WO1999016556A1 - Procede de metallisation de trous - Google Patents

Procede de metallisation de trous Download PDF

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Publication number
WO1999016556A1
WO1999016556A1 PCT/US1998/020494 US9820494W WO9916556A1 WO 1999016556 A1 WO1999016556 A1 WO 1999016556A1 US 9820494 W US9820494 W US 9820494W WO 9916556 A1 WO9916556 A1 WO 9916556A1
Authority
WO
WIPO (PCT)
Prior art keywords
holes
metal
mixture
needle
parmod
Prior art date
Application number
PCT/US1998/020494
Other languages
English (en)
Inventor
Paul H. Kydd
Original Assignee
Partnerships Limited, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Partnerships Limited, Inc. filed Critical Partnerships Limited, Inc.
Priority to AU95931/98A priority Critical patent/AU9593198A/en
Publication of WO1999016556A1 publication Critical patent/WO1999016556A1/fr

Links

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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
    • H05K3/4053—Through-connections; Vertical interconnect access [VIA] connections by thick-film techniques
    • 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
    • H05K2201/09—Shape and layout
    • H05K2201/09818—Shape or layout details not covered by a single group of H05K2201/09009 - H05K2201/09809
    • H05K2201/09981—Metallised walls
    • 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
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/0126—Dispenser, e.g. for solder paste, for supplying conductive paste for screen printing or for filling holes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0763—Treating individual holes or single row of holes, e.g. by nozzle
    • 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
    • H05K2203/08—Treatments involving gases
    • H05K2203/082—Suction, e.g. for holding solder balls or components

Definitions

  • Printed circuit boards are made by etching copper foil which is laminated to polymer-based sheets of insulation, typically epoxy-glass. Components are secured to the electrical traces thus created by inserting the wire leads of the components through holes drilled through the traces and the board and soldering them. In some cases it is desired to connect traces from one side of the board to the other via a hole even with no component lead. This is particularly true of multilayer boards in which the laminate consists of many layers of thin epoxy-glass, each with circuitry on both sides, and bonded together with thin sheets of prepreg between them.
  • a conventional method of interconnecting the conductive layers of multilayer printed circuit boards and the like consists of plating the walls of the hole with an electrically conductive material. The plating connects the exposed edges of the conductive layers. This operation consumes considerable time.
  • the first step in interconnecting single-sided, double-sided and multilayer boards is to drill a pattern of holes to serve as vias and through-hole component connections. Multilayer boards need to be "desmearded" to remove melted epoxy from the exposed copper in the bore of the hole to permit a good electrical connection to be made to each exposed layer.
  • the second step is to metallize the bores of the holes to create an electrical pathway covering the entire exposed surface.
  • the third step is to build up the thickness of the metal in the holes by electroplating. These plated-through holes provide rugged and reliable connections through the board and to buried circuitry penetrated by the drill.
  • the catalytic material most often comprises palladium metal.
  • the process of applying the catalytic material to the substrate surfaces typically involves contact of the surfaces with a true or colloidal solution of palladium and tin compounds. See, e.g. U.S. Pat. Nos. 3,011,920 and 3,532,518.
  • catalysis of the substrate surface is followed by an acceleration step which exposes or increases exposure of the active catalytic species.
  • the surface is electrolessly plated by contact with an aqueous metal solution in which plating by chemical reduction leads to the deposit of metal from the bath onto the catalyzed surface.
  • the through-holes are usually plated with a copper reduction procedure known to the art as electroless copper plating, such as that described by Clyde F. Coombs, Jr. in Printed Circuit Handbook, 3 rd Edition, McGraw-Hill Book Co., N.Y., N.Y., 1988, Chapter 12.5.
  • the present invention offers an alternative path to direct metallization which can put down a thick enough metal layer to eliminate electroless plating, and in many cases the electroplating process as well.
  • any planar (rigid or flexible) circuit board material containing through-holes which require metallization can be employed.
  • the circuit board to be treated can be a double-sided board, in which case the through-hole surfaces are composed solely of the material of the non-conductive substrate, or a multi-layer board, in which case the through-hole surfaces are comprised of alternating layers of non-conductive substrate and the exposed edges of metal (e.g., copper) inner layers.
  • the non-conductive substrate material typically will be a glass- filled epoxy or a polyimide, but can in general be a suitable insulating thermosetting or thermoplastic material or combination thereof, including glass or fiber impregnated forms thereof, such as allyl phthalates, epoxy resins, polyesters, phenolics, acrylics, polyethylene, ABS terpolymers and the like.
  • the process is applicable to any non- conductive substrate such as those recited above, inorganic materials such as ceramics, and the like.
  • the invention also has applicability to the metallization of molded printed circuit boards such as those molded, for example, from polysulfones.
  • the substrate board material such as copper-clad, glass-filled epoxy or copper-clad, flexible polyimide (e.g., DuPont Kapton) or multilayers of polyimide and adhesive-coated flexible polyimide, is provided with through-holes by drilling or punching, the holes are then scrubbed and de-burred.
  • PARMODTM compositions are then applied to the inner surface of the holes and cured to form consolidated metal conductors.
  • PARMODTM mixtures contain a Reactive Organic Medium and metal flakes and/or metal powders.
  • the ROM consists of either a Metallo-Organic Decomposition (MOD) compound or an organic reagent which can form such a compound upon heating in the presence of the metal constituents.
  • the ingredients are blended together with rheology modifying organic vehicles well known in the art, if necessary, to produce printing inks or pastes. These inks can be printed on a temperature sensitive substrate and cured to well-consolidated, well-bonded electrical conductors at a temperature low enough so that the substrate is not damaged. The curing process occurs in seconds at temperatures far below those used for conventional sintering of thick film inks and pastes.
  • Figure 1 is an illustration of the method of the invention using a modified needle for injecting composition into circuit board holes.
  • FIG. 2 is a cross sectional view of a modified needle used in the method of the invention. Detailed Description of the Invention
  • compositions useful for metallizing the holes are comprised of a metal mixture and a Reactive Organic Medium (ROM). These compositions can be applied to thermally stable substrates and cured to well-consolidated, pure metal conductor in the hole by heat treatment.
  • the compositions exhibit a critical temperature above which they undergo a transformation to well-consolidated electrical conductors with a resistivity only two to four times the bulk resistivity of the metal in question.
  • the electrical conductivity is equal to that obtained by conventional high temperature metal powder sintering in conventional thick film compositions on ceramic substrates.
  • this consolidation process takes place at temperatures 400 to 500 degrees Celsius lower than with compounds conventionally used in thick film technology, and in times which are an order of magnitude shorter than are required for sintering.
  • Suitable metals include copper, silver, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, cobalt, nickel, indium, tin, antimony, lead, bismuth and mixtures thereof.
  • Examples of typical proportions of PARMODTM mixtures containing an organic acid as the ROM and both metal flakes and colloidal metal powder are illustrated in Table 1 as follows:
  • the metal mixture contains metal flake and colloidal or semi-colloidal metal powder where the total of flake plus powder is preferred to be 60-85% of the total mixture, and the powder is preferred to be 30-50% of the total metal. Larger amounts of organic vehicle may be added to reduce viscosity for certain applications.
  • the metal flakes have a major dimension between 2 to 10 micrometers, preferably about 5 micrometers, and a thickness of less than 1 micrometer. They can be produced by techniques well known in the art by milling the corresponding metal powder with a lubricant, which is frequently a fatty acid or fatty acid soap. The starting powders are usually produced by chemical precipitation to obtain the desired particle size and degree of purity. The flakes are sold for electronic applications as constituents of thick film inks and silver-loaded conductive epoxies.
  • the flakes perform several functions. They form a skeleton structure in the printed image which holds the other ingredients together and prevents loss of resolution when the mixture is heated to cure it.
  • the flakes naturally assume a lamellar structure like a stone wall which provides electrical conductivity in the direction parallel to the surface of the substrate and provides a framework to lessen the amount of metal transport necessary to achieve the well-consolidated pure metal conductors which are the objective of this invention. They also provide low surface energy, flat surfaces to which the other constituents of the composition can bond.
  • the other metallic powder mixture constituent of the present invention are preferably colloidal or semi-colloidal powders with individual particle diameters below about 100 nanometers, preferably less than about 50 nanometers.
  • the colloidal or semi-colloidal powder is preferably present in about 40% by weight of the total weight of the metal powder mixture.
  • a primary function of these powders is to lower the temperature at which the compositions will consolidate to nearly solid pure metal conductors.
  • the presence of fine metal powder has been found to be helpful in advancing this low temperature process with silver and essential to the consolidation of copper mixtures. It is important that they be present as individual particles. Metal particles this small have a strong tendency to agglomerate into aggregates with an open skeletal structure.
  • Colloidal silver particles with a nominal diameter of 20 nanometers were shown to have an excellent state of dispersion and have been used in silver compositions and lowered the critical consolidation temperature from 300 to 260 degrees C.
  • Suitable surfactants include carboxylic acids and metal soaps of carboxylic acids. This favors chemical precipitation as a means of producing the powders, since they can be exposed to an environment which promotes stabilization from formation to final consolidation.
  • the Reactive Organic Medium provides the environment in which the metal mixture is bonded together to form well-consolidated conductors.
  • Many classes of organic compounds can function as the ROM.
  • the common characteristic which they share and which renders them effective is that they have, or can form, a bond to the metal via a hetero-atom.
  • the hetero-atoms can be oxygen, nitrogen, sulfur, phosphorous, arsenic, selenium and other nonmetallic elements, preferably oxygen, nitrogen or sulfur.
  • This bond is weaker than the bonds holding the organic moiety together, and can be thermally broken to deposit the metal. In most cases the reaction is reversible, so that the acid or other organic residue can react with metal to reform the metallo-organic compound, as shown schematically below:
  • R is a reactive organic compound and M is the metal.
  • M is the metal.
  • Acid + Metal powder MOD + H2 or lib
  • the effect is to consume the small particles and weld together the big ones to create macroscopic circuit conductors of pure metal.
  • some other active organic reagent which will produce an easily decomposed metallo-organic compound from either the oxide or the metal could be used.
  • An example would be the use of sulfur compounds to make mercaptides or nitrogen ligands to produce decomposable complexes.
  • Examples of useful compounds are soaps of carboxylic acids, in which the hetero-atom is oxygen; amino compounds, in which the hetero-atom is nitrogen; and mercapto compounds, in which the hetero-atom is sulfur.
  • ROM constituents are the carboxylic acids and the corresponding metallic soaps of neodecanoic acid and 2-ethyl hexanoic acid with silver and copper, such as. silver neodecanoate illustrated by the formula:
  • Gold amine 2-ethyl hexanoate is an example of a nitrogen compound.
  • Gold t-dodecyl mercaptide is an example of a sulfur compound:
  • Ri + R 2 + R3 C11H23
  • These ROM compositions can be made by methods well known in the art. All of the above compounds are capable of decomposition to the respective metals at relatively low temperatures.
  • the decomposition temperature is between 200 and 250°C .
  • the corresponding copper compounds it is between 300 and 315 C.
  • Gold sulfides decompose at very low temperatures in the neighborhood of 150°C .
  • Gold amine octoate decomposes between 300 and 500°C .
  • the copper and silver compounds can be reformed from the corresponding acids at the same temperature, so the reaction is reversible, as mentioned above.
  • Alpha-terpineol has been used to reduce the viscosity of copper and silver compositions to facilitate screen printing.
  • Alpha-terpineol also participates in the consolidation reaction by virtue of the acid character of the OH group bonded to an unsaturated ring.
  • the method employs the use of a needle in which the end is plugged and in which notches or holes are cut in the side of the needle barrel, as shown in Figure 1.
  • Tests performed with a single notch show that the two sides of the board can be connected, but the coating in the hole may not be complete. Using two notches in the needle is preferred, resulting in improved completeness of the coating. Three notches is even more preferable. Notches or slots are preferred over round holes, since they distribute the material into the bore of the hole more uniformly. The notches are preferably at the same height on the needle to prevent the majority of the material being injected from the notch nearest the material source. Notches are preferably spaced evenly around the circumference of the needle, e.g., 120°apart for three notches. Three slots have been cut to a depth of 0.007 inches in a needle with a wall thickness of 0.005 inches.
  • the direct injection method may not be preferable when all the holes in a board, which may number in the thousands, are to be filled simultaneously. Unlike the case with microvias, which are small and shallow, high aspect ratio holes in rigid boards may not be successfully metallized by simply filling them with PARMODTM paste, as mentioned above. However, if the excess material can be removed, this method can be used. This can be done by blowing or sucking the excess PARMODTM material out of the holes, either while it is being applied or afterwards in a separate operation.
  • Example of using vacuum to remove excess is disclosed by Ken Gileo in Polymer Thick Film, pages 58-62 (Van Nostrand 1996).
  • An alternate method is to use surface tension forces to remove excess PARMODTM material, such as, by blotting or using a porous backing strip underneath the board.
  • PARMODTM is applied to the drilled board with a squeegee or in some other way so as to ensure that all the holes are filled with PARMODTM material. Any excess PARMODTM could then be extracted by vacuum applied to the holes or by air pressure acting on the surface of the board with a relief behind the board to let the excess material pass through. This process could be performed immediately after drilling.
  • the boards are stacked three or more deep and drilled simultaneously with an aluminum entry plate and a backing plate to eliminate burrs in the circuit boards themselves. If the holes were drilled through the backing plate into a porous material PARMODTM could be applied to the entry plate and sucked or blown through all the holes simultaneously. The boards could then be separated and thermally cured to convert the PARMODTM to pure metal.
  • a copper PARMODT jnj- was prepared by mixing 77 grams of nanometer sized spherical copper powder with 23 grams of neodecanoic acid in a glove box. This premix was than further mixed on a 2-roll mill for 30 minutes in air. The gap setting on the mill was 0.006" - 0.008". After milling, the ink was removed from the mill and stored in a plastic syringe from which is also was dispensed.
  • the copper PARMOD ⁇ M [ ⁇ was applied to the inside walls of holes which had been drilled into rigid laminate with a 0.038" diameter drill. No adhesive was used in the holes prior to filling with the copper PARMOD ⁇ M ⁇ nk. he holes were filled by coating a 0.036" diameter needle with the ink, inserting and rotating the ink coated needle in the hole and than removing the needle. The injection process was repeated from the other side of the laminate. The laminate was than heat treated at 245°C for 8 minutes in a N 2 -H 2 O-H 2 gas mix. The resulting filled holes were bright copper and conductive, and when coated with solder flux and dipped into a solder bath, the internal surface of the holes, coated with copper, in turn become coated with solder.
  • Silver PARMOD screen ink was prepared by mixing together 12.0 grams of Degussa silver flake, 3.0 grams of silver neodecanoate, and 1.35 grams of neodecanoic acid using a spatula. The resulting mixture was then milled on roll mill to give a homogeneous paste.
  • the circuit board assembly was then mounted on the XY plane of an XYZ table.
  • the syringe from the paste dispensing system was mounted on the Z-axis arm of the table.
  • a 21 gage modified dispensing needle was used with 80 PSI worth of pressure to dispense the silver ink.
  • the dispensing needle was inserted into the through holes such that the ink was dispensed at the midpoint of the thickness of the circuit board.
  • the ink was dispensed for 3 seconds into the through hole.
  • the dispensing needle was then pushed through the hole before being pulled back out.
  • circuit board was removed from the assembly and any excess ink was wiped from the surface.
  • the circuit board was then thermally treated at 260°C in air to convert the ink to pure silver with good adhesion in the holes.
  • the silver coated the inside of the holes forming a "rivet-like" structure with the center of the hole remaining open.
  • Copper PARMODTM ink was prepared by mixing 31 grams of nanometer sized spherical copper powder with 38 grams of 9 micron diameter spherical copper powder, 15 grams of 3 micron diameter spherical powder, 14 grams of neodecanoic acid, and 2 grams of alpha terpineol in a glove box. This premix was then further mixed on a 2-roll mill for 30 minutes in air. The gap setting on the mill was 0.006" - 0.008". After milling, the ink was removed from the mill and stored in a plastic syringe from which it also was dispensed.
  • Copper PARMODTM ink was applied to the inside walls of holes which had been drilled into rigid laminate with a 0.038" diameter drill. No adhesive was used in the holes prior to filling with the copper PARMODTM ink.
  • the holes were filled by coating a 0.036" needle with the ink, inserting and rotating the ink coated needle into the hole and then removing the needle.
  • the laminate was then heat treated at 250°C for 7 minutes in a N 2 -H 2 0-H 2 gas mix.
  • the resulting filled holes were bright copper and conductive, and when coated with solder flux and dipped into a solder bath, the internal surface of the holes, coated with copper, in turn become coated with solder.

Abstract

La présente invention concerne une composition de matière pouvant être utilisée pour métalliser des trous de montage de composant et des traversées dans des cartes de circuits imprimés par un simple procédé d'application-chauffage. La matière métallisée est injectée dans les trous à l'aide d'une aiguille de forme spéciale. Selon un autre mode de réalisation, la matière est utilisée pour remplir les trous et l'excédent est aspiré ou éliminé des trous par soufflage avant le chauffage et le durcissement.
PCT/US1998/020494 1997-09-30 1998-09-30 Procede de metallisation de trous WO1999016556A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU95931/98A AU9593198A (en) 1997-09-30 1998-09-30 Method for metallizing holes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6043697P 1997-09-30 1997-09-30
US60/060,436 1997-09-30

Publications (1)

Publication Number Publication Date
WO1999016556A1 true WO1999016556A1 (fr) 1999-04-08

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ID=22029469

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/020494 WO1999016556A1 (fr) 1997-09-30 1998-09-30 Procede de metallisation de trous

Country Status (2)

Country Link
AU (1) AU9593198A (fr)
WO (1) WO1999016556A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7141185B2 (en) 2003-01-29 2006-11-28 Parelec, Inc. High conductivity inks with low minimum curing temperatures
US7211205B2 (en) 2003-01-29 2007-05-01 Parelec, Inc. High conductivity inks with improved adhesion
US7749299B2 (en) 2005-01-14 2010-07-06 Cabot Corporation Production of metal nanoparticles
US8167393B2 (en) 2005-01-14 2012-05-01 Cabot Corporation Printable electronic features on non-uniform substrate and processes for making same
US8334464B2 (en) 2005-01-14 2012-12-18 Cabot Corporation Optimized multi-layer printing of electronics and displays
US8597397B2 (en) 2005-01-14 2013-12-03 Cabot Corporation Production of metal nanoparticles

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576669A (en) * 1968-08-15 1971-04-27 Nasa Method for coating through-holes
US4544577A (en) * 1984-04-26 1985-10-01 E. F. Johnson Company Process for metallization of dielectric substrate through holes
US5356658A (en) * 1993-07-19 1994-10-18 Motorola, Inc. Flexible high speed liquid dispenser
US5630272A (en) * 1994-11-02 1997-05-20 Lpkf Cad/Cam Systeme Gmbh Method of forming contacts through bores in multi-layer circuit boards

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576669A (en) * 1968-08-15 1971-04-27 Nasa Method for coating through-holes
US4544577A (en) * 1984-04-26 1985-10-01 E. F. Johnson Company Process for metallization of dielectric substrate through holes
US5356658A (en) * 1993-07-19 1994-10-18 Motorola, Inc. Flexible high speed liquid dispenser
US5630272A (en) * 1994-11-02 1997-05-20 Lpkf Cad/Cam Systeme Gmbh Method of forming contacts through bores in multi-layer circuit boards

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7141185B2 (en) 2003-01-29 2006-11-28 Parelec, Inc. High conductivity inks with low minimum curing temperatures
US7211205B2 (en) 2003-01-29 2007-05-01 Parelec, Inc. High conductivity inks with improved adhesion
US7749299B2 (en) 2005-01-14 2010-07-06 Cabot Corporation Production of metal nanoparticles
US8167393B2 (en) 2005-01-14 2012-05-01 Cabot Corporation Printable electronic features on non-uniform substrate and processes for making same
US8334464B2 (en) 2005-01-14 2012-12-18 Cabot Corporation Optimized multi-layer printing of electronics and displays
US8597397B2 (en) 2005-01-14 2013-12-03 Cabot Corporation Production of metal nanoparticles

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Publication number Publication date
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