CA2103137A1 - Improved process for preparing a nonconductive substrate for electroplating - Google Patents

Abstract

A process for electroplating a conductive metal layer to the surface of a nonconductive material comprising pretreating the material with a carbon black dispersion followed by a graphite dispersion before the electroplating step.

Description

W092/19794 PCT/USg2/02063 La3l:3~7 IMPROVED PROCESS FOR PREPARING A

~ONCOND~CTIVE SUBSTRATE
,, FOR ELECTROPLATING

This invention is directed to an improved process for electroplating a conductive metal to the surface of a nonconductive material. In particular, this invention relates to a process for preparing the through hole walls of a printed wiring board (PWB) for electroplating. Further, this invention relates to a new liquid conductive graphite dispersion for preparing nonconductive material for electroplating. Still ,~ further, the present invention relates to the resulting .l 10 nonconductive material prepared by the above-noted 's p roces s .
;~ Conventional electroless processes have several commercial disadvantages. They require a relatively long process time. The multiple treatment baths have complex chemistry which may require constant monitoring .
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~llJ~l 3 7 -2-and individual ingredients which may require separate replenishment. The conventionally used palladium/tin activator also may require expensive waste treatment.
Furthermore, these electroless process baths may be very sensitive to contamination. Finally, the multiplicity of rinse baths may require large amounts of water.
Prior to the electroless method of plating through holes, graphite was employed to prepare the walls of the through holes for plating. For e~ample, U.S. Patent No. 3,099,608, which issued to Radovsky et al. on July 30, 1963, teaches a process for preparing ! the through hole walls of printed circuit boards (also called printed wiring boards or PWB's) for electro-plating by initially depositing in said through holes a thin electrically nonconductive film of palladium metal in at least a semi-colloidal form. The patent discloses that graphite had been used previously as a conductive layer for electroplating thereon. See column 1, lines 63-70 and column 4, line 72 to column 5, line 11. These i 20 patentees noted several deficiencies with that graphite process including lack of control of the graphite application, poor deposit of the resultant electroplated metal, nonuniform through hole diameters, and low electrical resistance of the graphite.
~ 25 U.S. Patent No. 3,163,588, which issued to .s Shortt et al. on December 29, 1964, also mentions that graphite or its equivalents may be employed to render through hole walls of electric circuit boards conductive for later electroplating metals thereon. See column 3, 30 line 45 to column 4, line 2.
, U.S. Patent No. 4,581,301, which issued to , Michaelson on April 8, 1986, teaches the application of a seed layer of conductive particles, such as ~carbon", on the walls of through holFs before electrolytically ,., .

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2 i~31 37 plating copper over the seed layer. This reference does not esplicitly teach the use of a continuous layer of carbon black`dispersion in the seed layer, and does not recognize the advantage of using very small particles of carbon black such as presently claimed. See column 7, lines 63-66 which refer to particles passing through a 400 mesh screen. A 400 mesh screen is equivalent to about 35 microns.
Separately, graphite has been employed in numerous processes for preparing a nonconducting material for a metal coating or plating. For example, U.S. Patent No. 409,096, which issued to Alois Blank on August 13, 1889, teaches a process for applying copper to asbestos roofing material which comprises first applying powdered plumbago (graphite) in a volatile liquid such as varnish to the surface of the asbestos, then evaporating the volatile liquid to coat the asbestos fibers with fine particles of plumbago. The plumbago coated asbestos sheets are then immersed in a copper electroplating solution and electric current is applied to the coated asbestos sheet to form a thin film of copper thereon. The copper coated sheet is then immersed in a bath of molten metal such as tin, lead, or ~ zinc, and is then removed from the molten bath to effect !,' 25 solidification of the molten metal. The resulting metal ~: coated asbestos sheet is described as being relatively ~ fle~ible, a nonconductor of heat and substantially `1 fireproof.
U.S. Patent No. 1,037,469, which issued to ! 30 Goldberg on September 3, 1912, and U.S. Patent No.
1,352,331, which issued to Unno on September 7, 1920, . disclose processes for electroplating nonconducting materials by first coating the nonconducting material with wa~, then coating the wax with a slurry of finely ....
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:,:. . . : , - . ~ . -.-W~92/19794 PCT/US92/02063 ~lv~137 -4-divided particles of graphite or other metal, followed by electroplating of the dust-coated surface with copper or other metal. Neither of these processes are particularly suitable for use in coating the hole walls of circuit boards because the holes are normally e~tremely narrow in diameter and immersing in wa~ would tend to plug the hole and prevent coating the hole walls with an electroplating material.
V.S. Patent No. 2,243,429, which issued to Lau~
on May 27, 1991, discloses a process for electroplating a nonconductive surface by "graphiting" a thin layer onto the nonconducting surface followed by applying a copper layer electrolytically and "finally a further electrolytic deposit of another metal" is placed thereon.
Separately, carbon black formulations have been employed as conductive coatings for nonconductive materials. For e~ample, U.S. Patent No. 4,035,265, which issued to Saunders on July 12, 1977, discloses conductive paint compositions containing both graphite and carbon black along with air-hardenable binder.
These paints are suitable for application to the walls of a building for use as a heating element.
U.S. Patent No. 4,090,984, which issued to Lin et al. on May 23, 1978, teaches a semiconductive coating - 25 for glass fibers comprising (a) a polyacrylate emulsion;
(b) electrically conductive carbon black dispersion and (c) a thi~otropic gelling agent. The conductive carbon black dispersions employed are those comprising elec-trically conductive carbon black dispersed, from about 3 to about 4~ by weight, in a suitable dispersing agent.
U.S. Patent No. 4,239,794, which issued to Allard on December 16, 1980, teaches dispersing a - conductive carbon black in a late~ binder with a selected dispersing agent,~ then impregnating this carbon ;

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~ W092/l9794 PCT/US92/02063 ~ ` 2i ~3137 black dispersion into a nonwoven fibrous web followed by drying any residual water, leaving a thin coating of carbon blac~ dispersed on the surfaces of said fibers.
U.S. Patent No. 4,619,714, which issued October 28, 1986, and its divisional, U.S. Patent Nos.

4,6B4,~60, which issued August 4, 1987 and 4,724,00~, which issued February 9, 1988, describe a process for electroplating a conductive metal to the surface of a nonconductive material, particularly a process of l0 electroplating the through holes of a printed wiring board. This process is a significant improvement over the known electroless techniques. By this process, a liquid dispersion of carbon black particles is first applied to the nonconductive material, such as the 15 nonconductive portions of through holes on a printed wire board; then the liquid dispersion medium is separated (i.e., evaporated) from the carbon black particles, thereby depositing a substantially continuous layer of carbon black particles on the nonconductive 20 surface; and ne~t a substantially continuous metal layer is electroplated over the deposited carbon black layer.
~1 This process of U.S. Patent No. 4,619,714 has several j advantages over the known electroless techniques includ-ing the elimination of the preactivator, the Pd/Sn 25 activator, and the accelerator; less possibility of pollution problems; better bath stability; and fewer ' possible side reactions.
In Comparisons 1 and 2, in columns 19 and 20 of U.S. Patent No. 4,619,714, two formulations containing 30 graphite were prepared and circuit boards were treated with the formulations. These graphite formulations s employed relatively large size graphite particles. The i mean particle size of the solids in these Comparisons ~' was found to be 3.1 microns. The circuit board was then :, . .

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, ~ WO92/19794 YCT/US92/02063 ~ 1 3 7 -6-plated. The patent states in column 20, lines 16-20, that in all, both graphite formulations were far inferior for` copper electroplating preparation as compared to formulations containing carbon black. The reason why these Comparisons failed may be attributed in part to the relative large size of the graphite particles in that dispersion.
Improvements and modifications of the electro-plating process of U.S. Patent Nos. 4,619,741, 4,684,560, and 9,724,005 are described in the following patents:
U.S. Patent No. 4,622,107, which issued November 11, 1986, describes the use of a gas-forming compound (e.g., sodium carbonate) to remove loosely or easily removable carbon black particles in the through holes.
U.S. Patent No. 4,622,108, which issued November 11, 1986, describes the contacting of an ' alkaline hydro~ide preconditioning solution to the through-hole walls before application of the carbon black dispersion so that the carbon black dispersion will have better adhesion to the walls.
U.S. Patent No. 4,631,117, which issued , December 23, 1986, describes the use of the carbon black jJI, 25 dispersion described in U.S. Patent No. 4,619,714 as a ~i preactivator for electroless plating of the through holes.
U.S. Patent No. 4,718,993, which issued January , 12, 1988, describes th~ use of an aqueous alkaline silicate solution to contact a printed wiring board ^............... prior to contacting with the carbon black dispersion.
,i U.S. Patent No. 4,874,477, which issued October 17, 1989, describes contacting a printed wire board with '~A~ a particular aqueous polyelectrolyte homopolymer ' , . " . ., : : . . .

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.- -2i~)313 `1 conditioner followed by contacting the printed wiring board with the carbon black dispersion.
U.S: Patent No. 4,897,164, which issued January 30, 1990, describes contacting a printed wiring board 5 with an aqueous solution of an alkali metal borate after it has been contacted with the carbon black dispersion and prior to microetching.
U.S. Patent No. 4,964,959, which issued October 23, 1990, describes the addition of a conductive polymer 10 or combinations thereof to the carbon back dispersion.
~ ~.S. Patent No. 4,994,153, which issued t February 19, 1991, describes a process for treating the ' tooling holes or slots which have been coated with a j carbon black dispersion in a nonconductive material which comprises removing said carbon black with an aqueous solution containing: (a) an alkanolamine; (b) an anionic surfactant which is the neutralized addition ¦ product of maleic and/or fumaric acid and a poly(o~ylated) alcohol; (c) a nonionic surfactant which 20 is an aliphatic mono and/or diphosphate ester; and (d) an alkali or alkaline earth metal hydro~ide.
U.S. Patent No. 5,015,339, which issued on May 14, 1991, describes an electroplating pretreatment wherein nonconductive material is first contacted with 25 an alkaline permanganate solution, then a neutralizer~
. conditioner solution and then a carbon black dispersion.~ While the above patents describe an effective ':,t~ means for electroplating a metal to the surface of a ;^, nonconductive material, particularly the through holes 30 of a printed wiring board (PWB), there is still a desire ~ to improve the overall quality of that electroplating `.' process.
l One of the limiting factors in the above-noted -:.; carbon black dispersion preplating process, described , .

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WO92~19794 PCT/US92J02063 2 i d 31 .3 7 -8-generally in U.S. Patent Nos. 4,619,714; 4,584,560; and 4,724,005 and their above-noted improvement patents, is the plating`speed of copper over the carbon black deposit, or in other words, the time needed to achieve complete coverage of the through holes by electro-deposited copper. Currently, the copper plating speed in PWB through holes is restricted by the relatively high resistance of the carbon black films. It has now been found that the deposition of a conductive graphite layer on top of the carbon black layer enhances the overall conductivity of the carbon black coating and, therefore, yields faster plating rates. Some of the patents mentioned above have described the use of graphite. However, such graphite films are usually plagued by adhesion problems. In the process of the present invention, fine particle-size conductive graphite is deposited on top of a carbon black deposit.
~ The carbon black deposit serves as an adhesion promoter '~ for the graphite film. The conductivity and particle size of graphite particles are critical parameters of the present invention.
Accordingly, the present invention is directed to a process of electroplating a conductive metal layer ' to the surface of a nonconductive material comprising the steps of:
(a) contacting said nonconductive material surface with a liquid carbon black dispersion comprising:
(1) carbon black particles having an average particle diameter of less than about 3.0 microns in said dispersion;
(2) an effective dispersing amount of a surfactant which is compatible with said ^ carbon black; and :
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(3) a first liquid dispersing medium, wherein the amount of carbon black is sufficient to coat substantially all of said noncon-ducting surfaces and is less than about 4%
by weight of said liquid carbon black dispersion;
(b) separating substantially all of said first liquid dispersing medium from said carbon black particles, whereby said particles are deposited on said nonconductive surface in a substantially continuous - layer;
(c) contacting said carbon black coated nonconductive surfaces with a liquid conductive graphite dispersion comprising:
(1) conductive graphite particles having an . average particle diameter of less than about 1.5 microns in said dispersion;
(2) an effective dispersing amount of a , surfactant which is compatible with said ! 20 conductive graphite; and . ~3) a second liquid dispersing medium wherein the amount of conductive graphite is less than about 4% by weight of said liquid conductive graphite dispersion;
(d) separating substantially all of said second liquid dispersing medium from said graphite particl.es, hereby said particles are deposited on said noncon-ductive surface; and . (e) electroplating a substantially continuous conductive metal layer over the deposited carbon - black layer and the deposited conductive graphite .,.~ layer and said nonconductive surface.
The process of this invention is particularly useful for applying a conductive metal layer such as a ^;~WO92/19794 PCT/US92/~2063 , ~ .
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~iiiu137 -lo-copper layer to the nonconducting portions of through hole walls of printed wiring boards. These printed wiring boards are usually composed of a nonconductive layer (e.g., epo~y resin/glass fiber mi~ture) positioned between two conductive metal layers ~e.g., copper or nickel plates or foils) or a multiplicity of said alternating layers. Applying a conducting metal layer :over said nonconducting portions of said through hole walls electrically connects the conductive metal layers. However, the process of this invention is effective for electroplating a conductive metal onto the surface of a nonconducting material of virtually any shape or surface area.
iFurther, the present invention also encompasses the resulting ~rinted nonconductive materials prepared by the above-noted process (i.e., those having their through hole walls coated with the carbon black deposit, the graphite deposit, and the metal plating thereover).
Still further, the present invention encompasses certain liquid dispersions of fine-sized conductive graphite particles.
As previously stated, one preferred embodiment of the present invention is preparing the through hole walls of a printed wiring board for the application of an electroplated layer of copper over a nonconducting layer separating two plates or foils of copper. This -preparation process entails placing a selected liquid carbon black dispersion followed by placing a selected liquid conductive graphite dispersion over the non-;30 conducting portions of the through hole walls before electroplating.
Printed wiring boards (also known as printed circuit boards or PWB's) are generally laminated materials comprised of two or more plates or foils of ~ .
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i- WO92/19794 PCT/US92/02063 '' '`' 2.l~3137 copper, which are separated from each other by a layer of nonconducting material. Although copper is generally used as the electroplating metal in printed wiring boards, those skilled in the art will recognize that other metals such as nickel, gold, palladium, silver and the like can also be electroplated by the process of this invention. The nonconducting layer or layers are preferably an organic material such as an epo~y resin impregnated with glass fibers. However, the nonconduct-ing layer may also be comprised of thermosetting resins,thermoplastic resins, and mi~tures thereof, with or without reinforcing materials such as fiberglass and fillers.
Suitable thermoplastic resins include the acetal resinsi acrylics, such as methyl acrylate;
cellulosic resins, such as ethyl cellulose, cellulose , acetate, cellulose propionate, cellulose acetate butyrate, cellulose nitrate, and the like; chlorinated polyethers; nylon; polyethylene; polypropylene;
polystyrene; styrene blends, such as acrylonitrile-styrene copolymers and acrylonitrile-butadiene-styrene (ABS) copolYmers; polycarbonates; polychlorotrifluoro-ethylene; and vinyl polymers and copolymers, such as vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, vinyl chloride-acetate copolymer, vinylidene chloride, vinyl formal, Teflon; and the like.
Suitable thermosetting resins include alkyl phthalate, furane; melamine-formaldehyde; phenol .i formaldehyde and phenol-furfural copolymers; alone or compounded with butadiene acrylonitrile copolymer or acrylonitrile-butadiene-styrene (ABS) copolymers; poly-acrylic esters; silicones; urea formaldehydes; epoxy resins; polyimides; alkyl resins; glyceryl phthalates;
polyesters; and the like.

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~ 33137 -12-In many printed wiring board designs, the elec~irical pathway or pattern requires a connection between the separated copper plates at certain points in the pattern. This is usually accomplished by drilling holes at the desired locations through the laminate of ; copper plates and the nonconducting layer and then connecting the separate metal plates. The hole diameters of printed wiring boards generally range from between about 0.S and about 10 millimeters in diameter, and preferably from about l to about 5 millimeters.
After drilling these through holes, it may be desirable to deburr the holes to make the hole walls relatively smooth. In the case of multilayer printed wiring boards, it may also be desirable to subject the boards to a desmear or etchback operations to clean the , inner copper interfacing surfaces of the through holes.
Suitable preparative operations include any or all of the presently available conventional operations includ-ing conventional permanganate desmearing processes.
Once the surfaces of through holes have been made relatively smooth for plating, it is preferred to subject the PWB to a precleaning process in order to $ place the printed wiring board in condition for receiving the liquid carbon black dispersion. In one preferred precleaning operation, the printed wiring board is first placed in a cleaner bath for about 1 to ` 10 minutes at a temperature of about 95C to about 70C
~'i to remove grease and other impurities from the hole wall surfaces. In this embodiment, one preferred cleaner is comprised of monoethanolamine, SA~DOLEC CF cationic polyelectrolyte and ethylene glycol in water, which is -~ available as "HLACRHOLE~ Cleaner 2" from the Olin Hunt Specialty Products, Inc. of West Paterson, NJ. Other suitable cleaners from Olin Hunt Specialty Products, -.

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WO92/19794 PCT/US92/02~3 ~ 1 0 ~ 1 ~, 7 Inc. include 1100 Series Cleaner (also an aqueous solution of monoethanolamine, SANDOLEC CF cationic polyelectrolyte and ethylene glycol), and 1200 Series Cleaner 2 (an aqueous solution containing mono-ethanolamine, NEODOL 91-8 nonionic surfactant, and ethylene glycol).
After the application of the cleaner, the PWB
is subsequently rinsed in water to remove e~cess cleaner from the board and then contacted with a conditioner solution. The preferred method of contacting with a conditioner is dipping the cleaned PWB into a room temperature aqueous conditioner bath for about 1-10 minutes. This conditioner solution is used to ensure that substantially all of the hole wall glass~epo~y surfaces are properly prepared to accept a continuous layer of the subsequent carbon black particles. Such conditioner solutions have been customarily used in electroless processing to precondition the boards for . the electroless chemistry. See U.S. Pat. No. 4,634,691, :~ 20 which issued to Lindsey on January 6, 1987, for a discussion of conditioner solution. The Lindsey patent is incorporated herein by reference in its entirety.
One preferred conditioner is "BLACKHOLE Conditioner"
available from Olin Hunt Specialty Products, Inc. of West Paterson, NJ. This conditioner formulation comprises the mixture of monoethanolamine and SANDOLEC
CF cationic polyelectrolyte. The preferred concentra-tion of total conditioner ingredients in water is from about 1% to about 10% by weight. Other preferred conditioners available from Olin ~unt Specialty Products, Inc. include the 1105 Conditioner (also an aqueous solution of monoethanolamine and SANDOLEC CF
cationic polyelectrolyte) and 1205 Conditioner (an aqueous solution of monoethanolamine and ETADURIN F

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~ l4-cationic polyamine polymer available from Akzo Chemical Company of Chicago, IL).
Ot~er conditioners include cationic poly-acrylamid~ polyelectrolytes such as MAGNIFLOC cationic 5 resins available from American Cyanimid Company of wayne, NJ.
The liquid carbon black dispersion is ne~t applied to or contacted with the conditioned PWB. This dispersion contains three critical ingredients, namely, 10 carbon black, one or more surfactants capable of dispers-ing the carbon black and a liquid dispersing medium such as water. The preferred methods of contacting the dispersion to the PWB include immersion, spraying or other methods of contacting chemicals used in the PW~
15 industry. A single working bath is sufficient for applying this carbon black dispersion; however, more than one bath may be used for rework or other puryoses.
In preparing this liquid carbon black disper-sion, the three critical ingredients and any other 20 preferred ingredients are thoroughly mixed together to form a stable dispersion. This may be accomplished by subjecting a concentrated form of the liquid carbon , black dispersion to ball milling, colloidal milling, s high-shear milling, ultrasonic techniques, or by high 25 speed mixing or other standard blending techniques. The thoroughly mixed carbon black dispersion is later -~ diluted with more water while agitating to the desired concentration for the working bath. The preferred methods of mixing are mixing a concentrated form of the 30 dispersion in a high speed mixer or in a ball mill - containing glass, mineral, or plastic beads therein for a period of about l to about 24 hours. This thorough mising allows for the carbon black particles to be intimately coated or wetted with the surfactant. This . .
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2la3l~7 mixed concentrate is then mixed with water or some other liquid dispersing medium to the desired concentration.
The carbon b~ack dispersion working bath is preferably kept agitated during both the diluting and contacting steps to aid in keeping the dispersion stable.
As stated above, the carbon black particles should have an average particle diameter below about 3 microns while in the dispersion. It is desirable to have this average particle diameter of carbon black as small as possible to obtain the desired plating characteristics of substantially even plating and no plating pullaways. It is preferred that the carbon black particles have an average particle diameter from about 0.05 to about 3.0 microns, more preferably from 0.08 to about 2.0 microns, when in said dispersion. The term "average particle diameter~ as employed herein as to carbon black particles in both the specification and claims refers to average mean diameter of the particles ~t (the average by number). The average mean diameter in the dispersion may be determined through the use of either a NiComp Model 270 submicron particle size i analyzer (Version 3.0) or a HIAC PA-720 automatic particle size analyzer (both available from the HIAC/ROYCO Instrument Division of Pacific Scientific of Menlo Park, CA).
All types of carbon blacks may be used for this invention including the commonly available furnace blacks. However, it is preferred to utilize carbon blacks which are initially acidic or neutral, i.e., those which have a pH of between about l and about 7.5 and more preferably between about 2 and about 4 when slurried with water. Carbon black particles of the preferred type contain between about 1% and about 10% by weight of volatiles and have an amorphous structure.
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: , ~l& jl'7 -16-These preferred carbon black particles are also very porous and generally their surface areas are from between abou`t 45 to about 1,100, and preferably between about 300 to about 600, square meters per gram as S measured by the BET method (method of Brunauer-Emmett-Teller).
Illustrative carbon blacks suitable for use of this invention include Cabot XC-72R Conductive, Cabot Monarch ~00, Cabot Monarch 1300, all manufactured by 10 Cabot Corporation of Boston, MA. Other suitable carbon blacks include Columbian T-10189, Columbian Conducte~
975 Conductive, Columbian CC-40-220, and Columbian Raven 3500, all available from Columbian Carbon Company of New York, NY. Monarch 800 and Raven 3500 are the two most J 15 preferred carbon blacks because of their ease of dispersion and low pH.
~ The term "liquid dispersing medium" for the liquid carbon black dispersion as used herein in the i~ present specification and claims includes water and 20 polar organic solvents (both protic and aprotic). Suit-able protic polar organic solvents may include lower alcohols (Cl - C4) such as methanol, ethanol, isopro-panol, and isobutanol; polyhydric alcohols such as j glycols (i.e. triethylene glycols); ether alcohols such '~ 25 as cellosolve; organic acids, such as formic acid and acetic acid; acid derivatives such as trichloroacetic acid; and sulfonic acids such as methane sulfonic acid.
Suitable aprotic polar organic solvents include aldehydes such as acetaldehyde; ketones such as acetone;
30 aprotic aromatic solvents such as toluene and mineral spirits; aprotic halogenated hydrocarbons such as dichlorofluoromethane and dichlorodifluoromethane -' (FREON); dimethylformamide (DMF); N-methylpyrrolidone;
,i dimethylsulfo~ide (DMSO); and esters of carboxylic acids .... .

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2la3~37 such as methylformate, ethylacetate, and cellosolve acetate. The preferred liquid dispersing medium is water because` of cost and ease of use considerations.
It is preferred to utilize deionized water which is free of lime, fluorine, iodine, and other impurities normally found in tap water, in order to minimize interference of foreign ions during the subsequent electroplating step.
In addition to the water and carbon black, a third critical ingredient is needed in the dispersion, narnely, a surfactant capable of dispersing said carbon black in said liquid dispersing medium (i.e., compatible with said carbon black and liquid dispersing ~edium).
One or more of these is added to the dispersion in order to enhance the wetting ability and stability of the carbon black and permit ma~imum penetration by the carbon black within the pores and fibers of the noncon-ducting layer. Suitable wetting agents include anionic, nonionic, and cationic surfactants (or combinations thereof such as amphoteric surfactants). The sur-factants should be soluble, stable and preferablynonfoaming in the liquid carbon black dispersion. In general, for a polar continuous phase as in water, the surfactants shou]d preferably have a high HL~ number (8-18). The preferred type of surfactant will depend mainly on the pH of the dispersion. If the total dispersion is alkaline (i.e., has an overall pH in the basic range), it is preferred to employ an anionic or nonionic surfactant. Acceptable anionic surfactants include sodium or potassium salts of naphthalene sulfonic acid such as DARVAN No. 1 (R.T. Vanderbilt Co.), ECCOWET LF (Eastern Color and Chemical), PETRO AA, ~ PETRO ULF (Petro Chemical Co., Inc.), and AEROSOL OT
;:J.s (American Cyanamid). Preferred anionic surfactants .~ include neutralized phosphate ester-type surfactants ~ ", . .~
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` W092t~9794 PCT/US92/0~063 . .

~ 3 1 37 -18-such as MAPHOS 55, 56, 8135, 60A, L6 (Mazer Chemicals Inc.). The most preferable anionic surfactant for a liquid carbon black dispersion is MAPHOS 56. Suitable nonionic surfactants include etho~ylated nonyl phenols such as POLY-TERGENT~ B-Series (Olin Corporation) or alkosylated linear alcohols such as POLY-TERGENT
SL-Series (Olin Corporation).
If the total dispersion is acidic, it is preferred to employ selected anionic surfactants or cationic surfactants. An acceptable group of anionic surfactants would be the sodium or potassium salts of naphthalene sulfonic acid described above. Acceptable cationic surfactants include cetyl dimethyl benzyl ammonium chloride such as AMMONYX T (Ony~ Chemical Corporation); an ethanolated alkylguanidine amine . comple~ such as AEROSOL C-61 (American Cyanamid);
lipocals; dodecyldiphenyl o~ide disulfonic acid ~DDODA) such as DOWFAX 2Al ~Dow Chemical); a sodium salt of DDODA such as STRODEX (Dester Chemical Corporation); and , 20 salts of comple~ organic phosphate esters. Preferred surfactants include amphoteric potassium salts of a complex amino acid based on fatty amines such as MAFO 13 and cationic etho~ylated soya amines such as MAZEEN S-5 or MAZTREAT (Mazer Chemicals Inc.). Preferred cationic surfactants also include the Duoquad Series such as : Duoquad T-50 obtained from Akzo Chemie. Combinations of ~ surfactants may be employed. The term "surfactantn, as , ., used herein for making the carbon black dispersion, may ~ include other forms of dispersing agents or aids such as ;~ 30 low molecular weight polyelectrolytes and polymers.
. The amount of carbon black in the dispersion . should be less than about 4% by weight of the disper-.. sion, preferably, less than about 2% by weight. It has been found that the use of higher concentrations of : .s :. .
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:; WO92/19794 PCT/US9~/02063 .
~ 2i~3137 carbon blacks provide undesirable plating character-istics. In the same regard, the solids content (i.e.
all of the ingredients other than the liquid dispersing medium) is preferably less than 10% by weight of the dispersion, more preferably, less than about 5.6% by weight.
One additional preferred component of the liguid carbon black-containing dispersion is a strong basic material such as an alkaline hydro~ide. Suitable strong basic materials include alkali metal hydro~ides ;; such as potassium hydro~ide, sodium hydro~ide, and lithium hydroxide. Ammonium hydro~ide may also be employed, if desired. Potassium hydroside is the most ;~ preferred strong basic material. The term "alkaline hydroxide is used throughout the description and claims to identify these strong basic materials. Sufficient alkaline hydroxide may be added to the liquid carbon black dispersion in a proportion sufficient to increase the pH of the resulting carbon black-containing dispersion to between about 10 and about 14, and preferably between about 10 and about 12.
Following is a typical formulation of a suit-able aqueous alkaline dispersion of carbon black showing the general range of proportions as well as the pre-ferred range of proportions for the various components:
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Com~onent General Ranae Preferred Ranae . Carbon Black 0.1 - 4% by wt. 0.15- 2% by wt.
~, Surfactant 0.01 - 4% 0.05 - 2%
. Alkaline Hydroxide 0 - 1% 0.4 - 0.8%
`~ 30 Water Balance Balance ;r.'l The liquid dispersion of carbon black is typically placed in a suitably agitated vessel and the . ,~, . ~ .
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:,.: , : , , '.5' ' ' '' -' ' , ~, ' , ' - ' ` ' ' ' ,': ~ ' ~'. ' ' . ~ : .:' ~: WO92/19794 PCT/US92/02063 2 ~137 zo printed wiring board to be treated is immersed in, sprayed with or otherwise contacted with the liquid dispersion. ` The temperature of the liquid dispersion in an immersion bath is maintained in the range of between about 15C and about 35C and preferably between about 20C and about 30C, while the conditioned printed ' wiring board is immersed therein. The period of immersion generally ranges from about 1 to 10, and preferably from about 3 to 5 minutes. During immersion, the liquid carbon black-containing dispersion penetrates the holes of the printed wiring board and wets and contacts the glass fiber as well as the epo~y resin ' which forms the components of the insulating layer. The immersed board is then removed from the liquid carbon black-containing dispersion bath.
The carbon black-covered board is then subjected to a step where substantially all (i.e., more , than about 95% by weight) of the water in the applied dispersion is removed and a dried deposit containing carbon black is left in the holes and on other e~posed surfaces of the nonconducting layer. This may be ; accomplished by several methods such as by evaporation at room temperature, by a vacuum, by heating the board for a short time at an elevated temperature, or by an `5,.' 25 air knife, or by other equivalent means. Heating at an ~A4~ elevated temperature is the preferred method. Heating is generally carried out for between about 30 seconds and 45 minutes at a temperature of from about 75 to ;............... 120C, more preferably from about 80 to 98C. To insure complete coverage of the hole walls, the ~, procedure of immersing the board in the liquid carbon black dispersion and then drying may be repeated one or more times.
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~^ WO92/19794 PCT/US92/02063 -21- ~ i '3137 The carbon black covered board is now subjected to the additional graphite treatment yielding the deposi-tion of a gràphite layer on top of the carbon layer.
Preferably, the carbon black-coated PWB board is first optionally contacted with a conditioner solution. The preferred method of contacting with a conditioner is dipping the coated PWB into a room temperature aqueous conditioner bath for about 1-10 minutes. This condi-tioner bath is used to promote subsequent adsorption of the dispersed graphite particles on the carbon black layer. The preferred conditioners for this step are the same ones as used before the contacting with the carbon black dispersion.
After the application of this optional second conditioner solution, the PWB is subsequently rinsed with water to remove e~cess conditioner from the board.
The board is ne~t contacted with a liquid graphite dispersion or suspension. This graphite disper-sion contains three critical ingredients; namely, graphite, one or more surfactants capable of dispersing the graphite, and a liquid dispersing medium such as water. The preferred methods of contacting the graphite dispersion to include immersion, spraying, or other , methods of contacting chemicals used in the PWB
industry. A single working bath is sufficient for , contacting this graphite dispersion; however, more than one bath may be used for rework or other purpose.
~ In preparing this liquid graphite dispersion, ;~ the three critical ingredients and any other preferred ingredients are thoroughly mixed together. The working !'~ graphite dispersion bath is preferably kept agitated during PWB processing to aid in keeping the solids . dispersed in the bath. The mi~ing may be accomplished ;, by subjecting a concentrated form of the liquid graphite -.~

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tliJ~ 1 37 -22-dispersion to ball milling, colloidal milling, high-shear milling, ultrasonic techniques, by a attritor, or by high speed mixing or other standard blending tech-niques. The thoroughly mi~ed graphite dispersion is 5 later diluted with more water while agitating to the desired concentration for the graphite dispersion working bath. The preferred methods of mi~ing are mi~ing in a attritor or high speed mi~er or in a ball mill containing glass, mineral, or plastic beads therein 10 for a period of about l to about 24 hours. This through mixing allows for the graphite particles to be inti-mately coated or wetted with the surfactant. This mi~ed concentrate is then mixed with water or some other liquid dispersing medium to the desired concentration.
15 The graphite dispersion bath is preferably kept aqitated during both the diluting and contacting steps to aid in keeping the solids dispersed.
As stated above, the graphite particles should ' have an average particle diameter below about l.5 s 20 microns while in the dispersion. It is desirable to , have this average particle diameter of graphite as small ~! as possible to obtain the desired plating charac-teristics of substantially even plating and no plating pullaways. Preferably, the average particle diameter of 25 the conductive graphite particles are in the range of about 0.05 to about 0.8 microns. More preferably, the average particle diameter is from about O.l to about 0.4 microns. It is also required that the graphite particles retain their crystal structure and, therefore, 30 their conductivity. Thus, if the graphite particles are too large, caution in grinding must be e~ercised since it is known that grinding can be associated with a loss in conductivity. Therefore, the term "conductive graphite particles" as used in the present specification .
. ' ` ' ' "' `' ' WO92/19794 PCT/U~92/02063 .
2~ 1 37 and claims means graphite particles which have a sub-stantially crystalline structure and are essentially free of crystal defects, thus possessing sufficient conductivity to increase the conductivity of the combined carbon black and graphite deposit.
The term "average particle diameter" as employed herein as to graphite particles in both the specification and claims refers to average mean diameter of the graphite particles (the average by number). The average mean diameter in the dispersion may be deter-mined through the use of either a NiComp Model 270 submicron particle size analyzer ~Version 3.0) or a HIAC
PA-720 automatic particle size analyzer (both available from the HIAC~ROYCO Instrument Division of Pacific Scientific of Menlo Park, CA).
Illustrative conductive graphite particles meeting the critical particle size limitation include Showa Denko Ultrafine Graphite, manufactured by Showa Denko ~.K. of Tokyo, Japan; Nippon AUP (0.7 micron), manufactured by Nippon Graphite Industries, Ltd. of 3' Ishiyama, Japan; and Asbury Graphite Micro-850, ~ manufactured by Asbury Graphite Mills of Asbury, NJ.
;~ The term ~liquid dispersion mediumn for the ~, liquid graphite dispersion as used herein in the present specification and claims includes water and polar organic solvents (both protic and aprotic). Suitable protic polar organic solvents may include lower alcohols .~ (Cl - C4) such as methanol, ethanol, isopropanol and `'.3' isobutanol; polyhydric alcohols such as glycols (i.e.
~`~ 30 triethylene glycols); ether alcohols such as cellosolve;
organic acids, such as formic acid and acetic acid; acid ~',3 derivatives such as trichloroacetic acid; and sulfonic acids such as methane sulfonic acid. Suitable aprotic ~ polar organic solvents include aldehydes such as :- ' .

.

WO92~19794 PCT/US92/02063 : ~ ~ 1 3 ~ - 24-acetaldehyde; ketones such as acetone; aprotic aromatic solvents such as toluene and mineral spirits; aprotic halogenated hydrocarbons such as dichlorofluoromethane and dichlorodifluoromethane (FREON); dimethylformamide (DMF); N-~ethylpyrrolidone; dimethylsulfoxide (DMSO);
and esters of carbo~ylic acids such as methylformate, ethylacetate, and cellosolve acetate. The preferred liquid dispersing medium for this step is water because of cost and ease of use considerations. It is preferred to utilize deionized water which is free of lime, fluorine, iodine and other impurities normally found in tap water, in order to minimize interference of foreign ions during the subsequent electroplating step.
ln addition to the water and graphite, a third critical ingredient is needed in the dispersion, namely, a surfactant capable of dispersing said graphite in said liquid dispersing medium (i.e., compatible with said graphite and liquid dispersing medium). One or more of these surfactants is added to the dispersion in order to ,~! 20 enhance the wetting ability and stability of the graphite dispersion. Suitable wetting agents include anionic, nonionic, and cationic surfactants (or combinations thereof such as amphoteric surfactants).
The surfactants should be soluble, stable, and prefer-ably nonfoaming in the liquid graphite dispersion. Ingeneral, for a polar continuous phase as in water, the .. surfactants should preferably have a high HLB number (8-18). The preferred type of surfactant will depend mainly on the pH of the dispersion. If the total dispersion is alkaline (i.e., has an overall pH in the basic range~, it is preferred to employ an anionic or nonionic surfactant. Acceptable anionic surfactants .~ include sodium or potassium salts of naphthalene ~, sulfonic acid such as DARVAN No. l (R.T. Vanderbilt .~, .
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, ' ' ` '`'`. ' . ': . ' ', ~; WO9~/19794 PCT/US92/02063 -25- ~i331.37 Co.), ECCOWET LF tEastern Color and Chemical), PETRO AA, PETRO ULF (Petro Chemical Co., Inc.), and AEROSOL OT
(American Cyànamid). Preferred anionic surfactants include neutralized phosphate ester-type surfactants 5 such as MAP~OS 5S, 56, 8135, 60A, L6 (Mazer Chemicals Inc.). The most preferable anionic surfactant for a liquid graphite dispersion is MAPHOS 56. Suitable nonionic surfactants include etho~ylated nonyl phenols such as POLY-TERGENT~ B-Series (Olin Corporation) or alko~ylated linear alcohols such as POLY-TERGENT
SL-Series (Olin Corporation).
Acceptable cationic surfactants include cetyl dimethyl benzyl ammonium chloride such as AMMONYX T
(Ony2 Chemical Corporation); an ethanolated alkyl-guanidine amine complex such as AEROSOL C-61 (American Cyanamid); lipocals; dodecyldiphenyl o~ide disulfonic , acid (DDODA) such as DOWFAX 2Al (Dow Chemical); a sodium j~ salt of DDODA such as STRODEX (Degter Chemical Corpora-'~ tion); and salts of comple~ organic phosphate esters.
: 20 Preferred surfactants include amphoteric potassium salts of a complex amino acid based on fatty amines such as MAFO 13 and cationic etho~ylated soya amines such as MAZEEN S-5 or MAZTREAT (Mazer Chemicals Inc.). Pre-.!, ferred cationic surfactants also include the Duoquad ~i 25 Series such as Duoquad T-50 obtained from Akzo Chemie.
Combinations of surfactants may be employed. The term ~3 ~surfactant", as used herein for making the graphite dispersion, may include other forms of dispersing agents i~ or aids such as low molecular weight polyelectrolytes "3 30 and polymers.
The amount of graphite in the dispersion should be less than about 4% by weight of the dispersion, pre-ferably, less than about 2~ by weight. It is believed that the use of higher concentrations of graphite ~'' ~' ~ .

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~la3l37 provide undesirable plating characteristics. In the same regard, the solids content (i.e., all of the ingredients`other than the liquid dispersing medium) is - preferably less than 10% by weight of the dispersion, 5 more preferably, less than about 6% by weight.
One additional preferred component of the liquid graphite-containing dispersion is a strong basic material such as an alkaline hydroxide. Suitable strong basic materials include alkali metal hydro~ides such as l0 potassium hydro~ide, sodium hydroxide, and lithium hydro~ide. Ammonium hydro~ide may also be employed, if desired. Potassium hydro~ide is the most preferred strong basic material. The term "alkaline hydro~ide" is . used throughout the description and claims to identify 3 15 these strong basic materials. Sufficient alkaline s hydroxide may be added to the liquid carbon black dispersion in a proportion sufficient to increase the pH
of the resulting graphite-containing dispersion to between about 10 and about 14, and preferably between ~ 20 about 10 and about 12.
;~ Following is a typical formulation of a suitable aqueous alkaline graphite dispersion showing the general range of proportions as well as the preferred range of proportions for the various 25 Components Component General Ranae Preferred Range ~i Graphite 0.1 - 4% by wt. 0.15- 2~ by wt.
Surfactant 0.0l - 4% 0.05 - 2%
Alkaline Hydro~ide 0 - 1% 0.4 - 0.8%
30 Water Balance Balance The liquid graphite dispersion is typically placed in a suitably agitated vessel and the printed ,.:
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.~: ' " ' '' '' : ' -27- 2 ii~3 1 37 wiring board to be treated is immersed in, sprayed with or otherwise contacted with the liquid dispersion. The temperature of the liquid dispersion in an immersion bath is maintained in the range of between about 15C
5 and about 35C and preferably between about 20C and about 30C, while the conditioned printed wiring board is immersed therein. The period of immersion generally ranges from about 1 to 10, and preferably from about 3 to 5 minutes. During immersion, the liquid graphite-- 10 containing dispersion coats the carbon black layer which was previously applied. The immersed board is then removed from the liquid graphite dispersion bath.
The board is then subjected to a step where substantially all (i.e., more than about 95% by weight) 15 of the water in the applied dispersion is removed and a dried graphite deposit is left in the holes over the carbon black deposit and on other e~posed surfaces of the nonconducting layer. This may be accomplished by several methods such as by evaporation at room tempera-20 ture, by a vacuum, by heating the board for a short time at an elevated temperature, or by an air knife, or by other equivalent means. Heating at an elevated .~ temperature is the preferred method. Heating is generally carried out for between about 30 seconds and 45 minutes at a temperature of from about 75 to 120C, more preferably from about 80 to 98C. To ensure sufficient coverage of the hole walls, the procedure of immersing the board in the liquid graphite dispersion :~ and then drying may be repeated one or more times.
The board is now completely coated with the carbon black and the graphite dispersions. These dispersions are not only coated on the drilled hole surfaces, which is desirable, but also entirely coat the copper plate or foil surfaces which is undesirable.
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Thus prior to many subsequent operations all carbon black and graphite must be removed from the copper plate or foil surfaces.
The further removal of e~cessive graphite S and/or carbon black specifically from the outer copper surfaces including, especially, the rims of the drilled holes while leaving the coating intact on the glass fibers and epo~y surface of the hole walls, may be achieved by the employment of a microetch bath.
10 Generally, this treatment is carried out at a temper-~ ature of about 20 to 30C for 35 seconds to about 3 A minutes. One suitable sodium persulfate-based microetch .' is "BLACKHOLE MICROCLEAN I available from Olin Hunt i Specialty Products, Inc. This product is preferably 15 combined with sufficient sulfuric acid to make a microetch bath containing 100-300 grams of sodium persulfate per liter of deionized water and about 1 to 10% by weight sulfuric acid. The mechanism by which this microetch works is by not attacking the carbon 20 black material or the graphite material deposited on the copper foil directly, but rather to attack e~clusively the first few atomic layers of copper directly below which provides the adhesion for the coating. Hence, the fully coated board is immersed in the microetch solution 25 to flake~ off the carbon black and the graphite from the copper surfaces in the form of micro-flakelets.
~ These micro-flakelets are removed from the microetch `~ bath either by filtration through a pump or via a weir type filter arrangement commonly used in the PWB
industry. The liquid carbon black dispersion, the liquid graphite dispersion, the microetch treatment, and . the intermittent water rinses are preferably carried out by immersing the PWB in baths constructed of poly--~, propylene or polyvinyl chloride (PVC) and kept agitated ,: .
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WO92/197~4 PCT/USg2/020~3 ''' 1`' -29~ 3 1 3 7 by a recirculation pump or pumped in air.
After the microetch step and a subsequent water rinse, the P~B may now either proceed to the photoimag-ing process and later be electroplated or be directly panel electroplated. It may be preferred to further clean the PW8 with a citric acid anti-tarnish solution or any other acid cleaner solution or both after the above microetch step.
The thus treated printed wiring board is then ready for electroplating operation which includes immersing the PWB in a suitable electroplating bath for applying a copper coating on the hole walls of the nonconducting layer.
The present invention contemplates the use of any and all electroplating operations conventionally employed in applying a metal layer to the through hole ; walls of a PWB. Therefore, this claimed invention should not be limited to any particular electroplating ~ bath parameters.
;~ 20 A typical copper electroplating bath is comprised of the following components in the following proportions:
;i .
~ General Preferred '~'! Com~onentPro~ortions Prooortions 25 Copper (as metal) 2-3 oz/gal 2.25-2.75 oz/gal Copper Sulfate 5-lO oz/gal 6-9 oz/gal 98% Concentrated 23-32 oz/gal 27-30 oz/gal H2SO4 (by weight) Chloride Ion20-lO0 mg/l 40-60 mg/l The electroplating bath is normally agitated and preferably maintained at a temperature of between about 20 and 25C. The elFctroplating bath is provided ~1~
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' i V 3 1 3 7 -30-with anodes, generally constructed of copper, and the printed wiring board to be plated is connected as a ; cathode to the electroplating circuit. For esample, a current of about 30 amps per square foot is impressed across the electroplating circuit for a period of between about 40 and 60 minutes in order to effect copper plating on the hole walls of the dielectric layer positioned between the two plates of copper up to a thickness of about l mil + 0.2 mil. This copper plating of the hole wall provides a current path between the ~ copper layers of the printed wiring board. Other - suitable electroplating conditions may be employed, if desired. Other electroplating bath compositions containing other copper salts or other metal salts such ,, 15 as salts of nickel, gold, palladium, silver, and the like may be employed, if desired.
, The printed wiring board is removed rom the :, copper electroplating bath and then washed and dried to provide a board which is further processed. For e~ample, the PWB may be subjected to a tin-lead ~i~ electroplating operation.
The following e~amples are presented to define .~ the invention more fully without any intention of being limited thereby. All parts and percentages are by weight and all temperatures are degrees Celsius unless e~plicitly stated otherwise.

~ Six double-sided control laminated printed ; wiring boards and eight double-sided test printed wiring ` 30 boards were treated by the process of this invention.
The boards were comprised of two 35 micron thick copper ~, .

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.- WO92/19794 PCT/US92/02063 '~193137 plates secured by pressure fusing to the opposite sides of an epo~y resin/glass fiber layer. These double-sided printed wiring boards were about 15.24 centimeters wide by 22.86 centimeters in length. There were about 500 to ` 5 1,000 holes each about 1.0 millimeters in diameter drilled through the copper plates and epo~y resin/glass iber layer.

s EXAMPLE 1 ., , `. A double-sided printed wiring board described above was prepared for copper electroplating their through holes by first mechanically scrubbing the ~ surfaces of the board. The board was then immersed in ;~ the following sequence of aqueous baths for the ~ indicated times:
:j `~ 15 1. Cleaner (5 mins.).
2. Rinse with tap water (2 mins.).
3. Conditioner (4 mins.).
4. Rinse with tap water (2 mins.) ;s 5. Carbon black preplating dispersion (4 mins.). (Then dry at 93C for 20 mins.) 6. Conditioner (4 mins.).
s 7. Rinse with tap water (2 mins.) 8. Graphite preplating dispersion (4 mins.).
(Then dry at 93C for Z0 mins.) 9. Sodium persulfate microetch (30 secs.).
~ 10. Rinse with tap water (20 secs.).
- 11. Anti-tarnish solution (20 secs. ? .
12. Rinse with tap water (20 secs.).
Bath 1 was an aqueous solution containing a cleaner formulation comprised of monoethanolamine, ,~ SANDOLEC CF cationic polyelectrolyte, and ethylene . .

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'~' ia3 137 -32-glycol in water to remove grease and other impurities ~` from the hole wall surfaces of the board. The bath was - heated to about 60C to facilitate this cleaning. The ' cleaner formulation is available as "BLACKHOLE Cleaner ` 5 2" from Olin Hunt Specialty Products, Inc. of West ;~ Paterson, NJ.
~ath 3 was a room temperature agueous alkaline , bath which contains monoethanolamine and SANDOLEC CF
polyelectrolyte and has a pH of about l0 to condition : 10 the hole wall surfaces of the board. The conditioner formulation is available as "8LACKHOLE Conditioner" from Olin Hunt Specialty Products, Inc.
Bath 5 was a room temperature deionized water bath containing the carbon black preplating formula-¦ 15 tion. In this bath, the proportions of each ingredient ~ were as follows:

v 0.38% by weight anionic surfactant (l) 0.6 % by weight KOH (2) 0.38% by weight carbon black (3) l.24% by weight solids , (l) MAPHOS 56--An anionic surfactan~ produced by Mazer : Chemical Inc. of Gurnee, IL (90% by weight "~ surfactant and lG% by weight H2O).
(2) Solid potassium hydro~ide pellets (86% by weight KOH, 14% by weight H2O).
. (3) RAVEN 3500 carbon black produced by Cabot Corp.
., `:~ The balance of the bath was deionized water.
This carbon black dispersion of bath 5 was prepared by high speed mixing a concentrated form of this dispersion in a high speed mixer. The surfactant was dissolved in deionized waterfKOH to give a continuous phase. Then the carbon black was added. Mi~ing time was 6 hours.
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`: W O 92/19794 PC~r/US92/02~63 ~iû31~7 After mi~ing the concentrate was diluted with sufficient deionized water to make the dispersion in the above indicated proportions.
After bath 5, the boards were placed in a hot air recirculatory oven and heated to 93~C for 20 mins.
This drying step removed the water from the carbon black . coating on the board, thereby leaving a dried deposit of carbon black all over the board and in the through holes of the board. The drying promotes adhesion between the carbon black and the nonconductive surfaces of the board.
' Bath 6 was the same as bath 3.
- ~ath 8 was a room temperature deionized water bath containing the graphite preplating formulation. In this bath, the proportions of each ingredient were as follows:
0.4 % by weight anionic surfactant tl) 0.6 % by weight KOH (2) 0.6 % by weight graphite (4) 1.48~ by weight solids (l) The anionic surfactant was MAPHOS 56 supplied by ; Mazer Chemical, Inc. of Gurnee, IL (90% by weight surfactant and 10% by weight water).
(2) Solid potassium hydroxide pellets (86% by weight KOH, 19% by weight H2O).
(~) The graphite in this e~ample was Showa Denko Ultrafine Graphite manufactured by Showa Denko of Tokyo, Japan.

The balance of the bath was deionized water.
This graphite dispersion of bath 8 was prepared by ball 30 milling a concentrated form of this dispersion in a glass jar with stainless steel balls so that the liquid level was above the l/8 inch diameter stainless steel ' !
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~ U~137 -34_ balls which occupied appro~imately 1/2 of the volume of the milling jar. The material was milled for 12 hours.
After milling, the concentrate was diluted with sufficient deionized water to make the dispersion in the above-indicated proportions. After bath 8, the boards were dried as described for bath 5 above.
Bath 9 was a room temperature aqueous bath and contained 200 g of sodium persulfate per liter of deionized water and 0.5% by volume of concentrated ~ lO H2SO4- Its function was to microetch the copper ; surfaces of the board so as to remove the deposited ;. carbon black from the surfaces. It does not act on the :~ resin~glass surfaces. This sodium persulfate microetch ; was made from "BLACKHOLE Microclean I" and is available from Olin Hunt Specialty Products, Inc. of West Paterson, NJ.
Bath 11 was a room temperature aqueous bath and contained 50 g of citric acid per liter of deionized water and 0.5% by volume of concentrated H2S04. Its function was to prevent the copper surfaces of the printed wiring boards from tarnishing.
Rinse baths 2, 4, 7, 10, and 12 w,ere employed to prevent the carryover of chemicals from one treatment bath into the ne~t.
~i~ 25 After treatment in bath 12, the boards were air .~ dried and evaluated by measuring the resistance between ~ the two copper plates. This was done by placing an .~ electrode from a Multimeter on each surface and record-,?,,~, ing the resistance. The results are tabulated in Table ` 30 No. 2 below.
After treatment with this sequence of baths, the printed wiring boards were placed in a commercial electroplating bath sequence including a VERSACLEAN 400 acid cleaner bath, rinse, microetch step, rinse, acid . .

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W092/~9794 PCT/US92/02063 21v'l31 37 dip, and electroplating bath. The electroplating bath was provided with agitation means and heating means which contained electrolyte chemistry comprised of the following:

s Platina Bath ComPosition Component Pro~ortion Copper (as metal) 2.5 oz./gal.
: Copper Sulfate 6.2 oz./gal.
98% Concentrated ~2SOg by weight 30 oz./gal.
Chloride ion 40 mg/1 The printed wiring board was connected as a cathode in the electroplating vessel having a volume of about 720 liters. Twelve copper bars were immersed in the electrolyte and connected to the cell circuits as anodes. The copper bars had a length of about 91 cm; a width of about 9 cm and a thickness of about 4 cm. Each face was about 819 square cm.
A direct current of 20 amps per square foot was impressed across the electrodes in the electroplating bath for 1 min. The bath was maintained at 25C during this period, and agitation was effected by air sparging. At the end of this period, the board was disconnected from the electroplating circuit, removed ~ 25 from the electrolyte, washed with tap water, and dried.
- An e~amination of the through holes of the resulting electroplated printed wiring boards was conducted and the completeness of copper coverage was noted. (See Table No. 1 below for comparison to standards.) Evaluation of the copper coverage, after 1 ~- minute of plating, was carried out by cross-sectioning and backlight methods.

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Jt-~1 3 ~ -36-A double-sided board described above was treated exactly as in E~ample 1, e~cept that it was electroplated for appro~imately 55 mins. in order to 5 build up a thickness of copper of appro~imately 0.001 inches on the hole wall surface. The holes were e~amined visually comparing them to standards described below. The board was then evaluated for adhesion by subjecting it to a standard solder shock test. The 10 graphite treated holes showed e~cellent uniformity of the electroplated layer and e~cellent adhesion to the hole walls.
COMPABISONS lA &I B
Two of the double-sided boards described above 15 were treated e~actly as in E~amples 1 and 2 e~cept that steps 6, 7, and 8 were omitted. One ~C-lA) of the boards was electroplated for 1 min.; the second one (C-lB) for approsimately 55 mins. This process is referred to as single-pass carbon black. The board C-lB
20 was evaluated for adhesion by subjecting it to a standard solder shock test. The results are shown in Table 3.
..
COMPARISONS 2A & 2B
Two double-sided boards described above were 25 treated exactly as in Examples 1 and 2 e~cept that step 8 (the graphite dispersion) was replaced by repeating step 5. One of the boards (C-2A) was electroplated for 1 minute and the other board (C-2B) was electroplated for approximately 55 mins. This process is referred to 30 as double-pass carbon black. The board C-28 was s evaluated for adhesion by subjecting it to a standard solder shock test. The results of that test are shown .
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` COMPARISQNS 3A & 3B
Two double-sided boards described above were treated exactly as in Examples l and 2 except that steps 5 5, 6, and 7 were omitted. One of the boards (C-3A) was electroplated for l min. and the other (C-3~) was electroplated for approximately 55 mins. This process is referred to as single-pass graphite. This board (C-3B) was not evaluated for adhesion since significant 10 voids were obversed even after 55 mins. of plating.

A double-sided board described above was treated exactly as in E~ample l except that step 8 was replaced in its entirety by an aqueous dispersion 15 comprised of:

0.4 % by weight anionic surfactant (l) 0.6 % by weight KOH (2) q.4 % by weight graphite (5) l.28% by weight solids ,.
20 (l) The anionic surfactant was MAPHOS 56, as described above.
-~ (2) KOH solid pellets as described above.
(5) The graphite in this example was Nippon AUP (0.7 micron) supplied by Nippon Graphite Industries, Ltd.
of Ishiyama, Japan.

The balance of the bath was deionized water.
The graphite dispersion was prepared by grinding a concentrated form of this dispersion in a laboratory ... .

:, . , WO92/~97g4 PCT/US92/02063 . .
~ 3137 -38-attritor (Model 0~1 made by Union Process of Akron, OH) so that the liquid level was just above the 1/8 inch diameter stalnless steel balls which occupied approximately one half of the volume of the chamber.
The material was ground for 12 hours at 70% full power.
After grinding, the concentrate was diluted with sufficient deionized water to make the dispersions in the above indicated proportions.

A double-sided board described was treated e~actly as in Example 2 except that Nippon AUP 0.7 micron graphite dispersion, prepared as described in j Example 3 above, replaced the Showa Denko graphite dispersion in step 8.
v EXAMP~E S

i A double-side board described above was treated e~actly as in Example 3 except that Asbury Graphite , Micro-8S0 supplied by Asbury Graphite Mills, Asbury, NJ, replaced the Nippon AUP (0.7 micron) graphite in the 20 dispersion described in step 8.

''' A double-sided board described above was , treated exactly as in Example 4 except that Asbury . Graphite Micro-850 replaced Nippon AUP (0.7 micron) 2S graphite in the dispersion described in step 8.

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~lu3~37 COPPER ~ovERAGE- OF THRO~GH HOLE AFTER
~LECTROPLATING EOR 1 MIN AT 20 AMPS/SO. FT.

`:., Process or Coverage 5 Board Gra~hite Used After 1 Min.
E~ample 1 Showa Denko 100%
Comparative E~ample lA Single-pass carbon black Less than 10%
Comparative E~ample 2A Double-pass carbon black Less than 50~
Comparative E~ample 3A Single-pass graphite Less than 50%
E~ample 3 Nippon AUP
0.7 micron 100%
15 E~ample 5 Asbury Micro-850 100%

. TABLE 2 :RESISTANCE BETWEEN COPPER PLATES FOR
- TREATED (BUT NOT ELECTRÇpLATED~ BOARDS
Process or Resistance BQard Gra~hite Used tOhms) E~ample 1 Showa Denko 15-35 Comparative E~ample lA Single-pass carbon black 200-250 Z5 Comparative E~ample 2A Double-pass carbon black 40-50 .~ .

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- WO92/19~94 PCT/US92/02063 , ~. .
313 ~ -40 TA~LE 3 THROUG~_HOLE COPPER COVERAGE & ADHESION
(SOL~ER ~HOCK) FOR FULLY-ELECTROPLATED (55 MI~S.
AT 20 AMPS/SO. FT.~ BOARDS. BOTH MEASUR~MENTS
S ARE RATED AS COMPARA~LE TO THE STANDARD 2~.

Process or Board Graphite Vsed Coverage Adhesion E~ample 2 Showa Denko Comparable Comparable Comp. E~ample lB Single-pass carbon black Comparable Comparable Comp. E~ample 2B Double-pass ; carbon black Acceptable Acceptable Comp. Example 3B Single-pass ~, graphite Some voids Not done 15 Example 4 Nippon AUP
0.7 micron Comparable Comparable ''.1 E~ample 6 Asbury 850 Comparable Comparable Coverage results mean that the cross-sectioned boards were evaluated as to voids and uniformity of 20 thickness. The E~amples of present in~ention (E-2, E-4, and E-6) were all comparable to standard dou~le-pass carbon black process. The adhesion results also show that they were comparable to standard double-pass carbon black process.
Accordingly, these results together show that boards tested according to Examples l, 3, and 5 exhibit , faster plating characteristics than all of Comparison process, while retaining the e~cellent coverage and adhesion characteristics of those processes.

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~ WO92/19794 PCT/US92/02063 ~1~3137 --gl--While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims.

'' ' 1 .

Claims (11)

WHAT IS CLAIMED IS:

1. A process for electroplating a conductive metal layer to the surface of a nonconductive material, characterized by the following steps:
(a) contacting said nonconductive surface with a liquid carbon black dispersion comprising:
(1) carbon black particles having an average particle diameter of less than about 3.0 microns in said dispersion;
(2) an effective dispersing amount of a surfactant which is compatible with said carbon black; and (3) a first liquid dispersing medium, wherein the amount of carbon black is sufficient to coat substantially all of said nonconduct-ing surfaces and is less than about 4% by weight of said liquid carbon black dispersion;
(b) separating substantially all of said first liquid dispersing medium from said carbon black particles, whereby said particles are deposited on said noncon-ductive surface in a substantially continuous layer; and (c) contacting said carbon black-coated nonconductive surface with a liquid conductive graphite dispersion comprising:
(1) conductive graphite particles having an average particle diameter of less than about 1.5 microns in said dispersion;
(2) an effective dispersing amount of a surfactant which is compatible with said conductive graphite; and (3) a second liquid dispersing medium, wherein the amount of conductive graphite is less than about 4% by weight of said liquid conductive graphite dispersion;
(d) separating substantially all of said second liquid dispersing medium from said conductive graphite particles, whereby said particles are deposited on said carbon black-coated nonconductive surface; and (e) electroplating a substantially continuous conductive metal layer over the deposited carbon black layer and the deposited conductive graphite layer and said nonconductive surface.

2. The process of Claim 1 characterized in that said carbon black particles have an average diameter of from about 0.05 to about 3.0 microns.

3. The process of Claim 1 characterized in that said graphite particles have an average particle diameter of from about 0.05 to about 0.8 microns.

4. The process of Claim 1 characterized in that said contacting steps (a) and (c) are carried out by immersing the nonconductive material into said liquid carbon black dispersion and liquid conductive graphite dispersion, respectively.

5. The process of Claim 1 characterized in that said separating steps (b) and (d) are carried out by heating the deposited dispersions.

6. The process for electroplating the walls of through holes in a laminated printed wiring board comprised of at least one nonconducting layer laminated to at least two separate conductive metal layers, said process characterized by the steps:
(a) contacting said printed wiring board having said through holes in a bath of a liquid carbon black dispersion comprised of:
(1) carbon black particles having an average particle diameter of less than about 3.0 microns in said dispersion;
(2) an effective dispersing amount of a surfactant which is compatible with said carbon black; and (3) a first liquid dispersing medium wherein the amount of carbon black is sufficient to coat substantially all of said noncon-ducting surfaces and is less than about 4%
by weight of said liquid carbon black dispersion;
(b) separating substantially all of the liquid dispersing medium from said dispersion, thereby depositing said carbon black particles in a substantially continuous layer on said nonconducting portions of said hole walls; and (c) contacting said carbon black-coated printed wiring board with a liquid conductive graphite dispersion comprising:
(1) conductive graphite particles having an average particle diameter of less than about 1.5 microns in said dispersion;
(2) an effective dispersing amount of a surfactant which is compatible with said conductive graphite; and (3) a second liquid dispersing medium, wherein the amount of conductive graphite is less than about 4% by weight of said liquid conductive graphite dispersion;
(d) separating substantially all of said second liquid dispersing medium from said conductive graphite particles, whereby said particles are deposited on said printed wiring board;
(e) microetching said metal layers of said printed wiring board to remove any deposited carbon black and graphite therefrom; and (f) electroplating a substantially continuous conduc-tive metal layer over the deposited carbon black layer and the deposited conductive graphite layer on said nonconductive portions of said hole walls, thereby electrically connecting said metal layers of said printed wiring board.

7. The process of Claim 6 characterized in that said process further comprises, before step (a), contacting said printed wiring board with a cleaning solution and a conditioner solution.

8. A nonconductive surface covered with a deposit of a substantially continuous layer of carbon black having an average particle diameter of less than about 3.0 microns thereon and a layer of conductive graphite having an average particle diameter of less than about 1.5 microns deposited over said carbon black deposit.

9. A metal-plated nonconductive surface covered with a deposit of a substantially continuous layer of carbon black having an average particle diameter of less than about 3.0 microns thereon and a layer of conductive graphite having an average particle diameter of less than about 1.5 microns deposited over said carbon black deposit and underlying the plated on metal.

10. The metal-plated nonconductive surface of Claim 8 or 9 characterized in that said nonconductive surface comprises at least one through hole of a printed wiring board.

11. A liquid dispersion suitable for use in enhancing the electroplating of a nonconducting surface characterized by:
(a) conductive graphite particles having an average particle diameter of less than about 1.5 microns in said dispersion;
(b) an effective dispersing amount of a surfactant which is compatible with said conductive graphite;
(c) optionally, a sufficient amount of at least one alkaline hydroxide to raise the pH of said liquid dispersion in the range from about 9 to 14; and (d) liquid dispersing medium, wherein the amount of conductive graphite is sufficient to coat substantially all of said nonconducting surface and is less than about 4% by weight of said liquid dispersion and wherein said liquid dispersion contains less than about 10% by weight solids constituents.