WO2012002118A1 - Dielectric ceramic material and laminated ceramic capacitor comprising same - Google Patents
Dielectric ceramic material and laminated ceramic capacitor comprising same Download PDFInfo
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- WO2012002118A1 WO2012002118A1 PCT/JP2011/063129 JP2011063129W WO2012002118A1 WO 2012002118 A1 WO2012002118 A1 WO 2012002118A1 JP 2011063129 W JP2011063129 W JP 2011063129W WO 2012002118 A1 WO2012002118 A1 WO 2012002118A1
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- dielectric
- dielectric ceramic
- ceramic
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- nitride
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 35
- 229910010293 ceramic material Inorganic materials 0.000 title abstract description 10
- 150000004767 nitrides Chemical class 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 5
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 87
- 239000010953 base metal Substances 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 20
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003989 dielectric material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000005717 Myeloma Proteins Human genes 0.000 description 1
- 108010045503 Myeloma Proteins Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
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- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
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- H01G4/08—Inorganic dielectrics
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- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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Definitions
- the present invention relates to a dielectric ceramic and a capacitor using the dielectric ceramic, and more particularly to a BaTiO 3 based dielectric ceramic and a multilayer ceramic capacitor using the dielectric ceramic as a constituent material of the dielectric layer.
- the multilayer ceramic capacitor has a ceramic layer (dielectric ceramic layer) 11 in which an internal electrode 12 disposed in a ceramic multilayer body (multilayer ceramic element) 10 is a dielectric layer. And a pair of external electrodes 13a and 13b are disposed on both end faces of the ceramic laminate 10 so as to be electrically connected to the internal electrodes 12 exposed on the opposite end faces. is doing.
- a BaTiO 3 -based ceramic material having a high dielectric constant is widely used as the dielectric layer.
- Patent Document 1 discloses a barium titanate powder and 100 mol of this barium titanate in terms of metal ions, 0.1 to 0.3 mol of Mn, 1.0 to 2.0 mol of Dy, Contains a metal compound containing 0.3 to 1.0 mol Mg, 0.5 to 1.5 mol Ba, 0.5 to 1.5 mol Ca and 1.0 to 2.5 mol Si, and aqueous ammonia. There has been proposed a method for producing a reduction-resistant dielectric composition through a step of preparing a mixed solution and heat-treating powder obtained from the mixed solution (see Patent Document 1).
- Patent Document 1 proposes a multilayer ceramic capacitor having a dielectric layer formed from the reduction-resistant dielectric composition produced as described above and a method for producing the same.
- the invention of the present application can be sintered at a low temperature without requiring a baking at a very high temperature without going through a step of preparing a mixed solution containing a metal compound and aqueous ammonia as in Patent Document 1.
- An object of the present invention is to provide a dielectric ceramic having characteristics that can be used for a multilayer ceramic capacitor and the like, and a multilayer ceramic capacitor using the dielectric ceramic.
- the dielectric ceramic of the present invention is ABO 3 (A site is Ba and may contain at least one of Sr and Ca in addition to Ba, and B site is Ti and contains at least one of Zr and Hf in addition to Ti.
- the main component is a perovskite type compound represented by O)
- the additive component is characterized by containing at least one selected from the group consisting of nitrides D: BN, AlN, Si 3 N 4 , TaN, ZrN and TiN represented by D below.
- the dielectric ceramic of the present invention further includes Si, R (R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and And M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W and V). It is possible to contain at least one selected from the group.
- the additive amount of the nitride D which is an additive component, is 0.5 mol part ⁇ D ⁇ 5.0 mol part with respect to 100 mol part of the perovskite type compound whose main component is the content in the dielectric ceramic. Such a range is desirable.
- the multilayer ceramic capacitor of the present invention is A ceramic laminate having a structure in which a plurality of internal electrodes are laminated so as to face each other through a dielectric ceramic layer, and one end of the internal electrode is drawn out to a predetermined surface, and the ceramic laminate
- the multilayer ceramic capacitor comprising a pair of external electrodes arranged to be electrically connected to the internal electrode on the surface from which one end of the internal electrode is drawn
- the dielectric ceramic layer is made of the dielectric ceramic of the present invention.
- the multilayer ceramic capacitor of the present invention can also be applied when the internal electrode includes a base metal.
- the multilayer ceramic capacitor of the present invention can also be applied when the external electrode includes a base metal.
- the dielectric ceramic of the present invention is mainly composed of a BaTiO 3 -based perovskite compound represented by ABO 3 , and nitride D (D is BN, AlN, Si 3 N) as an additive component. 4 , at least one selected from the group consisting of TaN, ZrN, and TiN) is provided, and a dielectric ceramic that can be sintered at a low temperature and has practical characteristics is provided. Can do.
- the nitride contributes as a sintering aid, enabling sintering at a low temperature, and a method in which no nitride is added (for example, the method of Patent Document 1 described above). It is possible to provide a dielectric ceramic having electrical characteristics equivalent to or better than those of dielectric ceramics manufactured by the conventional method.
- Si is at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y
- M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W, and V).
- the addition amount of the nitride D as an additive component is set to a range of 0.5 mol part ⁇ D ⁇ 5.0 mol part with respect to 100 mol part of the perovskite compound as the main component, thereby firing at a low temperature. Even in this case, a dielectric ceramic having practical characteristics can be obtained more reliably.
- the multilayer ceramic capacitor of the present invention is a multilayer ceramic capacitor having a structure in which internal electrodes are laminated so as to face each other through a dielectric ceramic layer.
- the dielectric ceramic layer is made of the dielectric ceramic of the present invention. Since the dielectric ceramic layer is used, a multilayer ceramic capacitor having desired characteristics can be obtained.
- the dielectric ceramic of the present invention can be sintered at a low temperature, the dielectric ceramic layer can be sufficiently sintered even when the internal electrode contains a base metal or when the external electrode contains a base metal.
- the dielectric ceramic layer can be sufficiently sintered even when the internal electrode contains a base metal or when the external electrode contains a base metal.
- BaCO 3 powder, TiO 2 powder, etc. which are main component raw materials, are prepared as starting raw materials, and a perovskite complex oxide represented by ABO 3 , that is, BaTiO 3 based oxidation.
- ABO 3 a perovskite complex oxide represented by ABO 3 , that is, BaTiO 3 based oxidation.
- the A site is Ba and may contain at least one of Sr and Ca in addition to Ba
- the B site is Ti and contains at least one of Zr and Hf in addition to Ti.
- the sample was weighed so as to have a composition of O) and then mixed by a ball mill. Then, this mixed powder was heat-treated at 1150 ° C. to obtain a BaTiO 3 -based powder.
- the average particle size of the BaTiO 3 powder was about 0.15 ⁇ m.
- the ratio (A / B ratio) between the A site and the B site of the BaTiO 3 powder was changed.
- the BaTiO 3 powder and Si, R (R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y are selected. At least one), M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W and V), and a nitride D (D is And at least one selected from the group consisting of BN, AlN, Si 3 N 4 , TaN, ZrN and TiN), respectively, and weighed so as to have the compositions shown in Table 1, Table 2A, Table 2B and Table 2C. Was mixed and dried to obtain a dielectric material composition (dielectric ceramic material). Note that oxide powders were used as raw materials for Si, R, and M.
- dielectric raw material blends (dielectric ceramic raw materials) of sample numbers R1 to R6 in Table 1 are comparative dielectric raw material blends that do not contain nitride D, and are shown in Tables 2A, 2B, and 2C.
- the dielectric raw material blends (dielectric ceramic raw materials) of sample numbers 1 to 31 are dielectric raw material blends containing nitride D that becomes the dielectric ceramic according to the example of the present invention after firing.
- the main component BaTiO 3 used this time was prepared by a solid phase synthesis method and heat-treated at a temperature at which a desired particle size was obtained, but BaTiO 3 prepared by a hydrothermal synthesis method, a hydrolysis method or the like was used. It is also possible to use it. Further, the raw material for preparing BaTiO 3 and the compound form of the additive component are not limited to oxides and carbonates, and various forms such as chlorides and metal organic compounds can be used.
- the case where the main component ABO 3 does not have a stoichiometric composition is included. Specifically, if the molar ratio A / B of A and B is in the range of 0.950 to 1.050, ABO 3 in the present invention can be obtained.
- this laminated single plate was analyzed for porcelain structure by energy dispersive X-ray spectroscopy (STEM-EDX) using a scanning transmission electron microscope, and 10 fields of 2 ⁇ m ⁇ 2 ⁇ m region were confirmed, and additive component D (nitriding) It was confirmed that the product was present in the porcelain.
- STEM-EDX energy dispersive X-ray spectroscopy
- Samples Nos. 1 to 31 in Tables 2A, 2B, and 2C are samples (examples) having the requirements of the present invention, and a dense porcelain having a BaTiO 3 theoretical density ratio of 85% or more is obtained. It was confirmed. This is because the samples Nos. 1 to 31 contain nitrides (BN, AlN, Si 3 N 4 , TiN, TaN, ZrN), so that the sintering of the ceramic is promoted and the BaTiO 3 theory A dense porcelain having a density ratio of 85% or more could be obtained.
- nitrides BN, AlN, Si 3 N 4 , TiN, TaN, ZrN
- the ceramic does not sinter sufficiently even when firing at a temperature of 1200 ° C. or higher, and a BaTiO 3 theoretical density ratio of 85% can be realized. It was confirmed that it was not possible. Since the samples of these comparative examples do not contain nitrides (BN, AlN, Si 3 N 4 , TiN, TaN, ZrN) that promote the sintering of ceramics, sufficient sinterability can be ensured. It was not.
- the samples of the comparative examples of the sample numbers R1 to R5 do not contain the nitride D but also do not contain the Si, R component, and M component.
- the BaTiO 3 theoretical density ratio is 85%.
- the sample of the comparative example of sample number R6 did not include nitride D, it was a sample containing Si, R component, and M component.
- this sample of R6 is also a BaTiO 3 theory. A density ratio of 85% could not be realized.
- the BaTiO 3 theoretical density ratio is also obtained when the composition includes at least one of Si, R component, and M component as in sample numbers 13 to 31. It was confirmed that a dielectric ceramic having a high density and excellent sinterability can be obtained. In addition, by setting it as the composition containing at least 1 or more of Si, R component, and M component, it becomes possible to control a characteristic and to obtain the dielectric ceramic provided with the desired characteristic.
- an internal electrode 12 disposed inside a monolithic ceramic element (fired ceramic laminate) 10 is laminated via a dielectric layer (dielectric ceramic layer) 11, and A pair of external electrodes 13 a and 13 b are arranged on both end faces of the multilayer ceramic element 10 so as to be electrically connected to the internal electrodes 12 exposed on the opposite end face alternately.
- a method for manufacturing the multilayer ceramic capacitor will be described.
- a polyvinyl butyral binder and an organic solvent were added to the dielectric material composition of Sample Nos. 1 to 31 prepared in Example 1 (A), and the ball mill was used for a predetermined time. And wet mixing to prepare a ceramic slurry.
- the ceramic slurry was formed into a sheet by the doctor blade method, and a ceramic green sheet having a rectangular shape after firing, that is, a dielectric ceramic layer thickness of 3.0 ⁇ m was produced.
- a conductive paste containing nickel powder as a conductive component was screen-printed to form a conductive paste layer (internal electrode pattern) that became an internal electrode after firing.
- a predetermined number of ceramic green sheets on which internal electrode patterns are formed are stacked in such a manner that the internal electrode patterns are alternately drawn to the opposite side, and further, a ceramic in which no conductive paste pattern is formed on both upper and lower sides
- a laminated block was produced by laminating green sheets as outer layers. There are no particular restrictions on the order of lamination of the ceramic green sheets.
- an unfired laminate obtained by cutting the laminate block to a predetermined size is debindered in an N 2 atmosphere, and then H 2 —N 2 — with an oxygen partial pressure of 10 ⁇ 10 MPa. Firing was performed at 1200 ° C. in a reducing atmosphere composed of H 2 O gas to obtain a fired laminated body (ceramic laminated body).
- a conductive layer containing copper powder as a conductive component and B 2 O 3 —Li 2 O—SiO 2 —BaO glass frit is formed on both end surfaces of the fired ceramic laminate from which the internal electrodes are drawn.
- an external electrode electrically connected to the internal electrode was formed by baking at 800 ° C. Thereby, a multilayer ceramic capacitor having a structure as shown in FIG. 1 is obtained.
- the outer dimensions of the obtained multilayer ceramic capacitor are: length: 2.0 mm, width: 1.25 mm, thickness: 1.0 mm, and a dielectric layer (dielectric ceramic layer) interposed between the internal electrodes 12 ) 11 had a thickness of 3.0 ⁇ m.
- the number of effective dielectric layers (capacitor forming layers) was 10, and the counter electrode area per layer was 1.6 mm 2 .
- nitride D is contained, and the content ratio of D is 0.5 mol part ⁇ D ⁇ 5.0 mol part with respect to 100 mol part of perovskite type compound as the main component.
- the dielectric ceramic layer satisfies the requirement of relative dielectric constant 2000 ⁇ ⁇ r, and good electrical characteristics It was confirmed that
- the additive of the nitride D is usually 0.5 mol part ⁇ D ⁇ 5.0 mol part with respect to 100 mol part of the perovskite type compound which is the main component. It can be seen that it is desirable to set the range.
- the ratio of A site to B site (A / B (mol ratio)) is in the range of 0.950 to 1.050, and at least in this range. It was confirmed that a practical dielectric ceramic could be obtained.
- one or more of Si, R component, and M component are blended to control the characteristics and are suitable for use.
- a dielectric ceramic having characteristics can be obtained. That is, according to the present invention, it is possible to provide a dielectric ceramic that can be sintered at a low temperature and has a high degree of freedom in characteristics.
- a part of Ba constituting the BaTiO 3 ceramic particles is replaced with Ca and / or Sr, or a part of Ti is replaced with Zr. It is also possible to substitute with Hf and / or Hf, in which case the characteristics can be controlled to obtain a dielectric ceramic having desired characteristics.
- the dielectric ceramic of the present invention is used as a dielectric layer of a multilayer ceramic capacitor as an example.
- the dielectric ceramic according to the present invention is not limited to a multilayer ceramic capacitor, and is an LC composite. It can also be applied to parts.
- the present invention is not limited to the above embodiment in other points as well, and the types of raw materials, specific conditions of the manufacturing process, nitride D, Si, and the like when the dielectric ceramic of the present invention is manufactured. With respect to specific blending ratios of R component, M component, etc., various applications and modifications can be added within the scope of the invention.
- Multilayer Ceramic Element 11 Ceramic Layer (Dielectric Ceramic Layer) 12 Internal electrode layer 13a, 13b External electrode
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Abstract
Disclosed are: a dielectric ceramic material which can be sintered at a low temperature and has practically available properties; and a laminated ceramic capacitor which comprises the dielectric ceramic material. The dielectric ceramic material has a composition which contains a perovskite-type compound represented by the following formula: ABO3 as the main component and a nitride (D) (at least one compound selected from the group consisting of BN, AlN, Si3N4, TaN, ZrN and TiN) as an additive component. The amount of the nitride (D) to be added is such an amount that the content of the nitride (D) in the dielectric ceramic material becomes 0.5 to 5.0 parts by mole inclusive relative to 100 parts by mole of the perovskite-type compound that is the main component. The dielectric ceramic material additionally contains at least one component selected from Si, R (any one of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y), and M (any one of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W and V).
Description
本発明は誘電体セラミックおよびそれを用いたコンデンサに関し、詳しくは、ＢａＴｉＯ3系の誘電体セラミックおよびそれを誘電体層の構成材料として用いた積層セラミックコンデンサに関する。
The present invention relates to a dielectric ceramic and a capacitor using the dielectric ceramic, and more particularly to a BaTiO 3 based dielectric ceramic and a multilayer ceramic capacitor using the dielectric ceramic as a constituent material of the dielectric layer.
近年、電子機器の小型・軽量化にともない、小型で、大容量を取得することが可能な積層セラミックコンデンサが広く用いられている。この積層セラミックコンデンサは、例えば、図１に示すように、セラミック積層体（積層セラミック素子）１０の内部に配設された内部電極１２が、誘電体層であるセラミック層（誘電体セラミック層）１１を介して積層され、かつ、セラミック積層体１０の両端面には、交互に逆側の端面に露出した内部電極１２と導通するように一対の外部電極１３ａ，１３ｂが配設された構造を有している。
In recent years, with the reduction in size and weight of electronic devices, multilayer ceramic capacitors that are small in size and capable of acquiring a large capacity have been widely used. For example, as shown in FIG. 1, the multilayer ceramic capacitor has a ceramic layer (dielectric ceramic layer) 11 in which an internal electrode 12 disposed in a ceramic multilayer body (multilayer ceramic element) 10 is a dielectric layer. And a pair of external electrodes 13a and 13b are disposed on both end faces of the ceramic laminate 10 so as to be electrically connected to the internal electrodes 12 exposed on the opposite end faces. is doing.
そして、このような積層セラミックコンデンサにおいては、誘電体層として、高い誘電率を有するＢａＴｉＯ3系のセラミック材料が広く用いられている。
In such a multilayer ceramic capacitor, a BaTiO 3 -based ceramic material having a high dielectric constant is widely used as the dielectric layer.
さらに、電気特性や、信頼性（寿命特性）などの特性を向上させる目的で、種々の副成分、例えば、希土類元素やＭｇなどを添加したものが用いられている。
Furthermore, for the purpose of improving characteristics such as electrical characteristics and reliability (life characteristics), those added with various subcomponents such as rare earth elements and Mg are used.
そして、特許文献１には、チタン酸バリウム粉末と、このチタン酸バリウム１００ｍｏｌに対し、金属イオン換算により表示して、０．１～０．３ｍｏｌのＭｎ、１．０～２．０ｍｏｌのＤｙ、０．３～１．０ｍｏｌのＭｇ、０．５～１．５ｍｏｌのＢａ、０．５～１．５ｍｏｌのＣａおよび１．０～２．５ｍｏｌのＳｉを含む金属化合物と、アンモニア水とを含む混合液を調製し、この混合液から得た粉末を熱処理する工程を経て、耐還元性誘電体組成物を製造する方法が提案されている（特許文献１参照）。
Patent Document 1 discloses a barium titanate powder and 100 mol of this barium titanate in terms of metal ions, 0.1 to 0.3 mol of Mn, 1.0 to 2.0 mol of Dy, Contains a metal compound containing 0.3 to 1.0 mol Mg, 0.5 to 1.5 mol Ba, 0.5 to 1.5 mol Ca and 1.0 to 2.5 mol Si, and aqueous ammonia. There has been proposed a method for producing a reduction-resistant dielectric composition through a step of preparing a mixed solution and heat-treating powder obtained from the mixed solution (see Patent Document 1).
また、この特許文献１には、上述のようにして製造された耐還元性誘電体組成物から形成された誘電体層を有する積層セラミックコンデンサおよびその製造方法が提案されている。
Further, this Patent Document 1 proposes a multilayer ceramic capacitor having a dielectric layer formed from the reduction-resistant dielectric composition produced as described above and a method for producing the same.
そして、上述の耐還元性誘電体組成物を用いることにより、初期特性および耐久性などの諸特性のばらつきの少ない積層セラミックコンデンサを歩留まりよく製造できるとされている。
And by using the above-mentioned reduction-resistant dielectric composition, it is said that a multilayer ceramic capacitor with little variation in various characteristics such as initial characteristics and durability can be manufactured with high yield.
本願発明は、特許文献１のように、金属化合物と、アンモニア水とを含む混合液を調製する工程を経ることなく、それほど高い温度で焼成することを必要とせず、低温で焼結させることが可能で、積層セラミックコンデンサなどに用いることが可能な特性を備えた誘電体セラミックおよびそれを用いた積層セラミックコンデンサを提供することを目的とする。
The invention of the present application can be sintered at a low temperature without requiring a baking at a very high temperature without going through a step of preparing a mixed solution containing a metal compound and aqueous ammonia as in Patent Document 1. An object of the present invention is to provide a dielectric ceramic having characteristics that can be used for a multilayer ceramic capacitor and the like, and a multilayer ceramic capacitor using the dielectric ceramic.
上記課題を解決するため、本発明の誘電体セラミックは、
ＡＢＯ3（ＡサイトはＢａであって、Ｂａ以外にＳｒおよびＣａの少なくとも１種を含んでいてもよく、また、ＢサイトはＴｉであって、Ｔｉ以外にＺｒおよびＨｆの少なくとも１種を含んでいてもよく、Ｏは酸素）で表されるペロブスカイト型化合物を主成分とし、
添加成分として、下記のＤで表される窒化物
Ｄ：ＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴａＮ，ＺｒＮおよびＴｉＮからなる群より選ばれる少なくとも１種を
含有することを特徴としている。 In order to solve the above problems, the dielectric ceramic of the present invention is
ABO 3 (A site is Ba and may contain at least one of Sr and Ca in addition to Ba, and B site is Ti and contains at least one of Zr and Hf in addition to Ti. The main component is a perovskite type compound represented by O)
The additive component is characterized by containing at least one selected from the group consisting of nitrides D: BN, AlN, Si 3 N 4 , TaN, ZrN and TiN represented by D below.
ＡＢＯ3（ＡサイトはＢａであって、Ｂａ以外にＳｒおよびＣａの少なくとも１種を含んでいてもよく、また、ＢサイトはＴｉであって、Ｔｉ以外にＺｒおよびＨｆの少なくとも１種を含んでいてもよく、Ｏは酸素）で表されるペロブスカイト型化合物を主成分とし、
添加成分として、下記のＤで表される窒化物
Ｄ：ＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴａＮ，ＺｒＮおよびＴｉＮからなる群より選ばれる少なくとも１種を
含有することを特徴としている。 In order to solve the above problems, the dielectric ceramic of the present invention is
ABO 3 (A site is Ba and may contain at least one of Sr and Ca in addition to Ba, and B site is Ti and contains at least one of Zr and Hf in addition to Ti. The main component is a perovskite type compound represented by O)
The additive component is characterized by containing at least one selected from the group consisting of nitrides D: BN, AlN, Si 3 N 4 , TaN, ZrN and TiN represented by D below.
また、本発明の誘電体セラミックは、さらに、添加成分として、Ｓｉ、Ｒ（ＲはＬａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，ＬｕおよびＹからなる群より選ばれる少なくとも１種）、およびＭ（ＭはＭｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ｍｇ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）からなる群より選ばれる少なくとも１種を含有させることが可能である。
The dielectric ceramic of the present invention further includes Si, R (R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and And M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W and V). It is possible to contain at least one selected from the group.
また、添加成分である前記窒化物Ｄの添加量を、誘電体セラミックにおける含有率が、主成分である前記ペロブスカイト型化合物１００ｍｏｌ部に対して、０．５ｍｏｌ部≦Ｄ≦５．０ｍｏｌ部となるような範囲とすることが望ましい。
Further, the additive amount of the nitride D, which is an additive component, is 0.5 mol part ≦ D ≦ 5.0 mol part with respect to 100 mol part of the perovskite type compound whose main component is the content in the dielectric ceramic. Such a range is desirable.
また、本発明の積層セラミックコンデンサは、
複数の内部電極が、誘電体セラミック層を介して互いに対向するように積層され、前記内部電極の一方端部が所定の面に引き出された構造を有するセラミック積層体を備えるとともに、前記セラミック積層体の前記内部電極の一方端部が引き出された面に前記内部電極と導通するように配設された一対の外部電極を備えた積層セラミックコンデンサにおいて、
前記の誘電体セラミック層が、本発明の誘電体セラミックからなること
を特徴としている。 The multilayer ceramic capacitor of the present invention is
A ceramic laminate having a structure in which a plurality of internal electrodes are laminated so as to face each other through a dielectric ceramic layer, and one end of the internal electrode is drawn out to a predetermined surface, and the ceramic laminate In the multilayer ceramic capacitor comprising a pair of external electrodes arranged to be electrically connected to the internal electrode on the surface from which one end of the internal electrode is drawn,
The dielectric ceramic layer is made of the dielectric ceramic of the present invention.
複数の内部電極が、誘電体セラミック層を介して互いに対向するように積層され、前記内部電極の一方端部が所定の面に引き出された構造を有するセラミック積層体を備えるとともに、前記セラミック積層体の前記内部電極の一方端部が引き出された面に前記内部電極と導通するように配設された一対の外部電極を備えた積層セラミックコンデンサにおいて、
前記の誘電体セラミック層が、本発明の誘電体セラミックからなること
を特徴としている。 The multilayer ceramic capacitor of the present invention is
A ceramic laminate having a structure in which a plurality of internal electrodes are laminated so as to face each other through a dielectric ceramic layer, and one end of the internal electrode is drawn out to a predetermined surface, and the ceramic laminate In the multilayer ceramic capacitor comprising a pair of external electrodes arranged to be electrically connected to the internal electrode on the surface from which one end of the internal electrode is drawn,
The dielectric ceramic layer is made of the dielectric ceramic of the present invention.
本発明の積層セラミックコンデンサは、前記内部電極が、卑金属を含むものである場合にも適用することができる。
The multilayer ceramic capacitor of the present invention can also be applied when the internal electrode includes a base metal.
また、本発明の積層セラミックコンデンサは、前記外部電極が、卑金属を含むものである場合にも適用することができる。
The multilayer ceramic capacitor of the present invention can also be applied when the external electrode includes a base metal.
上記課題を解決するため、本発明の誘電体セラミックは、ＡＢＯ3で表されるＢａＴｉＯ3系のペロブスカイト型化合物を主成分とし、添加成分として、窒化物Ｄ（ＤはＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴａＮ，ＺｒＮおよびＴｉＮからなる群より選ばれる少なくとも１種）を含有させるようにしているので、低温で焼結することが可能で、実用可能な特性を備えた誘電体セラミックを提供することができる。
In order to solve the above problems, the dielectric ceramic of the present invention is mainly composed of a BaTiO 3 -based perovskite compound represented by ABO 3 , and nitride D (D is BN, AlN, Si 3 N) as an additive component. 4 , at least one selected from the group consisting of TaN, ZrN, and TiN) is provided, and a dielectric ceramic that can be sintered at a low temperature and has practical characteristics is provided. Can do.
すなわち、上記窒化物を添加することで、窒化物が焼結助剤として寄与し、低温での焼結が可能になるとともに、窒化物を添加しない方法（例えば、上述の特許文献１の方法）やその他の従来の方法で製造される誘電体セラミックの電気特性と同等もしくはそれ以上の電気特性を備えた誘電体セラミックを提供することが可能になる。
That is, by adding the nitride, the nitride contributes as a sintering aid, enabling sintering at a low temperature, and a method in which no nitride is added (for example, the method of Patent Document 1 described above). It is possible to provide a dielectric ceramic having electrical characteristics equivalent to or better than those of dielectric ceramics manufactured by the conventional method.
さらに、添加成分として、Ｓｉ，Ｒ（ＲはＬａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，ＬｕおよびＹからなる群より選ばれる少なくとも１種）、およびＭ（ＭはＭｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ｍｇ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）からなる群より選ばれる少なくとも１種を含有させることにより、特性を制御して、所望の特性を備えた誘電体セラミックを得ることが可能になる。
Further, as an additive component, Si, R (R is at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y) ) And M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W, and V). Thus, it becomes possible to obtain a dielectric ceramic having desired characteristics by controlling the characteristics.
また、添加成分である窒化物Ｄの添加量を、主成分である前記ペロブスカイト型化合物１００ｍｏｌ部に対して、０．５ｍｏｌ部≦Ｄ≦５．０ｍｏｌ部の範囲にすることにより、低温で焼成した場合にも、実用可能な特性を備えた誘電体セラミックをさらに確実に得ることが可能になる。
Further, the addition amount of the nitride D as an additive component is set to a range of 0.5 mol part ≦ D ≦ 5.0 mol part with respect to 100 mol part of the perovskite compound as the main component, thereby firing at a low temperature. Even in this case, a dielectric ceramic having practical characteristics can be obtained more reliably.
また、本発明の積層セラミックコンデンサは、内部電極が誘電体セラミック層を介して互いに対向するように積層された構造を有する積層セラミックコンデンサにおいて、誘電体セラミック層として、本願発明の誘電体セラミックからなる誘電体セラミック層を用いているので、所望の特性を有する積層セラミックコンデンサを得ることができる。
The multilayer ceramic capacitor of the present invention is a multilayer ceramic capacitor having a structure in which internal electrodes are laminated so as to face each other through a dielectric ceramic layer. The dielectric ceramic layer is made of the dielectric ceramic of the present invention. Since the dielectric ceramic layer is used, a multilayer ceramic capacitor having desired characteristics can be obtained.
また、本発明の誘電体セラミックは低温焼結が可能であることから、内部電極が、卑金属を含むものである場合や、外部電極が、卑金属を含むものである場合にも、誘電体セラミック層が十分に焼結し、かつ、良好な内部電極や外部電極を備えた、特性の安定した積層セラミックコンデンサを提供することが可能になる。
Further, since the dielectric ceramic of the present invention can be sintered at a low temperature, the dielectric ceramic layer can be sufficiently sintered even when the internal electrode contains a base metal or when the external electrode contains a base metal. In addition, it is possible to provide a monolithic ceramic capacitor having a stable characteristic and having excellent internal electrodes and external electrodes.
以下に本発明の実施例を示して、本発明の特徴とするところをさらに詳しく説明する。
Hereinafter, the features of the present invention will be described in more detail with reference to examples of the present invention.
(Ａ)誘電体セラミック原料の作製
まず、出発原料として、主成分原料であるＢａＣＯ3粉末、ＴｉＯ2粉末等を準備して、ＡＢＯ3で表されるペロブスカイト系複合酸化物、すなわちＢａＴｉＯ3系酸化物（ＡサイトはＢａであって、Ｂａ以外にＳｒおよびＣａの少なくとも１種を含んでいてもよく、また、ＢサイトはＴｉであって、Ｔｉ以外にＺｒおよびＨｆの少なくとも１種を含んでいてもよく、Ｏは酸素）の組成になるように秤量した後、ボールミルにより混合した。それから、この混合粉末を１１５０℃で熱処理することにより、ＢａＴｉＯ3系粉末を得た。このＢａＴｉＯ3系粉末の平均粒径は０．１５μｍ程度であった。
また、実施例では、ＢａＴｉＯ3系粉末のＡサイトとＢサイトの比（Ａ／Ｂ比）を変化させた。 (A) Preparation of dielectric ceramic raw material First, BaCO 3 powder, TiO 2 powder, etc., which are main component raw materials, are prepared as starting raw materials, and a perovskite complex oxide represented by ABO 3 , that is, BaTiO 3 based oxidation. (The A site is Ba and may contain at least one of Sr and Ca in addition to Ba, and the B site is Ti and contains at least one of Zr and Hf in addition to Ti. The sample was weighed so as to have a composition of O) and then mixed by a ball mill. Then, this mixed powder was heat-treated at 1150 ° C. to obtain a BaTiO 3 -based powder. The average particle size of the BaTiO 3 powder was about 0.15 μm.
In the examples, the ratio (A / B ratio) between the A site and the B site of the BaTiO 3 powder was changed.
まず、出発原料として、主成分原料であるＢａＣＯ3粉末、ＴｉＯ2粉末等を準備して、ＡＢＯ3で表されるペロブスカイト系複合酸化物、すなわちＢａＴｉＯ3系酸化物（ＡサイトはＢａであって、Ｂａ以外にＳｒおよびＣａの少なくとも１種を含んでいてもよく、また、ＢサイトはＴｉであって、Ｔｉ以外にＺｒおよびＨｆの少なくとも１種を含んでいてもよく、Ｏは酸素）の組成になるように秤量した後、ボールミルにより混合した。それから、この混合粉末を１１５０℃で熱処理することにより、ＢａＴｉＯ3系粉末を得た。このＢａＴｉＯ3系粉末の平均粒径は０．１５μｍ程度であった。
また、実施例では、ＢａＴｉＯ3系粉末のＡサイトとＢサイトの比（Ａ／Ｂ比）を変化させた。 (A) Preparation of dielectric ceramic raw material First, BaCO 3 powder, TiO 2 powder, etc., which are main component raw materials, are prepared as starting raw materials, and a perovskite complex oxide represented by ABO 3 , that is, BaTiO 3 based oxidation. (The A site is Ba and may contain at least one of Sr and Ca in addition to Ba, and the B site is Ti and contains at least one of Zr and Hf in addition to Ti. The sample was weighed so as to have a composition of O) and then mixed by a ball mill. Then, this mixed powder was heat-treated at 1150 ° C. to obtain a BaTiO 3 -based powder. The average particle size of the BaTiO 3 powder was about 0.15 μm.
In the examples, the ratio (A / B ratio) between the A site and the B site of the BaTiO 3 powder was changed.
それから、上記ＢａＴｉＯ3系粉末と、Ｓｉ，Ｒ（ＲはＬａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，ＬｕおよびＹからなる群より選ばれる少なくとも１種），Ｍ（ＭはＭｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ｍｇ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）、および窒化物であるＤ（ＤはＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴａＮ，ＺｒＮおよびＴｉＮからなる群より選ばれる少なくとも１種）を、それぞれ表１、表２Ａ、表２Ｂ、表２Ｃに示す配合物となるよう秤量した後、ボールミルにより混合・乾燥し、誘電体原料配合物（誘電体セラミック原料）とした。
なお、Ｓｉ，ＲおよびＭの原料としては、いずれも酸化物粉末を用いた。 Then, the BaTiO 3 powder and Si, R (R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y are selected. At least one), M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W and V), and a nitride D (D is And at least one selected from the group consisting of BN, AlN, Si 3 N 4 , TaN, ZrN and TiN), respectively, and weighed so as to have the compositions shown in Table 1, Table 2A, Table 2B and Table 2C. Was mixed and dried to obtain a dielectric material composition (dielectric ceramic material).
Note that oxide powders were used as raw materials for Si, R, and M.
なお、Ｓｉ，ＲおよびＭの原料としては、いずれも酸化物粉末を用いた。 Then, the BaTiO 3 powder and Si, R (R is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y are selected. At least one), M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W and V), and a nitride D (D is And at least one selected from the group consisting of BN, AlN, Si 3 N 4 , TaN, ZrN and TiN), respectively, and weighed so as to have the compositions shown in Table 1, Table 2A, Table 2B and Table 2C. Was mixed and dried to obtain a dielectric material composition (dielectric ceramic material).
Note that oxide powders were used as raw materials for Si, R, and M.
なお、表１の試料番号Ｒ１～Ｒ６の誘電体原料配合物（誘電体セラミック原料）は、窒化物Ｄを含まない比較用の誘電体原料配合物であり、表２Ａ、表２Ｂ、表２Ｃの試料番号１～３１の誘電体原料配合物（誘電体セラミック原料）は、焼成後に本発明の実施例にかかる誘電体セラミックとなる窒化物Ｄを含む誘電体原料配合物である。
Note that the dielectric raw material blends (dielectric ceramic raw materials) of sample numbers R1 to R6 in Table 1 are comparative dielectric raw material blends that do not contain nitride D, and are shown in Tables 2A, 2B, and 2C. The dielectric raw material blends (dielectric ceramic raw materials) of sample numbers 1 to 31 are dielectric raw material blends containing nitride D that becomes the dielectric ceramic according to the example of the present invention after firing.
なお、今回使用した主成分ＢａＴｉＯ3は固相合成法により作製し、所望の粒径が得られる温度で熱処理したものであるが、水熱合成法、加水分解法などで作製されたＢａＴｉＯ3を用いることも可能である。
また、ＢａＴｉＯ3作製用の素材、添加成分の化合物形態は酸化物，炭酸物に限らず、塩化物、金属有機化合物など種々の形態のものを用いることが可能である。 The main component BaTiO 3 used this time was prepared by a solid phase synthesis method and heat-treated at a temperature at which a desired particle size was obtained, but BaTiO 3 prepared by a hydrothermal synthesis method, a hydrolysis method or the like was used. It is also possible to use it.
Further, the raw material for preparing BaTiO 3 and the compound form of the additive component are not limited to oxides and carbonates, and various forms such as chlorides and metal organic compounds can be used.
また、ＢａＴｉＯ3作製用の素材、添加成分の化合物形態は酸化物，炭酸物に限らず、塩化物、金属有機化合物など種々の形態のものを用いることが可能である。 The main component BaTiO 3 used this time was prepared by a solid phase synthesis method and heat-treated at a temperature at which a desired particle size was obtained, but BaTiO 3 prepared by a hydrothermal synthesis method, a hydrolysis method or the like was used. It is also possible to use it.
Further, the raw material for preparing BaTiO 3 and the compound form of the additive component are not limited to oxides and carbonates, and various forms such as chlorides and metal organic compounds can be used.
また、本発明において、主成分ＡＢＯ3は化学量論組成ではない場合も含む。具体的にはＡとＢのｍｏｌ比Ａ／Ｂが０．９５０～１．０５０の範囲であれば本願発明におけるＡＢＯ3とすることができる。
Further, in the present invention, the case where the main component ABO 3 does not have a stoichiometric composition is included. Specifically, if the molar ratio A / B of A and B is in the range of 0.950 to 1.050, ABO 3 in the present invention can be obtained.
(Ｂ)積層単板の作製
上記(Ａ)の工程で作製した試料番号Ｒ１～Ｒ６および試料番号１～３１の誘電体原料配合物（誘電体セラミック原料）に、ポリビニルブチラール系バインダーおよび有機溶媒（この実施例１ではエタノール）を加えて、ボールミルにより所定時間、湿式混合し、セラミックスラリーを作製した。
このセラミックスラリーをドクターブレード法によりシート成形し、厚みが４μｍの矩形のセラミックグリーンシートを作製した。 (B) Production of laminated single plate A dielectric material mixture (dielectric ceramic material) of sample numbers R1 to R6 and sample numbers 1 to 31 produced in the step (A) above was added to a polyvinyl butyral binder and an organic solvent ( In Example 1, ethanol) was added and wet-mixed for a predetermined time with a ball mill to prepare a ceramic slurry.
This ceramic slurry was formed into a sheet by a doctor blade method to produce a rectangular ceramic green sheet having a thickness of 4 μm.
上記(Ａ)の工程で作製した試料番号Ｒ１～Ｒ６および試料番号１～３１の誘電体原料配合物（誘電体セラミック原料）に、ポリビニルブチラール系バインダーおよび有機溶媒（この実施例１ではエタノール）を加えて、ボールミルにより所定時間、湿式混合し、セラミックスラリーを作製した。
このセラミックスラリーをドクターブレード法によりシート成形し、厚みが４μｍの矩形のセラミックグリーンシートを作製した。 (B) Production of laminated single plate A dielectric material mixture (dielectric ceramic material) of sample numbers R1 to R6 and sample numbers 1 to 31 produced in the step (A) above was added to a polyvinyl butyral binder and an organic solvent ( In Example 1, ethanol) was added and wet-mixed for a predetermined time with a ball mill to prepare a ceramic slurry.
This ceramic slurry was formed into a sheet by a doctor blade method to produce a rectangular ceramic green sheet having a thickness of 4 μm.
次に、上述のようにして作製したセラミックグリーンシートを複数枚積層し、未焼成の積層単板を作製した。この未焼成の積層単板をＮ2雰囲気中にて熱処理し、バインダーを除去した後、酸素分圧１０-10ＭＰａのＨ2－Ｎ2－Ｈ2Ｏガスからなる還元性雰囲気中にて１２００℃で焼成し、焼成済みの積層単板を得た。
Next, a plurality of ceramic green sheets produced as described above were laminated to produce an unfired laminated single plate. This unfired laminated single plate was heat-treated in an N 2 atmosphere to remove the binder, and then 1200 in a reducing atmosphere composed of H 2 —N 2 —H 2 O gas having an oxygen partial pressure of 10 −10 MPa. Firing was performed at 0 ° C. to obtain a fired laminated single plate.
それから、この積層単板を、走査透過電子顕微鏡を用いたエネルギー分散Ｘ線分光法（ＳＴＥＭ－ＥＤＸ）により磁器構造を分析し、２μｍ×２μｍの領域を１０視野確認して、添加成分Ｄ（窒化物）が磁器中に存在していることを確認した。
Then, this laminated single plate was analyzed for porcelain structure by energy dispersive X-ray spectroscopy (STEM-EDX) using a scanning transmission electron microscope, and 10 fields of 2 μm × 2 μm region were confirmed, and additive component D (nitriding) It was confirmed that the product was present in the porcelain.
また、焼成後の積層単板の寸法および重量から密度を求め、ＢａＴｉＯ3の理論密度比を求めることにより焼結状態を確認した。
その結果を表１、表２Ａ，表２Ｂ，表２Ｃに示す。 Further, the density was determined from the size and weight of the laminated single plate after firing, and the sintered state was confirmed by determining the theoretical density ratio of BaTiO 3 .
The results are shown in Table 1, Table 2A, Table 2B, and Table 2C.
その結果を表１、表２Ａ，表２Ｂ，表２Ｃに示す。 Further, the density was determined from the size and weight of the laminated single plate after firing, and the sintered state was confirmed by determining the theoretical density ratio of BaTiO 3 .
The results are shown in Table 1, Table 2A, Table 2B, and Table 2C.
＜積層単板の焼結状態についての評価＞
表２Ａ，表２Ｂ，表２Ｃの試料番号１～３１の試料は、本発明の要件を備えた試料（実施例の試料）であり、ＢａＴｉＯ3理論密度比８５％以上の緻密な磁器が得られることが確認された。これは、試料番号１～３１の試料には、窒化物（ＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴｉＮ，ＴａＮ，ＺｒＮ）が含まれていることから、セラミックの焼結が促進され、ＢａＴｉＯ3理論密度比が８５％以上の緻密な磁器を得ることができたものである。 <Evaluation of sintered state of laminated single plate>
Samples Nos. 1 to 31 in Tables 2A, 2B, and 2C are samples (examples) having the requirements of the present invention, and a dense porcelain having a BaTiO 3 theoretical density ratio of 85% or more is obtained. It was confirmed. This is because the samples Nos. 1 to 31 contain nitrides (BN, AlN, Si 3 N 4 , TiN, TaN, ZrN), so that the sintering of the ceramic is promoted and the BaTiO 3 theory A dense porcelain having a density ratio of 85% or more could be obtained.
表２Ａ，表２Ｂ，表２Ｃの試料番号１～３１の試料は、本発明の要件を備えた試料（実施例の試料）であり、ＢａＴｉＯ3理論密度比８５％以上の緻密な磁器が得られることが確認された。これは、試料番号１～３１の試料には、窒化物（ＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴｉＮ，ＴａＮ，ＺｒＮ）が含まれていることから、セラミックの焼結が促進され、ＢａＴｉＯ3理論密度比が８５％以上の緻密な磁器を得ることができたものである。 <Evaluation of sintered state of laminated single plate>
Samples Nos. 1 to 31 in Tables 2A, 2B, and 2C are samples (examples) having the requirements of the present invention, and a dense porcelain having a BaTiO 3 theoretical density ratio of 85% or more is obtained. It was confirmed. This is because the samples Nos. 1 to 31 contain nitrides (BN, AlN, Si 3 N 4 , TiN, TaN, ZrN), so that the sintering of the ceramic is promoted and the BaTiO 3 theory A dense porcelain having a density ratio of 85% or more could be obtained.
一方、表１の試料番号Ｒ１～Ｒ６の比較例の試料の場合、１２００℃以上の温度で焼成を行ってもセラミックが十分に焼結せず、ＢａＴｉＯ3理論密度比８５％を実現することができないことが確認された。これらの比較例の試料は、セラミックの焼結を促進させる窒化物（ＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴｉＮ，ＴａＮ，ＺｒＮ）を含まないことから、十分な焼結性を確保することができなかったものである。
On the other hand, in the case of the comparative samples of sample numbers R1 to R6 in Table 1, the ceramic does not sinter sufficiently even when firing at a temperature of 1200 ° C. or higher, and a BaTiO 3 theoretical density ratio of 85% can be realized. It was confirmed that it was not possible. Since the samples of these comparative examples do not contain nitrides (BN, AlN, Si 3 N 4 , TiN, TaN, ZrN) that promote the sintering of ceramics, sufficient sinterability can be ensured. It was not.
なお、試料番号Ｒ１～Ｒ５の比較例の試料は、窒化物Ｄを含まないばかりでなく、Ｓｉ、Ｒ成分、Ｍ成分を含まない試料であり、上述のようにＢａＴｉＯ3理論密度比８５％を実現することができず、試料番号Ｒ６の比較例の試料は、窒化物Ｄを含まないものの、Ｓｉ、Ｒ成分、およびＭ成分を含む試料であったが、このＲ６の試料も、ＢａＴｉＯ3理論密度比８５％を実現することはできなかった。
Note that the samples of the comparative examples of the sample numbers R1 to R5 do not contain the nitride D but also do not contain the Si, R component, and M component. As described above, the BaTiO 3 theoretical density ratio is 85%. Although the sample of the comparative example of sample number R6 did not include nitride D, it was a sample containing Si, R component, and M component. However, this sample of R6 is also a BaTiO 3 theory. A density ratio of 85% could not be realized.
これに対し、窒化物Ｄを含む実施例の試料の場合、試料番号１～１２の試料のように、Ｓｉ、Ｒ成分、およびＭ成分を含まない場合にも、ＢａＴｉＯ3理論密度比８５％を実現することが可能で、焼結性に優れた緻密性の高い誘電体セラミックが得られることが確認された。
In contrast, in the case of the sample of the example including the nitride D, even when the Si, R component, and M component are not included as in the samples of sample numbers 1 to 12, the BaTiO 3 theoretical density ratio is 85%. It was confirmed that a dielectric ceramic with high density and excellent sinterability could be obtained.
また、窒化物Ｄを含む実施例の試料の場合、試料番号１３～３１のように、Ｓｉ、Ｒ成分、およびＭ成分の少なくとも１つ以上を含む組成とした場合にも、ＢａＴｉＯ3理論密度比８５％を実現することが可能で、焼結性に優れた緻密性の高い誘電体セラミックが得られることが確認された。なお、Ｓｉ、Ｒ成分、およびＭ成分の少なくとも１つ以上を含む組成とすることにより、特性を制御して、所望の特性を備えた誘電体セラミックを得ることが可能になる。
Further, in the case of the sample of the example including the nitride D, the BaTiO 3 theoretical density ratio is also obtained when the composition includes at least one of Si, R component, and M component as in sample numbers 13 to 31. It was confirmed that a dielectric ceramic having a high density and excellent sinterability can be obtained. In addition, by setting it as the composition containing at least 1 or more of Si, R component, and M component, it becomes possible to control a characteristic and to obtain the dielectric ceramic provided with the desired characteristic.
(Ｃ)積層セラミックコンデンサの作製
上記(Ａ)で作製した誘電体原料配合物（誘電体セラミック原料）を用いて、図１に示すような構造を有する積層セラミックコンデンサを作製した。 (C) Production of Multilayer Ceramic Capacitor A multilayer ceramic capacitor having a structure as shown in FIG. 1 was produced using the dielectric material composition (dielectric ceramic material) produced in (A) above.
上記(Ａ)で作製した誘電体原料配合物（誘電体セラミック原料）を用いて、図１に示すような構造を有する積層セラミックコンデンサを作製した。 (C) Production of Multilayer Ceramic Capacitor A multilayer ceramic capacitor having a structure as shown in FIG. 1 was produced using the dielectric material composition (dielectric ceramic material) produced in (A) above.
なお、この積層セラミックコンデンサは、積層セラミック素子（焼成済みのセラミック積層体）１０の内部に配設された内部電極１２が、誘電体層（誘電体セラミック層）１１を介して積層され、かつ、積層セラミック素子１０の両端面には、交互に逆側の端面に露出した内部電極１２と導通するように一対の外部電極１３ａ，１３ｂが配設された構造を有している。
以下、この積層セラミックコンデンサの製造方法について説明する。 In this monolithic ceramic capacitor, aninternal electrode 12 disposed inside a monolithic ceramic element (fired ceramic laminate) 10 is laminated via a dielectric layer (dielectric ceramic layer) 11, and A pair of external electrodes 13 a and 13 b are arranged on both end faces of the multilayer ceramic element 10 so as to be electrically connected to the internal electrodes 12 exposed on the opposite end face alternately.
Hereinafter, a method for manufacturing the multilayer ceramic capacitor will be described.
以下、この積層セラミックコンデンサの製造方法について説明する。 In this monolithic ceramic capacitor, an
Hereinafter, a method for manufacturing the multilayer ceramic capacitor will be described.
まず、上記実施例１の(Ａ)で作製した、試料番号１～３１の誘電体原料配合物にポリビニルブチラール系バインダーおよび有機溶媒（この実施例１ではエタノール）を加えて、ボールミルにより所定の時間、湿式混合し、セラミックスラリーを作製した。
First, a polyvinyl butyral binder and an organic solvent (ethanol in this Example 1) were added to the dielectric material composition of Sample Nos. 1 to 31 prepared in Example 1 (A), and the ball mill was used for a predetermined time. And wet mixing to prepare a ceramic slurry.
このセラミックスラリーをドクターブレード法によりシート成形し、矩形で、焼成後の厚み、すなわち、誘電体セラミック層厚が３．０μｍになるようなセラミックグリーンシートを作製した。
The ceramic slurry was formed into a sheet by the doctor blade method, and a ceramic green sheet having a rectangular shape after firing, that is, a dielectric ceramic layer thickness of 3.0 μm was produced.
次に、このセラミックグリーンシート上に、ニッケル粉末を導電成分とする導電ペーストをスクリーン印刷し、焼成後に内部電極となる導電ペースト層（内部電極パターン）を形成した。
Next, on this ceramic green sheet, a conductive paste containing nickel powder as a conductive component was screen-printed to form a conductive paste layer (internal electrode pattern) that became an internal electrode after firing.
それから、内部電極パターンが形成されたセラミックグリーンシートを、内部電極パターンが交互に逆側に引き出されるような態様で所定枚数積層し、さらに、上下両面側に、導電ペーストパターンが形成されていないセラミックグリーンシートを外層として積層することにより、積層ブロックを作製した。なお、各セラミックグリーンシートの積層の順に特別の制約はない。
Then, a predetermined number of ceramic green sheets on which internal electrode patterns are formed are stacked in such a manner that the internal electrode patterns are alternately drawn to the opposite side, and further, a ceramic in which no conductive paste pattern is formed on both upper and lower sides A laminated block was produced by laminating green sheets as outer layers. There are no particular restrictions on the order of lamination of the ceramic green sheets.
次に、この積層ブロックを所定の寸法となるようにカットして得た未焼成の積層体を、Ｎ2雰囲気中で脱バインダーした後、酸素分圧１０-10ＭＰａのＨ2－Ｎ2－Ｈ2Ｏガスからなる還元性雰囲気中で、１２００℃で焼成し、焼成済みの積層体（セラミック積層体）を得た。
Next, an unfired laminate obtained by cutting the laminate block to a predetermined size is debindered in an N 2 atmosphere, and then H 2 —N 2 — with an oxygen partial pressure of 10 −10 MPa. Firing was performed at 1200 ° C. in a reducing atmosphere composed of H 2 O gas to obtain a fired laminated body (ceramic laminated body).
それから、焼成済みのセラミック積層体の、内部電極が引き出された両端面に、導電成分である銅粉末と、Ｂ2Ｏ3－Ｌｉ2Ｏ－ＳｉＯ2－ＢａＯ系のガラスフリットとを含有する導電ペーストを塗布した後、８００℃で焼き付けることにより、内部電極と電気的に接続された外部電極を形成した。
これにより、図１に示すような構造を有する積層セラミックコンデンサが得られる。 Then, a conductive layer containing copper powder as a conductive component and B 2 O 3 —Li 2 O—SiO 2 —BaO glass frit is formed on both end surfaces of the fired ceramic laminate from which the internal electrodes are drawn. After applying the paste, an external electrode electrically connected to the internal electrode was formed by baking at 800 ° C.
Thereby, a multilayer ceramic capacitor having a structure as shown in FIG. 1 is obtained.
これにより、図１に示すような構造を有する積層セラミックコンデンサが得られる。 Then, a conductive layer containing copper powder as a conductive component and B 2 O 3 —Li 2 O—SiO 2 —BaO glass frit is formed on both end surfaces of the fired ceramic laminate from which the internal electrodes are drawn. After applying the paste, an external electrode electrically connected to the internal electrode was formed by baking at 800 ° C.
Thereby, a multilayer ceramic capacitor having a structure as shown in FIG. 1 is obtained.
なお、得られた積層セラミックコンデンサの外形寸法は、長さ：２．０ｍｍ、幅：１．２５ｍｍ、厚さ：１．０ｍｍであり、内部電極１２間に介在する誘電体層（誘電体セラミック層）１１の厚みは３．０μｍであった。
また、有効誘電体層（コンデンサ形成層）の層数は１０であり、一層当たりの対向電極面積は１．６ｍｍ2であった。 The outer dimensions of the obtained multilayer ceramic capacitor are: length: 2.0 mm, width: 1.25 mm, thickness: 1.0 mm, and a dielectric layer (dielectric ceramic layer) interposed between the internal electrodes 12 ) 11 had a thickness of 3.0 μm.
The number of effective dielectric layers (capacitor forming layers) was 10, and the counter electrode area per layer was 1.6 mm 2 .
また、有効誘電体層（コンデンサ形成層）の層数は１０であり、一層当たりの対向電極面積は１．６ｍｍ2であった。 The outer dimensions of the obtained multilayer ceramic capacitor are: length: 2.0 mm, width: 1.25 mm, thickness: 1.0 mm, and a dielectric layer (dielectric ceramic layer) interposed between the internal electrodes 12 ) 11 had a thickness of 3.0 μm.
The number of effective dielectric layers (capacitor forming layers) was 10, and the counter electrode area per layer was 1.6 mm 2 .
なお、試料番号Ｒ１～Ｒ６の誘電体原料配合物は、ＢａＴｉＯ3理論密度比８５％を実現できず、焼結性が不十分で、特性の良好な積層セラミックコンデンサを得ることができないことが明らかであることから、試料番号Ｒ１～Ｒ６の誘電体原料配合物を用いた積層セラミックコンデンサは製造しなかった。
It is clear that the dielectric raw material blends of sample numbers R1 to R6 cannot realize a BaTiO 3 theoretical density ratio of 85%, have insufficient sinterability, and cannot obtain a multilayer ceramic capacitor with good characteristics. Therefore, a multilayer ceramic capacitor using the dielectric material composition of sample numbers R1 to R6 was not manufactured.
(Ｄ)積層セラミックコンデンサの特性の測定および評価
上述のようにして作製した試料番号１～３１の各試料（積層セラミックコンデンサ）について、温度２５℃，１ｋＨｚ，１．０Ｖｒｍｓの条件下で静電容量を測定し、得られた静電容量の値から、誘電体セラミック層の室温での比誘電率を計算により求めた。
各試料の誘電体セラミック層について求めた比誘電率の値を表２Ａ，表２Ｂ，２Ｃに併せて示す。 (D) Measurement and Evaluation of Characteristics of Multilayer Ceramic Capacitor Each of Sample Nos. 1-31 (Multilayer Ceramic Capacitor) produced as described above has a capacitance under the conditions of a temperature of 25 ° C., 1 kHz, and 1.0 Vrms. Was measured, and the relative dielectric constant at room temperature of the dielectric ceramic layer was calculated from the obtained capacitance value.
Tables 2A, 2B, and 2C show the relative dielectric constant values obtained for the dielectric ceramic layers of the respective samples.
上述のようにして作製した試料番号１～３１の各試料（積層セラミックコンデンサ）について、温度２５℃，１ｋＨｚ，１．０Ｖｒｍｓの条件下で静電容量を測定し、得られた静電容量の値から、誘電体セラミック層の室温での比誘電率を計算により求めた。
各試料の誘電体セラミック層について求めた比誘電率の値を表２Ａ，表２Ｂ，２Ｃに併せて示す。 (D) Measurement and Evaluation of Characteristics of Multilayer Ceramic Capacitor Each of Sample Nos. 1-31 (Multilayer Ceramic Capacitor) produced as described above has a capacitance under the conditions of a temperature of 25 ° C., 1 kHz, and 1.0 Vrms. Was measured, and the relative dielectric constant at room temperature of the dielectric ceramic layer was calculated from the obtained capacitance value.
Tables 2A, 2B, and 2C show the relative dielectric constant values obtained for the dielectric ceramic layers of the respective samples.
表２Ａ，表２Ｂ，表２Ｃより、窒化物Ｄを含有し、かつ、Ｄの含有割合が、主成分であるペロブスカイト型化合物１００ｍｏｌ部に対して、０．５ｍｏｌ部≦Ｄ≦５．０ｍｏｌ部の要件を満たす、試料番号１～３，５～９，１１～１８，２０～２５、２７～３１の試料の場合、誘電体セラミック層が比誘電率２０００≦εｒの要件を満たし、良好な電気特性が得られることが確認された。
From Table 2A, Table 2B, and Table 2C, nitride D is contained, and the content ratio of D is 0.5 mol part ≦ D ≦ 5.0 mol part with respect to 100 mol part of perovskite type compound as the main component. In the case of samples Nos. 1 to 3, 5 to 9, 11 to 18, 20 to 25, and 27 to 31 satisfying the requirements, the dielectric ceramic layer satisfies the requirement of relative dielectric constant 2000 ≦ εr, and good electrical characteristics It was confirmed that
一方、窒化物Ｄを含有するが、その含有割合が、０．５ｍｏｌ部≦Ｄ≦５．０ｍｏｌ部の要件を満たさない（窒化物Ｄの含有割合が０．５ｍｏｌ部を下回っている）、試料番号４，１０，１９，２６の試料の場合、比誘電率は１８２０～１９５０と、２０００を少し下回ったが、用途によっては実用可能なものであることが確認された。
On the other hand, a sample containing nitride D, but the content ratio does not satisfy the requirement of 0.5 mol part ≦ D ≦ 5.0 mol part (the content ratio of nitride D is less than 0.5 mol part). In the case of the samples Nos. 4, 10, 19, and 26, the relative dielectric constant was 1820 to 1950, which was slightly lower than 2000, but it was confirmed that it was practical depending on the application.
なお、表２Ａ，表２Ｂ，表２Ｃには示していないが、窒化物Ｄの含有割合が５．０ｍｏｌ部を超えると、焼結が進みすぎる傾向があることが確認されている。ただし、窒化物Ｄの含有割合が５．０ｍｏｌ部を超える場合にも、他の成分の組成を調整したり、焼結抑制用の成分を添加したりすることにより誘電体セラミックとして使用することは可能である。
Although not shown in Tables 2A, 2B, and 2C, it has been confirmed that when the content ratio of nitride D exceeds 5.0 mol parts, sintering tends to proceed excessively. However, even when the content ratio of nitride D exceeds 5.0 mol part, it is not possible to use it as a dielectric ceramic by adjusting the composition of other components or adding a component for suppressing sintering. Is possible.
上記実施例の結果から、本発明の誘電体セラミックにおいては、窒化物Ｄの添加料は、通常、主成分であるペロブスカイト型化合物１００ｍｏｌ部に対して、０．５ｍｏｌ部≦Ｄ≦５．０ｍｏｌ部の範囲とすることが望ましいことがわかる。
From the results of the above examples, in the dielectric ceramic of the present invention, the additive of the nitride D is usually 0.5 mol part ≦ D ≦ 5.0 mol part with respect to 100 mol part of the perovskite type compound which is the main component. It can be seen that it is desirable to set the range.
また、表２Ａ，表２Ｂ，表２Ｃに示した試料における、ＡサイトとＢサイトの比（Ａ／Ｂ（ｍｏｌ比））は０．９５０～１．０５０の範囲にあり、少なくともこの範囲においては、実用可能な誘電体セラミックが得られることが確認された。
In the samples shown in Table 2A, Table 2B, and Table 2C, the ratio of A site to B site (A / B (mol ratio)) is in the range of 0.950 to 1.050, and at least in this range. It was confirmed that a practical dielectric ceramic could be obtained.
また、Ｓｉ、Ｒ成分、およびＭ成分を配合しない場合（試料番号１～１１）、および、Ｓｉ、Ｒ成分、およびＭ成分の少なくとも１種を配合した場合（試料番号１２～２８）のいずれの場合にも、実用可能な比誘電率を有する誘電体セラミックが得られることが確認された。
In addition, when Si, R component, and M component are not blended (sample numbers 1 to 11), and when at least one of Si, R component, and M components are blended (sample numbers 12 to 28) In some cases, it was confirmed that a dielectric ceramic having a practical dielectric constant can be obtained.
したがって、本発明によれば、窒化物Ｄに加えて、必要に応じて、Ｓｉ、Ｒ成分、およびＭ成分の１種または２種以上を配合することにより、特性を制御して用途に適した特性を備えた誘電体セラミックを得ることができる。すなわち、本発明によれば、低温で焼結させることが可能で、特性の自由度の高い誘電体セラミックを提供することが可能になる。
Therefore, according to the present invention, in addition to the nitride D, if necessary, one or more of Si, R component, and M component are blended to control the characteristics and are suitable for use. A dielectric ceramic having characteristics can be obtained. That is, according to the present invention, it is possible to provide a dielectric ceramic that can be sintered at a low temperature and has a high degree of freedom in characteristics.
なお、本発明においては、表２Ａ，表２Ｂ，表２Ｃなどに示すように、ＢａＴｉＯ3系セラミック粒子を構成するＢａの一部をＣａおよび／またはＳｒで置換したり、Ｔｉの一部をＺｒおよび／またはＨｆで置換したりすることも可能であり、その場合には、特性を制御して、所望の特性を備えた誘電体セラミックを得ることができる。
In the present invention, as shown in Tables 2A, 2B, 2C, etc., a part of Ba constituting the BaTiO 3 ceramic particles is replaced with Ca and / or Sr, or a part of Ti is replaced with Zr. It is also possible to substitute with Hf and / or Hf, in which case the characteristics can be controlled to obtain a dielectric ceramic having desired characteristics.
また、この実施例では、本発明の誘電体セラミックを、積層セラミックコンデンサの誘電体層として用いる場合を例にとって説明したが、本発明にかかる誘電体セラミックは、積層セラミックコンデンサに限らず、ＬＣ複合部品などにも適用することが可能である。
Further, in this embodiment, the case where the dielectric ceramic of the present invention is used as a dielectric layer of a multilayer ceramic capacitor has been described as an example. However, the dielectric ceramic according to the present invention is not limited to a multilayer ceramic capacitor, and is an LC composite. It can also be applied to parts.
本発明はさらにその他の点においても上記実施例に限定されるものではなく、本発明の誘電体セラミックを製造する場合の各原料の種類、製造工程の具体的な条件、窒化物Ｄや、Ｓｉ、Ｒ成分、Ｍ成分などの具体的な配合割合などに関し、発明の範囲内において種々の応用、変形を加えることが可能である。
The present invention is not limited to the above embodiment in other points as well, and the types of raw materials, specific conditions of the manufacturing process, nitride D, Si, and the like when the dielectric ceramic of the present invention is manufactured. With respect to specific blending ratios of R component, M component, etc., various applications and modifications can be added within the scope of the invention.
１０ 積層セラミック素子
１１ セラミック層（誘電体セラミック層）
１２ 内部電極層
１３ａ，１３ｂ 外部電極 10Multilayer Ceramic Element 11 Ceramic Layer (Dielectric Ceramic Layer)
12 Internal electrode layer 13a, 13b External electrode
１１ セラミック層（誘電体セラミック層）
１２ 内部電極層
１３ａ，１３ｂ 外部電極 10
12
Claims (6)
- ＡＢＯ3（ＡサイトはＢａであって、Ｂａ以外にＳｒおよびＣａの少なくとも１種を含んでいてもよく、また、ＢサイトはＴｉであって、Ｔｉ以外にＺｒおよびＨｆの少なくとも１種を含んでいてもよく、Ｏは酸素）で表されるペロブスカイト型化合物を主成分とし、
添加成分として、下記のＤで表される窒化物
Ｄ：ＢＮ，ＡｌＮ，Ｓｉ3Ｎ4，ＴａＮ，ＺｒＮおよびＴｉＮからなる群より選ばれる少なくとも１種
を含有していることを特徴とする誘電体セラミック。 ABO 3 (A site is Ba and may contain at least one of Sr and Ca in addition to Ba, and B site is Ti and contains at least one of Zr and Hf in addition to Ti. The main component is a perovskite type compound represented by O)
A dielectric characterized in that it contains at least one selected from the group consisting of nitrides D: BN, AlN, Si 3 N 4 , TaN, ZrN and TiN represented by the following D as an additive component ceramic. - さらに、添加成分として、Ｓｉ，Ｒ（ＲはＬａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ，ＬｕおよびＹからなる群より選ばれる少なくとも１種）、およびＭ（ＭはＭｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ｍｇ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）からなる群より選ばれる少なくとも１種を含有することを特徴とする請求項１記載の誘電体セラミック。 Further, as an additive component, Si, R (R is at least one selected from the group consisting of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y) ), And M (M is at least one selected from the group consisting of Mn, Ni, Co, Fe, Cr, Cu, Mg, Al, Mo, W, and V). The dielectric ceramic according to claim 1.
- 添加成分である前記窒化物Ｄの添加量を、誘電体セラミックにおける含有率が、主成分である前記ペロブスカイト型化合物１００ｍｏｌ部に対して、０．５ｍｏｌ部≦Ｄ≦５．０ｍｏｌ部となるような範囲としたことを特徴とする請求項１または２記載の誘電体セラミック。 The additive amount of the nitride D as an additive component is such that the content in the dielectric ceramic is 0.5 mol part ≦ D ≦ 5.0 mol part with respect to 100 mol part of the perovskite compound as the main component. 3. The dielectric ceramic according to claim 1, wherein the dielectric ceramic is in a range.
- 複数の内部電極が、誘電体セラミック層を介して互いに対向するように積層され、前記内部電極の一方端部が所定の面に引き出された構造を有するセラミック積層体を備えるとともに、前記セラミック積層体の前記内部電極の一方端部が引き出された面に前記内部電極と導通するように配設された一対の外部電極を備えた積層セラミックコンデンサにおいて、
前記の誘電体セラミック層が、請求項１～３のいずれかに記載の誘電体セラミックからなること
を特徴とする積層セラミックコンデンサ。 A ceramic laminate having a structure in which a plurality of internal electrodes are laminated so as to face each other through a dielectric ceramic layer, and one end of the internal electrode is drawn out to a predetermined surface, and the ceramic laminate In the multilayer ceramic capacitor comprising a pair of external electrodes arranged to be electrically connected to the internal electrode on the surface from which one end of the internal electrode is drawn,
A multilayer ceramic capacitor, wherein the dielectric ceramic layer is made of the dielectric ceramic according to any one of claims 1 to 3. - 前記内部電極が、卑金属を含むものであることを特徴とする、請求項４に記載の積層セラミックコンデンサ。 The multilayer ceramic capacitor according to claim 4, wherein the internal electrode contains a base metal.
- 前記外部電極が、卑金属を含むものであることを特徴とする、請求項５に記載の積層セラミックコンデンサ。 The multilayer ceramic capacitor according to claim 5, wherein the external electrode contains a base metal.
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| PCT/JP2011/063129 WO2012002118A1 (en) | 2010-06-28 | 2011-06-08 | Dielectric ceramic material and laminated ceramic capacitor comprising same |
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| Country | Link |
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| WO (1) | WO2012002118A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2799811C1 (en) * | 2022-12-30 | 2023-07-12 | Акционерное общество "Научно-производственное предприятие "Исток" имени А.И. Шокина" | Method for manufacturing a thin-film capacitor for electronic equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04218207A (en) * | 1990-10-31 | 1992-08-07 | Murata Mfg Co Ltd | Dielectric porcelain composition |
| JP2000072538A (en) * | 1998-08-25 | 2000-03-07 | Murata Mfg Co Ltd | Production of barium titanate-based ceramic |
-
2011
- 2011-06-08 WO PCT/JP2011/063129 patent/WO2012002118A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04218207A (en) * | 1990-10-31 | 1992-08-07 | Murata Mfg Co Ltd | Dielectric porcelain composition |
| JP2000072538A (en) * | 1998-08-25 | 2000-03-07 | Murata Mfg Co Ltd | Production of barium titanate-based ceramic |
Non-Patent Citations (1)
| Title |
|---|
| HO, IN-CHYUAN: "Semiconducting Barium Titanate Ceramics Prepared by Boron-Containing Liquid- Phase Sintering", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 77, no. 3, 1994, pages 829 - 832, XP000673643, DOI: doi:10.1111/j.1151-2916.1994.tb05372.x * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2799811C1 (en) * | 2022-12-30 | 2023-07-12 | Акционерное общество "Научно-производственное предприятие "Исток" имени А.И. Шокина" | Method for manufacturing a thin-film capacitor for electronic equipment |
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