Classifications

• • 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
  • 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
  • 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
  • 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
  • C04B35/14—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 silica
• • 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
  • H01B3/08—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

Definitions

• the present invention relates to a glass-ceramic dielectric material having a low dielectric constant, a dielectric loss tangent, and a high coefficient of thermal expansion in a high frequency region of 20 GHz or more, a sintered body, and a circuit member for high frequency.
• Alumina ceramic is widely used as a wiring board and circuit parts.
• Alumina ceramic has a high relative permittivity of 10, so that it has a drawback that the signal processing speed is slow.
• tungsten having a high melting point must be used as the conductor material, there is a drawback that the conductor loss becomes high.
• a glass-ceramic dielectric material consisting of glass powder and ceramic powder
• the sintered body is used as a dielectric layer.
• a glass-ceramic dielectric material using a glass powder made of alkaline borosilicate glass has a relative permittivity of 6 to 8, which is lower than that of an alumina ceramic material.
• a metal material having a low melting point such as Ag and Cu, which has a low conductor loss, and has an advantage that these can be used as an inner layer conductor (Patent Document). See 1 and 2).
• the frequency band used has become as high as 20 GHz or more, and in the high frequency region, the glass ceramic dielectric material is further increased. There is a strong demand for low dielectric loss tangent.
• the transmission loss of an electromagnetic wave in an electronic circuit is proportional to the product of the square root of the permittivity of the circuit board, the dielectric loss tangent, and the frequency of the electromagnetic wave.
• the glass-ceramic dielectric material disclosed in the above patent document has a problem that the dielectric property in a high frequency region, particularly the dielectric loss tangent is not sufficiently low, so that the transmission loss becomes large.
• the conventional glass-ceramic dielectric material has a low coefficient of thermal expansion of 4 to 7 ppm / ° C., when a heat cycle is applied after soldering to a resin motherboard, distortion occurs due to the difference in thermal expansion, resulting in disconnection or cracking. There was a problem that the problem occurred.
• An object of the present invention is to provide a glass-ceramic dielectric material, a sintered body, and a circuit member for high frequency, which can be fired at a temperature of 1000 ° C. or lower and have a low dielectric property and a high coefficient of thermal expansion in a high frequency region at 20 GHz or higher. It is to be.
• the present inventor has found that the above technical problem can be solved by combining a glass powder having a specific glass composition and an ⁇ -quartz powder, and proposes the present invention. It is a thing. That is, the glass-ceramic dielectric material of the present invention is a glass-ceramic dielectric material containing glass powder and ⁇ -quartz powder, and the content of glass powder is 60 to 80% by mass and the content of ⁇ -quartz powder is 20. -40% by mass, and the glass powder has a glass composition of 238-50 %, MgO 10-20%, CaO 15-25%, ZnO 15-25%, Li 2O + Na 2 by mass%. It is characterized by containing O + K 2 O 0 to less than 2%.
• “Li 2 O + Na 2 O + K 2 O” refers to the total amount of Li 2 O, Na 2 O and K 2 O.
• the sintered body of the present invention is a sintered body obtained by sintering the above-mentioned glass-ceramic dielectric material, has a thermal expansion coefficient of 9 to 11 ppm / ° C., and has a relative permittivity of 5.5 to 28 GHz. It is preferably 5.9 and the dielectric loss tangent at 28 GHz is preferably 0.0010 to 0.0020.
• the "coefficient of thermal expansion” refers to a value measured by a thermomechanical analyzer in a temperature range of 30 to 380 ° C.
• "Relative permittivity” and "dielectric loss tangent” refer to values measured at a measurement temperature of 25 ° C. and a frequency of 28 GHz based on a method for measuring microwave dielectric properties of a fine ceramic substrate (JIS R1641).
• the high-frequency circuit member of the present invention is a high-frequency circuit member having a dielectric layer, and the dielectric layer is preferably the above-mentioned sintered body.
• the glass-ceramic dielectric material of the present invention can be fired at a low temperature of 1000 ° C. or lower, and a metal material having a low melting point such as Ag or Cu can be used as an inner layer conductor. Moreover, it has a low dielectric property in a high frequency region of 20 GHz or higher, and has a high coefficient of thermal expansion of 9 to 10 ppm / ° C. Therefore, the glass-ceramic dielectric material of the present invention is suitable as a high-frequency circuit member to be mounted on a resin motherboard.
• the content of glass powder is 60 to 80% by mass
• the content of ⁇ -quartz powder is 20 to 40% by mass
• the content of glass powder is 65 to 75% by mass
• ⁇ The content of the quartz powder is preferably 25 to 35% by mass.
• ceramic powder other ceramic powder may be introduced in addition to ⁇ -quartz.
• ⁇ -cristobalite, ⁇ -tridimite, mullite, zirconia, and cordierite can be used.
• the glass powder has a glass composition of SiO 2 38 to 50%, MgO 10 to 20%, CaO 15 to 25%, ZnO 15 to 25%, Li 2 O + Na in terms of glass composition.
• 2 O + K 2 O Contains less than 0-2%. The reason for limiting the content range of each component as described above will be described below.
• SiO 2 is a component that serves as a network former for glass.
• the content of SiO 2 is large, the firing temperature tends to be high, and there is a risk that Ag or Cu cannot be used as a conductor or an electrode.
• the content of SiO 2 is low, vitrification becomes difficult. Moreover, it becomes difficult to obtain low dielectric properties. Therefore, the content of SiO 2 is preferably 38 to 50%, particularly preferably 40 to 48%.
• MgO, CaO and ZnO all have the effect of lowering the softening point of the glass powder. In each region from the limited range to a large amount, vitrification becomes difficult, and in a region less than the limited range, the softening point becomes too high. Further, if it is out of the content range, the dielectric loss tangent tends to be 0.0020 or more.
• Alkali metal oxides are components that lower the firing temperature, but increase the dielectric loss tangent in the high frequency region. Therefore, the content of Li 2 O + Na 2 O + K 2 O is less than 2%, preferably less than 1%, less than 0.5%, particularly less than 0.1%.
• the content of Li 2 O is preferably less than 0.5%, particularly less than 0.1%.
• the content of Na 2 O is preferably less than 0.5%, particularly less than 0.1%.
• the content of K2O is preferably less than 0.5%, particularly less than 0.1%.
• components such as B 2 O 3 and Al 2 O 3 may be added up to 3% each as long as the dielectric properties are not impaired.
• the sintered body of the present invention is a sintered body obtained by sintering the above-mentioned glass-ceramic dielectric material.
• the coefficient of thermal expansion of the sintered body is preferably 9 to 11 ppm / ° C. If the coefficient of thermal expansion of the sintered body is too low, distortion is likely to occur due to the difference in thermal expansion when a heat cycle is applied after soldering to the resin motherboard.
• the relative permittivity at 28 GHz is preferably 5.5 to 5.9, and the dielectric loss tangent at 28 GHz is preferably 0.0010 to 0.0020.
• the relative permittivity and the dielectric loss tangent are high, the loss of the transmission signal tends to be large, and the speed of signal processing tends to be slow.
• a slurry is prepared by adding a predetermined amount of a binder, a plasticizer and a solvent to the above-mentioned mixed powder of glass powder and ⁇ -quartz powder.
• a binder for example, polyvinyl butyral resin, methacrylic acid resin and the like
• the plasticizer for example, dibutyl phthalate and the like
• the solvent for example, toluene, methyl ethyl ketone and the like are suitable.
• the above slurry is molded into a green sheet by the doctor blade method, dried, cut to a predetermined size, and then mechanically processed to form a via hole, for example, a low resistance to be a silver conductor or an electrode.
• the metallic material is printed on the via hole and the surface of the green sheet.
• a plurality of such green sheets are laminated and integrated by thermocompression bonding.
• a sintered body can be obtained by firing the laminated green sheet.
• the sintered body thus produced has conductors and electrodes inside and on the surface.
• the firing temperature is preferably 1000 ° C. or lower, particularly 800 to 950 ° C.
• An example of using a green sheet has been given as a method for producing a sintered body, but the present invention is not limited to this, and various methods such as producing granules containing a binder and performing press molding are applied. be able to.
• the circuit member for high frequency of the present invention is manufactured by forming a coil by wiring or connecting a chip of a Si-based or GaAs-based semiconductor element on the surface of the sintered body manufactured as described above. Can be done.
• Table 1 shows Examples (Samples Nos. 1 to 4) and Comparative Examples (Samples Nos. 5 and 6) of the present invention.
• R 2 O in the table refers to Li 2 O + Na 2 O + K 2 O.
• Each sample was prepared as follows. First, glass raw materials of various oxides are mixed so as to have the glass composition shown in the table, mixed uniformly, placed in a platinum crucible, melted at 1400 to 1500 ° C. for 3 to 8 hours, and melted by a water-cooled roller. The glass was formed into a thin plate. Next, the obtained glass film was roughly crushed, alcohol was added, and wet pulverized by a ball mill, and the mixture was classified so that the average particle size was 1.5 to 3 ⁇ m to obtain a glass powder.
• the above glass powder was uniformly mixed with the amount of ceramic powder (average particle size 2 ⁇ m) shown in the table to obtain a glass-ceramic dielectric material.
• the relative permittivity and dielectric tangent After sintering the green sheet molded product at the firing temperature shown in the table, it is processed to a size of 25 mm ⁇ 50 mm ⁇ 0.1 mm to make a measurement sample, and then fine ceramics. It was measured at a measurement temperature of 25 ° C. and a frequency of 28 GHz based on a method for measuring the microwave dielectric characteristics of a substrate (JIS R1641).
• the coefficient of thermal expansion is measured by a thermomechanical analyzer in the temperature range of 30 to 380 ° C.
• sample No. In Nos. 1 to 4 the relative permittivity at a frequency of 28 GHz was 5.5 to 5.9, the dielectric loss tangent at a frequency of 28 GHz was 0.0012 to 0.0019, and the dielectric properties in the high frequency region were low.
• the firing temperature was as low as 930 ° C. or lower, and the coefficient of thermal expansion was as high as 9.2 to 10.8 ppm / ° C.
• sample No. In No. 5 since the amount of alkali metal oxide in the glass powder was large, the dielectric loss tangent at a frequency of 28 GHz was 0.0055, and the dielectric property in the high frequency region was high.
• Sample No. In No. 6 since the ceramic powder was alumina, the relative permittivity was as high as 7.9 and the coefficient of thermal expansion was as low as 8.5 ppm / ° C.

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• Chemical & Material Sciences (AREA)
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• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Geochemistry & Mineralogy (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Inorganic Chemistry (AREA)
• Manufacturing & Machinery (AREA)
• Structural Engineering (AREA)
• Inorganic Insulating Materials (AREA)
• Glass Compositions (AREA)
• Compositions Of Oxide Ceramics (AREA)

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• 2020
  • 2020-09-23 JP JP2020158825A patent/JP2022052429A/ja active Pending
• 2021
  • 2021-08-19 CN CN202180057327.0A patent/CN116057019A/zh active Pending
  • 2021-08-19 KR KR1020237003560A patent/KR20230072471A/ko active Search and Examination
  • 2021-08-19 WO PCT/JP2021/030410 patent/WO2022064906A1/ja active Application Filing
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