WO2015141100A1 - セラミック素地及びその製造方法 - Google Patents

セラミック素地及びその製造方法 Download PDF

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Publication number
WO2015141100A1
WO2015141100A1 PCT/JP2014/084555 JP2014084555W WO2015141100A1 WO 2015141100 A1 WO2015141100 A1 WO 2015141100A1 JP 2014084555 W JP2014084555 W JP 2014084555W WO 2015141100 A1 WO2015141100 A1 WO 2015141100A1
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mass
powder
ceramic substrate
ceramic
terms
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PCT/JP2014/084555
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English (en)
French (fr)
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梅田勇治
伊藤陽彦
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日本碍子株式会社
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Priority to CN201480078507.7A priority Critical patent/CN106458761B/zh
Priority to JP2016508465A priority patent/JP6573872B2/ja
Publication of WO2015141100A1 publication Critical patent/WO2015141100A1/ja

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    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/405—Iron metal group, e.g. Co or Ni
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/62—Forming laminates or joined articles comprising holes, channels or other types of openings
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/706—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the metallic layers or articles
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/708—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the interlayers
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/72—Forming laminates or joined articles comprising at least two interlayers directly next to each other
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49822—Multilayer substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49827—Via connections through the substrates, e.g. pins going through the substrate, coaxial cables
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H05K1/0243—Printed circuits associated with mounted high frequency components

Definitions

  • the present invention relates to a ceramic substrate, for example, a ceramic substrate suitable for use in a ceramic package, a high-frequency circuit board, or the like in which elements such as vibrators are mounted, and a method for manufacturing the same.
  • a ceramic substrate having alumina as a main crystal phase that is, an alumina substrate, International Publication No. 2013/146500, Japanese Patent No. 4413223, Japanese Patent No. 4578076, Japanese Patent No. 4413224, and Patent An alumina substrate described in Japanese Patent No. 4220869 is known.
  • WO 2013/146500 pamphlet includes TiO 2 (titanium oxide) as an additive, contains only MnTiO 3 as a crystalline phase other than alumina, and has a bending strength of 600 MPa. Is disclosed.
  • Japanese Patent No. 4413223 includes Mn oxide and Si oxide, Al 2 O 3 as a main crystal phase, MnAl 2 O 4 crystal (excluding Mn 2 SiO 4 ), and a three-point bending strength of 500 MPa.
  • a ceramic package made of the above alumina sintered body is disclosed.
  • a metal powder or oxide powder of a transition metal such as W or Mo may be included as a coloring component.
  • alumina substrate made of (calcium: 2a group) is described.
  • This alumina substrate is an alumina substrate having a thermal conductivity of 10 W / mK or more, a dielectric loss tangent of 1 to 60 GHz, a high strength of 20 ⁇ 10 ⁇ 4 or less, a high thermal conductivity, and a low dielectric loss tangent.
  • Japanese Patent No. 4220869 describes measures for strength of a small package. Specifically, a method for producing a ceramic package is described in which a green sheet containing Mn 2 O 3 , MgCO 3 , and SiO 2 as additives is fired at 1350 to 1500 ° C.
  • the green body for a ceramic package WO 2013/146500 pamphlet described is a high strength, Mo (molybdenum), a conductor and cofiring W (tungsten), for firing in a reducing atmosphere, the Ti 4+ In the process of forming Ti 3+ , holes are formed and the dielectric loss tangent increases.
  • Mo mobdenum
  • W tungsten
  • an electric signal loss due to an increase in the dielectric loss tangent of the insulator is not a problem, but it is a problem in a high-frequency circuit board.
  • the MnTiO 3 crystal phase having high hardness exists at the grain boundary, chipping is likely to occur during chip division using a pressure roller, and the defect rate (NG rate) in quality increases.
  • the dielectric loss tangent of the alumina porcelain is obtained by simultaneous firing with the Mo conductor and the W conductor. It becomes a problem for high-frequency circuit boards.
  • the present invention has been made in consideration of such problems, has high bending strength, has a low dielectric loss tangent, is suitable for high-frequency circuit boards, and has a low chipping occurrence rate when chips are divided. It is an object of the present invention to provide a ceramic substrate that can improve the yield and can realize downsizing of a product (ceramic package or the like) using the ceramic substrate at a low cost.
  • Another object of the present invention is to produce a ceramic substrate having a high bending strength and capable of realizing downsizing of a ceramic package or the like at a low firing temperature, and using the ceramic substrate and the ceramic substrate.
  • An object of the present invention is to provide a method for manufacturing a ceramic substrate that can reduce the cost of a product.
  • the ceramic substrate according to the first aspect of the present invention is characterized in that the crystal phase includes Al 2 O 3 as a main crystal phase and includes only a BaAl 2 Si 2 O 8 crystal phase.
  • the bending strength is preferably 600 MPa or more.
  • the sintering is performed at a temperature of 1200 to 1400 ° C.
  • 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
  • Mn is 2 in terms of MnO. It is preferable to contain 0.0 to 5.0% by mass
  • Mg to be 0 to 2.0% by mass in terms of MgO
  • Ba to be 0.05 to 2.0% by mass in terms of BaO.
  • the method for producing a ceramic substrate according to the second aspect of the present invention is a method for producing a ceramic substrate having Al 2 O 3 as a main crystal phase, and comprising 89.0 to 92.0 mass of Al 2 O 3 powder. %, SiO 2 powder 2.0-5.0 mass%, MnCO 3 powder 3.2-8.1 mass% (MnO conversion 2.0-5.0 mass%), MgO powder 0-2.
  • the molded body may further include a step of forming a conductor layer containing a metal, and the firing step may fire the molded body on which the conductor layer is formed.
  • the firing step may be performed in a hydrogen and nitrogen forming gas containing 5% or more of hydrogen.
  • the bending strength is high, the dielectric loss tangent is small, it is suitable for a high frequency circuit board, the chipping occurrence rate at the time of chip division is small, and the yield can be improved.
  • downsizing of a product (ceramic package or the like) using a ceramic substrate can be realized at low cost.
  • a ceramic substrate having high bending strength and capable of realizing downsizing of a ceramic package or the like can be produced at a low firing temperature.
  • the cost of a product using a ceramic substrate can be reduced.
  • FIG. 1 is a cross-sectional view showing a first configuration example (first package) using a ceramic substrate according to the present embodiment.
  • FIG. 2 is a process block diagram showing the method for manufacturing the ceramic substrate according to the present embodiment together with the method for manufacturing the first package.
  • FIG. 3 is a cross-sectional view showing a second configuration example (second package) using the ceramic substrate according to the present embodiment.
  • FIG. 4 is a process block diagram showing a method for manufacturing a ceramic substrate according to the present embodiment together with a method for manufacturing a second package.
  • 5A is a plan view showing a multi-piece substrate
  • FIG. 5B is an enlarged view of a portion indicated by an arrow VB on FIG. 5A
  • FIG. 5C is a cross-sectional view taken along the line VC-VC in FIG. 5B. .
  • ⁇ indicating a numerical range is used as a meaning including numerical values described before and after the numerical value as a lower limit value and an upper limit value.
  • the ceramic substrate according to the present embodiment includes Al 2 O 3 as the main crystal phase and includes only the BaAl 2 Si 2 O 8 crystal phase.
  • 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
  • Mn is 2.0 to 5 mass in terms of MnO. It is preferable to contain 0% by mass, 0 to 2.0% by mass of Mg in terms of MgO, and 0.05 to 2.0% by mass of Ba in terms of BaO.
  • the ceramic base is composed of 89.0 to 92.0% by mass of Al 2 O 3 powder, 2.0 to 5.0% by mass of SiO 2 powder, and 3.2 to 8.1 of MnCO 3 powder.
  • % By mass (2.0 to 5.0% by mass in terms of MnO), 0 to 2.0% by mass of MgO powder, and 0.06 to 2.6% by mass of BaCO 3 powder (0.05 to 2% in terms of BaO) 0.0% by mass), and then the molded body is fired at 1200 to 1400 ° C.
  • MgO powder is added as a sintering aid for Al 2 O 3
  • SiO 2 powder is used as a sintering aid for Al 2 O 3
  • Mn 2 SiO 4 glass phase is generated to lower the sintering temperature. It is added to achieve BaCO 3 powder is added to suppress the formation of MnAl 2 O 4 with increased hardness.
  • any one or more of TiO 2 powder, Ce 2 O 3 powder, and Fe 3 O 4 powder is included.
  • the dielectric loss tangent is increased, it is preferable not to include it as much as possible. Even if it is included, it is 0.1% by mass or less.
  • the dielectric loss tangent is preferably 30 ⁇ 10 ⁇ 4 or less at 1 MHz to 10 GHz. More preferably, it is 15 ⁇ 10 ⁇ 4 or less, more preferably 10 ⁇ 10 ⁇ 4 or less.
  • the ceramic substrate can be applied to a high-frequency circuit board, which is preferable.
  • sintering can be performed at a low temperature of 1200 to 1400 ° C., and a ceramic body having a bending strength of 600 MPa or more can be realized.
  • Al is the less than 89.0 wt% in terms of Al 2 O 3 amount of Al 2 O 3 which is produced is reduced, resulting in a decrease in bending strength. If it exceeds 92.0% by mass, the amount of Mn 2 SiO 4 glass phase produced decreases, densification at 1200 to 1400 ° C. is not achieved, and bending strength is reduced.
  • Mg exceeds 2.0% by mass in terms of MgO, the amount of Mn 2 SiO 4 glass phase produced decreases, densification at 1200 to 1400 ° C. is not achieved, and bending strength is reduced. .
  • Si is less than 2.0% by mass in terms of SiO 2 , the amount of Mn 2 SiO 4 glass phase produced is reduced, densification at 1200-1400 ° C. is not achieved, and bending strength is reduced. Bring. If it exceeds 5.0% by mass, the amount of Al 2 O 3 produced decreases, resulting in a decrease in bending strength.
  • Mn is less than 2.0% by mass in terms of MnO
  • the amount of Mn 2 SiO 4 glass phase produced is reduced, densification at 1200 to 1400 ° C. is not achieved, and bending strength is reduced. . If it exceeds 5.0% by mass, the bending strength is reduced due to the reduction in the amount of Al 2 O 3 produced. Further, since the MnAl 2 O 4 crystal phase is generated, densification is inhibited and the strength is reduced.
  • the generation of MnAl 2 O 4 cannot be suppressed, and for example, the chipping occurrence rate at the time of chip division by a pressing roller can be suppressed to 0.1% or less. become unable. When it exceeds 2.0 mass%, softening will progress and it will become difficult to implement
  • the strength of the glass phase to be generated can be increased.
  • the bending strength is increased, and a product using a ceramic substrate ( It is possible to promote downsizing of a ceramic package or the like.
  • it can be produced at a low firing temperature, which is advantageous for cost reduction.
  • the generated BaAl 2 Si 2 O 8 crystal phase suppresses extremely high hardness, can reduce the chipping occurrence rate in chip division by the pressure roller, and can improve productivity. it can.
  • the ceramic package according to the first configuration example (hereinafter referred to as the first package 10A) is similar to the multilayer substrate 12 configured with the ceramic substrate according to the present embodiment.
  • a ceramic body according to the embodiment has a lid 14.
  • the laminated substrate 12 is configured by laminating at least a plate-like first substrate 16a, a plate-like second substrate 16b, and a frame 18 in this order.
  • the laminated substrate 12 includes an upper surface electrode 20 formed on the upper surface of the second substrate 16b, a lower surface electrode 22 formed on the lower surface of the first substrate 16a, an inner layer electrode 24 formed inside, and the inner layer.
  • a first via hole 26a that electrically connects the electrode 24 and the lower surface electrode 22 and a second via hole 26b that electrically connects the inner layer electrode 24 and the upper surface electrode 20 are provided.
  • a crystal resonator 30 is electrically connected to the upper surface electrode 20 via a conductor layer 32 in an accommodation space 28 surrounded by the upper surface of the second substrate 16b and the frame body 18. Yes. Further, in order to protect the crystal unit 30, the lid 14 is hermetically sealed on the upper surface of the frame 18 through the glass layer 34.
  • the crystal resonator 30 is mounted in the accommodation space 28 , but in addition, at least one or more of resistors, filters, capacitors, and semiconductor elements may be mounted. Good.
  • the dielectric loss tangent is 30 ⁇ 10 ⁇ 4 or less at 1 MHz to 10 GHz, it is also suitable as a high frequency circuit board.
  • the bending strength is 600 MPa or more. If the bending strength is lower than 600 MPa, thermal stress may be applied during the sealing of the lid body 14 or the secondary mounting, resulting in destruction. Alternatively, there is a risk of destruction due to an impact or the like during handling or use. If the bending strength is 600 MPa or more, such a risk of destruction can be avoided. Further, even when the ceramic substrate is used as the laminated substrate 12 and the lid body 14 of the first package 10A without polishing the surface, it is possible to prevent breakage when the lid body 14 is hermetically sealed. The manufacturing cost and reliability of 10A can be improved.
  • the “bending strength” refers to a four-point bending strength, which is a value measured at room temperature based on JIS R1601 (bending test method for fine ceramics).
  • the ceramic substrate according to the present embodiment has the above-described composition, it can be sintered at a low temperature of 1200 to 1400 ° C. Therefore, the precursor of the ceramic base (molded body before firing), the electrodes (upper surface electrode 20, lower surface electrode 22, inner layer electrode 24) and via hole 26 (first via hole 26a, second via hole 26b) are simultaneously fired. Thus, the laminated substrate 12 can be manufactured, and the manufacturing process can be simplified.
  • step S1a of FIG. 2 the Al 2 O 3 powder is 89.0 to 92.0% by mass, the SiO 2 powder is 2.0 to 5.0% by mass, and the MnCO 3 powder is 3.2 to 8.1%.
  • a mixed powder containing 1% by mass, 0 to 2.0% by mass of MgO powder and 0.06 to 2.6% by mass of BaCO 3 powder is prepared.
  • step S1b an organic component (binder) is prepared, and step S1c Prepare a solvent.
  • the average particle diameter of the Al 2 O 3 powder is preferably 0.7 to 2.5 ⁇ m.
  • the thickness is less than 0.7 ⁇ m, a MnAl 2 O 4 crystal phase is generated, so that densification is inhibited and strength is reduced. If it exceeds 2.5 ⁇ m, the strength is lowered due to the decrease in sinterability of Al 2 O 3 itself.
  • the average particle diameter of the SiO 2 powder is preferably 0.1 to 2.5 ⁇ m.
  • the average particle diameter of the MnCO 3 powder is preferably 0.5 to 4.0 ⁇ m.
  • the average particle size of the MgO powder is preferably 0.1 to 1.0 ⁇ m.
  • the average particle size of the BaCO 3 powder is preferably 0.5 to 4.0 ⁇ m.
  • Examples of the organic component (binder) prepared in step S1b include a resin, a surfactant, and a plasticizer.
  • examples of the resin include polyvinyl butyral
  • examples of the surfactant include tertiary amines
  • examples of the plasticizer include phthalic acid esters (for example, diisononyl phthalate: DINP).
  • Examples of the solvent prepared in step S1c include alcohol solvents and aromatic solvents.
  • Examples of the alcohol solvent include IPA (isopropyl alcohol), and examples of the aromatic solvent include toluene.
  • step S2 after mixing and dispersing the organic component and the solvent in the above-mentioned mixed powder, in step S3, by a known molding method such as a press method, a doctor blade method, a rolling method, an injection method, A ceramic molded body (also referred to as a ceramic tape) that is a precursor of the ceramic substrate is produced.
  • a known molding method such as a press method, a doctor blade method, a rolling method, an injection method
  • a ceramic molded body also referred to as a ceramic tape
  • an organic component or a solvent is added to the mixed powder to prepare a slurry, and then a ceramic tape having a predetermined thickness is formed by a doctor blade method.
  • an organic component is added to the mixed powder, and a ceramic tape having a predetermined thickness is produced by press molding, rolling molding, or the like.
  • step S4 the ceramic tape is cut and processed into a desired shape, a first tape having a large area for the first substrate, a second tape having a large area for the second substrate, and a third tape for the frame. Then, a fourth tape for the lid is produced, and further, through holes for forming the first via hole 26a and the second via hole 26b are formed by micro drilling, laser processing, or the like.
  • step S5 a conductor paste for forming the upper surface electrode 20, the lower surface electrode 22, and the inner layer electrode 24 is applied to the first tape and the second tape manufactured as described above by screen printing, gravure printing, or the like.
  • a printing paste is applied by a method, and further, a conductor paste is filled in the through holes as desired.
  • the conductor paste uses, as a conductor component, at least one of high melting point metals such as W (tungsten) and Mo (molybdenum), and is equivalent to Al 2 O 3 powder, SiO 2 powder, or ceramic substrate.
  • high melting point metals such as W (tungsten) and Mo (molybdenum)
  • W tungsten
  • Mo molybdenum
  • a powder added in an amount of 1 to 20% by mass, particularly 8% by mass or less is preferable.
  • step S6 the first tape and the second tape on which the conductive paste is printed and applied, and the third tape for the frame are aligned and laminated and pressure-bonded to produce a laminated body.
  • step S7 dividing grooves for dividing the chip are formed on both surfaces of the laminate by, for example, knife cutting.
  • a laminated original plate (multiple substrate) in which the laminate and the conductor paste are simultaneously fired is produced.
  • this firing as described above, it is possible to produce a ceramic substrate having a crystal phase of Al 2 O 3 as a main crystal phase and including only a BaAl 2 Si 2 O 8 crystal phase, that is, a multi-chip substrate. it can.
  • the oxidation of the metal in the conductor paste can be prevented by performing the firing atmosphere in the forming gas atmosphere as described above.
  • the firing temperature is preferably in the temperature range described above. When the firing temperature is lower than 1200 ° C., the densification is insufficient and the bending strength does not reach 600 MPa. When the firing temperature is higher than 1400 ° C., the first tape, the second tape, and the third tape constituting the laminated body Variations in shrinkage rate increase and dimensional accuracy decreases. This leads to a decrease in yield and increases the cost. Of course, the higher the firing temperature, the more expensive the equipment.
  • step S9 the above-mentioned multi-cavity substrate is plated, and the conductor layer formed on the surface of the multi-cavity substrate is made of Ni, Co, Cr, Au, Pd and Cu.
  • a plating layer composed of at least one kind is formed, and a large number of upper surface electrodes 20 and a large number of lower surface electrodes 22 are formed on the surface of the multi-piece substrate.
  • step S10 the multi-piece substrate is pressed with a pressing roller or the like to be divided into a plurality of pieces (chip division), and a plurality of laminated substrates 12 having the accommodation spaces 28 are produced.
  • step S ⁇ b> 11 the crystal resonator 30 is mounted on the upper surface electrode 20 via the conductor layer 32 in each accommodation space 28 of the plurality of laminated substrates 12.
  • step S12 the quartz resonator 30 is mounted inside by sealing hermetically with the ceramic lid 14 on which the sealing glass layer 34 is formed on the upper surface of each laminated substrate 12. A plurality of first packages 10A are completed.
  • the crystal phase includes Al 2 O 3 as the main crystal phase, and includes only the BaAl 2 Si 2 O 8 crystal phase.
  • a ceramic substrate having a bending strength of 600 MPa or more can be produced.
  • ceramic bodies that can be made smaller and thinner, and improved in bending strength, such as ceramic packages, can be produced at a low firing temperature, reducing the cost of ceramic bodies and products using ceramic bodies. can do.
  • a ceramic package according to a second configuration example (hereinafter referred to as a second package 10B) will be described with reference to FIGS.
  • the second package 10B has substantially the same configuration as the first package 10A described above, but differs in the following points.
  • the metal lid 40 is hermetically sealed on the frame 18 of the laminated substrate 12 using a high-temperature sealing material 42 such as silver solder.
  • a bonding layer 44 is interposed between the upper surface of the frame 18 of the laminated substrate 12 and the high temperature sealing material 42.
  • the bonding layer 44 includes a metallized layer 46 formed of the same material as the upper surface electrode 20 on the upper surface of the frame 18, an electrolytic plating layer 48 of, for example, nickel (Ni) formed on the metalized layer 46,
  • an electroless plating layer 50 made of gold (Au) is formed on the electrolytic plating layer 48 made of Ni.
  • the metal lid 40 is formed in a flat plate shape having a thickness of 0.05 to 0.20 mm, and is composed of an iron-nickel alloy plate or an iron-nickel-cobalt alloy plate.
  • a brazing material such as a silver-copper eutectic brazing which is a high-temperature sealing material 42 is formed on the lower surface (the entire surface or a portion corresponding to the frame 18) of the metal lid 40.
  • the thickness is about 5 to 20 ⁇ m.
  • the metal lid 40 is formed by punching a composite plate constituted by rolling an iron-nickel alloy plate or an iron-nickel-cobalt alloy plate with a brazing filler metal foil such as silver-copper brazing. It is produced by punching into a predetermined shape with a mold.
  • any one of the brazing material 1 (85Ag-15Cu), the brazing material 2 (72Ag-28Cu), and the brazing material 3 (67Ag-29Cu-4Sn) shown in Table 1 below is used. Can be used.
  • Ni electroplating layer 48 and the Au electroless plating layer 50 function as layers that improve the wettability of the high-temperature sealing material 42 to the metallized layer 46.
  • step S101 of FIG. 4 a mixed powder, an organic component, and a solvent for preparing a ceramic tape are prepared.
  • the mixed powder, organic component, and solvent to be prepared are the same as those in Step S1a, Step S1b, and Step S1c described above, and therefore redundant description thereof is omitted.
  • step S102 the organic component and the solvent are mixed and dispersed in the above-described mixed powder.
  • step S103 the ceramic substrate is formed by a known forming method such as a pressing method, a doctor blade method, a rolling method, or an injection method.
  • a ceramic molded body (ceramic tape) which is a precursor of the above is prepared.
  • step S104 the ceramic tape is cut and processed into a desired shape, a first tape having a large area for the first substrate 16a, a second tape having a large area for the second substrate 16b, and a frame for the frame 18.
  • a third tape is manufactured, and further, a through hole for forming the first via hole 26a and the second via hole 26b is formed by micro drilling, laser processing, or the like.
  • a raw material powder, an organic component and a solvent for the conductor paste are prepared.
  • the raw material powder to be prepared is at least one of metal powders such as W (tungsten), Mo (molybdenum), and nickel (Ni), and an Al 2 O 3 powder or SiO 2 powder as appropriate.
  • the organic component to be prepared include a resin (for example, ethyl cellulose) and a surfactant.
  • the solvent to be prepared include terpenol.
  • step S106 a conductive paste is prepared by mixing and dispersing the organic component and the solvent in the mixed powder.
  • step S107 a conductive paste is applied by printing such as screen printing or gravure printing to the first to third tapes produced as described above.
  • step S108 the first tape to the third tape on which the conductive paste is printed and applied are aligned and laminated and pressed to produce a laminated body.
  • step S109 dividing grooves for dividing the chip are formed on both surfaces of the laminate by, for example, knife cutting.
  • a forming gas atmosphere wetter temperature 25 to 47 ° C.
  • H 2 / N 2 30% / 70%.
  • a laminated original plate in which the laminate and the conductor paste are simultaneously fired is produced.
  • This multi-cavity substrate has a shape in which the shapes of a large number of frames 18 are integrally arranged.
  • the conductive paste becomes an electrode (the upper surface electrode 20 or the like) or the metallized layer 46 by this firing.
  • the surface of the metallized layer 46 is washed with alkali, acid, or the like (pretreatment). That is, acid cleaning is performed after alkali cleaning.
  • the alkali and acid may be used after diluted to an appropriate concentration.
  • the pretreatment is performed at a temperature of about 20 ° C. to 70 ° C. and between several minutes to several tens of minutes.
  • Ni electroplating is performed to form an Ni electroplating layer 48 (film thickness: 1.0 to 5.0 ⁇ m) on the metallized layer 46.
  • step S113 after performing an electroless plating process of palladium (Pd), an electroless plating process of Au is performed, and an electroless plating layer 50 of Au (film thickness: 0.05) is formed on the Ni electroplating layer 48. To 0.3 ⁇ m).
  • step S114 the multi-piece substrate is pressed with a pressing roller or the like and divided into a plurality of pieces (chip division), and a plurality of laminated substrates 12 each having an accommodation space 28 are produced.
  • step S 115 the crystal resonator 30 is mounted on the upper surface electrode 20 via the conductor layer 32 in each accommodation space 28 of the plurality of laminated substrates 12.
  • step S116 the metal lid 40 with the high temperature sealing material 42 formed on the back surface is placed on the frame 18 with the high temperature sealing material 42 and the upper surface (bonding layer 44) side of the frame 18 facing each other. Put on. Thereafter, while rolling the pair of roller electrodes of the seam welding machine in contact with the outer peripheral edges of the metal lid 40 facing each other, a current is passed between the roller electrodes, so that a part of the high-temperature sealing material 42 is removed. By melting, the metal lid body 40 is hermetically sealed on the frame body 18. The atmosphere at the time of sealing is performed in N 2 gas or vacuum. Thereby, a plurality of second packages 10B in which the crystal resonators 30 are mounted are completed.
  • Example 1 Raw material powder was prepared.
  • the raw material powder is an Al 2 O 3 powder having an average particle diameter of 1.5 ⁇ m, an MgO powder having an average particle diameter of 0.5 ⁇ m, an SiO 2 powder having an average particle diameter of 1.0 ⁇ m, an MnCO 3 powder having an average particle diameter of 1.0 ⁇ m, and an average BaCO 3 powder having a particle diameter of 1.0 ⁇ m and MoO 3 powder having an average particle diameter of 3.0 ⁇ m.
  • a ceramic tape having a thickness of 60 to 270 ⁇ m was produced by a doctor blade method.
  • the obtained ceramic tape was fired in a forming gas atmosphere with a firing temperature (maximum temperature) of 1380 ° C. and H 2 + N 2 to produce a ceramic substrate according to Example 1.
  • the conductor was formed by simultaneous firing.
  • As the ceramic substrate a first ceramic substrate for confirming the crystal phase and a second ceramic substrate for confirming the bending strength were prepared. The same applies to Examples 2 to 4 and Comparative Examples 1 to 7 described below.
  • Example 2 Among the raw material powders, 4.0% by mass of SiO 2 powder, 4.7% by mass of MnCO 3 powder (2.9% by mass in terms of MnO), 0.0% by mass (without addition) of MgO powder, BaCO 3
  • the ceramic substrate according to Example 2 was obtained in the same manner as in Example 1 except that the powder was 1.2% by mass (0.9% by mass in terms of BaO) and the firing temperature (maximum temperature) was 1360 ° C. Produced.
  • Example 3 A ceramic substrate according to Example 3 was fabricated in the same manner as in Example 2 described above except that the firing temperature (maximum temperature) was 1320 ° C.
  • Example 4 Among the raw material powders, Al 2 O 3 powder is 90.5% by mass, SiO 2 powder is 4.4% by mass, MnCO 3 powder is 5.7% by mass (MnO conversion 3.5% by mass), and MgO powder is 0%. 0.0 mass% (no addition), BaCO 3 powder was 1.3 mass% (1.0 mass% in terms of BaO), and the firing temperature (maximum temperature) was 1320 ° C. Example 1 described above In the same manner, a ceramic substrate according to Example 4 was produced.
  • Comparative Example 1 (Comparative Example 1) Among raw material powders, SiO 2 powder is 3.8% by mass, MnCO 3 powder is 6.0% by mass (MnO conversion 3.7% by mass), BaCO 3 powder is 0.0% by mass (not added), A ceramic substrate according to Comparative Example 1 was produced in the same manner as in Example 1 except that the firing temperature (maximum temperature) was 1360 ° C.
  • Comparative Example 2 Of the raw material powders, 91.0% by mass of Al 2 O 3 powder, 4.0% by mass of SiO 2 powder, 4.7% by mass of MnCO 3 powder (2.9% by mass in terms of MnO), and 0% of MgO powder 0.5 mass%, MoO 3 powder 0.0 mass% (without addition), BaCO 3 powder 0.0 mass% (without addition), TiO 2 powder 1.0 mass%, and firing temperature (maximum A ceramic substrate according to Comparative Example 2 was produced in the same manner as in Example 1 except that the temperature was 1330 ° C.
  • Comparative Example 3 A ceramic substrate according to Comparative Example 3 was produced in the same manner as Comparative Example 2 except that firing was performed in the air.
  • the conductor was not formed by simultaneous firing, but was formed after firing.
  • Comparative Example 4 Among the raw material powders, 90.5% by mass of Al 2 O 3 powder, 5.0% by mass of SiO 2 powder, 1.9% by mass of MnCO 3 powder (1.2% by mass in terms of MnO), 0% of MgO powder .8 wt%, MoO 3 powder 0.0 wt% (not added), BaCO 3 powder 1.0 wt% (BaO terms 0.8 wt%), a TiO 2 powder and 1.7 wt%, A ceramic substrate according to Comparative Example 4 was produced in the same manner as in Example 1 except that the firing temperature (maximum temperature) was 1300 ° C.
  • Comparative Example 5 (Comparative Example 5) Among the raw material powders, 92.0% by mass of Al 2 O 3 powder, 4.0% by mass of SiO 2 powder, 6.3% by mass of MnCO 3 powder (3.9% by mass in terms of MnO), 0% of MgO powder 0.5% by mass, MoO 3 powder 0.0% by mass (without addition), BaCO 3 powder 0.0% by mass (without addition), and the firing temperature (maximum temperature) at 1330 ° C. A ceramic substrate according to Comparative Example 5 was produced in the same manner as in Example 1 described above.
  • Comparative Example 7 Of the raw material powders, 91.0% by mass of Al 2 O 3 powder, 4.0% by mass of SiO 2 powder, 4.7% by mass of MnCO 3 powder (2.9% by mass in terms of MnO), and 0% of MgO powder 0.5% by mass, MoO 3 powder 0.0% by mass (without addition), BaCO 3 powder 0.0% by mass (without addition), Fe 3 O 4 powder 1.0% by mass, firing temperature
  • a ceramic substrate according to Comparative Example 7 was manufactured in the same manner as in Example 1 except that (maximum temperature) was 1300 ° C.
  • a multi-piece substrate 60 is manufactured.
  • the multi-chip substrate 60 is formed with division grooves 62 (depth: 2 ⁇ m) for chip division on the upper and lower surfaces of the base portion 16 at the stage of the laminated body before firing. .
  • the multi-piece substrate 60 in which the dividing grooves 62 are formed is pressed with a pressing roller to divide the chip into 529 laminated substrates 12, and then the divided end surfaces of the laminated substrates 12 are observed.
  • a recess having a diameter of 100 ⁇ m or more and a depth of 10 ⁇ m or more, or a protrusion having a diameter of 100 ⁇ m or more and a height of 10 ⁇ m or more is formed on at least one of the four divided end faces of one laminated substrate 12. If so, it is evaluated that chipping has occurred in the laminated substrate 12.
  • the chipping occurrence rate was defined as the ratio of the number of laminated substrates 12 in which chipping had occurred to 529, which is the chip division number of the multi-piece substrate 60.
  • 1/529 0.19%.
  • the chipping occurrence rate is (number of laminated substrates 12 on which chipping has occurred) / (529 ⁇ 5).
  • Table 2 shows the breakdown of Examples 1 to 4 and Comparative Examples 1 to 7, and Table 3 shows the evaluation results.
  • Comparative Examples 1 to 7 the chipping occurrence rate was 0.15% or more. Further, all of Comparative Examples 2 to 4 in which a MnTiO 3 phase was observed as a crystal phase had a large dielectric loss tangent. Among them, Comparative Example 4 in which the Mn 3 Al 2 (SiO 4 ) 3 phase was also observed had a bending strength as low as 500 MPa. Also, Comparative Examples 6 and 7 in which only Al 2 O 3 was observed as the crystal phase tended to have a large dielectric loss tangent.
  • the ceramic substrate and the manufacturing method thereof according to the present invention are not limited to the above-described embodiments, and various configurations can be adopted without departing from the gist of the present invention.

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Abstract

　本発明は、セラミック素地及びその製造方法に関する。結晶相が、Ａｌ2Ｏ3を主結晶相とし、その他、ＢａＡｌ2Ｓｉ2Ｏ8結晶相のみを含む。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％、ＢａをＢａＯ換算で０．０５～２．０質量％含む。

Description

セラミック素地及びその製造方法
　本発明は、セラミック素地に関し、例えば内部に振動子等の素子が実装されるセラミック製のパッケージや高周波用回路基板等に用いて好適なセラミック素地及びその製造方法に関する。
　従来のセラミック素地、例えばアルミナを主結晶相とするセラミック素地、すなわち、アルミナ素地として、国際公開第２０１３／１４６５００号パンフレット、特許第４４１３２２３号公報、特許第４５７８０７６号公報、特許第４４１３２２４号公報及び特許第４２２０８６９号公報記載のアルミナ素地が知られている。
　国際公開第２０１３／１４６５００号パンフレットには、ＴｉＯ2（酸化チタン）を添加物として含み、アルミナ以外の結晶相として、ＭｎＴｉＯ3のみを含み、曲げ強度が６００ＭＰａの、小型化対応のセラミックパッケージ用素地が開示されている。
　特許第４４１３２２３号公報には、Ｍｎ酸化物、Ｓｉ酸化物を含み、Ａｌ2Ｏ3を主結晶相とし、ＭｎＡｌ2Ｏ4結晶を含み（Ｍｎ2ＳｉＯ4を除く）、３点曲げ強度が５００ＭＰａ以上のアルミナ質焼結体からなるセラミックパッケージが開示されている。その他の添加物として、Ｍｇ酸化物、Ｃａ酸化物、Ｓｒ酸化物、Ｂａ酸化物のうち少なくとも１種を含むことが記載されている。さらに、Ｗ、Ｍｏ等の遷移金属の金属粉末や酸化物粉末を着色成分として含んでもよいことが記載されている。
　特許第４５７８０７６号公報及び特許第４４１３２２４号公報には、Ｚｒ（ジルコニウム）、Ｓｉ（シリコン）、Ｍｎ（マンガン）、Ｔｉ（チタン）、Ｍｇ（マグネシウム）、Ｓｒ（ストロンチウム）、Ｂａ（バリウム）、Ｃａ（カルシウム：２ａ族）からなるアルミナ素地が記載されている。このアルミナ素地は、熱伝導率が１０Ｗ／ｍＫ以上、誘電正接が１～６０ＧＨｚで、２０×１０-4以下の高強度、高熱伝導、低誘電正接のアルミナ素地である。
　特許第４２２０８６９号公報には、小型対応のパッケージの強度対策について記載がある。具体的には、Ｍｎ2Ｏ3、ＭｇＣＯ3、ＳｉＯ2を添加剤として含むグリーンシートを１３５０～１５００℃で焼成するセラミックパッケージの製造方法が記載されている。
　国際公開第２０１３／１４６５００号パンフレット記載のセラミックパッケージ用の素地は、高強度であるが、Ｍｏ（モリブデン）、Ｗ（タングステン）の導体と同時焼成で、還元雰囲気で焼成するため、Ｔｉ4+からＴｉ3+への形成過程でホール（正孔）が形成され、誘電正接が大きくなる。振動子等が実装されるパッケージ用途では、絶縁体の誘電正接が大きくなることによる電気信号損失は問題とならないが、高周波用回路基板では問題となる。また、硬度の高いＭｎＴｉＯ3結晶相が粒界に存在するため、押圧ローラーを使用してのチップ分割の際に、チッピングが生じ易くなり、品質上の不具合率（ＮＧ率）が高くなる。
　特許第４４１３２２３号公報記載のセラミックパッケージ並びに特許第４４１３２２４号公報記載のアルミナ素地は、硬度の高いＭｎＡｌ2Ｏ4結晶相を含むため、国際公開第２０１３／１４６５００号パンフレットと同様に、押圧ローラーを使用してのチップ分割の際に、チッピングが生じ易くなり、品質上の不具合率（ＮＧ率）が高くなる。
　特許第４５７８０７６号公報及び特許第４４１３２２４号公報記載のアルミナ素地は、国際公開第２０１３／１４６５００号パンフレットと同様にＴｉを含むため、Ｍｏ導体、Ｗ導体との同時焼成で、アルミナ磁器の誘電正接が増大し、高周波用回路基板では問題になる。
　特許第４２２０８６９号公報記載の製造方法は、特許第４４１３２２３号公報の記載内容から推定し、ＭｎＡｌ2Ｏ4結晶相が形成されるものと想定されるため、特許第４４１３２２３号公報に記載の技術と同様の問題がある。
　本発明はこのような課題を考慮してなされたものであり、曲げ強度が高く、しかも、誘電正接が小さく、高周波用回路基板にも好適であり、また、チップ分割時のチッピング発生率も小さく、歩留りを向上させることができ、セラミック素地を用いた製品（セラミックパッケージ等）の小型化を低コストで実現することができるセラミック素地を提供することを目的とする。
　また、本発明の他の目的は、曲げ強度が高く、セラミックパッケージ等の小型化を実現することができるセラミック素地を、低い焼成温度にて作製することができ、セラミック素地並びにセラミック素地を用いた製品のコストを低減することができるセラミック素地の製造方法を提供することにある。
［１］　第１の本発明に係るセラミック素地は、結晶相が、Ａｌ2Ｏ3を主結晶相とし、その他、ＢａＡｌ2Ｓｉ2Ｏ8結晶相のみを含むことを特徴とする。
［２］　この場合、曲げ強度が６００ＭＰａ以上であることが好ましい。
［３］　また、温度１２００～１４００℃にて焼結されていることが好ましい。
［４］　第１の本発明において、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％、ＢａをＢａＯ換算で０．０５～２．０質量％含むことが好ましい。
［５］　第２の本発明に係るセラミック素地の製造方法は、Ａｌ2Ｏ3を主結晶相とするセラミック素地の製造方法であって、Ａｌ2Ｏ3粉末を８９．０～９２．０質量％、ＳｉＯ2粉末を２．０～５．０質量％、ＭｎＣＯ3粉末を３．２～８．１質量％（ＭｎＯ換算２．０～５．０質量％）、ＭｇＯ粉末を０～２．０質量％、ＢａＣＯ3粉末を０．０６～２．６質量％（ＢａＯ換算０．０５～２．０質量％）含有する成形体を作製する成形体作製工程と、成形体を１２００～１４００℃にて焼成する焼成工程とを有することを特徴とする。
［６］　第２の本発明において、成形体に、金属を含む導体層を形成する工程をさらに有し、焼成工程は、導体層が形成された成形体を焼成してもよい。
［７］　第２の本発明において、焼成工程は、水素を５％以上含む、水素と窒素のフォーミングガス中で行ってもよい。
　本発明に係るセラミック素地によれば、曲げ強度が高く、しかも、誘電正接が小さく、高周波用回路基板にも好適であり、また、チップ分割時のチッピング発生率も小さく、歩留りを向上させることができ、セラミック素地を用いた製品（セラミックパッケージ等）の小型化を低コストで実現することができる。
　また、本発明に係るセラミック素地の製造方法によれば、曲げ強度が高く、セラミックパッケージ等の小型化を実現することができるセラミック素地を、低い焼成温度にて作製することができ、セラミック素地並びにセラミック素地を用いた製品のコストを低減することができる。
図１は、本実施の形態に係るセラミック素地を用いた第１の構成例（第１パッケージ）を示す断面図である。 図２は、本実施の形態に係るセラミック素地の製造方法を、第１パッケージの製造方法と共に示す工程ブロック図である。 図３は、本実施の形態に係るセラミック素地を用いた第２の構成例（第２パッケージ）を示す断面図である。 図４は、本実施の形態に係るセラミック素地の製造方法を、第２パッケージの製造方法と共に示す工程ブロック図である。 図５Ａは、多数個取り基板を示す平面図であり、図５Ｂは、図５Ａ上の矢印ＶＢに示す部分の拡大図であり、図５Ｃは、図５ＢにおけるＶＣ－ＶＣ線上の断面図である。
　以下、本発明に係るセラミック素地及びその製造方法の実施の形態例を図１～図５Ｃを参照しながら説明する。なお、本明細書において数値範囲を示す「～」は、その前後に記載される数値を下限値及び上限値として含む意味として使用される。
　本実施の形態に係るセラミック素地は、Ａｌ2Ｏ3を主結晶相とし、その他、ＢａＡｌ2Ｓｉ2Ｏ8結晶相のみを含む。
　具体的には、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％、ＢａをＢａＯ算で０．０５～２．０質量％含むことが好ましい。
　具体的には、セラミック素地は、Ａｌ2Ｏ3粉末を８９．０～９２．０質量％、ＳｉＯ2粉末を２．０～５．０質量％、ＭｎＣＯ3粉末を３．２～８．１質量％（ＭｎＯ換算で２．０～５．０質量％）、ＭｇＯ粉末を０～２．０質量％、ＢａＣＯ3粉末を０．０６～２．６質量％（ＢａＯ換算で０．０５～２．０質量％）含有する成形体を作製した後、成形体を１２００～１４００℃にて焼成することにより作製される。
　ＭｇＯ粉末は、Ａｌ2Ｏ3の焼結助剤として添加され、ＳｉＯ2粉末は、Ａｌ2Ｏ3の焼結助剤として、また、Ｍｎ2ＳｉＯ4ガラス相を生成させて焼結温度の低下を図るために添加される。ＢａＣＯ3粉末は、硬度が高くなるＭｎＡｌ2Ｏ4の生成を抑制するために添加される。
　従来では、ＴｉＯ2粉末、Ｃｅ2Ｏ3粉末、Ｆｅ3Ｏ4粉末のいずれか１以上を含むようにしているが、誘電正接が大きくなるため、できるだけ含まないことが好ましい。含めるとしても、０．１質量％以下である。誘電正接は、１ＭＨｚ～１０ＧＨｚにおいて、３０×１０-4以下が好ましい。さらに好ましくは、１５×１０-4以下、より好ましくは１０×１０-4以下である。これにより、セラミック素地を高周波用回路基板にも適用することができ、好ましい。
　なお、必要に応じて、着色剤としてＭｏ酸化物やＷ酸化物を１．０質量％以下含めるようにしてもよい。
　これにより、温度１２００～１４００℃という低温にて焼結することができ、曲げ強度が６００ＭＰａ以上のセラミック素地を実現することができる。
　そして、ＡｌがＡｌ2Ｏ3換算で８９．０質量％未満だと、生成されるＡｌ2Ｏ3の量が低下し、曲げ強度の低下をもたらす。９２．０質量％を超えると、生成されるＭｎ2ＳｉＯ4ガラス相の量が低下し、１２００～１４００℃での緻密化が達成されず、また、曲げ強度の低下をもたらす。
　ＭｇがＭｇＯ換算で２．０質量％を超えると、生成されるＭｎ2ＳｉＯ4ガラス相の量が低下し、１２００～１４００℃での緻密化が達成されず、また、曲げ強度の低下をもたらす。
　ＳｉがＳｉＯ2換算で２．０質量％未満だと、生成されるＭｎ2ＳｉＯ4ガラス相の量が低下し、１２００～１４００℃での緻密化が達成されず、また、曲げ強度の低下をもたらす。５．０質量％を超えると、生成されるＡｌ2Ｏ3の量が低下し、曲げ強度の低下をもたらす。
　ＭｎがＭｎＯ換算で２．０質量％未満だと、生成されるＭｎ2ＳｉＯ4ガラス相の量が低下し、１２００～１４００℃での緻密化が達成されず、また、曲げ強度の低下をもたらす。５．０質量％を超えると、生成されるＡｌ2Ｏ3の量の低下による曲げ強度の低下をもたらす。また、ＭｎＡｌ2Ｏ4結晶相が生成されることから、緻密化が阻害され強度低下をもたらす。
　ＢａがＢａＯ換算で０．０５質量％未満だと、ＭｎＡｌ2Ｏ4の生成を抑制することができなくなり、例えば押圧ローラーによるチップ分割の際のチッピング発生率を０．１％以下に抑えることができなくなる。２．０質量％を超えると、軟化が進行し、押圧ローラーによるチップ分割が実現できにくくなる。また、誘電正接が大きくなる傾向にある。
　従って、Ａｌ、Ｓｉ、Ｍｎ、Ｍｇ及びＢａを上述した比率で含有させることで、生成されるガラス相の強度を高めることができ、その結果、曲げ強度が高くなり、セラミック素地を用いた製品（セラミックパッケージ等）の小型化を促進させることができる。しかも、低い焼成温度にて作製することができ、コストの低廉化に有利になる。さらに、生成されるＢａＡｌ2Ｓｉ2Ｏ8結晶相によって、硬度が極度に高くなることが抑制され、押圧ローラーによるチップ分割でのチッピング発生率を低下させることができ、生産性を向上させることができる。
　ここで、本実施の形態に係るセラミック素地を用いたセラミックパッケージの２つの構成例について図１～図４を参照しながら説明する。
　第１の構成例に係るセラミックパッケージ（以下、第１パッケージ１０Ａと記す）は、図１に示すように、本実施の形態に係るセラミック素地にて構成された積層基板１２と、同じく本実施の形態に係るセラミック素地にて蓋体１４とを有する。
　積層基板１２は、少なくとも板状の第１基板１６ａと、板状の第２基板１６ｂと、枠体１８とがこの順番で積層されて構成されている。また、この積層基板１２は、第２基板１６ｂの上面に形成された上面電極２０と、第１基板１６ａの下面に形成された下面電極２２と、内部に形成された内層電極２４と、該内層電極２４と下面電極２２とを電気的に接続する第１ビアホール２６ａと、内層電極２４と上面電極２０とを電気的に接続する第２ビアホール２６ｂとを有する。
　また、この第１パッケージ１０Ａは、第２基板１６ｂの上面と枠体１８とで囲まれた収容空間２８に、水晶振動子３０が導体層３２を介して上面電極２０に電気的に接続されている。さらに、水晶振動子３０を保護するため、枠体１８の上面に、蓋体１４がガラス層３４を介して気密に封止されている。
　上述した第１パッケージ１０Ａでは、収容空間２８内に、水晶振動子３０を実装した例を示したが、その他、抵抗体、フィルタ、コンデンサ、半導体素子のうち、少なくとも１種以上を実装してもよい。本実施の形態では、誘電正接が１ＭＨｚ～１０ＧＨｚにおいて、３０×１０-4以下であるため、高周波用回路基板としても好適である。
　そして、第１パッケージ１０Ａを構成する積層基板１２及び蓋体１４は、本実施の形態に係るセラミック素地にて構成しているため、曲げ強度が６００ＭＰａ以上である。曲げ強度が６００ＭＰａよりも低くなると、蓋体１４の封止の際や２次実装の際に熱応力が加わって破壊するおそれがある。あるいは、ハンドリングの際や使用の際の衝撃等により破壊するおそれがある。曲げ強度が６００ＭＰａ以上であれば、このような破壊のリスクを回避することができる。また、セラミック素地を表面研磨せずに、第１パッケージ１０Ａの積層基板１２及び蓋体１４として使用しても、蓋体１４を気密封止する際の破壊を防止することができ、第１パッケージ１０Ａの製造コスト及び信頼性を改善することができる。なお、「曲げ強度」とは、４点曲げ強度をいい、ＪＩＳＲ１６０１（ファインセラミックスの曲げ試験方法）に基づいて室温にて測定した値をいう。
　そして、本実施の形態に係るセラミック素地が、上述した組成を有することから、温度１２００～１４００℃という低温にて焼結させることができる。そのため、セラミック素地の前駆体（焼成前の成形体）と、電極（上面電極２０、下面電極２２、内層電極２４）及びビアホール２６（第１ビアホール２６ａ、第２ビアホール２６ｂ）とを同時焼成することで、積層基板１２を作製することができ、製造工程を簡略化することができる。
　次に、セラミック素地の製造方法を、例えば第１パッケージ１０Ａの製造方法に沿って図２を参照しながら説明する。
　先ず、図２のステップＳ１ａにおいて、Ａｌ2Ｏ3粉末を８９．０～９２．０質量％、ＳｉＯ2粉末を２．０～５．０質量％、ＭｎＣＯ3粉末を３．２～８．１質量％、ＭｇＯ粉末を０～２．０質量％、ＢａＣＯ3粉末を０．０６～２．６質量％含有する混合粉末を準備し、ステップＳ１ｂにおいて、有機成分（バインダー）を準備し、ステップＳ１ｃにおいて、溶剤を準備する。
　Ａｌ2Ｏ3粉末の平均粒径は、０．７～２．５μｍが好ましい。０．７μｍ未満だと、ＭｎＡｌ2Ｏ4結晶相が生成されることから、緻密化が阻害され強度低下をもたらす。２．５μｍを超えると、Ａｌ2Ｏ3自身の焼結性の低下により、強度低下をもたらす。
　ＳｉＯ2粉末の平均粒径は、０．１～２．５μｍが好ましい。ＭｎＣＯ3粉末の平均粒径は、０．５～４．０μｍが好ましい。ＭｇＯ粉末の平均粒径は０．１～１．０μｍが好ましい。ＢａＣＯ3粉末の平均粒径は、０．５～４．０μｍが好ましい。
　これらＳｉＯ2粉末、ＭｎＣＯ3粉末、ＭｇＯ粉末、ＢａＣＯ3粉末において、好ましい範囲の下限値未満だと、粒子の凝集の発生により、分散性が低下し、組成の不均一化、強度低下をもたらす。好ましい範囲の上限値を超えると、粒子自体のサイズが大きくなってしまうため、粒子を均一に分散させることが困難となり、組成の不均一化、強度低下をもたらす。
　ステップＳ１ｂにおいて準備される有機成分（バインダー）は、樹脂、界面活性剤、可塑剤等が挙げられる。樹脂としては、例えばポリビニルブチラールが挙げられ、界面活性剤としては、例えば３級アミンが挙げられ、可塑剤としては、例えばフタル酸エステル（例えばフタル酸ジイソノニル：ＤＩＮＰ）が挙げられる。
　ステップＳ１ｃにおいて準備される溶剤は、アルコール系溶剤、芳香族系溶剤等が挙げられる。アルコール系溶剤としては、例えばＩＰＡ（イソプロピルアルコール）が挙げられ、芳香族系溶剤としては、例えばトルエンが挙げられる。
　そして、次のステップＳ２において、上述の混合粉末に、有機成分及び溶剤を混合、分散させた後、ステップＳ３において、プレス法、ドクターブレード法、圧延法、射出法等の周知の成形方法によって、セラミック素地の前駆体であるセラミック成形体（セラミックテープとも記す）を作製する。例えば混合粉末に有機成分や溶剤を添加してスラリーを調製した後、ドクターブレード法によって所定の厚みのセラミックテープを形成する。あるいは、混合粉末に有機成分を加え、プレス成形、圧延成形等により所定の厚みのセラミックテープを作製する。
　ステップＳ４において、セラミックテープを所望の形状に切断、加工して、第１基板用の広い面積の第１テープと、第２基板用の広い面積の第２テープと、枠体用の第３テープと、蓋体用の第４テープを作製し、さらに、マイクロドリル加工、レーザー加工等により、第１ビアホール２６ａ及び第２ビアホール２６ｂを形成するための貫通孔を形成する。
　次に、ステップＳ５において、上述のように作製した第１テープ及び第２テープに対して、上面電極２０、下面電極２２、内層電極２４を形成するための導体ペーストをスクリーン印刷、グラビア印刷等の方法により印刷塗布し、さらに、所望により、導体ペーストを貫通孔内に充填する。
　導体ペーストは、導体成分として、例えばＷ（タングステン）、Ｍｏ（モリブデン）等の高融点金属のうち少なくとも１種を用い、これにＡｌ2Ｏ3粉末、又はＳｉＯ2粉末、又はセラミック素地と同等の粉末を例えば１～２０質量％、特に８質量％以下の割合で添加したものが好ましい。これにより、導体層の導通抵抗を低く維持したままアルミナ焼結体と導体層の密着性を高め、めっき欠け等の不良の発生を防止することができる。
　その後、ステップＳ６において、導体ペーストを印刷塗布した第１テープ及び第２テープ並びに枠体用の第３テープを位置合わせし、積層圧着して、積層体を作製する。
　その後、ステップＳ７において、積層体の両面にチップ分割のための分割溝を例えばナイフカットにて形成する。
　次のステップＳ８において、積層体及び第４テープを、水素を５％以上含む、水素と窒素のフォーミングガス雰囲気、例えばＨ2／Ｎ2＝３０％／７０％のフォーミングガス雰囲気（ウェッター温度２５～４７℃）で、１２００～１４００℃の温度範囲で焼成する。これによって、積層体及び導体ペーストが同時焼成された積層原板（多数個取り基板）が作製される。この焼成によって、上述したように、結晶相が、Ａｌ2Ｏ3を主結晶相とし、その他、ＢａＡｌ2Ｓｉ2Ｏ8結晶相のみを含むセラミック素地、すなわち、多数個取り基板を作製することができる。
　焼成雰囲気を、上述のようなフォーミングガス雰囲気で行うことで、導体ペースト中の金属の酸化を防止することができる。焼成温度は、上述した温度範囲が好ましい。焼成温度が１２００℃よりも低いと、緻密化が不十分で曲げ強度が６００ＭＰａに達せず、また、１４００℃よりも高くなると、積層体を構成する第１テープ、第２テープ及び第３テープの収縮率のばらつきが大きくなり、寸法精度が低下する。これは歩留りの低下につながり、コストの高価格化を招く。もちろん、焼成温度が高くなれば、それだけ設備にコストがかかるという問題もある。
　次に、ステップＳ９において、上述の多数個取り基板にめっき処理を行って、該多数個取り基板の表面に形成されている導体層に、Ｎｉ、Ｃｏ、Ｃｒ、Ａｕ、Ｐｄ及びＣｕのうち、少なくとも１種からなるめっき層を形成し、多数個取り基板の表面に多数の上面電極２０及び多数の下面電極２２を形成する。
　その後、ステップＳ１０において、多数個取り基板を、押圧ローラー等で押し当てて複数に分割し（チップ分割）、収容空間２８を有する複数の積層基板１２を作製する。ステップＳ１１において、複数の積層基板１２の各収容空間２８にそれぞれ水晶振動子３０を上面電極２０に導体層３２を介して実装する。
　そして、ステップＳ１２において、各積層基板１２の上面に、封止用のガラス層３４が形成されたセラミック製の蓋体１４により気密に封止することによって、内部に水晶振動子３０が実装された複数の第１パッケージ１０Ａが完成する。
　この第１パッケージ１０Ａの製造方法（セラミック素地の製造方法）においては、上述したように、結晶相が、Ａｌ2Ｏ3を主結晶相とし、その他、ＢａＡｌ2Ｓｉ2Ｏ8結晶相のみを含み、曲げ強度が６００ＭＰａ以上のセラミック素地を作製することができる。すなわち、セラミックパッケージ等の小型化及び薄型化、並びに曲げ強度の向上を図ることができるセラミック素地を、低い焼成温度にて作製することができ、セラミック素地並びにセラミック素地を用いた製品のコストを低減することができる。
　次に、第２の構成例に係るセラミックパッケージ（以下、第２パッケージ１０Ｂと記す）について、図３及び図４を参照しながら説明する。
　この第２パッケージ１０Ｂは、図３に示すように、上述した第１パッケージ１０Ａとほぼ同様の構成を有するが、以下の点で異なる。
　すなわち、金属蓋体４０を、積層基板１２の枠体１８上に、銀ろう等の高温封止材４２を用いて気密封止している。
　また、積層基板１２の枠体１８の上面と高温封止材４２との間に接合層４４が介在されている。この接合層４４は、枠体１８の上面に、上面電極２０と同じ材料で形成されたメタライズ層４６と、該メタライズ層４６上に形成された例えばニッケル（Ｎｉ）の電解めっき層４８と、該Ｎｉの電解めっき層４８上に形成された例えば金（Ａｕ）の無電解めっき層５０とを有する。
　金属蓋体４０は、厚みが０．０５～０．２０ｍｍの平板状に形成され、鉄－ニッケル合金板あるいは鉄－ニッケル－コバルト合金板にて構成されている。この金属蓋体４０の下面（全面あるいは枠体１８に対応した部分）には、高温封止材４２である銀－銅共晶ろう等のろう材が形成されている。厚みは５～２０μｍ程度である。
　具体的には、金属蓋体４０は、鉄－ニッケル合金板あるいは鉄－ニッケル－コバルト合金板の下面に銀－銅ろう等のろう材箔を重ねて圧延して構成される複合板を打ち抜き金型で所定の形状に打ち抜くことによって作製される。
　高温封止材４２としては、具体的には、下記表１に示すろう材１（８５Ａｇ－１５Ｃｕ）、ろう材２（７２Ａｇ－２８Ｃｕ）、ろう材３（６７Ａｇ－２９Ｃｕ－４Ｓｎ）のいずれかを使用することができる。
Figure JPOXMLDOC01-appb-T000001
　Ｎｉの電解めっき層４８及びＡｕの無電解めっき層５０は、高温封止材４２のメタライズ層４６に対する濡れ性を向上させる層として機能する。
　次に、第２パッケージ１０Ｂの製造方法を図４を参照しながら説明する。なお、図２と重複する工程については説明を省略する。
　先ず、図４のステップＳ１０１において、セラミックテープを作製するための混合粉末、有機成分及び溶剤を準備する。準備する混合粉末、有機成分及び溶剤は、上述したステップＳ１ａ、ステップＳ１ｂ及びステップＳ１ｃと同じであるため、その重複説明を省略する。
　そして、ステップＳ１０２において、上述の混合粉末に、有機成分及び溶剤を混合、分散させた後、ステップＳ１０３において、プレス法、ドクターブレード法、圧延法、射出法等の周知の成形方法によって、セラミック素地の前駆体であるセラミック成形体（セラミックテープ）を作製する。
　ステップＳ１０４において、セラミックテープを所望の形状に切断、加工して、第１基板１６ａ用の広い面積の第１テープと、第２基板１６ｂ用の広い面積の第２テープと、枠体１８用の第３テープとを作製し、さらに、マイクロドリル加工、レーザー加工等により、第１ビアホール２６ａ及び第２ビアホール２６ｂを形成するための貫通孔を形成する。
　一方、ステップＳ１０５において、導体ペースト用の原料粉末、有機成分及び溶剤を準備する。準備する原料粉末は、上述したように、Ｗ（タングステン）、Ｍｏ（モリブデン）、ニッケル（Ｎｉ）等の金属粉末のうち少なくとも１種と、これに適宜Ａｌ2Ｏ3粉末、又はＳｉＯ2粉末、又はセラミック素地と同等の粉末を例えば１～２０質量％、特に８質量％以下の割合で添加した混合粉末が挙げられる。準備する有機成分は、樹脂（例えばエチルセルロース）、界面活性剤等が挙げられる。準備する溶剤は、ターペノール等が挙げられる。
　そして、ステップＳ１０６において、上述の混合粉末に、有機成分及び溶剤を混合、分散させて導体ペーストを調製する。
　次に、ステップＳ１０７において、上述のように作製した第１テープ～第３テープに対して、導体ペーストをスクリーン印刷、グラビア印刷等の方法により印刷塗布する。
　その後、ステップＳ１０８において、導体ペーストを印刷塗布した第１テープ～第３テープを位置合わせし、積層圧着して、積層体を作製する。
　その後、ステップＳ１０９において、積層体の両面にチップ分割のための分割溝を例えばナイフカットにて形成する。
　次のステップＳ１１０において、積層体を、Ｈ2／Ｎ2＝３０％／７０％のフォーミングガス雰囲気（ウェッター温度２５～４７℃）で、１２００～１４００℃の温度範囲で焼成する。これによって、積層体及び導体ペーストが同時焼成された積層原板（多数個取り基板）が作製される。この多数個取り基板は、多数の枠体１８の形状が一体に配列された形状を有する。また、この焼成によって、導体ペーストが電極（上面電極２０等）やメタライズ層４６となる。
　次のステップＳ１１１において、アルカリ、酸等で少なくともメタライズ層４６の表面を洗浄する（前処理）。すなわち、アルカリ洗浄を行った後、酸洗浄を行う。前処理では、アルカリ及び酸は適当な濃度に希釈されて使用されてもよい。また、前処理は、２０℃から７０℃程度の温度と、数分から数十分の間で実施される。
　ステップＳ１１２において、Ｎｉの電解めっき処理を行って、メタライズ層４６上にＮｉの電解めっき層４８（膜厚：１．０～５．０μｍ）を形成する。
　ステップＳ１１３において、パラジウム（Ｐｄ）の無電解めっき処理を行った後、Ａｕの無電解めっき処理を行って、Ｎｉの電解めっき層４８上にＡｕの無電解めっき層５０（膜厚：０．０５～０．３μｍ）を形成する。
　その後、ステップＳ１１４において、多数個取り基板を、押圧ローラー等で押し当てて複数に分割し（チップ分割）、それぞれ収容空間２８を有する複数の積層基板１２を作製する。その後、ステップＳ１１５において、複数の積層基板１２の各収容空間２８にそれぞれ水晶振動子３０を上面電極２０に導体層３２を介して実装する。
　そして、ステップＳ１１６において、裏面に高温封止材４２が形成された金属蓋体４０を、高温封止材４２と枠体１８の上面（接合層４４）側とを対向させて、枠体１８上に被せる。その後、金属蓋体４０の相対向する外周縁にシーム溶接機の一対のローラー電極を接触させながら転動させると共に、このローラー電極間に電流を流すことで、高温封止材４２の一部を溶融させることにより、枠体１８上に金属蓋体４０を気密封止する。封止時の雰囲気は、Ｎ2ガス又は真空中で行われる。これにより、内部に水晶振動子３０が実装された複数の第２パッケージ１０Ｂが完成する。
　実施例１～４、比較例１～７について、セラミック素地のＡｌ2Ｏ3以外の結晶相、曲げ強度（抗折強度）、誘電正接、チッピング発生率を確認した。
（実施例１）
　原料粉末を準備した。原料粉末は、平均粒径１．５μｍのＡｌ2Ｏ3粉末、平均粒径０．５μｍのＭｇＯ粉末、平均粒径１．０μｍのＳｉＯ2粉末、平均粒径１．０μｍのＭｎＣＯ3粉末及び平均粒径１．０μｍのＢａＣＯ3粉末、平均粒径３．０μｍのＭｏＯ3粉末である。
　原料粉末を下記表２に示す割合（Ａｌ2Ｏ3粉末：９１．８質量％、ＳｉＯ2粉末：４．５質量％、ＭｎＣＯ3粉末：４．４質量％（ＭｎＯ換算２．７質量％）、ＭｇＯ粉末：０．３質量％、ＭｏＯ3粉末：０．５質量％、ＢａＣＯ3粉末：０．３質量％（ＢａＯ換算０．２質量％））で混合して混合粉末を得た。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、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、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、拡散してスラリーを調製し、その後、ドクターブレード法にて厚さ６０～２７０μｍ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焼成温度（最高温度）が１３８０℃、Ｈ2＋Ｎ2のフォーミングガス雰囲気にて焼成して実施例１に係るセラミック素地を作製した。導体は同時焼成にて形成した。セラミック素地は、結晶相を確認するための第１セラミック素地と、曲げ強度を確認するための第２セラミック素地を作製した。以下に説明する実施例２～４並びに比較例１～７についても同様である。
（実施例２）
　原料粉末のうち、ＳｉＯ2粉末を４．０質量％、ＭｎＣＯ3粉末を４．７質量％（ＭｎＯ換算２．９質量％）、ＭｇＯ粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を１．２質量％（ＢａＯ換算０．９質量％）とし、焼成温度（最高温度）を１３６０℃とした点以外は、上述した実施例１と同様にして実施例２に係るセラミック素地を作製した。
（実施例３）
　焼成温度（最高温度）を１３２０℃とした点以外は、上述した実施例２と同様にして実施例３に係るセラミック素地を作製した。
（実施例４）
　原料粉末のうち、Ａｌ2Ｏ3粉末を９０．５質量％、ＳｉＯ2粉末を４．４質量％、ＭｎＣＯ3粉末を５．７質量％（ＭｎＯ換算３．５質量％）、ＭｇＯ粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を１．３質量％（ＢａＯ換算１．０質量％）とし、焼成温度（最高温度）を１３２０℃とした点以外は、上述した実施例１と同様にして実施例４に係るセラミック素地を作製した。
（比較例１）
　原料粉末のうち、ＳｉＯ2粉末を３．８質量％、ＭｎＣＯ3粉末を６．０質量％（ＭｎＯ換算３．７質量％）、ＢａＣＯ3粉末を０．０質量％（添加せず）とし、焼成温度（最高温度）を１３６０℃とした点以外は、上述した実施例１と同様にして比較例１に係るセラミック素地を作製した。
（比較例２）
　原料粉末のうち、Ａｌ2Ｏ3粉末を９１．０質量％、ＳｉＯ2粉末を４．０質量％、ＭｎＣＯ3粉末を４．７質量％（ＭｎＯ換算２．９質量％）、ＭｇＯ粉末を０．５質量％、ＭｏＯ3粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を０．０質量％（添加せず）、ＴｉＯ2粉末を１．０質量％とし、焼成温度（最高温度）を１３３０℃とした点以外は、上述した実施例１と同様にして比較例２に係るセラミック素地を作製した。
　（比較例３）
　大気中で焼成したこと以外は、比較例２と同様にして比較例３に係るセラミック素地を作製した。この比較例３では、導体を、同時焼成では形成せず、焼成後に形成した。
　（比較例４）
　原料粉末のうち、Ａｌ2Ｏ3粉末を９０．５質量％、ＳｉＯ2粉末を５．０質量％、ＭｎＣＯ3粉末を１．９質量％（ＭｎＯ換算１．２質量％）、ＭｇＯ粉末を０．８質量％、ＭｏＯ3粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を１．０質量％（ＢａＯ換算０．８質量％）、ＴｉＯ2粉末を１．７質量％とし、焼成温度（最高温度）を１３００℃とした点以外は、上述した実施例１と同様にして比較例４に係るセラミック素地を作製した。
　（比較例５）
　原料粉末のうち、Ａｌ2Ｏ3粉末を９２．０質量％、ＳｉＯ2粉末を４．０質量％、ＭｎＣＯ3粉末を６．３質量％（ＭｎＯ換算３．９質量％）、ＭｇＯ粉末を０．５質量％、ＭｏＯ3粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を０．０質量％（添加せず）とし、焼成温度（最高温度）を１３３０℃とした点以外は、上述した実施例１と同様にして比較例５に係るセラミック素地を作製した。
　（比較例６）
　原料粉末のうち、Ａｌ2Ｏ3粉末を９１．０質量％、ＳｉＯ2粉末を４．０質量％、ＭｎＣＯ3粉末を４．７質量％（ＭｎＯ換算２．９質量％）、ＭｇＯ粉末を０．５質量％、ＭｏＯ3粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を０．０質量％（添加せず）、Ｃｒ2Ｏ3粉末を１．０質量％とし、焼成温度（最高温度）を１３００℃とした点以外は、上述した実施例１と同様にして比較例６に係るセラミック素地を作製した。
　（比較例７）
　原料粉末のうち、Ａｌ2Ｏ3粉末を９１．０質量％、ＳｉＯ2粉末を４．０質量％、ＭｎＣＯ3粉末を４．７質量％（ＭｎＯ換算２．９質量％）、ＭｇＯ粉末を０．５質量％、ＭｏＯ3粉末を０．０質量％（添加せず）、ＢａＣＯ3粉末を０．０質量％（添加せず）、Ｆｅ3Ｏ4粉末を１．０質量％とし、焼成温度（最高温度）を１３００℃とした点以外は、上述した実施例１と同様にして比較例７に係るセラミック素地を作製した。
（評価）
＜結晶相の確認＞
　実施例１～４並びに比較例１～７の各第１セラミック素地を粉砕し、Ｘ線回折により同定した。
＜曲げ強度＞
　実施例１～４並びに比較例１～７の各第２セラミック素地を、ＪＩＳＲ１６０１の４点曲げ強度試験に基づいて室温にて測定した。
＜誘電正接＞
　ＪＩＳＣ２５６５に基づく、空洞共振法により、室温での周波数２ＧＨｚで測定した。
＜チッピング発生率＞
　図５Ａに示すように、多数個取り基板６０を作製する。多数個取り基板６０は、横方向に２３個の積層基板１２をチップ分割でき、縦方向に２３個の積層基板１２をチップ分割できるサイズを有する。つまり、この多数個取り基板６０は、図５Ｂに示すように、横Ｌｘが２．０ｍｍ、縦Ｌｙが１．６ｍｍ、厚みｔが０．４ｍｍ（ベース部分１６の厚みｔｂ：０．２ｍｍ）の積層基板１２を２３×２３＝５２９個取ることができるサイズを有する。
　多数個取り基板６０は、焼成前の積層体の段階で、図５Ｃに示すように、ベース部分１６の上面及び下面にチップ分割のための分割溝６２（深さ：２μｍ）が形成されている。
　そして、分割溝６２が形成された多数個取り基板６０を、押圧ローラーで押し当ててチップ分割して、５２９個の積層基板１２に分割した後、各積層基板１２の分割端面を観察する。１つの積層基板１２の４つの分割端面のうち、少なくとも１つの分割端面に、径が１００μｍ以上で深さが１０μｍ以上の窪み、あるいは、径が１００μｍ以上で高さが１０μｍ以上の突起が形成されていた場合に、当該積層基板１２にチッピングが発生したとして評価する。
　チッピング発生率は、多数個取り基板６０のチップ分割数である５２９個に対するチッピングが発生していた積層基板１２の個数の割合とした。１つの多数個取り基板６０に対して１個の積層基板１２についてチッピングが発生していた場合は、１／５２９＝０．１９％となる。
　この実施例では、５つの多数個取り基板６０にて評価したため、チッピング発生率は、（チッピングが発生していた積層基板１２の個数）／（５２９×５）となる。
　実施例１～４並びに比較例１～７の内訳を表２に示し、評価結果を表３に示す。
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
　実施例１～４については、いずれも結晶相としてＡｌ3Ｏ4相以外では、ＢａＡｌ2Ｓｉ2Ｏ8相のみが観察された。また、曲げ強度は６００ＭＰａ以上であり、誘電正接は１２×１０-4以下であった。チッピング発生率は０．１０％以下であった。
　一方、比較例１～７については、いずれもチッピング発生率が０．１５％以上であった。また、結晶相としてＭｎＴｉＯ3相が観察された比較例２～４はいずれも誘電正接が大きかった。そのうち、Ｍｎ3Ａｌ2（ＳｉＯ4）3相も観察された比較例４は、曲げ強度が５００ＭＰａと低かった。また、結晶相としてＡｌ2Ｏ3のみが観察された比較例６及び７についても誘電正接が大きい傾向にあった。
　なお、本発明に係るセラミック素地及びその製造方法は、上述の実施の形態に限らず、本発明の要旨を逸脱することなく、種々の構成を採り得ることはもちろんである。

Claims (7)

  1. 　結晶相が、Ａｌ2Ｏ3を主結晶相とし、その他、ＢａＡｌ2Ｓｉ2Ｏ8結晶相のみを含むことを特徴とするセラミック素地。
  2. 　請求項１記載のセラミック素地において、
    　曲げ強度が６００ＭＰａ以上であることを特徴とするセラミック素地。
  3. 　請求項１又は２記載のセラミック素地において、
    　温度１２００～１４００℃にて焼結されていることを特徴とするセラミック素地。
  4. 　請求項１～３のいずれか１項に記載のセラミック素地において、
    　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％、ＢａをＢａＯ換算で０．０５～２．０質量％含むことを特徴とするセラミック素地。
  5. 　Ａｌ2Ｏ3を主結晶相とするセラミック素地の製造方法であって、
    　Ａｌ2Ｏ3粉末を８９．０～９２．０質量％、ＳｉＯ2粉末を２．０～５．０質量％、ＭｎＣＯ3粉末を３．２～８．１質量％（ＭｎＯ換算２．０～５．０質量％）、ＭｇＯ粉末を０～２．０質量％、ＢａＣＯ3粉末を０．０６～２．６質量％（ＢａＯ換算０．０５～２．０質量％）含有する成形体を作製する成形体作製工程と、
    　前記成形体を１２００～１４００℃にて焼成する焼成工程とを有することを特徴とするセラミック素地の製造方法。
  6. 　請求項５記載のセラミック素地の製造方法において、
    　前記成形体に、金属を含む導体層を形成する工程をさらに有し、
    　前記焼成工程は、前記導体層が形成された成形体を焼成することを特徴とするセラミック素地の製造方法。
  7. 　請求項５又は６記載のセラミック素地の製造方法において、
    　前記焼成工程は、水素を５％以上含む、水素と窒素のフォーミングガス中で行うことを特徴とするセラミック素地の製造方法。
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