WO2015119113A1 - 積層体、積層デバイス及びそれらの製造方法 - Google Patents
積層体、積層デバイス及びそれらの製造方法 Download PDFInfo
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- WO2015119113A1 WO2015119113A1 PCT/JP2015/052984 JP2015052984W WO2015119113A1 WO 2015119113 A1 WO2015119113 A1 WO 2015119113A1 JP 2015052984 W JP2015052984 W JP 2015052984W WO 2015119113 A1 WO2015119113 A1 WO 2015119113A1
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- C04B2237/32—Ceramic
- C04B2237/34—Oxidic
- C04B2237/345—Refractory metal oxides
- C04B2237/346—Titania or titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Definitions
- the present invention relates to a laminated body, a laminated device, and a manufacturing method thereof.
- Patent Documents 1 to 3 various laminates have been proposed (see Patent Documents 1 to 3).
- Patent Document 2 a laminate including a dielectric material containing 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.
- a ceramic capacitor built-in type low temperature co-fired ceramic substrate has been proposed.
- Patent Document 3 a perovskite-based high dielectric constant layer containing lead oxide and a low dielectric constant layer having a dielectric constant of 15 or less are integrally co-fired at a low temperature of 800 to 1100 ° C.
- Patent Documents 1 and 2 auxiliary components such as CuO of the high dielectric constant layer may diffuse during co-firing, which may deteriorate the characteristics of each layer. Moreover, in patent document 3, the dielectric constant of a high dielectric constant layer may fall because lead oxide and glass reacted. For this reason, the novel laminated body and laminated
- a first grain raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a first grain boundary part containing ZnO.
- a first molded body obtained by molding a first prepared powder containing a raw material, a second prepared powder containing a second particle raw material having a relative dielectric constant smaller than that of the first particle raw material, and a second grain boundary raw material. It has been found that when a laminated molded body obtained by laminating two molded bodies is sintered, a new laminated body and a laminated device can be obtained, and the present invention has been completed.
- the laminate of the present invention is A first particle part which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 , and a first grain boundary part which is present between the particles of the first particle part and contains ZnO.
- the laminated device of the present invention is The laminate described above; An electrode that is integrated with the laminate and is Ag or an Ag alloy; It is equipped with.
- the method for producing the laminate of the present invention includes: A first molded body obtained by molding a first prepared powder containing a first particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a first grain boundary raw material containing ZnO; Laminated sintering which sinters a laminated molded body obtained by laminating a second molded body obtained by molding a second prepared powder containing a second particle raw material having a relative dielectric constant smaller than that of one particle raw material and a second grain boundary raw material. Process, Is included.
- the manufacturing method of the laminated device of the present invention includes: A first molded body obtained by molding a first prepared powder containing a first particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a first grain boundary raw material containing ZnO; A second molded body obtained by molding a second prepared powder containing a second particle raw material having a relative dielectric constant smaller than that of one particle raw material and a second grain boundary raw material, and an electrode material containing Ag or an Ag alloy were laminated. Laminated sintering process for sintering laminated molded body with electrodes, Is included.
- a novel laminate and laminated device can be provided.
- a metal element (auxiliary component) other than Ba and Ti is included in a part of BaTiO 3 as the first particle raw material, the remaining auxiliary component is reduced, and an element between different materials, etc. It is thought that diffusion can be suppressed.
- a first particle material moistened with auxiliary components BaTiO 3, for use with nobler first grain boundary portion material and BaTiO 3, a, BaTiO 3 and auxiliaries component and a first grain boundary part material It is thought that this reaction can be suppressed.
- FIG. 2 is a schematic cross-sectional view of a laminated body 10.
- 1 is a schematic cross-sectional view of a multilayer ceramic capacitor 50.
- FIG. 4 is an SEM photograph of the high dielectric material of Experimental Example 3.
- 4 is an SEM photograph of the high dielectric material of Experimental Example 42.
- the laminate of the present invention includes a first material layer having a first dielectric constant and a second material layer having a second dielectric constant lower than the first dielectric constant.
- the first material layer includes a first particle part which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3, a first grain boundary part which exists between the particles of the first particle part and contains ZnO, including.
- the first 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. Among 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. It is good. 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 first particle part may have one kind of compound particle containing a metal element other than Ba or 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 first particle portion has two or more kinds of different compositions and characteristics (especially temperature characteristics of dielectric constant).
- the phase comprises 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, Including one or more selected from the group consisting of Mn 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, and SrTiO 3 in solid solution and / or substituted phase (solid solution / substituted phase).
- 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, Including one or more selected from the group consisting of Mn 3 O 4 , ZrO 2 , SnO 2 , Nb 2 O 5 , SrO, and SrTiO 3 in 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 replace and may be included.
- 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 first grain boundary part contains ZnO.
- the first grain boundary part preferably contains 35% by mass or more of ZnO.
- the first grain boundary part 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 first grain boundary part, 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 first grain boundary part.
- the first 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 other elements as a secondary element, for example, 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%. Further, B 2 O 3 may be used as to include in the range of 50 to 10 mass%.
- the present invention may be those containing SiO 2 in a range of 5 mass% to 15 mass%.
- the first grain boundary part preferably does not contain Bi, Mg, or the like. If Bi or Mg is not included in the first grain boundary part, it is possible to further suppress the decrease in the insulation resistance of the first material layer.
- the ratio of the first grain boundary portion containing ZnO should be greater than 0% with respect to the entire first material layer, but is preferably 1% or more, and 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 first material layer may further include oxide particles in addition to the first particle part and the first 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 first material layer has Bi 2 O 3 of 3.5 mass% to 11 mass%, ZnO of 0.6 mass% to 5.0 mass%, and Mn 3 O 4 of 0.01 mass% to 1. It is preferable that the CuO content is within a range of 0% by mass or less, and the CuO content is within a range of 0.4% by mass or less. In such a case, the first material layer has a high relative dielectric constant of, for example, 1000 or more and a low dielectric loss tangent tan ⁇ of 0.05 or less, and the X7R characteristic (EIA standard: capacitance change in the range of ⁇ 55 ° C. to 125 ° C.
- EIA standard capacitance change in the range of ⁇ 55 ° C. to 125 ° C.
- the rate is within ⁇ 15% with respect to a capacity of 25 ° C.), and simultaneous firing with an Ag-based electrode can be performed satisfactorily. In addition, there is little decrease in insulation resistance due to use, and the life can be extended.
- the first material layer 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, and in the range of 80% by mass to 95% by mass. It may be a thing.
- the first material layer includes one or more selected from the group consisting of SnO 2 , ZrO 2 , Nb 2 O 5 and SrO, the SnO 2 content is 1.0 mass% or less, and the ZrO 2 content is 2.5 wt% or less, the content of Nb 2 O 5 is 1.0% by mass or less, the content of SrO may be as 10 mass% or less. If it contains at least one element selected from the group consisting of SnO 2, ZrO 2, Nb 2 O 5, SrO, its content, each of which may be more than 0.01 mass%.
- the first material layer may contain SiO 2 in the range of 0.01% by mass to 0.5% by mass.
- each metal component may exist with forms other than the oxide mentioned above.
- the first material layer may have a relative dielectric constant of 1000 or more and 3000 or less. In such a case, the first material layer can have a dielectric constant required for a BaTiO 3 -based dielectric.
- the first material layer 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 first material layer can have a small dielectric loss.
- the second material layer includes a second particle part and a second grain boundary part existing between the particles of the second particle part.
- the second particle part is preferably composed of particles having a relative dielectric constant lower than that of the first particle part.
- the particles constituting the second particle part may be bonded to each other.
- the second particle portion may be composed of particles of a complex oxide having a tungsten bronze structure including at least one of Ba and Ti, and preferably includes both Ba and Ti.
- the second material layer has a low relative dielectric constant and a large Q value (reciprocal of tan ⁇ ). It can be.
- the composite oxide having a tungsten bronze structure is selected from the group consisting of alkaline earth metal elements, rare earth elements, Si, Sc, Y, Zn, Nb, Ta, Pb, and Bi in addition to Ba and Ti.
- the above may be included.
- the composite oxide having a tungsten bronze structure is, for example, a general formula A x BO 3 (where A is an alkaline earth metal element, rare earth element, Si, Sc, Y, Zn, Pb, Bi). 1 or more selected from the group, and B is 1 or more selected from the group consisting of Ti, Zr, Nb, Hf, and Ta.
- X satisfies 0 ⁇ x ⁇ 1. Also good.
- the structure of this complex oxide is a structure in which unit blocks of oxygen octahedron (BO 6 ) are connected together sharing a vertex and a ridge, and the B element is partially due to the presence of the A element and / or the effect of the ridge sharing. It is a non-stoichiometric oxide structure reduced to.
- the composite oxide having a tungsten bronze structure preferably contains Ba, Nd, Bi, and Ti, and specifically includes Ba 4 (Nd, Bi) 9.3 Ti 18 O 54 and the like. In Ba 4 (Nd, Bi) 9.3 Ti 18 O 54 , Nd and Bi may be included in any ratio, and only one of Nd and Bi may be included. Of these, the ratio of Nd to Bi (Nd: Bi) is preferably in the range of 95: 5 to 70:30, and more preferably in the range of 90:10 to 80:20.
- the second grain boundary part is not particularly limited, but may be based on glass, for example, and more specifically, the glass may be crystallized.
- the glass Zn—B—O glass (Zn—B—Si—O glass, etc.), B—Si—Ba—Al—O glass, Si—B—Na—O glass, etc. Glass or the like can be suitably used. Since these glasses hardly react with BaTiO 3 , the characteristics of the first material layer can be further maintained. Further, since the difference in thermal shrinkage at the time of firing and the temperature shrinkage at the time of temperature drop is small with respect to the glass used for the first grain boundary part, for example, a Zn—B—O-based glass, warpage and peeling are less likely to occur.
- the B—Si—Ba—Al—O-based glass is glass containing B, Si, Ba, Al, and O.
- it may be a glass containing a B 2 O 3 and SiO 2 and BaO and Al 2 O 3.
- This glass may contain, for example, B 2 O 3 in a range of 20% by mass to 45% by mass.
- the present invention may be those containing SiO 2 in the range of not less than 45% by weight to 20% by weight.
- the Si—B—Na—O glass is a glass containing Si, B, Na, and O.
- the glass may be glass including a SiO 2, B 2 O 3 and Na 2 O.
- This glass may contain, for example, SiO 2 in a range of 60% by mass to 90% by mass.
- B 2 O 3 may be used as to include in the range of 30 to 10 mass%.
- the present invention may be those containing Na 2 O in the range of 10 wt% or more 0 mass%. Note that the description of the Zn—B—O-based and Zn—B—Si—O-based glasses is omitted because they are the same as those described in the first grain boundary portion.
- the second grain boundary part is preferably based on the same kind as the first grain boundary part, for example, Zn—B—O-based glass. In such a case, the firing shrinkage at the time of firing between the first material layer and the second material layer and the thermal shrinkage difference at the time of temperature drop are smaller, and the warpage and peeling associated therewith are less likely to occur.
- the second grain boundary part preferably does not contain Bi or Mg. Since these easily react with BaTiO 3 , if they are not included in the second grain boundary part, it is possible to further suppress the deterioration of the dielectric properties of the first material layer.
- the ratio of the second grain boundary part may be greater than 0% with respect to the entire second material layer, but is preferably 0.5% or more, and 1.5% or more. Is more preferable. Moreover, although it should just be less than 100%, 15% or less is preferable and 11% or less is more preferable.
- the difference between the ratio of the first grain boundary part in the first material layer and the ratio of the second grain boundary part in the second material layer may be within ⁇ 5%. By doing so, the ratio of the grain boundary portion included in the first material layer and the second material layer can be made relatively close, so the difference in thermal expansion (shrinkage) between the first material layer and the second material layer is small. , Warpage and peeling are less likely to occur.
- the second material layer may have a relative dielectric constant of 5 or more and 200 or less. In such a case, the second material layer can have a required dielectric constant.
- the laminated body of the present invention is formed, for example, by forming a first prepared powder containing a first particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a first grain boundary raw material containing ZnO.
- a product obtained by sintering a laminated molded body obtained by laminating the first molded body and the second molded body obtained by molding the second prepared powder containing the second particle raw material and the second grain boundary raw material.
- Such a laminated body is good also as what is obtained by the manufacturing method of the laminated body mentioned later.
- the dielectric constant of the second material layer only needs to be lower than the dielectric constant of the first material layer even if the relative dielectric constant of the second particle raw material is not smaller than the relative dielectric constant of the first particle raw material. .
- the laminate of the present invention may be included in a low temperature co-fired ceramic (LTCC) multilayer substrate.
- LTCC low temperature co-fired ceramic
- FIG. 1 is a schematic cross-sectional view of the laminate 10.
- the stacked body 10 includes a first material layer 20 having a first dielectric constant, and a second material layer 30 having a second dielectric constant lower than the first dielectric constant.
- the first material layer 20 includes a first particle part 22 and a first grain boundary part 24.
- the second material layer 30 includes a second particle part 32 and a second grain boundary part 34.
- the first particle 22, a compound containing Ba, a metal element other than Ti on a part of BaTiO 3 can be applied to various aspects of the first particle section described above.
- the 1st grain boundary part 24 exists between the particle
- the 2nd particle part 32 the various aspects of the 2nd particle part mentioned above are applicable.
- the 2nd grain boundary part 34 exists between the particle
- the laminated device of the present invention includes the laminated body described above and an electrode that is integrated with the laminated body 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 first material layer 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. By doing so, it is possible to manufacture a ceramic capacitor having different material layers while suppressing element diffusion between different materials and without damaging the Ag-based electrode.
- the multilayer device of the present invention may be, for example, a multilayer ceramic capacitor 50 shown in FIG. FIG. 2 is a schematic cross-sectional view of the multilayer ceramic capacitor 50.
- the multilayer ceramic capacitor 50 includes the above-described multilayer body 10 including the first material layer 20 and the second material layer 30, and electrodes (internal electrodes) 52 and 56 that are integrated with the multilayer body 10 and are Ag or an Ag alloy.
- the external electrodes 54 and 58 are provided. In the laminated device of the present invention, the external electrodes 54 and 58 may be omitted.
- the method for producing a laminate of the present invention comprises a first prepared powder containing a first particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a first grain boundary raw material containing ZnO.
- a laminate in which a molded first molded body and a second molded body formed by molding a second prepared powder containing a second particle raw material having a relative dielectric constant smaller than that of the first particle raw material and a second grain boundary raw material are stacked.
- This laminated sintering process may include, for example, (A) a first preparation powder manufacturing process, (B) a second preparation powder manufacturing process, (C) a laminated molded body manufacturing process, and (D) a sintering process. Good. Below, each process is demonstrated.
- the first preparation powder is manufactured by mixing the first particle raw material and the first grain boundary raw material.
- the first particle raw 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 first particle part.
- the first 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 first particle raw material may be a single-phase powder having a constant composition and characteristics within the particles, or may be multiphase particles having different compositions and characteristics within the particles, as in the first particle part.
- 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 first particle raw material has two or more kinds having different compositions and characteristics (particularly, temperature characteristics of dielectric constant). In the case where the phase is provided, two or more phases having different dielectric constant temperature characteristics are mixed. Therefore, it is considered that the temperature characteristics of the dielectric constant of the first material layer can be stabilized in the obtained laminate. .
- the first particle raw material was obtained, for example, through a first synthetic powder production step of producing a first synthetic powder by firing a first mixed powder containing a BaTiO 3 raw material and a metal element other than Ba and Ti. It is good also as a thing (1st synthetic powder).
- an auxiliary agent for example, Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SnO 2 , Nb
- a glass component and metal elements other than Ba and Ti at the time of production is used.
- the BaTiO 3 raw material may be BaTiO 3 itself, or BaTiO 3 obtained by firing, for example, a mixture of BaCO 3 and TiO 2 , or both of them. It may be included. Metal elements other than Ba and Ti may be included in any form, but are preferably included as oxides.
- the first mixed powder includes Bi 2 O 3 , ZnO, Mn 3 O 4 , ZrO 2 , SrO, SrTiO 3 , as a metal element other than Ba and Ti, in addition to the BaTiO 3 raw material.
- the first 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 first mixed powder may include one or more selected from the group consisting of ZrO 2 , SrO, SrTiO 3 , Nb 2 O 5 , and SnO 2 .
- the first 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. It is preferable that the content of CuO is in the range of 0% by mass or less, and the content of CuO is in the range of 0.4% by mass or less.
- the first mixed powder may contain the BaTiO 3 raw material in a range of 70% by mass to 97% by mass in terms of BaTiO 3 , or may contain 80% by mass or more and 95% by mass or less.
- the first mixed powder includes 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 May be 15% by mass or less, Nb 2 O 5 content may be 1.0% by mass or less, SrO content may be 10% by mass or less, and SrTiO 3 content may be 18% by mass or less. If it contains at least one element selected from the group consisting of SnO 2, ZrO 2, Nb 2 O 5, SrO, its content, each of which may be more than 0.01 mass%.
- ZrO 2 may be supplied from, for example, ZrO 2 boulders used for pulverization when the first mixed powder is prepared by pulverization and mixing.
- the firing conditions are not particularly limited, and heat treatment is performed at a firing temperature of 700 ° C. or higher and 1200 ° C. or lower for 1 hour to 24 hours in an oxidizing atmosphere such as air or oxygen atmosphere. It is good also as what to do.
- one type of synthetic powder may be produced, or two or more types of synthetic powders having different dielectric constant temperature characteristics produced under different compositions and production conditions may be produced.
- the first grain boundary part raw material contains ZnO.
- the first grain boundary part raw material preferably contains 35% by mass or more of ZnO.
- the first grain boundary part raw material 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 first grain boundary part 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 first grain boundary raw material.
- the first grain boundary raw material may be any material that can be melted in the subsequent sintering step to fill the space between the particles of the first particle raw material, but is preferably glass (first glass), and Zn—B— O-based (for example, Zn—B—Si—O based) glass is preferable. Since the Zn—B—O-based glass does not easily react with BaTiO 3 , the characteristics of the first material layer can be further maintained. Note that since the Zn—B—O and Zn—B—Si—O based glasses are the same as those described in the first grain boundary portion, description thereof is omitted here.
- the first preparation powder preferably contains the first grain boundary raw material in a range of 0.5 volume% or more and 15 volume% or less, and more preferably contains 1.5 volume% or more and 11 volume% or less.
- the first preparation powder may include oxide particles different from these in addition to the first particle raw material and the first 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.
- the second particle raw material is not particularly limited as long as it has a relative dielectric constant smaller than that of the first particle raw material, but may include a composite oxide having a tungsten bronze structure including at least one of Ba and Ti. , Ba and Ti are preferably included.
- the composite oxide having a tungsten bronze structure is selected from the group consisting of alkaline earth metal elements, rare earth elements, Si, Sc, Y, Zn, Nb, Ta, Pb, and Bi in addition to Ba and Ti. The above may be included. Examples of the composite oxide having a tungsten bronze structure include those exemplified in the second particle part.
- the composite oxide having a tungsten bronze structure preferably contains Ba, Nd, Bi, and Ti, and specifically includes Ba 4 (Nd, Bi) 9.3 Ti 18 O 54 and the like.
- the second particle raw material contains a composite oxide of Ba, Nd, Bi, and Ti, a laminate including the second material layer 30 having a low relative dielectric constant and a large Q value (reciprocal of tan ⁇ ) can be easily obtained. Obtainable.
- the second grain boundary raw material may be any material that can be melted in the subsequent sintering step to fill the space between the particles of the second particle raw material, but is preferably glass (second glass), and Zn—B— O-based glass (which may be Zn-B-Si-O-based glass, etc.), B-Si-Ba-Al-O-based glass, and Si-B-Na-O-based glass are more preferable. Since these glasses hardly react with BaTiO 3 , the characteristics of the first particle raw material can be further maintained. In addition, since the difference between the thermal shrinkage during firing and the temperature decrease during firing is small with respect to the first grain boundary raw material, for example, Zn—B—O-based glass, warping and peeling are not likely to occur.
- the second grain boundary part raw material is the same kind as the first grain boundary part raw material, for example, a Zn—B—O-based glass, the first molded body and the second molded body at the time of firing.
- the difference in thermal shrinkage during firing shrinkage and temperature drop is small, and warping and peeling associated therewith are less likely to occur.
- the Zn—BO—glass, B—Si—Ba—Al—O glass, and Si—B—Na—O glass are described in the first grain boundary part and the second grain boundary part. Since it is the same as what was done, description is abbreviate
- the second prepared powder preferably contains the second grain boundary raw material in the range of 0.5% by volume to 15% by volume, and more preferably in the range of 1.5% by volume to 11% by volume. By doing so, it is possible to easily obtain a laminate including the second material layer having a low relative dielectric constant and a large Q value.
- the difference between the ratio of the first grain boundary part raw material contained in the first preparation powder and the ratio of the second grain boundary part raw material contained in the second preparation powder may be within ⁇ 5% by volume. By doing so, since the ratio of the grain boundary portion raw materials included in the first molded body and the second molded body can be made relatively close, the difference in thermal expansion (shrinkage) between the first molded body and the second molded body is small. , Warpage and peeling are less likely to occur.
- (C) Laminated molded body manufacturing step In this step, a laminated molded body in which a first molded body obtained by molding the first prepared powder and a second molded body obtained by molding the second prepared powder is produced.
- the method of forming the first preparation powder and the second preparation powder is not particularly limited. For example, by press molding, die molding, extrusion molding, printing, doctor blade, etc. You may shape
- the first prepared powder and the second 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 dispersant, etc. It may be used in the form of a paste, paste, slurry or the like.
- the method for forming the first prepared powder and the method for forming the second prepared powder may be the same or different.
- the laminated body mentioned above is baked (sintered) and a laminated body is manufactured.
- 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 the sintering is performed at 1000 ° C. or less, for example, simultaneous lamination firing with a low dielectric material sintered using an Ag-based electrode or glass having a low specific resistivity can be made possible.
- the first particle raw material is the first particle part
- the first grain boundary raw material is the first grain boundary part
- the second particle raw material is the second particle part
- the second grain boundary raw material is the second.
- the first grain part, the first grain boundary part, the second grain part, and the second grain boundary part take in components other than each raw material, or a part of each raw material. Or may be obtained.
- the method for manufacturing a laminated device of the present invention includes a first prepared powder containing a first particle raw material which is a compound containing a metal element other than Ba and Ti in a part of BaTiO 3 and a first grain boundary raw material containing ZnO.
- This laminated sintering process includes, for example, (A) a first preparation powder manufacturing process, (B) a second preparation powder manufacturing process, (C ′) a laminated molded body manufacturing process with electrodes, and (D) a sintering process. It may be a thing.
- processes other than the (C ') electrode laminated laminate manufacturing process are the same as the method for manufacturing the laminate, the (C') electrode laminated laminate manufacturing process will be described below, and other processes. Description of is omitted.
- (C ′) Process for producing laminated molded body with electrode In this step, a first molded body obtained by molding the first prepared powder, a second molded body obtained by shaping the second prepared powder, and an electrode material containing Ag or an Ag alloy, , Are produced. What is necessary is just to shape
- the Ag alloy include those exemplified in the description of the laminated molded body.
- the electrode material may be formed by, for example, adding Ag or an Ag alloy powder to a paste or slurry by adding an organic solvent or the like and applying it to at least one of the first molded body and the second molded body.
- a novel laminated body and laminated device can be provided.
- the first particle raw material in which an auxiliary component is dissolved in BaTiO 3 the remaining auxiliary component can be reduced and element diffusion between different materials can be suppressed.
- the first and the particle material was a solid solution of auxiliary components BaTiO 3, for use with nobler first grain boundary portion material and BaTiO 3, a, BaTiO 3 and auxiliaries component and the first grain boundary part material It is thought that the reaction with can be suppressed.
- the insulation deterioration of a 1st material layer can be suppressed when the 1st grain boundary part containing ZnO exists between the particle
- the electrode is divided by the diffusion of the CuO component and the electrode is effective. It can suppress that an area becomes small.
- the laminated body needs to be fired at a low temperature such as 1000 ° C. or lower. Therefore, it can be manufactured relatively easily.
- Experimental examples 1 to 37, 46, 47, and 50 to 62 correspond to examples of the present invention, and experimental examples 38 to 45, 48, and 49 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 high dielectric material 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-described high dielectric material pre-synthetic powder (first particle raw material), glass (first grain boundary raw material), and SrTiO 3 in Experimental Examples 50 and 51 are added in predetermined amounts as shown in Tables 3 and 4. Further, IPA was added, and zirconia boulder was used for wet grinding and mixing in 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 high dielectric material preparation 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 glass (second grain boundary raw material) shown in Table 2 is added in a predetermined amount shown in Tables 3 and 4, and IPA is further added, and zirconia cobblestone is added. Then, after wet-grinding and mixing for 24 hours in a ball mill, the slurry passed through a 200 mesh sieve was dried and sized with a 100 mesh sieve to obtain a low dielectric material powder.
- FIG. 2 shows a schematic cross-sectional view of such a multilayer ceramic capacitor (however, it has 16 high dielectric layers and 1 low dielectric layer (the number of each layer is sandwiched between electrodes)).
- the multilayer ceramic capacitor 50 includes a first material layer 20 as a high dielectric layer 20a and a high dielectric dummy layer 20b, an internal electrode 52, an external electrode 54 including a via conductor 54a, a low dielectric layer 30a, and a low dielectric layer 30a.
- a second material layer 30 as a dielectric dummy layer 30b, an internal electrode 56, and an external electrode 58 including a via conductor 58a are provided.
- low dielectric ceramic capacitors Three layers of low dielectric green sheets (low dielectric layer (parts sandwiched between electrodes): 1 layer, dummy layer: 2 layers) are stacked and thermocompression bonded to obtain a pressed body. It was manufactured by the same manufacturing method as the capacitor. The thickness of the single layer of the low dielectric was 15 ⁇ m, and the thickness of the Ag electrode was 2.5 ⁇ m.
- the above-mentioned high dielectric material powder is uniaxial press-molded at 100 kg / cm 2 at ⁇ 30, and cold at a pressure at which the molding density of each sample is in the range of 51-56%, which is almost the same as the green sheet molding density.
- An isotropic pressurization method was performed. This molded body was sintered at a temperature shown in Tables 3 and 2 for 2 hours to obtain a sample of a sintered body for density measurement and chemical analysis.
- grain boundary phase derived from glass (first grain boundary part) ratio For the grain boundary phase having a contrast different from that of the first particle part in the 10,000 times image of the scanning electron microscope (SEM) of the first material layer, the area of the part is calculated by image analysis, and the ratio to the total area was calculated. For each experimental example, 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 of high dielectric material 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 an SEM photograph of the high dielectric material of Experimental Example 3 as an example of the embodiment of the present invention.
- FIG. 4 shows an SEM photograph of the high dielectric material of Experimental Example 42 as an example of the comparative example of the present invention.
- a high-dielectric material pre-synthetic powder obtained by firing a mixed powder containing BaTiO 3 , Bi 2 O 3 , ZnO, and Mn 3 O 4 in advance and a Zn—B—Si—O-based glass were mixed. It was found that in the case where the first prepared powder was molded and sintered, the first particle part and the first grain boundary part could be distinguished.
- FIG. 3 shows an SEM photograph of the high dielectric material of Experimental Example 3 as an example of the embodiment of the present invention.
- FIG. 4 shows an SEM photograph of the high dielectric material of Experimental Example 42 as an example of the comparative example of the present invention.
- a high-dielectric material pre-synthetic powder obtained by firing a mixed powder containing
- the relative dielectric constant and Q value of the low dielectric material (second material layer), the density of the high dielectric material (first material layer), the relative dielectric constant, tan ⁇ , X7R characteristics, and the maximum capacitance change Tables 7 and 8 show the rate, life time, grain boundary phase ratio, Ag electrode observation results, presence / absence of element diffusion and warpage of the multilayer ceramic capacitor (laminated body, multilayer device).
- Tables 5 to 8 a high dielectric material preparation powder in which a pre-synthetic powder obtained by firing a mixed powder containing BaTiO 3 , Bi 2 O 3 , ZnO, and Mn 3 O 4 and glass is mixed is molded.
- the difference in baking shrinkage can be suppressed and curvature can be suppressed by making the difference in the glass amount between different materials small.
- the laminated body and the laminated device can be reduced, the number of parts can be reduced, and the number of man-hours can be reduced. It was found that it can be reduced and the working time can be shortened.
- low dielectric materials can achieve the same characteristics as when fired using only low dielectric materials. It was found that the X7R characteristic can be satisfied at 1000 or more, and a laminated body in which different materials with little warpage can be laminated.
- the present invention can be used in the field of electronic equipment.
- 10 laminates 20 first material layer, 20a high dielectric layer, 20b high dielectric dummy layer, 22 first particle part, 24 first grain boundary part, 30 second material layer, 30a low dielectric layer, 30b low Dielectric dummy layer, 32 second particle part, 34 second grain boundary part, 50 multilayer ceramic capacitor, 52 internal electrode, 54 external electrode, 54a via conductor, 56 internal electrode, 58 external electrode, 58a via conductor.
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Abstract
Description
BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子部と、前記第1粒子部の粒子間に存在しZnOを含む第1粒界部と、を含み、第1の誘電率を有する第1材料層と、
第2粒子部と、前記第2粒子部の粒子間に存在する第2粒界部と、を含み、前記第1の誘電率よりも低い第2の誘電率を有する第2材料層と、
を備えたものである。
上述した積層体と、
前記積層体と一体化されAg又はAg合金である電極と、
を備えたものである。
BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、前記第1粒子原料よりも比誘電率が小さい第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、を積層した積層成形体を焼結する積層焼結工程、
を含むものである。
BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、前記第1粒子原料よりも比誘電率が小さい第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、Ag又はAg合金を含む電極材料と、を積層した電極付き積層成形体を焼結する積層焼結工程、
を含むものである。
本発明の積層体は、第1の誘電率を有する第1材料層と、第1の誘電率よりも低い第2の誘電率を有する第2材料層とを備えている。
本発明の積層デバイスは、上述した積層体と、積層体と一体化されAg又はAg合金である電極とを備えている。Ag合金は、Agを50質量%以上含むものであることが好ましく、Agを80質量%以上含むものとしてもよい。Agと合金を構成する金属としては、例えば、Pdなどが挙げられる。この積層デバイスでは、第1材料層は、CuOを含まないか、CuOが少ない組成とすることが好ましい。例えば、CuOの含有量は、0.4質量%以下の範囲であることが好ましい。こうすれば、異種材間などにおける元素拡散を抑制しつつ、さらにAg系電極を損なうこと無く、異種材積層のセラミックスコンデンサを作製できる。
本発明の積層体の製造方法は、BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、第1粒子原料よりも比誘電率が小さい第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、を積層した積層成形体を焼結する積層焼結工程、を含む。
この工程では、第1粒子原料と第1粒界部原料とを混合して第1調製粉を製造する。
この工程では、第1粒子原料よりも比誘電率が小さい第2粒子原料と、第2粒界部原料と、を混合して第2調製粉を製造する。
この工程では、第1調製粉を成形した第1成形体と、第2調製粉を成形した第2成形体と、を積層した積層成形体を製造する。
この工程では、上述した積層成形体を焼成(焼結)して積層体を製造する。焼結工程では、800℃以上1000℃以下の焼結温度で焼結するものとしてもよい。BaTiO3系の材料は、1000℃以下で焼結することが望まれているからである。1000℃以下での焼結であれば、例えば、比抵抗率の低いAg系電極やガラスを用いて焼結される低誘電材料と同時積層焼成を可能とすることができる。また、800℃以上で焼結すれば、密度が高く、誘電特性に優れた積層体が得られるからである。焼成時間は、例えば、1時間以上24時間以下の範囲内とすることができる。なお、この焼結工程では、第1粒子原料が第1粒子部、第1粒界部原料が第1粒界部、第2粒子原料が第2粒子部、第2粒界部原料が第2粒界部、となると考えられるが、この際、第1粒子部、第1粒界部、第2粒子部、第2粒界部は、各原料以外の成分を取り込んだり、各原料の一部を放出したりして、得られるものとしてもよい。
本発明の積層デバイスの製造方法は、BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、前記第1粒子原料よりも比誘電率が小さい第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、Ag又はAg合金を含む電極材料と、を積層した電極付き積層成形体を焼結する積層焼結工程を含む。
この工程では、第1調製粉を成形した第1成形体と、第2調製粉を成形した第2成形体と、Ag又はAg合金を含む電極材料と、を積層した積層成形体を製造する。第1成形体や第2成形体については、上述した積層成形体製造工程と同様に成形すればよい。Ag合金としては、積層成形体の説明で例示したものが挙げられる。電極材料は、例えば、AgやAg合金の粉末を有機溶剤などを加えてペースト状やスラリー状とし、第1成形体及び第2成形体の少なくとも一方に塗布して成形してもよい。
(高誘電材料調製粉(第1調製粉)の作製)
表1に示す各組成となるように、BaTiO3、Bi2O3、ZnO、Mn3O4、CuO、BaCO3、TiO2、Nb2O5、SnO2、ZrO2の各原料粉末を秤量した。なお、チタン酸バリウムについては、純度99.9%、平均粒径0.5μmの市販品を使用した。他の原料粉末についても、純度99.9%以上の市販品を用いた(平均粒径は、Bi2O3:5μm、ZnO:5μm、Mn3O4:5μm、CuO:5μm、BaCO3:1μm、TiO2:1μm、Nb2O5:5μm、SnO2:5μm、ZrO2:0.5μm)。さらに、イソプロピロアルコール(IPA)を適量加え、ジルコニア玉石を用いて、ボールミルにて48時間湿式粉砕混合し、200メッシュふるいを通したスラリーを乾燥し、100メッシュふるいにて整粒した。その混合粉を、大気中で表1に示す所定の温度で2時間事前合成し、高誘電材料事前合成粉(6.15g/cm3)を得た。事前合成前の混合粉については、N2-BET法により比表面積の測定を行った(表1)。
BaOが18質量%、Nd2O3が34質量%、Bi2O3が10質量%、TiO2が39質量%となるように、BaO、Nd2O3、Bi2O3、TiO2の各原料粉末を秤量した。なお、各原料は純度99.9%以上の市販品を用いた。さらに、イソプロピルアルコール(IPA)を適量加え、ジルコニア玉石を用いて、ボールミルにて48時間湿式粉砕混合し、200メッシュふるいを通したスラリーを乾燥し、100メッシュふるいにて整粒した。その混合粉を、大気中で1100℃で2時間事前合成し、低誘電材料事前合成粉(5.5g/cm3)を得た。
前述の高誘電材料調製粉及び低誘電材料調製粉に、ポリビニルブチラール等の有機バインダーや可塑剤、トルエン,IPAなどの有機溶剤を適量加えて、ボールミルで12時間湿式混合した後、ドクターブレード法によって、厚み20μmのグリーンシートを得た。このグリーンシートに内部電極パターンとして、表3,4に示すAg/Pd(質量比85wt%/15wt%)、もしくはAgのペーストを用いて、厚み4μmとなるように印刷した。
高誘電体のグリーンシートを17層(高誘電体層(電極に挟まれた部分):16層、高誘電体ダミー層:1層)積み重ね、さらに低誘電体のグリーンシートを3層(低誘電体層(電極に挟まれた部分):1層、低誘電体ダミー層:2層)積み重ねて、熱圧着し、圧着体(電極付き積層成形体)を得た。その圧着体にビア孔を形成し、そのビア孔に高誘電体側の内部電極および低誘電体側の内部電極とそれぞれ独立に導通を取れるようにビア導体を形成した。さらにそれぞれのビア導体と接続するように、圧着体の表面にそれぞれ外部電極を形成した。この圧着体から長さ6mm,幅2mmの成形体を切り出し、大気中、表3,4に示す温度で2時間焼結を行い、焼成体(積層デバイス)を得た。焼成後の各積層セラミックコンデンサのサイズは約4.8mm×1.6mmであり、高誘電体、および低誘電体の一層の厚みは15μmであり、Ag電極の厚みは2.5μmであった。図2に、こうした積層セラミッコンデンサ(但し、高誘電体層16層、低誘電体層1層のもの(各層数は電極に挟まれた層数))の概略の断面図を示す。積層セラミックコンデンサ50は、高誘電体層20a及び高誘電体ダミー層20bとしての第1材料層20と、内部電極52と、ビア導体54aを備えた外部電極54と、低誘電体層30a及び低誘電体ダミー層30bとしての第2材料層30と、内部電極56と、ビア導体58aを備えた外部電極58と、を備えている。
低誘電体のグリーンシートを3層(低誘電体層(電極に挟まれた部分):1層、ダミー層:2層)積み重ねて、熱圧着し、圧着体を得て、それ以外は積層セラミックコンデンサと同様の作製方法で作製した。低誘電体の一層の厚みは15μmであり、Ag電極の厚みは2.5μmであった。
前述の高誘電材料調製粉をφ30で100kg/cm2にて一軸プレス成形し、さらに各サンプルの成形密度がグリーンシートの成形密度とほぼ同等な51-56%の範囲内になる圧力で冷間等方加圧法を行った。この成形体を表3,4に示す温度で2時間焼結を行い、密度測定、および化学分析用焼成体のサンプルを得た。
各積層セラミックコンデンサのサンプルを恒温層に入れ、25℃で保持した後に、LCRメーターにて1kHz、1Vrmsにおける静電容量、およびtanδを測定した。容量、電極寸法、および誘電層の厚みから比誘電率を算出した。また、同様に、測定温度を-55℃~125℃の範囲で、静電容量を測定し、25℃での静電容量を基準として、-55℃~125℃の間における静電容量変化率の絶対値が最大である値を求め(容量最大変化率)、X7R特性(EIA規格:-55℃~125℃の範囲における容量変化率が25℃の容量に対して±15%以内)を満たすか評価した。X7R特性を満たす場合は「A」、X7R特性を満たさない場合は「B」とした。
各積層セラミックコンデンサ及び各低誘電体セラミックコンデンサのサンプルを恒温層に入れ、25℃で保持した後に、LCRメーターにて1kHz、1Vrmsにおける静電容量、およびQ値(tanδの逆数)を測定した。容量、電極寸法、および誘電層の厚みから比誘電率を算出した。
各積層セラミックコンデンサのサンプルを、170℃にて、8V/μmの電界下で加速試験を行い、絶縁抵抗が1MΩ以下になるまでの時間を寿命時間とした。なお、絶縁抵抗にまったく劣化がみられず、1MΩ以上を1000時間以上維持した場合、寿命時間を1000h以上とした。また、加速試験開始直後に1MΩ以下となった場合、寿命時間を0hとした。
第1材料層の走査型電子顕微鏡(SEM)の10000倍の像における、第1粒子部とはコントラストの異なる粒界相について、画像解析によりその部分の面積を算出し、全体の面積に占める割合を算出した。各実験例について、3視野の平均値を粒界相の占める粒界相面積の割合とした。コントラストの異なる粒界相は、FE-EPMAで元素分布を確認し、ガラス由来であり、ZnOを含むものであると判断した。
研磨により、積層セラミックコンデンサの断面を出し、走査型電子顕微鏡(SEM)にて、Ag電極及び焼成体の観察を行った。Ag電極の観察では、電極部位の電極成分以外の異物や空孔の観察を行った。電極層中のAgの占める面積が95%以上の場合は「A」、90%以上95%未満の場合は「B」、90%未満の場合は「C」とした。
研磨により、積層セラミックコンデンサの断面を出し、EPMAにて元素分布を観察した。低誘電体側でBaの元素ムラ、およびCuO等の低誘電体に含まれない元素が観察されない場合は「A」、観察された場合は「B」として評価した。
反りの評価は、4.8mm×1.6mmの異種積層サンプルの反りが50μm以下の場合は「A」、50μmより大きく100μm以下の場合は「B」、100μmより大きい場合は「C」として評価した。
密度測定用の焼成体を用意し、アルキメデス法により密度を測定した。
化学分析用の各焼成体を粉砕し、酸溶液で溶解させ、ICP発光分光分析法により、各成分を定量した。なお、ZrO2未添加の水準で検出されたZrO2は、ジルコニア玉石に起因するものと推察される。B2O3については、検出限界以下のため、0wt%と表記した。
図3に、本発明の実施例の一例として実験例3の高誘電材料のSEM写真を示す。また、図4に、本発明の比較例の一例として実験例42の高誘電材料のSEM写真を示す。図3より、BaTiO3、Bi2O3、ZnO、Mn3O4を含む混合粉を事前に焼成した高誘電材料事前合成粉と、Zn-B-Si-O系のガラスと、を混合した第1調製粉を成形して焼結したものでは、第1粒子部と第1粒界部とが区別できることがわかった。これに対して、図4より、高誘電材料事前合成粉やZn-B-Si-O系のガラスを用いない場合には、第1粒子部と第1粒界部との区別がなく、互いに反応してしまうことがわかった。実験例1~62について、高誘電体材料(第1材料層)の化学組成を表5,6に示した。また、実験例1~62について、低誘電材料(第2材料層)の比誘電率及びQ値、高誘電材料(第1材料層)の密度、比誘電率、tanδ、X7R特性、容量最大変化率、寿命時間、粒界相割合、Ag電極の観察結果、積層セラミックコンデンサ(積層体、積層デバイス)の元素拡散の有無及び反りの有無を表7,8に示した。表5~8に示すように、BaTiO3、Bi2O3、ZnO、Mn3O4を含む混合粉を事前に焼成した事前合成粉とガラスと、を混合した高誘電材料調製粉を成形して焼結した実験例1~37,46,47,50~62のものでは、新規な積層体が得られた。表5~8より、CuOを含まないか、CuOが少ない組成とすることで、異種材間の元素拡散を抑制しつつ、さらにAg電極を損なうこと無く、異種材積層のセラミックスコンデンサを作製できることがわかった。また、BaTiO3に助剤成分を事前に反応固溶させることで、残留する助剤成分を低減し、異種材間の元素拡散を抑制でき、異種材の同時焼成が可能となることがわかった。また、CuOが含まれないと1000℃以下などの低温での焼結が困難であるが、BaTiO3と反応固溶しにくい元素からなるガラスを用いることで、1000℃以下の焼結が可能となることがわかった。また、BaTiO3と助剤成分とを事前合成することで、ガラスを添加した場合でも、良好な誘電率の温度特性(静電容量の温度変化率)が得られることがわかった。なお、事前合成しないとガラスと助剤成分が先に反応して安定な物質となってしまうことにより、助剤が固溶していないBaTiO3が多量に残留し、良好な温度特性が得られないことがあった。また、異種材間のガラス量の差異を小さくすることで、焼成収縮の違いを抑制し、反りを抑制できることがわかった。また、こうした積層体、積層デバイス及びそれらの製造方法では、異種材料を一体焼成により一体化できるため、積層体や積層デバイスを小さくすることができるし、部品点数を減らすことができるし、工数を削減することができるし、作業時間を短縮することができることがわかった。また、高誘電材料および低誘電材料の異種材同士を低温同時積層焼成しても、低誘電材については、低誘電材のみで焼成したときと同等の特性が得られ、高誘電材は誘電率1000以上でX7R特性を満たすものとすることができ、反りの少ない異種材料を積層した積層体とすることができることがわかった。
Claims (27)
- BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子部と、前記第1粒子部の粒子間に存在しZnOを含む第1粒界部と、を含み、第1の誘電率を有する第1材料層と、
第2粒子部と、前記第2粒子部の粒子間に存在する第2粒界部と、を含み、前記第1の誘電率よりも低い第2の誘電率を有する第2材料層と、
を備えた、積層体。 - 前記第1材料層は、Bi2O3、ZnO、Mn3O4、ZrO2、SnO2、Nb2O5、SrOからなる群より選ばれる1以上を含む、請求項1に記載の積層体。
- 前記第1材料層は、Bi2O3、ZnO及びMn3O4を含む、請求項1又は2に記載の積層体。
- BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、を積層した積層成形体を焼結して得られた、請求項1~3のいずれか1項に記載の積層体。
- 前記第1粒界部原料は、Zn-B-O系のガラスであり、前記第2粒界部原料は、Zn-B-O系のガラス、B-Si-Ba-Al-O系のガラス、Si-B-Na-O系のガラス、からなる群より選ばれる1以上である、請求項4に記載の積層体。
- 前記第1材料層は、Bi2O3を3.5質量%以上11質量%以下、ZnOを0.6質量%以上5.0質量%以下、Mn3O4を0.01質量%以上1.0質量%以下の範囲で含み、CuOの含有量が0.4質量%以下である、請求項1~5のいずれか1項に記載の積層体。
- 前記第1材料層は、SnO2、ZrO2、Nb2O5、SrOからなる群より選ばれる1以上を含み、前記SnO2の含有量は1.0質量%以下、前記ZrO2の含有量は2.5質量%以下、前記Nb2O5の含有量は1.0質量%以下、前記SrOの含有量は10質量%以下である、請求項1~6のいずれか1項に記載の積層体。
- 前記第1材料層は、比誘電率が1000以上3000以下である、請求項1~7のいずれか1項に記載の積層体。
- 前記第1材料層は、誘電正接tanδが0.05以下である、請求項1~8のいずれか1項に記載の積層体。
- 前記第2粒子部は、Ba及びTiのうち少なくとも一方を含むタングステンブロンズ構造を持つ複合酸化物を含む、請求項1~9のいずれか1項に記載の積層体。
- 前記第2材料層は、比誘電率が5以上200以下である、請求項1~10のいずれか1項に記載の積層体。
- 請求項1~11のいずれか1項に記載の積層体と、
前記積層体と一体化されAg又はAg合金である電極と、
を備えた積層デバイス。 - BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、前記第1粒子原料よりも比誘電率が小さい第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、を積層した積層成形体を焼結する積層焼結工程、
を含む、積層体の製造方法。 - 前記第1粒子原料は、BaTiO3原料と、Ba、Ti以外の金属元素とを含む第1混合粉を焼成したものである、請求項13に記載の積層体の製造方法。
- 前記第1混合粉は、Bi2O3、ZnO、Mn3O4、ZrO2、SnO2、Nb2O5、SrTiO3からなる群より選ばれる1以上を含む、請求項14に記載の積層体の製造方法。
- 前記第1混合粉は、Bi2O3、ZnO及びMn3O4を含む、請求項14又は15に記載の積層体の製造方法。
- 前記第1混合粉は、Bi2O3を3.5質量%以上11質量%以下、ZnOを0.6質量%以上5.0質量%以下、Mn3O4を0.01質量%以上1.0質量%以下の範囲で含み、CuOの含有量が0.4質量%以下である、請求項14~16のいずれか1項に記載の積層体の製造方法。
- 前記第1混合粉は、SnO2、ZrO2、Nb2O5からなる群より選ばれる1以上を含み、前記SnO2の含有量は15質量%以下、前記ZrO2の含有量は25質量%以下、前記Nb2O5の含有量は1.0質量%以下である、請求項14~17のいずれか1項に記載の積層体の製造方法。
- 前記第1調製粉は、前記第1粒界部原料を0.5体積%以上15体積%以下の範囲で含む、請求項13~18のいずれか1項に記載の積層体の製造方法。
- 前記第2調製粉は、前記第2粒界部原料を0.5体積%以上15体積%以下の範囲で含む、請求項13~19のいずれか1項に記載の積層体の製造方法。
- 前記第1調製粉は、前記第1粒子原料として、組成の異なる2種以上の粒子を含む、請求項13~20のいずれか1項に記載の積層体の製造方法。
- 前記第1調製粉は、さらに、SrTiO3を含む、請求項13~21のいずれか1項に記載の積層体の製造方法。
- 前記積層焼結工程では、前記積層成形体を800℃以上1000℃以下の焼結温度で焼結する、請求項13~22のいずれか1項に記載の積層体の製造方法。
- 前記第2粒子原料は、Ba及びTiのうち少なくとも一方を含むタングステンブロンズ構造を持つ複合酸化物を含む、請求項13~23のいずれか1項に記載の積層体の製造方法。
- 前記第1粒界部原料は、Zn-B-O系のガラスであり、前記第2粒界部原料は、Zn-B-O系のガラス、B-Si-Ba-Al-O系のガラス、Si-B-Na-O系のガラス、からなる群より選ばれる1以上である、請求項13~24のいずれか1項に記載の積層体の製造方法。
- 前記第1調製粉に含まれる前記第1粒界部原料の割合(体積%)と前記第2調製粉に含まれる前記第2粒界部原料の割合(体積%)との差が±5体積%以内である、請求項13~25のいずれか1項に記載の積層体の製造方法。
- BaTiO3の一部にBa、Ti以外の金属元素を含む化合物である第1粒子原料とZnOを含む第1粒界部原料とを含む第1調製粉を成形した第1成形体と、前記第1粒子原料よりも比誘電率が小さい第2粒子原料と第2粒界部原料とを含む第2調製粉を成形した第2成形体と、Ag又はAg合金を含む電極材料と、を積層した電極付き積層成形体を焼結する積層焼結工程、
を含む、積層デバイスの製造方法。
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