CN102348833B - Etching device and etching method - Google Patents

Etching device and etching method Download PDF

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Publication number
CN102348833B
CN102348833B CN2010800112685A CN201080011268A CN102348833B CN 102348833 B CN102348833 B CN 102348833B CN 2010800112685 A CN2010800112685 A CN 2010800112685A CN 201080011268 A CN201080011268 A CN 201080011268A CN 102348833 B CN102348833 B CN 102348833B
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China
Prior art keywords
nozzle
etched
etching
etching solution
spray
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CN102348833A (en
Inventor
加藤真
山根宪吾
石田麻里子
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Mitsubishi Paper Mills Ltd
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Mitsubishi Paper Mills Ltd
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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
    • C23F1/08—Apparatus, e.g. for photomechanical printing surfaces
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/068—Apparatus for etching printed circuits
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0736—Methods for applying liquids, e.g. spraying
    • H05K2203/075—Global treatment of printed circuits by fluid spraying, e.g. cleaning a conductive pattern using nozzles

Abstract

An etching device including full-cone spray nozzles which have a spray angle of 85-130 and have been arranged so that a spray from each spray nozzle has, on a surface to be etched, a pattern having an area that is at least four times the area of the region surrounded by median lines each including the point on the surface from which the center of the spray nozzle, the center being defined as the intersection of the spray axis of the spray nozzle and the surface, and the center of one of adjacent spray nozzles, the center being defined as the intersection of the spray axis of the adjacent spray nozzle and the surface, are equidistant. An etching method is provided in which the etching device is used. By using the method, a printed wiring board having a microfine conductor pattern with a nearly rectangular cross-sectional shape can be efficiently produced. With this etching device, use of an etchant containing a compound which reacts with copper to form a substance that inhibits etchingcan give a conductor pattern having a very nearly rectangular cross-sectional shape.

Description

Etching system and engraving method
Technical field
The present invention relates to a kind of etching system and engraving method.
Background technology
As the technology that is used for machicolated form is formed in metallic substance, use etching technique always.Particularly in the manufacturing of printed wiring board, produce short advantage of time less and that step is required owing to have defective, so etching technique is extensive use of.In the manufacturing of the printed wiring board that has used etching technique; with method such as bonding after tinsels such as laminated copper foil on the insulativity substrate; use printing technology, photoetching technique etc. metal foil surface as conductive pattern and remaining part forms the resist pattern; utilize etching subsequently and dissolve the tinsel of the part that removal do not protected by the resist pattern, form conductive pattern thus.
In recent years, for High Level, the miniaturization of tackling e-machine, printed wiring board is also required the granular of conductive pattern.When granular, there is problem how to take into account insulating reliability and low conductor resistance.When making printed wiring board with etching technique, in most cases, the section shape of conductive pattern becomes top width (instructing the width of the face side of body pattern) than the narrow trapezoidal shape of bottom width (instructing the width of the substrate-side of body pattern).In addition, the situation that becomes following shape is also arranged: bottom width than top width narrow fall trapezoidal shape, the central part spool-like thinner than upper surface or lower surface, central part than upper surface or the thick tubbiness of lower surface.
Insulating reliability between the contiguous conductor pattern is to be determined by the immediate part of the distance between two conductive patterns, and in addition, conductor resistance is that the sectional area by conductive pattern determines.Therefore, when the distance between the contiguous conductor pattern all equates in the arbitrfary point of thickness direction, that is, and when the section shape of conductive pattern is rectangle, can take into account high insulating reliability highest standard and hang down conductor resistance both.On the other hand, when the section shape of conductive pattern be trapezoidal shape, when falling situation such as trapezoidal shape, spool-like, tubbiness, be difficult to take into account high insulating reliability and low conductor resistance both.
As being used for the technology of acquisition near the etching shape of rectangle, a kind of etching solution is proposed, it is added with a kind of compound, and this compound and copper reaction back form and hinder etched material.For example disclose following etching solution: iron(ic) chloride (III) aqueous solution (for example with reference to patent documentation 1) that is added with thiocarbamide; Be added with iron(ic) chloride (III) aqueous solution (for example with reference to patent documentation 2) of curing two carbonamidines; Be added with iron(ic) chloride (III) aqueous solution (for example with reference to patent documentation 3) of ethylene thiourea; Be added with thiocarbamide and nonionic or anionic surfactant's iron(ic) chloride (III) aqueous solution (for example with reference to patent documentation 4); Be added with cupric chloride (II) aqueous solution (for example with reference to patent documentation 5) of 2-amido benzothiazole compound, polyoxyethylene glycol and polyamino compound; Be added with cupric chloride (II) aqueous solution (for example with reference to patent documentation 6) of 2-amido benzothiazole compound, benzotriazole cpd, ethanolamine compound, glycol ethers compound and N-N-methyl-2-2-pyrrolidone N-or dimethyl formamide etc.
In addition, in patent documentation 2, also mention engraving method, openly go out following preferred method: with respect to etched, spray iron(ic) chloride (III) aqueous solution that is added with curing two formamidine salt with vertical or subvertical direction.Known when using other etching solution, also to spray etching solution with respect to etched for subvertical as far as possible direction, thereby the etching shape is arranged near the tendency of rectangle, in order to realize this tendency, can use the narrower nozzle (for example with reference to patent documentation 7) in spray angle.In addition, as being used for the technology of acquisition near the etching shape of rectangle, following technology is proposed: etching solution is sprayed with gas, thereby make the drop high-speed flight (for example with reference to patent documentation 8) of etching solution, perhaps heat this gas in advance, the temperature that prevents etching solution descends, thereby improves etching (for example with reference to patent documentation 9) etc.And then, also to propose in order obtaining near the etching shape of rectangle and to make the spray pattern non-overlapping copies (for example with reference to patent documentation 10) of the etching solution that goes out from nozzle ejection.
Patent documentation 1: No. 2746848 specification sheets of United States Patent (USP)
Patent documentation 2: Japanese Patent Publication 37-15009 communique (claim, hurdle, a page 2 left side, the 10th～18 row)
Patent documentation 3: Japanese Patent Publication 39-27516 communique
Patent documentation 4: Japanese Patent Publication 50-20950 communique
Patent documentation 5: Japanese kokai publication hei 6-57453 communique
Patent documentation 6: TOHKEMY 2006-274291 communique
Patent documentation 7: Japanese kokai publication sho 58-221280 communique
Patent documentation 8: TOHKEMY 2002-256458 communique
Patent documentation 9: TOHKEMY 2006-77299 communique
Patent documentation 10: TOHKEMY 2002-69673 communique
Summary of the invention
The problem that invention will solve
In the background technology, be added with in the employed etching solution with copper reaction back and form the compound that hinders etched material, disclosed like that as patent documentation 2 for this technology, preferably being vertical or subvertical direction injection etching solution with respect to etched.Yet, spray etching solution in order to be subvertical direction with the arbitrary position with respect to etched, nozzle must be carried out the configuration of very high-density ground.Because nozzle such as need clean at regular maintenance, therefore dispose big flow nozzle and the etching system that forms needs miscellaneous maintenance operation.
In addition, in background technology, for with etching solution in the technology that the gas of pressurization sprays, a large amount of gases are supplied in the etching system, its result can produce corrosive gases such as the hydrogenchloride that formed by the etching solution volatilization in large quantities or contain the exhaust of the mist of etching solution.Therefore, need large-scale exhaust gas treatment device, and owing to the volatilization of hydrogenchloride etc. changes the composition of etching solution, so also be difficult to stably carry out etching.
The present invention not only will solve the problem that produces when implementing background technology, that is: need miscellaneous maintenance operation, need large-scale exhaust gas treatment device or be difficult to carry out stable etching, will realize that also the section shape of conductive pattern is near the etching of rectangle.
Solve the method for problem
The various physics that the present inventor etc. enclose to etching, chemical phenomenon studies in great detail, found that, in order to obtain good etching shape, importantly, when spraying etching solution to etched, increase with respect to etched be vertical direction the speed composition (below, be designated as " vertical speed composition "), even with the important significance level of its same degree more than it be, reduce on etched the flowing of the etching solution parallel with etched (below, be designated as " surface flow ") speed composition (below, be designated as " surface velocity composition "), thereby invented etching system and the engraving method of the following stated.
Namely, find a kind of etching system and the engraving method that uses this device to carry out, this etching system system is used for etched from below injection etching solution person, its feature: spray etching solution as follows, namely, with respect to being injected into etched etching solution at the speed composition of the direction vertical with etched, the speed composition with the etching solution of etched surperficial split flow is diminished.
In addition, as the method that reduces surface flow as far as possible, find a kind of etching system and the engraving method that uses this device to carry out, described etching system be for from the below to etched etching system that sprays etching solution, and dispose face and etched almost parallel of a plurality of nozzles, nozzle fills the circular cone nozzle for 85 °～130 ° at angle of spray, and disposes nozzle as follows and form: from the area S of the spray pattern of etching solution on etched of each nozzle ejection A, the area S in the zone that surrounds with each mid-line that is constituted by the point on following etched BRatio (S A/ S B) be more than 4, the point on above-mentioned etched be positioned at a distance of by the distance of the central point of this represented nozzle of the injection axis of this nozzle and etched intersection point, and be equidistant position by the distance of the central point of each represented adjoining nozzles of the injection axis of each adjoining nozzles and etched 's intersection point apart.Thus, can obtain that surface flow is suppressed, section shape is near the conductive pattern of rectangle.
The inventor also finds: in this etching system and engraving method, preferred so that S A/ S BBe that mode more than 9 disposes nozzle, more preferably so that S A/ S BBe that mode more than 16 disposes nozzle.
The inventor also finds: in the engraving method that uses etching system of the present invention to carry out, the preferred use is added with the etching solution that forms the compound that hinders etched material with copper reaction back.
The invention effect
In the etching system of the present invention, do not dispose nozzle to high-density, therefore maintenance easily.In addition, also need not large-scale exhaust gas treatment device.And, utilize etching system of the present invention and engraving method, can obtain stably that surface flow is subjected to highly suppressing, section shape is near the conductive pattern of rectangle.
Description of drawings
Fig. 1 is the side-view relevant with spray pattern.
Fig. 2 is the vertical view relevant with spray pattern.
Fig. 3 be expression with the nozzle arrangement of nozzle arrangement when the central point of each zoning of square lattice, and by with the figure in the zone that mid-line surrounded of adjoining nozzles.
Fig. 4 is expression with the nozzle arrangement of nozzle arrangement when the central point of each zoning of hexagonal lattice, and and the figure of the mid-line of adjoining nozzles.
Fig. 5 is that expression is obtained S with the area in the outer peripheral line 5c divided by the number of nozzle AThe explanatory view of example.
Fig. 6 is expression S A/ S BIt is 4 o'clock, by the figure of the formed spray pattern of nozzle arrangement of Fig. 4.
Fig. 7 is expression S A/ S BIt is 9 o'clock, by the figure of the formed spray pattern of nozzle arrangement of Fig. 4.
Fig. 8 is an example of the configuration of the unequal nozzle in the interval between nozzle.
Fig. 9 is an example of the configuration of the unequal nozzle in the interval between nozzle.
Figure 10 is in a part of nozzle of expression, with the figure of an example of the inhomogeneous situation in the interval of adjoining nozzles.
Figure 11 is the interval of expression between adjoining nozzles along the throughput direction of the etched material figure of an example of condition of enlarged gradually.
Figure 12 is the sectional view of the conductive pattern on the substrate.
Figure 13 is the diagrammatic side view that the etching solution of etching system in the past flows.
Figure 14 is the diagrammatic top view that the etching solution in the past etched of etching system flows.
Embodiment
At first, to existing etched is gone up when spraying etching solution, because etching solution makes the section shape of conductive pattern become not to be the mobile of etching solution of existing etching system of the technical problem that the shape of (spool-like etc.) rectangle is such to describe along the influence of the surface flow on etched surface.
Figure 13 is the diagrammatic side view that the etching solution of etching system in the past flows, and Figure 14 is the diagrammatic top view that the etching solution on etched flows.13d and 14c schematically show to arrive flowing of etched after etching liquid.The etching solution that sprays from nozzle 13a becomes spraying 13b, arrive etched the 13f of etched material 13e after, with opposed some 13g of the spray orifice of nozzle and 14a (below, be designated as " central point of nozzle ") centered by and flow with radial.And, can with the mid-line 13c of adjoining nozzles and 14b near with the liquid interflow of spraying from adjoining nozzles, because gravity falls, break away from from etched 13f.
Herein, so-called " mid-line of nozzle and adjoining nozzles ", it is the line on the etching face 13f, finger is by the central point 13g and the 14a that are positioned at a distance of nozzle, the central point that reaches adjoining nozzles is the straight line that the point of equidistant position constitutes, particularly, be the equal of the vertical mean line that connects central point with the straight line of the central point of adjoining nozzles of nozzle.In order to suppress surface flow, must shorten the central point 13g of nozzle and 14a apart be positioned at the distance of the point at the mid-line 13c of adjoining nozzles and near the above-mentioned interflow of generation the 14b (below, be designated as " stroke of surface flow "), in other words, it is effective that interval with adjoining nozzles is reduced.
Yet, when distance with adjoining nozzles is reduced, can produce following problem.That is, what is called reduces the distance with adjoining nozzles, namely means more nozzle is set in equal area, and certainly, the etching solution emitted dose of per unit area can increase.When the etching solution emitted dose of per unit area increases, can produce following problem: at etched the liquid film that formation is thicker, perpendicular flow can decay because of this thicker liquid film, thereby is difficult to carry out the etching of minute interval.And it is big that the influence of surface flow becomes relatively, and the section shape that also can produce conductive pattern is easy to become the problem of spool-like.In addition, when a large amount of nozzles is set, the problem that also exists the required labor force of its maintenance to increase.
In order to reduce the etching solution emitted dose of per unit area, can supply with and press under (below, be designated as " spray and press ") condition and use the less nozzle of emitted dose applying identical etching solution at nozzle in theory.In order to reduce the emitted dose of nozzle, must dwindle its spray orifice footpath, but the less nozzle in spray orifice footpath stops up because inclusion contained in the etching solution easily produces except meeting, and when spray orifice has abrasion slightly or damage, also can cause bigger influence to the homogeneity of flow or spray pattern, therefore nozzle must be replaced with new product etc. continually, maintaining required labor force or cost of parts can significantly increase, so impracticable fully.
Reduce to spray and press, or in the inside of nozzle the structure that can cut down injection pressure and so on is set, can reduce the etching solution emitted dose of per unit area thus, but can produce following problem: can not keep perpendicular flow, the vertical speed composition becomes too small.
Therefore, discoveries such as the present inventor, the relation of the spray pattern that is formed by each nozzle by suitable regulation and the configuration of each nozzle and can addressing the above problem, thus can suppress surface flow, obtain section shape near the conductive pattern of rectangle.Details is as described below.
Among the present invention, the face that disposes a plurality of nozzles in the etching system and etched are the relation of almost parallel.Among the present invention, so-called spray pattern refers on etched, and 95 quality % of the drop that goes out from nozzle ejection are injected into the area inside of this face, and it is the circular regions centered by the injection axis of nozzle.In other words, being positioned at from the axle of the center of the circle expansion of the etching solution of nozzle ejection is the injection axis of nozzle.Fig. 1 is the side-view relevant with spray pattern, sprays etching solution towards etched material 1b with spray angle s from nozzle 1a.The profile that sprays is 1d, and the distance till etched from nozzle 1a to etched material 1b is h.Fig. 2 is the vertical view relevant with spray pattern, and it is the skeleton view of observing from the arrow A direction of Fig. 1.The profile of the formed spray pattern of nozzle 2a is 2b, the area S in the zone (netting twine portion) that is surrounded by this profile 2b ACan use the spray angle s of nozzle and nozzle 1a and etched 's distance h, with S A=π { htan (s/2) } 2Expression.Among the present invention, in order to increase the vertical speed composition as much as possible, the injection axis 1c of preferred nozzle is approximate vertical with respect to etched.
In addition, the central point of the nozzle of Fig. 2 is represented with etched the intersection point of the injection axis 1c of nozzle and etched material 1b.In the present invention, area S BBe the area in the zone that surrounded by each mid-line that the point on following etched constitutes, the point on described etched be positioned at a distance of with the distance of the central point of the represented nozzle of the injection axis 1c of nozzle and etched intersection point, and be the point of equidistant position by the central point of each represented adjoining nozzles of the injection axis of each adjoining nozzles and etched 's intersection point apart.This mid-line is that to connect (on etched) vertical mean line of each straight line of central point of the central point of nozzle and each adjoining nozzles represented.
So-called adjoining nozzles refers to the part with the mid-line of this nozzle, be positioned at than with the nozzle of the mid-line inside of other arbitrary nozzle.If the distance between the central point of adjoining nozzles is d, then as shown in Figure 3, when the central spot of each zoning on the square lattice has the central point of nozzle, by the area S of the zone that mid-line surrounded of each adjoining nozzles of nozzle (netting twine portion) BCan be by d 2Obtain.In addition, as shown in Figure 4, when the central spot of each zoning on the hexagonal lattice has the central point of nozzle, by the area S of the zone that mid-line surrounded of nozzle and each adjoining nozzles (netting twine portion) BCan by Obtain.
The average area S of a plurality of nozzles BThe area that the line of the central point of nozzle that can be by connection being positioned at most peripheral (below, be designated as " outer peripheral line ") surrounds is obtained divided by the method for the number of the nozzle that is positioned at the outer peripheral line inboard.In addition, about the number of the nozzle that is positioned at the outer peripheral line inboard, be to multiply by the ratio of the spray pattern that is positioned at the outer peripheral line inboard and the number calculated.Use the example of Fig. 5 to specify.The nozzle 5a that all zones of spray pattern 5b is positioned at outer peripheral line 5c inboard is called A group nozzle, represents with bullet.The nozzle 5a that 1/2 of spray pattern 5b is positioned at outer peripheral line 5c inboard is called B group nozzle, represents with the grid round dot.The nozzle 5a that 1/4 of spray pattern 5b is positioned at outer peripheral line 5c inboard is called C group nozzle, represents with the oblique line round dot.A group nozzle is 1, and B group nozzle is 4, and C group nozzle is 4, and therefore, the number that is positioned at the nozzle of outer peripheral line inboard is calculated as: 1+4 * 1/2+4 * 1/4=4, the area that will be surrounded by outer peripheral line 5c calculates average area S thus divided by 4 B
Among the present invention, fill in the etching system that the circular cone nozzle sprays etching solution, so that S in use A/ S BBe that mode more than 4 disposes each nozzle.This means that etching solution arrives etched each point from average nozzle more than 4.Fig. 6 is expression S A/ S BBe the figure of the spray pattern 6b of the etching solution that sprayed from each nozzle 6a in 4 o'clock.Arrive etched the roughly all point except periphery as can be known from the etching solution of the nozzle ejection more than 4.By such configuration nozzle, can make by the caused surface flow of each nozzle and cancel each other, so can obtain etching shape near rectangle.
S A/ S BMore big, then surface flow more can be cancelled each other more to heavens, thereby can obtain more the etching shape near rectangle.Especially preferred S A/ S BBe more than 9, more preferably S A/ S BBe more than 16.At S A/ S BWhen 9 the and 16 such degree that reach are above, can infer by the caused surface flow of the nozzle of farther place and also can cancel each other, therefore can obtain more the etching shape near rectangle.Fig. 7 is expression S A/ S BBe the figure of the spray pattern 7b of the etching solution that sprayed from each nozzle 7a in 9 o'clock.Arrive etched all points except periphery as can be known from the etching solution of 9 above nozzle ejection.
Yet, at S A/ S BArrive under the very large situation more than 60, then be difficult on the contrary obtain the etching shape near the effect of rectangle.From this viewpoint, in the present invention, be preferably S A/ S BLess than 60.
Among the present invention, if the configuration of nozzle and unequal then can produce the part closeer from the interval of nozzle to the surface flow of the part of dredging.From this viewpoint, in etching system of the present invention, preferably shown in the example among Fig. 3 and Fig. 4, like that nozzle is disposed equably.Yet if allow to cut down slightly effect of the present invention, can allow nozzle is not that strictness is configured equably yet.Represent that with concrete example even adopt the arrangements of Fig. 8 that nozzle 8a are configured in the central point of 2 and non-orthogonal grid, the arrangement with nozzle 9a is configured in Fig. 9 of the point that departs from slightly from each grid point of square lattice 9b also can obtain effect of the present invention.In Fig. 8,8b is the mid-line with adjoining nozzles.Particularly by increasing S A/ S B, always utilize from the etching solution of many nozzle ejection and carry out etching, thereby can reduce the influence by the unequal generation of nozzle arrangement, therefore be preferably S A/ S BBe more than 9.
In addition, as shown in figure 10, when the part of nozzle 10a is not the situation of configuration equably, also can obtain effect of the present invention.And then, when the inaccessible situation of the part of nozzle, still can proceed roughly etching uniformly, can obtain the etching shape near rectangle, this is the outstanding advantage of engraving method of the present invention.In addition, from these viewpoints, S A/ S BPreferred higher value is preferably more than 9.
In addition, between the nozzle of keeping off each other, there are differences also passable with the interval of adjoining nozzles.Lift an example, as shown in figure 11, also can adopt the configuration of following nozzle: enlarge interval between adjoining nozzles 11a gradually towards the throughput direction of etched material.
In engraving method of the present invention, preferred carry out etching so that have the mode that the part of resist pattern enters into the outer peripheral line inboard in the etched material.This is because though also can spray etching solution for the outside of outer peripheral line, this part can not obtain the inhibition of surface flow.In addition, when when carrying etched material to carry out etching, near the entrance and outlet of device, be difficult to carry out etching than outer peripheral line more lateral with avoiding, but etched time and whole etching periods are in a ratio of shortlyer in should the zone, do not manifest so do not influence effect of the present invention.
Among the present invention, as the nozzle that be used for to spray etching solution, use spray angle s be 85 °～130 ° fill the circular cone nozzle.More preferably spraying angle s is 110 °～130 °.What is called is filled the circular cone nozzle, refers to the nozzle that the drop with injected liquid carries out coniform injection from the spray orifice of front end, its circular centered by injection axis, and drop directly arrives its inboard mode and constitutes.Fill the circular cone nozzle and be also referred to as full cone nozzle (full cone spray nozzle).As nozzle, except fill the circular cone nozzle, also have fan-shaped nozzle, pyramidal nozzle etc., but these nozzles have anisotropy at injection direction, so surface flow is difficult to cancel each other, be not suitable for the present invention.
Be 40～70 ° with the spray angle of common nozzle and compare that spray angle s is that the circular cone nozzle that fills of above-mentioned scope has wider spray angle, therefore, usually can be as " extensively spray dihedral and fill the circular cone nozzle " and commercially available.If enumerate the example that this wide spray dihedral fills the circular cone nozzle, GG-W type, HH-W type, the QPHA-W type that can buy from Spraying Systems Japan Co., Ltd. are then arranged, the BBXP type that can buy from Ikeuchi Co., Ltd., but the available nozzle of the present invention is not limited to these certainly.
Below, for using the reason of the nozzle at the spray angle with above-mentioned scope to describe as nozzle used in the etching system of the present invention.
When using the spray angle less than 85 ° nozzle, S ADiminish, so in order to make S A/ S BBe more than 4, must reduce area S BThat is, must dwindle between the central point of adjoining nozzles apart from d, just many nozzles are disposed to high-density.In addition, in order to realize the S in the optimal way of the present invention A/ S BBe more than 9 or more than 16, must further dwindle injector spacing d.At this moment, the etching solution emitted dose of per unit area can become too much, at etched the liquid film that formation is thicker.Vertical speed becomes branch to be cut down by this thicker liquid film, thereby produces the problem that is difficult to obtain near the section shape of rectangle.
By using the less nozzle in spray orifice footpath, reduce the emitted dose of the etching solution of per 1 nozzle, can make etched to go up formed thinning of liquid film thus, but the less nozzle in spray orifice footpath can easily produce obstruction because of inclusion contained in the etching solution, therefore can produce the problem that the maintenance operation becomes miscellaneous.
In addition, reducing etching solution presses for the supply of nozzle, minimizing is from the emitted dose of the etching solution of each nozzle, also can make etched to go up formed thinning of liquid film thus, but when the reduction etching solution is pressed for the supply of nozzle, the speed of drop can be slack-off, so the vertical speed composition is also slack-off, thereby produce the problem that is difficult to obtain near the section shape of rectangle.
By increasing distance h between etched material and nozzle to enlarge spray pattern, also can enlarge S thus A, but as disclosed in the patent documentation 10, when the distance h that increases between etched material and nozzle, the drop that sprays can arrive etched material front reduction gear, so the vertical speed composition still can be slack-off.That is to say, if the distance h between etched material and nozzle is too small, emitted dose with respect to the etching solution of unit surface can increase, thereby be difficult to carry out the etching of fine pattern, if it is excessive, then the liquid drop speed of etching solution can be cut down because of atmospheric drag in flight course, is difficult to carry out the etching of fine pattern equally.And then, when h is big, also can produce because the height of the maximization of etching system or etched material input port uprises the problem of the operability deterioration that causes.After considering above situation, distance h is preferably the scope of 50～400mm, more preferably the scope of 50～300mm, more preferably 100～200mm.
In the present invention, must be the nozzle that etching solution is had patience for the nozzle that carries out the etching solution injection.From this viewpoint, when using with iron(ic) chloride (III), cupric chloride (II) etc. to the acidic etching liquid of principal constituent as etching solution, can use plastics nozzles processed such as polypropylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, polyvinyl chloride.When using the ammonia sodium chlorite aqueous solution to wait alkaline etching liquid as etching solution, except above-mentioned plastics nozzle processed, also can use comprise stainless steel, be the nozzle of metal such as alloy with the nickel-chromium-molybdenum of the title of Hirst alloy (hastelloy) (registered trademark, Haynes International company) circulation.Structure of nozzle used in the present invention is compared with 2 fluid tips that need in the technology that proposes in the patent documentation 8～9, and structure is very simple, therefore can make by easy methods such as injection-molded moulding.
In etching system of the present invention and engraving method, use to be added with the etching solution that forms the compound that hinders etched material with copper reaction back, can similarly obtain very etching shape near rectangle with the situation of vertical injection etching solution thus.As this etching solution, for example can use the etching solution that proposes in the patent documentation 1～6.That is, but illustration is added with iron(ic) chloride (III) aqueous solution of thiocarbamide; Be added with iron(ic) chloride (III) aqueous solution of curing two formamidine salt; Be added with iron(ic) chloride (III) aqueous solution of ethylene thiourea; Be added with thiocarbamide and nonionic or anionic surfactant's iron(ic) chloride (III) aqueous solution; Be added with 2-amido benzothiazole compound, polyoxyethylene glycol, and cupric chloride (II) aqueous solution of polyamino compound; Be added with 2-amido benzothiazole compound, benzotriazole cpd, ethanolamine compound, glycol ethers compound, and cupric chloride (II) aqueous solution of N-N-methyl-2-2-pyrrolidone N-or dimethyl formamide.
Be the etching solution that contains iron(ic) chloride (III) and oxalic acid as being added with what form that the etching solution of the compound that hinders etched material especially preferably uses with copper reaction back.By using this etching solution can obtain more etching shape near rectangle.Also have following advantage in addition: the biological degradability as the class of thiocarbamide based compound, the azole compounds of record in the patent documentation 1～6 is low, and does not contain and must use the composition that just can fully handle of drain treatment apparatus on a large scale such as ozonize, burning disposal.
In the used etched material of the present invention, can use with utilizing etching system beyond the present invention or engraving method and carry out printed wiring board identical materials when making.Namely, can use material that following mode makes as etched material: with methods such as bonding, plating, evaporations, the stacked layer that is constituted by copper or copper alloy on insulativity substrates such as paper phenol, epoxy paper, epoxy glass, bismaleimide-triazine resin reinforced glass, and then utilize methods such as silk screen printing, photoetching that the etched material that the resist pattern forms is set on its surface.The method that is used for this etched material of making for example is documented in electronic mounting association and compiles " printed circuit technique brief guide the 3rd edition ", Nikkan Kogyo Shimbun's distribution, on May 30th, 2006, the 3rd chapter.In addition, no matter whether the document is on the books, can make with the printed wiring board that utilizes etching technique manufacturing in the past according to technology of the present invention and compare the trickleer printed wiring board of conductive pattern, at this moment self-explantory.
In that to utilize the present invention to make spacing wide when being the printed wiring board of the special trickle conductive pattern below the 25 μ m, the thickness of preferred resist patterned layer is below the 10 μ m.That is, be preferably used thickness and be the following dry film photoresists of 10 μ m, or be that mode below the 10 μ m is coated with aqueous resist and uses with the thickness after the film forming.
Embodiment
[embodiment 1～22 and comparative example 1～10]
In embodiment 1～11 and the comparative example 1～5, use to be added with the etching solution A that forms the compound that hinders etched material with copper reaction back.In embodiment 12～22 and the comparative example 6～10, use and do not add the etching solution B that forms the compound that hinders etched material with copper reaction back.
The preparation of＜etching solution A 〉
Be to add water among 40 iron(ic) chloride (III) aqueous solution (concentration is 37 quality %) 6.00kg (be 2.22kg as anhydride), the oxalic acid dihydrate 252g (be 180g as anhydride) at commercially available degree Beaume, make 30kg, prepare the etching solution A that contains 7.4 quality % iron(ic) chloride (III), 0.60 quality % oxalic acid.Leave standstill the electrolytic copper foil of dipping thickness 18 μ m in this etching solution, the result only is formed with the light green material on the surface of Copper Foil, does not carry out etching.Stir this etching solution on one side, Yi Bian flood identical electrolytic copper foil therein, about 5 minutes time, Copper Foil dissolving, disappearance.
The preparation of＜etching solution B 〉
Add water in iron(ic) chloride (III) aqueous solution (concentration the is 37 quality %) 6.00kg of commercially available degree Beaume 40 (be 2.22kg as anhydride), make 30kg, preparation contains the etching solution B of 7.4 quality % iron(ic) chloride (III).In this etching solution, leave standstill the above-mentioned electrolytic copper foil of dipping, about 5 minutes time, Copper Foil dissolving, disappearance.Stir this etching solution on one side, Yi Bian flood identical electrolytic copper foil therein, about 3 minutes time, Copper Foil dissolving, disappearance.
The making of＜etched material 〉
At the aqueous resist of stacking material coating eurymeric that is laminated with the electrolytic copper foil that polyimide insulative substrate that thickness is 40 μ m and thickness is 18 μ m, make its drying, making dried thickness is 8 μ m, exposure live width/spacing is wide=evaluation of 30 μ m/30 μ m with conductive pattern after, develop, wash, made etched material.
＜etching system 〉
Use following etching system: with between the nozzle of record in the table 1 apart from d, and etched and nozzle between distance h, the circular cone nozzle that fills that will have spray angle s forms according to the Pareto diagram configuration of Fig. 4.
＜etching 〉
Use above-mentioned etching system, suitably reverse with the speed of the 50cm/min throughput direction with etched material on one side, etched material is carried out etching on one side, the top width T in the sectional view of the conductive pattern 12a on substrate 12b shown in Figure 12 or the arbitrary wideer person of bottom width B reach till the 30 μ m.The etching period note is in table 2.Etching solution is pressed for the supply of nozzle and is 200kPa.The etching solution emitted dose of per 1 nozzle is per minute 1.5L.After etching finishes, as aftertreatment, at once etched material is washed, be immersed in again in the aqueous sodium hydroxide solution that concentration is 3 quality %, the resist pattern is removed in dissolving, after the washing, is immersed in the hydrochloric acid that hydrogen cloride concentration is 5 quality % again, after washing again, drying.
＜estimate
After etched material after utilizing acrylic resin to aftertreatment carries out embedding, use razor to cut off, produce section observation sample.Use this sample of digital micro-analysis sem observation, measure bottom width T shown in Figure 12, top width B, minimum wide w.For embodiment 1～11 and comparative example 1～5, obtain shrinkage (being deducted the value of gained behind the w by arbitrary smaller of T, B).In addition, the situation that shrinkage is big represents that the section shape of conductive pattern is spool-like.These evaluations the results are shown in table 2.
[table 1]
Figure GDA0000097695700000131
[table 2]
After embodiment 1～11 compared with comparative example 1～5 as can be known, be added with when forming the etching solution A of the compound that hinders etched material with copper reaction back in use, utilize the present invention can obtain that section shape does not become spool-like but near the conductive pattern of rectangle.Namely, in any one of embodiment 1～11 and comparative example 1～5, the maximum value of the difference of top width and bottom width is all 7 μ m, smaller, shrinkage is 0～3 μ m among the embodiment 1～11, and is smaller, with respect to this, shrinkage is 6～9 μ m in the comparative example 1～5, and is relatively large, and the section of conductive pattern becomes spool-like.
Relatively reach the as can be known mutual of embodiment 4～10 by the mutual of embodiment 1～3, among the present invention, increase S A/ S BThe time, shrinkage can further reduce, and can obtain section shape near the conductive pattern of rectangle.Particularly, at S A/ S BBe that shrinkage is about 2 μ m more than 4 and less than among 9 the embodiment 4,5, but at S A/ S BBe among the embodiment 6,7 more than 9, shrinkage is little of 1 μ m, and then at S A/ S BBe among the embodiment 8～11 more than 16, shrinkage is 0.In addition we know, as embodiment 11, work as S A/ S BWhen very big, top width can narrow down slightly.
In addition, after embodiment 12～22 compared with comparative example 6～10 as can be known, add when forming the etching solution B of the compound that hinders etched material with copper reaction back using, utilize that the present invention can obtain also that the difference of top width and bottom width is less, section is more near the conductive pattern of rectangle.That is, in embodiment 12～22, the difference of top width and bottom width is 12～14 μ m, and with respect to this, in comparative example 6～10, the difference of top width and bottom width is 16～18 μ m.
Relatively reach the as can be known mutual of embodiment 15～21 by the mutual of embodiment 12～14, among the present invention, increase S A/ S BThe time, the missionary society of top width and bottom width is littler, can obtain section shape near the conductive pattern of rectangle.Particularly, with S A/ S BTop width is that 16～18 μ m compare among the embodiment 15～18 less than 16, at S A/ S BBe more than 16 and less than among 60 the embodiment 19～21, top width is 19 μ m, can obtain section shape more near the conductive pattern of rectangle.In addition we know, S as embodiment 22 A/ S BWhen very big, top width can narrow down slightly.
Compare with having used the improvement of not adding with copper reaction back forms the etching solution B of the compound that hinders etched material with respect to the section shape of comparative example 6～10 of embodiment 12～22, used to be added with that to form the improvement of section shape of the relatively example 1～5 among the embodiment 1～11 of etching solution A of the compound that hinders etched material more remarkable with copper reaction back.That is, be added with when forming the situation of etching solution of the compound that hinders etched material with copper reaction back in use, etching system of the present invention shows significant especially effect.
[embodiment 23 and comparative example 11]
In embodiment 23 and the comparative example 11,1 nozzle exchange is become to end the liquid bolt, except this, implement in the mode identical with embodiment 9 and comparative example 3 respectively.Among the embodiment 23, obtain the result identical with embodiment 9, in the comparative example 11, the position relative with the nozzle that is replaced with liquid bolt only produces banded undercut portion.
By embodiment 23 as can be known, the etching system of the application of the invention when the situation of a part of nozzle obturation, still can be proceeded roughly etching uniformly.With respect to this, by comparative example 11 as can be known, when using the situation of etching system in the past, even if when the situation of a part of nozzle obturation only, also can produce the inhomogeneous problem of etching at once.
Need to prove that the nozzle that uses among each embodiment is the nozzle that can obtain the flow of the degree identical with the nozzle that uses in the past the etching system, so its spray orifice footpath is also identical with the degree of the nozzle that uses in the past the etching system.Therefore, the obstruction that produces because of the inclusion in the etching solution is the frequency of same degree with in the past etching system also, and the maintenance shop of nozzle is every also can be identical with etching system in the past.In addition, even because the configuration number of the nozzle of each embodiment and etching system in the past are that same degree is less, even therefore 1 maintenance required time of operation can be that same degree is shorter with etching system in the past also.
The industrial possibility of utilizing
Etching system of the present invention and engraving method not only are suitable for the manufacturing of printed wiring board, for lead frame, precision gear, accurate laminated spring, encoder other various industry purposes such as manufacturing with disc or striped, various templates, also be applicable to the copper that must carry out high degree of controlled or the etched situation of copper alloy.
Description of reference numerals
The 1a nozzle
The etched material of 1b
The injection axis of 1c nozzle
The profile that 1d sprays
The 2a nozzle
The profile of 2b spray pattern
The 3a nozzle
The mid-line of 3b and adjoining nozzles
3c by with the area S that mid-line surrounded of adjoining nozzles B1 zoning
The 4a nozzle
The mid-line of 4b and adjoining nozzles
4c by with the area S that mid-line surrounded of adjoining nozzles B1 zoning
The 5a nozzle
The 5b spray pattern
The 5c outer peripheral line
The 6a nozzle
The 6b spray pattern
The 7a nozzle
The 7b spray pattern
The 8a nozzle
The mid-line of 8b and adjoining nozzles
The 9a nozzle
The 9b square lattice
The 10a nozzle
The 11a nozzle
The 12a conductive pattern
The 12b substrate
The 13a nozzle
The 13b spraying
The mid-line of 13c and adjoining nozzles
Flowing of 13d etching solution
The etched material of 13e
Etched of 13f
The central point of 13g nozzle
The central point of 14a nozzle
The mid-line of 14b and adjoining nozzles
Flowing of 14c etching solution
The top width of T conductive pattern
The bottom width of B conductive pattern
The narrowest portion of w conductive pattern wide

Claims (5)

1. an etching system is characterized in that, it is for being used for from the below etched etching system that sprays etching solution, and it sprays etching solution in the following manner,
With respect to the speed composition of the direction vertical with etched that is injected into etched etching solution, the speed composition with the etching solution of etched surperficial split flow is diminished,
Dispose face and etched almost parallel of a plurality of nozzles in the described etching system, nozzle fills the circular cone nozzle for 85 °～130 ° at angle of spray, and this nozzle is disposed as follows and forms:
Area S from the spray pattern of etching solution on etched of each nozzle ejection A, the area S in the zone that surrounds with each mid-line that is constituted by the point on following etched BRatio be S A/ S BBe more than 4, the point on described etched is positioned at a distance of with the distance of the central point of this represented nozzle of the injection axis of this nozzle and etched intersection point be equidistant position with the distance of the central point of each represented adjoining nozzles of the injection axis of each adjoining nozzles and etched 's intersection point apart.
2. etching system as claimed in claim 1, wherein S A/ S BBe more than 9.
3. etching system as claimed in claim 1, wherein S A/ S BBe more than 16.
4. engraving method is characterized in that: its right to use requires each described etching system in 1～3 and carries out.
5. engraving method as claimed in claim 4 contains the compound that forms the etched material of obstruction with copper reaction back in the wherein said etching solution.
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