WO1996033813A1 - Procede de preparation d'une structure multicouche isolee - Google Patents

Procede de preparation d'une structure multicouche isolee Download PDF

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Publication number
WO1996033813A1
WO1996033813A1 PCT/US1996/005810 US9605810W WO9633813A1 WO 1996033813 A1 WO1996033813 A1 WO 1996033813A1 US 9605810 W US9605810 W US 9605810W WO 9633813 A1 WO9633813 A1 WO 9633813A1
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WO
WIPO (PCT)
Prior art keywords
substrate
dielectric
weight percent
recited
glass frit
Prior art date
Application number
PCT/US1996/005810
Other languages
English (en)
Inventor
Kalman F. Zsamboky
Leon M. Balents
Yong S. Cho
Sudhaker Gopalakrishnan
Walter A. Schulze
Vasantha R. W. Amarakoon
Original Assignee
Ceramic Packaging, Inc.
Alfred University
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 Ceramic Packaging, Inc., Alfred University filed Critical Ceramic Packaging, Inc.
Priority to AU57159/96A priority Critical patent/AU5715996A/en
Publication of WO1996033813A1 publication Critical patent/WO1996033813A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4857—Multilayer substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4867—Applying pastes or inks, e.g. screen printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • 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
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4661—Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor
    • 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
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • 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
    • H05K2203/03—Metal processing
    • H05K2203/0315—Oxidising metal
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/108—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by semi-additive methods; masks therefor

Definitions

  • a process for preparing an insulated multilayer struc ⁇ ture in which a metallized substrate is patterned with a layer of dielectric material.
  • Multilayer electronic structures are known to those skilled in the art.
  • the use of copper in these structures is desirable because of copper's thermal and electrical condcu- tivities.
  • the use of copper presents several dis ⁇ tinct problems. Poor adhesion between the copper and the the ceramic often occurs because of the differences in thermal expansion coefficients between the layers of copper and the layers of ceramic material
  • United States patents 5,100,714 and 5,058,799 describe a process for preparing a metallized ceramic substrate having an enhanced bond strength.
  • the substrate produced by the process of these patents may be used to produce the products described and claimed in this patent application.
  • FIG. 1 is a flow diagram of one preferred process of this invention
  • Figure 2 is a sectional view of one substrate which may be used in applicants' preferred process
  • Figure 3 is a sectional view of another substrate which may be used in applicants' preferred process
  • Figure 4 is a sectional view of yet another substrate which may be used in applicants' preferred process
  • Figure 5 is a flow diagram of a preferred cleaning process which may be used as one aspect of applicants' claimed process
  • Figure 6 is a schematic of one preferred metallized ceramic substrate
  • Figures 7, 8, 9, 9A, 10, 11, 12, 13, 14, 15, and 16 present sectional views of a ceramic/metal substrate and its configurations as it is processed through various steps and stages of applicants' process;
  • Figure 17 is a top view of a mask used to prepare a conductor pattern on a ceramic substrate
  • Figure 18 is a top view of a mask used to prepare a dielectric pattern
  • Figure 19 is a top view of the top conductor pattern produced during one stage and in one preferred embodiment of applicant's process
  • Figure 20 is a top view of the areas to be machined in one device made in accordance with applicants' process
  • Figure 21 is a top view of a planar transformer made in accordance with applicants' process.
  • a metallized substrate is first provided, and its surfaces are then treated prior to the time they are contacted with a mixture of liquid and ceramic material.
  • Figure 1 is a flow chart illustrating one preferred embodiment.
  • a metallized substrate is produced in the first step (step 10) of the process de ⁇ picted.
  • the process of United States patents 5,058,799 and 5,100,714 may be used to prepare the metallized substrate.
  • the substrate is passed via line 12 to cleaner 14, wherein it is cleaned to remove contaminants.
  • the cleaned substrate is then passed via line 16 to oxidizer 18 in which at least a portion of the exterior faces of the substrate is oxidized while exposing it to an inert gas comprised of a specified amount of oxygen.
  • the oxidized substrate is then passed via line 20 to printer 22 in which a patterned layer of dielectric is applied to the exterior faces of the substrate.
  • the printed substrate is then passed via line 24 to dryer 26 in which solvent present in the dielectric is removed.
  • the dried substrate is then passed via line 28 to binder removal furnace 30 to effect removal of organic matter from the dried slurry coating.
  • the substrate is then passed via line 32 to sintering furnace 34, in which the dried slurry layer is densified.
  • This densified substrate is then passed via line 36 to metal oxide remover 38, in which metal oxide on the surface of the substrate which was not covered by the dielec ⁇ tric applied in printer 22 is removed.
  • the treated substrate from which metal oxide has been removed is then passed via line 40 to surface preparer 42, in which the exterior surfaces of the substrate are treated in preparation for subsequent deposition of metal.
  • the prepared substrate is then passed via line 44 to electroless metal deposition step 46, in which a layer of metal is electrolessly deposited onto the substrate structure.
  • the substrate coated with metal from step 46 is then passed via line 48 to step 50, in which a coating of photoresistive material is applied to the substrate.
  • the coated substrate from step 50 is then passed via line 52 to step 54, in which the photoresistive coating is selectively exposed to ultraviolet radiation to selectively harden areas of the coating.
  • the exposed substrate from step 54 is then passed via line 56 to developer 58, in which a portion of the photoresistive coating is removed.
  • the substrate from step 58 is then passed via line 60 to metal plater 62, in which metal is then plated onto those areas from which the photoresistive coating has been removed.
  • the plated substrate is then passed via line 64 to photoresist stripper 66, in which excess photo ⁇ resist material is removed.
  • the printed sub ⁇ strate is then passed via line 68 to electroless metal remov ⁇ al step 70 and, thereafter, via line 71 to machiner 73, wher ⁇ ein the printed substrate may be cut to the desired size.
  • the printed substrate may be passed to cleaner 14, where the process may be repeated as required to add additional layers of ceramic material and/or metal material prior to the time the printed substrate is cut to the desired size(s).
  • the metallized substrate used in applicants' process is a workpiece, such as a ceramic workpiece, having a working surface unitary with the workpiece and containing a layer of electrically conductive metal on the working surface.
  • a heterogeneous juncture band exists between the workpiece and the conductive metal layer which is substan ⁇ tially coextensive with the conductive metal layer and the working surface. It is preferred, but not essential, that this heterogeneous juncture band has a metal-wetted surface area which is at least about twice the apparent surface area of the metal layer overlying the juncture band, consists es ⁇ sentially of workpiece grains unitary with said workpiece and conductive metal unitary with said conductive metal layer, and it is constituted by finger-like metal protuberances unitary with the metal layer and occupying the space between the ce ⁇ ramic grains.
  • the metallized substrate used is preferably capable of withstanding repeated firing cycles at a temperature in excess of 400 degrees centigrade without separation of the metal layer from the working surface of the workpiece. In one embodiment, the metallized substrate s capable of withstanding repeated firing cycles at a temperature in excess of 600 degrees centigrade without separation of the metal layer from the working surface of the workpiece. In another preferred embodiment, the metallized substrate is capable of withstand ⁇ ing repeated firing cycles at a temperature in excess of 850 degrees without separation of the metal layer.
  • the substrate used in step 14 is a metallized ceramic substrate.
  • the preparation of such a substrate is described in the aforementioned United States patents 5,058,799 and 5,100,714.
  • Ceramic substrates, and/or substrates comprised of ce ⁇ ramic material are well known to those skilled in the art.
  • the ceramic material used is alumina.
  • the alumina is a "white alumina" substrate which has a density of at least about 3.7 grams per cubic centimeter and is comprised of at least about 90 weight percent of aluminum oxide.
  • the ceram ⁇ ic substrate 72 consists essentially of alumina and is com ⁇ prised of a base 74 of relatively low density alumina material and, integrally bonded thereto, a layer 76 of higher density alumina material.
  • the porosity of layer 76 be less than the porosity of layer 74.
  • layer 76 has a porosity such that it is substantially impervious to liquid penetration.
  • layer 76 preferably has a thickness of at least about 5 times the average grain size of the particles in layer 76.
  • the ceramic substrate used in step 14 may be a porcelain covered metal or metal alloy material. Furthermore, the ceramic substrate may be porcelain/ceramic covered graphite, porcelain/ceramic covered silicon carbide, and the like.
  • the ceramic substrate is comprised of or consists essentially of a ferromagnetic material, such as a ferrite such as, e.g., a garnet ferrite, a spinel ferr- ite, a lithium ferrite, a hexagonal ferrite, and the like.
  • a ferrite such as, e.g., a garnet ferrite, a spinel ferr- ite, a lithium ferrite, a hexagonal ferrite, and the like.
  • the ceramic substrate is comprised of a superconductive material which, preferably, has a critical temperature of greater than 77 degrees Kelvin.
  • the ceramic material may be, e.g., barium titanate, neodymium nitride, neodymium oxide, and the like.
  • the substrate may be comprised of ceram ⁇ ic microspheres.
  • FIG 3 illustrates one typical laminated structure which may be used as the ceramic substrate.
  • Substrate 78 is comprised of metal and/or metal alloy base 80 and, bonded thereto, porcelain layers 84 and 86.
  • Base 80 may be a sub ⁇ stantially homogeneous material consisting essentially of only one metal or metal alloy.
  • base 80 may be a laminated structure.
  • the ceramic substrate preferably used in step 14 may, but need not, contain ceramic throughout its entire structure, as long as the exterior layers of such structure consist essentially of one or more ceramic materials.
  • the ceramic substrate used have a volume resistivity of at least about 10 10 ohm-centimeters and, additionally, have a thermal conductivity at least about 10 watts/meter-degrees Centigrade.
  • Ceramic substrates sold by the Coors Ceramics Company of 17750 West 32nd Avenue, Golden, Colorado as product numbers ADO-90, AD-94, and AD-96. These products have a bulk density of from about 3.7 to about 3.8 grams per cubic centimeter, a Rockwell hardness of from about 75 to about 80), a coefficient of linear thermal expansion of from about 3 to 8 x 10 "6 per degree Centigrade, a flexural strength of from about 40,000 to 60,000 pounds per square inch, a water absorption of 0 percent, and a compressive strength of from about 300,000 to about 400,00 pounds per square inch.
  • the substrate used in step 14 contain at least one through hole which extends from its top surface to or towards its bottom surface.
  • the substrate may contain a multiplicity of vias extending into the ceramic substrate to a depth of at least about one-fifth of its thickness up to about 100 percent of its thickness.
  • the extensions are circular in cross-section and preferably have a diameter of from about 4 to about 20 mils.
  • the ceramic substrate contains a through hole 88 (see Figure 4).
  • sub ⁇ strate 90 is comprised of ceramic material 92, via 88 which extends from top surface 94 to bottom surface 96 of substrate 90, and a layer of metal 98 covering the wall of hole 88.
  • FIG. 5 is a flow diagram illustrating one cleaning process.
  • the substrate is prefer ⁇ ably charged via line 100 to washer 102, wherein it is washed.
  • a soapy mixture of industrial detergent is applied to the substrate; the the substrate may be allowed to soak in a soapy mixture of the detergent for up to about 20 minutes and thereafter may be rinsed with deionized water.
  • the substrate Prior to the time the substrate is washed in washer 102 its surface is preferably etched in texturizer 103.
  • texturizer 103 e.g., when the metal layer involved is copper, one may utilize "ENPLATE" ad-485, which is a mild etchant for copper surfaces sold by the Enthone-OMI Inc. Company of New Haven, Connecti ⁇ cut. Other comparable etchants also may be used. After such etching, the etched device may be passed to washer 102 via line 105 for processing.
  • the washed substrate may then be passed via line 104 to dryer 106, wherein it is preferably dried to a moisture content of less than about 5 weight percent.
  • a layer of metal ox ⁇ ide is formed on the surface of the metal in the substrate.
  • the dried substrate is passed via line 108 to inert gas furnace 110, wherein it is preferably fired at a tempera ⁇ ture of at least 800 degrees centigrade for at least about 5 minutes while being contacted with an inert atmosphere, which may be introduced via line 112.
  • the inert atmosphere consists essentially of nitrogen, which is preferably allowed to flow over the substrate. It is preferred that the oxygen content in the furnace 110 be less than about 10 parts per million.
  • the dried substrate is passed through a conveyor furnace (not shown) in which the middle of furnace is at the desired peak temperature and the ends of the furnace are each preferably at less than about 100 degrees Centigrade.
  • the substrate is to be transferred to a second furnace for the oxidation heat treat ⁇ ment processing
  • the substrate is heated at a temperature in excess of 100 degrees centigrade, however, it preferably is contacted with the inert atmosphere which is comprised of less than 10 parts per million of oxygen.
  • a temperature of at least about 900 degrees centigrade is used in furnace 110.
  • the substrate passing from furnace 110 is preferably at ambient temperature. Thereafter, this substrate is passed via line 114 to oxidizing furnace 116, wherein it is subjected to a specified firing profile.
  • Both of the heat-treatment cycles could be effected in the same furnace by changing the atmosphere used at the appro ⁇ priate time(s). In this embodiment, however, the need to cool the substrate after exposure to inert gas and then again raise it to peak temperature prior to exposing it to the mild oxi ⁇ dizing atmosphere may be omitted.
  • the temperature of the furnace is raised from ambient to about at least about 800 degrees centigrade over a period of at least about 5 minutes; it is preferred to raise the tem ⁇ perature of the substrate to a temperature of at least about 800 to about 950 degrees centigrade over a period of from about 5 minutes to about 20 minutes.
  • the atmosphere in the furnace is preferably substantially inert, containing less than about 10 parts per million of elemental oxygen.
  • an oxygen- containing gas such as, e.g., oxygen, air, mixtures thereof, and the like
  • an oxygen-containing gas such as, e.g., oxygen, air, mixtures thereof, and the like
  • an oxygen-containing gas such as, e.g., oxygen, air, mixtures thereof, and the like
  • the substrate produced via this process is schemati ⁇ cally represented in Figure 6, which illustrates a copper/ceramic/copper device.
  • Figure 6 illustrates a copper/ceramic/copper device.
  • Substrate 130 is comprised of a ceramic core 132 (such as, e.g., alumina) and, bonded to portions thereto, copper patterned layers 134 and 136.
  • a ceramic core 132 such as, e.g., alumina
  • Each of copper layers 134 and 136 has a thickness of from about 10 to about 250 microns and, more preferably, from about 25 to about 125 microns.
  • ceramic layer 132 generally has a thickness of from about 250 to about 30,000 microns and, more preferably, from about 500 to about 1500 microns.
  • cuprous oxide Formed on top of each of copper layers 134 and 136 is a relatively thin layer of cuprous oxide (Cu 2 0). This cuprous oxide is believed to be a reddish, crystalline material with a specific gravity of about 6 and a melting point of about 1,235 degrees centigrade; it is insoluble in water.
  • Each of cuprous oxide layers 138 and 140 has a thick ⁇ ness of less than 10 microns and preferably is from about 1 to about 10 microns thick.
  • the aforementioned oxidation step has been described with reference to forming a metal oxide (such as cuprous ox ⁇ ide) on the surface of the metal layer (such as copper). How ⁇ ever, other oxides also may be formed on the metal layer, or deposited on such layer, to provide a layer of oxide material which is of the desired thickness (from 1 to 10 microns thick) and, furthermore, provide an oxidation-resistant layer on top of the metal.
  • a metal oxide such as cuprous ox ⁇ ide
  • other oxides also may be formed on the metal layer, or deposited on such layer, to provide a layer of oxide material which is of the desired thickness (from 1 to 10 microns thick) and, furthermore, provide an oxidation-resistant layer on top of the metal.
  • Printer 22 is preferably a screen printing apparatus.
  • the combined metal/metal oxide layers (such as layers 136/140 and 134/138 of Figure 6) preferably provide a resistivity of less than about 1.9 x 10 ohm-centimeters. In one preferred em ⁇ bodiment, the combined metal/metal oxide layers preferably have a melting point of at least 1,000 degrees centigrade.
  • the desired structure is an insulated metallized sub ⁇ strate which comprises a workpiece having a working surface unitary with the workpiece, a layer of electrically conductive metal on said working surface, a layer of metal oxide on said layer of conductive metal, and a layer of ceramic material on said layer of metal oxide, and a heterogeneous juncture band between said workpiece and said conductive metal layer, sub ⁇ stantially coextensive with said conductive metal layer and said working surface, wherein: (1) said heterogeneous junc ⁇ ture band consists essentially of grains unitary with said workpiece and conductive metal unitary with said conductive metal layer and is constituted by finger-like metal protuber ⁇ ances unitary with the metal layer and occupying the space between said grains, wherein said metallized substrate is cap- ' able of withstanding repeated firing cycles at a temperature in excess of 400 degrees centigrade without separation of the metal layer from the working surface of the workpiece, (2) the layer of electrically conductive metal has a thickness of from
  • Figure 7 is sectional view of a ceramic substrate 160 onto which layers of copper 134 have been selectively pat ⁇ terned in substantial accordance with the procedure of United States patent 5,058,799.
  • the structure is comprised of a through-hole 162 formed by conven ⁇ tional means in substrate 160.
  • Layers 138 of copper oxide are preferably formed over layer 134. Thereafter, layers of dielectric "ink" are selec ⁇ tively patterned over the structure.
  • the screen (not shown) is preferably patterned to prevent deposition of material in certain areas.
  • the screen (not shown) is preferably patterned to prevent deposition of material in certain areas.
  • two such masked areas are areas 164 and 166.
  • a layer 168 of dielectric "ink” is selectively pat ⁇ terned onto the structure in the screen printing process. Thereafter, after drying, binder removal, and sintering, the layer of "ink” so deposited tends to shrink and conform to the shape of the surface onto which it was deposited. In one embodiment, not shown, at least two layers of the dielectric "ink” are separately deposited, dried, pro ⁇ Ded to remove binder, and then sintered. In another em ⁇ bodiment, at least three layers of such dielectric "ink” are so deposited.
  • the dielectric ink used in the process is preferably deposited as a layer with a thickness of at least about 25 microns and, preferably, at least about from 25 microns to about 100 microns.
  • the dielectric ink used in the process of this inven ⁇ tion is preferably a mixture of liquid material and solid material which preferably contains at least about 80 weight percent of solid material and at least about 10 weight percent of liquid material.
  • the liquid in the dielectric ink is preferably non-aqueous and preferably has a boiling point in excess of 100 degrees centigrade.
  • the viscosity of the dielectric ink used in the pro ⁇ cess when measured with a Brookfield RVT viscometer and an ABZ spindle at 10 revolutions per minute and room temperature, is preferably less than 500 Pascals.
  • the solid material in the dielectric preferably has a particle size distribution such that at least about 95 percent (by weight) of such particles are smaller than 25 microns.
  • dielectric composition 4906 which is sold by Electro-Science Laborato ⁇ ries, Inc. of 416 East Church Road, King of Prussia, Pennsyl ⁇ vania.
  • This material has a dielectric constant of from about 5 to about 11 and is insoluble in water. It is comprised of at least about 5 weight percent of liquid, and at least about 0.5 weight percent of organic binder, and at least about 80 weight percent of solid particulate matter; the solid particu ⁇ late matter comprises glass and alumina. Substantially all of the particles of such ink are less than about 54 microns in size. The solid particulate matter liquefies and sinters at a temperature in excess of 800 degrees centigrade.
  • dielectric ink is "Fodel 6050 Dielectric Paste,” which is also sold by the E.I. duPont de Nemours & Company of Wilmington, Delaware.
  • This material has a dielectric constant of from about 7 to about 9, a breakdown voltage in excess of 1,000 volts per 25 microns of thickness of dielectric, and an insulation resistance in excess of 10 11 ohms at ambient temperature.
  • this dielectric is used to coat the substrate, it is preferred to fire it in nitrogen at ⁇ mosphere comprised of water vapor; such atmosphere may be readily produced by bubbling an inert or relatively inert gas (such as nitrogen) through water maintained at a substantially constant temperature prior to flowing the inert gas over the heated substrate.
  • the aforementioned "Fodel" material in addition to being comprised of glass particles and organic solvent, also contains photosensitive plastic binder material which enables a user to expose the dried dielectric layer to ultraviolet ra ⁇ diation and to selectively harden certain areas thereof. Thereafter, the unexposed areas may be washed away prior to the firing of the binder removal step and the sintering step. This feature allows the patterning of fine features in the dielectric layer.
  • a layer of dielec ⁇ tric material is applied to the structure, it is then passed via line 24 to dryer 26, wherein the solvent is removed. It is preferred that the temperature in dryer 22 be below the boiling point of the organic solvent in the dielectric ink. In one preferred embodiment, the structure is subjected to a temperature of less than about 150 degrees centigrade (and, more preferably, less than about 130 degrees centigrade) until substantially all of the solvent in the dielectric layer has evaporated.
  • the steps of printing and drying are repeated at least once, and often at least twice, to provide several layers of the dried dielectric material.
  • different dielectric materials are used in each of the printing/drying sequences to provide printed layers with different characteristics.
  • a three-layer dielectric structure is produced with a substantially non-porous dielectric materi ⁇ al on top, and relatively porous dielectric material in the middle, and a lower porosity dielectric material on the bot ⁇ tom.
  • one layer of dielectric materi ⁇ al is deposited, dried, and thereafter fired. Thereafter a second layer of dielectric material is deposited upon the first sintered layer, dried, and fired.
  • the structure is then passed via line 28 to binder removal furnace 30.
  • the structure in binder removal furnace 30 it is preferred to heat the structure in binder removal furnace 30 to a temperature of at least about 400 degrees centigrade (and, preferably, from about 400 to about 500 degrees centigrade) for from about 30 minutes to about 60 minutes.
  • the structure from which binder has been removed is then passed via line 32 to sintering furnace 34. Thereafter, the temperature of the structure is raised from ambient to a peak temperature of from about 800 to about 950 degrees Centi ⁇ grade over a period of at least about 20 minutes and prefer ⁇ ably from about 20 to about 40 minutes; during this portion of the firing, the structure is contacted with flowing inert gas containing less than about 100 parts per million of oxy ⁇ gen.
  • the struc ⁇ ture is maintained at this temperature for at least 3 minutes (and, preferably, from about 3 to about 15 minutes) while con ⁇ tacting the structure with inert gas containing less than about 100 parts per million of oxygen). Thereafter, the structure is cooled to ambient over a period of at least about 10 minutes (and, preferably, at least about 20 minutes).
  • the shrinkage which occurred with dielectric 168 may be determined by comparing it with the wet-printed dielectric surface (see Figure 7)
  • the sintered structure will have certain of its copper/copper oxide areas exposed af ⁇ ter the sintering.
  • areas 180 and 182 are two of such unmasked areas.
  • the metal oxide layer 138 is removed, preferably by chemical means.
  • the structure is preferably dipped into a metal oxide etchant which will attack the metal oxide preferentially but will not attack the sintered dielectric or the copper or the substrate 160 to any appreciable extent.
  • the structure is dipped into an aqueous solution of hydrochloric acid at a concentration of from about 10 to about 50 volume percent. It is preferred to use hydrochloric acid at a concentration of from about 15 to about 30 volume percent.
  • the hydrochloric acid may be used at ambient tempera ⁇ ture. Alternatively, it may be at a temperature of from about 40 to about 80 degrees centigrade.
  • hydrochloric acid instead of hydrochloric acid, or in addition thereto, one may use other conventional etchants which selectively at ⁇ tack the metal oxide.
  • the metal oxide removal is time and temperature de ⁇ pendent.
  • the structure is contacted with the removal agent for a time sufficient to remove substantially only the metal oxide.
  • the dielectric ink used is a mixture of the aforementioned “dielectric composition 4906" and “Fodel 6050" materials.
  • the dielectric ink is comprised of glass.
  • the dielectric ink is comprised of cordierite.
  • cordierite is a material often represented by the formula
  • cordierite materials known to those skilled in the art may be used in the dielectric ink.
  • the cordierite composition con ⁇ tain in addition to the stoichiometric amounts of alumina (34.9 weight percent of Al 2 0 3 ), magnesium oxide (13.8 weight percent of MgO), and silica (51.3 weight percent of Si0 , from about 0 to about 10 weight percent (by weight of total compo ⁇ sition) of B 2 0 3 , from about 0 to about 10 weight percent( (by weight of total composition) of P2°5, an d from about 10 to about 40 weight percent of excess MgO.
  • alumina 34.9 weight percent of Al 2 0 3
  • magnesium oxide (13.8 weight percent of MgO)
  • silica 51.3 weight percent of Si0 , from about 0 to about 10 weight percent (by weight of total compo ⁇ sition) of B 2 0 3 , from about 0 to about 10 weight percent( (by weight of total composition) of P2°5, an d from about 10 to about 40 weight percent of excess MgO.
  • a batch comprised of 34.9 parts of alumina, 13.8 parts of MgO, and 51.3 parts of silica were added either 10 weight percent of excess MgO, 20 weight percent of excess MgO, or 40 weight percent of excess MgO. In one embodiment, 40 weight of excess MgO was added to a cordierite composition which had 10 weight percent less than the stoichiometric amount of alumina.
  • P 2 0 5 When P 2 0 5 is added to the stoichiometric cordierite composition, it is preferred to add from about 0 to about 3 weight percent of it. Without wishing to be bound to any par ⁇ ticular theory, it is believed that the P 2 ⁇ 5 aids sinterabili- ty and forms a cordierite phase.
  • the 2 ⁇ 5 can De added in the form of, e.g., NH ⁇ PO ⁇ .
  • from about 0 to about 10 weight percent of Bi 2 0 3 is added to the stoichiometric cor ⁇ dierite mixture.
  • from about 0 to about 10 weight percent of zinc oxide is added to the stoichiometric cordierite mixture.
  • from about 0 to about 10 weight percent of vanadium pentoxide is added to the stoichio ⁇ metric cordierite mixture.
  • the cordierite stoichiometric ma ⁇ terial, and whatever additional additives be present in the dielectric ink be in the form of a glass frit.
  • the cordierite composi ⁇ tion is formed into a glass batch by melting.
  • this cordierite composition can be heated at 1,550 degrees centigrade for 6 hours in a platinum crucible.
  • the glass melt thus formed can then be quenched in, e.g., deionized water.
  • the glass thus formed can then be milled.
  • it can be wet-milled with yttria-stabilized zirconia media.
  • the milled material can then be sieved through, e.g., a 325 mesh sieve to remove oversize particles.
  • at least about 95 weight percent of the milled material is smaller than 25 microns.
  • at least about 95 weight percent of the milled material is smaller than 10 microns.
  • at least about 80 weight percent of the milled particles are between 2 and 4 microns in size.
  • the sieved particles can the be mixed with any addi ⁇ tional additives desired (such as copper oxide, zinc oxide, lead oxide, bismuth oxide, and the like) and, thereafter, with the binder system.
  • any addi ⁇ tional additives desired such as copper oxide, zinc oxide, lead oxide, bismuth oxide, and the like
  • each part (by weight) of the cordierite frit is mixed with from about 0.14 to about 0.50 parts (by weight) of binder and from about 0.12 to about 0.72 parts (by weight) of solvent.
  • one may use one or more of the vinyl binders described on pages 176-177 of the Reed book such as, e.g., an acrylic-based binder system (V-633, sold by Heraeus Inc.).
  • V-633 acrylic-based binder system
  • Heraeus Inc. e.g., one may use ethylcellulose as a binder.
  • the solvent may be an organic solvent such as, e.g., terpineol.
  • the glass batch is then wet milled in ethyl alcohol for ten hours, using yttria stabilized zirconia ball media. Thereafter, the slurry is charged to a beaker, stirred with a magnetic stirrer, and dried on a hot plate at a temperature of 150 degrees centigrade.
  • the dried powder thus produced is charged to a plati ⁇ num crucible and heated at a temperature of 1,550 degrees centigrade for 6 hours in a box-type supercanthal furnace to form a glass melt.
  • the melt thus produced is then quenched in deionized water to form cordierite glass.
  • the quenched glass is then pulverized into glass frit by using a metal die and by ball-milling with yttria sta ⁇ bilized zirconia; the milled particles are then sieved through a 325 mesh screen.
  • additives such as Bi 2 0 , ZnO, PbO, and/or CuO. It is preferred to add these additives to the sieved particles and then to ball mill the mixture using yttria stabilized zirconia ball media for 10 hours.
  • the glass frit with or without the additives, is then mixed with an acrylic-based binder system (V-633, Heraeus In ⁇ corporated, Cermalloy Division, 24 Union Hill Road, West Con- shohocken. Pa. 19428) to form a dielectric ink by manually us ⁇ ing a knife.
  • the dielectric ink may then be screen-printed onto the multilayer substrate.
  • the structure, and its exposed surfaces, are now sub ⁇ jected to the acid etching process described in United States patents 5,100,714 of 5,058,799.
  • the acid etched structure is then passed via line 44 to electroless metal deposition step 46 in which electroless metal deposition occurs.
  • photoresistive coating is applied in step 50.
  • a film of photosensitive resist material is applied to the exterior surfaces of structure 189 (see Figure 9A) .
  • a sheet of "DYNACHEM” photoresistive dry film manufactured by the Thiokol/Dyachem Corporation of Tustin, California
  • this film may be ap ⁇ plied by means of a "MODEL 300 LAMINATOR” manufactured by such Thiokol/Dynachem Corporation.
  • Figure 10 is view of the structure of Figure 9A to which a layer of photoresistive film 190 has been applied. Attached to photoresistive film 190 is a removable layer of carrier film 192, which is removed prior to development.
  • mask segments 194 and 196 will tend to block the transmission of ultraviolet light in dark masked areas 198, 200 , 202 , and 204 .
  • the masked structure is then exposed to ultraviolet radiation.
  • ultraviolet radiation will be transmit ⁇ ted through the masks in every area except for masked segments 198, 200, 202, and 204; and, consequently, the areas in which such radiation is transmitted will cause the corresponding areas of photoresistive film disposed underneath them to polymerize.
  • Such polymerized areas are resistant to degrada ⁇ tion by the developer subsequently used.
  • the carrier film 192 is removed form the photoresistive material 190. Thereafter, the exposed structure is contacted with a developer which tends to dissolve those areas of film 190 which have not polymerized. Thus, e.g., the areas of film 190 underneath masks 198, 200, 202, and 204 will be removed by the developer.
  • Any conventional developer which selectively removes unpolymerized photoresistive film may be used in this process.
  • aqueous sodium bicarbonate By way of illustration and not limitation, one may use aqueous sodium bicarbonate.
  • Figure 12 shows the product produced after the expo ⁇ sure of the substrate to developer 58. Note that, where the masks 198, 200, 202, and 204 had been disposed over the structure (see Figure 11), the photoresistive material has been removed. This open areas now can be built up further with the deposition of electroplated metal in metal plater 62.
  • the electroplating operation is well known to those skilled in the art and may be conducted, e.g., in substantial accordance with the procedure of one or more of United States patents 5,108,554, 5,108,552, 5,106,537, 5,104,563, 5,103,637, 5,102,521, 5,102,506, 5,101,682, 5,100,524, 5 , 098 , 860 , 5 , 098 , 544 , 5 , 098 , 542 , and the like .
  • metal plating step 62 is il ⁇ lustrated in Figure 13. Note the presence of the layer 189 of electroplated metal.
  • the structure is then passed via line 68 (see Figure 1) to electroless metal removal step 70, wherein the electroless metal is removed by conventional means by prefer ⁇ ably contacting it with an etchant capable of removing the metal.
  • an etchant capable of removing the metal.
  • one may contact the structure with an aqueous solution of potassium persulfate which removes the relatively thin layer of electroless metal (such as copper) but leaves the remainder of the structure relatively unaffect ⁇ ed.
  • FIG 15. The structure produced after the electroless metal removal step is illustrated in Figure 15. Note that, comparing this structure with Figure 7, an additional layer of sintered dielectric and metal has been added to the structure of Figure 7. As will also be apparent to those skilled in the art, this process may be repeated indefinitely to add addi ⁇ tional patterned layers of dielectric and metal. Alternative ⁇ ly, or additionally, the structure may be passed via line 71 to machiner 73, wherein desired machining operations may be performed. Thus, for example, end portions 220 and 222 may be cut at lines 224 and 226 as shown in Figure 16.
  • a metallized substrate was produced on a 4.5" x 6.5" white alumina blank which was 0.025 inches thick and contained patterned copper on each of its top and bottom surfaces which was 0.002 inches thick.
  • the copper pattern used on the top surface of the substrate is illustrat ⁇ ed in Figure 17.
  • the metallized alumina substrate was heat treated in a conveyor furnace, model number 14CF-154S, which was manufac ⁇ tured by the Watkins-Johnson Company of Scotts Valley, Cali ⁇ fornia.
  • the substrate was conveyed through the furnace, it was contacted with nitrogen which flowing at a rate of 5 cubic feet per minute; during this stage, less than 10 parts per million of oxygen were detected in the furnace environment.
  • the substrate was heated from ambient to a tem ⁇ perature of 900 degrees centigrade over a period of 45 minutes. Thereafter, the substrate was maintained at the 900 degrees centigrade temperature for ten minutes. Thereafter the substrate was cooled to ambient over a period of 30 minutes.
  • the cooled substrate was then run through the same conveyor furnace. It was heated from ambient to a temperature of 900 degrees centigrade over a period of 45 minutes while being contacted with nitrogen flowing at a rate of 5 cubic feet per minute; during this time, the nitrogen contained less than ten parts per million of oxygen.
  • the atmosphere was changed to a mixture of nitrogen at 200 parts per million of oxygen.
  • the substrate was sub jected to the 900 degree centigrade temperature for ten minutes while being contacted with the flowing gas mixture at a rate of 5 cubic feet per minute.
  • the atmosphere was changed to nitrogen containing less than 10 parts per million of oxygen and flow ⁇ ing at 5 cubic feet per minute.
  • the substrate was cooled from the 900 degree centigrade temperature to ambient over a period of 30 minutes.
  • a dielectric pattern was screen printed on top of the top surface of metallized substrate; the pattern used is de ⁇ picted in Figure 18.
  • the dielectric ink used was prepared from "Type 4906 dielectric composition, " which is sold by the Electro- Sciences Laboratories, Inc. of 416 East Church Road, King of Prussia, Pennsylvania. 50 grams of this material were diluted with 4 drops of "Type 401 Thinner,” which is also sold by such Electro-Sciences Laboratories Company.
  • the screen printer used was a model CP-885 Screen Printer, which is sold by the Presco Divi ⁇ sion of affiliated Manufacturers, Inc., U.S. Route 22, P.O. Box 5049, North Branch, New Jersey.
  • the substrate to be printed was disposed under a 12" x 12" frame with a 200 mesh metal stainless steel screen.
  • the dielectric was manually forced through the screen pattern with a trailing edge squeegee applied at an angle of 20 degrees. Prior to each pass, the screen was covered with dielectric in a "flood stroke". One pass in each direction was made with the squeegee.
  • the substrate was then allowed to stand while in a horizontal position in air for 10 minutes in a light-free environment. Thereafter the substrate was placed on the bottom heated plate, at a temperature of 250 degrees Fahrenheit, which was part of a Dake Corporation model 44183 press and maintained on said plate for 20 minutes. Thereafter it was removed from the heated plate and allowed to cool.
  • the cooled substrate was then returned to the Screen Printer, and an intermediate layer of dielectric material was applied to it in the manner described above.
  • the intermediate dielectric material was a 50/50 mixture of Ferro 10- 008 "nitrogen fireable dielectric paste" (manufactured by the Ferro Corporation of 27 Castillian Drive, Santa Barbara, Cali ⁇ fornia) and of duPont's Q-Plus QP445 dielectric paste (manu ⁇ factured by the E.I. duPont deNemours and Company of Wilming ⁇ ton, Delaware). After the intermediate dielectric material was applied in the aforementioned matter, it was allowed to stand in a dark atmosphere for ten minutes and thereafter dried on the Dake hot plate.
  • the dried substrate was then placed into another Wat- kins-Johnson conveyor furnace and, while in air, raised from ambient temperature to a temperature of 500 degrees centigrade over a period of 60 minutes, maintained at 500 degrees centi ⁇ grade for 30 minutes, and then cooled to ambient over a period of 15 minutes.
  • the substrate was then charged to the first Watkins- Johnson conveyor furnace and, while being contacted with ni ⁇ trogen (and less than 10 parts per million of oxygen) flowing at a rate of 5 cubic feet per minutes, raised from ambient to 900 degrees centigrade over a period of 45 minutes, maintained at a temperature of 900 degrees centigrade for 10 minutes, and cooled to ambient over a period of 30 minutes.
  • ni ⁇ trogen and less than 10 parts per million of oxygen
  • the sintered substrate was then treated to remove sin ⁇ tered dielectric from the substrate.
  • About 100 tiny (0.007 inch diameter) through holes were drilled by a laser through the dielectric to expose the layer of copper underneath such dielectric. These through holes were drilled in those areas of the structure where connection was to be made to the copper pattern.
  • the substrate was then rinsed with hot water for five minutes. Thereafter it was dipped into methanol for two minutes, and thereafter into acetone for 1 minute.
  • the substrate was then allowed to air dry for 5 minutes. Thereafter, it was dipped into a 50/50 mixture (by volume) of 36.5 volume percent hydrochloric acid and water; and it was allowed to stand in this solution for 3.0 minutes.
  • the substrate was then removed from the solution of hydrochloric acid and rinsed with water. Thereafter, the sub ⁇ strate was blown dry with air over a period of 30 seconds.
  • the dried substrate was then dipped into a solution of "ALCONOX” (a detergent sold by Alconox, Inc. of New York, New York) for two minutes. Thereafter, the substrate was rinsed with water.
  • ALCONOX a detergent sold by Alconox, Inc. of New York, New York
  • the substrate was then dipped into an 85 percent solu ⁇ tion of phosphoric acid (sold by Chemical Distributors, Inc. of Buffalo, New York) for thirty seconds. Thereafter, the substrate was rinsed with water.
  • phosphoric acid sold by Chemical Distributors, Inc. of Buffalo, New York
  • the substrate was dipped into solution of "Neoganth 834," a palladium-ion containing solution sold by such Atotech Company for four minutes. The substrate was then rinsed twice in water.
  • a solution of 138 grams of boric acid, 28 grams of said "AA reduction solution), and 24 gallons of water was prepared. A portion of this solution was transferred to a beaker, and the substrate was dipped into it for 1 minute.
  • An “electroless plating solution” for depositing copper was prepared by mixing 2,520 milliliters of "NOVIIGANTH HC Makeup Solution” (sold by the Chemcut Company of 45 South Street, Hopkinton, Ma.), 36 milliliters of "NOVINGANTH HC Stabilizer” (sold by such Chemcut Company), 900 milliliters of "rayon grade” liquid caustic soda (sold by the Chemical Distribution, Inc. company of Buffalo, New York), and 1,350 milliliters of "Reduction Solution Copper” (a formaldehyde preparation sold by the Atotech company of Pennsylvania. This mixture was then mixed with 50 gallons of water to make up the electroless bath.
  • the substrate was then removed from this bath, rinsed with water, and then dipped into a citric acid solution which was made from a mixture of 380 grams of citric acid, 690 mil ⁇ liliters of 98% sulfuric acid, , and 24 gallons of water. A portion of this solution were transferred to a large beaker, and the substrate was dipped into it and maintained therein for four minutes.
  • a citric acid solution which was made from a mixture of 380 grams of citric acid, 690 mil ⁇ liliters of 98% sulfuric acid, , and 24 gallons of water. A portion of this solution were transferred to a large beaker, and the substrate was dipped into it and maintained therein for four minutes.
  • a film of photosensitive resist material was applied to the top and bottom surfaces of the substrate.
  • a sheet of "DYNACHEM” photoresistive dry film (manufactured by the Thiokol/Dyachem Corporation of Tustin, California) was applied by means of a "MODEL 300 LAMINATOR” manufactured by such Thiokol/Dynachem Corporation to such top and bottom sur ⁇ faces.
  • the carrier film was then manually removed from the photoresistive material. Thereafter, the exposed substrate was exposed to potassium carbonate developer.
  • One part, by volume, of "DEVCONC 11-A” (which is sold by the RBP Chemical Corporation) was mixed with 33 parts of water, and this devel oper was used in a "CHEMCUT SYSTEM 547" apparatus run at a speed of 2 feet per minute, at temperature of 85 degrees Fah ⁇ renheit, and a top and bottom pressure of 15 pounds per square inch to spray both sides of the substrate and wash out the unexposed photoresistive material in the pattern.
  • the developed substrate was then rinsed in water and dried.
  • a cleaning solution was made up in a rectangular tank (which was 12"x 36" x 34") containing 5 gallons of "DYNACHEM CLEANER LAC-81" (sold by Morton Electronics Materials, 2631 Michelle Drive, Tustin, California) and sufficient deionized water to fill such tank. This solution was heated to a tem ⁇ perature of 120 degrees Fahrenheit, and the substrate was dipped into this solution for 4 minutes.
  • the substrate was then dipped into a tank containing hot water at a temperature of 85 degrees Fahrenheit and kept there for four minutes. Thereafter, the substrate was dipped into a tank of hot running water at 85 degrees Fahrenheit and maintained there for 5 minutes.
  • An electroplating bath was prepared by mixing deion ⁇ ized water, 10 volume percent of 98 percent sulfuric acid (obtained from Chemical Distributors Inc.), and 10 volume percent of a solution of reagent grade copper sulfate, which was made by mixing 2.2 pounds of copper sulfate (obtained from Chemical Distributors Inc.) with a gallon of water.
  • the substrate was electroplated using the aforemen ⁇ tioned bath in an electroplating apparatus which moved the substrate back and forth while in the bath, bubbled air through the bath, and delivered 0.54 volts and an amperage of 10 amperes per square foot of the area of to be plated on the substrate.
  • the substrate was plated for one hour, and a layer of copper approximately 0.001 inches thick was deposited.
  • the substrate was then removed from the bath, rinsed in deionized water, and blow dried. Thereafter it was heated to a temperature of 150 degrees Fahrenheit in air and main ⁇ tained under these conditions for one hour.
  • the substrate was then dipped into a solution of photoresistive stripping solution.
  • One gallon of "DYNACHEM ALKASTRIP SQ-1" was charged into a rectangular tank (12" x 36" x 21") with sufficient water to fill the tank, and the solu ⁇ tion was heated to a temperature of 135 degrees Fahrenheit. The substrate was maintained in this hot solution for sixty minutes and thereafter removed, rinsed with water, and dried.
  • An electroless copper removal solution was then pre ⁇ pared by mixing 55 pounds of sodium persulfate, 1,750 millili ⁇ ters of .85 percent phosphoric acid, and 35 gallons of water. This solution was heated to a temperature of 118 degrees Fah ⁇ renheit. The substrate was exposed to this solution in the aforementioned CHEMCUT SYSTEM 547 at a pressure of 15 pounds per square inch and a rate of 2 feet per minute.
  • the substrate was then machined so that areas 250 (see Figure 20) were cut through by a laser machining device.
  • a ferrite pot core manufactured as model number 2123 by the TDK Corporation of Japan, was pressed through openings 250.
  • the structure thus produced had the appearance il ⁇ lustrated in Figure 21.
  • the device depicted in Figure 21 contains several transformers and several inductors Referring to Figure 21, one lead may be attached to coil 254, another lead may be at tached to coil 256, and these coils maybe used as the primary and the secondary of a transformer (or vice versa).
  • the ferr ⁇ ite core 260 improves the performance of the planar transform ⁇ er.
  • Another portion of the substrate may be used as a pla ⁇ nar inductor, with lead 262 and lead 264 being connected to planar inductor 266.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
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Abstract

Cette invention concerne un procédé de préparation d'un substrat métallisé isolé dans lequel un substrat métallisé est sérigraphié avec une matière diélectrique de manière à obtenir un substrat recouvert. Le substrat métallisé comporte une pièce à travailler ayant une surface de travail solidaire de ladite pièce, une couche d'un métal électriquement conducteur disposée sur la surface de travail et une bande de jointure hétérogène placée entre la pièce à travailler et la couche de métal conducteur, de dimension sensiblement identique à celle de la couche de métal conducteur et à celle de la surface de travail, la bande de jointure hétérogène étant constituée principalement de grains solidaires de la pièce à travailler et de métal conducteur solidaire de la couche de métal conducteur.
PCT/US1996/005810 1995-04-26 1996-04-26 Procede de preparation d'une structure multicouche isolee WO1996033813A1 (fr)

Priority Applications (1)

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AU57159/96A AU5715996A (en) 1995-04-26 1996-04-26 Process for preparing an insulated multilayer structure

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US42789495A 1995-04-26 1995-04-26
US08/427,894 1995-04-26

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4732780A (en) * 1985-09-26 1988-03-22 General Electric Company Method of making hermetic feedthrough in ceramic substrate
US4882301A (en) * 1985-10-09 1989-11-21 Ferro Corporation Decorative and protective borders for automobile side and rear lights
US5058799A (en) * 1986-07-24 1991-10-22 Zsamboky Kalman F Metallized ceramic substrate and method therefor
US5100714A (en) * 1986-07-24 1992-03-31 Ceramic Packaging, Inc. Metallized ceramic substrate and method therefor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4732780A (en) * 1985-09-26 1988-03-22 General Electric Company Method of making hermetic feedthrough in ceramic substrate
US4882301A (en) * 1985-10-09 1989-11-21 Ferro Corporation Decorative and protective borders for automobile side and rear lights
US5058799A (en) * 1986-07-24 1991-10-22 Zsamboky Kalman F Metallized ceramic substrate and method therefor
US5100714A (en) * 1986-07-24 1992-03-31 Ceramic Packaging, Inc. Metallized ceramic substrate and method therefor

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