WO1992000925A1 - Compositions de verre - Google Patents

Compositions de verre Download PDF

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Publication number
WO1992000925A1
WO1992000925A1 PCT/GB1991/001124 GB9101124W WO9200925A1 WO 1992000925 A1 WO1992000925 A1 WO 1992000925A1 GB 9101124 W GB9101124 W GB 9101124W WO 9200925 A1 WO9200925 A1 WO 9200925A1
Authority
WO
WIPO (PCT)
Prior art keywords
low melting
glass composition
glass
composition
melting point
Prior art date
Application number
PCT/GB1991/001124
Other languages
English (en)
Inventor
John Francis Clifford
Simon Edward Pettitt
Original Assignee
Cookson Group Plc
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 Cookson Group Plc filed Critical Cookson Group Plc
Publication of WO1992000925A1 publication Critical patent/WO1992000925A1/fr

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Classifications

    • 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
    • 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • 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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
    • 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
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/291—Oxides or nitrides or carbides, e.g. ceramics, 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
    • H01L23/482—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 lead-in layers inseparably applied to the semiconductor body
    • H01L23/4827—Materials
    • H01L23/4828—Conductive organic material or pastes, e.g. conductive adhesives, inks
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/04—Particles; Flakes
    • 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

  • the present invention relates to novel glass compositions and, in particular, to novel low temperature glasses which are useful as sealing glasses or solder glasses, and in electronic paste formulations.
  • solder glass or "sealing glass” is a term which is used to describe glasses which form an adhesive bond between two glasses, or between a combination of glass, metal, or a ceramic material. It is well known in the art that commercially available solder glasses capable of sealing ceramic and electrical component parts, such as television tube and semiconductor devices, are practical in the 400° to 500°C range. These solder glasses are generally based upon the lead oxide-boron oxide binary system. The lead oxide-boron oxide eutectic comprises 13% by weight of boron oxide and 87% by weight of lead oxide and represents the most fluid glass in that binary system. It is the starting point from which most commercial solder glasses have been derived. Whilst these glasses, with the addition of certain fillers, have been very successful, there is a need in the art for a solder glass which will seal at temperatures below the lower limit of the range of use for the lead oxide-boron oxide based glasses.
  • a second useful feature of these glasses is their high thermal expansion which can be modified to be comparable with high expansion materials including copper, silver and aluminium.
  • a solder glass In order for a glass to qualify as a solder glass it has to meet certain physical criteria. These criteria will depend to a great extent upon the properties of the materials which the solder glass is to unite. Thus, in general, a solder glass should possess the following characteristics: i) a low viscosity in the melting phase; ii) a thermal expansion which will match the - thermal expansion of the workpiece; iii) a sealing temperature which is below the lowest annealing and strain points of the materials to which it is to be sealed, iv) good physical and chemical stability; and v) a good adhesion to the workpiece.
  • W087/05006 describes a solder glass for low temperature applications which is based upon the addition of bismuth oxide, zinc oxide and phosphorus pentoxide to the lead oxide-vanadium oxide eutectic.
  • US-A-3408212 describes the effect of adding large quantities of lead fluoride to lead oxide-vanadium oxide mixtures. A narrow glass forming region was found to exist in the centre of the lead oxide-lead fluoride-vanadium pentoxide ternary diagram, with improved glass life stability.
  • US-A-3837866 describes the addition of arsenic oxides to both the lead oxide-vanadium pentoxide and caesium oxide-vanadium pentoxide eutectics to prevent early recrystallization. However, the addition of arsenic oxide tends to increase the viscosity of the resulting glasses.
  • US-A-4186023 describes lead borate and lead zinc borate glasses containing from 0.1 to 10% by weight of cuprous oxide and a non-volatile metal fluoride, the mol ratio of cuprous oxide to the fluoride content of the metal fluoride being in the range of from 1:0.25 to 1:10.
  • solder glass compositions some of which have dilatometric softening temperatures of below 350°C, which are capable of wetting and bonding to a wide range of glasses, metals and ceramics including typical electronic substrates such as alumina, metallised alumina and silicon, and which are not derived from the lead oxide-boron oxide eutectic or the lead oxide- vanadium pentoxide eutectic mixtures.
  • the present invention provides a low melting glass composition which comprises in mole percent calculated on an oxide basis: i) from 50 to 95% of Te0 , or an appropriate amount of a precursor for Te0 2 , ii) from o.l to 20% of an oxide of copper, or an appropriate amount of a precursor therefor, iii) from 0.1 to 40% of one or more oxides of Mg, Ba, Ti, Nb, Ta, Mo, Ag, Zn, B, W, Tl, or an appropriate amount of a precursor for one or more of the chosen oxides, and iv) optionally up to 30% of one or more oxides of Pb, V, Li, Na, K, Rb, Cs, Ca, Sr, Zr, Hf, Si, Ge, Al, Ga, In, P, Sn, Sb, Bi, La or a rare earth metal, or an appropriate amount of a precursor for one or more of the chosen oxides, and the glass composition having a dilatometric softening temperature, Ts, typically of 380
  • the low melting glass composition of the present invention thus contain Te ⁇ 2 as the major component in an amount of from 50-95 mol %, preferably 60 to 90 mol %, more preferably 65-85 mol %.
  • the oxide as component (iii) is preferably selected from the following oxides: Ag 2 0, Mo0 3 , WO 3 and ZnO.
  • the low melting glass composition of the present invention may be a three oxide system, the first oxide comprising Te0 2 , with the second and third oxides comprising components (ii) and (iii) as defined above.
  • the second oxide, component (ii) will generally be present in an amount of at least 0.5 mol %, preferably 0.5 to 10 mol %, whilst the third oxide, component (iii) will generally be present in an amount of at least 1.0%, preferably from 10 to 25 mol %.
  • the low melting glass composition may be a four or more component system, in which the additional components are as defined above for component (iv) .
  • the preferred low melting glass compositions of the present invention have a dilatometric softening point, Ts, in the range of from 210 to 380°C, preferably 350°C or below and more preferably 300°C or below and linear thermal coefficients of expansion in the range of from 150 to 245 X 10 ⁇ 7 , although the latter may on occasion be advantageously lowered by the use of a filler as described below.
  • Ts dilatometric softening point
  • a composition having a thermal coefficient of expansion of greater than 190 x 10" 7 is preferred for sealing to high expansion.
  • the low melting glass compositions of the present invention may additionally contain at least one solid halide of low volatility, such as lithium or sodium fluoride, in an amount of ⁇ 5% by weight.
  • a further and surprising attribute of many of the glasses of the present invention is their good water and chemical durability. It is the combination of this property with either or both the high expansion and low melting temperature that makes the glasses of this invention such good sealing/bonding materials.
  • the various oxides used in the preparation of the compositions of the present invention are usually in the form of fine powders. Precursors of these oxides can also be useful, providing that they decompose to form the required oxides at a temperature below the melting temperature of the glass. Suitable precursors are the nitrites, nitrates, carbonates, metal organic salts, for example citrates, acetates, etc. and telluric acid.
  • the invention also includes within its scope a mixture of the above-described glass compositions of the invention with from 1 to 50% by weight, based on the mixture, of an inert refractory filler material having a thermal coefficient of expansion below that of the glass composition. The filler should be insoluble or only slightly soluble in the glass composition.
  • the filler material is preferably used in an amount of from 5 to 30% by weight, based on the mixture, but the amount will depend upon the thermal expansion of the substrate or parts which the composition is intended to join, and on the specific gravity of the materials, a larger amount of filler resulting in a greater decrease in the thermal coefficient of expansion of the composition.
  • the filler materials are used in order to modify the thermal coefficient of expansion of the glass composition, without effecting significantly the bonding temperature, of the glass.
  • the filler material may thus be added to the glass composition of the invention as a means of controlling the overall thermal expansion and contraction of the resulting solder glass mixture. Increased amounts of a low thermal expansion filler will correspondingly decrease the linear expansion of the glass composite.
  • Suitable filler materials include amorphous Si0 2 , zircon, aluminium titanate, corderite, Nb 05, Ta 0s and lithium aluminium silicates e.g. ⁇ -spodumene.
  • The,fillers are mixed with the glass composition in amounts in the range of from 1 to 50% by weight based on the mixture.
  • the mixtures may be prepared, for example, by ball milling in a conventional manner to produce a finely divided, uniformly mixed material.
  • the low melting glass compositions of the present invention may be applied to the substrate surfaces which are to be bonded together either as a molten glass, or as a shaped preform, or the powdered glass may be admixed with an organic vehicle to form a glass paste which is used to coat the substrate.
  • the substrate is then heated initially to a temperature at which the organic vehicle will "burn off” and then at a temperature sufficient to melt the glass and form the seal.
  • the composite is heated to a temperature in the range of from 300° to 450°C to melt the glass and form the bond.
  • the organic vehicle may be any synthetic organic solvent which preferably boils or decomposes at a temperature below the softening point of the glass composition.
  • the glasses of this invention may also successfully be employed in passivating, dielectric, resistor, conducting, die attach or similar electronic paste formulations in which the glass acts wholely or in part as the adhesive bond.
  • the invention includes within its scope the use of a filler to modify mechanical properties such as thermal expansion. It is also intended to provide, where appropriate, for the use of fillers to modify electrical properties such as conductivity, resistivity and dielectric constant by the inclusion of; high and low resistivity metals, semiconducting oxides, nitrides, borides and carbides and dielectrics such as barium titanate or other insulating oxide materials.
  • a metal flake or powder filler such as silver, gold, copper or aluminium may be admixed with the low melting glass composition of the present invention in an amount of from 25% to 95% by weight based on the total dry weight of the composition, preferably 60 to 95% by weight based on the total dry weight of the composition.
  • the metal-glass mixture may be formulated into a paste by admixture with an organic vehicle.
  • the organic vehicle will generally be used in an amount such that the total solids content of the metal-filled glass paste is in the range of from 70 to 90% solids.
  • the metal-glass mixture is particularly suitable for electronic applications, such as "thick film" conducting pastes and die attach applications in bonding semiconductor devices to a ceramic substrate, such as alumina.
  • solder glasses and pastes of the present invention may be coated onto metal-glass or ceramic substrates at any chosen thickness but usually at thicknesses in the range of from about 0.5 to 500 micrometres.
  • the paste will generally be applied to the substrate surface in a conventional manner, for example by brush coating, screen printing, stencilling or stamping.
  • the paste is typically syringe dispensed.
  • the die is attached by placing it in the centre of the wet paste and setting it by the application of pressure so that the paste flows up the side of the die and leaves a thin film beneath the die.
  • the structure is then heat treated to "burn off" the organic vehicle and the temperature then raised to melt the low melting glass composition.
  • a range of three oxide tellurite based glasses were made of the composition Te0 2 :X:Y, investigating the tellurite rich glass region.
  • the compositions which were made are given, in mol %, as points 1 to 6 on Figure 1 of the accompanying drawings which is a phase diagram of the compositions.
  • the oxides X and Y which were incorporated into the tellurite glass systems were selected from the following:
  • composition TXY1 85:7.5:7.5 mol %
  • composition TXY2 • 80:15:5 mol %
  • composition TXY4 70:25:5 mol %
  • composition TXY6 ** 70:5:25 mol %
  • compositions in the Te ⁇ 2 :Ag 0:CU2 ⁇ system were prepared, by fusing the respective oxide mixtures at a temperature of 775°c for 10 minutes in a recrystallized alumina crucible.
  • the compositions, in mol %, are given in Table 2 below:
  • Three five oxide tellurite glasses were prepared by adding both fourth and fifth oxides in amounts of 1 and 5 mol % to certain of the three oxide systems previously described. Glasses were prepared from mixtures of the five oxides by fusing at a temperature of 775°C for 10 minutes in a recrystallized alumina crucible. The abbreviations used were as described above, with the fourth and fifth oxide additions being represented by a letter indicating which oxide was added and the number 1 or 5 indicating whether it was added in an amount of 1 or 5 mol %. The results are given in Table 5 below: ble 5
  • a five oxide tellurite based glass was made from the following components by fusing at a temperature of 775°C for 10 minutes in a recrystallised alumina crucible.
  • tellurite glasses could have a use in hermetically sealing high expansion metal joins.
  • Various tellurite glasses were selected to fuse to a selection of high expansion metals, these being 303 steel, aluminium, copper and nickel.
  • the glass selected for bonding purposes had a slightly lower TCE value than that of the metal to be bonded so that the glass was put into compression on sealing.
  • the glass was, in each case, ground to sub 38 micrometre particle size, suspended in heptane and spread thinly and evenly onto the flat metal surface.
  • Another piece of metal was placed over the top of the glass to create a "sandwich" which was heated to 350° to 450°C to bond the two metal pieces together. A manual inspection indicated that a good bond had been obtained in each case.
  • Table 7 The results are given in Table 7 below:
  • Polycarbonates prepared from 2,5-dimethyl0,0'bis- (l-imidazolylcarbonyl)-2,5-hexanediol and the following diols a, b, c and d were designated as polymers A, B, C and D respectively:-
  • polymers A, B and C were combined with a silver flake and a low melting glass powder of Example 17 to form a paste.
  • the three pastes were applied to a number of substrate materials including alumina, black alumina and silicon wafer.
  • the coated substrates were heated up to a temperature of 350°C.

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

Abstract

Une composition de verre à bas point de fusion contient un pourcentage molaire de TeO2 compris entre 50 et 95 %, un pourcentage molaire d'oxyde de cuivre compris entre 0,1 et 20 %, un pourcentage molaire d'un ou plusieurs oxydes de Mg, Ba, Ti, Nb, Ta, Mo, W, Ag, Zn, B ou Tl compris entre 0,1 et 40 %, et éventuellement jusqu'à 30 % d'un ou plusieurs autre(s) oxyde(s), la composition de verre présentant une température de ramollissement dilatométrique typique (Ts) inférieure opu égale à 380 °C.
PCT/GB1991/001124 1990-07-09 1991-07-09 Compositions de verre WO1992000925A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9015072A GB9015072D0 (en) 1990-07-09 1990-07-09 Glass composition
GB9015072.3 1990-07-09

Publications (1)

Publication Number Publication Date
WO1992000925A1 true WO1992000925A1 (fr) 1992-01-23

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PCT/GB1991/001123 WO1992000924A1 (fr) 1990-07-09 1991-07-09 Compositions de verre de tellurite
PCT/GB1991/001124 WO1992000925A1 (fr) 1990-07-09 1991-07-09 Compositions de verre

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PCT/GB1991/001123 WO1992000924A1 (fr) 1990-07-09 1991-07-09 Compositions de verre de tellurite

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WO (2) WO1992000924A1 (fr)

Cited By (14)

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EP0718249A1 (fr) * 1994-11-29 1996-06-26 Ube Industries, Ltd. Matériau composite à matrice vitreuse ayant une résistance et une tenacité élevée, poudre composite vitreuse, et procédés pour leur production
US6344425B1 (en) * 1999-11-19 2002-02-05 Corning Incorporated Fluorotellurite, amplifier glasses
WO2011140189A1 (fr) * 2010-05-04 2011-11-10 E. I. Du Pont De Nemours And Company Pâtes pour film épais contenant des oxydes de plomb-tellure-bore, et leur utilisation dans la fabrication de dispositifs semi-conducteurs
US20130049148A1 (en) * 2011-02-22 2013-02-28 E I Du Pont De Nemours And Company Conductive paste composition and semiconductor devices made therewith
CN103155159A (zh) * 2010-10-07 2013-06-12 昭荣化学工业株式会社 太阳能电池元件及其制造方法
US20130186463A1 (en) * 2011-12-06 2013-07-25 E I Du Pont De Nemours And Company Conductive silver paste for a metal-wrap-through silicon solar cell
US8512463B2 (en) 2011-04-05 2013-08-20 E I Du Pont De Nemours And Company Thick film paste containing bismuth-tellurium-oxide and its use in the manufacture of semiconductor devices
EP2654085A1 (fr) * 2012-04-17 2013-10-23 Heraeus Precious Metals North America Conshohocken LLC Système de réaction inorganique pour composition de pâte électro-conductrice
EP2654086A1 (fr) * 2012-04-17 2013-10-23 Heraeus Precious Metals North America Conshohocken LLC Pâte pour film épais conducteur pour contacts de cellule solaire
US20130298982A1 (en) * 2012-05-10 2013-11-14 E I Du Pont De Nemours And Company Glass composition and its use in conductive silver paste
US8845932B2 (en) 2012-04-26 2014-09-30 E I Du Pont De Nemours And Company Thick film paste containing bismuth-tellurium-oxide and its use in the manufacture of semiconductor devices
DE102013226636A1 (de) * 2013-12-19 2015-06-25 Friedrich-Schiller-Universität Jena Glaszusammensetzung, Bauelement und Verfahren zur Herstellung eines Bauelements
CN104813414A (zh) * 2012-09-18 2015-07-29 株式会社村田制作所 导电性膏以及太阳能电池
US10658528B2 (en) 2017-04-18 2020-05-19 Dupont Electronics, Inc. Conductive paste composition and semiconductor devices made therewith

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DE10139904A1 (de) * 2001-08-15 2003-02-27 Univ Schiller Jena Optische Telluritgläser für Lichtwellenleiterverstärker und Oszillatoren sowie Verfahren zu ihrer Herstellung
IL155435A0 (en) * 2003-04-14 2003-11-23 Bromine Compounds Ltd Solid biocide formulations
JP5559509B2 (ja) * 2009-10-28 2014-07-23 昭栄化学工業株式会社 太陽電池電極形成用導電性ペースト
CN103547542A (zh) * 2011-03-24 2014-01-29 E.I.内穆尔杜邦公司 导电糊料组合物及由其制成的半导体器件
JP6350127B2 (ja) * 2014-08-29 2018-07-04 日立化成株式会社 無鉛低融点ガラス組成物並びにこれを含む低温封止用ガラスフリット、低温封止用ガラスペースト、導電性材料及び導電性ガラスペースト並びにこれらを利用したガラス封止部品及び電気電子部品

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JPS6236040A (ja) * 1985-08-08 1987-02-17 Iwaki Glass Kk 低融点封着用硝子
US4652536A (en) * 1985-06-28 1987-03-24 Hoya Corporation Tellurite glass
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WO1992000924A1 (fr) 1992-01-23

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