CN101381873B - Etching solution and conductor pattern forming method - Google Patents
Etching solution and conductor pattern forming method Download PDFInfo
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- CN101381873B CN101381873B CN2008102143288A CN200810214328A CN101381873B CN 101381873 B CN101381873 B CN 101381873B CN 2008102143288 A CN2008102143288 A CN 2008102143288A CN 200810214328 A CN200810214328 A CN 200810214328A CN 101381873 B CN101381873 B CN 101381873B
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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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- Inorganic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Weting (AREA)
Abstract
The invention provides a copper etching solution capable of maintaining top shapes of patterns and etching at the same time even being used continuously or repeatedly, and a method for forming conductor patterns by using the etching solution. The etching solution is characterized in that the copper etching solution contains a copper ion source, acid and water, azole and an aromatic compound, wherein the azole only has a nitrogen atom as a hetero atom existed in a ring, and the aromatic compound is at least one selected from phenols and aromatic amines. In addition, the method for forming the conductor patterns is characterized by comprising the step of using the etching solution to etch the part of a copper layer not covered by etchant (3), so as to form the conductor patterns (2).
Description
Technical field
The present invention relates to the etching solution of copper and use the formation method of its conductive pattern.
Background technology
In the manufacturing of printed substrate, when forming the conductive pattern (Wiring pattern, terminal patterns etc.) that is made of copper with photo-engraving process, using chloride series etching solution, cupric chloride is that etching solution, alkaline etching liquid etc. are as etching solution.But, in these etching solutions, have the copper dissolved problem from the side under the resist (etching resist) be called as undercutting (undercut).That is, produce following phenomenon: hope the part (being the distribution part) of not removed, carved by lateral erosion and remove by original etching through being covered by resist, along from the bottom of this distribution to the top, the phenomenon that wide cut attenuates (undercutting).When particularly Wiring pattern was fine, such undercutting must be the least possible.
In the past, studied the etching solution that can suppress said undercutting.For example in following patent documentation 1, propose to contain the technical scheme of the aqueous solution of cupric chloride, hydrochloric acid, 2-aminobenzothiazole compounds, polyoxyethylene glycol and specific alkylene polyamine compound.
In addition, in the following patent documentation 2, disclose through cooperating specific azoles, and undercutting is few, can prevents that pattern that the top of copper wiring attenuates from forming to use etching solution.
Patent documentation 1: the spy opens flat 6-57453 communique
Patent documentation 2: the spy opens the 2005-330572 communique
Summary of the invention
Yet, concerning the etching solution in the past described in the above-mentioned patent documentation 1, the inadequate situation of the undercutting of inhibition being arranged, requirement can further suppress the etching solution of undercutting.
In addition, there is following problems in above-mentioned patent documentation 2 described etching solutions.
If use the oxygenant of cupric ion as etching solution, then in etching process, cupric ion and the reaction of etched metallic copper generate cuprous ion, and the concentration of this cuprous ion rises.If the concentration of cuprous ion surpasses 5g/L, then etching performance descends, thereby, in etching solution, add the oxygenant of hydrogen peroxide etc. usually, carry out cuprous ion is regenerated as the reaction of cupric ion.
But if add hydrogen peroxide, the azole that then contains in the etching solution also is decomposed, and the top of Wiring pattern attenuates and becomes violent.
In order to prevent this situation, make azoles concentration more than certain, carry out etching while must manage, manage very numerous and diverse.
The purpose of this invention is to provide etching solution and use the formation method of its conductive pattern; Said etching solution is that the oxygenant that when so etching performance descends, adds hydrogen peroxide etc. is regenerated as cupric ion with cuprous ion, and can be prolonged and repeated or the copper etchant solution of continuous use; Wherein, Can undercutting less the pattern top shape be etched into desired shapes, and, even use continuously; Also can be easily with azoles concentration maintain certain more than, while and the top shape that can keep pattern carry out etching.
Being characterized as of etching solution of the present invention; Be the copper etchant solution that contains copper ion source, acid and water, wherein, contain azoles and aromatics; Said azoles only has nitrogen-atoms as being present in the intra-annular heteroatoms, and said aromatics is selected from least a in phenols and the aromatic amine.
" copper " in the invention described above can be processed by fine copper, also can be processed by copper alloy.In addition, in this manual, " copper " is meant fine copper or copper alloy.
Being characterized as of the formation method of conductive pattern of the present invention, the etching solution of use the invention described above does not carry out etching with the part that is covered by resist of copper layer on the electrical insulation, forms conductive pattern.
Etching solution of the present invention and use the formation method of its conductive pattern; Can lateral erosion less the pattern top shape be etched into desired shapes quarter; Even and use etching solution continuously or repeatedly; Also can be easily with azoles concentration maintain certain more than, while and the top shape that can keep pattern carry out etching.
Description of drawings
Fig. 1: expression is used etching solution of the present invention and the schematic cross-section of an example of the Wiring pattern that obtains.
Fig. 2: the azoles concentration change during the continuous etching of copper plating plate that expression is used as the basis with the etching solution of embodiment 2 and comparative example 2 and the figure of cuprous concentration change.
Nomenclature
1 substrate
2 copper wirings
3 resist resins (resist resin)
The thickness of T copper wiring (highly)
W
1The wide cut at the top of copper wiring
W
2The wide cut of the bottom of copper wiring
Embodiment
The present invention as object, that is, produces cuprous ion and etching performance when descending with the copper etchant solution of following type in etching, the oxygenant that adds hydrogen peroxide etc. on one side is regenerated as cupric ion with cuprous ion, on one side repeatedly or the copper etchant solution of continuous use.Each one-tenth for constituting this etching solution grades, and specifies as follows.
(copper ion source)
Copper ion source is the composition that adds as with the oxygenant of metallic copper oxidation.As the kind of copper ion source, can give an example out for example cupric chloride, copper sulfate, cupric bromide, organic acid mantoquita, verditer etc.Wherein, because solvability is high, the preferred soon and especially cupric chloride of etching speed.
In addition, as the concentration range of said copper ion source, the preferably copper ionic concn is the scope of 14～155g/L, the scope of preferred especially 33～122g/L.If in this scope, can prevent that then etching speed from descending, and can stably keep etching speed owing to the favorable solubility of cupric ion.When the cupric chloride that uses as preferred copper ion source, the preferred 30～330g/L of the concentration of cupric chloride, the more preferably scope of 70～260g/L.
(acid)
Acid is for by the metallic copper of cupric ion oxidation dissolving and the composition that adds.As the kind of the acid of using, can enumerate and be selected from least a in mineral acid and the organic acid.
As above-mentioned mineral acid, can enumerate sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc.As above-mentioned organic acid, can enumerate formic acid, acetate, oxalic acid, toxilic acid, phenylformic acid, oxyacetic acid etc.As wherein preferred especially acid, from the viewpoint of the stability of etching speed and the steady dissolution property of copper (the high situation of ability that cuprous ion and cupric ion are kept etching solution), preferably hydrochloric acid.
As the concentration of acid, preferred 7～180g/L, more preferably 18～110g/L, further preferred 18～80g/L.As long as the concentration of acid is more than the 7g/L, just can obtains stable etching speed, and can prevent the decline of the steady dissolution property of copper.On the other hand, as long as the concentration of acid just can prevent that etching solution from corroding between resist and the copper below 180g/L, and can prevent reoxidizing of copper surface.
(only having nitrogen-atoms) as being present in the heteroatomic azoles of intra-annular
In order to suppress undercutting, in etching solution of the present invention, add and only have nitrogen-atoms as being present in the heteroatomic azoles of intra-annular (below, also abbreviate " azoles " as).
It is also indeterminate that azoles suppresses the mechanism of undercutting, and consideration is following cause: the cuprous ion through near the liquid the top of conductive pattern and the side combines, and form in the side from the top of conductive pattern and protect epithelium, thus the inhibition undercutting.
As the kind of the azoles that uses, can be the monocyclic compound, also can be the compound that cyclic condensation forms.Particularly preferred glyoxaline compound, triazole class compounds and tetrazole compound also can make up and use more than 2 kinds of these azoles.
Example as above-mentioned glyoxaline compound; Can give an example out the imidazoles of imidazoles, glyoxal ethyline, 2-undecyl-4-methylimidazole, 2-phenylimidazole etc., the benzimidazoles of benzoglyoxaline, 2-tolimidazole, 2-undecyl benzoglyoxaline, 2-Phenylbenzimidazole, 2-mercaptobenzimidazole etc. etc.
As the example of above-mentioned triazole class compounds, the 1,2,3-triazoles of can giving an example out, 1,2,4-triazole, 5-phenyl-1,2,4-triazole, 5-amino-1,2,4-triazole, benzotriazole, 1-methyl-benzotriazole, tolyl-triazole etc.
Example as above-mentioned tetrazole compound; Can give an example out 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, 5,5 '-two-1H-tetrazolium, and their metal-salt etc. of ammonium salt or Na salt, Zn salt, Ca salt, K salt etc.
In above-mentioned illustrative azoles, preferred especially tetrazole compound.This is high because not only suppress the performance of undercutting, and can form pattern brightly.
And then; In tetrazole compound; Preferred 1H-tetrazolium, 5-phenyl-1H-tetrazolium, 5-amino-1H-tetrazolium, 5,5 '-two-1H-tetrazolium, and their ammonium salt or metal-salt etc., preferred especially 1H-tetrazolium, 5-amino-1H-tetrazolium, and their ammonium salt or metal-salt.Infer these tetrazole compounds and can approach and be formed uniformly the protection epithelium in the side from the top of conductive pattern.
5-amino-1H-tetrazolium and ammonium salt or metal-salt, especially easily by hydrogen peroxide decomposition, when cuprous ion is regenerated as cupric ion, under the situation that excessive hydrogen peroxide exists, concentration through the time change the tendency that becomes greatly arranged.Therefore, through the effect of keeping concentration that the aromatics of stating after adding obtains, compare with the situation of not adding, effect is remarkable, thereby is suitable for the present invention.
As the concentration of azoles, preferred 0.1～50g/L, more preferably 0.1～15g/L, further preferred 0.2～10g/L.As long as the concentration of azoles just can suppress undercutting definitely more than 0.1g/L.On the other hand, the concentration of azoles is 50g/L when following, can prevent the decline of etching speed, and etching should etched part definitely, thereby can prevent the generation of short circuit (defective insulation).
(being selected from least a aromatics in phenols and the aromatic amine)
In order to prevent the decomposition of the azoles due to the oxygenant such as hydrogen peroxide, in etching solution of the present invention, add at least a aromatics that is selected from phenols and the aromatic amine (below, also abbreviate " aromatics " as).Do not comprise azoles in above-mentioned " aromatics ".
The mechanism of the decomposition of the azoles due to the agent of above-mentioned aromatics inhibited oxidation is also indeterminate; But consider it is following cause: above-mentioned aromatics has the effect of seizure material with strong oxidation that generate, that be called as hydroxyl radical free radical when adding oxygenant such as hydrogen peroxide.Azoles is decomposed by this hydroxyl radical free radical, but through the good above-mentioned aromatics of interpolation in advance, and hydroxyl radical free radical is caught by aromatics, thereby, even add oxygenant, also can suppress azoles and decomposed by hydroxyl radical free radical.
In the above-mentioned aromatics, particularly phenols suppresses the effect excellence of the decomposition of azoles, thereby preferred.Below, concrete illustration aromatics.
Concrete example as phenols; But illustration has: 2; 4; 6-three (dimethylamino methyl) phenol (monobasic), sulfocarbolic acid or its salt (monobasic), cresol sulfonic acid or its salt (monobasic), Whitfield's ointment or its salt (monobasic), lignin sulfonic acid or its salt (monobasic), phenol (monobasic), catechol (binary, hydroxyl asymmetric), xylenol (monobasic), gallic acid (ternary), phenylphenol (monobasic), Phloroglucinol monomethyl ether (ternary), pyrogallol (ternary), Resorcinol (binary, hydroxyl symmetry), 2; 6-two-tertiary butyl-p-cresol (monobasic), 2,6-two-tertiary butyl-4-ethylphenol (monobasic), 3-tertiary butyl-4-hydroxy phenylmethylether (monobasic) etc.In above-mentioned, first number is corresponding to the number of hydroxyl.
In these phenols, the material of comparing monobasic with the material more than the binary produces effect especially.In addition, under the situation (situation) of binary, asymmetricly have the phenol of hydroxyl, have than symmetry ground and have the higher tendency of phenol effect of hydroxyl for the center of aromatic nucleus with phenol of 2 hydroxyls.And then the effect of the phenol that solvability is high in water is higher.
In each above-mentioned phenols, because the effect of the decomposition of the azoles due to the inhibited oxidation agent is high, and preferred especially sulfocarbolic acid or its salt, cresol sulfonic acid or its salt, Whitfield's ointment or its salt, lignin sulfonic acid or its salt, 2,4,6-three (dimethylamino methyl) phenol etc.
As the concrete example of aromatic amine, can illustration go out naphthylene diamine, aniline, ALPHA-NAPHTHYL AMINE, monomethylaniline, xylidine, phenyl ethyl amine, benzylamine, dibenzyl amine, phenylenediamine, trichloroaniline, tolylene diamine, diphenylamine, triphenylamine, adjacent nitro-p-Chlorobenzoic acid amide, Tolylamine etc.
In these aromatic amines, because the effect of the decomposition of the azoles due to the inhibited oxidation agent is high, and preferred especially naphthylene diamine, aniline, ALPHA-NAPHTHYL AMINE etc.
As the concentration of above-mentioned aromatics, preferred 0.01～20g/L, more preferably 0.1～10g/L.So long as in this scope, just can prevent the decomposition of azoles definitely, and can prevent the reduction of etching speed.
(hydrogen peroxide)
If carry out the etching of copper with etching solution of the present invention, then in the etching progression, cupric ion, metallic copper change and the cuprous ion increase of generation in etching solution.Therefore, can add hydrogen peroxide as the oxygenant that is used for this cuprous ion oxidation is regenerated as cupric ion.
Hydrogen peroxide can add in the etching solution in advance, also can add etched midway.Perhaps, also can use the etching solution that is added with hydrogen peroxide in advance, at the etched hydrogen peroxide that further adds midway.Usually, more in etched situation of adding hydrogen peroxide midway.
The preferred addition of hydrogen peroxide; Amount according to the cuprous ion that produces changes, thereby can not stipulate entirely with numerical value, for example; If the concentration range in etching solution is the scope of 0.01～20g/L, then can easily the cuprous ion that produces be regenerated as cupric ion.The addition of hydrogen peroxide changes according to the amount of cuprous ion and to get final product as stated, for example; Consider the ratio etc. of amount of amount and the etch target thing of etching solution; And to carry out time etc. be benchmark with etched, so long as those skilled in the art just can suitably adjust.Certainly; Can measure the variation of cuprous ion concentration on one side, cuprous ion concentration increased when add hydrogen peroxide on one side, perhaps; Also can measure cuprous ion concentration in advance and what kind of takes place change, add hydrogen peroxide as benchmark along with etched.
Cuprous ion does not work as the etched oxygenant of copper, through there being small quantity, just has the function that auxiliary said azoles suppresses the effect of undercutting.
Below the preferred 5g/L of the concentration range of cuprous ion, more preferably below the 2.5g/L, further be preferably below the 2.0g/L, further more preferably below the 0.7g/L.As long as cuprous ion concentration is below 5g/L, just can prevent the decline of etching speed, and etching should etched part definitely, thereby can prevent the generation of short circuit (defective insulation).The lower limit of the concentration of cuprous ion is not special to be limited, and as stated, through there being small quantity, just has the function that auxiliary said azoles suppresses the effect of undercutting.
Be used for cuprous ion concentration is maintained the addition of the hydrogen peroxide of above-mentioned scope, as stated, can suitably adjust; For example; For the 10g cuprous ion is regenerated as cupric ion, must the 2.7g hydrogen peroxide, thereby can add hydrogen peroxide according to the concentration of the cuprous ion that produces.But, if the hydrogen peroxide in the etching solution is excessive, then produce chlorine or heating etc., be dangerous, thereby, preferably can the scope that cuprous ion concentration maintains above-mentioned scope added.
As the management process that is used for cuprous ion concentration is maintained the etching solution of above-mentioned scope, can directly measure the concentration of cuprous ion, perhaps, also can measure the redox potential of etching solution, it is converted into the concentration of cuprous ion.
(other additive)
In order to improve the stability of liquid; Carry out uniform etching; Surface shape system after the etching is even; Can be as required in etching solution of the present invention, cooperate and be selected from least a in cats product, divalent alcohol and the glycol ether, various additives such as alcohols, amides, AS, solvent, nonionogenic tenside, amphoterics, cation property copolymer.The concrete illustration of these additives is following.
Cats product: the alkyl type quaternary ammonium salt of benzalkonium chloride, alkyltrimethylammonium chloride etc. etc.
Divalent alcohol: terepthaloyl moietie, Diethylene Glycol, Ucar 35, polyalkylene glycol (carbonatoms of alkylidene group is about 4～500) etc.
Glycol ether: dihydroxypropane single-ether, ethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, dipropylene glycol methyl ether, Diethylene Glycol butyl ether etc.
Alcohols: methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, butanols, benzylalcohol, 2-phenoxyethyl alcohol etc.
Amides: N, dinethylformamide, dimethyl-imidazolinone, N-Methyl pyrrolidone etc.
AS: soap, alkyl sulfuric ester salt, alkyl phosphate salt etc.
Solvent: the sulfoxide class of DMSO 99.8MIN. etc. etc.
Nonionic surfactant: the block polymer of Voranol EP 2001, polyoxypropylene alkyl oxide, T 46155 and polyoxypropylene etc.
Amphoterics: the trimethyl-glycine of lauryl dimethylamino acetate trimethyl-glycine, octadecyl dimethylamino acetate trimethyl-glycine, lauryl hydroxyl sulfo betaine etc., lauryl dimethyl amine oxide, aminocarboxylic acid etc.
In addition, as cation property copolymer, preferred water-soluble and show that the behavior and the molecular weight of cationic are the material thousand or more, more preferably molecular weight is thousands of millions of macromolecular compounds that arrive.Concrete example can be enumerated the polymkeric substance, cationic derivatived cellulose etc. of salt of multipolymer, aminoalkyl group acrylic amide of polymkeric substance, quaternary diallylamine and acrylic amide of polymkeric substance, the quaternary diallylamine of polymine, polyalkylenepolyamines, the cinnamic polymkeric substance of quaternary, quaternary aminoalkyl group (methyl) propenoate.As above-mentioned salt, the hydrochloride of can giving an example out.In the said cation property copolymer, preferably polyethylene imines, polyalkylenepolyamines.Said cation property copolymer can be also with more than 2 kinds.In addition, as above-mentioned cation property copolymer, the polymer coagulant, hair that can use antistatic agent as resin, fiber, use in waste water treatment is with the hair conditioner of the flushing commercially available material that becomes to grade.
Etching solution of the present invention through each above-mentioned composition is dissolved in the water, can easily be modulated.As above-mentioned water, the water of deionizing property material such as preferred ion exchanged water, pure water, ultrapure water and impurity.
When using etching solution of the present invention repeatedly,, can use bulking liquor in order each composition to be carried out the concentration management.
As bulking liquor, contain the bulking liquor of following each composition through use, can keep each composition in the etching solution.
A) acid
B) only has nitrogen-atoms as being present in the heteroatomic azoles of intra-annular
C) be selected from least a aromatics in phenols and the aromatic amine
These various compositions preferably use the material with the same kind of etching solution.
As said bulking liquor, the concentration range that is 7～360g/L that preferably contains said a composition, concentration range, the c composition that the b composition is 0.1～50g/L are the bulking liquor of the concentration range of 0.01～20g/L.
Through adding said bulking liquor, suitably keep each composition ratio of said etching solution, thereby, can stably form the few conductive pattern of undercutting.
In said acid, consider preferred hydrochloric acid from the viewpoint of the steady dissolution property of copper.In said bulking liquor, the concentration range that can be further be no more than 14g/L with copper ion concentration contains cupric chloride.In addition, also can contain above-mentioned additive.
Usually, as stated, when adding hydrogen peroxide, azoles is by hydrogen peroxide decomposition and concentration sharply descends, and in the present invention, owing to be added with above-mentioned aromatics, thereby can suppress the minimizing of the azoles due to the hydrogen peroxide.
Therefore, even when regulating each concentration with above-mentioned bulking liquor, also can not consider to carry out the concentration management of each composition because of the minimizing due to the oxygenant of hydrogen peroxide etc., the concentration management transfiguration of etching solution is prone to.Be not to be special qualification, at this moment,, can also prevent the reduction of etching speed if, then as stated, not only can suppress undercutting definitely on one side on one side azoles concentration is maintained 0.1～50g/L carries out etching.
If use etching solution of the present invention to form Wiring pattern, then can obtain the few copper wiring of undercutting (also comprising the copper alloy distribution, down together).Particularly, for example can stably form etching factor and surpass 5 copper wiring.The concentration of etching solution management transfiguration is prone to when in addition, carrying out etching.
Said etching factor is meant, the thickness (highly) of copper wiring is made as T, the wide cut at the top of copper wiring is made as W
1, the wide cut of the bottom of copper wiring is made as W
2The time, with 2T/ (W
2-W
1) value (with reference to Fig. 1) calculated.Fig. 1 is that expression is used etching solution of the present invention and the schematic cross-section of an example of the Wiring pattern that obtains.Reference marks 1 in glasscloth, contain the so-called glass epoxide base material that is soaked with epoxy resin, in paper, contain the so-called paper phenol base material that is soaked with resol, in the aromatic polyamide fibre non-woven fabrics, contain the so-called aromatic polyamide epoxy base material that is soaked with epoxy resin, the substrate (electrical insulation) of polyimide film, ceramic base material etc.Reference marks 2 is copper wirings.Reference marks 3 is resist resin (resists).In addition, W
1The wide cut at the top of expression copper wiring, W
2The wide cut of the bottom of expression copper wiring.If form copper wiring, then can make the wide cut W of the bottom of copper wiring with etching solution of the present invention
2Wide cut W with the top of copper wiring
1Poor (W
2-W
1) reduce, can increase above-mentioned etching factor.
[embodiment]
Below, in order to understand the present invention easily, enumerate embodiment, comparative example, further specify the present invention, but the present invention is not restricted to these embodiment.
(1) about the decomposition of the azoles due to the hydrogen peroxide
Composition shown in table 1 and the table 2 is dissolved in the ion exchanged water etching solution of modulation embodiment 1～13 and comparative example 1～8.As the hydrochloric acid shown in table 1 and the table 2, using the concentration of hydrogenchloride is the material of 35 weight %.
On the other hand; Preparation is stained with the copper-clad laminated board that thickness is the Copper Foil of 12 μ m (use in printed circuit board base material) on glass epoxide base material (Hitachi changes into industry system " GEA-67N "); Adhere to the dry film photoresist that thickness is 15 μ m (Asahi Chemical Industry's system " SUNFORT SPG-152 ") above that; Form the resist pattern of live width and spacing (line and space)=25 μ m/25 μ m (wide cut of line is 25 μ m, and the gap of line and line is 25 μ m).
Then; Use the etching solution of embodiment 1～13 and comparative example 1～8; Press under the condition of 0.15MPa and spray at 40 ℃, spraying, with not by the Copper Foil etching of above-mentioned resist pattern covers, form copper wiring pattern after; With the aqueous sodium hydroxide solution spraying of 3 weight %, peel off above-mentioned dry film photoresist.
The plywood that obtains is cut off, observe the cross-sectional shape (shape of Fig. 1) of formed copper wiring pattern, measure the wide cut (W of the bottom of copper wiring
2) and the wide cut (W at top
1) poor (W
2-W
1), it is made as the value at the initial stage in table 1 and the table 2.
And then; With above-mentioned different; After the modulation of the etching solution of the comparative example 1～8 shown in embodiment shown in the table 1 1～13 and the table 2, in each etching solution, add aquae hydrogenii dioxidi (concentration of hydrogen peroxide: 25g/L 35 weight %), the gained material was placed 24 hours at normal temperatures.
, use this etching solution, use with above-mentioned same gimmick and form copper wiring pattern, measure the wide cut (W of the bottom of copper wiring thereafter
2) and the wide cut (W at top
1) poor (W
2-W
1), be shown in table 1 and the table 2 as adding hydrogen peroxide to place the value of back (add and place the back).In addition, with the remaining quantity of the azoles of liquid chromatography for measuring this moment.For the remaining quantity of 1H-tetrazolium,, therefore only show W owing to be difficult to measure with liquid phase chromatography
2-W
1Value.
Table 1
* Nippon Paper chemistry society system
nSANX P252
n
Table 2
Shown in table 1 and table 2, each embodiment compares with each comparative example, though add place behind the hydrogen peroxide 24 hours also can both be with the shape maintains of copper wiring in good state.Even considering this as owing to after adding hydrogen peroxide, the cause that various azoles are also remaining.
The concentration change of the azoles during (2) about continuous the use
The concentration change of the azoles when then, having measured continuous use etching solution.
The etching solution of comparative example 2 shown in modulometer 1 illustrated embodiment 2 and the table 2.And then, composition shown in following is dissolved in modulates bulking liquor in the ion exchanged water.
< composition of bulking liquor >
Hydrochloric acid (the concentration of hydrogenchloride: 183g/L 35 weight %)
5-amino-1H-tetrazolium 1.5g/L
2-phenoxyethyl alcohol 1g/L
2,4,6-three (dimethylamino methyl) phenol 3g/L
After being respectively charged into the etching solution of embodiment 2 and comparative example 2 in the 1L spray cistern; The copper of in each spray cistern, packing into plating plate;, 40 ℃, spraying spray under pressing the condition of 0.15MPa on one side the copper etching, per 20 second measure cuprous concentration (cuprous ion concentration) on one side.At this moment, if cuprous concentration surpasses 0.65g/L, then add the hydrogen peroxide (concentration of hydrogen peroxide: 250 μ L 35 weight %).As above-mentioned copper plating plate, use following material: to carry out thickness be the material that gets of the electrolytic copper plating of 18 μ m (3.5cm * 3.5cm) on glass epoxide base material (Hitachi changes into industry system " GEA-67N "), being stained with the copper-clad laminated board that thickness is the Copper Foil of 35 μ m (use in printed circuit board base material).
Above-mentioned spraying is handled, and 1 copper plating plate is carried out dissolving fully up to copper in 2 minutes, and the average dissolution rate of copper is PM 0.29g/L during this period.In addition, for the etching solution of embodiment 2,1 copper plating of every processing plate adds the above-mentioned bulking liquor of 8mL.Then,, carry out aforesaid operations repeatedly, up to handling 62 copper plating plates for the etching solution of embodiment 2 and comparative example 2.Then, in the embodiment 2 after processing finishes and the etching solution of comparative example 2,, calculate survival rate with the remaining quantity of liquid chromatography for measuring azoles.The result is shown in the graphic representation of Fig. 2.
Graphic representation by Fig. 2 can know, concerning the etching solution of embodiment 2, even carry out etching continuously while add hydrogen peroxide, owing to add specific aromatics, thereby also can keep the concentration of azoles.
Possibility of its application on the industry
According to the present invention; The formation method of etching solution with the conductive pattern that uses it of following copper can be provided: even use continuously or repeatedly; More than also can easily maintaining azoles concentration necessarily, the top shape ground that can not change pattern carries out the etching solution of etched copper.And then the present invention also is applicable to the formation of the various conductive patterns of the conductive pattern on the glass substrate, the conductive pattern on plastic base surface, the conductive pattern of semiconductor surface etc. except the formation of the conductive pattern that is applicable to printed substrate.
Claims (11)
1. an etching solution is characterized in that, is the copper etchant solution that contains copper ion source, acid and water, wherein,
Contain azoles and aromatic amine, said azoles only has nitrogen-atoms as being present in the intra-annular heteroatoms.
2. etching solution according to claim 1 is characterized in that, further contains hydrogen peroxide.
3. etching solution according to claim 1 is characterized in that, the concentration range of said aromatic amine is 0.01～20g/L.
4. etching solution according to claim 1 is characterized in that, contains said copper ion source and counts 14～155g/L, said sour 7～180g/L and said azoles 0.1～50g/L with copper ion concentration.
5. etching solution according to claim 1 is characterized in that, said azoles is a tetrazole compound.
6. etching solution according to claim 2 is characterized in that, the concentration range of said hydrogen peroxide is 0.01～20g/L.
7. the formation method of a conductive pattern is characterized in that, uses each described etching solution in the claim 1～6, and the part that is not covered by resist of copper layer on the electrical insulation is carried out etching, forms conductive pattern.
8. the formation method of conductive pattern according to claim 7 is characterized in that, so that the concentration of the cuprous ion that produces in the said etching solution becomes the mode below the 5g/L, to said etching solution in add hydrogen peroxide and on one side carry out etching on one side.
9. the formation method of conductive pattern according to claim 7 is characterized in that, on one side the concentration of the said azoles that contains in the said etching solution is maintained 0.1～50g/L, carry out etching on one side.
10. the formation method of conductive pattern according to claim 7 is characterized in that, carries out etching while add bulking liquor, and said bulking liquor contains acid, azoles and aromatic amine, and said azoles only has nitrogen-atoms as being present in the intra-annular heteroatoms.
11. the formation method of conductive pattern according to claim 10; It is characterized in that the concentration range that said bulking liquor contains said acid is that the concentration range of 7～360g/L, said azoles is that the concentration range of 0.1～50g/L and said aromatic amine is 0.01～20g/L.
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| JP2008-141133 | 2008-05-29 | ||
| JP2008141133 | 2008-05-29 | ||
| JP2008141133A JP4472006B2 (en) | 2007-09-04 | 2008-05-29 | Etching solution and method of forming conductor pattern |
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| US8758634B2 (en) | 2010-05-26 | 2014-06-24 | Atotech Deutschland Gmbh | Composition and method for micro etching of copper and copper alloys |
| KR101318733B1 (en) * | 2013-06-13 | 2013-10-18 | 주식회사 에이씨엠 | Ethant composition comprising organic copper complex |
| JP6164614B2 (en) * | 2013-12-06 | 2017-07-19 | メック株式会社 | Etching solution, replenisher, and method for forming copper wiring |
| JP6557575B2 (en) | 2015-10-23 | 2019-08-07 | 株式会社Adeka | Etching solution composition and etching method |
| CN107012465B (en) * | 2017-03-28 | 2019-09-03 | 江苏和达电子科技有限公司 | A kind of copper etchant solution and its application |
| KR101916157B1 (en) * | 2017-04-11 | 2018-11-08 | 켄스코 주식회사 | Etchant additives and etchant using the same |
| JP6736088B2 (en) | 2017-05-22 | 2020-08-05 | メック株式会社 | Etching solution, replenishing solution and method for forming copper wiring |
| JP6573055B1 (en) * | 2017-11-29 | 2019-09-11 | 大日本印刷株式会社 | Wiring board and method for manufacturing wiring board |
| CN110117791B (en) * | 2019-05-23 | 2023-11-10 | 电子科技大学 | Binding force promoter for brown oxide liquid of high-density interconnection printed circuit board |
| CN110418509B (en) * | 2019-07-29 | 2020-10-23 | 广州兴森快捷电路科技有限公司 | Circuit compensation method for meeting specific etching factor requirement of PCB |
| CN110819991B (en) * | 2019-11-08 | 2022-07-15 | 日月光半导体(上海)有限公司 | Etching solution and method for manufacturing package substrate using same |
| JP7129711B2 (en) * | 2020-01-24 | 2022-09-02 | メック株式会社 | Etching liquid, replenishing liquid and method for forming copper wiring |
| KR20220033141A (en) * | 2020-09-09 | 2022-03-16 | 동우 화인켐 주식회사 | Silicon etchant composition, pattern formation method and manufacturing method of array substrate using the etchant composition, and array substrate manufactured therefrom |
| CN113445052A (en) * | 2021-07-28 | 2021-09-28 | 南通群安电子材料有限公司 | Differential etching solution suitable for MSAP (multiple-site-sensitive protection) process |
| WO2024096006A1 (en) * | 2022-11-01 | 2024-05-10 | 三菱瓦斯化学株式会社 | Aqueous composition for etching, etching method using same, and semiconductor substrate manufacturing method |
| JP7436070B1 (en) * | 2022-11-22 | 2024-02-21 | メック株式会社 | copper etchant |
| CN116732520B (en) * | 2023-08-14 | 2023-11-14 | 昆山市板明电子科技有限公司 | Long-acting side etching inhibition additive for acid etching solution, preparation method and application |
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| JP4472006B2 (en) | 2010-06-02 |
| TWI422711B (en) | 2014-01-11 |
| KR20090024638A (en) | 2009-03-09 |
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| CN102691064A (en) | 2012-09-26 |
| JP2009079284A (en) | 2009-04-16 |
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| KR101412281B1 (en) | 2014-06-25 |
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