WO2012066976A1 - Poudre de verre cristallin - Google Patents

Poudre de verre cristallin Download PDF

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Publication number
WO2012066976A1
WO2012066976A1 PCT/JP2011/075700 JP2011075700W WO2012066976A1 WO 2012066976 A1 WO2012066976 A1 WO 2012066976A1 JP 2011075700 W JP2011075700 W JP 2011075700W WO 2012066976 A1 WO2012066976 A1 WO 2012066976A1
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Prior art keywords
glass
powder
crystals
dielectric
mass
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PCT/JP2011/075700
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English (en)
Japanese (ja)
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克 岩尾
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日本電気硝子株式会社
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Priority to KR1020137012726A priority Critical patent/KR101974907B1/ko
Priority to CN201180055513.7A priority patent/CN103221355B/zh
Publication of WO2012066976A1 publication Critical patent/WO2012066976A1/fr

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    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • 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
    • 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
    • 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
    • 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
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/16—Compositions for glass with special properties for dielectric glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • 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
    • 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
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/15—Ceramic or glass substrates

Definitions

  • the present invention relates to a crystalline glass powder used as a glass ceramic dielectric material.
  • glass ceramic dielectrics are known as insulating materials for ceramic multilayer substrates, thick film circuit components, semiconductor packages and the like on which ICs, LSIs and the like are mounted at high density.
  • thinning is also required for substrates used in electronic components.
  • a glass ceramic dielectric formed by depositing diopside crystals (2SiO 2 ⁇ CaO ⁇ MgO) obtained by firing glass ceramic powder containing crystalline glass powder is used for the substrate.
  • diopside crystals (2SiO 2 ⁇ CaO ⁇ MgO) obtained by firing glass ceramic powder containing crystalline glass powder is used.
  • the presence of minute bubbles (voids) inside the glass ceramic dielectric makes the problem of wiring disconnection prominent. Also, dielectric loss tends to increase due to bubbles.
  • Bubbles generated inside the glass ceramic dielectric are caused by the high rate of formation of non-flowing parts due to crystallization in the sintering process of the raw crystalline glass powder, which hinders softening deformation of the entire sintered body. Arises. That is, when crystallization proceeds without the crystalline glass powder being softened and deformed, volume shrinkage due to crystallization does not spread over the entire sintered body, and bubbles remain in the gaps between the glass powders.
  • an object of the present invention is to provide a crystalline glass powder that can reduce internal bubbles and has low dielectric loss characteristics that can sufficiently cope with a high-performance high-frequency circuit.
  • the present inventor has found that the above problem can be solved by a crystalline glass powder in which a specific crystal is precipitated together with a diopside crystal as a main crystal, and proposes as the present invention.
  • the present invention relates to a crystalline glass powder characterized in that diopside crystals and feldspar crystals are precipitated as main crystals by heat treatment.
  • the present inventor has made it possible to crystallize part or all of the glass phase remaining after the precipitation of the diopside crystal into a feldspar crystal having a crystallization start temperature higher than that of the diopside crystal and a small volume shrinkage. It has been found that by using glass powder, the residual glass phase can be reduced while suppressing the generation of bubbles accompanying crystal precipitation as much as possible. This makes it possible to produce a glass ceramic dielectric with a low bubble rate and low low dielectric loss.
  • the “crystalline glass” means an amorphous glass having a property that crystals are precipitated from the glass matrix upon heat treatment.
  • the “diopside crystal” includes not only diopside crystals but also diopside solid solution crystals.
  • heat treatment means that crystallization sufficiently proceeds at a temperature higher than the crystallization start temperature of diopside crystals and feldspar crystals, for example, heat treatment at 800 to 1000 ° C. for 20 minutes or more.
  • the crystalline glass of the present invention is characterized in that the feldspar crystal is a barium feldspar crystal (BaAl 2 Si 2 O 8 ).
  • the crystalline glass of the present invention has a glass composition of mass%, SiO 2 20 to 65%, CaO 3 to 25%, MgO 7 to 30%, Al 2 O 3 0 to 20%, BaO 5 to It is characterized by containing 40% and satisfying the relationship of 1 ⁇ SiO 2 / BaO ⁇ 4 by mass ratio.
  • the crystalline glass of the present invention has the above composition, diopside crystals and feldspar crystals are likely to be precipitated as the main crystals by heat treatment.
  • SiO 2 —CaO—MgO-based glass has a strong tendency to devitrify, it can be stabilized by adding alkaline earth oxides such as Al 2 O 3 and BaO, and has excellent mass productivity. Glass can be obtained.
  • the present invention relates to a glass ceramic material comprising any one of the above crystalline glass powders 60 to 100% by mass and ceramic powders 0 to 40% by mass.
  • the glass ceramic material of the present invention is characterized in that the ceramic powder contains an Al component.
  • the ceramic powder contains an Al component, Si or Ba in the remaining glass phase after the precipitation of the diopside crystal reacts with the Al component in the ceramic powder, and feldspar crystals are likely to precipitate.
  • the present invention relates to a glass ceramic dielectric obtained by firing any one of the above glass ceramic materials.
  • the glass-ceramic dielectric of the present invention is characterized by containing 20 to 65% by mass of feldspar crystals.
  • the glass ceramic dielectric of the present invention is characterized in that the bubble ratio is 3% by volume or less.
  • the glass ceramic dielectric of the present invention is characterized in that the dielectric constant ⁇ is 6 to 11 and the dielectric loss tan ⁇ at a frequency of 0.1 GHz or more is 20 ⁇ 10 ⁇ 4 or less.
  • the glass-ceramic dielectric of the present invention is characterized by being used for a microwave circuit component material.
  • the crystalline glass powder of the present invention is characterized in that diopside crystals and feldspar crystals are precipitated as main crystals by heat treatment.
  • the feldspar crystal is preferably a barium feldspar crystal.
  • barium feldspar crystals By precipitating barium feldspar crystals, the residual glass phase after the heat treatment can be effectively reduced, and a glass-ceramic dielectric having a small bubble ratio and dielectric loss can be easily obtained.
  • calcium feldspar crystals (CaAl 2 Si 2 O 8 ) or the like may be precipitated within a range in which the dielectric loss and the bubble ratio do not increase.
  • the crystalline glass powder of the present invention has a glass composition of mass%, SiO 2 20 to 65%, CaO 3 to 25%, MgO 7 to 30%, Al 2 O 3 0 to 20%, BaO 5 to 40%. in content and, and the weight ratio, it is preferable to satisfy a relation of 1 ⁇ SiO 2 / BaO ⁇ 4 .
  • % means “% by mass” unless otherwise specified.
  • SiO 2 is a glass network former and is a constituent of diopside crystals and feldspar crystals.
  • the content of SiO 2 is preferably 20 to 65%, 30 to 65%, particularly 40 to 55%. If the content of SiO 2 is 20% or more, it becomes easier to vitrify, and if it is 65% or less, low-temperature firing (for example, 1000 ° C. or less) tends to be easier.
  • CaO is a constituent component of diopside crystal, and its content is preferably 3 to 25%, 3 to 20%, and particularly preferably 7 to 15%. If the CaO content is 3% or more, diopside crystals are more likely to precipitate, and as a result, the dielectric loss of the glass ceramic dielectric tends to be low. If the content of CaO is 25% or less, the fluidity of the glass tends to be improved.
  • MgO is also a constituent component of the diopside crystal, and its content is preferably 7 to 30%, 8 to 30%, 11 to 30%, particularly 12 to 20%. If the MgO content is 7% or more, crystals are more likely to precipitate, and if it is 30% or less, vitrification is easier.
  • Al 2 O 3 is a component for stabilizing the glass, and its content is preferably 0 to 20%, 0.5 to 20%, particularly 1 to 10%. If the content of Al 2 O 3 is 20% or less, diopside crystals are more likely to precipitate, and as a result, the dielectric loss of the glass ceramic dielectric tends to be low.
  • BaO is a constituent of barium feldspar crystals, and its content is preferably 5 to 40%, particularly 10 to 35%. If the content of BaO is 5% or more, barium feldspar crystals are more likely to precipitate. On the other hand, if the BaO content is 40% or less, the amount of diopside crystals deposited tends to increase, and as a result, the dielectric loss of the glass ceramic dielectric is unlikely to increase.
  • feldspar crystals can be efficiently precipitated from the remaining glass phase after firing. Specifically, it is preferable that the relationship 1 ⁇ SiO 2 / BaO ⁇ 4, particularly 1.05 ⁇ SiO 2 /BaO ⁇ 3.95 is satisfied. When the ratio of SiO 2 and BaO is within this range, feldspar crystals are more likely to precipitate or vitrification is more likely.
  • ZnO is a component that facilitates vitrification, and its content is preferably 0 to 20%, particularly preferably 0.1 to 15%. If the ZnO content is 20% or less, the crystallinity becomes stronger and the amount of precipitated diopside crystals tends to increase. As a result, the dielectric loss of the glass ceramic dielectric is difficult to increase.
  • CuO is a component that has an effect of suppressing the coloring of the glass ceramic dielectric due to Ag used as the wiring in the insulating material substrate.
  • the CuO content is preferably 0 to 1%, particularly preferably 0.01 to 0.2%. If the content of CuO is 1% or less, the dielectric loss of the glass ceramic dielectric tends to be small.
  • CeO 2 , MnO, Sb 2 O 3 , and SnO are components having the effect of suppressing coloring of the glass ceramic dielectric by Ag used as wiring in the insulating material substrate, similarly to CuO.
  • the contents of CeO 2 , MnO, Sb 2 O 3 and SnO are each preferably 0 to 1%, particularly preferably 0.01 to 0.8%. If the contents of CeO 2 , MnO, Sb 2 O 3 and SnO are each 1% or less, the dielectric loss of the glass ceramic dielectric tends to be small.
  • TiO 2 and ZrO 2 are components that have the effect of improving the chemical resistance (acid resistance and alkali resistance) of the glass ceramic dielectric.
  • the content of TiO 2 is preferably 0 to 15%, particularly preferably 0.1 to 13%. If the content of TiO 2 is 15% or less, the dielectric loss of the glass ceramic dielectric tends to be small.
  • the content of ZrO 2 is preferably 0 to 15%, particularly preferably 0.1 to 13%. If ZrO 2 is 15% or less, the dielectric loss of the glass ceramic dielectric tends to be small.
  • alkali metal oxides such as Li 2 O, Na 2 O, and K 2 O tend to cut the glass network and increase the dielectric loss.
  • the insulating properties of the glass ceramic dielectric tend to decrease. Accordingly, the total amount of alkali metal oxides is preferably 5% or less, particularly 1% or less, and most preferably not substantially contained (specifically, less than 0.1%).
  • the average particle diameter D 50 of the crystallizable glass powder of the present invention is 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the lower limit is not particularly limited, but is preferably 0.1 ⁇ m or more from the viewpoint of ease of handling and processing cost.
  • the particle size of the crystalline glass powder is measured by a laser diffraction scattering method.
  • the crystalline glass of the present invention has an alumina powder, cordierite powder, mullite powder, quartz powder, zircon powder, titania powder, zirconia as necessary for the purpose of improving characteristics such as thermal expansion coefficient, toughness and dielectric constant.
  • Ceramic powder such as powder or quartz glass powder or the like may be used alone or in combination as a glass ceramic material.
  • the glass ceramic material of the present invention comprises crystalline glass powder 60-100% by weight and ceramic powder 0-40% by weight, preferably crystalline glass powder 65-99.5% by weight and ceramic powder 0.05-35% by weight, More preferably, it contains 70 to 99% by mass of crystalline glass powder and 1 to 30% by mass of ceramic powder. When the content of the ceramic powder exceeds 40% by mass, densification of the glass ceramic dielectric tends to be difficult.
  • the average particle size D 50 of the ceramic powder is 0.01 ⁇ 100 [mu] m, in particular 0.1 ⁇ 50 [mu] m.
  • the average particle diameter D 50 of the ceramic powder is 0.01 ⁇ m or more, not dissolve the crystalline glass powder, thermal expansion coefficient, toughness, dielectric constant, tends to obtain the effect of improving properties such as chemical resistance.
  • the average particle diameter D 50 of the ceramic powder 100 ⁇ m or less not interfere with the flow of the crystallizable glass powder during firing, bubbles are less likely to occur in the glass ceramic dielectric.
  • each component of Si and Ba in the residual glass phase after diopside crystal precipitation reacts with Al component in the ceramic powder to produce feldspar crystals. Precipitates easily.
  • the ceramic powder containing Al component include alumina powder, cordierite powder, mullite powder, anorthite feldspar, albite feldspar, barium aluminate, aluminum titanate, spinel, calcium aluminate, magnesium aluminate, aluminum nitride, and the like. .
  • the crystallinity can be improved by mixing about 0.1 to 1% by mass of diopside or barium feldspar crystals as crystal nuclei.
  • the glass ceramic material containing the crystalline glass of the present invention is heat-treated at a temperature equal to or higher than the crystallization start temperature of the crystalline glass, thereby obtaining a glass ceramic dielectric in which diopside crystals and feldspar crystals are precipitated as main crystals.
  • the content of diopside crystals in the glass ceramic dielectric is preferably 35% by mass or more, particularly preferably 40% by mass or more. If the content of the diopside crystal is 35% by mass or more, the dielectric loss tends to be small.
  • the upper limit of the content of the diopside crystal is preferably 80% by mass or less, particularly preferably 70% by mass or less. If the content of the diopside crystal is 80% by mass or less, bubbles in the glass ceramic dielectric are reduced.
  • the content of feldspar crystals in the glass ceramic dielectric is preferably 20 to 65% by mass, 25 to 60% by mass, particularly 30 to 55% by mass. If the content of feldspar crystals is 20% by mass or more, the bubble ratio in the glass ceramic dielectric is decreased, and as a result, the low dielectric loss tends to be decreased. If the content of the feldspar crystal is 65% by mass or less, the diopside crystal is relatively increased, so that the dielectric loss tends to be reduced and the mechanical strength tends to be improved.
  • the residual glass phase is preferably 0.5% by mass or more, particularly 1% by mass or more. If the residual glass phase is 0.5% by mass or more, bubbles are hardly generated in the glass ceramic dielectric. In addition, it is preferable that the upper limit of content of a residual glass phase is 20 mass% or less, especially 10 mass% or less. If the content of the residual glass phase is 20% by mass or less, diopside crystals and feldspar crystals are relatively small, and the dielectric loss tends to be small.
  • the glass ceramic dielectric of the present invention preferably has a bubble ratio of 3% by volume or less, particularly 2% by volume or less.
  • the bubble ratio is 3% by volume or less, when used as an insulating material substrate, there is a tendency that disconnection of wiring hardly occurs or dielectric loss is reduced.
  • the glass ceramic dielectric of the present invention is characterized by a low dielectric constant and low dielectric loss in a high frequency region.
  • the glass ceramic dielectric of the present invention has a dielectric loss tan ⁇ of 20 ⁇ 10 ⁇ 4 or less at 25 ° C. in a high frequency region having a dielectric constant of 6 to 11, particularly 6 to 10, and 0.1 GHz or more. It is preferably 18 ⁇ 10 ⁇ 4 or less, particularly preferably 16 ⁇ 10 ⁇ 4 or less.
  • the crystalline glass powder of the present invention can be obtained by preparing a raw material powder so as to have a predetermined composition, melting at a temperature of 1300 to 1650 ° C., forming, cooling, and pulverizing.
  • the glass ceramic dielectric of the present invention is manufactured as follows, for example. First, ceramic powder is mixed as necessary with the crystalline glass powder obtained as described above, and a predetermined amount of binder, plasticizer and solvent are added to prepare a slurry.
  • binder include polyvinyl butyral resin and methacrylic acid resin
  • plasticizer include dibutyl phthalate
  • solvent include toluene and methyl ethyl ketone.
  • the resulting slurry is formed into a green sheet by the doctor blade method.
  • the green sheet is dried and cut into predetermined dimensions. If necessary, mechanical processing is performed to form a through hole, and a low resistance metal material to be a conductor or an electrode is printed on the surface of the through hole and the green sheet. Subsequently, a plurality of green sheets are laminated and integrated by thermocompression bonding.
  • the laminated green sheet is fired at 800 to 1000 ° C., 800 to 950 ° C., particularly 850 to 900 ° C. to deposit diopside crystals and feldspar crystals from the crystalline glass powder, and has an insulating layer made of glass ceramic.
  • a multilayer substrate i.e. a glass ceramic dielectric, can be obtained.
  • substrate was demonstrated here, it is not limited to this, For example, it can apply also to electronic component materials, such as a thick film circuit component and a semiconductor package. Is possible.
  • Tables 1 to 3 show examples of the present invention (sample Nos. 1 to 15), and Table 4 shows comparative examples (samples Nos. 16 to 20).
  • Each sample was prepared as follows. First, a raw material powder was prepared so as to have the composition shown in the table, melted at 1550 ° C., and then molded and cooled to produce crystalline glass. The resulting milled crystalline glass, the average particle diameter D 50 was prepared crystalline glass powder 2 [mu] m.
  • the ceramic powder shown in the table was mixed at a predetermined ratio with each crystalline glass powder, and the crystal was deposited by holding at the firing temperature shown in the table for 20 minutes to obtain a glass ceramic dielectric.
  • the precipitated crystals were identified, and the ratio of precipitated crystals and glass phase, bubble ratio, dielectric constant at 25 ° C. and dielectric loss were measured. The results are shown in Tables 1 to 4.
  • Precipitated crystals in the glass ceramic dielectric were identified by a powder X-ray diffractometer (Rigaku RINT 2100). The ratio of the precipitated crystals and the remaining glass phase was calculated from the X-ray diffraction pattern by a multiple peak separation method.
  • the bubble ratio was determined by image analysis of the SEM image of the glass ceramic dielectric cross section.
  • WINROOF of Mitani Corporation was used for image analysis. The image analysis procedure is shown below.
  • the outline of the bubble part appears brighter than the glass matrix part due to the edge effect. Therefore, the SEM image was binarized using WINROOF, and the outline of the bubble portion and the glass matrix portion were color-coded. Further, the bubble portion and the glass matrix portion were color-coded by painting the inside of the bubble with the same color as the outline of the bubble portion. Thereafter, the bubble ratio was calculated according to the following formula. It is generally known that the area ratio of bubbles in the glass ceramic dielectric cross section is equal to the volume ratio of bubbles in the glass ceramic dielectric (for example, Yoshihiro Kiyomiya, “Volume ratio of particles in composite material”). "Relationship between area ratio” and Meisei University, Faculty of Science and Engineering Bulletin 42, 2006, p. 21-24).
  • Bubble rate (volume%) (total area of bubble part / total area of processed image) ⁇ 100
  • the crystalline glass of the present invention Since the crystalline glass of the present invention has few internal bubbles and low dielectric loss in the high frequency band, it is suitable as a glass ceramic dielectric material used for small or thin multilayer substrates, microwave circuit components, packages, and the like. is there.

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Abstract

L'invention concerne une poudre de verre cristallin qui présente une teneur réduite en bulles d'air internes, tout en ayant des caractéristiques de perte diélectrique faible qui sont suffisamment appropriées pour un circuit à haute fréquence et à haute performance. La poudre de verre cristallin est caractérisée en ce qu'un cristal de diopside et un cristal de feldspath sont déposés en tant que cristaux primaires par un traitement thermique. On préfère que la poudre de verre cristallin ait une composition de verre qui contient, en % en masse, 20-65 % de SiO2, 3-25 % de CaO, 7-30 % de MgO, 0-20 % d'Al2O3 et 5-40 % de BaO et ait un rapport massique satisfaisant la relation de 1 ≤ SiO2/BaO ≤ 4.
PCT/JP2011/075700 2010-11-17 2011-11-08 Poudre de verre cristallin WO2012066976A1 (fr)

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CN115724589A (zh) * 2022-11-29 2023-03-03 西安创联电气科技（集团）有限责任公司 一种射频连接器用封接玻璃粉及其制备与封接方法
CN116057019A (zh) * 2020-09-23 2023-05-02 日本电气硝子株式会社 玻璃陶瓷电介质材料、烧结体及高频用电路部件

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CN104464884A (zh) * 2014-12-26 2015-03-25 常熟联茂电子科技有限公司 一种有机功率电阻浆料
JP6293704B2 (ja) * 2015-05-28 2018-03-14 スナップトラック・インコーポレーテッド ガラスセラミックス焼結体及び配線基板
CN108030228A (zh) * 2017-11-29 2018-05-15 浙江大学 一种除垢牙刷丝及其制备方法
CN107898126A (zh) * 2017-11-29 2018-04-13 浙江大学 一种复合型除垢牙刷丝及其制备方法
JP7348587B2 (ja) * 2018-03-07 2023-09-21 日本電気硝子株式会社 ガラスセラミック誘電体
WO2019172042A1 (fr) * 2018-03-07 2019-09-12 日本電気硝子株式会社 Corps diélectrique en vitrocéramique
CN108439804A (zh) * 2018-04-19 2018-08-24 苏州凌科特新材料有限公司 一种玻璃陶瓷复合材料及其制备方法
CN112537947B (zh) * 2020-12-09 2022-03-29 江苏科技大学 一种低损耗低介电常数微波介质陶瓷材料及其制备方法
CN115925262A (zh) * 2022-12-30 2023-04-07 中国电子科技集团公司第十二研究所 玻璃陶瓷及其制备方法与静电卡盘

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