CN102257180A - Etching solution for copper or copper alloy, etching method, and method for managing reproduction of etching solution - Google Patents
Etching solution for copper or copper alloy, etching method, and method for managing reproduction of etching solution Download PDFInfo
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- CN102257180A CN102257180A CN2009801510475A CN200980151047A CN102257180A CN 102257180 A CN102257180 A CN 102257180A CN 2009801510475 A CN2009801510475 A CN 2009801510475A CN 200980151047 A CN200980151047 A CN 200980151047A CN 102257180 A CN102257180 A CN 102257180A
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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
- 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
- C23F1/46—Regeneration of etching compositions
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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
- H05K3/067—Etchants
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Abstract
Disclosed is an etching solution for copper or a copper alloy, which is mainly composed of water and contains (1) 5 to 20 mass% of iron chloride (III), (2) 0.5 to 3 mass% of copper chloride (II), and (3) a compound capable of, together with copper, forming an insoluble salt in an amount of 5 to 20 mass% relative to the amount of iron chloride (III). Also disclosed is an etching method using the etching solution as a new solution. Further disclosed is a method for managing the reproduction of an etching solution, in which the management of reproduction is carried out by employing the ratio of permeability among two or more different wavelengths.
Description
Technical field
The present invention relates to the playback management method of etching solution, engraving method and etching solution that copper or copper alloy use.
Background technology
In recent years, the miniaturisation high-performanceization of electronic machine develops hastily, and for built-in printed-wiring board (PWB) in these instruments, also strong request has high current densities.
As the manufacture method of printed-wiring board (PWB), being widely used in advance adhesion and having on the substrate of Copper Foil and form resist pattern, use the etching solution of iron(ic) chloride (III) aqueous solution etc. to remove the not subtractive process of the Copper Foil of part.But, when making printed-wiring board (PWB) by this method, the so-called lateral erosion of known generation (ア ン ダ ー カ ッ ト), promptly, etching solution spreads the back side to resist pattern, make line width become thinner than the line width of resist pattern, or the shape in circuit cross section does not form rectangle.If lateral erosion takes place, then there is the electrology characteristic variation of formed circuit, maybe can not guarantees that parts install the problem of necessary area that it is difficult therefore making the high printed-wiring board (PWB) of current densities with subtractive process.
In addition, in of the continuous etching of iron(ic) chloride (III) aqueous solution, carry out along with etched as the Copper Foil of main body, iron(ic) chloride (III) becomes iron(ic) chloride (II), generate cupric chloride (II) as by product, finally degrade to the state that etching solution can't use, therefore be difficult to continuous operation.
In order to make the continuous operation possibility that becomes, attempt passing in time and read the chemical numerical value of etching solution, according to the variation of this numerical value, Yi Bian add various reclaiming aids, Yi Bian carry out the method for successive regeneration operating.But, can get back to the etched state of energy though regenerate, can not get back to the state of new liquid.And when repeating to regenerate for several times, big variation takes place in the composition concentration of the etching solution before and after the final regeneration, and etching speed also has big variation as a result, Yi Bian be difficult to carry out guaranteeing the stable etching speed of liquid of making a fresh start, Yi Bian carry out the cyclic regeneration running.Moreover, because temperature or be present in the foamy influence of etching solution can't correctly read the chemical numerical value of etching solution, also be difficult to carry out stable regeneration management.
For example, as the technology that is used to suppress lateral erosion, propose to use with iron(ic) chloride (III) as principal constituent and be added with the etching solution (for example with reference to patent documentation 1) of thiocarbamide.Perhaps, proposing at the oxidisability metal-salt that waits with iron(ic) chloride (III) and mineral acid or organic acid is in the etching solution of composition, the azole compounds (for example with reference to patent documentation 2) of interpolation benzotriazole etc.In the technology of patent documentation 1 and 2, can suppress lateral erosion to a certain extent.But, in the continuous etching of utilization based on the Copper Foil of the etching solution of iron(ic) chloride (III) aqueous solution, carry out along with etched, iron(ic) chloride (III) becomes iron(ic) chloride (II), generate cupric chloride (II) as by product, finally degrade to the state that etching solution can't use.Therefore, in the technology of patent documentation 1 and 2, be difficult to carry out the stable continuous regeneration operating.
The principal constituent that also proposes at etching solution is not iron(ic) chloride (III), but with the copper halide of divalence as principal constituent, further add in the etching solution of iron halide, measure the concentration of iron halide and copper halide, based on this result, add the method (for example with reference to patent documentation 3) of oxygenant.But, in the technology of patent documentation 3, not only can't suppress lateral erosion, and in regenerative process, etching speed changes significantly, can't carry out the stable continuous regeneration operating.
In order to carry out the stable continuous regeneration operating, the redox potential that has proposed to detect etching solution and cl concn etc. are with respect to 1 normal oxymuriate, with the method (for example with reference to patent documentation 4 and 5) of a certain specified proportion interpolation hydrogenchloride, iron(ic) chloride.But in the technology of patent documentation 4 and 5, if regenerate, then the composition concentration in the etching solution changes, and can not guarantee the etching speed of continous-stable.In addition, suppressing ability for lateral erosion, is inadequate fully.
Regenerating unit as etching solution, proposed with the acidic etching liquid is object, make its regeneration by the ozone that blasts as regeneration gas, as the method for measuring its degradation, use the color of the photometric determination etching solution of flow-through cell type, the etching solution regenerating unit (for example with reference to patent documentation 6) of absorbancy.But in the technology of patent documentation 6, along with regenerating repeatedly, cupric chloride concentration raises, and can not utilize photometric suitable management, and etching speed changes simultaneously, can't carry out the stable continuous regeneration operating.In addition, suppressing ability for lateral erosion, is inadequate fully.Moreover because variation of temperature causes the value of absorbancy to change or is present in foamy influence in the etching solution, significantly vibration takes place in the color of etching solution, absorbancy, can't carry out stable regeneration management.
Automatic management device as no electrolysis compositive lining liquid, proposed to measure transmissivity or absorbancy, calculated purpose by this measured value by the calculation processing and form the automatic analysis management device of concentration (for example with reference to patent documentation 7) with the different wave length more than at least 2.But, in the technology of patent documentation 7,, use its concentration of calculating unknown no electrolysis compositive lining liquid by the basic data production standard curve that concentration changes of forming of the plating liquid that makes cooperation in advance, can't get rid of the influence of Temperature Influence or foamy.
As the measuring method of the metal content of acid solution, the method (for example with reference to patent documentation 8) of calculating metal content by different multiple transmissivity of wavelength or reflectivity has been proposed.In the method, little change can be proofreaied and correct really as the distortion of the sensitivity change of the change of luminous intensity, photo detector, optical system, but can't get rid of Temperature Influence or foamy influence.
As the spectral photometry method, change reason separately for various outputs has been proposed, in the output change of each wavelength measurement with respect to the output change reason of per unit, convert projection to after the data of segment space, try to achieve the typical curve formula, get rid of the spectral photometry method (for example with reference to patent documentation 9) of various error changes thus.But, in the technology of patent documentation 9, need whole incremental datas of various change reasons, and when causing that owing to the processing Copper Foil composition of etching solution changed along with the time, it is difficult preparing this all data in advance, can't be practical.
Patent documentation 1: No. 3144368 specification sheets of United States Patent (USP)
Patent documentation 2: No. 2005/0016961 specification sheets of U.S. Patent Application Publication (TOHKEMY 2005-330572 communique)
Patent documentation 3: TOHKEMY 2006-124740 communique
Patent documentation 4: No. 3193152 communique of Japan's special permission
Patent documentation 5: No. 3320111 communique of Japan's special permission
Patent documentation 6: Japanese kokai publication hei 8-302487 communique
Patent documentation 7: No. 2003/049169 specification sheets of U.S. Patent Application Publication (TOHKEMY 2002-47575 communique)
Patent documentation 8: TOHKEMY 2004-294205 communique (it is of the same clan not have foreign country)
Patent documentation 9: No. 5227986 specification sheets of United States Patent (USP) (Japanese kokai publication hei 3-209149 communique).
Summary of the invention
Even problem of the present invention is for providing the considerably less etching of lateral erosion and regenerating, also can keep the copper of stable etching speed or etching solution and the engraving method that copper alloy is used when building bath (building bath).In addition, provide the variation of etching speed before and after the regeneration little, can suppress the temperature of etching solution or be present in the playback management method of the etching solution of foamy influence in the etching solution, maintainability excellence.
The inventor has carried out research in depth to described problem points, and the result finishes following invention.Promptly, the present invention is the etching solution that a kind of copper or copper alloy are used, it is characterized by with water as principal constituent, the cupric chloride (II), (3) that contains iron(ic) chloride (III), (2) 0.5～3 quality % of (1) 5～20 quality % for iron(ic) chloride (III) 5～20 quality % form the compound of insoluble salt with copper; A kind of engraving method is characterized by this etching solution is used as new liquid; And a kind of playback management method of etching solution, it is characterized by the management of recently regenerating of the transmissivity of use under 2 above different wave lengths.
In engraving method, preferably the compound that forms insoluble salt with copper is an oxalic acid.
In the playback management method of etching solution, preferably in same light path, measure the ratio of trying to achieve 2 transmissivities under the above different wave length simultaneously, carry out the regeneration management of etching solution.
First feature of the present invention is an etching solution.Etching solution of the present invention is because the scope that iron(ic) chloride (III) and cupric chloride (II) concentration are being stipulated, and contain the compound that forms insoluble salt with copper, therefore can carry out the considerably less etching of lateral erosion of difficulty in the past, make printed-wiring board (PWB) by the subtractive process manufacturing possibility that becomes with high current densities.In addition; particularly by using oxalic acid conduct and copper to form the compound of insoluble salt; can further suppress lateral erosion; in the use of etching solution, do not produce simultaneously toxic gas; in addition owing to the composition of only being established by treatment process constitutes; therefore the processing after using also can be carried out easily and fully, also avoids the labour hygiene aspect easily, prevents the problem of public hazards aspect and environment protection aspect.
Second feature of the present invention is the stable continuous regeneration operating that is brought by etching solution.Etching solution of the present invention is owing to be that a kind of etching solution cooperates, it has considered that in advance the etch quantity of Copper Foil and suitable with it following regenerate and the cupric chloride of overflow, the change in concentration of other additive, even therefore directly build to bathe and begin regeneration, also almost can't see the variation of the various composition concentration in the etching solution, the composition concentration that can keep new liquid works the etching speed that keeps stable constantly in the time of can self-builtly bathing.
The 3rd feature of the present invention is the stable continuous regenerative operation that is brought by the regeneration management.The transmissivity of etching solution is measured in regeneration of the present invention management, compares with general used redox potential (hereinafter to be referred as " ORP "), owing to react very sensitively for the variation of the meltage of copper, so can be by the small circulation management of regenerating.Therefore, the variation of the various composition concentration in etching solution before and after the regeneration is also considerably less, can keep stable etching speed before and after regeneration.
The 4th feature of the present invention is by management transmissivity ratio, can suppress the influence of temperature variation and the foamy influence that is present in the etching solution of etching solution.When measuring with iron(ic) chloride (III) and cupric chloride (II),, loss of transmission along with the temperature of etching solution rises as the transmissivity of the etching solution of composition.Thereby though the method that also has the relation of the temperature of measuring etching solution in advance and transmissivity to revise because the composition of etching solution changes at any time along with the dissolving of copper, therefore is difficult to carry out correct correction.In addition, when having tiny bubble in the etching solution, transmissivity equally also reduces.Usually, use the mode of being sprayed etching solution by spray nozzle in etching, but its rework solution contains many tiny bubbles, when using this etching solution that contains bubble, transmissivity is significantly vibrated, and is difficult to as level of control.Also have to make etching solution be circulated to other groove, alleviating the method for influence of air bubbles, but if prolong circulation, then can't measure in real time, being used for being added with of regenerated soup may postpone.Moreover, when particularly utilizing the regeneration of hydrogen peroxide etc., because foam produces along with regenerative response, in any case also can't remove bubble.When carrying out the regeneration management of etching solution with optical means, these phenomenons are fatefulue, but calculate the ratio of the transmissivity that the wavelength more than at least 2 in the wavelength of sneaking into the characteristic variation that causes of wavelength, variation of temperature or bubble that characteristic that the dissolving with copper causes changes measures, with the index that acts on regenerating tube reason, can significantly suppress the influence that influence of temperature variation, bubble are sneaked into thus.
The 5th feature of the present invention is by measuring the ratio of obtaining the transmissivity under the wavelength different more than 2 simultaneously in same light path, can further suppressing to be present in the foamy influence in the etching solution.Composition concentration in the etching solution, particularly foamy content and its shape along with locate, time and changing at any time, therefore in order correctly to grasp the state of certain etching solution in a flash, the transmissivity of measuring different wave length in same light path simultaneously is effective, by carrying out this operation, can further suppress the foamy influence in the etching solution.
The 6th feature of the present invention is the point of maintainability excellence.In the past by ORP or ionic concn, when pH waits and manages etching solution, various transmitters are immersed in the etching solution measure, but if be immersed in for a long time in the acid strong etching solution, then because the adhering to or the deterioration of transmitter itself of oxide compound, correct value can't be measured, upkeep operation must be carried out termly.Relative therewith, when measuring transmissivity, owing to for example can make etching solution circulation in flow-through cell etc., direct contact etch liquid ground is by the etching solution of external measurement by flow-through cell, therefore do not need regular maintenance fully, can be for a long time with non-maintaining state METHOD FOR CONTINUOUS DETERMINATION.
In sum, the etching solution of the application of the invention can extremely suppress lateral erosion first, and can change few subtractive process by etching speed and come stably to make continuously.In addition, the playback management method of the application of the invention, the variation of etching speed before and after the regeneration is little, can suppress the temperature of etching solution or be present in foamy influence in the etching solution, can not need to safeguard ground regeneration management etching solution.
Description of drawings
Fig. 1 is the cross-sectional of the pattern that obtains by etching method.
Fig. 2 is a sketch of measuring transmissivity in same light path simultaneously.
Fig. 3 is a sketch of measuring transmittance in different light paths.
Nomenclature
W
1The top width of copper foil circuit
W
2The bottom width of copper foil circuit
W
3The line width of resist
1 resist
2 Copper Foils
3 base materials
4 flow-through cells
5,7,9 fiber sensors (luminescent part)
6,8,10 fiber sensors (light-receiving part).
Embodiment
Etching solution of the present invention contains iron(ic) chloride (III) as first neccessary composition.The concentration of iron(ic) chloride in the etching solution of the present invention (III) for the total amount of etching solution, is necessary for 5～20 quality %, is preferably 5～10 quality %.This be because, when the concentration ratio 5 quality % of iron(ic) chloride (III) were low, etching speed is significantly slack-off, and was impracticable, when the concentration ratio 20 quality % of iron(ic) chloride (III) were high, the inhibition of lateral erosion became insufficient in addition.
There is no particular limitation for the form of used iron(ic) chloride (III) when preparing etching solution of the present invention, and solubilized anhydride or hexahydrated solid use, and also commercially available iron(ic) chloride (III) suitably can be diluted and use as the aqueous solution.Should illustrate that solid-state iron(ic) chloride (III) is supplied with the form of hexahydrate (formula weight 270.3) usually, but the calculating of the iron(ic) chloride among the present invention (III) concentration is that benchmark carries out with anhydride (formula weight 162.21).For example, when preparation contains 1.0 kilograms of the etching solutions of the present invention of iron(ic) chloride (III) of 10 quality %, use the gram of iron(ic) chloride (III) hexahydrate 1 kilogram * 10 quality % * (270.3/162.21)=167.
Etching solution of the present invention contains cupric chloride (II) as second neccessary composition.The concentration of cupric chloride in the etching solution of the present invention (II) for the total amount of etching solution, is necessary for 0.5～3 quality %, is preferably 0.5～2 quality %.This be because, when the concentration ratio 0.5 quality % of cupric chloride is low, in carrying out the regenerated process, the cupric chloride change in concentration causes the variation of etching speed to become big, be difficult to guarantee stable etching period, when the concentration ratio 3 quality % of cupric chloride (II) were high, the inhibition of lateral erosion became insufficient.
There is no particular limitation for the form of used cupric chloride (II) when preparing etching solution of the present invention, and the solid of solubilized anhydride or dihydrate uses, and also commercially available cupric chloride (II) suitably can be diluted and use as the aqueous solution.Should illustrate that solid-state cupric chloride (II) is supplied with the form of dihydrate (formula weight 170.48) usually, but the calculating of the cupric chloride among the present invention (II) concentration is that benchmark carries out with anhydride (formula weight 134.45).For example, when preparation contains 1 kilogram of the etching solution of the present invention of cupric chloride (II) of 2 quality %, use the gram of cupric chloride (II) dihydrate 1 kilogram * 2 quality % * (170.48/134.45)=25.36.
Etching solution of the present invention contains with copper and forms the compound of insoluble salt as the 3rd neccessary composition.As forming the compound of insoluble salt with copper, be not particularly limited, particularly, can use oxalic acid or contain the azoles etc. of 5 element heterocycle compounds of the nitrogen more than 1.As azoles, can use imidazole compound, triazole compounds, tetrazole compound etc.Wherein, more preferably use oxalic acid.Used the etching solution of the present invention of oxalic acid; can further suppress lateral erosion; do not produce toxic gas as hydrogen sulfide and so on; in addition owing to the composition of only being established by treatment process constitutes; therefore the processing after using also can be carried out easily and fully, also avoids the labour hygiene aspect easily, prevents the problem of public hazards aspect and environment protection aspect.Addition is 5～20 quality % for iron(ic) chloride (III), is preferably 5～15 quality %.This be because, when addition than 5 quality % after a little while, the inhibition that lateral erosion the takes place inadequate problem that becomes, in addition, when addition than 20 quality % for a long time, the time that etching need be grown very much takes place, or the problem of etching fine clearance fully.
When preparation etching solution of the present invention, the form of used oxalic acid is not particularly limited, and the solid of solubilized anhydride or dihydrate uses, and also commercially available oxalic acid suitably can be diluted and use as the aqueous solution.Should illustrate that solid-state oxalic acid is supplied with the form of dihydrate (formula weight 126.07) usually, but the calculating of the concentration of oxalic acid among the present invention is that benchmark carries out with anhydride (formula weight 90.04).For example, when preparation contained 1 kilogram of the etching solution of the present invention of oxalic acid of 1 quality %, oxalic acid dihydrate was used the gram of 1 kilogram * 1 quality % * (126.07/90.04)=14.
When using etching solution of the present invention to carry out etching, the temperature of preferred etching solution is 15～45 ℃, more preferably 25～35 ℃.This be because, when this temperature is also hanged down than it, have the significantly reduced situation of etching speed, in addition, when this temperature is also higher than it, have the inhibition of the lateral erosion inadequate situation that becomes.
In etching solution of the present invention, also can contain the wetting enhancer (moistening れ Cu Jin drug) of tensio-active agent, defoamer, alcohol, glycol etc. etc., but not necessarily.
Etching solution of the present invention is to can be used as the etching solution that new liquid uses.If use etching solution of the present invention as new liquid, when then regenerating, can regenerate to form the composition concentration of etching solution of the present invention.
In the present invention, the regenerated oxygenant that is used for etching solution is not particularly limited, and can use general used oxygenant.For example, can use chlorine, ozone, hydrogen peroxide, chloric acid salt etc., but, preferably use the chloric acid salt, more preferably sodium chlorate, Potcrate from the viewpoint of environment and security.
In the present invention, the regeneration of etching solution management gimmick can be used general used management process.For example, can measure various ionic concns, ORP, pH, proportion, transmissivity waits and manages.From the viewpoint of the variation that reduces the etching speed before and after the regeneration, expectation is carried out regenerative response repeatedly with small circulation, the preferred main high transmissivity of detection sensitivity of using.
In the playback management method of the transmissivity of measuring etching solution, be not particularly limited as the instrument of measuring transmissivity, can use general used instrument such as photoelectric photometer, spectrophotometer, color sensor, fiber sensor.As measuring method, for example be contemplated to be etching solution is circulated in flow-through cell etc. constantly, directly contact etch liquid ground does not carry out method for measuring by the outside.Like this, by the numerical value of on-line determination and the set(ting)value of predetermined management degradation are made comparisons, that can add necessary amount is used for regenerated oxygenant etc.
The wavelength of measuring exists the scope of the 400～750nm at transmissivity peak to carry out at the etching solution that contains iron(ic) chloride (III) and cupric chloride (II).The method according to this invention when using the ratio of wavelength different more than 2 transmissivity down, is used the wavelength about the maximal point at the interior transmissivity peak of the wavelength region that is present in 400～750nm.By measuring the wavelength longer than maximal point, measure the degradation of the etching solution due to the dissolving of copper, measure the wavelength shorter than maximal point, by calculating its ratio, can suppress the influence of temperature or foamy.For example, when maximal point is present in 550nm, can use 500nm and 600nm etc.Measure the selection of the wavelength of transmissivity, can set at any time according to the cooperation of etching solution.Preferred only the needs selects a plurality of only wavelength to use.
When measuring transmissivity, preferably in same light path, measure simultaneously.Measure simultaneously among the present invention and be meant, at 0～100msec with the transmissivity under the plural wavelength of interior mensuration.As simultaneously-measured method, for example can use the coloured light that turns white, the method for the transmissivity of the wavelength region may that only optionally measure to need at light-receiving part is switched the wavelength that needs and the luminous method of measuring etc. successively in the said determination scope.
In playback management method of the present invention, the regenerated liquid of interpolation is new liquid and oxygenant.New liquid is by according to having carried out etched deterioration liquid and degradation is replaced in certain proportion, can remove the various oxide compounds or the by product that produce in etching treatment procedure or regenerative response.New liquid is the etching solution that contains iron(ic) chloride (III) and the needed hydrochloric acid of regenerative response, as required, can add with copper and form the wetting enhancer etc. of the compound of insoluble salt or tensio-active agent, defoamer, alcohol, glycol etc. as other composition.
In the present invention, the regenerated oxygenant that is used for etching solution is not particularly limited, and can use general used oxygenant.For example can use chlorine, ozone, hydrogen peroxide, chloric acid salt etc., but consider, preferably use the chloric acid salt, more preferably sodium chlorate, Potcrate from the viewpoint of environment and security.
In the present invention, the kind of copper-surfaced paper tinsel base material that is used for the manufacturing of printed-wiring board (PWB) is not particularly limited.As base material, can use infiltrating of paper phenolic resin, paper Resins, epoxy, glass epoxy resin etc. that the base material of heat reactive resin is arranged at fiber base material, or used the base material of sheet material of various thermoplastic resins of the fluoride resin etc. of polyester, polyimide, tetrafluoroethylene etc., or the material of the tabular or film like of other various insulativity, in addition, as Copper Foil, can use the Copper Foil that comprises rolling copper, electrolytic copper etc., or comprise the paper tinsel of each Albatra metal-.The applying method of base material and Copper Foil also is not particularly limited, can use the tackiness agent of epoxy system etc. adhere base material and Copper Foil, the resin that also can the be used in base material Copper Foil of before curing, fitting, resin solidification is adhered, perhaps also can use behind the solution or heat fusing thing of the resin that launches to be used for base material on the Copper Foil, remove solvent or carry out the method for cooling curing etc.
In the present invention, the resist that is used for the manufacturing of printed-wiring board (PWB) is not particularly limited, can use develops with alkali removes that liquefiable part forms positive light anti-etching agent pattern, so-called by rayed, or develop to remove that uncured portion forms negative type photoresist pattern, so-called by rayed, other pass through the various resists that silk screen print method or other print process form pattern.
Etching solution of the present invention is suitable for the etching of copper or copper alloy.Copper alloy among the present invention is meant, the alloy that contains the above copper of 50 quality %, as its example, the alloy (copper-nickel alloy) of alloy (brass), copper and the nickel of alloy (German silver), copper and the zinc of alloy (phosphor bronze), copper and the nickel and the zinc of the alloy of representational copper and tin (bronze), copper and tin and phosphorus, but be not limited thereto.
Should illustrate; after using etching solution of the present invention; or with overflowing liquid when discarded; treatment step by a kind of heavy metal the most basic; promptly add calcium hydroxide with pH regulator to weakly alkaline step; can precipitate all iron (II) ion, iron (III) ion, copper (I) ion, copper (II) ion and the oxalic ion of removal fully as contained harmful chemical species; therefore the processing after use also can be carried out easily and fully, also avoids the labour hygiene aspect easily, prevents the problem of public hazards aspect and environment protection aspect.
Embodiment
(embodiment 1)
[preparation of etching solution]
Iron(ic) chloride (III) aqueous solution (concentration 37 quality %), 25 grams (is 20 grams with anhydrate form) cupric chloride (II) dihydrate, 14 at the commercially available 40o Baume of 270 grams (is 100 grams with anhydrate form) restrain in (being 10 grams with anhydrate form) oxalic acid dihydrate, add 1 kg water, contain the etching solution of oxalic acid of cupric chloride, the 1 quality % of 10 quality % iron(ic) chloride (III), 2 quality % with preparation.
[etching and regeneration]
Have on the surface on the glass epoxy resin base material of rolled copper foil of 9 μ m thickness, use positive light anti-etching agent to form circuit (w
3Respectively the do for oneself resist pattern of 25 μ m/25 μ m of the width in)/gap.Wherein, use the diameter of jet face to be the tapered nozzle of the wholecircle of 14cm, the liquid of nozzle is being supplied with under the condition of pressing 150kPa, emitted dose 1320mL/min, the above-mentioned etching solution that is adjusted to 20 ℃ is carried out etching towards above-mentioned base material injection.
The regeneration of etching solution is about 10% time point that is consumed at the iron(ic) chloride of building bath (III), regulate on one side so that proportion is constant, add on one side sodium chlorate aqueous solution, the 10 quality % of 10 quality % of necessary amount aqueous hydrochloric acid, 10 quality % ferric chloride in aqueous solution and carry out, repeat this manipulation of regeneration of 30 times and 60 times.
Fig. 1 is the cross-sectional by the pattern of etching method gained, w
1Be the top width of copper foil circuit, w
2Be the bottom width of copper foil circuit, w
3It is the line width of resist pattern.As assessment item, measure w
2=w
3Etching period when (25 μ m) and etching factor (being called for short E.F sometimes).Should illustrate that E.F is meant, with the thickness/(w of E.F=2 * Copper Foil
2-w
1) represented numerical value, represent the ratio of the etched amount of carrying out to longitudinal direction with respect to the amount of carrying out of depth direction, the big more expression lateral erosion of numerical value is suppressed more, is the good etched index of expression.
(embodiment 2～9, comparative example 1～13)
Similarly to Example 1, preparation contains the etching solution of respectively forming concentration shown in table 1～3, and the substrate for forming the resist pattern identical with embodiment 1 carries out same regeneration and etch processes, carries out same evaluation.
[table 1]
[table 2]
[table 3]
As shown in Table 1, even to be lateral erosion few and the also few etching solution of variation of the etching speed of regenerating for etching solution of the present invention.Especially, using oxalic acid conduct and the etching solution that copper forms the compound of insoluble salt as can be known is the few etching solution of lateral erosion.
Relative therewith, as comparative example 1,2,7, do not add the etching solution that forms the compound of insoluble salt with copper, almost do not see the inhibition of lateral erosion.In addition, in the comparative example 3,4,5 that does not add cupric chloride (II), though lateral erosion is suppressed, the variation of the etching speed when repeating to regenerate is big, is difficult to carry out stable operation.In comparative example 6, produce white precipitate, can't build bath.
Moreover the etching of the comparative example 8 of the concentration of oxalic acid outside institute's claimed range is not carried out, and the inhibition of the lateral erosion of comparative example 9 is insufficient.The etching period of the comparative example 10 of iron(ic) chloride (III) concentration outside institute's claimed range is elongated and impracticable, and the inhibition of the lateral erosion of comparative example 11 is insufficient.For the comparative example 12 and 13 of cupric chloride (II) concentration outside institute's claimed range, though lateral erosion is suppressed, the variation of the etching speed when repeating to regenerate is big, is difficult to carry out stable operation.According to more than, the etching solution of the application of the invention is even can provide lateral erosion to be inhibited first and the also few etching solution and the engraving method of variation of the etching speed of regenerating.
(embodiment 10)
[preparation of etching solution]
Iron(ic) chloride (III) aqueous solution (concentration 37 quality %), 25 grams (is 20 grams with anhydrate form) cupric chloride (II) dihydrate, 7 at the commercially available 40o Baume of 216 grams (is 100 grams with anhydrate form) restrain in (being 5 grams with anhydrate form) oxalic acid dihydrate, add 1 kg water, contain the etching solution of oxalic acid of cupric chloride, the 0.5 quality % of iron(ic) chloride (III), the 2 quality % of 8 quality % with preparation.
[etching]
Have on the surface on the glass epoxy resin base material of rolled copper foil of thickness 9 μ m, use the diameter of jet face to be the tapered nozzle of the wholecircle of 20cm, the liquid of nozzle is being supplied with under the condition of pressing 150kPa, emitted dose 1000mL/min, the above-mentioned etching solution that is adjusted to 30 ℃ is being carried out etching towards above-mentioned base material injection.
[numerical evaluation of regeneration management usefulness]
Transmissivity is used the digital fiber sensor E3X-DAG-S(trade(brand)name of OMRON corporate system, wavelength 525nm) and the E3X-NA11(trade(brand)name, wavelength 680nm) measure.Condition determination is, at the spray that stops etching, etching solution under the round-robin state, is measured with different light paths in flow-through cell simultaneously.ORP and pH use the hole field to make the pH meter D-52S of institute's corporate system, transmitter is immersed in the etching solution directly measures.
[regeneration of etching solution]
The regeneration of etching solution is to build about 5% time point that is consumed of the iron(ic) chloride of bath (III), regulate so that proportion is constant on one side, add on one side the ferric chloride in aqueous solution of the sodium chlorate aqueous solution of 10 quality % of necessary amount, hydrochloric 8 quality % and carry out, repeat the circulation of 100 these manipulation of regeneration.
Show the result who carries out manipulation of regeneration in the table 4.
[table 4]
As shown in Table 4,, make the regeneration in the small circulation that the numerical value before and after regeneration does not have to change and can not judge degradation for ORP or pH become possibility by measuring transmissivity.Therefore, the etching speed before and after the regeneration does not almost have difference yet, and the stable etching before and after the regeneration becomes possibility.After finishing 100 times manipulation of regeneration, ORP and pH transmitter be owing to adhering to of oxide compound needs laundry operation, and used the transmissivity transmitter of flow-through cell not need such maintenance fully.
(embodiment 11)
In order to observe when changing the temperature of the prepared etching solution of embodiment 10, the variation of transmissivity and the influence of the foamy in the etching solution, similarly to Example 10, to of the variation of etching spray with the transmissivity before and after the pump running, measure simultaneously in different light paths, the result is as shown in table 5.
[table 5]
As shown in Table 5, the numerical value of the transmissivity under single wavelength though reduce along with the rising of temperature, by measuring the transmissivity ratio, can suppress influence of temperature variation.In addition,, bubble is mixed when existing in etching solution,,, can suppress influence of air bubbles by measuring the transmissivity ratio though the numerical value of the transmissivity under single wavelength reduces when starting spray pump.
(embodiment 12)
Use Fig. 2 and measuring method shown in Figure 3, the effect when checking is measured simultaneously in same light path.Fig. 2 is the sketch when measuring in same light path, and Fig. 3 is the sketch when different light paths is measured transmissivity.Luminous with fiber sensor 5,7 and 9, see through etching solution constantly from after the below is upward in the round-robin flow-through cell 4, be subjected to light with fiber sensor 6,8 and 10.Use this 2 kinds of measuring methods, use is added with the commercially available tensio-active agent (trade(brand)name: エ マ Le ゲ Application 103 of 0.05 quality % in the prepared etching solution of embodiment 10, KAO. Corp. SA's system) etching solution, carry out the mensuration of transmissivity under the state that bubbles volume in making etching solution increases, its result is as shown in table 6.Should illustrate, used fiber sensor in measuring the different mensuration mode of light path as shown in Figure 3, be to use with the identical fiber sensor that uses at embodiment 10 and measure, used fiber sensor in measuring the identical mensuration mode of light path as shown in Figure 2, be to use the digital fiber sensor E3MC-Y81(trade(brand)name of OMRON corporate system, wavelength 525nm and 680nm) measure.In addition, distance and the distance between fiber sensor 8 and 10 between the asynchronous fiber sensor 7 of mensuration light path and 9 shown in Figure 3 is 10mm.The mensuration of transmissivity was carried out 20 times at interval with 1 second, when Measuring Time not simultaneously, the transmissivity ratio when using the transmissivity of measuring low wavelength side in slow 1 second.
[table 6]
As shown in Table 6, when measuring transmissivity, simultaneously-measured measuring method of the present invention is the measuring method that more can suppress the foamy influence in same light path.When Measuring Time not simultaneously, transmissivity is than vibration up and down more significantly, the hunting range maximum of the transmissivity ratio of being tried to achieve under the time at different light paths, different measuring.
Industrial applicability
Etching solution of the present invention, engraving method and playback management method are not only applicable to the manufacturing of printed-wiring board (PWB), and be applicable to the formation of various circuits such as circuit of circuit, the semiconductor surface on circuit on the glass substrate, plastic base surface, in other various industry purposes, the also copper of highly controlling applicable to needs or the etched situation of copper alloy.
Claims (5)
1. the etching solution used of copper or copper alloy, it is characterized in that, with water as principal constituent, the cupric chloride (II), (3) that contains iron(ic) chloride (III), (2) 0.5～3 quality % of (1) 5～20 quality % with respect to iron(ic) chloride (III) be 5～20 quality % form the compound of insoluble salt with copper.
2. the etching solution used of described copper of claim 1 or copper alloy is an oxalic acid with the compound that copper forms insoluble salt wherein.
3. engraving method is characterized in that, the etching solution that claim 1 or 2 described copper or copper alloy are used uses as new liquid.
4. the playback management method of etching solution, it is to the regenerate method of management of the etching solution that claim 1 or 2 described copper or copper alloy are used, and it is characterized in that, uses the management of recently regenerating of the transmissivity under 2 different above wavelength.
5. the playback management method of the described etching solution of claim 4 is characterized in that, measures described 2 above wavelength in same light path simultaneously.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008320698 | 2008-12-17 | ||
| JP2008-320698 | 2008-12-17 | ||
| JP2009-192035 | 2009-08-21 | ||
| JP2009192035 | 2009-08-21 | ||
| PCT/JP2009/070713 WO2010071078A1 (en) | 2008-12-17 | 2009-12-04 | Etching solution for copper or copper alloy, etching method, and method for managing reproduction of etching solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102257180A true CN102257180A (en) | 2011-11-23 |
| CN102257180B CN102257180B (en) | 2014-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200980151047.5A Expired - Fee Related CN102257180B (en) | 2008-12-17 | 2009-12-04 | Etching solution for copper or copper alloy, etching method, and method for managing reproduction of etching solution |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5604307B2 (en) |
| KR (1) | KR20110093996A (en) |
| CN (1) | CN102257180B (en) |
| TW (1) | TWI486488B (en) |
| WO (1) | WO2010071078A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762620A (en) * | 2014-06-13 | 2015-07-08 | 叶涛 | High-efficient high-quality acidic copper chloride circuit board etching solution |
| TWI627308B (en) * | 2016-02-19 | 2018-06-21 | Mec Co Ltd | Micro-etching agent for copper and manufacturing method of wiring substrate |
| CN111411361A (en) * | 2020-05-07 | 2020-07-14 | 宁波福至新材料有限公司 | Etching solution for improving quality of etching product |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5594779B2 (en) * | 2011-02-17 | 2014-09-24 | Ｊｘ日鉱日石金属株式会社 | Copper discoloration prevention liquid |
| CN102321908A (en) * | 2011-09-02 | 2012-01-18 | 广州市天承化工有限公司 | Recycling and regenerating process method and metal copper recovery system of acid chloride etching solution |
| WO2017141799A1 (en) * | 2016-02-19 | 2017-08-24 | メック株式会社 | Microetchant for copper and method for producing wiring board |
| KR20180066289A (en) * | 2016-12-07 | 2018-06-19 | (주)화백엔지니어링 | Etching solution composition for gravure printing roll |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6468483A (en) * | 1987-09-08 | 1989-03-14 | Seiko Instr & Electronics | Method for administrating etching liquid |
| JP2004077469A (en) * | 1994-02-25 | 2004-03-11 | Hitachi Ltd | Degradation level measurement system and measurement device for material |
| JPH08302487A (en) * | 1995-05-08 | 1996-11-19 | Fuji Electric Co Ltd | Liquid etchant regenerating device |
| JP2003075338A (en) * | 2001-09-07 | 2003-03-12 | Shimadzu Corp | Absorbance measuring device |
| JP2003306784A (en) * | 2002-04-19 | 2003-10-31 | Asahi Kagaku Kogyo Co Ltd | Additive for suppressing side etching of copper printed circuit board |
| JP4018559B2 (en) * | 2003-02-27 | 2007-12-05 | メック株式会社 | Manufacturing method of electronic substrate |
| JP4455043B2 (en) * | 2003-12-24 | 2010-04-21 | 倉敷紡績株式会社 | System for regeneration of acid solutions |
| JP2006111953A (en) * | 2004-10-18 | 2006-04-27 | Mec Kk | Etching agent for copper or copper alloy, its manufacturing method, replenishing liquid, and method for manufacturing wiring substrate |
| JP4917872B2 (en) * | 2006-12-08 | 2012-04-18 | 三新化学工業株式会社 | Chemical solution for copper and / or copper alloy |
| JP4967800B2 (en) * | 2007-05-17 | 2012-07-04 | 凸版印刷株式会社 | Copper solution and method for etching copper or copper alloy using the same |
-
2009
- 2009-12-04 WO PCT/JP2009/070713 patent/WO2010071078A1/en active Application Filing
- 2009-12-04 CN CN200980151047.5A patent/CN102257180B/en not_active Expired - Fee Related
- 2009-12-04 KR KR1020117010603A patent/KR20110093996A/en not_active Application Discontinuation
- 2009-12-04 JP JP2010542948A patent/JP5604307B2/en not_active Expired - Fee Related
- 2009-12-11 TW TW098142551A patent/TWI486488B/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104762620A (en) * | 2014-06-13 | 2015-07-08 | 叶涛 | High-efficient high-quality acidic copper chloride circuit board etching solution |
| CN104762620B (en) * | 2014-06-13 | 2018-10-23 | 叶涛 | Efficient high-quality type acidic copper chloride circuit board etching liquid |
| TWI627308B (en) * | 2016-02-19 | 2018-06-21 | Mec Co Ltd | Micro-etching agent for copper and manufacturing method of wiring substrate |
| CN111411361A (en) * | 2020-05-07 | 2020-07-14 | 宁波福至新材料有限公司 | Etching solution for improving quality of etching product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5604307B2 (en) | 2014-10-08 |
| TW201030185A (en) | 2010-08-16 |
| CN102257180B (en) | 2014-05-07 |
| TWI486488B (en) | 2015-06-01 |
| KR20110093996A (en) | 2011-08-19 |
| WO2010071078A1 (en) | 2010-06-24 |
| JPWO2010071078A1 (en) | 2012-05-31 |
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