WO1990008110A1 - Compositions a base de verre devitrifiant pour substrats de circuits imprimes a faible expansion et encres - Google Patents

Compositions a base de verre devitrifiant pour substrats de circuits imprimes a faible expansion et encres Download PDF

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Publication number
WO1990008110A1
WO1990008110A1 PCT/US1990/000005 US9000005W WO9008110A1 WO 1990008110 A1 WO1990008110 A1 WO 1990008110A1 US 9000005 W US9000005 W US 9000005W WO 9008110 A1 WO9008110 A1 WO 9008110A1
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WO
WIPO (PCT)
Prior art keywords
percent
oxide
glass
weight
composition
Prior art date
Application number
PCT/US1990/000005
Other languages
English (en)
Inventor
Ashok Narayan Prabhu
Kenneth Warren Hang
Edward James Conlon
Original Assignee
David Sarnoff Research Center, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB898921386A external-priority patent/GB8921386D0/en
Application filed by David Sarnoff Research Center, Inc. filed Critical David Sarnoff Research Center, Inc.
Publication of WO1990008110A1 publication Critical patent/WO1990008110A1/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
    • H01L21/4803—Insulating or insulated parts, e.g. mountings, containers, diamond heatsinks
    • H01L21/481—Insulating layers on insulating parts, with or without metallisation
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • 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

Definitions

  • This invention relates to novel devitrifying glasses and to substrates and inks made therefrom.
  • novel devitrifying glasses which have temperature coefficients of expansion very closely matched to that of silicon and which are suitable for use as substrate material for direct mounting of very large silicon chips.
  • the substrates are made by mixing the devitrifying glass with a ceramic filler. The mixture is then pressed and sintered into a fused body.
  • the use of large silicon chips permits high density packaging of circuits, subassemblies and the like with the fewest number of processing steps.
  • heat is generated in the chip, and thus large chips cannot be successfully mounted on a substrate unless the temperature coefficient of expansion of the chip material closely matches that of the substrate material.
  • the devitrifying glasses which we formulated in the past in addition to having temperature coefficients of expansion essentially the same as that of silicon also have a high flow temperature (i.e., from 800°-900°C) during initial firing and possess excellent reheat stability up to about 1000°C after devitrification.
  • the devitrifying glasses which were formulated in the past are comprised of zinc-barium-aluminum-silicate glasses that also contain minor amounts of phosphorous pentoxide, zirconium silicate and a member of the group of calcium oxide, magnesium oxide or mixtures thereof.
  • the devitrifying glasses that we formulated in the past were made up of a mixture of seven or eight different materials. These different materials were mixed, on a weight basis, in the proper proportions.
  • the present invention is directed to new formulations for a devitrifying glass having a temperature coefficient of expansion which closely matches that of silicon, and which requires only five materials mixed in the proper proportions. Moreover the thermal coefficient of expansion of a substrate comprised of this new devitrifying glass may be adjusted by the addition of an appropriate dielectric filler material to match that of gallium arsenide as well as silicon. Further, this devitrifying glass is particularly suitable for use as a constituent of various inks including (1) an overglaze ink coating compatible with copper electrodes, (2) a hermetic dielectric ink compatible with copper electrodes, (3) a copper via-fill ink for copper-dielectric multilayers, and (4) an inner layer copper ink for copper-dielectric multilayers.
  • the relatively high softening temperature of the subject glasses means their inks can be refired in making subsequent layers without undue adverse effects on previous layers.
  • the devitrifying glass formulations of the present invention comprise, on a weight basis: from about 26 to about 33 percent of zinc oxide (ZnO); from about 4 to about 8 percent of magnesium oxide
  • MgO barium oxide
  • SrO strontium oxide
  • the above ingredients are mixed, dried and melted in an inert, e.g., platiunum, vessel at a temperature of about 1600°-1650°C .
  • the melt is then quenched on counter rotating rollers to form vitreous glass flakes. These flakes are then made into a fine powder, having a particle size of about 1-5 micrometers, by a combination of dry and wet grinding in known manner.
  • devitrifying glass suitably having a particle size of about 3-8 micrometers and ceramic filler, such as alumina, are blended with a suitable organic binder, solvent, surfactant and plasticizer, and tape cast and sintered to form a substrate.
  • the ceramic filler aluminum oxide powder useful herein has a mean particle size of 0.62 micrometer.
  • a commercially available useful product is AKP-20 from Sumitomo Chemical Company, Ltd. of Japan.
  • the thermal coefficient of expansion can be increased to match that of gallium arsenide.
  • the thermal coefficient of expansion can be decreased by adding willemite, cordierite or silicon dioxide as fillers in the fabrication of the substrate.
  • devitrifying glass formulations of the present invention are superior to co-fired substrates based on alumina ceramics for several reasons.
  • alumina ceramics require very high processing temperatures (1400° - 1 550° C), thus making it necessary to utilize more refractory metallizations, such as tungsten and molybdenum in making electrical contacts.
  • substrates comprised of devitrifying glass based dielectrics can be processed at relatively low temperatures (900°C), permitting more conductive metals
  • alumina ceramics have thermal expansion coefficients higher than that of silicon or gallium arsenide, and, hence, are not suitable for large area chip bonding.
  • the devitrifying glass of the present invention is also suitable for use in preparing various types of inks employed in the fabrication of printed circuits by adding the glass particles to suitable metal powders and adding a suitable organic vehicle. Such printing inks can then be used for forming multilayer circuit boards on aluminum nitride or silicon carbide.
  • Suitable metals for use as inks can be copper, for firing in nitrogen, or silver, silver-platinum alloy, gold or gold-platinum alloy, which can be fired in air.
  • the organic vehicles are solutions of resin binders such as, for example, cellulose derivatives, particularly ethyl cellulose commercially available as ET-100 from Hercules, Inc.,. synthetic resins such as poly aery lates, polymethacrylates, polyesters, polyolefins and the like in a suitable solvent.
  • resin binders such as, for example, cellulose derivatives, particularly ethyl cellulose commercially available as ET-100 from Hercules, Inc.,. synthetic resins such as poly aery lates, polymethacrylates, polyesters, polyolefins and the like in a suitable solvent.
  • a preferred binder is poly(isobutylmethacrylate).
  • conventional solvents utilized in inks of the type described herein may be used.
  • Preferred commercially available solvents include, for example, pine oil, terpineol, butyl carbitol acetate, 2,2,4- trimethyl-2,3- ⁇ entanediol monisobutyrate, available from Texas Eastman Company under the trademark Texanol and the like.
  • the above resin binders may be utilized individually or in any combination of two or more.
  • a suitable viscosity modifier can be added to the resin material if desired.
  • a modifier can be, for example, a castor oil derivative available from N. L. Industries under the trademark Thixatrol.
  • the organic vehicles also suitably contain a surfactant such as olelyamine, available as Armeen O, or a high molecular weight N-alkyl-l,3-diaminopropane dioleate, available as Duomeen TDO, both from AKZO Chemie America.
  • a surfactant such as olelyamine, available as Armeen O, or a high molecular weight N-alkyl-l,3-diaminopropane dioleate, available as Duomeen TDO, both from AKZO Chemie America.
  • mixing is suitably carried out in a conventional apparatus which mixes in combination with subjecting the dispersion to high shearing action, such as a three roll mill.
  • overglaze inks comprise between 50-90% by weight of the devitrifying glass of the invention and about 10- 50% of an organic vehicle.
  • Dielectric inks comprise between 50- 90% of a mixture of ceramic fillers and the devitrifying glass of the invention, preferably 50-85% of the mixture being the devitrifying glass, and 10-15% of an organic vehicle.
  • Copper via-fill inks can comprise at least about 50% by weight of copper, at least 25% by weight of the devitrifying glass of the invention and an organic vehicle.
  • Copper inner layer inks can comprise copper, a small amount of the devitrifying glass of the invention, a small amount of metal oxides and an .organic vehicle.
  • percent is by weight and temperature is given in degrees Celsius.
  • EXAMPLE 1 Preparation of a Barium Oxide Containing Glass. The following oxides were mixed and melted at 1600°-
  • the above oxides were mixed, melted at 1 00°-1650°C in a platinum crucible and quenched.
  • Duomeen TDO 0.2 The glass powder and the organic vehicle were mixed on a three roll mill.
  • the ink was screen printed and fired in nitrogen at 900° C , and tested for hermeticity and resistance to mild acids and mild alkali. The results were satisfactory. Leakage current was less than 10 ⁇ 6 A/cm ⁇ , which was also satisfactory.
  • Duomeen TDO 0.2 The ink was screen printed and fired in nitrogen at 900° C .
  • the ink was inert to mild acid and mild alkali and had a satisfactory leakage current of less than 10" 6 A/cm ⁇ .
  • This ink was formulated as in Example 3 and used in combination with the dielectric ink of Example 4 to make a copper - dielectric multilayer printed circuit. There was no cracking or blistering in the vias.
  • Example 3 This ink was formulated as in Example 3 and used in combination with the dielectric ink of Example 4 to make a copper - dielectric multilayer printed circuit. There was no via cracking or blistering in multilayer structures.
  • EXAMPLE 7 Preparation of an Inner Layer Copper Ink.
  • the above ink was also used for buried copper conductors in the copper/dielectric structure as above. No blistering was noted after firing, and the adhesion of a copper layer formed from the above ink was good on both the substrate and the dielectric.
  • the devitirfying glass formulations of the present invention are useful both in making a substrate and in making multilayer copper-dielectric structures supported by a substrate of printed circuits on which silicon or gallium arsenide chips may be mounted, and then applying a hermetic-sealing overglaze to such fabricated printed circuits.
  • such printed circuits may be comprised of co-fired buried copper layers within the substrate that make use of the devitrifying glass formulations of the present invention.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

Les compositions à base de verre dévitrifiant à faible expansion décrites sont utiles dans des substrats monocouche ou multicouche destinés à la fabrication de cartes de circuits imprimés et présentant des coefficients d'expansion thermique qui correspondent à ceux des puces en silicium ou en arséniure de gallium de grande dimension. De telles compositions à base de verre dévitrifiant sont également utiles pour des encres à film épais compatibles avec de tels substrats, que ces encres soient du type couche de glaçage terminale, du type diélectrique, du type servant pour le remplissage de passages pour cuivres ou du type servant pour cuivres de couches internes.
PCT/US1990/000005 1989-01-19 1990-01-02 Compositions a base de verre devitrifiant pour substrats de circuits imprimes a faible expansion et encres WO1990008110A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US29910489A 1989-01-19 1989-01-19
GB898921386A GB8921386D0 (en) 1989-09-21 1989-09-21 Devitrifying glass composition for low expansion substrate
GB8921386.2 1989-09-21
US45099089A 1989-12-15 1989-12-15
US450,990 1989-12-15
US299,104 1994-09-02

Publications (1)

Publication Number Publication Date
WO1990008110A1 true WO1990008110A1 (fr) 1990-07-26

Family

ID=27264703

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/000005 WO1990008110A1 (fr) 1989-01-19 1990-01-02 Compositions a base de verre devitrifiant pour substrats de circuits imprimes a faible expansion et encres

Country Status (3)

Country Link
EP (1) EP0454734A4 (fr)
JP (1) JPH04502750A (fr)
WO (1) WO1990008110A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7037944B2 (en) 2000-10-04 2006-05-02 Aventis Pharma S.A. Combination of a CB1 receptor antagonist and of sibutramine, the pharmaceutical compositions comprising them and their use in the treatment of obesity

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191789A (en) * 1978-11-02 1980-03-04 Bell Telephone Laboratories, Incorporated Fabrication of bi-level circuits
US4570337A (en) * 1982-04-19 1986-02-18 Olin Corporation Method of assembling a chip carrier
US4620264A (en) * 1983-12-23 1986-10-28 Hitachi, Ltd. Multi-layer ceramic wiring circuit board and process for producing the same
US4714687A (en) * 1986-10-27 1987-12-22 Corning Glass Works Glass-ceramics suitable for dielectric substrates

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3460967A (en) * 1965-10-23 1969-08-12 Owens Illinois Inc Surface treatment of glasses

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191789A (en) * 1978-11-02 1980-03-04 Bell Telephone Laboratories, Incorporated Fabrication of bi-level circuits
US4570337A (en) * 1982-04-19 1986-02-18 Olin Corporation Method of assembling a chip carrier
US4620264A (en) * 1983-12-23 1986-10-28 Hitachi, Ltd. Multi-layer ceramic wiring circuit board and process for producing the same
US4714687A (en) * 1986-10-27 1987-12-22 Corning Glass Works Glass-ceramics suitable for dielectric substrates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0454734A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7037944B2 (en) 2000-10-04 2006-05-02 Aventis Pharma S.A. Combination of a CB1 receptor antagonist and of sibutramine, the pharmaceutical compositions comprising them and their use in the treatment of obesity

Also Published As

Publication number Publication date
EP0454734A4 (en) 1992-03-11
EP0454734A1 (fr) 1991-11-06
JPH04502750A (ja) 1992-05-21

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