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WO1990000966A1 - Compositions dielectriques pour couches epaisses - Google Patents

Compositions dielectriques pour couches epaisses Download PDF

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Publication number
WO1990000966A1
WO1990000966A1 PCT/US1989/003102 US8903102W WO9000966A1 WO 1990000966 A1 WO1990000966 A1 WO 1990000966A1 US 8903102 W US8903102 W US 8903102W WO 9000966 A1 WO9000966 A1 WO 9000966A1
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WO
WIPO (PCT)
Prior art keywords
weight
composition
glass
dielectric
sio
Prior art date
Application number
PCT/US1989/003102
Other languages
English (en)
Inventor
Robert D. Gardner
Dineen M. Hopp
Aziz S. Shaikh
Gordon J. Roberts
Original Assignee
Ferro Corporation
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 Ferro Corporation filed Critical Ferro Corporation
Publication of WO1990000966A1 publication Critical patent/WO1990000966A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/22—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions containing two or more distinct frits having different compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
    • H01B3/085—Particles bound with glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
    • H01B3/087—Chemical composition of glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
    • H01B3/088—Shaping of glass or deposition of glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49894—Materials of the insulating layers or coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

Definitions

  • This invention relates to one-, two- or three-glass systems that are useful as dielectric compositions. These dielectric compositions are adapted for use on alumina containing substrates utilized in producing multi-layer hybrid circuits, which are compatible with thick film copper conductor pastes, and which are firable in non-oxidizing atmospheres.
  • dielectrics on suitable substrates in the making of multi-layer hybrid microelectronic components is well known in the electronics art.
  • substrates In practice, such substrates have been fabricated from numerous types of materials, including alumina, beryllia, aluminum nitride, and silicon carbide.
  • the glass compositions used in connection with thick film dielectric compositions are critical in several respects.
  • the vehicle In firing the paste onto the substrate the vehicle is evaporated or burned off, and the glass is melted and flows over the surface of the substrate to form a homogeneous surface which should be essentially free of pores or bubbles.
  • Most thick film multi-layer hybrid circuits are presently produced using precious metal conductors in combination with compatible dielectric compositions. These dielectric compositions generally contain large percentages of lead oxide in the glasses used, and typically have a glass transition temperature (Tg) of about 300°C to 400°C. Dielectric compositions designed for use with precious metal conductors usually perform well, both physically and electrically, after firing in oxidizing atmospheres.
  • compositions perform poorly when fired in non-oxidizing atmospheres such as nitrogen, which reduces lead or bismuth oxide to metallic lead or bismuth, which in turn often volatilize.
  • the volatile metal may travel down the length of furnaces used to fire the hybrid circuit and condense onto parts in the cooler sections of the furnace.
  • the low glass transition temperature of such glass systems enhances the possibility of binder entrapment through premature fluidity during the firing cycle, thereby sealing over the glassy matrix and not allowing the escape of decomposition products, and promotes the potential for reactivity with base metal electrodes, i.e., dissolution and blistering.
  • Base metal multi-layer circuitry offers advantages not available with precious metal systems. For example, conductivity that is approx- imately equal to silver without the solder leaching and migration problems associated with silver conductor systems.
  • the base metal systems however, also have their own special disadvantages, particularly vis-a-vis the dielectric compositions.
  • Base metal compositions must be formulated such that (1) the individual components in the glass or glasses used within the system remain stable when fired in non-oxidizing atmospheres, (2) allow for the removal of the organic decomposition products created by the organic binder, and (3) exhibit compatibility or minimal reactivity with the copper or other base metal conductors being used to fabricate the multi-layer circuitry, while still yielding physical and electrical properties comparable to air-fired systems.
  • This invention relates to a dielectric composition
  • a dielectric composition comprising:
  • a-1) a bismuth-free, lead-free or low-lead containing glass composition having a glass transition temperature in the range of about 600°C to about 800°C;
  • a-2) a mixture of two bismuth-free, lead-free or low-lead containing glass compositions comprising a first glass composition having a glass transition temperature in the range of about 585°C to about 620°C and a second glass composition having a glass transition temperature in the range of about 765°C to about 815°C; or
  • (a-3) a mixture of three bismuth-free, lead-free or low-lead containing glass compositions comprising a first glass composition having a glass transition temperature in the range of about 585°C to about 620°C, a second glass composition having a glass transition temperature in the range of about 765°C to about 815°C, and a third glass composition having a glass transition temperature in the range of about 650°C to about 720°C;
  • This invention also relates to thick film dielectric pastes and dielectric tapes employing the foregoing dielectric composition.
  • the invention also relates to alumina base substrates having the foregoing dielectric composition bonded to at least one surface thereof, and to a method of bonding the foregoing dielectric composition to such alumina base substrates.
  • the term "alumina” or "alumina base substrate” is intended to mean a substrate containing in excess of about 50% by weight alumina.
  • the term “low lead glass” is intended to mean a glass containing about 20% or less by weight lead oxide.
  • the glass (a) is (a-1) a bismuth-free, lead-free or low-lead containing glass composition having a glass transition temperature, Tg, preferably in the range of about 600°C to about 800°C, more preferably in the range of about 650°C to about 770°C. This glass preferably has the following composition:
  • glass compositions (a-1) are as follows:
  • These glass compositions have the following properties: ( a-1 -1 ) ( a-1 -2 ) ( a-1 -3 ) ( a-1 -4 ) ( a-1 -5 )
  • CTE refers to coefficient of thermal expansion.
  • CTE @ 300°C refers to the amount of expansion exhibited by an expansion bar that is heated from room temperature to 300°C.
  • CTE @ 600°C refers to the amount of expansion exhibited by an expansion bar that is heated from room temperature to 600°C.
  • DSP dilatometric softening point. CTE and DSP are measured using a dilatometer. In measuring these thermal properties, the samples are fired in nitrogen at 900°C with a ten-minute peak temperature using known procedures.
  • the glass (a) is (a-2) a mixture of two bismuth-free, lead-free or low-lead containing glass compositions comprising a first glass composition (a-2-1) having a glass transition temperature in the range of about 585°C to about 620°C, and a second glass composition (a-2-2) having a glass transition temperature in the range of about 765°C to about 815°C.
  • a-2-1 first glass composition
  • a-2-2 having a glass transition temperature in the range of about 765°C to about 815°C.
  • These glasses preferably have the following compositions (all numerical values being in percent by weight): Glass ( a-2-1 ) Glass ( a-2-2 )
  • the weight ratio of glass (a-2-1) to glass (a-2-2) is preferably about 7:3 to about 3:7, more preferably about 2:1 to about 1:2, more preferably about 1.5:1 to about 1:1.5, more preferably about 1:1.
  • Specific examples of these glasses are as follows (all numerical values being in percent by weight):
  • the glass (a) is (a-3) a mixture of three bismuth-free, lead-free or low-lead containing glasses comprising a first glass composition (a-3-1) having a glass transi- tion temperature in the range of about 585°C to about 620°C, a second glass composition (a-3-2) having a glass transition temperature in the range of about 765°C to about 815°C, and a third glass composition (a-3-3) having a glass transition temperature in the range of about 650°C to about 720°C.
  • These glasses preferably have the following compositions (all numerical values being in percent by weight):
  • Glass (a-3-3) preferably has a coefficient of thermal expansion in the range of about 80 x 10 -7 /°C to about 105 x 10 -7 /°C.
  • the weight ratio of glass (a-3-1) to glass (a-3-2) is preferably about 7:3 to about 3:7, more preferably about 2:1 to about 1:2, more preferably about 1.5:1 to about 1:1.5, more preferably about 1:1.
  • the weight ratio of the combined weight of glass (a-3-1) and glass (a-3-2) to the weight of glass (a-3-3) is preferably about 10:1 to about 1.5:1, more preferably about 5:2 to about 7:3.
  • each of the above glass compositions (a) can be prepared in any conventional manner. For example, a mixture of the appropriate ingredients can be placed in a platinum crucible and melted (e.g., 1450°C-1550°C), the resulting glass composition is then poured onto cold steel rolls to form thin flakes suitable for milling. These flakes are then milled to a suitable particle size distribution (e.g., about 0.5 to about 20 microns).
  • the inventive dielectric compositions preferably contain from about 30% to about 100% by weight, more preferably about 30% to about 95% by weight, more preferably about 30% to about 85% by weight, more preferably about 30% to about 75% by weight of the glass (a).
  • the inventive dielectric compositions contain about 50% to about 100% by weight, more preferably about 60% to about 100% by weight, more preferably about 60% to about 95% by weight, more preferably about 60% to about 80% by weight of the glass (a).
  • the inventive dielectric compositions can include an expansion modifier (b) which can be any material which causes the coefficient of thermal expansion of the thick film compositions of the invention to satisfactorily close to that of the alumina substrate.
  • Typical expansion modifiers include SiO 2 , CaZrO 3 , CaSiO 3 , Mg 2 SiO 4 , CaTiO 3 , BaZrO 3 and SrZrO 3 .
  • SiO 2 , Mg 2 SiO 4 and CaSiO 3 are preferred.
  • the expansion modifiers are preferably present in the inventive dielectric composition at concentrations of up to about 30% by weight, more preferably about 2% to about 30% by weight, more preferably about 5% to about 30% by weight, more preferably about 10% to about 30% by weight.
  • the inventive dielectric compositions can also include a refractory oxide (c) which can be any material which is compatible with the thick film composition of the invention and which during heating of the applied composition will permit the binder material to be removed from the thick film composition without deleteriously effecting the same.
  • Typical refractory compositions include Al 2 O 3 , TiO 2 and ZrO 2 , with Al 2 O 3 being preferred.
  • These refractory oxides are preferably present in the inventive dielectric compositions at concentrations of up to about 40% by weight, more preferably about 2% to about 40% by weight, more preferably about 5% to about 40% by weight, more preferably about 10% to about 40% by weight.
  • the glass particles (a) and, if used, the expansion modifier (b) and refractory oxide (c), are preferably ball-milled together in a suitable vehicle, such as isopropyl alcohol. This method of milling is well known and results in a homogeneous solids mixture. The solids are dried, then dispersed in a suitable binder or vehicle to form a dielectric paste.
  • a suitable vehicle such as isopropyl alcohol
  • the binder or vehicle is preferably an organic binder or vehicle and is provided in an amount sufficient to disperse the solids in the binder or vehicle and to at least temporarily bond the dielectric composition to a substrate prior to firing.
  • the solid components i.e., glass composition (a) and, if used, expansion modifier (b) and refractory oxide (c) are preferably present in the range of from about 60% to about 80% by weight of the inventive dielectric paste compositions and the binder or vehicle is preferably present in an amount ranging from about 20% to about 40% by weight of such dielectric paste composition.
  • the organic binder or vehicle is usually an organic resin dissolved in a suitable solvent.
  • Any essentially inert binder can be used in the practice of the present invention, including various organic liquids, with or without thickening and/or stabilizing agents and/or other common additives.
  • Exemplary of the organic liquids which can be used are the aliphatic alcohols; esters of such alcohols, for example, the acetates and propionates; terpenes such as pine oil, terpineol and the like; solutions of resins such as the polymethacrylates of lower alcohols, or solutions of ethyl cellulose, in solvents such as pine oil, the monobutyl ether of ethylene glycol monoacetate, and carbinol.
  • the binder can contain volatile liquids to promote fast setting after application to the substrate.
  • the vehicle or binder contains from about 0.1% to about 10% by weight resin and about 90% to about 99.9% by weight solvent or mixture of solvents.
  • the resin can be ethyl cellulose or an acrylate resin (e.g., methyl methacrylate).
  • the solvent can be terpineol, 2,4,4-trimethyl-1,3-pentanediol monoisobutylrate, N-methyl-2-pyrrolidone or mixtures thereof.
  • the vehicle or binder can include a thixotropic material, preferably at a concentration of less than about 0.25% by weight.
  • the inventive thick film dielectric paste composition is applied to a substrate such as an alumina base substrate in accordance with the invention using techniques well-known to those skilled in the art.
  • An example of such a technique is silk screening wherein the paste is forced through a fine mesh stainless steel screen in a desired pattern. Typically the size of such a screen varies from about 200 to about 325 mesh.
  • Other examples include spraying, dipping, spinning, brushing and application using a doctor blade.
  • This invention also relates to a method of bonding the inventive dielectric composition to an alumina base substrate comprising applying to at least one surface of said substrate a dielectric paste comprising the inventive dielectric composition, heating the substrate in a non-oxidizing atmosphere (e.g., nitrogen) to a temperature sufficient to permit the glass (a) in the dielectric paste to fuse (e.g., about 800°C to about 950°C), and then cooling the substrate to a temperature sufficient to permit the dielectric composition to adhere to the substrate.
  • a non-oxidizing atmosphere e.g., nitrogen
  • This invention also relates to an alumina base substrate having the inventive dielectric composition bonded to at least one surface thereof using the foregoing method.
  • This invention also relates to the use of the inventive dielectric composition in conjunction with base metal conductors, such as copper, to produce a functional electronic circuit on an alumina base substrate.
  • This invention also provides for a multi-layered circuit comprising a plurality of layers of interconnected electronic circuitry, each of said layers being separated by a dielectric material, the dielectric material comprising the inventive dielectric composition.
  • This invention also provides for a thick-filmed circuit comprising at least one layer of electronic circuitry in contact with a dielectric material, said dielectric material comprising the inventive dielectric composition.
  • the inventive dielectric composition when bonded to an alumina substrate preferably has a dielectric constant (K) of about 4 to about 10, more preferably about 5 to about 8, more preferably about 5.5 to about 6.5; an insulation resistance (IR) of preferably greater than about 10 11 , more preferably greater than about 10 12 ohms and typically in the range of about
  • K dielectric constant
  • IR insulation resistance
  • a dissipation factor (DF) of preferably about 0.2% to about 0.65%, more preferably about 0.3%
  • BDV breakdown voltage
  • T thickness
  • the inventive dielectric pastes are fired in a non-oxidizing atmosphere at a peak temperature preferably in the range of about 875°C to about 925°C, more preferably about 900°C to about 905°C.
  • firing at the peak temperature is maintained for about 8 to about 12 minutes, more preferably about 9 to about 11 minutes.
  • the heat-up time is preferably about 20 to about 26 minutes, more preferably about 22 to about 26 minutes.
  • the cool-down time is preferably about 22 to about 32 minutes, more preferably about 23 to about 29 minutes.
  • the non-oxidizing atmosphere is preferably nitrogen, but can also be helium or argon.
  • the nonoxidizing atmosphere can include up to about 10 ppm oxygen and up to about 200 ppm CO 2 , NO 2 or H 2 0 On firing zone.
  • firing is used herein to mean heating to a temperature and for a time sufficient to volatilize (burnout) all of the organic material in the dielectric paste and to sinter the glass (a) and, if used, the expansion modifier (b) and refractory oxide (c).
  • the invention also relates to tapes or "green tapes" comprising a flexible substrate and the inventive dielectric composition adhered to the flexible substrate.
  • These tapes are made by casting a dispersion of the inventive dielectric composition in the above-discussed organic binder or vehicle onto a flexible substrate, such as a steel belt or polymeric film, and then heating the cast layer to remove the volatile solvent.
  • the solvent preferably has a boiling point below about 150°C and the heating step used to remove the solvent is conducted at a sufficient temperature to vaporize the solvent.
  • solvents examples include acetone, xylene, methanol, ethanol, isopropanol, methyl ethyl ketone, 1,1,1-trichlorethane, tetrachloroethylene, amyl acetate, 2,2,4-triethyl pentanediol-1,3-monoisobutyrate, toluene, methylene chloride and fluorocarbons.
  • solvents include acetone, xylene, methanol, ethanol, isopropanol, methyl ethyl ketone, 1,1,1-trichlorethane, tetrachloroethylene, amyl acetate, 2,2,4-triethyl pentanediol-1,3-monoisobutyrate, toluene, methylene chloride and fluorocarbons.
  • individual components of the solvent may not be complete solvents for the binder polymer. Yet, when blended with other solvent components,
  • the green tape can be used as a dielectric or insulating material for multilayer electronic circuits.
  • a roll of green tape is blanked with registration holes in each corner to a size somewhat larger than the actual dimensions of the circuit.
  • via holes are formed in the green tape. This is typically done by mechanical punching. However, a sharply focused laser can be used to volatilize the green tape. Typical via hole sizes range from about 0.006" to about 0.25".
  • the interconnections between layers are formed by filling the via holes with a thick film conductive ink. This ink is usually applied by standard screen printing techniques. Each layer of circuitry is completed by screen printing conductor tracks.
  • resistor inks or high dielectric capacitor inks can be printed on each layer to form resistive or capacitive circuit elements.
  • high dielectric constant green tapes similar to those used in the multilayer capacitor industry can be incorporated as part of the multilayer circuitry.
  • the individual layers are stacked and laminated.
  • a confined pressing die is used to insure precise alignment between layers.
  • the laminates are trimmed with a hot stage cutter. Firing can be carried out in a standard thick film conveyor belt furnace.
  • the inventive dielectric composition can also be used as a glaze.
  • an article comprising a substrate has a glaze covering at least one surface thereof, the glaze comprising the inventive dielectric composition.
  • An example of such an article is a multilayered cirucit covered by such glaze.
  • the glaze or overglaze is useful in enhancing hermiticity.
  • the glaze is preferably printed over the desired surface areas of the composite circuit structure and then fired at the same temperature and using the same firing procedures used in firing the dielectric layers used in building the circuit.
  • the firing temperature for the overglazing step can, however, be less than that used in firing the dielectric layers.
  • Preferably one layer of overglaze is used, but additional layers (e.g., total of 2 or 3 layers) can be used.
  • the formulations identified in Tables I-III below are prepared using the glass compositions a-1-1, a-1-2, a-1-3, a-1-4, a-1-5, a-2-1, a-2-2, a-3-1-1, a-3-2-1 and a-3-3-1 identified above. These glass compositions along with the expansion modifiers and refractory oxides identified in Tables I-III are milled in the presence of isopropyl alcohol using standard milling procedures, then dried. The dry solids are blended with an organic vehicle to form dielectric pastes having solids contents of 68.48% by weight and a vehicle or binder content of 31.52% by weight.
  • the organic vehicle or binder has the following ingredients:
  • Thixatrol ST product of NL Industries identified as a low molecular weight amide useful as a
  • Composite structures for each example are prepared as follows.
  • a copper conductor paste, DP50-002 (a product of Ferro Corporation identified as a mixed bonded copper conductor paste) is printed on an alumina substrate.
  • the printed layer is allowed to level at room temperature, and is then dried at about 100°C.
  • the dried printed layer is fired at about 900°C in a nitro- gen atmosphere containing about 1-3 ppm oxygen; the temperature of the printed layer being increased from ambient to about 900°C over a 25-minute period, maintained at about 900°C for 10 minutes, then reduced to ambient over a 25-minute period.
  • a first dielectric layer using the dielectric pastes described above and the dielectric compositions reported in Tables I-III is then printed over the conductor layer using the same printing, levelling, drying and firing procedure used for the conductor layer.
  • a second dielectric layer using the same formulation as the first dielectric layer is then printed over the first dielectric layer, the same printing, levelling, drying and firing procedure used for the conductor layer being used.
  • a third dielectric layer using the same formulation as the first dielectric layer is then printed over the second dielectric layer, the same printing, levelling, drying and firing procedure used for the conductor layer being used.
  • a second conductor layer using DP50-009 (a product of Ferro Corporation identified as a mixed bonded copper conductor paste) is then printed over the third dielectric layer using the same printing, levelling, drying and firing procedure as with the first conductor layer.
  • the combined dielectric layers of the resulting composite structures have the thicknesses, T, reported in Tables I and II.
  • the combined dielectric layers of the composite structures reported in Table III have thicknesses of about 55 microns.
  • the dielectric constant (K) and the dissipation factor (DF) are measured using a Model 4192A Hewlett Packard bridge.
  • the dielectric breakdown voltage (DBV) is determined by increasing the voltage applied across the thickness of the sample until breakdown occurs.
  • a fluke Model 412B high voltage power supply is used.
  • Insulation resistance (IR) is determined using a General Radio Model 1864 Megohmeter at 200 volts D.C.
  • the CTE and DSP are determined using a dilatometer.
  • the terms "CTE @ 300°C” and “CTE @ 600°C” are the same as defined above.
  • the term “CTE @ 900°C” refers to the amount of expansion exhibited by an expansion bar that is heated from room temperature to 900°C.
  • I 1 is current leakage through the dielectric film measured using Institute of Printed Circuits test method 2.5.31.
  • A-17 Alumina is Al 2 O 3 powder having an average particle size of
  • Aluminalux is Al 2 O 3 powder having an average particle size of
  • the dielectric compositions disclosed in Examples 1-42 are adherently bonded to the substrate, substantially free of bubbles or pores, and essentially devoid of any carbonized binder.
  • inventive dielectric compositions herein include their ability to bond to an alumina base substrate, as well as their low porosity, good wetting properties and good thermal coefficients of expansion. These dielectric compositions exhibit minimal undesirable reactions, such as binder entrapment and reactivity, when fired in non-oxidizing atmospheres and used with base metal conductors such as copper conductors.

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  • Inorganic Insulating Materials (AREA)

Abstract

Une composition diélectrique comprend: (a) entre 30 % et 100 % en poids d'une composition vitreuse sélectionnée dans le groupe formé par (a-1) une composition vitreuse sans bismuth, sans plomb ou à faible teneur en plomb ayant une température de transition vitreuse comprise entre 600°C et 800°C environ; (a-2) un mélange de deux compositions vitreuses sans bismuth, sans plomb ou à faible teneur en plomb dont la première a une température de transition vitreuse comprise entre 585°C et 620°C environ et dont la deuxième a une température de transition vitreuse comprise entre 765°C et 815°C environ; ou (a-3) un mélange de trois compositions vitreuses sans bismuth, sans plomb ou à faible teneur en plomb dont la première a une température de transition vitreuse comprise entre 585°C et 620°C environ, dont la deuxième a une température de transition vitreuse comprise entre 765°C et 815°C et dont la troisième a une température de transition vitreuse comprise entre 650°C et 720°C environ; (b) jusqu'à 30 % en poids environ d'au moins un modificateur de la dilatation; et (c) jusqu'à 40 % en poids environ d'au moins un oxyde réfractaire. L'invention concerne également des pâtes et des bandes diélectriques pour couches épaisses comprenant ladite composition diélectrique, des substrats à base d'alumine dont au moins une surface est liée à ladite composition diélectrique, et un procédé de liaison de ladite composition diélectrique à des substrats à base d'alumine.
PCT/US1989/003102 1988-07-19 1989-07-14 Compositions dielectriques pour couches epaisses WO1990000966A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US22110588A 1988-07-19 1988-07-19
US221,105 1988-07-19
US37755189A 1989-07-13 1989-07-13
US377,551 1989-07-13

Publications (1)

Publication Number Publication Date
WO1990000966A1 true WO1990000966A1 (fr) 1990-02-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1989/003102 WO1990000966A1 (fr) 1988-07-19 1989-07-14 Compositions dielectriques pour couches epaisses

Country Status (4)

Country Link
EP (1) EP0422127A4 (fr)
AU (1) AU3977789A (fr)
MX (1) MX170062B (fr)
WO (1) WO1990000966A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991002363A1 (fr) * 1989-08-04 1991-02-21 Ferro Corporation Compositions dielectriques poreuses
US5071794A (en) * 1989-08-04 1991-12-10 Ferro Corporation Porous dielectric compositions
EP0552522A1 (fr) * 1988-10-14 1993-07-28 Ferro Corporation Vitrocéramiques à constante diélectrique faible, fritté à températures basses
US5258335A (en) * 1988-10-14 1993-11-02 Ferro Corporation Low dielectric, low temperature fired glass ceramics
EP0709346A1 (fr) * 1994-10-24 1996-05-01 Corning Incorporated Pâtes de frittes scellement
EP0896571A4 (fr) * 1996-04-29 2000-05-24 Corning Inc Procede concernant une pate de verre de scellement
KR20010096522A (ko) * 1999-12-15 2001-11-07 김창선 의류 패턴 제도 방법

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US4084976A (en) * 1977-07-20 1978-04-18 Champion Spark Plug Company Lead-free glaze for alumina bodies
JPS54154079A (en) * 1978-05-25 1979-12-04 Fujitsu Ltd Method of producing multiilayer circuit board
US4369220A (en) * 1980-10-17 1983-01-18 Rca Corporation Crossover dielectric inks used in forming a multilayer electrical circuit
US4396682A (en) * 1980-12-27 1983-08-02 Central Glass Company, Limited Glazed ceramic substrate
US4634634A (en) * 1981-10-19 1987-01-06 Ngk Spark Plug Co., Ltd. Glaze ceramic base
US4547467A (en) * 1983-06-22 1985-10-15 Burroughs Corporation Dielectric composition and devices using it
US4761325A (en) * 1984-05-31 1988-08-02 Fujitsu Limited Multilayer ceramic circuit board
US4752531A (en) * 1985-03-25 1988-06-21 E. I. Du Pont De Nemours And Company Dielectric composition
EP0209776A2 (fr) * 1985-07-20 1987-01-28 Bayer Ag Emaux à structures hétérogène
US4672152A (en) * 1985-08-05 1987-06-09 Hitachi, Ltd. Multilayer ceramic circuit board
EP0232767A2 (fr) * 1986-02-12 1987-08-19 W.C. Heraeus GmbH Pâte de surglaçure
US4777092A (en) * 1986-05-02 1988-10-11 Asahi Glass Company, Ltd. Composition for ceramic substrate and substrate

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* Cited by examiner, † Cited by third party
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See also references of EP0422127A4 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0552522A1 (fr) * 1988-10-14 1993-07-28 Ferro Corporation Vitrocéramiques à constante diélectrique faible, fritté à températures basses
US5258335A (en) * 1988-10-14 1993-11-02 Ferro Corporation Low dielectric, low temperature fired glass ceramics
WO1991002363A1 (fr) * 1989-08-04 1991-02-21 Ferro Corporation Compositions dielectriques poreuses
US5071794A (en) * 1989-08-04 1991-12-10 Ferro Corporation Porous dielectric compositions
EP0709346A1 (fr) * 1994-10-24 1996-05-01 Corning Incorporated Pâtes de frittes scellement
EP0896571A4 (fr) * 1996-04-29 2000-05-24 Corning Inc Procede concernant une pate de verre de scellement
KR20010096522A (ko) * 1999-12-15 2001-11-07 김창선 의류 패턴 제도 방법

Also Published As

Publication number Publication date
EP0422127A1 (fr) 1991-04-17
EP0422127A4 (en) 1992-02-19
AU3977789A (en) 1990-02-19
MX170062B (es) 1993-08-04

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