JPH07111383A - Method for manufacturing circuit board - Google Patents

Abstract

PURPOSE:To simultaneously performing punching for forming a through hole to be continuous and that to be insulated by depositing a metal plating layer on the conductive polymer layer surface on the wall surface within a first through hole which is not forced to be non-conductive by a non-conductor process. CONSTITUTION:A conductive polymer layer 6 is formed on each inner wall surface of first and second through holes 3 and 4 at a conductivity-giving process for a base 1 made of an insulation material such as plastic with first and second through holes 3 and 4. Then, the surface of the conductive polymer layer 6 formed on the inner wall surface of the second through hole (device hole) 4 in the non-conductor process is turned into non-conductive state and a metal plating layer is deposited on the surface of the conductive polymer layer 6 on the inner wall surface of the first through hole 3 which is not turned into non-conductive state by the non-conductor process in the plating process, thus simultaneously performing punching for forming the through hole 3 and the device hole 4, reducing the number of etchings, and simply manufacturing a circuit board.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible circuit board, and particularly when connecting a terminal portion of a semiconductor chip such as an IC or LSI to a terminal portion of an external container (so-called package). The present invention relates to a method of manufacturing a circuit board applied to a chip carrier used in.

[0002]

2. Description of the Related Art In recent years, flexible circuit boards have been provided with circuit wiring on both sides of an insulating film base material for high-density packaging, and signals handled have become faster. Further, it is necessary to provide a ground electrode wiring on the surface opposite to the circuit wiring surface for impedance matching. Conventionally, these flexible circuit boards with double-sided wiring are
In order to connect the wirings on both sides, a so-called through hole, which is plated with metal, is formed on the inner wall surface of the through hole provided in the substrate for electrical connection.

In such a circuit board, a through hole for alignment, a through hole to be insulated which should not be electrically connected to both side wirings such as an outer lead window of a TAB chip carrier and a device hole, and the above-mentioned through hole. In the case of manufacturing a circuit board having both through-holes through which the double-sided wiring should be conducted, the following methods A to C can be considered as methods considering only the productivity.

In the method A, the wiring on both sides is provided with a through hole (non-conductive hole) which should not be conducted and a through hole (conductive hole) which should be conducted in the film substrate. Then, after applying a resist mask to the through holes to be non-conductive holes, electroless plating and electroplating are performed.

In the method B, electroless copper plating is applied to all of the through holes formed in the film base material, then through copper plating is applied to form through hole plating, and then through holes which become non-conductive holes are formed. The plating layer is removed by subjecting only to the etching by lithography.

Further, in the C method, after first forming a through hole,
A through hole that becomes a non-conducting hole is formed by punching.

However, using these methods A to C,
An attempt was made to manufacture a circuit board, such as a chip carrier such as a TAB tape carrier, having a conductive hole and a non-conductive hole, and further having a metal wiring projecting in an overhang shape or hanging in a bridge shape on a through hole. In this case, the following problems occur.

That is, in the method A, metal plating is formed on the resist mask, the resist cannot be removed, and the non-conducting hole itself cannot be formed. Also, B
In the method, when removing the plating layer formed in the non-conducting holes, there is a possibility that the metal wirings provided in the overhang shape or the bridge shape on these through holes may be thinned or disappear. Further, in the C method, not only the insulating layer but also the metal wiring layer is punched out due to the mechanical working called punching, and it is not possible to form overhang-shaped or bridge-shaped metal wiring. As described above, according to the methods A to C, it was not possible to manufacture a circuit board having a conductive hole, a non-conductive hole, an overhang-shaped metal wiring, and the like.

Therefore, the present inventors have examined the following manufacturing method by the D method. That is, in the method D, through-holes which become non-conductive holes are resisted after the catalyst activation treatment by, for example, palladium during the step of performing electroless copper plating on all through-holes formed in the film base material. It is a method of masking with and blocking the subsequent plating reaction. However, in the D method, the effect of the catalyst activation treatment of the unmasked through-holes which should be the conductive holes is lost due to the drying treatment performed at the time of applying the resist, and the through-holes which are to be the conductive holes are not affected. There is a problem that electrolytic copper plating cannot be applied.

A method (method E) of masking electrolytic copper plating by masking a through hole which becomes a non-conducting hole after electroless copper plating with a resist instead of during the electroless copper plating step like method D is also possible. investigated. However, in this E method, a copper oxide film is formed on the non-masked electroless copper plating layer of the through hole to be a conductive hole due to a drying process at the time of resist application. Need to do. However, if the electroless copper plating layer is not densely plated, the electroless copper plating layer will be dissolved by this copper oxide film removal treatment. In order to obtain a sufficient thickness so that the electroless copper plating layer remains, it is necessary to perform plating for a very long time, which is not realistic. Thus, the method of masking the non-conducting holes with a resist causes inconvenience in any step of electroless copper plating.

As described above, A with emphasis on production efficiency
The ~ E method cannot satisfactorily manufacture a circuit board such as a TAB tape carrier. Therefore, at present, a method of forming a through hole and then removing the insulating film layer by etching to form a through hole corresponding to a non-conductive hole at the sacrifice of production efficiency is adopted. As such a method, a method for manufacturing a double-sided TAB tape carrier by the following methods 1 to 3 is carried out.

Method 1: Method of punching through holes in a type with a glue layer (1) Bonding copper foil to both sides of a polyimide film substrate with a glue layer on both sides. (2) A through hole corresponding to the through hole is punched. (3) Electroless plating is applied to the inner wall surface of the through hole corresponding to the through hole. (4) Apply electrolytic copper plating to increase the thickness. (5) The device layer on the back side of the substrate and the copper layer at the portion where the outer lead window is to be formed are removed by etching. (6) The glue layer, the polyimide layer, and the glue layer are sequentially removed from the back surface side by etching to form through holes corresponding to the device hole and the outer lead window. (7) Circuit wiring is provided by lithography on the copper layers on both sides.

Method 2; Method of etching all perforations with glue layer type (1) Bonding copper foil to both sides of a double-sided glue layer-coated polyimide film substrate. (2) The copper layer on the back surface side of the substrate where the through holes are to be formed is removed by etching. (3) The glue layer, the polyimide layer, and the glue layer are sequentially removed from the back surface side by etching to form a through hole corresponding to a through hole. (4) Apply through-hole electroless copper plating to the inner wall surface of the through hole. (5) Apply electrolytic copper plating to increase the thickness. (6) The device layer on the back side of the substrate and the copper layer at the site where the outer lead window is to be formed are removed by etching. (7) The glue layer, the polyimide layer and the glue layer are sequentially removed from the back side of the substrate by etching to form through holes corresponding to the device hole and the outer lead window. (8) Circuit wiring is provided by lithography on the copper layers on both sides.

Method 3; type without glue layer (so-called two-layer T
(AB tape carrier) (1) Copper foil is formed on both surfaces of a polyimide film substrate by sputtering, and electrolytic copper plating is applied to thicken it. (2) The copper layer on the rear surface side of the substrate where the through holes are to be formed is removed by etching. (3) The polyimide layer is removed from the back side of the substrate by etching to form a through hole corresponding to a through hole. (4) Electroless copper plating is applied to the inner wall surface of the through hole corresponding to the through hole. (5) Apply electrolytic copper plating to increase the thickness. (6) The device layer on the back side of the substrate and the copper layer at the site where the outer lead window is to be formed are removed by etching. (7) The polyimide layer is removed from the back surface side by etching to form a through hole corresponding to the device hole and outer lead window. (8) Provide circuit wiring by lithography on the copper layers on both sides of the substrate.

Since the through hole for the through hole which is a through hole has a small diameter of 0.3 mm or less and the number of holes is generally as large as ten or more, the through hole and device hole are large. There is a problem in accuracy when punching and etc. at the same time, and the punching die becomes expensive, so
As shown in the above method 2 to 3, such as device holes,
The method of drilling by etching is advantageous.

However, the actually used etching method is an etching excimer laser with high running cost.
A dry etching method using plasma etching or the like, or a wet etching method using a strong alkaline reaction liquid having a low reaction rate and poor productivity. Further, in the type of so-called three-layer TAB tape carrier, in which polyimide and copper foil are joined by a glue layer, it is difficult to etch depending on the kind of glue, or the etching shape is bad, so the glue layer Restricts the choice of and sacrifices properties or price.

Therefore, in manufacturing the double-sided circuit board having the conductive holes and the non-conductive holes, and the non-conductive holes arranged on the through holes in the form of overhangs or on the bridge are mixed, the method 2 In the method of performing perforation such as through holes by etching removal as shown in 3, the extremely complicated etching treatment as described above is performed a plurality of times,
The whole manufacturing process of the circuit board is complicated.

The present invention solves the above problems and produces a double-sided circuit board in which conducting holes and non-conducting holes and through holes in which metal wirings are arranged in a protruding shape or a bridge shape are mixed. An object of the present invention is to provide a simple manufacturing method in which the number of times of etching an insulating material layer, which is very complicated, can be reduced without using punching processing with low accuracy.

[0019]

In order to achieve the above object, in the method for manufacturing a circuit board according to the invention described in claim 1, a base material made of an insulating material and a metal formed on both surfaces of the base material are used. A layer, a conductive hole having an inner wall surface with a metal plating layer for electrically connecting these metal layers to each other, and a non-conductive hole having an insulated inner wall surface that does not electrically connect the metal layers on both surfaces to each other. A method for manufacturing a circuit board including: a base material having a first through hole and a second through hole, wherein each of the first through hole and the second through hole is provided. A conductivity imparting step of forming a conductive polymer layer on the wall surface, and a non-conducting step of rendering at least the surface of the inner wall surface of the second through hole in which the conductive polymer layer is formed non-conductive,
A plating step of depositing a metal plating layer on the surface of the conductive polymer layer on the inner wall surface of the first through hole that has not been made non-conductive in the non-conducting step.

According to a second aspect of the present invention, there is provided a method of manufacturing a circuit board according to the first aspect, wherein the non-conducting step is performed on the inner wall surface of the second through hole. The step of dissolving or etching the formed conductive polymer layer was included.

Further, in the method for manufacturing a circuit board according to the invention described in claim 3, in the method for manufacturing the circuit board according to claim 1, the deconductoring step is performed on the inner wall surface of the second through hole. The method includes a step of erasing, destroying, or invalidating the formed conductive polymer layer by irradiation with an energy beam.

Further, in the method for manufacturing a circuit board according to the invention described in claim 4, in the method for manufacturing a circuit board according to claim 1, the non-conducting step is performed on the inner wall surface of the second through hole. The step of masking the surface of the formed conductive polymer layer with a resist was included.

Further, in the method of manufacturing a circuit board according to the invention described in claim 5, in the method of manufacturing the circuit board according to any one of claims 1 to 4, the surface of the conductive polymer layer is The method further includes a step of doping a dopant for improving conductivity.

Further, in the method of manufacturing a circuit board according to the sixth aspect of the present invention, a circuit board having a base material made of an insulating material and a metal wiring layer formed on the base material is manufactured. In the method, a conductive polymer layer is formed on the entire surface of a predetermined region on the base material, and the conductive polymer is used for an insulating portion in the region except a conductive portion where the metal wiring layer is to be formed. Is removed or the conductivity is lost, and then a metal wiring layer is formed on the conductive portion by metal plating.

Further, in the method for manufacturing a circuit board according to the invention described in claim 7, in the method for manufacturing the circuit board according to claim 6, the insulating portion is electrically disconnected from the first circuit board. A through hole and / or an adjacent insulating portion of the metal wiring layer is included, and the conductive portion includes a second through hole that is electrically connected and / or a conductive portion of the metal wiring layer. .

[0026]

According to the present invention, the base material made of an insulating material such as plastic having the first and second through holes is electrically conductive to the inner wall surfaces of the first and second through holes in the step of imparting conductivity. A polymer layer is formed, and at least the surface of the conductive polymer layer formed on the inner wall surface of the second through hole is made non-conductive in the non-conducting step, and made non-conductive in the non-conducting step in the plating step. The metal plating layer is deposited on the surface of the conductive polymer layer on the inner wall surface of the first through hole which has not been formed.

According to the above method, of the through holes,
For the conductive polymer formed on the inner wall surface of which the conductive polymer is made non-conductive (second through hole), the metal plating layer is not deposited, so only the inner wall surface of the first through hole to be selectively conducted. In addition, a metal plating layer can be applied through the conductive polymer layer. Therefore, it is not necessary to separately form the holes for forming the conductive holes and the holes for forming the non-conductive holes as in the conventional case, and the holes for forming the first and second through holes can be simultaneously formed. Therefore, the number of etchings of the insulating material base material for perforation is reduced as compared with the conventional case, and the process is simplified. In addition, since the metal plating layer is not deposited on the second through hole to be insulated, it is not necessary to remove the plating layer of the through hole to be insulated after the plating step as in the conventional case. Also, there is no fear that the protruding or bridge-shaped metal wiring formed on the through hole to be insulated such as the chip carrier will be reduced or removed.

The step of punching the insulating material base material for forming the through-hole is not limited to the dry etching method such as plasma etching or excimer laser irradiation etching, but the reaction to the base material made of an insulating material such as a plastic material is performed. A wet etching method using a liquid may be used.
Here, when the plastic material is the most general-purpose polyimide, a mixed aqueous solution of hydrazine and ethylenediamine, water alone of an alkaline chemical such as potassium hydroxide or a mixed aqueous solution of an organic solvent such as ethanol is used. Is preferred.

Further, in the present invention, the non-conducting step for making at least the surface of the conductive polymer layer formed on the inner wall surface of the second through hole non-conductive is performed by the inner wall surface of the second through hole. If the conductive polymer layer formed on the substrate is removed by dissolution or etching, the conductive polymer is removed and the inner wall surface of the second through hole becomes non-conductive, and the metal plating layer is deposited. First, metal plating is selectively applied only to the inner wall surface of the first through hole where the conductive polymer layer maintains conductivity. In this case, the step of making the conductor nonconductive and the step of removing the conductive polymer layer made non-conductive can be combined, and the process becomes simpler.

Further, in the case where the above-mentioned non-conducting step is carried out by erasing, destroying or invalidating the conductive polymer layer formed on the inner wall surface of the second through hole by the irradiation of the energy beam, the irradiation of the energy beam is carried out. As a result, the inner wall surface of the second through hole becomes non-conductive, and the metal plating layer is not deposited.

Further, when the step of making the conductor nonconductive includes the step of masking the surface of the conductive polymer layer formed on the inner wall surface of the second through hole with a resist, the conductive polymer layer is formed by the resist. This means that the surface is made non-conductive, and the second through hole is not plated with metal. In the treatment step for removing the resist, the conductive polymer can also be removed as the conductive polymer layer removing step. For example, by adding a solvent that dissolves and swells the conductive polymer in the resist stripping solution, the resist can be stripped and the conductive polymer layer can be removed at the same time.

According to a sixth aspect of the present invention, there is provided a method of manufacturing a circuit board in which a metal wiring layer is formed on an insulating material base material, which is formed on the entire surface of a predetermined area on the base material. Among the conductive polymer layers, the metal wiring layer is formed on the conductive portion by metal plating after removing or eliminating the conductive portion except the conductive portion where the metal wiring layer is to be formed. Is.

According to the method as described above, metal plating is not deposited on the insulated portion where the conductive polymer layer on the substrate has been removed or the conductivity disappeared, so that the conductive polymer is selectively formed. The metal plating can be applied only to the portion where the formed metal wiring layer is to be formed. Therefore, it is possible to easily form the metal wiring layer without performing a complicated operation of etching a portion of the metal layer other than the portion where the metal wiring layer is to be formed unlike the conventional case.

Also, the second through hole in which the insulated portion is electrically non-conducting and / or the adjacent insulating portion of the metal wiring layer includes, and the conductive portion is electrically conducting. And / or by including a conductive portion of the metal wiring layer, even when a circuit board in which conductive holes and non-conductive holes are mixed is manufactured, not only the portion where the metal wiring layer is to be formed but also the metal wiring layer is simultaneously formed. Since a conductive polymer can be selectively formed also on the inner wall surface of the through hole to be conducted, and the metal plating layer can be deposited through this, a hole for forming a through hole as in the conventional case. Since it is not necessary to separately perform the perforation for forming the non-conduction hole and the perforation for forming the first and second through holes,
The number of times the insulating layer for etching holes is etched is smaller than in the conventional case, and the manufacturing process is simplified.

The solvent used here is appropriately selected according to the kind of the conductive polymer used,
For example, ketones such as acetone, diethyl ketone, methyl propyl ketone, hydroxyacetone, methoxyacetone, phenylacetone, 4-phenylbutanone-2, tetrahydrofuran, dioxane, dimethyl ether, diethyl ether, methyl-ethyl ether, dimethoxyethane, diether Ethoxymethane, methyl glycol,
Ethers such as anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, and 1,3-dioxolane, and also methyl acetate, ethyl acetate, trimethyl orthoformate, ethyl oxalate, trimethyl phosphate, etc. Ester, formamide, N-methylformamide, dimethylformamide, N-methylacetamide,
Amides such as dimethylacetamide, N-methylpropioamide, and hexamethylphosphoramide, nitriles such as acetonitrile, valeronitrile, and benzonitrile, carboxylic acid such as propylene carbonate, ethylene carbonate, and dimethyl carbonate. -Carbonates, carboxylic acids such as formic acid, acetic acid, benzoic acid, oxalic acid, etc., and chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, benzoyl chloride, benzoyl bromide, benzenesulfonyl chloride, benzenesulfonyl dicloloid, benzene Halogen such as thiophosphonyl dichloride, methanesulfonyl chloride, acetyl chloride, dimethylsulfamyl chloride, ethyloxalyl chloride, chlorosulfonylacetyl chloride, etc.,
Sulfolane compounds such as sulfolane and 3-methyl-sulfolane, nitro compounds such as nitromethane and nitrobenzene, sulfoxides such as dimethyl sulfoxide, N-
Lactams such as methylpyrrolidone, actones such as γ-ptyrolactone, tetrahydrothiophene, 3-methyl-2-oxazolidone, pyrrole, 1-methylpyrrole, 2,4-dimethylthiazole, heterocyclic compounds such as furan, etc. Is mentioned.

At this time, if the solvent is an aqueous solution of diethylene glycol, methyl cellosolve, N-methylpyrrolidone or the like, the treatment such as washing with water is easy and preferable. Further, the conductive polymer can be removed together with the surface of the plastic material by etching the surface of the plastic material of the insulating layer.

The formation of the conductive polymer layer in the step of imparting conductivity in the present invention may be carried out by a conventionally known method for forming a conductive polymer. For example, a method of coating a conductive polymer solution on the surface of an insulating material base material or on the inner wall surface of the second through hole to be conducted, or by oxidizing an oxidizing agent with the oxidizing agent on the surface of these base materials. There is a method of producing a conductive polymer by bringing it into contact with a monomer capable of forming a conductive polymer by a polymerization reaction. As the latter method, the insulating material film base material provided with through holes is immersed in a solution containing an oxidizing agent to oxidize the surface of the base material, and then the conductive polymer is formed by oxidative polymerization.
A method of forming an electrically conductive polymer thin film by causing an oxidative polymerization reaction on the surface of the insulating material film by immersing it in a solution containing a monomer capable of forming And the like to form a thicker conductive polymer layer. Of course, the order of dipping in the oxidant solution and dipping in the monomer solution may be reversed.

The conductive polymer used may be a soluble conductive polymer, and examples thereof include polyanilines, polyparaphenylene vinylenes, polythiophenylene vinylenes, polyfuran vinylenes, polypyrro-rubinylenes, polythiophenes. And polyazines, polyfurans, polyselenofurans, poly-P-phenylene sulfides and the like.

As a method of forming a conductive polymer layer on each inner wall surface of the first through hole and the second through hole by oxidative polymerization, for example, a gel-like material formed by hydrolysis of a plastic material is formed on the inner wall surface of each through hole. Forming a surface layer portion composed of a product (gel-like layer forming treatment), and impregnating any one of an oxidizing agent or a monomer that forms a conductive polymer by an oxidative polymerization reaction with the oxidizing agent into the surface layer portion, After that, the surface layer portion is solidified, and an oxidative polymerization reaction is caused by bringing the other of the oxidant or the monomer into contact with the solidified surface layer portion to form a conductive polymer layer on the surface layer portion. Can be used.

According to such a method, the conductive polymer layer is formed on the surface of the inner wall surface of the through hole while being integrally fixed to the base material by the neutralizing and solidifying substance of the gel-like product of the plastic material. Therefore, the adhesiveness between the base material and the conductive polymer layer is strong, and thus the adhesiveness between the metal plating layer via the electrically conductive polymer layer is also strong, and the gel of the plastic material is formed on the predetermined surface layer portion. Since the conductive polymer layer is formed only on the inner wall surface of the through-hole where the neutralized solidified substance of the granular product is formed, a conductive polymer is formed on other parts, for example, the circuit wiring part, and a short circuit occurs between the wirings. It is possible to obtain a highly reliable circuit board without the possibility that the conductive polymer will penetrate into the metal plated layer of the circuit wiring portion as a foreign matter. Thus, when the conductive polymer layer is integrally fixed to the surface layer portion of the neutralized solidified substance of the gelled product, in the step of removing the conductive polymer layer made non-conductive, the surface layer portion is removed. All can be removed.

The reaction solution used to form the surface layer portion of the gel-like product is, for example, a gel-like product such as a mixed solution of alkaline chemicals such as potassium hydroxide with water or an organic solvent such as ethanol. Any substance may be used as long as it is poorly soluble in the reaction solution. The formation of the surface layer portion made of the gel-like product can also be performed together with the etching for forming the through holes. However, considering the advantage of controlling the thickness of the surface layer portion formed of the gel-like product to an optimum value, it is desirable to perform the surface layer portion formation and the etching for forming the through holes in separate steps.

The oxidizing agent used for forming the conductive polymer layer by the oxidative polymerization of the present invention is, for example, ferric chloride,
Ferric perchlorate, ferric nitrate, ferric sulfate, ferric citrate, ferric phosphate, cupric chloride, metal oxides such as lead dioxide, potassium dichromate, anhydrous chromium Chromium compounds such as acids, manganese compounds such as potassium permanganate and sodium permanganate, persulfate compounds such as sodium persulfate, potassium persulfate and ammonium persulfate, quinones such as chloranine, naphthoquinone, benzoquinone and anthraquinone, benzene chloride Examples thereof include diazonium salts such as diazonium, and an aqueous solution of these oxidizing agents or an acidic aqueous solution thereof can be used.

The monomer can be widely used as long as it can form a conductive polymer by oxidative polymerization. For example, pyrrole, N-methylpyrrole, N
-Pyrrole derivatives such as ethylpyrrole, 3-methylpyrrole, 3,4-dimethylpyrrole and N-phenylpyrrole, thiophine and 3-methylthiophene, 3,4-
Thiophene derivatives such as dimethylthiophene, N-methylaniline, N-butylaniline, N-phenylaniline, O- and m-toluidine, O- and m-anisidine, anilines such as O- and m-chloroaniline and derivatives thereof, Etc., but these can be used alone or 2
You may use together more than one kind. The form of the monomer can be gas, liquid or solution.

The solvent of this monomer solution is, for example, water,
Examples thereof include alcohol esters, ketones, aromatic hydrocarbons, organic acids, ethers, nitro compounds and nitrile compounds. When a mixed solution of water and an organic solvent is preferable in handling, methanol, ethanol, propanol, dimethylformamide (DMF), ketones, N-
Methylpyrrolidone, ethyl esters and the like can be used.
It is also preferable to add a surfactant.

Solutions of these oxidizers or monomers are
It may be an alkaline, neutral or acidic solution, but the formation of a gel-like product by the hydrolysis of the plastic material at the surface layer of the inner wall of the through hole and the formation of an oxidizing agent or a monomer into the gel-like product. When it also serves as impregnation, it should be an alkaline solution (reaction solution), and when it serves as both the neutralization and solidification of the gel product and the impregnation of an oxidizing agent or a monomer, it should be an acidic solution (neutralization solution). It may be set as appropriate according to the actual process. Needless to say, when the monomer is added to the neutralizing solution, the neutralizing solution used is a weak acid that does not cause polymerization of the monomer. Further, when the solution is an aqueous solution, a water-compatible organic solvent such as a surfactant or alcohol may be added.

The removal of the conductive polymer layer of the present invention,
Alternatively, as a method for treating the disappearance of conductivity, there are a direct writing method in which only a desired portion is locally processed, and a method in which a portion other than the desired portion is masked with a resist.

As the direct drawing method, an excimer laser,
There is a method of irradiating a site to be treated with radiation such as X-rays, electron beams, and neutron rays that can chemically change the conductive polymer. For example, when an excimer laser is used, the conductive polymer can be volatilized when the irradiation amount is large, and the conductive polymer can be destroyed when the irradiation amount is small. When a carbon dioxide gas laser is used, the conductive polymer is burned when the irradiation amount is large, and when the irradiation amount is small, the dopant doped in the conductive polymer can be volatilized to eliminate the conductivity. . However, since such loss of conductivity can be recovered by re-doping, it is necessary to consider this in the actual process.

On the other hand, the masking method using a resist is effective when the removal of the conductive polymer or the process of disappearing the conductivity can be performed only over the entire area. The treatment using the resist mask can be applied to a dry removal process such as plasma ashing, a dissolution removal of the conductive polymer with a solvent, and an etching removal for each surface of the insulating material substrate to which the conductive polymer is attached. The solvent for removing the conductive polymer with a solvent cannot be specified depending on the type of the conductive polymer used, but examples thereof include the solvent for the conductive polymer described above.

As the method of eliminating the conductivity by dedoping the dopant doped in the conductive polymer, for example, the method of immersing in the alkaline solution,
There are electrochemical methods such as discharge and overcharge of dedoping potential. Other than this, dedoping by heating is possible. For example, dedoping can be performed by heating at 170 ° C. for 10 minutes.

Further, in the present invention, by further comprising a step of doping the surface of the conductive polymer layer with a dopant for improving conductivity,
The electroconductivity of the electroconductive polymer in the portion that should not be removed or lost in electroconductivity, including the inner wall surface of the second through hole, can be more exerted. This is because the resist used in the circuit board manufacturing process is not always selected to have less loss of conductivity because of problems such as manufacturing cost. If the conductivity of the conductive polymer disappears due to dedoping, or if the thickness of the formed conductive polymer layer is small and the conductivity is insufficient, further during the etching treatment step of the conductive polymer layer. This is effective when the used resist is dedoped when it is peeled off. In the case of performing the above-described dedoping process, first, after dedoping the entire region, masking only the place where the conductivity should be lost with a resist and performing the redoping on the other region. There may be cases.

As the dopant to be used, for example, fluorine, chlorine, bromine, iodine, iodine chloride in the electron acceptor,
Iodine trichloride, halogen compounds such as iodine bromide, phosphorus pentafluoride, arsenic pentafluoride, antimony pentafluoride, boron trifluoride, boron trichloride, boron tribromide, Lewis acids such as sulfur trioxide, Proton acids such as hydrogen fluoride, hydrogen chloride, nitric acid, sulfuric acid, perchloric acid, fluorosulfonic acid, chlorosulfonic acid, trifluoromethanesulfonic acid, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, niobium pentachloride ,
There are transition metal chlorides such as tantalum pentachloride, molybdenum pentachloride, tungsten hexachloride, iron trichloride, organic compounds such as tetracyanoethylene, tetracyanoquinodimethane, chloranil, dichlorodicyanobenzoquinone, and electron donors. Examples thereof include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and quaternary ammonium salts such as tetraalkylammonium ion.

In the step of contacting the monomer with an oxidizing agent to form a conductive polymer by an oxidative polymerization reaction, if the oxidizing agent used here is generally made protonic with a mineral acid or the like, the protonic acid is converted into a conductive polymer. The conductivity can be improved. In addition, as described above, when the doping is naturally performed by the oxidizing agent used in the step of forming the conductive polymer, or when the re-doping process is performed, the dopant is the metal plating applied on the conductive polymer. It is necessary to select one that does not corrode. Further, it is also effective to plate a conductor after plating a conductive polymer with a barrier metal such as gold, nickel, titanium, or chromium as a means for blocking corrosion.

[0053]

EXAMPLES The present invention will be described below with reference to examples. (Embodiment 1) FIG. 1 shows, as a first embodiment of the present invention, a through hole as a through hole to be electrically conducted, a device hole as a through hole to be insulated, and an outer lead window. A method of manufacturing a chip carrier will be described.

(1) Formation of through holes: 50 μm thick polyimide (Kapton KB: trade name, manufactured by Toray-DuPont) film substrate 1 was subjected to oxygen plasma treatment on both sides, and then sputter deposition method using argon as a carrier gas. To form a 1μm thick copper layer, and then electroplating to 10μm
A copper layer 2 having a thickness of m was formed on both sides of A and B (a).

Next, a resist layer is formed on the copper layer 2 by photolithography, and the copper layer 4 on the B side is etched by using an aqueous solution of ferric chloride, so that the through hole 3, the device hole 4 and the outer lead are formed. The B-side copper layer at the site where the window 5 is to be formed is removed. Thereafter, the substrate 1 was placed in a 15N potassium hydroxide aqueous solution at 50 ° C. for 12 hours.
After immersion for a minute, the polyimide in the portions corresponding to the through holes 3, the device holes 4, and the outer lead window 5 was hydrolyzed, washed with water, and immersed in a 10% sulfuric acid aqueous solution at 20 ° C. for 1 minute.

Then, a degreasing solution mainly composed of an aqueous solution of a surfactant obtained by adding sodium pyrosulfite to an anionic surfactant of sodium alkylbenzene sulfonate (Nutra Clean 68: trade name, manufactured by Shipley Co.) at 50 ° C. for 3 minutes. The polyimide hydrolyzate was removed by immersion. Through the above process, through holes corresponding to the through hole 3, the device hole 4, and the outer lead window 5 were formed (b).

(2) Formation of conductive polymer (polypyrrole) layer: Next, the substrate 1 on which each through hole was formed was 50 g /
Immerse in 1 liter of potassium permanganate at 90 ° C. for 3 minutes, wash with water, then soak in an aqueous solution of 20% pyrrole and 20% isopropanol for 1 minute at 20 ° C., then 10 ml
It was immersed in an aqueous solution of sulfuric acid / l of sulfuric acid and sodium peroxodisulfate of 10 g / l at 20 ° C. for 1 minute. As a result, potassium permanganate as an oxidant and pyrrole as a monomer are formed on the inner wall surface of the through hole corresponding to the through hole 3 and the surface of the inner wall surface of the through hole corresponding to the device hole 4 and the outer lead window portion 5. Upon contact, an oxidative polymerization reaction was caused, and further contact was made with sodium oxodisulfate, which is an oxidizing agent, and the oxidative polymerization reaction was continued to form a thicker black-brown polypyrrole layer 6 (c). Then, it was washed with water and dried naturally.

(3) Formation of resist layer: Next, a positive type resist (exposed portion is dissolved in a developing solution) resist (PMER P-R30S: trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on the entire surfaces of the substrates A and B. After drying at 90 ° C for 30 minutes and exposing, it is exposed to 1.2% sodium hydroxide aqueous solution at 20 ° C for about 2 minutes.
The resist layer 7 having a thickness of about 5 μm was formed only on the inner wall surface of each through hole corresponding to the device hole 4 and the outer lead window 5 by immersing for 3 minutes, developing, washing with water, and natural drying (d). At this time, the color tone of the polypyrrole layer 6 of the through-hole part 3 became slightly bright. Then, the substrate 1 was immersed in a 5N sulfuric acid aqueous solution at 20 ° C. for 5 minutes. At this time, the color tone of the polypyrrole layer 6 returned to the original.

(4) Electrolytic plating: Further, the substrate 1 on which the polypyrrole layer 6 is formed is electrolytically plated at a current density of 3 A / dm ² in a copper sulfate bath containing 1N sulfuric acid to obtain copper of 15 μm. Layer 2 was stacked on the entire surface of the copper foil layer on both sides of the through hole 3 and the substrate AB. As a result, the thicknesses of the copper layers 2 on both sides of A and B were both 25 μm except for the device hole 4 and the outer lead window 5 (e).

(5) Stripping of resist and conductive polymer layer: Then, the substrate 1 was dipped in an alkaline stripping solution (PMER stripping solution PS) at 45 ° C. for 3 minutes to strip the resist layer 7, and then 15 standard 50 ℃ in potassium hydroxide solution
Soak for 2 minutes in water, wash with water, and then add 2
Device hole 4, by soaking for 1 minute at 0 ° C,
The polypropylene layer 6 on the inner wall surface of the through hole of the outer lead window 5 was peeled off (f). At this time, when the cross-section of the through-hole plating was observed with a scanning electron microscope, the copper plating was surely adhered to the polyimide surface on the inner wall surface of the through hole via the polypropylene layer without a gap.

Then, the copper layers 2 on both sides were etched by photolithography to form a predetermined circuit pattern. Through the above steps, a chip carrier having an inner lead 8 and an outer lead 9 having a good pattern shape was obtained (g).

(Embodiment 2) Next, as a second embodiment of the present invention, a through hole as a through hole to be electrically conducted, a device hole as an through hole to be insulated, and an outer lead window. The chip carrier has a through hole and is plated with metal through a conductive polymer in a state of being integrally fixed to a neutralized solidified substance of a gel-like product by hydrolysis of a plastic material of an insulating layer. The manufacturing method of is shown in FIG.

(1) Formation of surface layer portion consisting of through-holes and gel-like product: 50 μm thick polyimide (Kapton KB)
After performing oxygen plasma treatment on both surfaces of the film substrate 11, a copper layer having a thickness of 1 μm was provided by a sputtering method using argon as a carrier gas, and then a copper layer 12 having a thickness of 10 μm was formed on both sides of A and B by electrolytic plating ( a).

Next, a resist layer is formed on the copper layer 12 by photolithography, and the copper foil layer on the B side is etched with an aqueous solution of ferric chloride, so that the through holes 13, the device holes 14 and the outer leads are formed. The B-side copper layer on the site where the window 15 is to be formed is removed. After that, the substrate 11 is immersed in a 15 N potassium hydroxide aqueous solution at 50 ° C. for 10 minutes to hydrolyze the polyimide in the portions corresponding to the through holes 13, the device holes 14, and the outer lead window 15. Wash with water,
It was immersed in a 10% sulfuric acid aqueous solution at 20 ° C. for 1 minute.

Then, it was immersed for 3 minutes at 50 ° C. in a degreasing solution (Nutraclean 68) mainly composed of an aqueous solution of a surfactant obtained by adding sodium pyrosulfite to the anionic surfactant of sodium alkylbenzene sulfonate, and the above polyimide Through hole 1 by removing hydrolyzate
3, device hole 14, outer lead window 1
A through hole corresponding to No. 5 was formed. Then, in an 8N potassium hydroxide aqueous solution consisting of a mixed aqueous solution of 20% isopropanol and 20% pyrrole as a monomer at 50 ° C.
It was soaked in water for 3 minutes and washed with water. By this treatment, the surface layer portion G made of a gel-like product by hydrolysis of polyimide was formed on the inner wall surface of each through hole, and at the same time, the surface layer portion G was impregnated with the monomer pyrrole (b).

(2) Formation of conductive polymer (polypyrrole) layer: Furthermore, a substrate in which pyrrole, which is a monomer, is impregnated in a surface layer portion G formed of a gel-like product on the inner wall surface of each through hole is used as an oxidant at 10 g / By dipping in a mixed aqueous solution of sodium peroxodisulfate (1) and sulfuric acid (25 ml / l) at 20 ° C. for 5 minutes, the pyrrole, which is a monomer, is brought into contact with an oxidizing agent to form a conductive polymer of polypyrrole by an oxidative polymerization reaction. The surface layer portion G composed of a gel-like product was neutralized and solidified with an acid. Here, the inner wall surfaces of the through holes corresponding to the through hole 13, the device hole 14, and the outer window 15 are dark brown in a state of being integrally fixed to the neutralized and solidified substance of the gel product, which is a polyimide hydrolyzate. The polypyrrole layer 16 was formed (c).

(3) Formation of resist layer: Next, a positive type (exposed portion is dissolved in a developing solution) resist (PMER P-R30S: manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied to the entire surface of the substrate and dried at 90 ° C. for 30 minutes. Then, after exposure, it is immersed in a 1.2% sodium hydroxide aqueous solution at 20 ° C. for about 2 minutes to develop,
Device hole 1 by washing with water and air-drying
4. A resist layer 17 having a thickness of about 5 μm was formed only on the inner wall surface of the through hole corresponding to the outer lead window 15 (d). At this time, the polypyrrole layer 16 of the through-hole 13
Became slightly lighter in color. Then, this substrate was immersed in a 5N sulfuric acid aqueous solution at 20 ° C. for 5 minutes. At this time, the color tone of the polypyrrole layer 16 returned to the original.

(4) Electrolytic plating: Further, this substrate 11
For copper sulphate bath containing 1N sulfuric acid, current density is 3A
Electroplating was performed at / dm ² to deposit 15 μm of copper on the entire surface of the through hole 13 and the copper foil layer 12 on both surfaces of the substrate AB. As a result, the thicknesses of the copper layers 12 on both sides of A and B were 25 μm except for the regions of the device hole 14 and the outer lead window 15 (e).

(5) Stripping of resist and conductive polymer layer: Next, the substrate 11 is a degreasing solution containing a surfactant aqueous solution obtained by igniting sodium pyrosulfite as an anionic surfactant of sodium alkylbenzene sulfonate (Neutra). Clean 66: trade name, manufactured by Shipley Co., Ltd.) The resist layer 17 on the inner wall surface of the through hole of the device hole portion 14 and the outer window portion 15 is peeled off by immersing at 50 ° C. for 3 minutes, and the polypropylene layer 16 is integrated. The surface layer portion consisting of the neutralized and solidified substance of the gel product due to the hydrolysis of the polyimide, which has been fixed, was removed. Simultaneously with the removal of the surface layer portion, the polypyrrole layer 16 is also removed (f). This time,
When the cross-section of the through-hole plating was observed with a scanning electron microscope, the copper plating was surely adhered to the polyimide surface on the inner wall surface of the through hole via the polypropylene layer without a gap.

Thereafter, the copper foil layers 12 on both sides were etched by photolithography to form a predetermined circuit pattern. Through the above steps, a chip carrier having an inner lead 18 and an outer lead 19 having a good pattern shape was obtained (g).

(Third Embodiment) Next, as a third embodiment,
FIG. 3 shows a through-hole as a through hole to be electrically conducted, a device hole as a through hole to be insulated, and an outer lead window. A method of manufacturing a chip carrier, in which the conductive polymer layer formed here is irradiated with an excimer laser to be extinguished, will be described.

(1) Formation of through-holes: Both sides of a polyimide (Kapton KB) film substrate 21 having a thickness of 50 μm were subjected to oxygen plasma treatment, and then nickel was used as a target and argon was used as a carrier gas to form a through-vapor deposition method.
A nickel layer N having a thickness of nm was provided, and a copper layer 22 having a thickness of 1 μm was provided by sputtering using argon as a carrier gas, and then a copper layer 22 having a thickness of 10 μm was formed on both surfaces A and B by electrolytic plating (a).

Subsequently, a resist layer is formed on the B-side by photolithography, and the B-side copper layer is etched with an aqueous solution of ferric chloride to form through holes 23, device holes 24, and outer lead windows 25. Then, the copper layer 22 at the site where the copper is to be formed is removed. This board 21
Is immersed in 50N aqueous potassium hydroxide solution of 15 N for 12 minutes to hydrolyze the polyimide corresponding to the through holes 23, the device holes 24, and the outer lead window 25, and the resultant is washed with water to prepare a 10% sulfuric acid aqueous solution 20%. It was immersed in a temperature of 1 ° C for 1 minute.

Then, a degreasing solution (Nutra Clean 68) consisting mainly of an aqueous solution of a surfactant prepared by adding sodium pyrosulfite to an anionic surfactant of sodium alkylbenzene sulfonate is immersed in 50 ° C. for 3 minutes to hydrolyze the polyimide. The thing was removed. Through these processes, through holes 23, device holes 24, and through holes corresponding to the outer lead windows 25 were formed (b).

(2) Formation of conductive polymer (polypyrrole) layer: 50 g / l of the substrate 21 on which each through hole was formed
Immerse in a liquid containing potassium permanganate and 40 g / l sodium hydroxide at 90 ° C. for 3 minutes, wash with water, then 20%
Immerse in an aqueous solution of pyrrole and 20% isopropanol at 20 ° C. for 1 minute, and further add 10 ml / l sulfuric acid and 10 g / l.
It was immersed for 1 minute at 20 ° C. in an aqueous solution of 1 sodium peroxodisulfate. Then, it was washed with water and naturally dried. By the above treatment, potassium permanganate, which is an oxidant, first contacts with pyrrole, which is a monomer, on the inner wall surface of each through hole to cause an oxidative polymerization reaction, and further, sodium oxodisulfate, which is an oxidant, is contacted and oxidized. Polymerization reaction is continued and thicker blackish brown polypyrrole conductive polymer layer 2
6 was formed (c).

(3) Removal of conductive polymer layer: Next, a KrF excimer laser was applied to the polypyrrole layer 26 formed on the inner wall surface of the through hole corresponding to the device hole 24 and the outer lead window 25 with an energy density of 1 J.
Irradiation was performed for 20 pulses at a repetition rate of 20 pulses / sec at 20 cm / cm ² / pulse. By this laser irradiation, polypyrrole was volatilized and disappeared (d). At this time, the polyimide surface on the inner wall surface of the through hole was also slightly etched.

(4) Electrolytic plating: Next, the substrate 21 is set to 1
After re-doping the polypyrrole layer 26 on the inner wall surface of the through hole corresponding to the through hole 23 by immersing it in an aqueous solution of 0 ml / l sulfuric acid and 10 g / l sodium peroxodisulfate for 5 minutes at 20 ° C., 1 Electrolytic plating is performed with a current density of 3 A / dm ² in a copper sulfate bath containing normal sulfuric acid.
Copper having a thickness of 15 μm was stacked on the polypyrrole layer 26 on the inner wall surface of the through hole corresponding to the through hole 23 and on the copper layer 22 on both surfaces of the substrate (e).

At this time, the thicknesses of the copper layers 22 on both surfaces of the substrates A and B are both 25 μm except for the regions of the device hole 24 and the outer lead window 25, and the device hole 24 and the outer lead window 2 on the back surface of the A surface.
The area 5 is plated with 32 μ from the nickel layer N.
It became m. Here, when the cross section of the through-hole plating was observed with a scanning electron microscope, the copper plating was surely attached to the inner wall surface of the through-hole of the through-hole 23 via the polypyrrole layer 26 without a gap.

After that, a resist layer 27 is formed on the B surface except for the regions of the device hole 24 and the outer lead window 25 on the back surface of the A surface (f), and the resist layer 27 is formed.
Then, a pattern is drawn by lithography on the copper layer 22 on the B side to form a predetermined pattern by etching with ferric nitrate, and the nickel layer N in the area of the device hole 24 and the outer lead window 25 on the back side of the A side. The copper plating layer deposited on top was removed (g). After that, the same window 22 on the A side is etched by photolithography,
Good inner lead 2 with a predetermined pattern shape
A chip carrier having 8 and outer leads 29 was obtained.

(Embodiment 4) Next, as a fourth embodiment,
4 has a through hole 33 as a through hole to be electrically conducted, a device hole 34 as a through hole to be insulated, and an outer lead window 35,
A method of manufacturing a chip carrier formed by dissolving a conductive polymer layer formed here as a non-conducting step of an inner wall surface of a through hole to be insulated will be described.

(1) Formation of through-holes: After oxygen plasma treatment is applied to the A surface of the polyimide (Kapton KB) film substrate 31 having a thickness of 50 μm, nickel is used as a target, and argon is used as a carrier gas.
A nickel layer N having a thickness of nm is provided, and further a copper layer 32 having a thickness of 1 μm is provided by sputtering using argon as a carrier gas, and then a copper layer 22 having a thickness of 10 μm is formed on the surface A by electrolytic plating (a).

A cyclized isoprene rubber-based negative photoresist (ZPN100: trade name, manufactured by Nippon Zeon Co., Ltd.) having a thickness of 15 μm was applied to the polyimide surface on the entire surface of B and dried. This is exposed and developed with an organic solvent-based developer (ZPN 100: trade name, manufactured by Zeon Corporation),
A resist layer was formed except the regions where the device holes and the outer lead windows were to be formed. This board 31
By dipping in 5N potassium hydroxide aqueous solution at 50 ° C. for 12 minutes, the polyimide corresponding to the through holes 33, device holes 34, and outer lead windows 35 is hydrolyzed, washed with water, and then 10% sulfuric acid aqueous solution. It was immersed in 20 ° C. for 1 minute. Then, the resist was peeled off by immersing it in toluene.

Then, a degreasing solution (Nutra Clean 68) mainly composed of an aqueous solution of a surfactant obtained by adding sodium pyrosulfite to an anionic surfactant of sodium alkylbenzene sulfonate (Nutra Clean 68) was immersed for 3 minutes in the above polyimide. Was removed. Through the above processing, through holes 33, device holes 34,
Through holes corresponding to the outer lead windows 35 were formed (b).

(2) Formation of conductive polymer (polypyrrole) layer: Next, 50 g of the substrate 31 on which each through hole is formed
/ L Potassium permanganate and 40g / l sodium hydroxide in a liquid containing 3 minutes at 90 ℃, washed with water, and then immersed in an aqueous solution of 20% pyrrole and 20% isopropanol for 1 minute at 20 ℃ Then, add 20 ml of an aqueous solution of 10 ml / l sulfuric acid and 10 g / l sodium peroxodisulfate.
It was immersed for 1 minute at ℃. By these processes, the substrate 31
Of the through hole 33, the device hole 34, and the inner wall of each through hole corresponding to the outer lead window 35, the potassium permanganate, which is an oxidant, and the pyrrole, which is a monomer, are first brought into contact with each other on the polyimide surface in the entire B surface. Oxidative polymerization reaction occurs, further contact with oxidant sodium peroxodisulfate to continue the oxidative polymerization reaction,
A thicker black-brown polypyrrole conductive polymer layer 36 was formed (c). Then, it was washed with water and naturally dried.

(3) Removal of conductive polymer layer: Thereafter, cyclization is performed on the polypyrrole layer 36 over the entire B surface including the inner wall surfaces of the through holes 33, the device holes 34, and the through holes corresponding to the outer lead window 35. The isoprene rubber-based negative photoresist is applied to a thickness of 15 μm and dried, and then exposed and developed to form the device hole 34,
The inner wall of the through hole of the through hole 33 and the B surface were masked with a resist 37 except for the inner wall surface of the through hole corresponding to the outer lead window 35, and a circuit pattern was formed on the B surface resist layer 37 (d).

Next, this substrate 31 was immersed in a 15N potassium hydroxide aqueous solution at 50 ° C. for 1 minute, washed with water, and then washed with 10
% Sulfuric acid aqueous solution was immersed in 20 ° C. for 1 minute and washed with water. As a result, the portion of the polypyrrole layer 36 not masked with the resist 37 including the inner wall surface of the through hole corresponding to the device hole 34 and the outer lead window 35 was removed (e). At this time, the polyimide surface was slightly etched. After that, the substrate 31 was dipped in toluene to remove the resist 37.

(4) Electrolytic plating: Next, the substrate 31 is set to 10
The polypyrrole layer 36 was dipped in an aqueous solution of ml / l sulfuric acid and 10 g / l sodium peroxodisulfate for 5 minutes at 20 ° C.
Was doped. After that, it was immersed in an aqueous solution of 0.5M palladium chloride and 0.06M hydrochloric acid for 3 minutes to perform natural plating of palladium P on the polypyrrole layer 36. Then, the current density is 3 in a copper sulfate bath containing 1N sulfuric acid.
Electrolytic plating was performed at A / dm ² , and copper having a thickness of 15 μm was stacked on the inner wall surface of the through hole of the through hole 33, the entire A-side copper layer, and the B-side palladium wiring pattern surface (f).

By this electrolytic plating, the thickness of the copper layer 32 on the A surface becomes 25 μm except for the regions of the device hole 34 and the outer lead window 35 on the back surface of the A surface,
The thickness of the copper layer 32 on the B side was 15 μm. Further, the regions of the device hole 34 and the outer lead window 35 on the back surface of the A surface were also plated from the nickel layer N to have a thickness of 32 μm. At this time, when the cross-section of the through-hole plating was observed with a scanning electron microscope, the copper plating was surely attached to the inner wall surface of the through hole via the polypyrrole layer 36 and the palladium layer P without any gap.

Then, the device hole 34 on the back side of the A side is formed.
And B excluding the area of the outer lead window 35
A resist layer 28 was formed on the surface and a circuit wiring pattern was formed on the resist layer 38 on the A surface by lithography (g). Then, the copper layer deposited on the nickel layer N in the region of the device hole 34 on the back surface of the A side and the outer lead window 35 was removed by etching with ferric nitrate. Subsequently, the copper layer 32 on the A surface was also etched to form a predetermined pattern shape (h). By the above operation, a chip carrier having a good inner lead 39 and an outer lead 40 was obtained.

When the metal foil layer is formed on the insulating base material, it is desirable to provide an anchor layer between them in order to enhance the adhesion between them, as shown in the third and fourth embodiments. When the metal is copper, it is advisable to deposit chromium, nickel or the like by the sputter deposition method.

Further, in the above-described first to fourth embodiments, the through holes are provided in the polyimide substrate by wet etching, but the present invention is not limited to this, for example, dry etching by plasma etching or excimer laser irradiation. You may go by law.

Further, when forming a conductive polymer on the surface of the insulating base material such as the inner wall surface of the through hole, a surface activation treatment may be performed in advance, if necessary. As a result, the monomer and oxidant for forming the conductive polymer on the surface of the insulating base material are favorably retained. Examples of such surface activation treatment include, in the case of a polyimide film substrate, surface roughening treatment by immersion in an aqueous sodium hydroxide solution, plasma bombardment treatment with oxygen or the like, physical or chemical treatment such as corona treatment, etc. There are various types, but they may be appropriately selected depending on the types of monomers, oxidizing agents and these solvents actually used.

When a resist mask is formed on the inner wall surface of a through hole to be insulated such as a device hole or outer lead window during electrolytic plating as in the first and second embodiments, the resist used is Any material can be used as long as it can withstand electrolytic plating and can be peeled off. However, with respect to the resist developing solution and the stripping solution used in the present invention, it is preferable to use an aqueous solution rather than a solvent because the apparatus does not become complicated, waste solution processing is easy, and there is no environmental damage. Therefore, for example, in the case of forming a resist pattern by screen printing, an alkali peeling type resist is preferable, and in the case of forming a resist pattern by photolithography, alkali developing and alkali peeling type resist are desirable.

When electrolytic plating is applied to the through holes to be made conductive such as through holes, it may be applied to one or both metal layers of the insulating material base material, or one or both metal layers. When a lift-off type pattern is formed on the entire layer by resist, semi-additive plating may be applied to form a circuit pattern.

When circuit wiring is provided on the copper layers on both sides of the substrate by lithography, it can be performed by a generally used method. That is, a subtraction method of forming a wiring pattern by forming a resist pattern by screen printing or a photoresist and etching a metal layer, or an additive plating method of forming a wiring circuit by lift-off.

The circuit wiring may be formed before the through-hole plating. For example, in the subtractive method, after forming each through hole in the polyimide substrate, in the additive plating method, the circuit wiring can be formed also as the electrolytic plating after depositing the copper foil on the polyimide substrate before forming the through hole. When forming a pattern by this subtraction method, for example, the resist layer 7 before electrolytic plating in the first embodiment is applied to the entire circuit wiring pattern except the through-hole portion 3. Further, in the additive plating method, it is also possible to form a pattern with the resist layer 7 and form circuit wiring also for electrolytic plating.

Further, in the above-mentioned first to fourth embodiments, the two-layer type chip carrier consisting of the insulating layer (polyimide) and the copper layer has been shown. Needless to say, it is similarly effective for a three-layer type carrier such as / paste layer / copper layer.

(Fifth Embodiment) Next, as another embodiment, a chip carrier having a through hole as a through hole to be electrically conducted and an alignment hole as a through hole to be insulated in FIG. The manufacturing method of is shown.

(1) Formation of through-holes: 50 μm-thick polyimide (Kapton KB: trade name, manufactured by DuPont Toray) film substrate 41 on both sides of a cyclized isoprene-based negative photoresist (ZPN100: trade name, manufactured by ZEON CORPORATION). Made) 1
The entire surface was coated to a thickness of 5 μm and dried. Further, it is exposed to light, and an organic solvent-based developer (ZPN100: trade name, manufactured by Zeon Corporation)
Then, the resist layer 42 was formed over the entire area of the A surface, and the B surface was formed except for the portions where the through holes 43 and the alignment holes 44 were to be formed (a).

Thereafter, the substrate 41 is immersed in a 15 N potassium hydroxide aqueous solution at 50 ° C. for 12 minutes to hydrolyze the polyimide in the portions to be the through holes 43 and the alignment holes 44, followed by washing with water. 10%
It was dipped in the sulfuric acid aqueous solution of 1 at 20 degrees for 1 minute and washed with water. Then, the resist layer 42 was peeled off by immersing it in toluene.

Next, the substrate 41 was changed to a degreasing solution (Nutra Clean 68: trade name, manufactured by Shipley Co., Ltd.) mainly containing an aqueous solution of a surfactant obtained by adding sodium pyrosulfite to an anionic surfactant of sodium alkylbenzene sulfonate. Fifty
By immersing at 3 ° C. for 3 minutes, the above-mentioned polyimide hydrolyzate was removed. Through the above process, through holes corresponding to the through holes 43 and the alignment holes 44 were formed (b).

(2) Formation of conductive polymer (polypyrrole) layer: Next, the substrate 41 having the through holes formed therein.
Was immersed in an aqueous 8 N potassium hydroxide solution at 50 ° C. for 1 minute and then washed with water to roughen the surface of the polyimide substrate. Then, it was immersed in a 50 g / l potassium permanganate aqueous solution at 90 ° C. for 3 minutes and washed with water.

Then, it was immersed in an aqueous solution of 20% pyrrole and 20% isopropanol at 20 ° C. for 1 minute, and then in an aqueous solution of 10 ml / l sulfuric acid and 10 g / l sodium peroxodisulfate at 20 ° C. for 1 minute. did. By these treatments, on the roughened substrate surface of the polyimide,
First, potassium permanganate, which is an oxidant, and pyrrole, which is a monomer, contact each other to generate an oxidative polymerization reaction to generate polypyrrole, and the oxidative polymerization reaction is continued by contact with sodium peroxodisulfate, which is an oxidant, A thicker black-brown polypyrrole layer 45 was formed on the surfaces of the polyimide substrates on both sides of A and B and on the inner wall surface of each through hole corresponding to the through hole 43 and the alignment hole 44 (c). Then, it was washed with water and dried naturally.

(3) Formation of resist layer: After that, A,
A cyclized isopropylene rubber-based negative photoresist (ZPN100) was coated on the entire surface of the conductive polymer layer 45 on both sides of the B substrate to a thickness of 15 μm and dried. Next, the resist layer 46 is exposed and developed to draw a circuit pattern on both surfaces of the A and B substrates, the inner wall surface of the through hole corresponding to the through hole 43 is masked, and the inner wall surface of the through hole corresponding to the alignment hole 44 is masked. It was formed so as not to do (d).

As described above, the substrate 41 having the resist mask formed on the predetermined portion thereof was placed in a 15N potassium hydroxide aqueous solution to form 5 parts.
After immersion at 0 ° C. for 1 minute, it was washed with water, then immersed in a 10% sulfuric acid aqueous solution at 20 ° C. for 1 minute and washed with water. As a result, the polypyrrole in the portion not protected by the resist 46 was removed. At this time, the polyimide surface was also slightly etched. Then, the substrate 41 was immersed in toluene to remove the resist layer 46.

(4) Electrolytic plating: Next, the substrate 41 is set to 1
The polypyrrole layer 45 was re-doped by immersing it in an aqueous solution of 0 ml / l sulfuric acid and 10 g / l sodium peroxodisulfate at 20 ° C. for 5 minutes. After that, 0.
The polypyrrole layer 45 was naturally plated with palladium by immersing it in an aqueous solution of 5M palladium chloride and 0.06M hydrochloric acid for 3 minutes.

After that, electrolytic plating was performed at a current density of 3 A / dm ² in a copper sulfate bath containing 1N sulfuric acid to obtain 15 μm.
5 m of copper plating layer 48 is stacked on the inner wall surface of the through hole to be the through hole 34 and the palladium wiring pattern surface 47 on both surfaces of the A and B substrates, through hole plating and additive pattern plating are performed, and the circuit pattern is formed as shown in FIG. It was formed as shown in FIG. At this time, when the cross-section of the through-hole plating was observed with a scanning electron microscope, it was confirmed that the copper plating adhered to the polyimide surface without a gap via the conductive polymer layer 45 and the palladium plating layer.

In the present embodiment, before the step of forming the conductive polymer layer 45, the above-mentioned gel is formed on the surface of the polyimide film substrate 41 having the through holes shown in FIG. 5B. You may perform the gel-form layer formation process which forms the surface layer part which consists of a product in the form of a gel. This has the advantage that the adhesion of the circuit (metal wiring layer) to the substrate can be improved.

Further, in the fifth embodiment described above, the perforation for forming the through hole was carried out by the wet etching method using the alkaline reaction solution, but it may be appropriately selected according to the insulating material base material to be used. . Further, not limited to the wet etching method, for example, a dry etching method such as plasma etching or excimer laser irradiation etching,
Perforation may be performed by punching.

Furthermore, in the above-mentioned first to fifth embodiments, the case where the electrolytic plating is performed has been described.
It can also be applied when performing electroless plating. Instead of the catalyst activation treatment for adhering a noble metal such as palladium on the surface of the insulating layer as the pretreatment in the electroless plating, a conductive polymer film can be formed and electroless plating can be performed. Further, as in the fourth and fifth embodiments, a method of performing natural plating of a noble metal such as palladium or silver and then performing electrolytic plating may be used.

[0111]

According to the method of manufacturing a circuit board of the present invention,
The metal plating layer can be selectively applied only to the through holes to be electrically conducted by the conductive polymer by the oxidative polymerization, and the holes for forming the through holes to be conducted and the through holes to be insulated are formed. Since they can be performed simultaneously, the number of times of etching can be reduced as compared with the conventional method, and a circuit board can be easily manufactured.

In particular, when manufacturing a circuit board in which metal wiring is projected on one surface of the through hole to be insulated or is arranged on a bridge, the metal wiring is reduced or eliminated by punching the through hole. Therefore, a good circuit board can be easily prepared. Through-hole plating is formed in the through holes to be electrically connected.

For example, in the manufacturing process of the double-sided TAB tape carrier, the through holes of the through hole portion, the device hole portion, and the outer lead window portion are sufficiently insulated, and the device hole is also formed. The shape of the outer lead extending over the inner lead and the outer lead window straddling the bridge in the shape of a bridge is good, and no reduction of metal foil occurs.

Further, the plastic material of the insulating substrate is hydrolyzed to form a surface layer portion made of a gel-like product, and either the monomer or the oxidizing agent is contained in the surface layer portion, and then the surface layer is acidified. To neutralize and solidify the part, and then contact either the monomer or the oxidant with the other to cause an oxidative polymerization reaction to form a conductive polymer layer while being integrally fixed to the surface layer part. Therefore, it is possible to perform highly reliable plating with strong adhesion through the conductive polymer layer.

[Brief description of drawings]

FIG. 1 is a schematic view showing a method of manufacturing a chip carrier according to a first embodiment of the present invention.

FIG. 2 is a schematic view showing a method of manufacturing a chip carrier according to a second embodiment of the present invention.

FIG. 3 is a schematic view showing a method of manufacturing a chip carrier according to a third embodiment of the present invention.

FIG. 4 is a schematic diagram showing a method of manufacturing a chip carrier according to a fourth embodiment of the present invention.

FIG. 5 is a schematic view showing a method of manufacturing a circuit board according to a fifth embodiment of the present invention.

[Explanation of symbols]

 1, 11, 21, 31, 41: Polyimide film substrate 2, 12, 22, 32, 48: Copper layer 3, 13, 23, 33, 43: Through hole 4, 14, 24, 34: Device hole 5, 15 , 25, 35: outer lead window 44: alignment hole 6, 16, 26, 36, 47: conductive polymer layer 7, 17, 27, 37, 38, 42, 46: resist layer 8, 18, 28, 39: Inner lead 9, 19, 29.40: Outer lead

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sekisho 2-6-1, Marunouchi, Chiyoda-ku, Tokyo Furukawa Electric Co., Ltd. (72) Inventor Noboru Matsuki 601-2, Ogizawa, Imaichi, Tochigi Prefecture Furukawa Sarkic Tofoil Co., Ltd. Imaichi Office

Claims (7)

[Claims] 1. A base material made of an insulating material, metal layers formed on both surfaces of the base material, and a conductive hole having an inner wall surface with a metal plating layer for electrically connecting these metal layers to each other. A method for manufacturing a circuit board, comprising: a non-conducting hole having an insulated inner wall surface that does not electrically connect the metal layers on both surfaces to each other, comprising a first through hole and a second through hole. For a substrate having
A conductivity imparting step of forming a conductive polymer layer on each inner wall surface of the first through hole and the second through hole; and at least the surface of the inner wall surface of the second through hole having the conductive polymer layer formed thereon. A non-conducting non-conducting step, and a plating step of depositing a metal plating layer on the surface of the conductive polymer layer on the inner wall surface of the first through hole which has not been non-conducting in the non-conducting step. A method for manufacturing a circuit board, comprising: 2. The circuit according to claim 1, wherein the non-conducting step includes a step of removing the conductive polymer layer formed on the inner wall surface of the second through hole by dissolving or etching. Substrate manufacturing method. 3. The non-conducting step includes a step of causing the conductive polymer layer formed on the inner wall surface of the second through hole to disappear, destroy or expire by irradiation with an energy beam. 1. The method for manufacturing a circuit board as described in 1. 4. The circuit according to claim 1, wherein the non-conducting step includes a step of masking the surface of the conductive polymer layer formed on the inner wall surface of the second through hole with a resist. Substrate manufacturing method. 5. The circuit board according to claim 1, further comprising a step of doping the surface of the conductive polymer layer with a dopant for improving conductivity. Production method. 6. A method for producing a circuit board having a base material made of an insulating material and a metal wiring layer formed on the base material, wherein the predetermined area is formed on the entire surface of the base material. After forming a conductive polymer layer and performing a treatment for removing the conductive polymer or eliminating the conductivity on the insulated portion except the conductive portion where the metal wiring layer is to be formed in the region, metal plating is performed. A method of manufacturing a circuit board, comprising forming a metal wiring layer on the conductive portion. 7. The insulating portion includes a first through hole that is electrically non-conductive and / or an adjacent insulating portion of the metal wiring layer, and the conductive portion is electrically conductive. 8. The method for manufacturing a circuit board according to claim 7, wherein the through hole and / or the conductive portion of the metal wiring layer are included.