WO2015119112A1 - Composition de porcelaine diélectrique, dispositif diélectrique, et procédé de fabrication de ceux-ci - Google Patents

Composition de porcelaine diélectrique, dispositif diélectrique, et procédé de fabrication de ceux-ci Download PDF

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WO2015119112A1
WO2015119112A1 PCT/JP2015/052983 JP2015052983W WO2015119112A1 WO 2015119112 A1 WO2015119112 A1 WO 2015119112A1 JP 2015052983 W JP2015052983 W JP 2015052983W WO 2015119112 A1 WO2015119112 A1 WO 2015119112A1
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dielectric
mass
ceramic composition
dielectric ceramic
zno
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Japanese (ja)
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渡辺　篤
援 八木
義政 小林
川崎　真司
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日本碍子株式会社
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Priority to JP2015560985A priority Critical patent/JP6539589B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • C04B35/46—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 titanium oxides or titanates
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Definitions

  • the present invention relates to a dielectric ceramic composition, a dielectric device, and a method for producing them.
  • Patent Documents 1 to 3 Conventionally, BaTiO 3 dielectric materials that can be sintered at low temperature have been proposed (see Patent Documents 1 to 3).
  • Patent Document 1 a dielectric material that is sintered at 900 ° C. to 1000 ° C. with BaTiO 3 as a main component, at least one selected from the group consisting of CuO, ZnO, and MgO and Bi 2 O 3 as a subcomponent.
  • Patent Document 2 proposes a dielectric material that is made of BaTiO 3 as a main component, CuBi 2 O 4 and ZnO—B 2 O 3 —SiO 2 glass as a minor component, and fired at 600 ° C. to 950 ° C. or the like. ing.
  • Patent Document 3 a composition containing BaTiO 3 , ZnO, Bi 2 O 3 , Nb 2 O 5 , and Re 2 O 3 is used as a main component, and SiO 2 glass is used as a subcomponent, and the temperature is 1160 ° C. or lower.
  • a fired dielectric material has been proposed.
  • the insulation resistance may be lowered by use due to remaining auxiliary components such as Bi 2 O 3 and CuO.
  • the temperature characteristic of the dielectric constant (for example, the rate of change in the temperature of the capacitance) may be poor due to the auxiliary component reacting with the glass component.
  • a dielectric particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a grain boundary raw material containing ZnO. It has been found that when the prepared powder containing is molded and sintered, a novel dielectric ceramic composition and dielectric device can be provided, and the present invention has been completed.
  • the dielectric ceramic composition of the present invention is A dielectric particle part which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 ; A grain boundary portion that is present between the particles of the dielectric particle portion and contains ZnO; It is equipped with.
  • the dielectric device of the present invention is The dielectric ceramic composition described above; An electrode that is integrated with the dielectric ceramic composition and is Ag or an Ag alloy; It is equipped with.
  • the method for producing the dielectric ceramic composition of the present invention includes: A forming and sintering step of forming and sintering a prepared powder containing a dielectric particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a grain boundary raw material containing ZnO, Is included.
  • the dielectric device manufacturing method of the present invention includes: A molded body obtained by molding a prepared powder containing a dielectric particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a grain boundary raw material containing ZnO, and an electrode material containing Ag or an Ag alloy, , A molding and sintering step for sintering a molded body with an electrode integrated, Is included.
  • the present invention can provide a novel dielectric ceramic composition and dielectric device.
  • a compound in which a metal element other than Ba and Ti (auxiliary component) is included in a part of BaTiO 3 as a dielectric particle raw material the remaining auxiliary component can be reduced and element diffusion can be suppressed. It is done.
  • the reaction of a dielectric particle material impregnated with auxiliary components in a part of BaTiO 3, nobler and a grain boundary portion material and BaTiO 3, for using, as BaTiO 3 and auxiliaries component and a grain boundary portion material It is thought that it can be suppressed.
  • FIG. 1 is a schematic cross-sectional view of a dielectric ceramic composition 10.
  • FIG. 1 is a schematic cross-sectional view of a multilayer ceramic capacitor 50.
  • FIG. 4 is an SEM photograph of the fired body of Experimental Example 3.
  • 4 is an SEM photograph of a fired body of Experimental Example 36.
  • the dielectric ceramic composition of the present invention includes a dielectric particle part which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 , a grain boundary part which exists between particles of the dielectric particle part and contains ZnO, including.
  • the dielectric particle part is composed of particles of a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 , and the particles may be bonded to each other.
  • the general formula (Ba 1-x M1 x ) (Ti 1-y M2 y ) O 3 (wherein M1 and M2 are metal elements other than Ba and Ti, and x and y are greater than 0 and less than 1) (It is a numerical value).
  • a part of BaTiO 3 contains a metal element other than Ba and Ti means, for example, a compound containing BaTiO 3 , a metal element other than Ba and Ti, or a metal element other than Ba and Ti (such as an oxide). It is good also as what is dissolved.
  • metal elements other than Ba and Ti include alkaline earth metal elements, rare earth elements, Sb, Ni, Cu, Cr, Fe, Co, Mn, Ta, Nb, W, Mo, Zn, Bi, Zr, Ag, and Sn. Or one or more elements selected from the group consisting of Sr. Of these, one or more elements selected from the group consisting of Bi, Zn, Mn, Zr, Nb, Sn, and Sr may be used.
  • Bi, Zn, and Mn may be used, and Bi, Zn, Mn, and Zr may be used.
  • Metal elements other than Ba and Ti are contained as oxides such as Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, and SrTiO 3. Also good. Zr may be inevitably included in the manufacturing process.
  • the dielectric particle part may have one kind of compound particles containing a metal element other than Ba and Ti in a part of BaTiO 3 , or may have two or more kinds. Further, particles of a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 may be single-phase particles having a constant composition and characteristics within the particles, or a plurality of particles having different compositions and characteristics within the particles. Multiphase particles having phases may be used.
  • Examples of multiphase particles include a core-shell structure in which the composition and properties differ between the part that becomes the core of the particle and the part that becomes the shell formed so as to cover the core, and the center part of the particle And a structure in which the composition and characteristics change continuously or intermittently from the outer periphery to the outer periphery.
  • a part of the phase may not be a phase containing a metal element other than Ba and Ti in a part of BaTiO 3 .
  • the dielectric particle portion has two or more kinds of phases having different compositions and characteristics (especially temperature characteristics of dielectric constant).
  • the temperature characteristics of the dielectric constant of the dielectric particle portion can be stabilized.
  • the dielectric particles portion is provided with two or more phases, for example, a BaTiO 3 phase consisting of BaTiO 3, Ba in BaTiO 3, oxides of metal elements other than Ti, for example, Bi 2 O 3, ZnO, Mn
  • a BaTiO 3 phase consisting of BaTiO 3, Ba in BaTiO 3, oxides of metal elements other than Ti, for example, Bi 2 O 3, ZnO, Mn
  • 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, SrTiO 3 , and the like are included in a solid solution and / or substituted phase (solid solution / substituted phase).
  • a solid solution / substitution phase having a different solid solution / substitution amount such as Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, SrTiO 3 , or the BaTiO 3 phase It may be included instead.
  • This solid solution / substitution phase may include Bi 2 O 3 , ZnO and Mn 3 O 4 , or may include Bi 2 O 3 , ZnO, Mn 3 O 4 and ZrO 2 .
  • This solid solution / substitution phase may contain, for example, one or more selected from the group consisting of ZrO 2 , SrO, SrTiO 3 , Nb 2 O 5 , SnO 2 .
  • the solid solution / substitution phase does not contain CuO, and even when it contains CuO, it is preferable that it is a trace amount. Note that the phase characteristics can be changed by adjusting the phase composition, production conditions, and the like.
  • the grain boundary part contains ZnO.
  • the grain boundary part preferably contains 35% by mass or more of ZnO.
  • the grain boundary portion is preferably mainly composed of ZnO and B 2 O 3 , and may be composed mainly of ZnO.
  • the ZnO and B 2 O 3 as the main shows that among the components of the grain boundary, the largest total mass ratio of ZnO and B 2 O 3.
  • “mainly composed of ZnO” means that the mass ratio of ZnO is the largest among the constituent components of the first grain boundary part.
  • the grain boundary part may be based on a glass containing ZnO, and more specifically, the glass containing ZnO may be crystallized.
  • the glass containing ZnO examples include Zn—B—O glass.
  • the Zn—B—O-based glass is glass containing Zn, B, and O.
  • a glass containing ZnO and B 2 O 3 may be used.
  • the Zn—B—O-based glass may contain several other elements as secondary elements.
  • it may be a Zn—B—Si—O-based glass.
  • the Zn—B—Si—O-based glass may be glass containing Zn, B, Si, and O.
  • the Zn—B—O-based glass may contain, for example, ZnO in a range of 35 mass% to 80 mass%.
  • B 2 O 3 may be used as to include in the range of 50 mass% 10 mass% or more.
  • the present invention may be those containing SiO 2 in a range of 5 mass% to 15 mass%.
  • the grain boundary part preferably does not contain Bi or Mg. If Bi or Mg is not included in the grain boundary part, it is possible to further suppress a decrease in insulation resistance.
  • the proportion of the grain boundary part containing ZnO should be greater than 0% with respect to the entire dielectric ceramic composition, but is preferably 1% or more, preferably 2% or more. More preferred. Moreover, although it should just be less than 100%, 20% or less is preferable and 13% or less is more preferable.
  • the dielectric ceramic composition may further include oxide particles in addition to the dielectric particle part and the grain boundary part.
  • oxide particles include oxides of metal elements other than Ba and Ti described above.
  • the oxide particles may include, for example, one or more selected from the group consisting of Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, and SrTiO 3. 2 O 3 , ZnO and Mn 3 O 4 may be included, or Bi 2 O 3 , ZnO, Mn 3 O 4 and ZrO 2 may be included.
  • the oxide particles may contain one or more selected from the group consisting of ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, and SrTiO 3 .
  • the dielectric ceramic composition has Bi 2 O 3 of 3.5% by mass to 11% by mass, ZnO of 0.6% by mass to 5.0% by mass, and Mn 3 O 4 of 0.01% by mass to 1%. It is preferable that the CuO content is within a range of 0.0 mass% or less, and the CuO content is within a range of 0.4 mass% or less.
  • the relative dielectric constant is high, for example, 1000 or more
  • the dielectric loss tangent tan ⁇ is low, such as 0.05 or less
  • the X7R characteristic (EIA standard: capacity change rate in the range of ⁇ 55 ° C. to 125 ° C. is 25 ° C.
  • the dielectric ceramic composition may include BaTiO 3 (which may be the sum of BaO and TiO 2 ) in the range of 70% by mass to 97% by mass, or in the range of 80% by mass to 95% by mass. It may be included.
  • the dielectric ceramic composition includes one or more selected from the group consisting of SnO 2 , ZrO 2 , Nb 2 O 5 , and SrO, the content of SnO 2 is 1.0 mass% or less, and the content of ZrO 2 May be 2.5% by mass or less, the Nb 2 O 5 content may be 1.0% by mass or less, and the SrO content may be 10% by mass or less. If containing at least one element selected from a group consisting of SnO 2, ZrO 2, Nb 2 O 5, SrO, the content thereof, each of which may be more than 0.01 mass%.
  • the dielectric ceramic composition may contain SiO 2 in the range of 0.01% by mass to 0.5% by mass. In addition, although content which converted each metal component into the oxide was shown here, each metal component may exist with forms other than the oxide mentioned above.
  • the dielectric ceramic composition may have a relative dielectric constant of 1000 or more and 3000 or less. Such a material can have a dielectric constant required for a BaTiO 3 dielectric.
  • the dielectric ceramic composition may have a dielectric loss tangent tan ⁇ of 0.05 or less, preferably 0.04 or less, and more preferably 0.03 or less. In such a case, the dielectric loss can be reduced.
  • the dielectric ceramic composition of the present invention forms, for example, a preparation powder containing a dielectric particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a grain boundary raw material containing ZnO. Then, it may be obtained by sintering. Such a dielectric ceramic composition may be obtained by a dielectric ceramic composition manufacturing method described later.
  • the dielectric ceramic composition of the present invention may be included in a low temperature co-fired ceramic (LTCC) multilayer substrate.
  • LTCC low temperature co-fired ceramic
  • the dielectric ceramic composition of the present invention may be, for example, the dielectric ceramic composition 10 shown in FIG. FIG. 1 is a schematic cross-sectional view of a dielectric ceramic composition 10.
  • the dielectric ceramic composition 10 includes dielectric particle portions 22 and grain boundary portions 24.
  • the dielectric particle part 22 is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 , and various aspects of the dielectric particle part described above can be applied.
  • the grain boundary part 24 exists between the particles of the dielectric particle part 22 and contains ZnO, and various aspects of the grain boundary part described above can be applied.
  • the dielectric device of the present invention includes the above-described dielectric ceramic composition and an electrode that is integrated with the dielectric ceramic composition and is Ag or an Ag alloy.
  • the Ag alloy preferably contains 50% by mass or more of Ag, and may contain 80% by mass or more of Ag. Examples of the metal constituting the alloy with Ag include Pd.
  • the dielectric ceramic composition preferably does not contain CuO or has a low CuO composition.
  • the CuO content is preferably in the range of 0.4% by mass or less. In this way, a multilayer ceramic capacitor or the like can be produced without damaging the Ag-based electrode.
  • the dielectric device of the present invention may be, for example, the multilayer ceramic capacitor 50 shown in FIG. 2.
  • FIG. 2 is a schematic cross-sectional view of the multilayer ceramic capacitor 50.
  • the multilayer ceramic capacitor 50 includes the dielectric ceramic composition 10 described above, an electrode (internal electrode) 52 that is integrated with the dielectric ceramic composition 10 and is Ag or an Ag alloy, and an external electrode 54.
  • the external electrode 54 may be omitted.
  • the method for producing a dielectric ceramic composition of the present invention forms a prepared powder containing a dielectric particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a grain boundary raw material containing ZnO.
  • the molding and sintering step may include, for example, (A) a preparation powder manufacturing step, (B) a molded body manufacturing step, and (C) a sintering step. Below, each process is demonstrated.
  • the dielectric particle material is a powder (particle) of a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 .
  • the general formula (Ba 1-x M1 x ) (Ti 1-y M2 y ) O 3 (wherein M1 and M2 are metal elements other than Ba and Ti, and x and y are numerical values from 0 to 1) It is good also as what is represented by this.
  • a part of BaTiO 3 contains a metal element other than Ba and Ti means, for example, a compound containing BaTiO 3 , a metal element other than Ba and Ti, or a metal element other than Ba and Ti (such as an oxide). It is good also as what is dissolved.
  • metal elements other than Ba and Ti include those exemplified in the description of the dielectric particle portion.
  • the dielectric particle raw material may have one kind of compound powder containing a metal element other than Ba and Ti in a part of BaTiO 3 , or two or more kinds.
  • the dielectric particle material may be single-phase particles having a constant composition and characteristics within the particles, or multilayer particles having different compositions and characteristics within the particles, as in the case of the dielectric particle portion.
  • the multiphase particles for example, the core-shell structure described above, or those having a structure in which the composition and characteristics change continuously or intermittently from the center to the outer periphery of the particles can be suitably used.
  • the dielectric particle material has two or more kinds of phases having different compositions and characteristics (particularly, temperature characteristics of dielectric constant). When two or more phases having different dielectric constant temperature characteristics are mixed, it is considered that the temperature characteristics of the dielectric constant of the dielectric particle portion can be stabilized in the obtained dielectric ceramic composition. It is done.
  • the dielectric particle raw material is, for example, a product obtained through a synthetic powder manufacturing process (synthetic powder) in which a synthetic powder is manufactured by baking a mixed powder containing a BaTiO 3 raw material and a metal element other than Ba and Ti. Good.
  • synthetic powders synthesized in advance auxiliary substances containing glass elements and metal elements other than Ba and Ti at the time of production (for example, Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, SrTiO 3, etc.) are hardly generated, and a dielectric ceramic composition having good characteristics such as dielectric characteristics can be produced.
  • the same effect can be expected if it is a powder of a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 .
  • the BaTiO 3 raw material may be BaTiO 3 itself, or may be obtained by firing BaTiO 3 , for example, a mixture of BaCO 3 and TiO 2 , or both of them. It is good. Metal elements other than Ba and Ti may be included in any form, but are preferably included as oxides.
  • the mixed powder is not only BaTiO 3 raw material but also metal elements other than Ba and Ti, such as Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SrO, SrTiO 3 , Nb 2 O 5. And one or more selected from the group consisting of SnO 2 .
  • the mixed powder may include Bi 2 O 3 , ZnO, and Mn 3 O 4 , or may include Bi 2 O 3 , ZnO, Mn 3 O 4 , and ZrO 2 .
  • the mixed powder may contain one or more selected from the group consisting of ZrO 2 , SrO, SrTiO 3 , Nb 2 O 5 , and SnO 2 .
  • the mixed powder has Bi 2 O 3 of 3.5% by mass to 11% by mass, ZnO of 0.6% by mass to 5.0% by mass, and Mn 3 O 4 of 0.01% by mass to 1.0% by mass. It is preferable that the content of CuO is in the range of 0.4% by mass or less. By doing so, it is possible to easily obtain a dielectric ceramic composition that has a high relative dielectric constant, a low dielectric loss tangent tan ⁇ , satisfies the X7R characteristics, has little decrease in insulation resistance due to use, and has a long life. In the sintering process, simultaneous firing with an Ag-based electrode can be performed satisfactorily.
  • the mixed powder may contain the BaTiO 3 raw material in a range of 70% by mass or more and 97% by mass or less in terms of BaTiO 3 , or may contain 80% by mass or more and 95% by mass or less.
  • the mixed powder contains one or more selected from the group consisting of ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, and SrTiO 3 , the ZrO 2 content is 25% by mass or less, and the SnO 2 content is 15
  • the content of Nb 2 O 5 may be 1.0% by mass or less
  • the content of SrO may be 10% by mass or less
  • the content of SrTiO 3 may be 18% by mass or less.
  • the content may be 0.01% by mass or more.
  • ZrO 2 may be supplied from, for example, ZrO 2 boulders used for pulverization when a mixed powder is prepared by pulverization and mixing.
  • the firing conditions are not particularly limited, but heat treatment is performed at a firing temperature of 700 ° C. to 1200 ° C. for 1 hour to 24 hours in an oxidizing atmosphere such as air or oxygen atmosphere. It is good.
  • one kind of synthetic powder may be produced, or two or more kinds of synthetic powders having different temperature characteristics of dielectric constant produced under different compositions and production conditions may be produced.
  • the grain boundary part raw material contains ZnO.
  • the grain boundary part raw material preferably contains 35% by mass or more of ZnO.
  • a grain boundary part raw material is mainly composed of ZnO and B 2 O 3 , and may be composed mainly of ZnO.
  • the ZnO and B 2 O 3 as the main shows that among the components of the grain boundary material, most often the total mass ratio of ZnO and B 2 O 3.
  • “mainly composed of ZnO” means that the mass ratio of ZnO is the largest among the constituent components of the grain boundary raw material.
  • the grain boundary raw material is not particularly limited as long as it can be melted in the subsequent sintering step to fill the space between the particles of the particle raw material, but is preferably glass, and Zn—B—O based glass (for example, Zn—B). —Si—O-based glass) is preferable. Since Zn—B—O-based glass does not easily react with BaTiO 3 , the characteristics of the dielectric ceramic composition can be further maintained. Note that since Zn—B—O and Zn—B—Si—O based glasses are the same as those described in the grain boundary portion, description thereof is omitted here.
  • the prepared powder preferably contains the grain boundary raw material in a range of 0.5% by volume or more and 15% by volume or less, and more preferably in a range of 1.5% by volume or more and 11% by volume or less.
  • the prepared powder may contain oxide particles different from these in addition to the dielectric particle raw material and the grain boundary raw material.
  • the oxide particles may have a relative dielectric constant in the range of 500 to 100,000, for example, and may be a double oxide such as SrTiO 3 or BaTiO 3 without additives.
  • the temperature characteristic of the dielectric constant can be improved in a wider temperature range, for example, the absolute value of the capacitance change rate can be reduced in a wider temperature range in the fired body.
  • a double oxide it is preferably included in the range of 1% by volume to 60% by volume, and more preferably in the range of 1% by volume to 50% by volume.
  • (B) Molded body manufacturing process In this process, a molded body obtained by molding the prepared powder is manufactured.
  • the method of molding the prepared powder is not particularly limited, but may be molded by press molding, mold molding, extrusion molding, printing, doctor blade, or the like.
  • the prepared powder may be used alone, or by adding an organic solvent such as toluene or isopropyl alcohol (IPA), an organic binder, a plasticizer, a dispersing agent, etc., green sheet, clay, paste, slurry It may be used as such.
  • IPA isopropyl alcohol
  • (C) Sintering step In this step, the above-mentioned formed body is fired (sintered) to produce a dielectric ceramic composition.
  • the sintering may be performed at a sintering temperature of 800 ° C. or higher and 1000 ° C. or lower. This is because BaTiO 3 -based materials are desired to be sintered at 1000 ° C. or lower. If sintering is possible at 1000 ° C. or lower, for example, simultaneous lamination firing with a low dielectric material sintered using an Ag electrode or glass having a low specific resistivity can be made possible. Also, if sintered at 800 ° C. or higher, a dielectric ceramic composition having a high density and excellent dielectric properties can be obtained.
  • the firing time can be, for example, in the range of 1 hour to 24 hours.
  • the dielectric particle material becomes the dielectric particle part and the grain boundary part material becomes the grain boundary part.
  • the dielectric particle part and the grain boundary part take in components other than the respective raw materials. Or may be obtained by discharging a part of each raw material.
  • the dielectric device manufacturing method of the present invention is a molded body obtained by molding a prepared powder containing a dielectric particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a grain boundary raw material containing ZnO. And an electrode material containing Ag or an Ag alloy, and a forming and sintering step of sintering a formed body with an electrode.
  • the molding and sintering step may include, for example, (A) a preparation powder manufacturing step, (B ′) a molded body with electrode manufacturing step, and (C) a sintering step.
  • A a preparation powder manufacturing step
  • B ′ a molded body with electrode manufacturing step
  • C a sintering step.
  • (B ′) Molded body manufacturing process with electrode In this step, the molded body molded with the prepared powder and the electrode material containing Ag or an Ag alloy are integrated to manufacture a molded body with an electrode. What is necessary is just to shape
  • the Ag alloy include those exemplified in the description of the dielectric device.
  • the electrode material may be formed, for example, by adding an organic solvent or the like to Ag or Ag alloy powder to form a paste or slurry, and then applying and molding.
  • the dielectric ceramic composition, dielectric device, and manufacturing method thereof of the present invention can provide a BaTiO 3 -based novel dielectric ceramic composition.
  • a compound containing a metal element (auxiliary component) other than Ba and Ti in part of BaTiO 3 as a dielectric particle material (for example, a solid solution)
  • the remaining auxiliary component is reduced, It is thought that element diffusion can be suppressed.
  • the insulation deterioration of the dielectric ceramic composition can be suppressed by the presence of the grain boundary portion containing ZnO between the particles of the dielectric particle portion.
  • the electrode is divided by diffusion of the CuO component, and the electrode It can suppress that an effective area becomes small.
  • the dielectric ceramic composition needs to be fired at a low temperature such as 1000 ° C. or less. Since it can be fired at such a low temperature, it can be manufactured relatively easily.
  • Experimental examples 1 to 31 and 42 to 52 correspond to examples of the present invention, and experimental examples 32 to 41 correspond to comparative examples.
  • the present invention is not limited to the following examples.
  • IPA isopropyl alcohol
  • zirconia cobblestone was used for wet pulverization and mixing for 48 hours in a ball mill, and the slurry passed through a 200 mesh sieve was dried and sized with a 100 mesh sieve.
  • the mixed powder was pre-synthesized in the air at a predetermined temperature shown in Table 1 for 2 hours to obtain a pre-synthesized powder (6.15 g / cm 3 ).
  • the specific surface area was measured by the N 2 -BET method (Table 1).
  • glasses having the respective compositions shown in Table 2 were prepared.
  • the above-mentioned pre-synthetic powder (dielectric particle raw material), the above-mentioned glass (grain boundary raw material), and in Examples 42 and 43, SrTiO 3 is further added in a predetermined amount shown in Tables 3 and 4, and IPA is further added.
  • zirconia cobblestone was used for wet grinding and mixing with a ball mill for 24 hours, and then the slurry passed through a 200 mesh sieve was dried and sized with a 100 mesh sieve to obtain a prepared powder.
  • SrTiO 3 a commercial product having a purity of 99%, an average particle diameter of 1 ⁇ m, and a specific surface area of 11.7 m 2 / g was used.
  • the body layers (portions sandwiched between the upper and lower electrodes) were stacked so as to form 16 layers, and thermocompression bonded to obtain a pressure-bonded body (molded body with electrodes).
  • the laminate was sintered in the atmosphere at the firing temperatures shown in Tables 3 and 2 for 2 hours to obtain a fired body.
  • An external electrode was formed on the fired body to establish electrical connection with the internal electrode, and a multilayer ceramic capacitor sample was obtained.
  • the thickness of the dielectric layer of the ceramic capacitor after firing was 15 ⁇ m, and the thickness of the Ag electrode was 2.5 ⁇ m.
  • FIG. 2 shows a schematic cross-sectional view of such a multilayer ceramic capacitor.
  • the multilayer ceramic capacitor 50 includes a dielectric layer (dielectric ceramic composition) 10, an internal electrode 52, and an external electrode 54.
  • grain boundary phase (grain boundary part) ratio derived from glass)
  • SEM scanning electron microscope
  • the area of the portion was calculated by image analysis, and the proportion of the total area was calculated.
  • the average value of the three visual fields was defined as the ratio of the grain boundary phase area occupied by the grain boundary phase.
  • Grain boundary phases having different contrasts were confirmed to have element distribution by FE-EPMA, and were derived from glass and contained ZnO.
  • composition of fired body Each fired body for chemical analysis was pulverized, dissolved in an acid solution, and each component was quantified by ICP emission spectroscopy. Incidentally, ZrO 2 detected at a level of ZrO 2 is not added, is presumed to be due to zirconia boulder. B 2 O 3 was expressed as 0 wt% because it was below the detection limit.
  • FIG. 3 shows a prepared powder obtained by mixing a pre-synthetic powder obtained by pre-baking a mixed powder containing BaTiO 3 , Bi 2 O 3 , ZnO, and Mn 3 O 4 and a Zn—B—Si—O-based glass. It was found that the dielectric particle part and the grain boundary part can be distinguished from those molded and sintered. In contrast, FIG.
  • Tables 5 and 6 show the density, relative dielectric constant, tan ⁇ , X7R characteristics, maximum capacity change rate, lifetime, grain boundary phase ratio, observation results of the Ag electrode, and the chemical composition of the fired bodies of Experimental Examples 1 to 52.
  • the present invention can be used in the field of electronic equipment.
  • dielectric ceramic composition 10 dielectric ceramic composition, 22 dielectric particle parts, 24 grain boundary parts, 50 multilayer ceramic capacitor, 52 internal electrode, 54 external electrode.

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Abstract

La composition de porcelaine diélectrique (10) de l'invention est équipée : d'une partie particule diélectrique (22) qui consiste en un composé contenant dans une partie BaTiO3, un élément métallique autre que Ba et Ti ; et d'une partie joint de grains (24) se trouvant entre les particules de la partie particule diélectrique (22), et contenant ZnO. Cette composition de porcelaine diélectrique (10) peut être obtenue par moulage et frittage d'une poudre préparée contenant, par exemple : une matière première de partie particule diélectrique qui consiste en un composé contenant dans une partie BaTiO3, un élément métallique autre que Ba et Ti ; et une matière première de partie joint de grains contenant ZnO.
PCT/JP2015/052983 2014-02-04 2015-02-03 Composition de porcelaine diélectrique, dispositif diélectrique, et procédé de fabrication de ceux-ci WO2015119112A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2022264626A1 (fr) * 2021-06-16 2022-12-22 株式会社村田製作所 Composition céramique diélectrique et condensateur céramique multi-couches

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JPH11278926A (ja) * 1998-03-30 1999-10-12 Kyocera Corp 誘電体磁器
JP2009132606A (ja) * 2007-11-29 2009-06-18 Samsung Electro Mech Co Ltd 誘電体組成物及びこれを用いた積層セラミックキャパシタ内蔵型低温同時焼成セラミック基板
JP2010235327A (ja) * 2009-03-30 2010-10-21 Tdk Corp 誘電体磁器組成物

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Publication number Priority date Publication date Assignee Title
JPH11278926A (ja) * 1998-03-30 1999-10-12 Kyocera Corp 誘電体磁器
JP2009132606A (ja) * 2007-11-29 2009-06-18 Samsung Electro Mech Co Ltd 誘電体組成物及びこれを用いた積層セラミックキャパシタ内蔵型低温同時焼成セラミック基板
JP2010235327A (ja) * 2009-03-30 2010-10-21 Tdk Corp 誘電体磁器組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022264626A1 (fr) * 2021-06-16 2022-12-22 株式会社村田製作所 Composition céramique diélectrique et condensateur céramique multi-couches

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