WO2019172042A1 - Corps diélectrique en vitrocéramique - Google Patents

Corps diélectrique en vitrocéramique Download PDF

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Publication number
WO2019172042A1
WO2019172042A1 PCT/JP2019/007565 JP2019007565W WO2019172042A1 WO 2019172042 A1 WO2019172042 A1 WO 2019172042A1 JP 2019007565 W JP2019007565 W JP 2019007565W WO 2019172042 A1 WO2019172042 A1 WO 2019172042A1
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Prior art keywords
glass
glass ceramic
ceramic dielectric
powder
layer
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PCT/JP2019/007565
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English (en)
Japanese (ja)
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北村　嘉朗
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日本電気硝子株式会社
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Priority claimed from JP2019015504A external-priority patent/JP7348587B2/ja
Application filed by 日本電気硝子株式会社 filed Critical 日本電気硝子株式会社
Priority to CN201980016831.9A priority Critical patent/CN111801308A/zh
Publication of WO2019172042A1 publication Critical patent/WO2019172042A1/fr

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    • 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
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes
    • 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

Definitions

  • the present invention relates to a glass ceramic dielectric used for a circuit board or the like.
  • 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 (see, for example, Patent Document 1).
  • a metal wiring having a predetermined pattern is formed on the surface of a glass ceramic dielectric and used as a circuit board.
  • the metal wiring is formed by a plating process, but the glass component contained in the glass ceramic dielectric is altered by the plating process, which may adversely affect characteristics such as dielectric constant and dielectric loss.
  • an object of the present invention is to provide a glass ceramic dielectric capable of plating the surface without causing alteration of the glass component.
  • the glass ceramic dielectric of the present invention comprises a glass ceramic layer and a barrier layer formed on the main surface thereof. If it does in this way, when forming metal wiring, such as gold
  • the glass ceramic dielectric of the present invention preferably has barrier layers formed on both main surfaces of the glass ceramic layer. If it does in this way, generation
  • the barrier layer is preferably made of an inorganic material. If it does in this way, when the surface of a glass ceramic dielectric material is plated, it will become easy to suppress that the glass component contained in a glass ceramic layer changes in quality.
  • the barrier layer is preferably made of amorphous glass. If it does in this way, when plating the surface of a glass ceramic dielectric material, it will become still easier to suppress that the glass component contained in a glass ceramic layer changes in quality.
  • the amorphous glass contains, by mass%, SiO 2 40% or more and B 2 O 3 15% or less as a glass composition. In this way, since a barrier layer having excellent acid resistance can be obtained, the function as a barrier layer can be enhanced.
  • the amorphous glass does not substantially contain an alkali metal component.
  • substantially no alkali metal component means that the alkali metal component is not intentionally contained as a raw material, and does not exclude inevitable contamination. Objectively, it means that the content of the alkali metal component is less than 0.1% by mass.
  • the glass-ceramic layer is preferably made of a powdered sintered body containing crystalline glass powder.
  • crystalline glass powder means a glass powder that precipitates crystals by heat treatment.
  • heat treatment means that crystallization sufficiently proceeds at a temperature higher than the crystallization start temperature, for example, a heat treatment at 800 to 1000 ° C. for 20 minutes or longer.
  • the crystalline glass powder has a glass composition in mass% of SiO 2 20 to 65%, CaO 3 to 25%, MgO 7 to 30%, Al 2 O 3 0 to 20%, It is preferable that BaO is contained in an amount of 5 to 40% and the relationship of 1 ⁇ SiO 2 / BaO ⁇ 4 is satisfied by mass ratio.
  • the crystalline glass powder having the composition has a property that feldspar crystals are precipitated together with diopside crystals (2SiO 2 ⁇ CaO ⁇ MgO) as main crystals by heat treatment. By precipitating both crystals, the degree of crystallinity due to firing is increased, and the residual glass phase that causes an increase in dielectric constant and dielectric loss can be reduced.
  • the feldspar crystal has a small volume shrinkage rate at the time of crystal precipitation, the generation of pores accompanying the crystal precipitation is suppressed. As a result, a glass ceramic dielectric having a low dielectric constant and dielectric loss can be obtained.
  • the glass ceramic layer is preferably composed of a sintered powder of a powder containing crystalline glass powder 30 to 100% by mass and filler powder 0 to 70% by mass.
  • the filler powder preferably contains an Al component. If it does in this way, each component of Si and Ba in the residual glass phase after diopside crystal precipitation will react with the Al component in filler powder, and a feldspar crystal will precipitate easily.
  • the glass ceramic layer preferably contains diopside crystals and feldspar crystals. For the above reasons, when both crystals are contained, a glass ceramic layer having a high degree of crystallinity and few pores can be easily obtained, and a glass ceramic dielectric having a low dielectric constant and dielectric loss can be obtained.
  • the glass ceramic dielectric of the present invention is suitable for circuit boards.
  • the circuit board of the present invention is characterized in that a metal wiring is formed on the surface of the barrier layer in the glass ceramic dielectric.
  • a method for producing a glass-ceramic dielectric of the present invention is a method for producing the above-mentioned glass-ceramic dielectric, which contains a green sheet for a glass-ceramic layer containing a crystalline glass powder and an amorphous glass powder.
  • the “non-crystalline glass powder” refers to a glass powder that does not substantially precipitate crystals by heat treatment. “Substantially no precipitation of crystals” means that the crystallinity of the glass after heat treatment is approximately 1% or less, including inevitable precipitation of devitrified substances.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the glass ceramic dielectric of the present invention.
  • the glass ceramic dielectric 1 includes a glass ceramic layer 2 and a barrier layer 3 formed on each of the main surface 2a and the main surface 2b of the glass ceramic layer 2. By plating the surface of the barrier layer 3 to form a metal wiring (not shown), it can be used as a circuit board. If necessary, a thermal via or the like may be formed inside the glass ceramic layer 2.
  • the glass ceramic dielectric 1 is a plate-like member whose planar shape is rectangular or circular.
  • the barrier layers 3 are not necessarily formed on both main surfaces of the glass ceramic layer 2, and the barrier layers 3 may be formed only on one main surface of the glass ceramic layer 2.
  • Glass ceramic layer consists of a sintered compact of the powder containing crystalline glass powder, for example.
  • the glass composition contains, by 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%. and a mass ratio include those satisfying the relation of 1 ⁇ SiO 2 / BaO ⁇ 4 .
  • the glass-ceramic dielectric obtained by firing the crystalline glass powder having the above composition has the property that a feldspar crystal is precipitated together with the diopside crystal as a main crystal by heat treatment, and the dielectric constant and dielectric loss. Low glass ceramic dielectric.
  • the dielectric loss tan ⁇ is 20 ⁇ 10 ⁇ 4 or less, 18 ⁇ 10 ⁇ 4 or less, particularly 16 or less in a high frequency region where the dielectric constant is 6 to 11, particularly 6 to 10, and 0.1 GHz or more. It becomes possible to achieve ⁇ 10 ⁇ 4 or less.
  • the feldspar crystals are preferably barium feldspar crystals (BaAl 2 Si 2 O 8 ). By precipitating barium feldspar crystals, the residual glass phase after heat treatment can be effectively reduced, and a glass-ceramic dielectric having a low porosity 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 where dielectric loss and porosity do not increase.
  • 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%. When the content of SiO 2 is too small, vitrification is difficult, and when it is too large, low-temperature firing (for example, 1000 ° C. or less) tends to be difficult.
  • 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 content of CaO is too small, diopside crystals are difficult to precipitate, and as a result, the dielectric loss of the glass ceramic dielectric tends to increase. On the other hand, when there is too much content of CaO, the fluidity
  • 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%. When the content of MgO is too small, crystals are difficult to precipitate, and when it is too large, vitrification is difficult.
  • 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%.
  • content of Al 2 O 3 is too large, diopside crystal becomes difficult precipitated, as a result there is a tendency that the dielectric loss of the glass ceramic dielectric increases.
  • BaO is a constituent of barium feldspar crystals, and its content is preferably 5 to 40%, particularly 10 to 35%. When there is too little content of BaO, it will become difficult to precipitate a barium feldspar crystal. On the other hand, if the content of BaO is too large, the amount of diopside crystals deposited tends to decrease, and as a result, the dielectric loss of the glass ceramic dielectric tends 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 out of the range, feldspar crystals are difficult to precipitate or vitrification is difficult.
  • the following components can be added to the crystalline glass powder.
  • ZnO is a component that facilitates vitrification, and its content is preferably 0 to 20%, particularly preferably 0.1 to 15%.
  • crystallinity will become weak and there exists a tendency for the precipitation amount of a diopside crystal to decrease. As a result, the dielectric loss of the glass ceramic dielectric tends to increase.
  • TiO 2 and ZrO 2 are components that improve 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%. When the content of TiO 2 is too large, the dielectric loss of the glass ceramic dielectric tends to be too large.
  • the content of ZrO 2 is preferably 0 to 15%, particularly preferably 0.1 to 13%. When ZrO 2 is too large, there is a tendency that the dielectric loss of the glass ceramic dielectric becomes too large.
  • SrO, Nb 2 O 5 , La 2 O 3 , Y 2 O 3 , P 2 O 5 , B 2 O 3 as long as the characteristics such as dielectric loss of the glass ceramic dielectric are not impaired.
  • Bi 2 O 3 , CuO, CeO 2 , MnO, Sb 2 O 3 , SnO or the like may be added up to 30% in total.
  • alkali metal components 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 is 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less. When the average particle diameter D 50 of the crystallizable glass powder is too large, pores are likely to occur in the glass ceramic dielectric.
  • the lower limit of the average particle diameter D 50 of the crystalline glass powder is not particularly limited, but is preferably 0.1 ⁇ m or more, particularly preferably 1 ⁇ m or more from the viewpoint of ease of handling and processing cost.
  • the particle diameter of the powder refers to a value measured by a laser diffraction scattering method.
  • a glass ceramic layer may be obtained by mixing and sintering filler powder in addition to crystalline glass powder.
  • the filler powder include alumina powder, cordierite powder, mullite powder, quartz powder, zircon powder, titania powder, zirconia powder and the like, or quartz glass powder. These may be used alone or in combination of two or more. Can be used.
  • Ceramic powder containing Al component As filler powder, Si and Ba components in the residual glass phase after diopside crystal precipitation react with Al component in 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 a small amount (for example, about 0.1 to 1% by mass) of a diopside or barium feldspar crystal as a crystal nucleus.
  • the mixing ratio of the crystalline glass powder and the filler powder is preferably 30 to 100% by mass of the crystalline glass powder, 0 to 70% by mass of the filler powder, 40 to 90% by mass of the crystalline glass powder, and 10 to 60% of the filler powder. More preferably, the crystalline glass powder is 45 to 80 mass%, the filler powder is 20 to 55 mass%, more preferably the crystalline glass powder is 50 to 70 mass%, and the filler powder is 30 to 50 mass%. It is particularly preferred. If the content of the filler powder is too large, it tends to be difficult to densify the glass ceramic dielectric.
  • the average particle diameter D 50 of the filler powder is preferably 0.01 to 100 ⁇ m, 0.1 to 50 ⁇ m, 0.5 to 20 ⁇ m, particularly 1 to 10 ⁇ m.
  • the average particle diameter D 50 of the filler powder is too small, penetration into the crystallizable glass powder, thermal expansion coefficient, toughness, dielectric constant, the effect of improving characteristics such as chemical resistance is hardly obtained.
  • the average particle diameter D 50 of the filler powder is too large, it hinders the flow of crystalline glass powder during firing, the pores are likely to occur in the glass ceramic dielectric.
  • a glass ceramic layer in which diopside crystals and feldspar crystals are precipitated as main crystals is obtained by heat-treating crystalline glass powder or a mixture of crystalline glass powder and filler powder at a temperature higher than the crystallization start temperature of crystalline glass powder. can get.
  • the content of diopside crystals in the glass ceramic layer is preferably 35% by mass or more, particularly preferably 40% by mass or more.
  • the content of the diopside crystal is too small, the dielectric loss tends to increase.
  • the upper limit is preferably 80% by mass or less, particularly preferably 70% by mass or less.
  • the content of feldspar crystals in the glass ceramic layer is preferably 20 to 65% by mass, 25 to 60% by mass, and particularly preferably 30 to 55% by mass.
  • the content of feldspar crystals is too small, the porosity in the glass ceramic layer increases, and as a result, the dielectric loss tends to increase.
  • the content of the feldspar crystal is too large, the diopside crystal is relatively decreased, so that the dielectric loss tends to increase or the mechanical strength tends to decrease.
  • the residual glass phase is preferably 0.5% by mass or more, particularly preferably 1% by mass or more. If the residual glass phase is too small, pores are easily generated in the glass ceramic layer. In addition, when there is too much content of a residual glass phase, since a diopside crystal and a feldspar crystal will decrease relatively and there exists a tendency for a dielectric loss to become large, an upper limit is 20 mass% or less, especially 10 mass% or less. Preferably there is.
  • the glass ceramic layer preferably has a porosity of 3% by volume or less, particularly 2% by volume or less.
  • porosity increases, when a glass ceramic dielectric is used as a circuit board, there is a tendency that the disconnection of the wiring tends to occur or the dielectric loss increases.
  • the thickness of the glass ceramic layer is preferably adjusted as appropriate in the range of, for example, 200 to 2000 ⁇ m, 300 to 1500 ⁇ m, and more preferably 500 to 1000 ⁇ m so as to obtain a desired mechanical strength.
  • the barrier layer is preferably made of an inorganic material, particularly preferably amorphous glass. If it does in this way, when the surface of a glass ceramic dielectric material is plated, it will become easy to suppress that the glass component contained in a glass ceramic layer changes in quality.
  • the barrier layer (amorphous glass layer) made of amorphous glass is made of, for example, a sintered body of amorphous glass powder.
  • Amorphous glass (non-crystalline glass powder) is preferably contained in mass% as a glass composition, and SiO 2 40% or more and B 2 O 3 15% or less. The reason for limiting the glass composition in this way will be described below. In the following description of the content of each component, “%” means “% by mass” unless otherwise specified.
  • SiO 2 is a component that forms a glass network.
  • the content of SiO 2 is preferably 40% or more, 42% or more, 45% or more, particularly 47% or more. If the content of SiO 2 is too small, the acid resistance is inferior, and the amorphous glass layer hardly functions as a barrier layer when forming metal wiring on the surface of the glass ceramic dielectric. Incidentally, the content of SiO 2 is too large, poor sinterability, it difficult to obtain a dense amorphous glass layer, functions as a barrier layer tends to decrease. Therefore, the content of SiO 2 is preferably 85% or less, 80% or less, 70% or less, and particularly preferably 60% or less.
  • B 2 O 3 is a component that significantly improves the meltability by lowering the melting temperature, and has the effect of improving the fluidity of the glass powder during sintering for forming an amorphous glass layer.
  • the content of B 2 O 3 is preferably 15% or less, 12% or less, 10% or less, and particularly preferably 8% or less.
  • the content of B 2 O 3 is preferably 1% or more, 2% or more, particularly 3% or more.
  • the amorphous glass layer can contain the following components.
  • Al 2 O 3 is a component that improves the acid resistance of the amorphous glass layer.
  • the content of Al 2 O 3 is preferably 0 to 25%, 0.1 to 20%, 1 to 15%, particularly 2 to 10%. When the content of Al 2 O 3 is too large, there is a tendency that the melting is lowered.
  • MgO, CaO, SrO and BaO are components that lower the melting temperature to improve the meltability and lower the softening point.
  • the total amount of these components is preferably 0 to 45%, 0.1 to 45%, particularly 1 to 40%. When there is too much total amount of these components, acid resistance will fall easily.
  • the content of each component of MgO, CaO, SrO and BaO is preferably 0 to 35%, 0.1 to 33%, particularly 1 to 30%, respectively. When there is too much content of these components, there exists a tendency for acid resistance to fall.
  • ZnO is a component that improves the meltability by lowering the melting temperature.
  • the content of ZnO is preferably 0 to 10%, 0.1 to 7%, particularly 1 to 5%. When there is too much content of ZnO, there exists a tendency for acid resistance to fall.
  • P 2 O 5 , La 2 O 3 , Ta 2 O 5 , TeO 2 , TiO 2 , Nb 2 O 5 , Gd 2 O 3 , Y 2 O 3 , CeO 2 , Sb 2 O 3 , SnO 2 , Bi 2 O 3 , As 2 O 3, ZrO 2, etc. may each be contained in a range of 15% or less, further 10% or less, particularly 5% or less, and a total amount of 30% or less.
  • the alkali metal component Li 2 O, Na 2 O , K 2 O , etc.
  • the alkali metal component to reduce significantly the acid resistance of the amorphous glass layer preferably substantially free.
  • the softening point of the glass constituting the amorphous glass layer is preferably 700 to 1000 ° C., particularly preferably 750 to 900 ° C. If the softening point is too low, it will flow excessively during firing, making it difficult to obtain a barrier layer having a uniform thickness. As a result, the function as a barrier layer may be reduced. On the other hand, if the softening point is too high, it is difficult to obtain a dense barrier layer, and the function as a barrier layer may be reduced.
  • the thickness of the barrier layer is preferably 30 ⁇ m or more, 50 ⁇ m or more, particularly 80 ⁇ m or more so as to sufficiently perform its function. If the thickness of the barrier layer is too large, the dielectric constant and dielectric loss as a whole of the glass-ceramic dielectric increases, and therefore it is preferably 300 ⁇ m or less, 200 ⁇ m or less, particularly 150 ⁇ m or less.
  • FIG. 2 is a schematic cross-sectional view showing an embodiment of a method for producing a glass ceramic dielectric of the present invention.
  • a green sheet 2 ′ for a glass ceramic layer containing a crystalline glass powder and a green sheet 3 ′ for a barrier layer (amorphous glass layer) containing an amorphous glass powder are prepared by a known green sheet method. And prepare. Specifically, a glass paste is prepared by adding and kneading a vehicle containing a resin binder or an organic solvent to a crystalline glass powder or an amorphous glass powder as a raw material, and the obtained glass paste is PET. Each green sheet is obtained by sheet-forming with a doctor blade on base materials, such as a (polyethylene terephthalate) film.
  • the thickness of the green sheet may be appropriately selected according to the thickness of the target glass ceramic layer 2 or barrier layer 3, but is usually about 100 to 250 ⁇ m, more preferably about 120 to 200 ⁇ m. If necessary, each green sheet may be mechanically processed to provide through holes for forming conductors and electrodes.
  • the obtained glass ceramic layer green sheet 2 ′ and barrier layer green sheet 3 ′ are laminated to obtain a laminate.
  • FIG. 2 (a) three green sheets 2 'for glass ceramic layers are laminated, and one green sheet 3' for barrier layers is laminated on both sides to produce a laminate 1 '.
  • the number of glass ceramic layer green sheets 2 ' may be appropriately selected according to the desired thickness of the glass ceramic layer 2, but is usually 2 to 10, more preferably 3 to 7.
  • the number of the barrier layer green sheets 3 ′ may be one, or two or more.
  • the laminate 1 ′ is fired while being sandwiched between the pair of restraint sheets 4 (FIG. 2B).
  • the glass ceramic layer green sheet 2 ′ and the barrier layer green sheet 3 ′ become the glass ceramic layer 2 and the barrier layer (amorphous glass layer) 3, respectively.
  • the glass ceramic dielectric 1 in which the barrier layers 3 are formed on both principal surfaces of the glass ceramic layer 2 is obtained ((c) in FIG. 2).
  • the restraint sheet 4 plays a role of suppressing shrinkage in the surface direction of the laminated body 1 ′ during firing.
  • the constraining sheet 4 for example, a green sheet containing ceramic powder such as alumina powder can be used.
  • the ceramic powder contained in the constraining sheet 4 may adhere to the surface of the barrier layer 3.
  • the ceramic powder has characteristics such as dielectric loss of the glass ceramic dielectric 1. Since it has almost no influence, it is not always necessary to remove it by polishing or the like.
  • the firing temperature is preferably a temperature at which the crystalline glass powder contained in the glass ceramic layer green sheet 2 'is sufficiently crystallized. Specifically, the firing temperature is equal to or higher than the crystallization temperature of the crystalline glass powder, more than (crystallization start temperature of the crystalline glass powder + 50 ° C.) or more, particularly (crystallization start temperature of the crystalline glass powder + 100 ° C.) or more. (Sintering condition A) is preferable. In this way, it is possible to obtain a glass ceramic dielectric 1 that satisfies characteristics such as desired dielectric loss.
  • the firing temperature is preferably a temperature at which the amorphous glass powder contained in the barrier layer green sheet 3 ′ is sufficiently softened and fluidized to be sintered.
  • the firing temperature is equal to or higher than the softening point of the amorphous glass powder, more than (softening point of the amorphous glass powder + 50 ° C.), and particularly higher than (softening point of the amorphous glass powder + 100 ° C.). It is preferable (firing condition B). In this way, it is possible to obtain the glass ceramic dielectric 1 in which the barrier layer 3 having desired characteristics is formed.
  • the firing temperature preferably satisfies both the firing condition A and the firing condition B described above. Thereby, it is possible to obtain the glass ceramic dielectric 1 having desired characteristics.
  • the specific firing temperature is preferably 800 to 1000 ° C., 800 to 950 ° C., and particularly preferably 850 to 900 ° C.
  • a circuit board is obtained by performing a plating process on the surface of the barrier layer 3 in the obtained glass ceramic dielectric 1 to form a metal wiring (not shown).
  • Example 1 Production of Green Sheet for Glass Ceramic Layer As a glass composition, it is mass%, SiO 2 43.4%, Al 2 O 3 4%, BaO 28%, CaO 10%, MgO 14.5%, CuO 0.1.
  • the raw material powder was prepared so as to be%, melted at 1550 ° C., and then molded and cooled to produce crystalline glass.
  • the obtained crystalline glass was pulverized to produce a crystalline glass powder (crystallization start temperature of 890 ° C.) having an average particle diameter D 50 of 2 ⁇ m.
  • the glass composition is in mass%, SiO 2 50%, B 2 O 3 5%, Al 2 O 3 6%, ZnO 2%, CaO 12%.
  • a raw material powder was prepared so that the BaO would be 25%, melted at 1200 to 1700 ° C., and then molded and cooled to produce an amorphous glass.
  • the obtained amorphous glass was pulverized to produce an amorphous glass powder (softening point 850 ° C.) having an average particle diameter D 50 of 2 ⁇ m.
  • the thickness is 150 ⁇ m by the doctor blade method.
  • a green sheet for a barrier layer was obtained.
  • Example 2 (A) Production of Green Sheet for Glass Ceramic Layer A green sheet for a glass ceramic layer having a thickness of 150 ⁇ m was obtained in the same manner as in Example 1.
  • the glass composition is in mass%, SiO 2 43%, B 2 O 3 5%, Al 2 O 3 6%, ZnO 7%, CaO 8%.
  • a raw material powder was prepared so as to be 8% SrO and 23% BaO, melted at 1200 to 1700 ° C., and then molded and cooled to produce an amorphous glass.
  • the obtained amorphous glass was pulverized to produce an amorphous glass powder (softening point 800 ° C.) having an average particle diameter D 50 of 1.5 ⁇ m.
  • the thickness is 150 ⁇ m by the doctor blade method.
  • a green sheet for an amorphous glass layer was obtained.
  • a barrier layer (amorphous glass layer) was formed on both main surfaces of the glass ceramic layer (thickness 300 ⁇ m) in the same manner as in Example 1 using each of the green sheets obtained above. ) (Thickness of 100 ⁇ m) was obtained to obtain a glass ceramic dielectric.
  • the precipitated crystal in the glass ceramic layer was identified by a powder X-ray diffractometer (Rigaku RINT2100, Inc.), it was confirmed that diopside and barium feldspar were precipitated.
  • the glass ceramic dielectric of the present invention has excellent acid resistance due to the formation of a barrier layer (amorphous glass layer) on the surface of the glass ceramic layer. I understand. Therefore, it is considered that when the metal wiring is formed by the plating process, the alteration of the glass ceramic layer is suppressed, and as a result, characteristics such as dielectric loss are unlikely to deteriorate.
  • a barrier layer amorphous glass layer
  • the glass ceramic dielectric of the present invention is suitable for circuit boards for microwaves and the like.

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  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un corps diélectrique en vitrocéramique capable d'empêcher la détérioration d'un composant en verre lorsque le câblage métallique est formé sur la surface de celui-ci. Le corps diélectrique en vitrocéramique est caractérisé en ce qu'il est pourvu d'une couche de vitrocéramique et de couches barrières formées sur les surfaces principales de celle-ci.
PCT/JP2019/007565 2018-03-07 2019-02-27 Corps diélectrique en vitrocéramique WO2019172042A1 (fr)

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JP2019015504A JP7348587B2 (ja) 2018-03-07 2019-01-31 ガラスセラミック誘電体
JP2019-015504 2019-01-31

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Citations (6)

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JP2006137618A (ja) * 2004-11-10 2006-06-01 Sanyo Electric Co Ltd 誘電体セラミック基板
JP2007015878A (ja) * 2005-07-06 2007-01-25 Murata Mfg Co Ltd セラミック組成物、セラミック基板および電子部品
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JP2012144417A (ja) * 2010-11-17 2012-08-02 Nippon Electric Glass Co Ltd 結晶性ガラス粉末
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JP2006137618A (ja) * 2004-11-10 2006-06-01 Sanyo Electric Co Ltd 誘電体セラミック基板
JP2007015878A (ja) * 2005-07-06 2007-01-25 Murata Mfg Co Ltd セラミック組成物、セラミック基板および電子部品
JP2012111681A (ja) * 2010-11-04 2012-06-14 Nippon Electric Glass Co Ltd 半導体封入用無鉛ガラス及び半導体封入用外套管
JP2012144417A (ja) * 2010-11-17 2012-08-02 Nippon Electric Glass Co Ltd 結晶性ガラス粉末
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