CN1093892C - Unconducting surface electroplating - Google Patents

Unconducting surface electroplating Download PDF

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Publication number
CN1093892C
CN1093892C CN94100873A CN94100873A CN1093892C CN 1093892 C CN1093892 C CN 1093892C CN 94100873 A CN94100873 A CN 94100873A CN 94100873 A CN94100873 A CN 94100873A CN 1093892 C CN1093892 C CN 1093892C
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CN
China
Prior art keywords
graphite
layer
hole
electrical insulator
copper
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Expired - Fee Related
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CN94100873A
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Chinese (zh)
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CN1092118A (en
Inventor
坂本佳宏
中村幸子
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MIKATSU CO Ltd
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MIKATSU CO Ltd
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Publication of CN1092118A publication Critical patent/CN1092118A/en
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Classifications

    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
    • H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0323—Carbon
    • 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
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/427—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in metal-clad substrates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The object of this invention is to directly electroplate the surface of a nonconductor such as a printed circuit board with a conductive metal at a low cost and with high reliability. A dispersion of the graphite grains having <=2mum average diameter and a binder in water is brought into contact with the surface of a nonconductor to form a graphite-grain layer, and the nonconductor is electroplated with the grain layer as a substrate layer.

Description

The electro-plating method on electrical insulator surface
The present invention relates to a kind of at electrical insulator, particularly on the through-hole wall of printed circuit board (PCB) (PWB), the method for Direct Electroplating conductive metal.
In so-called two panels or multiple-plate printed circuit board (PCB), but, must on substrate, offer the communicating pores that is called through hole, and electroplate conductive metal on the wall within it in order to make circuit conducting each other.
Relevant on the through-hole wall of electrical insulator electric plating method, for example in No. 3163588 specification sheets of the United States Patent (USP) that the people had such as Shortt, gave after the electroconductibility thereby once disclose a kind of particles such as silver, copper, graphite that on through-hole wall, adhere to, gave electric plating method again.Yet, the method of using this specification sheets to put down in writing, to too much electroplate when partly peeling off, can produce defectives such as pin hole on the electrolytic coating of through-hole wall, therefore, must re-plating on this inwall, not only can make the process complexity, can't adapt to high-density fully simultaneously and require the manufacturing of the printed circuit board (PCB) at present of high reliability.
Again, No. 3099608 specification sheetss of the United States Patent (USP) that Radovsky etc. had were once pointed out: use graphite as the shortcoming for galvanized conductive layer, the sticking power that is the conductive metal that is coated with is low, and the through-hole diameter after the plating is inhomogeneous, and the electric durability of graphite itself is poor.
So, at present with electroless plating copper, as the electro-plating method of the metal plating of through-hole wall.But electroless plating copper has following shortcoming:
(1) technological process needs the long time.
(2) must often monitor that a plurality of treatment troughs (must distinguish supply for the composition in the groove.Because treatment trough is very responsive for polluting, the used composition of last technological process is brought in so must fill a part attention.
(3) a plurality of ablution grooves must be arranged, and need a large amount of clean water.
(4) wastewater treatment must expense.
Do not use the method for electroless plating copper with the problems referred to above, once disclose in all No. 5139642 specification sheetss of United States Patent (USP) such as Rondolph: make contain median size about less than 3 μ m carbon black and the dispersion liquid of interfacial agent contacts the formation carbon black layer with through-hole wall after, make again and contain median size and contact with this carbon black layer less than the dispersion liquid of the graphite particle of 1.5 μ m and interfacial agent approximately and form after the graphite linings, carry out electric plating method again.Yet, according to this method, must form carbon black layer and the two-layer bottom of graphite linings as coating, so complex technical process, cost can increase.
Contriver etc. for provide a kind of than use two layers of reliability such as carbon black layer and graphite linings as the aforesaid method of the bottom of electrolytic coating higher and do not consume cost at electrical insulator, particularly on the through-holes of printed circuit boards inwall, electroplate the electro-plating method of conductive metal, carry out investigation repeatedly with keen determination, finish the present invention eventually.
Particularly, the present invention relates to the electro-plating method on a kind of electrical insulator surface, it is characterized in that:
The pH value that order contains the inorganic adhesive of the graphite particle of 2～6 weight %s of median size below 2 μ m and 0.05～5 weight % is 9～13 aqueous dispersions, contact with the electrical insulator surface, make graphite particle attached to it, and formation granular graphite sublayer, then, above-mentioned granular graphite sublayer is electroplated as conductive layer.
In addition, the invention still further relates to a kind of electro-plating method of through-hole wall of printed-wiring board (PWB), it is characterized in that:
(a) to contain the pH value of the inorganic adhesive of the graphite particle of 2～6 weight %s of median size below 2 μ m and 0.05～5 weight % be 9～13 aqueous dispersions in order, with close its surface that forms by conductive metal layer and electrical insulator layer by layer and have the conductive metal layer and have the substrate surface of through hole to contact, after making graphite particle attached to aforesaid substrate surface and described through-hole wall formation granular graphite sublayer
(b) this is attached to the granular graphite sublayer of conductive gold metal surface, so that the mode of this metal level ablation 0.01-1.8 μ m is removed,
(c) then, again the granular graphite sublayer of through-hole wall described in this conductive metal layer and the electrical insulator layer is electroplated as conductive layer.
The method according to this invention at first makes specific graphite aqueous dispersions contact with the surface of the electrical insulator of electroplated, and graphite particle is adhered to, and forms the granular graphite sublayer.
Above-mentioned graphite particle, its median size below 2 μ m, with below 1 μ m for well, the following ultramicron of 0.7 μ m preferably.When above-mentioned median size surpasses 2 μ m, electroconductibility can reduce, moreover, also can reduce to electrical insulator and by the tack of galvanized conductive metal layer.
The content of the graphite particle in the above-mentioned specific graphite aqueous dispersions below 6% (weight %, as follows), is preferably in 2-5%.When above-mentioned content surpasses 6%, connect airtight with electrical insulator and galvanized conductive metal interlayer and to have bad tendency; When less than 2% the time, the graphite particle density in the granular graphite sublayer is little, does not have the electroconductibility of filling part.
Though above-mentioned tackiness agent can be attached to through hole inside in order to make graphite particle securely with organic binder bond or inorganic adhesive, the most handy inorganic adhesive for example uses water glass or potassium silicate etc. more satisfactory.
The content of above-mentioned tackiness agent in the graphite aqueous dispersions is generally 0.05-5%.If the content of tackiness agent is too much, then electroconductibility and the decline of system film.
In above-mentioned specific graphite aqueous dispersions,, preferably add the water-soluble polymer of carboxymethyl cellulose, starch, gum arabic etc. in order to improve the stability of this liquid.And also can add ammonia, sodium hydroxide, potassium hydroxide etc., preferably add ammonia, preferably make its pH value keep the degree of 9-13.And in order to improve the tack of graphite particle to electrical insulator, for example preferably adding, the negatively charged ion of carboxylic acid system, poly carboxylic acid system etc. is an interfacial agent.
Again, above-mentioned specific graphite aqueous dispersions, be with the wet type mode pulverize, dispersion, classification and make, have stable dispersiveness, graphite particle diameter narrow distribution range etc., satisfactory performance.
The general characteristic that coating is required, be requirement its can bedew ground, the formation uniform films that can flow can obtain the tack of excellence when drying, can keep the continuity of film and thoroughness or the like.These characteristics, can form uniform graphite film at through-hole wall, and when follow-up plating, can form the zero defect metal level if suitably use the graphite aqueous dispersions with these characteristics with identical in the desired characteristic in through-hole wall formation granular graphite sublayer.
Utilize above-mentioned specific graphite dispersion liquid to there is no particular restriction in the method that the electrical insulator surface forms the granular graphite sublayer, for example, can adopt easily: with the graphite particle aqueous dispersions, after coating the surface of electrical insulator with methods such as sprinkling, dipping, coatings, the method that dispersion medium is removed with methods such as drying, bake again.
Then, again with above-mentioned granular graphite sublayer as conductive layer, conductive metal is electroplated up.
Above-mentioned electric plating method there is no particular restriction, for example, can use general plating tank, with normal temperature, 1.5-3A/dm 2, the condition about 60-90 minute, electroplate.Above-mentioned conductive metal there is no particular restriction, can be for example copper, nickel or the like.
Method of the present invention is applicable to the plating of various electrical insulators, particularly is applicable to the plating of the through-holes of printed circuit boards inwall that for example paper base material phenol resins copper-surfaced laminated wood, glass baseplate Resins, epoxy copper-surfaced laminated wood, matrix material copper-surfaced laminated wood, polyimide copper-surfaced laminated wood, fluoro-resin copper-surfaced laminated wood, pliability copper-surfaced laminated wood etc. are constituted.Electrochemical plating of the present invention, it is very good all over attached property, even the path in through hole and be called as inclined hole, the aperture is the hole inwall of 0.3-0.5mm, also can implement the plating that thickness is even and tack is good, reliability is high.
Exemplary process when secondly, the present applies the present invention to the plating of printed circuit board through-hole inwall is described as follows.
At this, being taken at through-hole wall that the surface has the glass baseplate Resins, epoxy copper-surfaced laminated wood of Copper Foil, to implement galvanized situation be that example describes, and with following (1)-(6) process, electroplate.Again, the graphite coating is repeated twice process, that is the process that the order of employing (1), (2), (3), (4), (2), (3), (4), (5), (6) is formed can be carried out the higher plating of reliability if adopt.(1) cleaning of substrate surface:
This one handles, and in order to the through-hole wall purifying treatment, is to be that the pH of interfacial agent is the weak lye of 9-12 scope with substrate to contain negatively charged ion just like phosphoric acid ester etc., cleans about 20-60 down after second in 35-65 ℃, gives washing again.(2) conditioning is handled:
This processing, system is attached to the processing of the through-hole wall of peace and quietization in order to promote graphite particle, be to be that the pH of interfacial agent is the weak lye of 9-12 scope to contain positively charged ion just like polyamide-based, polyamine system etc., handle 20-60 down after second in 20-60 ℃, give washing again substrate.(3) graphite coating:
In the graphite dispersion liquid, usually with aforesaid substrate under 20-60 ℃, make the about 30-90 dip treating of second.(4) removal of dispersion medium (water):
In 30-60 ℃ air-supply, with exposure of substrates 30-90 second.(5) little etch:
In the granular graphite sublayer of adhering on the electrical insulator of copper surface and through-hole wall, the granular graphite sublayer on copper surface can reduce tack and the conduction between copper surface and galvanized conductive metal.This processing is the processing of removing for the granular graphite sublayer on this copper surface.This processing is not to directly act on graphite particle, but the copper surface of graphite particle lower floor is given ablation, thereby removes graphite particle; For example, the sulfuric acid/hydrogen peroxide that substrate be impregnated in 20-30 ℃ is in the etchant, makes 0.01-1.8 μ m, be preferably the ablation of 0.1-1.2 μ m degree after, give washing, drying again.Again, if above-mentioned ablation amount is during discontented 0.0 1 μ m, can residual graphite particle on the copper surface; When surpassing 1.8 μ m, the then excessive ablation of copper, and the conducting of the graphite particle interlayer on copper and electrical insulator surface is lost, so that have generation to electroplate the tendency of hole.(6) electroplate:
With general plating tank, at normal temperatures, with 1.5-3A/dm 2, 60-90 minute condition electroplate.
Clean and the conditioning of (2) of the substrate surface of above-mentioned (1) are handled and can be carried out during the course.At this moment, be that the pH of interfacial agent, thanomin equal solvent is the weak lye of 9-12 scope with containing just like polyamine system, polyamide-based etc. positively charged ion, handle about 20-60 down after second at 20-60 ℃, wash and get final product.
Embodiment 1
In this embodiment, used substrate is to contain thing that epoxy resin dipping becomes as insulation layer on glass baseplate, with thick be that the Copper Foil of 35 μ m clips this insulation layer and is fixed in its two sides and forms (wide about 10cm is about 25cm), it is about 960 of the through hole of 0.3-0.8mm that diameter is arranged on this substrate.This substrate is handled with following manner.
At first, with aforesaid substrate, impregnated under 45 ℃ by positively charged ion is that interfacial agent 0.5%, amine 1.0%, residue are in the liquid formed of water 40 seconds, and then gives washing (clean, nurse one's health).Then, impregnated under 25 ° by the graphite particle of 4% mean diameter 0.4 μ m, 0.5% carboxymethyl cellulose, 0.5% water glass, 1% negatively charged ion is that interfacial agent, residue are that water is formed and to modulate pH with ammonia be in 10 the graphite dispersion liquid after 60 seconds, blow 40 ℃ air 45 seconds again with the air-supply method, remove dispersion medium.Then, again this substrate be impregnated in above-mentioned sanitising agent, the amendment 40 seconds under 25 ℃, and then give the washing conditioning.Continue it, this substrate be impregnated under 25 ℃ in the above-mentioned graphite dispersion liquid after 60 seconds, blow 40 ℃ air 45 seconds again with the air-supply method, remove dispersion medium.Afterwards, this substrate be impregnated under 25 ℃ in the liquid of being formed by sulfuric acid, hydrogen peroxide etc. (CA-90 of U.S.'s storehouse corporate system) after 20 seconds, give washing, dry (little erosion) again.A little erosion whereby, copper is by ablation 1 μ m.
Secondly, utilize general copper plating tank, with aforesaid substrate with 2A/dm 2Current density, 25 ℃ of following copper facing 90 minutes.
With the result that the substrate that is obtained is checked with method of testing backlight, find to be coated with on its hole wall the copper layer of uniform thickness, and, being not only the aperture is the bigger through hole of 0.6-0.8mm, connecting the aperture is the small-bore through hole of 0.3-0.5mm, also all electroplates well the electroless plating hole.Again, with wicking test (according to JIS C 5012, oil is transformed into 260-265 ℃ scolding tin, carries out ten circulations) connecting airtight property of test, find to there is no and peel off phenomenon through electroplating copper on hole wall.
Embodiment 2
In this embodiment, except the amount of the graphite particle of graphite dispersion liquid replaces with 3.0%, other steps are all identical with embodiment 1, and treatment substrate is electroplated according to this.
The substrate that obtained is assessed according to the method identical with embodiment 1, found to be electroplate with on the hole wall of substrate the copper layer of uniform thickness,, also electroplate well, there is no the plating hole even the aperture is the path through hole of 0.3-0.5mm.Do not see after the test of connecting airtight property that galvanized copper peeled off by hole wall again, yet.
Embodiment 3
In this embodiment, except use by the graphite particle of 3% median size 0.4 μ m, 0.5% potassium silicate, 1% positively charged ion be interfacial agent, all the other form as water and be that other steps of treatment substrate are all identical with embodiment 1 10 the graphite dispersion liquid with ammonia modulation pH.
The substrate that obtained is assessed according to the method identical with embodiment 1, found to be electroplate with on the hole wall of substrate the copper layer of uniform thickness,, also electroplate well, there is no the plating hole even the aperture is the path through hole of 0.3-0.5mm.Do not see after the test of connecting airtight property that galvanized copper peeled off by hole wall again, yet.
Embodiment 4
In this embodiment, the dispersion liquid of graphite particle that contains 4.5% average particle diameter 0.5 μ m except use is as the graphite dispersion liquid, and other steps are all identical with embodiment 1, and treatment substrate is electroplated according to this.
The substrate that obtained is assessed according to the method identical with embodiment 1, found to be electroplate with on the hole wall of substrate the copper of uniform thickness,, also electroplate well, there is no the plating hole even the aperture is the path through hole of 0.3-0.5mm.Do not see after the test of connecting airtight property that galvanized copper peeled off by hole wall again.Comparative example 1
In this comparative example, the dispersion liquid of graphite particle that contains 3.0% average particle diameter 3 μ m except use is as the graphite dispersion liquid, and other steps are all identical with embodiment 1, and treatment substrate is electroplated according to this.
The substrate that obtained is assessed according to the method identical with embodiment 1, found that the aperture is in the through hole of 0.6-0.8mm, about 70% has the plating hole, is the through hole of 0.3-0.5mm as for the aperture, and the plating hole is almost all arranged.Again, be the hole of 0.8mm for the aperture, connecting airtight property test-results shows that galvanized copper-stripping is defective in the hole.Comparative example 2
In this comparative example, except use contain 4.5% average particle diameter be the graphite dispersion liquid of 3 μ m as the graphite dispersion liquid, other steps are all identical with embodiment 1, treatment substrate is electroplated according to this.
The substrate that obtained is assessed according to the method identical with embodiment 1, found that the aperture is in the through hole of 0.6-0.8mm, about 50% has the plating hole, is the through hole of 0.3-0.5mm as for the aperture, and the plating hole is almost all arranged.Again, be the hole of 0.8mm for the aperture, connecting airtight property test-results shows, the copper-stripping of electroplating in the hole is defective.
By The above results as can be known, the method according to this invention is compared in the comparative example of the graphite dispersion liquid that surpasses 2 mu m ranges with using the graphite average particle size distribution, can obtain the plating all over attached property and sticking power excellence.
The method according to this invention can not consume the method for cost, be carried out the plating of high reliability on electrical insulator.Method of the present invention, but high reliability be applicable to the printed circuit board (PCB) of multilayer small-bore.

Claims (2)

1. the electro-plating method on an electrical insulator surface is characterized in that:
The pH value that order contains the inorganic adhesive of the graphite particle of 2～6 weight %s of median size below 2 μ m and 0.05～5 weight % is 9～13 aqueous dispersions, contact with the electrical insulator surface, make graphite particle attached to it, and formation granular graphite sublayer, then, above-mentioned granular graphite sublayer is electroplated as conductive layer.
2. the electro-plating method of the through-hole wall of a printed-wiring board (PWB) is characterized in that:
(a) to contain the pH value of the inorganic adhesive of the graphite particle of 2～6 weight %s of median size below 2 μ m and 0.05～5 weight % be 9～13 aqueous dispersions in order, with close its surface that forms by conductive metal layer and electrical insulator layer by layer and have the conductive metal layer and have the substrate surface of through hole to contact, after making graphite particle attached to aforesaid substrate surface and described through-hole wall formation granular graphite sublayer
(b) this is attached to the granular graphite sublayer of conductive gold metal surface, so that the mode of this metal level ablation 0.01-1.8 μ m is removed,
(c) then, again the granular graphite sublayer of through-hole wall described in this conductive metal layer and the electrical insulator layer is electroplated as conductive layer.
CN94100873A 1993-01-29 1994-01-24 Unconducting surface electroplating Expired - Fee Related CN1093892C (en)

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Application Number Priority Date Filing Date Title
JP3240393 1993-01-29
JP32403/1993 1993-01-29

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CN1092118A CN1092118A (en) 1994-09-14
CN1093892C true CN1093892C (en) 2002-11-06

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DE (1) DE4402413C2 (en)
GB (1) GB2274853B (en)
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TW (1) TW222313B (en)

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JPH07268682A (en) * 1994-03-28 1995-10-17 Mec Kk Method for electroplating surface of electric nonconductor
JP3481379B2 (en) * 1995-08-23 2003-12-22 メック株式会社 Electroplating method
GB2338715B (en) * 1998-06-24 2003-03-19 Hang Fung Jewellery Co Ltd A method of depositing a metal on an article
US6375731B1 (en) * 2000-01-06 2002-04-23 Electrochemicals Inc. Conditioning of through holes and glass
CN105231604A (en) * 2014-05-27 2016-01-13 中色金银贸易中心有限公司 Gold jewelry
CN114351197B (en) * 2021-11-30 2023-04-28 武汉格智新材料有限公司 Graphite shadow metallization auxiliary agent and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
US4964959A (en) * 1990-04-12 1990-10-23 Olin Hunt Specialty Products Inc. Process for preparing a nonconductive substrate for electroplating

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GB2274853A (en) 1994-08-10
DE4402413C2 (en) 1998-08-06
SG52489A1 (en) 1998-09-28
GB2274853B (en) 1996-05-15
TW222313B (en) 1994-04-11
DE4402413A1 (en) 1994-08-04
CN1092118A (en) 1994-09-14

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