
| KR101697460B1 (en) | 2017-01-17 |
| JP2011017053A (en) | 2011-01-27 |
| JP5443863B2 (en) | 2014-03-19 |
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