WO2020085148A1 - Ceramic green body - Google Patents

Ceramic green body Download PDF

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Publication number
WO2020085148A1
WO2020085148A1 PCT/JP2019/040478 JP2019040478W WO2020085148A1 WO 2020085148 A1 WO2020085148 A1 WO 2020085148A1 JP 2019040478 W JP2019040478 W JP 2019040478W WO 2020085148 A1 WO2020085148 A1 WO 2020085148A1
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Prior art keywords
mass
less
ceramic
content
ceramic base
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PCT/JP2019/040478
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French (fr)
Japanese (ja)
Inventor
浩 河野
孝友 緒方
間瀬　淳
Original Assignee
日本碍子株式会社
Ｎｇｋエレクトロデバイス株式会社
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Application filed by 日本碍子株式会社, Ｎｇｋエレクトロデバイス株式会社 filed Critical 日本碍子株式会社
Priority to CN202310527850.6A priority Critical patent/CN116715512A/en
Priority to CN201980048264.5A priority patent/CN112601727A/en
Priority to JP2020553197A priority patent/JP7108704B2/en
Publication of WO2020085148A1 publication Critical patent/WO2020085148A1/en

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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
    • 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
    • C04B35/10—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 aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/404—Refractory metals
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/02—Containers; Seals
    • H01L23/06—Containers; Seals characterised by the material of the container or its electrical properties
    • H01L23/08—Containers; Seals characterised by the material of the container or its electrical properties the material being an electrical insulator, e.g. glass

Definitions

  • the present invention relates to a ceramic substrate.
  • Patent Document 1 as an example of a ceramic base, 90% by mass or more of Al 2 O 3 , 1 to 6% by mass of SiO 2, and 2 to 8% by mass of MnAl 2 O 4 in terms of Mn 2 O 3 are included.
  • An insulating substrate containing 2 mass% or less of Mo is disclosed. It is said that the insulating substrate described in Patent Document 1 preferably contains Mg in a proportion of 0.1 to 3 mass% in terms of oxide in order to improve the stability of strength.
  • Patent Document 2 as an example of a ceramic substrate, Al 2 O 3 as a main component, 3 to 7.5 mass% SiO 2 , 2 to 5 mass% Mn in terms of Mn 2 O 3 , and MgO.
  • An insulating substrate containing 0.3 to 0.7 mass% of Mg in terms of conversion and 0.3 to 0.7 mass% of Mo in terms of MoO is disclosed.
  • Patent Document 3 Al is 89.0 to 92.0 mass% in terms of Al 2 O 3 , Si is 2.0 to 5.0 mass% in terms of SiO 2 , and Mn is 2.0 to 5 in terms of MnO. Disclosed is a ceramic base containing 0.0 mass% of Mg, 0 to 2.0 mass% of Mg in terms of MgO, and 0.05 to 2.0 mass% of Zr in terms of ZrO 2 .
  • Patent Documents 1 to 3 have a problem that dimensional variations easily occur.
  • the present inventors have made a balance except for Al 2 O 3 as a main component, SiO 2 and MnO as a sintering aid, and Mo or / and Cr 2 O 3 as a colorant.
  • a new finding was obtained that the content of P has an influence on dimensional variation.
  • the present invention aims to provide a ceramic base capable of suppressing dimensional variations.
  • the ceramic substrate according to the present invention contains Al 2 O 3 , SiO 2 and MnO as essential components, and contains at least one of Mo and Cr 2 O 3 as optional components.
  • the content of Al 2 O 3 is 82.0% by mass or more and 95.0% by mass or less
  • the content of SiO 2 is 3.0% by mass or more and 8.0% by mass or less
  • the content of MnO is 2.0% by mass or more and 6.0% by mass or less
  • the sum of the content of Mo in terms of MoO 3 and the content of Cr 2 O 3 is 4.0% by mass or less. Yes, and the content of the balance is less than 0.1% by mass.
  • the ceramic base is a composition obtained by sintering a green sheet formed by molding a ceramic material powder into a tape shape or a compact formed by compacting a ceramic material powder.
  • the ceramic substrate according to the present embodiment includes a ceramic package for encapsulating an oscillator such as a crystal oscillator, a ceramic package for encapsulating a semiconductor element such as a CMOS image sensor, or a ceramic package for encapsulating an optical semiconductor element. Suitable for use in various ceramic packages.
  • the ceramic body according to the present embodiment contains Al 2 O 3 (alumina) as a main component, and SiO 2 (silica) and MnO (manganese oxide) as sintering aids as essential components.
  • the ceramic base contains at least one of Mo (molybdenum) and Cr 2 O 3 (chromium oxide) as an optional component as a colorant.
  • the ceramic base may contain only Mo as a colorant, may contain only Cr 2 O 3 , or may contain both Mo and Cr 2 O 3 , Furthermore, it may not contain both Mo and Cr 2 O 3.
  • Mo molecular weight
  • Cr 2 O 3 chromium oxide
  • the ceramic base may contain Mo as a colorant, at least a part of Mo may be present as a metal, or at least a part of Mo may be present in an oxide form (for example, MoO 3 ). Good.
  • the content of each component that constitutes the ceramic base is as follows.
  • ⁇ Al 2 O 3 82.0 mass% or more and 95.0 mass% or less ⁇ SiO 2 : 3.0 mass% or more and 8.0 mass% or less ⁇ MnO: Sum of the amount of content and Cr 2 O 3 of Mo in 2.0% to 6.0% by mass ⁇ MoO 3 terms: 4.0 mass% or less-The balance: Less than 0.1% by mass
  • the content of the balance other than Al 2 O 3 , SiO 2 , MnO and the colorant (Mo or / and Cr 2 O 3 ) is suppressed to less than 0.1% by mass. Therefore, each component is uniformly sintered in a dispersed state without segregation. Therefore, in the ceramic base material according to the present embodiment, dimensional variation is suppressed.
  • the content of the balance of the ceramic base is suppressed to less than 0.1% by mass, the respective components are uniformly sintered in a dispersed state without segregation. It is possible to suppress local generation of the melting point region. Therefore, it is possible to prevent the ceramic base material from sticking to the firing setter.
  • the respective components are uniformly sintered in a dispersed state without segregation, so that in the backside region on the firing setter side.
  • the timing at which the glass component melts can be matched with the timing at which the glass component melts in the front side region opposite to the firing setter. Therefore, it is possible to suppress the ceramic base from warping in the thickness direction.
  • the content of the balance in the ceramic base is more preferably less than 0.05% by mass. As a result, the dimensional variation of the ceramic base can be further suppressed.
  • the content of the balance in the ceramic body is particularly preferably 0% by mass. As a result, it is possible not only to further suppress the dimensional variation of the ceramic base material, but also to further suppress the sticking of the ceramic base material to the firing setter.
  • the ratio of the content of SiO 2 to the content of MnO is not particularly limited, but it is preferably 0.8 or more and 3.5 or less. Within this range, the precipitation of Mn 3 Al 2 Si 3 O 12 in the ceramic matrix can be suppressed, so that the occurrence of color unevenness due to the precipitation of Mn 3 Al 2 Si 3 O 12 can be reduced. . Furthermore, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the ratio of the content of SiO 2 to the content of MnO is particularly preferably 0.8 or more and 2.1 or less. Thereby, the bending strength of the ceramic base can be particularly improved.
  • the ratio of the content of SiO2 to the content of MnO is particularly preferably 1.9 or more and 3.5 or less.
  • the ceramic matrix contains a crystalline phase and a glass phase.
  • the crystal phase includes an Al 2 O 3 crystal phase as a main crystal phase and a Mo crystal phase as a sub crystal phase.
  • the crystal phase may include a crystal phase other than the Al 2 O 3 crystal phase and the Mo crystal phase (hereinafter, referred to as “residual crystal phase”).
  • the crystal phase includes an Al 2 O 3 crystal phase as a main crystal phase.
  • the crystal phase may include the remaining crystal phase in addition to the Al 2 O 3 crystal phase.
  • the crystal phase may contain only one kind of crystal phase or a plurality of kinds of crystal phases as the remaining crystal phase.
  • the main peak intensity of the X-ray diffraction pattern of the remaining crystal phase is the main peak of the X-ray diffraction pattern of the Al 2 O 3 crystal phase.
  • the strength is preferably 0.5% or less.
  • the bending strength of the ceramic base is set according to the characteristics required for the ceramic package to which the ceramic base is applied. For example, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the bending strength of the ceramic base is preferably 700 MPa or more. Further, when the ceramic base is applied to a ceramic package that seals an optical semiconductor element, the bending strength of the ceramic base is preferably 390 MPa or more. In the present embodiment, “bending strength” means three-point bending strength, and is a value measured at room temperature in accordance with JISR1601 (bending test method for fine ceramics).
  • the relative permittivity of the ceramic base is set according to the characteristics required for the ceramic package to which the ceramic base is applied.
  • the relative permittivity of the ceramic base is not particularly limited.
  • the relative permittivity of the ceramic base is preferably 8.0 or more and 9.0 or less.
  • the porosity of the ceramic substrate is set according to the characteristics required for the ceramic package to which the ceramic substrate is applied. For example, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the porosity of the ceramic base is preferably 3% or less. When the ceramic base is applied to a ceramic package that seals an optical semiconductor element, the porosity of the ceramic base is preferably 3% or more and 8% or less.
  • the "porosity" is a value obtained by photographing a polished ceramic cross section with an electron microscope and binarizing it with image processing software.
  • FIG. 1 is a sectional view of the first ceramic package 100.
  • the first ceramic package 100 includes an insulating substrate 1, a plurality of conductor layers 2, a metallization layer 3, a crystal oscillator 4, a CMOS image sensor 6, a plating layer 8 and a lid 10.
  • the first ceramic package 100 encapsulates the crystal unit 4 and the CMOS image sensor 6.
  • the insulating substrate 1 is composed of the ceramic base described above.
  • the content of each component forming the insulating substrate 1 is as follows.
  • ⁇ Al 2 O 3 82.0 mass% or more and 95.0 mass% or less ⁇ SiO 2 : 3.0 mass% or more and 8.0 mass% or less ⁇ MnO: Sum of the amount of content and Cr 2 O 3 of Mo in 2.0% to 6.0% by mass ⁇ MoO 3 terms: 4.0 mass% or less-The balance: Less than 0.1% by mass
  • the insulating substrate 1 since the content of the balance is suppressed to less than 0.1% by mass, the respective components are uniformly sintered in a dispersed state without segregation. As a result, dimensional variation is suppressed.
  • the bending strength of the insulating substrate 1 is preferably 700 MPa or more.
  • the porosity of the insulating substrate 1 is preferably 3% or less.
  • the insulating substrate 1 has a bottom portion 1a and a side wall portion 1b.
  • the side wall portion 1b is arranged on the outer edge of the bottom portion 1a.
  • the bottom portion 1a and the side wall portion 1b may be integrally formed.
  • Each conductor layer 2 is provided so as to penetrate the bottom portion 1a.
  • the metallized layer 3 is arranged on the upper surface of the side wall portion 1b.
  • the metallized layer 3 is formed in a ring shape.
  • the metallized layer 3 can be formed by using W or Mo as a main component as a conductor and adding a ceramic component to it.
  • the insulating substrate 1 according to the present embodiment and the metallized layer 3 are produced by simultaneous firing in a reducing atmosphere containing hydrogen, nitrogen and water vapor.
  • the crystal unit 4 is an example of a unit.
  • the crystal unit 4 is connected to the conductor layer 2 via the conductive adhesive 5.
  • the CMOS image sensor 6 is an example of a semiconductor element.
  • the CMOS image sensor 6 is connected to the conductor layer 2 via the wire bonding 7.
  • the plating layer 8 is arranged on the upper surface of the metallization layer 3.
  • the plating layer 8 is formed in a ring shape.
  • the lid 10 is arranged on the plating layer 8 with the eutectic Ag—Cu brazing material 9 interposed therebetween.
  • the lid 10 closes the opening of the side wall portion 1b.
  • the lid 10 can be made of a metal material.
  • FIG. 2 is a sectional view of the second ceramic package 200.
  • the second ceramic package 200 includes a base 11, an electronic cooling element 12, an optical semiconductor element 13, a multilayer circuit board 14, a frame 15, a seal ring 16, a lid 17, a transparent window member 18, a pipe 19, and an optical fiber connection.
  • the tube 20a and the optical fiber 20b are provided.
  • the second ceramic package 200 seals the optical semiconductor element 13.
  • the second ceramic package 200 is a so-called optical module.
  • the base 11 is formed in a plate shape.
  • the base 11 is made of a material having a high thermal conductivity such as copper tungsten.
  • the electronic cooling element 12 is arranged on the base 11.
  • the optical semiconductor element 13 is arranged on the electronic cooling element 12.
  • the multilayer circuit board 14 is arranged on the outer edge of the base 11.
  • the multilayer circuit board 14 is provided with input terminals 30a and 30b exposed to the outside of the package and output terminals 31a and 31b exposed to the inside of the package.
  • a positive phase signal is externally input to the input terminal 30a.
  • a negative phase signal having a negative phase and a positive phase signal is input to the input terminal 30b.
  • the positive phase signal input to the input terminal 30a is output to the optical semiconductor element 13 from the output terminal 31a via the bonding wire 13a.
  • the negative phase signal input to the input terminal 30b is output to the optical semiconductor element 13 from the output terminal 31b via the bonding wire 13b.
  • the positive phase signal and the negative phase signal are collectively referred to as a differential signal.
  • the frame body 15 is arranged on the multilayer circuit board 14.
  • the seal ring 16 is arranged on the upper surface of the frame body 15.
  • the seal ring 16 is a member for welding the lid 17.
  • Each of the seal ring 16 and the lid 17 can be made of Kovar in which iron is mixed with nickel and cobalt.
  • a pipe 19 is fitted into a hole 19a formed between the multilayer circuit board 14 and the frame 15.
  • the pipe 19 houses the translucent window member 18.
  • the translucent window member 18 is made of sapphire, glass, or the like.
  • An optical fiber connecting pipe 20a is connected to the pipe 19.
  • Each of the pipe 19 and the optical fiber connecting pipe 20a can be configured by Kovar or the like.
  • An optical fiber 20b is fixed to the optical fiber connecting tube 20a.
  • FIG. 3 is an exploded perspective view showing the configuration of the multilayer circuit board 14.
  • the multilayer circuit board 14 includes six layers of circuit boards 14a to 14f, first signal lines 21a, 22a, 23a, second signal lines 21b, 22b, 23b, ground layers 24a, 24b, 24c, ground vias 25a, 25b, 25c. , And ground terminals 26a, 26b, 26c.
  • Each of the circuit boards 14a to 14f is composed of the above-mentioned ceramic base.
  • the content of each component constituting each circuit board 14a to 14f is as follows.
  • ⁇ Al 2 O 3 82.0 mass% or more and 95.0 mass% or less ⁇ SiO 2 : 3.0 mass% or more and 8.0 mass% or less ⁇ MnO: Sum of the amount of content and Cr 2 O 3 of Mo in 2.0% to 6.0% by mass ⁇ MoO 3 terms: 4.0 mass% or less-The balance: Less than 0.1% by mass
  • each of the circuit boards 14a to 14f since the content of the balance is suppressed to less than 0.1% by mass, the respective components are uniformly baked without being segregated. By being tied, dimensional variation is suppressed.
  • the relative permittivity of each of the circuit boards 14a to 14f is preferably 8.0 or more and 9.0 or less.
  • the bending strength of each of the circuit boards 14a to 14f is preferably 390 MPa or more.
  • the porosity of each of the circuit boards 14a to 14f can be set to 3% or more and 8% or less.
  • the 6-layer circuit boards 14a to 14f are stacked in this order.
  • the above-mentioned input terminals 30a and 30b and output terminals 31a and 31b are provided on the sixth-layer circuit board 14f.
  • the input-side via connection portion 21a of the first signal lines 21a, 22a, and 23a is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the third-layer circuit board 14c, and is connected to the first input terminal 30a.
  • the interlayer wiring portions 22a are connected to each other.
  • the input-side via connection portion 21b of the first signal lines 21b, 22b, and 23b is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the fifth-layer circuit board 14e, and is connected to the second input terminal 30b.
  • the interlayer wiring portions 22b are connected to each other.
  • the output-side via connection portion 23a of the first signal lines 21a, 22a, and 23a is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the third-layer circuit board 14c, and the first output terminal 31a.
  • the interlayer wiring part 22a are connected.
  • the output-side via connection portion 23b of the second signal lines 21b, 22b, and 23b is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the fifth-layer circuit board 14e, and is connected to the second output terminal 31b.
  • the interlayer wiring portions 22b are connected to each other.
  • a ground layer 24b is arranged between the two interlayer wiring parts 22a and 22b.
  • the ground layer 24a is provided on the first-layer circuit board 14a provided with the interlayer wiring portion 22a.
  • a ground layer 24c is provided on the fifth-layer circuit board 14e provided with the interlayer wiring portion 22b.
  • the ground layers 24a, 24b, 24c form a conductive metal electrode.
  • the ground layers 24a, 24b, 24c are connected to the ground terminals 26a, 26b, 26c on the sixth-layer circuit board 14f via the ground vias 25a, 25b, 25c.
  • the positive phase signal input to the input terminal 30a is transmitted to the output terminal 31a via the first signal lines 21a, 22a and 23a, and then via the bonding wire 13a. It is output to the optical semiconductor element 13.
  • the negative phase signal input to the input terminal 30b is transmitted to the second output terminal 31b via the second signal lines 21b, 22b, 23b, and then output to the optical semiconductor element 13 via the bonding wire 13b.
  • the optical semiconductor element 13 is driven by a differential signal input from the output terminals 31a and 31b, and outputs a laser light signal to the transparent window member 18 side.
  • the optical signal output from the optical semiconductor element 13 is transmitted by the optical fiber 20b.
  • Polyvinyl butyral, a tertiary amine, and a phthalic acid ester were mixed as an organic component with the obtained mixed powder, and IPA (isopropyl alcohol) and toluene were further mixed as a solvent to prepare a slurry.
  • DINP diisononyl phthalate
  • a ceramic tape with a thickness of 50 to 400 ⁇ m was produced by the doctor blade method.
  • the obtained ceramic tape was cut into a length of 50 mm and a width of 50 mm, arranged on a firing setter made of Mo, and fired at the firing temperature (maximum temperature) shown in Table 1 (2 hours).
  • the firing temperature maximum temperature
  • 100 fired substrates of each of Examples 1 to 17 and Comparative Examples 1 to 8 were prepared.
  • the temperature variation in the furnace when fired at the firing temperatures shown in Table 1 was within ⁇ 5 ° C.
  • Examples 15 to 17 in which the ratio of the content of SiO 2 to the content of MnO was 1.9 or more and 3.5 or less, the relative dielectric constant of 8.0 or more and 9.0 or less and the bending strength of 390 MPa or more. It was possible to achieve both strength and strength. Therefore, it was found that Examples 15 to 17 are suitable for a ceramic package (for example, one for encapsulating an optical semiconductor element) which requires a relatively low relative dielectric constant.

Abstract

The ceramic green body includes Al2O3, SiO2 and MnO as essential components, and includes at least one of Mo and Cr2O3 as optional components. In the ceramic green body, the amount of Al2O3 is 82.0%-95.0% by mass (inclusive), the amount of SiO2 is 3.0%-8.0% by mass (inclusive), the amount of MnO is 2.0%-6.0% by mass (inclusive), the total of the amount of Mo in terms of MoO3 and the amount of Cr2O3 is 4.0% by mass or less, and the remaining amount is less than 0.1% by mass.

Description

セラミック素地Ceramic substrate
　本発明は、セラミック素地に関する。 The present invention relates to a ceramic substrate.
　特許文献１には、セラミック素地の一例として、９０質量％以上のＡｌ２Ｏ３と、１～６質量％のＳｉＯ２と、Ｍｎ２Ｏ３換算で２～８質量％のＭｎＡｌ２Ｏ４と、２質量％以下のＭｏとを含む絶縁基板が開示されている。特許文献１に記載の絶縁基板では、強度の安定性改善のために、Ｍｇを酸化物換算で０．１～３質量％の割合で含むことが好ましいとされている。 In Patent Document 1, as an example of a ceramic base, 90% by mass or more of Al 2 O 3 , 1 to 6% by mass of SiO 2, and 2 to 8% by mass of MnAl 2 O 4 in terms of Mn 2 O 3 are included. An insulating substrate containing 2 mass% or less of Mo is disclosed. It is said that the insulating substrate described in Patent Document 1 preferably contains Mg in a proportion of 0.1 to 3 mass% in terms of oxide in order to improve the stability of strength.
　特許文献２には、セラミック素地の一例として、主成分としてのＡｌ２Ｏ３と、３～７．５質量％のＳｉＯ２と、Ｍｎ２Ｏ３換算で２～５質量％のＭｎと、ＭｇＯ換算で０．３～０．７質量％のＭｇと、ＭｏＯ換算で０．３～０．７質量％のＭｏとを含む絶縁基板が開示されている。 In Patent Document 2, as an example of a ceramic substrate, Al 2 O 3 as a main component, 3 to 7.5 mass% SiO 2 , 2 to 5 mass% Mn in terms of Mn 2 O 3 , and MgO. An insulating substrate containing 0.3 to 0.7 mass% of Mg in terms of conversion and 0.3 to 0.7 mass% of Mo in terms of MoO is disclosed.
　特許文献３には、ＡｌをＡｌ２Ｏ３換算で８９．０～９２．０質量％、ＳｉをＳｉＯ２換算で２．０～５．０質量％、ＭｎをＭｎＯ換算で２．０～５．０質量％、ＭｇをＭｇＯ換算で０～２．０質量％、ＺｒをＺｒＯ２換算で０．０５～２．０質量％含むセラミック素地が開示されている。 In Patent Document 3, Al is 89.0 to 92.0 mass% in terms of Al 2 O 3 , Si is 2.0 to 5.0 mass% in terms of SiO 2 , and Mn is 2.0 to 5 in terms of MnO. Disclosed is a ceramic base containing 0.0 mass% of Mg, 0 to 2.0 mass% of Mg in terms of MgO, and 0.05 to 2.0 mass% of Zr in terms of ZrO 2 .
特許第４４１３２２４号公報Japanese Patent No. 4413224 特許第５７８４１５３号公報Japanese Patent No. 5784153 国際公開第２０１５／１４１０９９号International Publication No. 2015/141099
　特許文献１～３に記載のセラミック素地では、寸法ばらつきが生じやすいという問題がある。本発明者等は、鋭意検討した結果、主成分であるＡｌ２Ｏ３と、焼結助剤としてのＳｉＯ２及びＭｎＯと、着色剤としてのＭｏ又は／及びＣｒ２Ｏ３とを除いた残部の含有量が寸法ばらつきに影響を与えているという新たな知見を得た。 The ceramic bases described in Patent Documents 1 to 3 have a problem that dimensional variations easily occur. As a result of diligent studies, the present inventors have made a balance except for Al 2 O 3 as a main component, SiO 2 and MnO as a sintering aid, and Mo or / and Cr 2 O 3 as a colorant. A new finding was obtained that the content of P has an influence on dimensional variation.
　本発明は、寸法ばらつきを抑制可能なセラミック素地の提供を目的とする。 The present invention aims to provide a ceramic base capable of suppressing dimensional variations.
　本発明に係るセラミック素地は、Ａｌ２Ｏ３、ＳｉＯ２及びＭｎＯを必須成分として含み、Ｍｏ及びＣｒ２Ｏ３の少なくとも一方を任意成分として含む。セラミック素地において、Ａｌ２Ｏ３の含有量が、８２．０質量％以上９５．０質量％以下であり、ＳｉＯ２の含有量が、３．０質量％以上８．０質量％以下であり、ＭｎＯの含有量が、２．０質量％以上６．０質量％以下であり、ＭｏＯ３換算でのＭｏの含有量とＣｒ２Ｏ３の含有量との合計が、４．０質量％以下であり、残部の含有量が、０．１質量％未満である。 The ceramic substrate according to the present invention contains Al 2 O 3 , SiO 2 and MnO as essential components, and contains at least one of Mo and Cr 2 O 3 as optional components. In the ceramic substrate, the content of Al 2 O 3 is 82.0% by mass or more and 95.0% by mass or less, and the content of SiO 2 is 3.0% by mass or more and 8.0% by mass or less, The content of MnO is 2.0% by mass or more and 6.0% by mass or less, and the sum of the content of Mo in terms of MoO 3 and the content of Cr 2 O 3 is 4.0% by mass or less. Yes, and the content of the balance is less than 0.1% by mass.
　本発明によれば、寸法ばらつきを抑制可能なセラミック素地を提供することができる。 According to the present invention, it is possible to provide a ceramic body capable of suppressing dimensional variation.
実施形態に係る第１セラミックパッケージの構成を示す断面図である。It is sectional drawing which shows the structure of the 1st ceramic package which concerns on embodiment. 実施形態に係る第２セラミックパッケージの構成を示す断面図である。It is sectional drawing which shows the structure of the 2nd ceramic package which concerns on embodiment. 実施形態に係る第２セラミックパッケージのうち多層回路基板の構成を示す断面図である。It is a sectional view showing composition of a multilayer circuit board among the 2nd ceramic packages concerning an embodiment.
　（セラミック素地）
　セラミック素地とは、セラミックス材料粉末をテープ状に成形したグリーンシートやセラミックス材料粉末を圧粉成形した成形体を焼結することによって得られる組成物である。本実施形態に係るセラミック素地は、水晶振動子などの振動子を封止するセラミックパッケージ、ＣＭＯＳイメージセンサなどの半導体素子を封止するセラミックパッケージ、或いは、光半導体素子を封止するセラミックパッケージなどの各種セラミックパッケージに好適に用いられる。 (Ceramic substrate)
The ceramic base is a composition obtained by sintering a green sheet formed by molding a ceramic material powder into a tape shape or a compact formed by compacting a ceramic material powder. The ceramic substrate according to the present embodiment includes a ceramic package for encapsulating an oscillator such as a crystal oscillator, a ceramic package for encapsulating a semiconductor element such as a CMOS image sensor, or a ceramic package for encapsulating an optical semiconductor element. Suitable for use in various ceramic packages.
　本実施形態に係るセラミック素地は、主成分としてのＡｌ２Ｏ３（アルミナ）と、焼結助剤としてのＳｉＯ２（シリカ）及びＭｎＯ（酸化マンガン）とを必須成分として含む。 The ceramic body according to the present embodiment contains Al 2 O 3 (alumina) as a main component, and SiO 2 (silica) and MnO (manganese oxide) as sintering aids as essential components.
　セラミック素地は、着色剤としてＭｏ（モリブデン）及びＣｒ２Ｏ３（酸化クロム）の少なくとも一方を任意成分として含む。セラミック素地は、着色剤として、Ｍｏのみを含有していてもよいし、Ｃｒ２Ｏ３のみを含有していてもよいし、Ｍｏ及びＣｒ２Ｏ３の両方を含有していてもよいし、さらに、Ｍｏ及びＣｒ２Ｏ３の両方を含有していなくてもよい。セラミック素地が着色剤としてＭｏを含有する場合、Ｍｏの少なくとも一部は金属として存在していてもよいし、Ｍｏの少なくとも一部は酸化物の形態（例えば、ＭｏＯ３）で存在していてもよい。 The ceramic base contains at least one of Mo (molybdenum) and Cr 2 O 3 (chromium oxide) as an optional component as a colorant. The ceramic base may contain only Mo as a colorant, may contain only Cr 2 O 3 , or may contain both Mo and Cr 2 O 3 , Furthermore, it may not contain both Mo and Cr 2 O 3. When the ceramic base contains Mo as a colorant, at least a part of Mo may be present as a metal, or at least a part of Mo may be present in an oxide form (for example, MoO 3 ). Good.
　セラミック素地を構成する各成分の含有量は、以下の通りである。 The content of each component that constitutes the ceramic base is as follows.
　　・Ａｌ２Ｏ３：
　　　８２．０質量％以上９５．０質量％以下
　　・ＳｉＯ２：
　　　３．０質量％以上８．０質量％以下
　　・ＭｎＯ：
　　　２．０質量％以上６．０質量％以下
　　・ＭｏＯ３換算でのＭｏの含有量とＣｒ２Ｏ３の含有量との合計：
　　　４．０質量％以下
　　・残部：
　　　０．１質量％未満 · Al 2 O 3:
82.0 mass% or more and 95.0 mass% or less ・ SiO 2 :
3.0 mass% or more and 8.0 mass% or less ・ MnO:
Sum of the amount of content and Cr 2 O 3 of Mo in 2.0% to 6.0% by mass · MoO 3 terms:
4.0 mass% or less-The balance:
Less than 0.1% by mass
　このように、本実施形態に係るセラミック素地では、Ａｌ２Ｏ３、ＳｉＯ２、ＭｎＯ及び着色剤（Ｍｏ又は／及びＣｒ２Ｏ３）以外の残部の含有量が０．１質量％未満に抑えられているため、各成分が偏析することなく分散された状態で均一に焼結されている。そのため、本実施形態に係るセラミック素地では、寸法ばらつきが抑制されている。 As described above, in the ceramic substrate according to the present embodiment, the content of the balance other than Al 2 O 3 , SiO 2 , MnO and the colorant (Mo or / and Cr 2 O 3 ) is suppressed to less than 0.1% by mass. Therefore, each component is uniformly sintered in a dispersed state without segregation. Therefore, in the ceramic base material according to the present embodiment, dimensional variation is suppressed.
　また、セラミック素地は、残部の含有量が０．１質量％未満に抑えられることによって、各成分が偏析することなく分散された状態で均一に焼結されるため、ガラス成分のフラックス中に低融点領域が局所的に発生することを抑制できる。そのため、セラミック素地が焼成セッターに貼り付くことを抑制できる。 In addition, since the content of the balance of the ceramic base is suppressed to less than 0.1% by mass, the respective components are uniformly sintered in a dispersed state without segregation. It is possible to suppress local generation of the melting point region. Therefore, it is possible to prevent the ceramic base material from sticking to the firing setter.
　さらに、セラミック素地は、残部の含有量が０．１質量％未満に抑えられることによって、各成分が偏析することなく分散された状態で均一に焼結されるため、焼成セッター側の裏側領域でガラス成分が溶融するタイミングを、焼成セッターと反対側の表側領域でガラス成分が溶融するタイミングに合わせることができる。そのため、セラミック素地が厚み方向に反ることを抑制できる。 Furthermore, since the remaining content of the ceramic base is suppressed to less than 0.1% by mass, the respective components are uniformly sintered in a dispersed state without segregation, so that in the backside region on the firing setter side. The timing at which the glass component melts can be matched with the timing at which the glass component melts in the front side region opposite to the firing setter. Therefore, it is possible to suppress the ceramic base from warping in the thickness direction.
　セラミック素地における残部の含有量は、０．０５質量％未満がより好ましい。これによって、セラミック素地の寸法ばらつきを更に抑制できる。 The content of the balance in the ceramic base is more preferably less than 0.05% by mass. As a result, the dimensional variation of the ceramic base can be further suppressed.
　セラミック素地における残部の含有量は、０質量％であることが特に好ましい。これによって、セラミック素地の寸法ばらつきを更に抑制できるだけでなく、セラミック素地が焼成セッターに貼り付くことを更に抑制できる。 The content of the balance in the ceramic body is particularly preferably 0% by mass. As a result, it is possible not only to further suppress the dimensional variation of the ceramic base material, but also to further suppress the sticking of the ceramic base material to the firing setter.
　セラミック素地において、ＭｎＯの含有量に対するＳｉＯ２の含有量の比は特に制限されないが、０．８以上３．５以下が好ましい。この範囲であれば、セラミック素地中にＭｎ３Ａｌ２Ｓｉ３Ｏ１２が析出することを抑制できるため、Ｍｎ３Ａｌ２Ｓｉ３Ｏ１２の析出に起因する色むらの発生を低減することができる。さらに、セラミック素地が、振動子又は半導体素子を封止するセラミックパッケージに適用される場合、ＭｎＯの含有量に対するＳｉＯ２の含有量の比は、０．８以上２．１以下が特に好ましい。これにより、セラミック素地の曲げ強度を特に向上させることができる。一方、セラミック素地が、光半導体素子を封止するセラミックパッケージに適用される場合、ＭｎＯの含有量に対するＳｉＯ２の含有量の比は１．９以上３．５以下が特に好ましい。これにより、セラミック素地の曲げ強度は若干低下するものの、セラミック素地の比誘電率を８．０以上９．０以下に調整しやすくなる。 In the ceramic base, the ratio of the content of SiO 2 to the content of MnO is not particularly limited, but it is preferably 0.8 or more and 3.5 or less. Within this range, the precipitation of Mn 3 Al 2 Si 3 O 12 in the ceramic matrix can be suppressed, so that the occurrence of color unevenness due to the precipitation of Mn 3 Al 2 Si 3 O 12 can be reduced. . Furthermore, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the ratio of the content of SiO 2 to the content of MnO is particularly preferably 0.8 or more and 2.1 or less. Thereby, the bending strength of the ceramic base can be particularly improved. On the other hand, when the ceramic base is applied to a ceramic package for sealing an optical semiconductor element, the ratio of the content of SiO2 to the content of MnO is particularly preferably 1.9 or more and 3.5 or less. As a result, although the bending strength of the ceramic base material is slightly lowered, it becomes easy to adjust the relative dielectric constant of the ceramic base material to 8.0 or more and 9.0 or less.
　セラミック素地は、結晶相とガラス相とを含む。セラミック素地が着色剤としてＭｏを含有している場合、結晶相は、主結晶相としてのＡｌ２Ｏ３結晶相と、副結晶相としてのＭｏ結晶相とを含む。結晶相は、Ａｌ２Ｏ３結晶相及びＭｏ結晶相以外の結晶相（以下、「残部の結晶相」という。）を含んでいてもよい。一方、セラミック素地が着色剤としてＭｏを含有しない場合、結晶相は、主結晶相としてのＡｌ２Ｏ３結晶相を含む。結晶相は、Ａｌ２Ｏ３結晶相以外に残部の結晶相を含んでいてもよい。結晶相は、残部の結晶相として、１種の結晶相のみを含んでいてもよいし、複数種の結晶相を含んでいてもよい。 The ceramic matrix contains a crystalline phase and a glass phase. When the ceramic base contains Mo as a colorant, the crystal phase includes an Al 2 O 3 crystal phase as a main crystal phase and a Mo crystal phase as a sub crystal phase. The crystal phase may include a crystal phase other than the Al 2 O 3 crystal phase and the Mo crystal phase (hereinafter, referred to as “residual crystal phase”). On the other hand, when the ceramic base does not contain Mo as a colorant, the crystal phase includes an Al 2 O 3 crystal phase as a main crystal phase. The crystal phase may include the remaining crystal phase in addition to the Al 2 O 3 crystal phase. The crystal phase may contain only one kind of crystal phase or a plurality of kinds of crystal phases as the remaining crystal phase.
　ここで、セラミック素地を粉砕してＸ線回折パターンから結晶相を同定した場合、残部の結晶相のＸ線回折パターンのメインピーク強度は、Ａｌ２Ｏ３結晶相のＸ線回折パターンのメインピーク強度に対して、０．５％以下であることが好ましい。これにより、残部の結晶相の存在によりガラス相に歪みが生じることを抑制できるため、セラミック素地の曲げ強度（いわゆる、抗折強度）を向上させることができる。 Here, when the ceramic base is crushed and the crystal phase is identified from the X-ray diffraction pattern, the main peak intensity of the X-ray diffraction pattern of the remaining crystal phase is the main peak of the X-ray diffraction pattern of the Al 2 O 3 crystal phase. The strength is preferably 0.5% or less. As a result, distortion of the glass phase due to the presence of the remaining crystal phase can be suppressed, so that the bending strength (so-called bending strength) of the ceramic base can be improved.
　セラミック素地の曲げ強度は、セラミック素地が適用されるセラミックパッケージに求められる特性に応じて設定される。例えば、セラミック素地が、振動子又は半導体素子を封止するセラミックパッケージに適用される場合、セラミック素地の曲げ強度は、７００ＭＰａ以上が好ましい。また、セラミック素地が、光半導体素子を封止するセラミックパッケージに適用される場合、セラミック素地の曲げ強度は、３９０ＭＰａ以上が好ましい。本実施形態において、“曲げ強度”とは、３点曲げ強度を意味し、ＪＩＳＲ１６０１（ファインセラミックスの曲げ試験方法）に準拠し室温にて測定した値である。 The bending strength of the ceramic base is set according to the characteristics required for the ceramic package to which the ceramic base is applied. For example, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the bending strength of the ceramic base is preferably 700 MPa or more. Further, when the ceramic base is applied to a ceramic package that seals an optical semiconductor element, the bending strength of the ceramic base is preferably 390 MPa or more. In the present embodiment, “bending strength” means three-point bending strength, and is a value measured at room temperature in accordance with JISR1601 (bending test method for fine ceramics).
　セラミック素地の比誘電率は、セラミック素地が適用されるセラミックパッケージに求められる特性に応じて設定される。例えば、セラミック素地が、振動子又は半導体素子を封止するセラミックパッケージに適用される場合、セラミック素地の比誘電率は特に制限されない。セラミック素地が、光半導体素子を封止するセラミックパッケージに適用される場合、セラミック素地の比誘電率は、８.０以上９．０以下が好ましい。 The relative permittivity of the ceramic base is set according to the characteristics required for the ceramic package to which the ceramic base is applied. For example, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the relative permittivity of the ceramic base is not particularly limited. When the ceramic base is applied to a ceramic package for encapsulating an optical semiconductor element, the relative permittivity of the ceramic base is preferably 8.0 or more and 9.0 or less.
　セラミック素地の気孔率は、セラミック素地が適用されるセラミックパッケージに求められる特性に応じて設定される。例えば、セラミック素地が、振動子又は半導体素子を封止するセラミックパッケージに適用される場合、セラミック素地の気孔率は、３％以下が好ましい。また、セラミック素地が、光半導体素子を封止するセラミックパッケージに適用される場合、セラミック素地の気孔率は、３％以上８％以下が好ましい。本実施形態において、“気孔率”とは、研磨したセラミック断面を電子顕微鏡で撮影し、画像処理ソフトにより２値化して測定した値である。 -The porosity of the ceramic substrate is set according to the characteristics required for the ceramic package to which the ceramic substrate is applied. For example, when the ceramic base is applied to a ceramic package that seals a vibrator or a semiconductor element, the porosity of the ceramic base is preferably 3% or less. When the ceramic base is applied to a ceramic package that seals an optical semiconductor element, the porosity of the ceramic base is preferably 3% or more and 8% or less. In the present embodiment, the "porosity" is a value obtained by photographing a polished ceramic cross section with an electron microscope and binarizing it with image processing software.
　（セラミックパッケージ）
　ここで、本実施形態に係るセラミック素地を適用したセラミックパッケージの２つの構成例について、図面を参照しながら説明する。 (Ceramic package)
Here, two structural examples of the ceramic package to which the ceramic base according to the present embodiment is applied will be described with reference to the drawings.
　（１）第１セラミックパッケージ１００
　図１は、第１セラミックパッケージ１００の断面図である。 (1) First ceramic package 100
FIG. 1 is a sectional view of the first ceramic package 100.
　第１セラミックパッケージ１００は、絶縁基板１、複数の導体層２、メタライズ層３、水晶振動子４、ＣＭＯＳイメージセンサ６、メッキ層８、及び蓋体１０を備える。第１セラミックパッケージ１００は、水晶振動子４及びＣＭＯＳイメージセンサ６を封止している。 The first ceramic package 100 includes an insulating substrate 1, a plurality of conductor layers 2, a metallization layer 3, a crystal oscillator 4, a CMOS image sensor 6, a plating layer 8 and a lid 10. The first ceramic package 100 encapsulates the crystal unit 4 and the CMOS image sensor 6.
　絶縁基板１は、上述したセラミック素地によって構成される。絶縁基板１を構成する各成分の含有量は、以下の通りである。 The insulating substrate 1 is composed of the ceramic base described above. The content of each component forming the insulating substrate 1 is as follows.
　　・Ａｌ２Ｏ３：
　　　８２．０質量％以上９５．０質量％以下
　　・ＳｉＯ２：
　　　３．０質量％以上８．０質量％以下
　　・ＭｎＯ：
　　　２．０質量％以上６．０質量％以下
　　・ＭｏＯ３換算でのＭｏの含有量とＣｒ２Ｏ３の含有量との合計：
　　　４．０質量％以下
　　・残部：
　　　０．１質量％未満 · Al 2 O 3:
82.0 mass% or more and 95.0 mass% or less ・ SiO 2 :
3.0 mass% or more and 8.0 mass% or less ・ MnO:
Sum of the amount of content and Cr 2 O 3 of Mo in 2.0% to 6.0% by mass · MoO 3 terms:
4.0 mass% or less-The balance:
Less than 0.1% by mass
　このように、本実施形態に係る絶縁基板１では、残部の含有量が０．１質量％未満に抑えられているため、各成分が偏析することなく分散された状態で均一に焼結されることによって、寸法ばらつきが抑制されている。絶縁基板１の曲げ強度は、７００ＭＰａ以上が好ましい。絶縁基板１の気孔率は、３％以下が好ましい。 As described above, in the insulating substrate 1 according to the present embodiment, since the content of the balance is suppressed to less than 0.1% by mass, the respective components are uniformly sintered in a dispersed state without segregation. As a result, dimensional variation is suppressed. The bending strength of the insulating substrate 1 is preferably 700 MPa or more. The porosity of the insulating substrate 1 is preferably 3% or less.
　絶縁基板１は、底部１ａと、側壁部１ｂとを有する。側壁部１ｂは、底部１ａの外縁上に配置される。底部１ａと側壁部１ｂは、一体的に形成されていてもよい。 The insulating substrate 1 has a bottom portion 1a and a side wall portion 1b. The side wall portion 1b is arranged on the outer edge of the bottom portion 1a. The bottom portion 1a and the side wall portion 1b may be integrally formed.
　各導体層２は、底部１ａを貫通するように設けられる。メタライズ層３は、側壁部１ｂの上面に配置される。メタライズ層３は、環状に形成される。メタライズ層３は、導体としてＷ又はＭｏを主成分とし、これにセラミック成分を若干添加することによって構成できる。また、本実施形態に係る絶縁基板１と上記メタライズ層３は、水素、窒素、水蒸気を含む還元雰囲気で同時焼成することによって作製される。 Each conductor layer 2 is provided so as to penetrate the bottom portion 1a. The metallized layer 3 is arranged on the upper surface of the side wall portion 1b. The metallized layer 3 is formed in a ring shape. The metallized layer 3 can be formed by using W or Mo as a main component as a conductor and adding a ceramic component to it. Further, the insulating substrate 1 according to the present embodiment and the metallized layer 3 are produced by simultaneous firing in a reducing atmosphere containing hydrogen, nitrogen and water vapor.
　水晶振動子４は、振動子の一例である。水晶振動子４は、導電性接着剤５を介して導体層２に接続される。ＣＭＯＳイメージセンサ６は、半導体素子の一例である。ＣＭＯＳイメージセンサ６は、ワイヤボンディング７を介して導体層２に接続される。 The crystal unit 4 is an example of a unit. The crystal unit 4 is connected to the conductor layer 2 via the conductive adhesive 5. The CMOS image sensor 6 is an example of a semiconductor element. The CMOS image sensor 6 is connected to the conductor layer 2 via the wire bonding 7.
　メッキ層８は、メタライズ層３の上面に配置される。メッキ層８は、環状に形成される。蓋体１０は、共晶Ａｇ－Ｃｕロウ材９を介して、メッキ層８上に配置される。蓋体１０は、側壁部１ｂの開口を塞ぐ。蓋体１０は、金属材料によって構成することができる。 The plating layer 8 is arranged on the upper surface of the metallization layer 3. The plating layer 8 is formed in a ring shape. The lid 10 is arranged on the plating layer 8 with the eutectic Ag—Cu brazing material 9 interposed therebetween. The lid 10 closes the opening of the side wall portion 1b. The lid 10 can be made of a metal material.
　（２）第２セラミックパッケージ２００
　図２は、第２セラミックパッケージ２００の断面図である。 (2) Second ceramic package 200
FIG. 2 is a sectional view of the second ceramic package 200.
　第２セラミックパッケージ２００は、基台１１、電子冷却素子１２、光半導体素子１３、多層回路基板１４、枠体１５、シールリング１６、蓋１７、透光性窓部材１８、パイプ１９、光ファイバ接続管２０ａ、及び光ファイバ２０ｂを備える。第２セラミックパッケージ２００は、光半導体素子１３を封止する。第２セラミックパッケージ２００は、いわゆる光モジュールである。 The second ceramic package 200 includes a base 11, an electronic cooling element 12, an optical semiconductor element 13, a multilayer circuit board 14, a frame 15, a seal ring 16, a lid 17, a transparent window member 18, a pipe 19, and an optical fiber connection. The tube 20a and the optical fiber 20b are provided. The second ceramic package 200 seals the optical semiconductor element 13. The second ceramic package 200 is a so-called optical module.
　基台１１は、板状に形成される。基台１１は、銅タングステンなどの熱伝導率の高い材料によって構成される。電子冷却素子１２は、基台１１上に配置される。光半導体素子１３は、電子冷却素子１２上に配置される。 The base 11 is formed in a plate shape. The base 11 is made of a material having a high thermal conductivity such as copper tungsten. The electronic cooling element 12 is arranged on the base 11. The optical semiconductor element 13 is arranged on the electronic cooling element 12.
　多層回路基板１４は、基台１１の外縁上に配置される。多層回路基板１４には、パッケージ外部に露出する入力端子３０ａ，３０ｂと、パッケージ内部に露出する出力端子３１ａ，３１ｂとが設けられている。入力端子３０ａには、外部から正相信号が入力される。入力端子３０ｂには、正相信号と逆相の逆相信号が入力される。入力端子３０ａに入力された正相信号は、ボンディングワイヤ１３ａを介して、出力端子３１ａから光半導体素子１３に出力される。入力端子３０ｂに入力された逆相信号は、ボンディングワイヤ１３ｂを介して、出力端子３１ｂから光半導体素子１３に出力される。以下の説明では、正相信号と逆相信号とを合わせて差動信号と略称する。 The multilayer circuit board 14 is arranged on the outer edge of the base 11. The multilayer circuit board 14 is provided with input terminals 30a and 30b exposed to the outside of the package and output terminals 31a and 31b exposed to the inside of the package. A positive phase signal is externally input to the input terminal 30a. A negative phase signal having a negative phase and a positive phase signal is input to the input terminal 30b. The positive phase signal input to the input terminal 30a is output to the optical semiconductor element 13 from the output terminal 31a via the bonding wire 13a. The negative phase signal input to the input terminal 30b is output to the optical semiconductor element 13 from the output terminal 31b via the bonding wire 13b. In the following description, the positive phase signal and the negative phase signal are collectively referred to as a differential signal.
　枠体１５は、多層回路基板１４上に配置される。シールリング１６は、枠体１５の上面に配置される。シールリング１６は、蓋１７を溶接するための部材である。シールリング１６及び蓋１７のそれぞれは、ニッケル及びコバルトを鉄に配合したコバールなどによって構成することができる。 The frame body 15 is arranged on the multilayer circuit board 14. The seal ring 16 is arranged on the upper surface of the frame body 15. The seal ring 16 is a member for welding the lid 17. Each of the seal ring 16 and the lid 17 can be made of Kovar in which iron is mixed with nickel and cobalt.
　多層回路基板１４と枠体１５との間に形成された孔１９ａには、パイプ１９が嵌め込まれる。パイプ１９は、透光性窓部材１８を収容する。透光性窓部材１８は、サファイア、ガラスなどによって構成される。パイプ１９には、光ファイバ接続管２０ａが接続される。パイプ１９及び光ファイバ接続管２０ａのそれぞれは、コバールなどによって構成することができる。光ファイバ接続管２０ａには、光ファイバ２０ｂが固定される。 A pipe 19 is fitted into a hole 19a formed between the multilayer circuit board 14 and the frame 15. The pipe 19 houses the translucent window member 18. The translucent window member 18 is made of sapphire, glass, or the like. An optical fiber connecting pipe 20a is connected to the pipe 19. Each of the pipe 19 and the optical fiber connecting pipe 20a can be configured by Kovar or the like. An optical fiber 20b is fixed to the optical fiber connecting tube 20a.
　ここで、図３は、多層回路基板１４の構成を示す分解斜視図である。 Here, FIG. 3 is an exploded perspective view showing the configuration of the multilayer circuit board 14.
　多層回路基板１４は、６層の回路基板１４ａ～１４ｆ、第１信号線２１ａ，２２ａ，２３ａ、第２信号線２１ｂ，２２ｂ，２３ｂ、グランド層２４ａ，２４ｂ，２４ｃ、グランドビア２５ａ，２５ｂ，２５ｃ、及びグランド端子２６ａ，２６ｂ，２６ｃを備える。 The multilayer circuit board 14 includes six layers of circuit boards 14a to 14f, first signal lines 21a, 22a, 23a, second signal lines 21b, 22b, 23b, ground layers 24a, 24b, 24c, ground vias 25a, 25b, 25c. , And ground terminals 26a, 26b, 26c.
　各回路基板１４ａ～１４ｆは、上述したセラミック素地によって構成される。各回路基板１４ａ～１４ｆを構成する各成分の含有量は、以下の通りである。 Each of the circuit boards 14a to 14f is composed of the above-mentioned ceramic base. The content of each component constituting each circuit board 14a to 14f is as follows.
　　・Ａｌ２Ｏ３：
　　　８２．０質量％以上９５．０質量％以下
　　・ＳｉＯ２：
　　　３．０質量％以上８．０質量％以下
　　・ＭｎＯ：
　　　２．０質量％以上６．０質量％以下
　　・ＭｏＯ３換算でのＭｏの含有量とＣｒ２Ｏ３の含有量との合計：
　　　４．０質量％以下
　　・残部：
　　　０．１質量％未満 · Al 2 O 3:
82.0 mass% or more and 95.0 mass% or less ・ SiO 2 :
3.0 mass% or more and 8.0 mass% or less ・ MnO:
Sum of the amount of content and Cr 2 O 3 of Mo in 2.0% to 6.0% by mass · MoO 3 terms:
4.0 mass% or less-The balance:
Less than 0.1% by mass
　このように、本実施形態に係る各回路基板１４ａ～１４ｆでは、残部の含有量が０．１質量％未満に抑えられているため、各成分が偏析することなく分散された状態で均一に焼結されることによって、寸法ばらつきが抑制されている。各回路基板１４ａ～１４ｆの比誘電率は、８．０以上９．０以下が好ましい。各回路基板１４ａ～１４ｆの曲げ強度は、３９０ＭＰａ以上が好ましい。各回路基板１４ａ～１４ｆの気孔率は、３％以上８％以下とすることができる。 As described above, in each of the circuit boards 14a to 14f according to the present embodiment, since the content of the balance is suppressed to less than 0.1% by mass, the respective components are uniformly baked without being segregated. By being tied, dimensional variation is suppressed. The relative permittivity of each of the circuit boards 14a to 14f is preferably 8.0 or more and 9.0 or less. The bending strength of each of the circuit boards 14a to 14f is preferably 390 MPa or more. The porosity of each of the circuit boards 14a to 14f can be set to 3% or more and 8% or less.
　６層の回路基板１４ａ～１４ｆは、この順で積層される。６層目の回路基板１４ｆには、上述した入力端子３０ａ，３０ｂと出力端子３１ａ，３１ｂとが設けられる。 The 6-layer circuit boards 14a to 14f are stacked in this order. The above-mentioned input terminals 30a and 30b and output terminals 31a and 31b are provided on the sixth-layer circuit board 14f.
　第１信号線２１ａ，２２ａ，２３ａのうち入力側ビア接続部２１ａは、６層目の回路基板１４ｆから３層目の回路基板１４ｃまでを貫通するビア導体として構成され、第１入力端子３０ａと層間配線部２２ａの間を接続する。第１信号線２１ｂ，２２ｂ，２３ｂのうち入力側ビア接続部２１ｂは、６層目の回路基板１４ｆから５層目の回路基板１４ｅまでを貫通するビア導体として構成され、第２入力端子３０ｂと層間配線部２２ｂの間を接続する。 The input-side via connection portion 21a of the first signal lines 21a, 22a, and 23a is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the third-layer circuit board 14c, and is connected to the first input terminal 30a. The interlayer wiring portions 22a are connected to each other. The input-side via connection portion 21b of the first signal lines 21b, 22b, and 23b is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the fifth-layer circuit board 14e, and is connected to the second input terminal 30b. The interlayer wiring portions 22b are connected to each other.
　第１の信号線２１ａ，２２ａ，２３ａのうち出力側ビア接続部２３ａは、６層目の回路基板１４ｆから３層目の回路基板１４ｃまでを貫通するビア導体として構成され、第１出力端子３１ａと層間配線部２２ａの間を接続する。第２信号線２１ｂ，２２ｂ，２３ｂのうち出力側ビア接続部２３ｂは、６層目の回路基板１４ｆから５層目の回路基板１４ｅまでを貫通するビア導体として構成され、第２出力端子３１ｂと層間配線部２２ｂの間を接続する。 The output-side via connection portion 23a of the first signal lines 21a, 22a, and 23a is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the third-layer circuit board 14c, and the first output terminal 31a. And the interlayer wiring part 22a are connected. The output-side via connection portion 23b of the second signal lines 21b, 22b, and 23b is configured as a via conductor penetrating from the sixth-layer circuit board 14f to the fifth-layer circuit board 14e, and is connected to the second output terminal 31b. The interlayer wiring portions 22b are connected to each other.
　２本の層間配線部２２ａ，２２ｂの間には、グランド層２４ｂが配置される。層間配線部２２ａが設けられた１層目の回路基板１４ａには、グランド層２４ａが設けられる。層間配線部２２ｂが設けられた５層目の回路基板１４ｅには、グランド層２４ｃが設けられる。 A ground layer 24b is arranged between the two interlayer wiring parts 22a and 22b. The ground layer 24a is provided on the first-layer circuit board 14a provided with the interlayer wiring portion 22a. A ground layer 24c is provided on the fifth-layer circuit board 14e provided with the interlayer wiring portion 22b.
　グランド層２４ａ，２４ｂ，２４ｃは、導電性の金属電極を構成する。グランド層２４ａ，２４ｂ，２４ｃは、グランドビア２５ａ，２５ｂ，２５ｃを介して、６層目の回路基板１４ｆ上のグランド端子２６ａ，２６ｂ，２６ｃに接続される。 The ground layers 24a, 24b, 24c form a conductive metal electrode. The ground layers 24a, 24b, 24c are connected to the ground terminals 26a, 26b, 26c on the sixth-layer circuit board 14f via the ground vias 25a, 25b, 25c.
　以上の構成を有する多層回路基板１４によって、入力端子３０ａに入力された正相信号は、第１信号線２１ａ，２２ａ，２３ａを介して出力端子３１ａに伝送された後、ボンディングワイヤ１３ａを介して光半導体素子１３に出力される。また、入力端子３０ｂに入力された逆相信号は、第２信号線２１ｂ，２２ｂ，２３ｂを介して第２出力端子３１ｂに伝送された後、ボンディングワイヤ１３ｂを介して光半導体素子１３に出力される。光半導体素子１３は、出力端子３１ａ，３１ｂから入力される差動信号によって駆動され、レーザ光信号を透光性窓部材１８側に出力する。光半導体素子１３から出力された光信号は、光ファイバ２０ｂによって伝送される。 With the multilayer circuit board 14 having the above configuration, the positive phase signal input to the input terminal 30a is transmitted to the output terminal 31a via the first signal lines 21a, 22a and 23a, and then via the bonding wire 13a. It is output to the optical semiconductor element 13. In addition, the negative phase signal input to the input terminal 30b is transmitted to the second output terminal 31b via the second signal lines 21b, 22b, 23b, and then output to the optical semiconductor element 13 via the bonding wire 13b. It The optical semiconductor element 13 is driven by a differential signal input from the output terminals 31a and 31b, and outputs a laser light signal to the transparent window member 18 side. The optical signal output from the optical semiconductor element 13 is transmitted by the optical fiber 20b.
　実施例１～１７及び比較例１～８に係るセラミック素地について、寸法ばらつき、焼成セッターへの貼り付き、反り、色むら、曲げ強度及び比誘電率を確認した。
（サンプルの作製）
　各原料粉末を表１に示す割合で混合して混合粉末を得た。 Regarding the ceramic bodies according to Examples 1 to 17 and Comparative Examples 1 to 8, dimensional variations, sticking to a fired setter, warpage, color unevenness, bending strength, and relative dielectric constant were confirmed.
(Preparation of sample)
The raw material powders were mixed at the ratio shown in Table 1 to obtain a mixed powder.
　得られた混合粉末に、有機成分としてポリビニルブチラール及び３級アミン及びフタル酸エステル（フタル酸ジイソノニル：ＤＩＮＰ）を混合し、さらに、溶剤としてＩＰＡ（イソプロピルアルコール）及びトルエンを混合してスラリーを調製した。 Polyvinyl butyral, a tertiary amine, and a phthalic acid ester (diisononyl phthalate: DINP) were mixed as an organic component with the obtained mixed powder, and IPA (isopropyl alcohol) and toluene were further mixed as a solvent to prepare a slurry. .
　調製したスラリーを用いて、ドクターブレード法にて厚さ５０～４００μｍのセラミックテープを作製した。得られたセラミックテープを、縦５０ｍｍ×横５０ｍｍにカットし、Ｍｏ製の焼成セッター上に並べて、表１に示す焼成温度（最高温度）で焼成（２時間）した。これによって、実施例１～１７及び比較例１～８それぞれの焼成基板を１００枚ずつ作成した。なお、表１に示す焼成温度で焼成した際の炉内の温度ばらつきは±５℃の範囲内であった。 Using the prepared slurry, a ceramic tape with a thickness of 50 to 400 μm was produced by the doctor blade method. The obtained ceramic tape was cut into a length of 50 mm and a width of 50 mm, arranged on a firing setter made of Mo, and fired at the firing temperature (maximum temperature) shown in Table 1 (2 hours). As a result, 100 fired substrates of each of Examples 1 to 17 and Comparative Examples 1 to 8 were prepared. The temperature variation in the furnace when fired at the firing temperatures shown in Table 1 was within ± 5 ° C.
　（寸法ばらつき）
　実施例１～１７及び比較例１～８それぞれについて、表１に示す焼成温度で焼成した際の寸法ばらつきを測定した。具体的には、寸法測定装置を用いて焼成基板の外形寸法を測定し、その平均値および標準偏差を算出し、標準偏差を平均値で割った値を寸法ばらつきとした。表１では、寸法ばらつきが０．２０未満のものを○と評価し、寸法ばらつきが０．２０以上０．５０未満のものを△と評価し、寸法ばらつきが０．５０以上のものを×と評価した。 (Dimensional variation)
For each of Examples 1 to 17 and Comparative Examples 1 to 8, dimensional variations were measured when firing at the firing temperatures shown in Table 1. Specifically, the external dimensions of the fired substrate were measured using a dimension measuring device, the average value and standard deviation thereof were calculated, and the value obtained by dividing the standard deviation by the average value was taken as the dimensional variation. In Table 1, those having a dimensional variation of less than 0.20 are evaluated as ◯, those having a dimensional variation of 0.20 or more and less than 0.50 are rated as Δ, and those having a dimensional variation of 0.50 or more are evaluated as x. evaluated.
　（焼成セッターへの貼り付き）
　実施例１～１７及び比較例１～８それぞれについて、焼成セッターに貼り付いてセラミック素地に欠損が生じた焼成基板の枚数を数えた。表１では、１枚も欠損が生じなかったものを○と評価し、１～４枚に欠損が生じたものを△と評価し、５枚以上に欠損が生じたものを×と評価した。 (Attached to the firing setter)
For each of Examples 1 to 17 and Comparative Examples 1 to 8, the number of fired substrates that were attached to the fired setter and had a defect in the ceramic substrate was counted. In Table 1, those in which no defect was generated were evaluated as ◯, those in which 1 to 4 were damaged were evaluated as Δ, and those in which 5 or more were damaged were evaluated as x.
　（反り）
　実施例１～１７及び比較例１～８それぞれについて、三次元形状測定器を用いて、焼成基板の反り量の平均値を測定した。表１では、反り量が１００μｍ未満のものを○と評価し、反り量が１００μｍ以上２００μｍ未満のものを△と評価し、反り量が２００μｍ以上のものを×と評価した。 (warp)
For each of Examples 1 to 17 and Comparative Examples 1 to 8, the average value of the amount of warpage of the fired substrate was measured using a three-dimensional shape measuring instrument. In Table 1, those having a warp amount of less than 100 μm were evaluated as ◯, those having a warp amount of 100 μm or more and less than 200 μm were evaluated as Δ, and those having a warp amount of 200 μm or more were evaluated as x.
　（色むら）
　実施例１～１７及び比較例１～８それぞれについて、実体顕微鏡を用いて、焼成基板の色むらを観察した。表１では、色むらが無かったものを○と評価し、色むらが有ったものを×と評価した。 (Color unevenness)
For each of Examples 1 to 17 and Comparative Examples 1 to 8, the color unevenness of the fired substrate was observed using a stereoscopic microscope. In Table 1, those having no color unevenness were evaluated as ◯, and those having color unevenness were evaluated as x.
　（強度）
　実施例１～１７及び比較例１～８それぞれについて、焼成基板の曲げ強度を、ＪＩＳＲ１６０１の３点曲げ強度試験に従って室温で測定した。 (Strength)
For each of Examples 1 to 17 and Comparative Examples 1 to 8, the bending strength of the fired substrate was measured at room temperature according to the three-point bending strength test of JIS R1601.
　（比誘電率）
　実施例１～１７及び比較例１～８それぞれについて、焼成基板の比誘電率を、ＪＩＳＲ１６４１の空洞共振法に従って室温、周波数１０ＧＨｚで測定した。 (Relative permittivity)
For each of Examples 1 to 17 and Comparative Examples 1 to 8, the relative dielectric constant of the fired substrate was measured at room temperature and a frequency of 10 GHz according to the cavity resonance method of JIS R1641.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～１７では、比較例１～８に比べて、寸法ばらつき、セッターへの貼り付き、及び反りを抑制することができた。これは、セラミック素地が含有するＡｌ２Ｏ３、ＳｉＯ２、ＭｎＯ及び着色剤（Ｍｏ又は／及びＣｒ２Ｏ３）以外の残部の含有量を０．１質量％未満に抑えたため、各成分が偏析することなく分散された状態で均一に焼結させることができたためである。なお、ＭｇＯ、ＺｒＯ２、ＣａＯ及びＢａＯ以外の添加物を添加した場合においても、同様の結果を得られることが実験的に確認されている。 In Examples 1 to 17, as compared with Comparative Examples 1 to 8, dimensional variations, sticking to the setter, and warpage could be suppressed. This is because the content of the balance other than Al 2 O 3 , SiO 2 , MnO and the colorant (Mo or / and Cr 2 O 3 ) contained in the ceramic base was suppressed to less than 0.1% by mass. This is because it was possible to sinter uniformly in a dispersed state without segregation. It has been experimentally confirmed that similar results can be obtained even when additives other than MgO, ZrO 2 , CaO and BaO are added.
　また、残部の含有量を０．０７質量％以下とした実施例１～９及び１２～１７では、反りを更に抑制することができた。 Further, in Examples 1 to 9 and 12 to 17 in which the content of the balance was 0.07 mass% or less, the warp could be further suppressed.
　また、残部の含有量を０．０５質量％未満とした実施例１～８及び１２～１７では、寸法ばらつきを更に抑制することができた。 Further, in Examples 1 to 8 and 12 to 17 in which the content of the balance was less than 0.05% by mass, the dimensional variation could be further suppressed.
　また、残部の含有量を０質量％未満とした実施例１～５及び１２～１７では、寸法ばらつきだけでなくセッターへの貼り付きも更に抑制することができた。 Further, in Examples 1 to 5 and 12 to 17 in which the content of the balance was less than 0% by mass, not only the dimensional variation but also the sticking to the setter could be further suppressed.
　また、ＭｎＯの含有量に対するＳｉＯ２の含有量の比を０．８以上２．１以下とした実施例１～１５では、曲げ強度を７００ＭＰａ以上とすることができた。従って１～１５は、強度を要するセラミックパッケージ（例えば、振動子又は半導体素子を封止するもの）に好適であることが分かった。 Further, in Examples 1 to 15 in which the ratio of the content of SiO 2 to the content of MnO was 0.8 or more and 2.1 or less, the bending strength could be 700 MPa or more. Therefore, it was found that 1 to 15 are suitable for a ceramic package that requires strength (for example, one that seals a vibrator or a semiconductor element).
　また、ＭｎＯの含有量に対するＳｉＯ２の含有量の比を１．９以上３．５以下とした実施例１５～１７では、８．０以上９．０以下の比誘電率と３９０ＭＰａ以上の抗折強度とを両立することができた。従って、実施例１５～１７は、比較的低い比誘電率を要するセラミックパッケージ（例えば、光半導体素子を封止するもの）に好適であることが分かった。 Further, in Examples 15 to 17 in which the ratio of the content of SiO 2 to the content of MnO was 1.9 or more and 3.5 or less, the relative dielectric constant of 8.0 or more and 9.0 or less and the bending strength of 390 MPa or more. It was possible to achieve both strength and strength. Therefore, it was found that Examples 15 to 17 are suitable for a ceramic package (for example, one for encapsulating an optical semiconductor element) which requires a relatively low relative dielectric constant.
１００　第１セラミックパッケージ
１　　　絶縁基板
２００　第２セラミックパッケージ
６　　　多層回路基板
１４ａ～１４ｆ　回路基板 100 First Ceramic Package 1 Insulation Board 200 Second Ceramic Package 6 Multilayer Circuit Boards 14a-14f Circuit Board

Claims (5)

  1. 　Ａｌ２Ｏ３、ＳｉＯ２及びＭｎＯを必須成分として含み、Ｍｏ及びＣｒ２Ｏ３の少なくとも一方を任意成分として含み、
    　Ａｌ２Ｏ３の含有量が、８２．０質量％以上９５．０質量％以下であり、
    　ＳｉＯ２の含有量が、３．０質量％以上８．０質量％以下であり、
    　ＭｎＯの含有量が、２．０質量％以上６．０質量％以下であり、
    　ＭｏＯ３換算でのＭｏの含有量とＣｒ２Ｏ３の含有量との合計が、４．０質量％以下であり、
    　残部の含有量が、０．１質量％未満である、
    セラミック素地。     Al 2 O 3 , SiO 2 and MnO are contained as essential components, and at least one of Mo and Cr 2 O 3 is contained as an optional component,
    The content of Al 2 O 3 is 82.0% by mass or more and 95.0% by mass or less,
    The content of SiO 2 is 3.0% by mass or more and 8.0% by mass or less,
    The content of MnO is 2.0 mass% or more and 6.0 mass% or less,
    The sum of the Mo content and the Cr 2 O 3 content in terms of MoO 3 is 4.0 mass% or less,
    The content of the balance is less than 0.1% by mass,
    Ceramic substrate.
  2. 　残部の含有量が、０．０５質量％未満である、
    請求項１に記載のセラミック素地。     The content of the balance is less than 0.05% by mass,
    The ceramic base according to claim 1.
  3. 　ＭｎＯの含有量に対するＳｉＯ２の含有量の比が、０．８以上３．５以下である、
    請求項１又は２に記載のセラミック素地。     The ratio of the content of SiO 2 to the content of MnO is 0.8 or more and 3.5 or less,
    The ceramic base according to claim 1.
  4. 　抗折強度が、７００ＭＰａ以上である、
    請求項１乃至３のいずれかに記載のセラミック素地。     The bending strength is 700 MPa or more,
    The ceramic base according to any one of claims 1 to 3.
  5. 　１０ＧＨｚでの比誘電率が、８．０以上９．０以下であり、
    　抗折強度が、３９０ＭＰａ以上である、
    請求項１乃至３のいずれかに記載のセラミック素地。     The relative dielectric constant at 10 GHz is 8.0 or more and 9.0 or less,
    The bending strength is 390 MPa or more,
    The ceramic base according to any one of claims 1 to 3.
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