WO2009119613A1 - Multilayer ceramic capacitor - Google Patents
Multilayer ceramic capacitor Download PDFInfo
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- WO2009119613A1 WO2009119613A1 PCT/JP2009/055866 JP2009055866W WO2009119613A1 WO 2009119613 A1 WO2009119613 A1 WO 2009119613A1 JP 2009055866 W JP2009055866 W JP 2009055866W WO 2009119613 A1 WO2009119613 A1 WO 2009119613A1
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- dielectric
- barium titanate
- powder
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 85
- 239000000919 ceramic Substances 0.000 claims abstract description 55
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 47
- 239000011575 calcium Substances 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 17
- 239000011572 manganese Substances 0.000 claims abstract description 17
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 14
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 13
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 13
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 13
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 13
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 13
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 12
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010030 laminating Methods 0.000 claims abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000002245 particle Substances 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 description 89
- 239000003990 capacitor Substances 0.000 description 19
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 14
- 238000010304 firing Methods 0.000 description 13
- 230000001965 increasing effect Effects 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 7
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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 monolithic ceramic capacitor, and more particularly to a small-sized, high-capacity monolithic ceramic capacitor having a dielectric ceramic layer composed mainly of barium titanate.
- multilayer ceramic capacitors mounted on such electronic devices are required to be smaller and have higher capacities.
- the dielectric layer constituting the multilayer ceramic capacitor is required to be thin and highly multilayered.
- a dielectric porcelain serving as a dielectric layer constituting a multilayer ceramic capacitor a dielectric material having barium titanate as a main component has been conventionally used.
- barium titanate powder has been made of magnesium.
- Dielectrics composed of so-called core-shell structure crystal particles in which magnesium or rare earth elements are dissolved in the vicinity of the surface of the crystal particles mainly composed of barium titanate by adding oxide powder of rare earth elements Porcelain has been developed and put into practical use as a multilayer ceramic capacitor.
- the core-shell structure of the crystal particles refers to a structure in which the core portion, which is the center portion of the crystal particles, and the shell portion, which is the outer shell portion, form physically and chemically different phases. That is, in the crystal particles mainly composed of barium titanate, the core portion is occupied by a tetragonal crystal phase, while the shell portion is occupied by a cubic crystal phase.
- a multilayer ceramic capacitor using a dielectric ceramic layer composed of such core-shell crystal grains as a dielectric layer is improved in relative dielectric constant and temperature characteristics of relative dielectric constant as X7R (based on 25 ° C.).
- the temperature change rate of the relative permittivity is within ⁇ 15% at -55 to 125 ° C), and the change in the relative permittivity when the applied AC voltage is increased is small. ing.
- the thickness of the dielectric is reduced to, for example, about 2 ⁇ m, there is a problem that the life characteristics in the high temperature load test are greatly deteriorated. JP 2001-220224 A
- the main objects of the present invention are excellent in stability of temperature characteristics of high dielectric constant and relative dielectric constant, small increase of relative dielectric constant when AC voltage is increased, and excellent life characteristics in high temperature load test.
- Another object of the present invention is to provide a multilayer ceramic capacitor having a dielectric layer.
- the multilayer ceramic capacitor of the present invention is composed of (i) crystal particles mainly composed of barium titanate, and at least one selected from calcium, magnesium, vanadium, manganese, terbium, and yttrium, dysprosium, holmium, and erbium. It is formed by alternately laminating dielectric layers made of dielectric porcelain containing a rare earth element (RE) and (ii) internal electrode layers.
- the vanadium is 0.02 to 0.2 mol in terms of V 2 O 5
- the magnesium is 0.2 to 0.00 in terms of MgO with respect to 100 mol of titanium constituting the barium titanate.
- the dielectric porcelain includes 0.02 to 0.08 mol of vanadium in terms of V 2 O 5 and 0.3 to 0.3 mg in terms of MgO with respect to 100 mol of titanium constituting the barium titanate.
- RE rare earth element
- the average crystal grain size of the crystal particles constituting the dielectric ceramic is 0.22 to 0.28 ⁇ m.
- the average crystal grain size of the crystal particles is preferably 0.13 to 0.19 ⁇ m.
- the temperature change rate of the dielectric constant can be reduced with a high dielectric constant, and the increase in the relative dielectric constant when the applied AC voltage is increased is small (the relative dielectric constant has an AC voltage dependency). Small) and a multilayer ceramic capacitor having a dielectric layer having a long life in a high-temperature load test can be obtained.
- FIG. 2 is an enlarged view of a dielectric layer constituting the multilayer ceramic capacitor of FIG. 1, and is a schematic diagram showing crystal grains and grain boundary phases.
- Sample No. in the examples. 3 is an X-ray diffraction chart of I-3. Sample No. in the examples. It is a graph which shows the temperature characteristic of the electrostatic capacitance of I-3.
- FIG. 1 is a schematic sectional view showing an example of the multilayer ceramic capacitor of the present invention
- FIG. 2 is an enlarged view of a dielectric layer constituting the multilayer ceramic capacitor of FIG. 1, showing crystal grains and grain boundary phases. It is a schematic diagram.
- the multilayer ceramic capacitor of the present invention has external electrodes 3 formed at both ends of the capacitor body 1.
- the external electrode 3 is formed, for example, by baking Cu or an alloy paste of Cu and Ni.
- the capacitor body 1 is configured by alternately laminating a plurality of dielectric layers 5 made of dielectric ceramics and internal electrode layers 7.
- FIG. 1 the laminated state of the dielectric layer 5 and the internal electrode layer 7 is shown in a simplified manner, but the laminated ceramic capacitor of the present invention has a laminated layer in which the dielectric layer 5 and the internal electrode layer 7 are several hundred layers. It is a body.
- the dielectric layer 5 made of dielectric porcelain is composed of crystal grains 9 and grain boundary phases 11, and the thickness is preferably 2 ⁇ m or less, particularly preferably 1 ⁇ m or less, thereby reducing the size and capacity of the multilayer ceramic capacitor. It becomes possible to do.
- the thickness of the dielectric layer 5 is 0.4 ⁇ m or more, it is possible to reduce the variation in capacitance and stabilize the capacitance-temperature characteristic.
- the internal electrode layer 7 is preferably a base metal such as nickel (Ni) or copper (Cu) in that the manufacturing cost can be suppressed even when the number of layers is increased, and in particular, simultaneous firing with the dielectric layer 5 in the present invention can be achieved.
- nickel (Ni) is more desirable.
- the dielectric ceramic constituting the dielectric layer 5 in the multilayer ceramic capacitor of the present invention is composed of crystal particles mainly composed of barium titanate, and includes calcium, magnesium, vanadium, and manganese, yttrium, dysprosium, and holmium. And a sintered body containing at least one rare earth element selected from erbium and terbium.
- the crystal particles 9 constituting the dielectric ceramic according to the present invention have a calcium concentration of 0.4 atomic% or more, and particularly preferably 0.5 to 2.5 atomic%.
- concentration of calcium is within this range, the solid solution of calcium in barium titanate can be made sufficient.
- the Ca compound remaining in the grain boundary or the like without being dissolved can be reduced, the dependency of the relative permittivity on the AC voltage is increased, so that the permittivity can be increased.
- the transmission electron microscope provided with an elemental analysis device for the crystal particles 9 existing on the polished surface obtained by polishing the cross section of the dielectric layer 5 constituting the multilayer ceramic capacitor. Elemental analysis is performed using At this time, the spot size of the electron beam is 5 nm, and the analysis location is 4 to 5 points at almost equal intervals from the grain boundary on the straight line drawn from the vicinity of the grain boundary to the center of the crystal grain 9.
- the ratio of calcium when the total amount of detected Ba, Ti, Ca, V, Mg, RE (rare earth element) and Mn is 100%, and calculate the average value of the ratio of calcium obtained at each measurement point. Calculate as concentration.
- the dielectric ceramic is composed of 0.02 to 0.2 mol in terms of V 2 O 5 and 0.2 to 0.8 mol in terms of MgO with respect to 100 mol of titanium constituting barium titanate, Manganese is 0.1 to 0.5 mol in terms of MnO, and at least one rare earth element (RE) selected from yttrium, dysprosium, holmium and erbium is 0.3 to 0.8 mol in terms of RE 2 O 3. And terbium in an amount of 0.02 to 0.2 mol in terms of Tb 4 O 7 .
- RE is an abbreviation that represents a rare earth element.
- the dielectric ceramic constituting the dielectric layer 5 in the multilayer ceramic capacitor of the present invention has a tetragonal crystal (200) plane diffraction intensity indicating cubic barium titanate in the X-ray diffraction chart of the dielectric ceramic. Greater than the diffraction intensity of the (002) plane of the barium titanate of The Curie temperature is 90 to 100 ° C.
- the Curie temperature is a temperature at which the relative dielectric constant becomes maximum in the range ( ⁇ 60 to 150 ° C.) in which the temperature characteristic of the relative dielectric constant is measured.
- the relative permittivity at room temperature (25 ° C.) is 3400 or more, the dielectric loss is 12.5% or less, and the temperature characteristic of the relative permittivity is X6S (the rate of change in the relative permittivity with respect to 25 ° C. is (Within ⁇ 22% at -55 to 105 ° C), the relative permittivity when the AC voltage is 1V is less than twice the relative permittivity when the AC voltage is 0.01V, high temperature load test (temperature : 105 ° C., voltage: 1.5 times the rated voltage, test time: 1000 hours), a highly reliable multilayer ceramic capacitor free from defects can be obtained.
- the content of at least one rare earth element selected from yttrium, dysprosium, holmium and erbium is less than 0.3 mol in terms of RE 2 O 3 with respect to 100 mol of titanium constituting barium titanate, In this case also, the reliability in the high temperature load test is lowered. On the other hand, if the content of the rare earth element is more than 0.8 mol in terms of RE 2 O 3 , the relative dielectric constant at room temperature becomes low.
- the relative permittivity when the AC voltage is 1 V is increased (the relative permittivity has a large AC voltage dependency) as compared with the relative permittivity when the AC voltage is 0.01 V, and the rated voltage is The change in capacitance when changed is increased.
- vanadium is 0.02 to 0.08 mol in terms of V 2 O 5 and magnesium is 0.3 to 0.6 mol in terms of MgO, with respect to 100 mol of titanium constituting barium titanate, Manganese is 0.2 to 0.4 mol in terms of MnO, and at least one rare earth element (RE) selected from yttrium, dysprosium, holmium and erbium is 0.4 to 0.6 mol in terms of RE 2 O 3. And 0.02 to 0.08 mol of terbium in terms of Tb 4 O 7 is preferable.
- RE rare earth element
- the relative dielectric constant at room temperature can be increased to 3900 or more, and the relative dielectric constant when the AC voltage is 1 V is 1 as the relative dielectric constant when the AC voltage is 0.01 V. .6 or less.
- the rare earth element yttrium is particularly preferable in that a higher relative dielectric constant is obtained and an insulation resistance is high.
- FIG. 3 shows the sample Nos.
- Tables 1 to 3 of Examples described later. 4 shows an X-ray diffraction chart of a dielectric ceramic constituting the multilayer ceramic capacitor of I-3.
- the multilayer ceramic capacitor of the present invention has a diffraction pattern as shown in the X-ray diffraction chart of FIG.
- FIG. 4 shows the sample Nos. It is a graph which shows the temperature characteristic of the electrostatic capacitance of the multilayer ceramic capacitor of I-3.
- the multilayer ceramic capacitor of the present invention has a capacitance temperature characteristic as shown in FIG.
- the multilayer ceramic capacitor of the present invention has a Curie temperature (Tc) of 90 to 100 ° C. It has a dielectric characteristic different from that of a conventional dielectric ceramic having a core / shell structure with a temperature of 125 ° C.
- a dielectric ceramic having a core / shell structure obtained by dissolving additive components such as magnesium, manganese and rare earth elements in barium titanate, which is the main component, has a Curie temperature (125 ° C.) of pure barium titanate.
- the dielectric ceramic constituting the dielectric layer 5 in the multilayer ceramic capacitor of the present invention is composed of vanadium and magnesium with respect to barium titanate containing calcium as described above.
- manganese, at least one rare earth element selected from yttrium, dysprosium, holmium and erbium, and terbium are dissolved.
- the X-ray diffraction chart has a crystal structure in which the diffraction intensity of the (200) plane showing cubic barium titanate is larger than the diffraction intensity of the (002) plane showing tetragonal barium titanate,
- the Curie temperature is 90-100 ° C., which is shifted to the room temperature side.
- the additive component diffuses into the dielectric ceramic by dissolving a small amount of terbium.
- the Curie temperature can be set to 90 to 100 ° C.
- the diffused element compensates for oxygen defects in the crystal grains 9, thereby increasing the insulation of the dielectric ceramic and improving the life in the high temperature load test.
- the dielectric ceramic when the solid solution amount of magnesium and rare earth elements in the crystal particles is small, the ratio of the core portion containing many defects such as oxygen vacancies increases, so that when a DC voltage is applied, the dielectric ceramic is It is considered that oxygen vacancies or the like are likely to be carriers that carry electric charges inside the crystal grains 9 constituting the dielectric particles, and the insulating properties of the dielectric ceramic are lowered.
- terbium is added together with vanadium to increase the solid solution of the additive component containing these to bring the Curie temperature to a range of 90 to 100 ° C. is there. Therefore, the carrier density such as oxygen vacancies in the crystal particles 9 can be reduced, the rare earth elements and magnesium can be increased, and the inside of the crystal particles 9 can be reduced in oxygen vacancies. It is thought that can be obtained.
- the average crystal grain size of the crystal grains 9 may be 0.1 ⁇ m or more from the viewpoint of enabling a high dielectric constant. If the variation in capacitance is to be reduced, the range is preferably 0.3 ⁇ m or less. Preferably, the average particle diameter of the crystal particles 9 is 0.22 to 0.28 ⁇ m, or 0.13 to It is good that it is 0.19 ⁇ m.
- the relative permittivity is 3400 or more, the dielectric loss is 12% or less, and the temperature characteristics of the relative permittivity is X6S (when 25 ° C. is used as a reference) Of the relative dielectric constant when the AC voltage is 1 V and the relative dielectric constant is within the range of ⁇ 22% at ⁇ 55 to 105 ° C.
- a high temperature load test temperature: 105 ° C., voltage: 1.5 times the rated voltage, test time: 1000 hours
- the average crystal grain size of the crystal grains 9 is 0.13 to 0.19 ⁇ m, conditions under a more severe high temperature load test (for example, temperature: 125 ° C., voltage: 1.5 times the rated voltage, test time) : 1000 hours).
- the specific surface area of a powder (BCT powder) in which calcium is solid-solved in barium titanate, which is a raw material powder as described later may be adjusted.
- the average crystal grain size of the crystal grains 9 constituting the dielectric layer 5 is obtained as follows. First, after the fracture surface of the dielectric layer 5 of the capacitor body 1 is polished, a picture of the internal structure is taken using a scanning electron microscope. A circle containing 20 to 30 crystal grains 9 is drawn on the photograph, crystal grains covering the circle and the circumference thereof are selected, and the contour of each crystal grain 9 is image-processed to obtain the area of each grain. Then, the diameter when replaced with a circle having the same area as this is calculated and obtained from the average value.
- a glass component may be included as an auxiliary for enhancing the sinterability as long as desired dielectric characteristics can be maintained.
- raw material powder powder in which calcium is solid-solved in barium titanate having a purity of 99% or more (hereinafter referred to as BCT powder), V 2 O 5 powder and MgO powder, Y 2 O 3 powder, Dy At least one rare earth element oxide powder selected from 2 O 3 powder, Ho 2 O 3 powder and Er 2 O 3 powder, Tb 4 O 7 powder and MnCO 3 powder are added and mixed.
- the BCT powder is a solid solution mainly composed of barium titanate in which part of the A site is replaced with calcium (Ca), and is represented by (Ba 1-x Ca x ) TiO 3 .
- the Ca substitution amount is within this range, excellent capacitance temperature characteristics can be obtained in the operating temperature range when used as a multilayer ceramic capacitor. Note that Ca contained in the crystal particles 9 is dissolved in a state dispersed in the crystal particles 9.
- the BCT powder to be used preferably has a specific surface area of 2 to 6 m 2 / g.
- the specific surface area of the BCT powder is 2 to 6 m 2 / g
- the crystal particles 9 maintain a crystal structure close to the core / shell structure, and the additive components are dissolved in these crystal particles to lower the Curie temperature. It becomes easy to shift to the side.
- the dielectric constant can be improved, and the insulating property of the dielectric ceramic can be enhanced, thereby improving the reliability in the high temperature load test.
- Y 2 O 3 powder, Dy 2 O 3 powder, Ho 2 O 3 powder, and Er 2 O 3 powder which are additives, oxide powder of at least one rare earth element selected from powders of T 2 4 O 7 , V
- oxide powder of at least one rare earth element selected from powders of T 2 4 O 7 , V For the 2 O 5 powder, the MgO powder, and the MnCO 3 powder, it is preferable to use those having a particle size (or specific surface area) equivalent to that of the dielectric powder.
- these raw material powders were prepared by using 0.02 to 0.2 mol of V 2 O 5 powder, 0.2 to 0.8 mol of MgO powder, and oxide powder of rare earth element with respect to 100 mol of BCT powder.
- 0.3 to 0.8 mol, MnCO 3 powder is blended in a proportion of 0.1 to 0.5 mol
- Tb 4 O 7 powder is blended in a proportion of 0.02 to 0.2 mol
- a raw material powder is obtained by adding glass powder as a sintering aid to the extent that desired dielectric properties can be maintained.
- the addition amount of the glass powder is preferably 0.5 to 2 parts by mass when the BT powder is 100 parts by mass.
- a ceramic slurry is prepared by adding a dedicated organic vehicle to the above raw material powder, and then a ceramic green sheet is formed from the ceramic slurry using a sheet forming method such as a doctor blade method or a die coater method.
- the thickness of the ceramic green sheet is preferably 0.5 to 3 ⁇ m from the viewpoint of reducing the thickness of the dielectric layer 5 to increase the capacity and maintaining high insulation.
- Ni, Cu, or an alloy powder thereof is suitable for the conductor paste that forms the internal electrode pattern.
- the sheet laminate is cut into a lattice shape to form a capacitor body molded body so that the end of the internal electrode pattern is exposed.
- the internal electrode pattern can be formed so as to be alternately exposed on the end surface of the cut capacitor body molded body.
- the firing temperature is preferably 1100 to 1200 ° C. for the purpose of controlling the solid solution of the additive in the BCT powder and the grain growth of the crystal grains in the present invention.
- a BCT powder having a specific surface area of 2 to 6 m 2 / g is used, and as described above, selected from magnesium, manganese and yttrium, dysprosium, holmium and erbium.
- a predetermined amount of each of the oxides of vanadium and terbium is added as an additive together with at least one kind of various oxide powders of the rare earth elements, and firing is performed at the above temperature.
- various additives are included in the crystal particles obtained using BCT powder as a main raw material, and the crystal structure shown by the crystal particles 9 is made close to the core-shell structure, while the Curie temperature is set to The range is lower than the Curie temperature of the dielectric ceramic showing the shell structure.
- the crystal particles 9 increase in the solid solution of the additive. And a dielectric ceramic having a long life in a high temperature load test can be obtained.
- heat treatment is performed again in a weak reducing atmosphere.
- This heat treatment is performed to re-oxidize the dielectric ceramic reduced in firing in a reducing atmosphere and recover the reduced insulation resistance reduced during firing.
- the temperature is preferably 900 to 1100 ° C. for the purpose of increasing the amount of reoxidation while suppressing the grain growth of the crystal grains 9.
- the dielectric ceramic becomes highly insulating, and a multilayer ceramic capacitor showing a Curie temperature of 90 to 100 ° C. can be manufactured.
- an external electrode paste is applied to the opposing ends of the capacitor body 1 and baked to form the external electrodes 3. Further, a plating film may be formed on the surface of the external electrode 3 in order to improve mountability.
- the ratio of MgO powder, Y 2 O 3 powder, Dy 2 O 3 powder, Ho 2 O 3 powder, Er 2 O 3 powder, Tb 4 O 7 powder, MnCO 3 powder and V 2 O 5 powder is BT powder. Is the ratio when 100 moles. All of these raw material powders had a purity of 99.9%, and BCT powder having a specific surface area of 4 m 2 / g was used. MgO powder, Y 2 O 3 powder, Dy 2 O 3 powder, Ho 2 O 3 powder, Er 2 O 3 powder, Tb 4 O 7 powder, MnCO 3 powder and V 2 O 5 powder have an average particle size of 0.1 ⁇ m. The thing of was used.
- the addition amount of the glass powder was 1 part by mass with respect to 100 parts by mass of the BT powder.
- these raw material powders were wet mixed by adding a mixed solvent of toluene and alcohol as a solvent using zirconia balls having a diameter of 5 mm.
- the wet-mixed powder is put into a mixed solvent of polyvinyl butyral resin, toluene and alcohol, and wet-mixed using a zirconia ball having a diameter of 5 mm to prepare a ceramic slurry, and has a thickness of 1.5 ⁇ m and 2.
- a 5 ⁇ m ceramic green sheet was prepared.
- a plurality of rectangular internal electrode patterns mainly composed of Ni were formed on the upper surface of 1.5 ⁇ m and 2.5 ⁇ m thick ceramic green sheets.
- the conductive paste for forming the internal electrode pattern was obtained by adding a small amount of BT powder to 100 parts by mass of Ni powder having an average particle size of 0.3 ⁇ m.
- the molded body of the capacitor body was treated to remove the binder in the atmosphere and then fired in hydrogen-nitrogen at 1125 to 1135 ° C. for 2 hours to produce a capacitor body.
- the sample was subsequently reoxidized at 1000 ° C. for 4 hours in a nitrogen atmosphere.
- the size of this capacitor body was 0.95 ⁇ 0.48 ⁇ 0.48 mm 3
- the thickness of the dielectric layer was 1 ⁇ m or 2 ⁇ m
- the effective area of one layer of the internal electrode layer was 0.3 mm 2 .
- the effective area is the area of the overlapping portion of the internal electrode layers that are alternately formed in the stacking direction so as to be exposed at different end faces of the capacitor body.
- an external electrode paste containing Cu powder and glass was applied to both ends of the capacitor body and baked at 850 ° C. to form external electrodes. Thereafter, using an electrolytic barrel machine, Ni plating and Sn plating were sequentially performed on the surface of the external electrode to produce a multilayer ceramic capacitor.
- the relative dielectric constant and dielectric loss were measured from the thickness of the dielectric layer and the effective area of the internal electrode layer by measuring the capacitance at a temperature of 25 ° C., the frequency of 1.0 kHz, and the measurement voltage of 0.01 Vrms or 1 Vrms.
- the temperature characteristic of the relative dielectric constant was measured by measuring the capacitance in the temperature range of ⁇ 55 to 150 ° C.
- a case where X6S (within ⁇ 22% with respect to 25 ° C. in the range of ⁇ 55 to 105 ° C.) was satisfied was evaluated as “ ⁇ ”, and a case where it was not satisfied was evaluated as “X”.
- the Curie temperature was determined as the temperature at which the relative dielectric constant was maximum in the range in which the temperature characteristic of the relative dielectric constant was measured.
- the high temperature load test was conducted under the conditions of a temperature of 105 ° C., an applied voltage of 6 V / ⁇ m, and 1000 hours.
- the number of samples in the high temperature load test was 20 for each sample, and those that had no defects up to 1000 hours were regarded as non-defective products.
- the average crystal grain size of the crystal grains constituting the dielectric layer is determined by polishing the fracture surface of the capacitor body sample after firing, then taking a picture of the internal structure using a scanning electron microscope, and Draw a circle with 20 to 30 particles, select the crystal particles in and around the circle, image the outline of each crystal particle, determine the area of each particle, and the circle with the same area The diameter at the time of replacement was calculated and obtained from the average value.
- the composition analysis of the obtained sintered body sample was performed by ICP (Inductively Coupled Plasma) analysis or atomic absorption analysis.
- ICP Inductively Coupled Plasma
- the obtained dielectric porcelain mixed with boric acid and sodium carbonate and dissolved in hydrochloric acid is first subjected to qualitative analysis of the elements contained in the dielectric porcelain by atomic absorption spectrometry, and then specified.
- the diluted standard solution for each element was used as a standard sample and quantified by ICP emission spectroscopic analysis. Further, the amount of oxygen was determined using the valence of each element as the valence shown in the periodic table.
- the concentration of calcium in the crystal particles is determined based on the elemental analysis equipment for the crystal particles present on the polished surface obtained by sampling three multilayer ceramic capacitors from each sample and polishing the cross section of the dielectric layer constituting the capacitor. Elemental analysis was carried out using a transmission electron microscope provided with. As the crystal particles to be selected, a circle containing 20 to 30 crystal particles was drawn on an image observed with a transmission electron microscope, and the crystal particles were placed in and around the circle. The spot size of the electron beam for performing elemental analysis was 5 nm. The points to be analyzed are 4 to 5 points at almost equal intervals from the grain boundary on the straight line drawn from the vicinity of the grain boundary toward the center, and Ba, Ti, Ca, V, Mg detected from each measurement point.
- Tables 1 and 2 show the preparation composition and firing temperature
- Tables 3 and 4 show the oxide equivalent composition of each element in the sintered body, and the thickness, average crystal grain size, and X-rays of the dielectric layer after firing. Shows the results of peak intensity ratio and characteristics (specific permittivity, dielectric loss, temperature characteristics of relative permittivity (determined from the temperature characteristics of capacitance), life in high temperature load test) of diffraction and cubic crystals. Shown in 5 and 6, respectively.
- the temperature characteristics of relative permittivity satisfy X6S (temperature change rate of relative permittivity with respect to 25 ° C is within ⁇ 22% at -55 to 105 ° C), and AC voltage is 1V
- the relative dielectric constant is less than twice the relative dielectric constant when the AC voltage is set to 0.01 V.
- the high temperature load test (temperature: 105 ° C., 1.5 times the rated voltage, 1000 hours) There was no.
- vanadium is 0.02 to 0.08 mole in terms of V 2 O 5 and magnesium is in terms of MgO with respect to 100 moles of titanium constituting the barium titanate.
- magnesium is in terms of MgO with respect to 100 moles of titanium constituting the barium titanate.
- Sample No. 4 to 0.6 mol, and terbium 0.02 to 0.08 mol in terms of Tb 4 O 7 were used.
- the relative dielectric constant was 3900 or more, and the relative dielectric constant when the AC voltage was 1 V was 1.6 times or less than the relative dielectric constant when the AC voltage was 0.01 V. .
- sample Nos. In which the average crystal grain size of the crystal grains constituting the dielectric layer is in the range of 0.22 to 0.28 ⁇ m. In I-2 to 5, 8 to 12, 16 to 19, 22 to 25, 28 to 31, 33 to 52, 54 and 55, the dielectric loss was 12% or less.
- the characteristic satisfies X6S (temperature change rate of relative permittivity with respect to 25 ° C is ⁇ 22% at -55 to 105 ° C), relative permittivity when AC voltage is 1V
- the dielectric constant is 2 times or less of the relative dielectric constant at 0.01 V
- the temperature is 105 ° C., 1.5 times the rated voltage
- the lifetime in the high temperature load test is zero defect at 1000 hours or more. The characteristics were not satisfied.
- Example II Each raw material powder was mixed in the ratio shown in Table 7 in the same manner as in Example 1 except that the BCT powder having a specific surface area of 6 m 2 / g was used instead of the BCT powder having a specific surface area of 4 m 2 / g.
- a ceramic green sheet was obtained, and the capacitor body molded body was fired at 1130 to 1160 ° C. to produce a capacitor body, and further a multilayer ceramic capacitor was produced.
- the obtained multilayer ceramic capacitor was evaluated in the same manner as in Example I. However, unlike the conditions of Example I (temperature: 105 ° C., voltage: 6 V, test time: 1000 hours), the high temperature load test satisfies temperature: 125 ° C., voltage: 6 V, test time: 1000 hours. Was evaluated.
- Table 7 shows the composition and firing temperature of each sample
- Table 8 shows the oxide equivalent composition of each element in the sintered body
- Table 9 and Table 10 show the results of the peak intensity ratio and characteristics (relative permittivity, dielectric loss, temperature characteristics of relative permittivity, lifetime in high temperature load test) of cubic and tetragonal crystals, respectively.
- the temperature characteristics of relative permittivity satisfy X6S (temperature change rate of relative permittivity with respect to 25 ° C is ⁇ 22% at -55 to 105 ° C), and AC voltage is 1V.
- the relative permittivity is less than twice the relative permittivity when the AC voltage is 0.01 V, and there is no defect in the high temperature load test (temperature: 125 ° C., 1.5 times the rated voltage, 1000 hours). It was. As a result, it can be seen that when the average crystal grain size of the crystal grains is reduced (0.13 to 0.19 ⁇ m), the high temperature load characteristics are improved.
- sample Nos. II, 21, and 27 that do not satisfy the high temperature load characteristics are those in which the blending amount of any raw material does not satisfy the scope of the present invention. Even within the range of 0.13 to 0.19 ⁇ m, the high temperature load characteristics are not satisfied.
- Sample No. II-50 was satisfactory in high temperature load characteristics at 105 ° C. because the average crystal grain size of crystal grains exceeded 0.19 ⁇ m, but had high temperature load characteristics at 125 ° C. I'm not satisfied.
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Abstract
Description
3 外部電極
5 誘電体層
7 内部電極層
9 結晶粒子
11 粒界相 DESCRIPTION OF
かつキュリー温度が90~100℃である。なお、本発明におけるキュリー温度は比誘電率の温度特性を測定した範囲(-60~150℃)において比誘電率が最大となる温度である。 Further, the dielectric ceramic constituting the
The Curie temperature is 90 to 100 ° C. In the present invention, the Curie temperature is a temperature at which the relative dielectric constant becomes maximum in the range (−60 to 150 ° C.) in which the temperature characteristic of the relative dielectric constant is measured.
<実施例I>
まず、原料粉末として、BCT粉末(組成:(Ba1-xCax)TiO3、X=0.05),MgO粉末,Y2O3粉末,Dy2O3粉末,Ho2O3粉末,Er2O3粉末,Tb4O7粉末,MnCO3粉末およびV2O5粉末を準備した。これらの各種粉末を表1に示す割合で混合した。このときMgO粉末,Y2O3粉末,Dy2O3粉末,Ho2O3粉末,Er2O3粉末,Tb4O7粉末,MnCO3粉末およびV2O5粉末の割合は、BT粉末を100モルとしたときの割合である。これらの原料粉末はいずれも純度が99.9%であり、BCT粉末は比表面積が4m2/gのものを用いた。MgO粉末,Y2O3粉末,Dy2O3粉末,Ho2O3粉末,Er2O3粉末,Tb4O7粉末,MnCO3粉末およびV2O5粉末は平均粒径が0.1μmのものを用いた。焼結助剤はSiO2=55,BaO=20,CaO=15,Li2O=10(モル%)組成のガラス粉末を用いた。ガラス粉末の添加量はBT粉末100質量部に対して1質量部とした。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited by a following example.
<Example I>
First, as raw material powder, BCT powder (composition: (Ba 1-x Ca x ) TiO 3 , X = 0.05), MgO powder, Y 2 O 3 powder, Dy 2 O 3 powder, Ho 2 O 3 powder, Er 2 O 3 powder, Tb 4 O 7 powder, MnCO 3 powder and V 2 O 5 powder were prepared. These various powders were mixed in the proportions shown in Table 1. At this time, the ratio of MgO powder, Y 2 O 3 powder, Dy 2 O 3 powder, Ho 2 O 3 powder, Er 2 O 3 powder, Tb 4 O 7 powder, MnCO 3 powder and V 2 O 5 powder is BT powder. Is the ratio when 100 moles. All of these raw material powders had a purity of 99.9%, and BCT powder having a specific surface area of 4 m 2 / g was used. MgO powder, Y 2 O 3 powder, Dy 2 O 3 powder, Ho 2 O 3 powder, Er 2 O 3 powder, Tb 4 O 7 powder, MnCO 3 powder and V 2 O 5 powder have an average particle size of 0.1 μm. The thing of was used. As the sintering aid, glass powder having a composition of SiO 2 = 55, BaO = 20, CaO = 15, Li 2 O = 10 (mol%) was used. The addition amount of the glass powder was 1 part by mass with respect to 100 parts by mass of the BT powder.
<実施例II>
比表面積が4m2/gのBCT粉末に代えて、比表面積が6m2/gのBCT粉末を用いた他は、実施例1と同様にして、各原料粉末を表7に示す割合で混合して、セラミックグリーンシートを得、かつコンデンサ本体成形体を1130~1160℃で焼成してコンデンサ本体を作製し、さらに積層セラミックコンデンサを作製した。得られた積層セラミックコンデンサについて、実施例Iと同様にして評価を行った。ただし、高温負荷試験は、実施例Iの条件(温度:105℃,電圧:6V,試験時間:1000時間)と異なり、温度:125℃,電圧:6V,試験時間:1000時間を満足するか否かを評価した。 On the other hand, sample no. In I-1, 6, 7, 14, 15, 20, 21, 26, 27 and 32, the relative dielectric constant at room temperature (25 ° C.) is 3400 or more, the dielectric loss is 12.5% or less, the temperature of the relative dielectric constant The characteristic satisfies X6S (temperature change rate of relative permittivity with respect to 25 ° C is ± 22% at -55 to 105 ° C), relative permittivity when AC voltage is 1V Either the dielectric constant is 2 times or less of the relative dielectric constant at 0.01 V, and the temperature is 105 ° C., 1.5 times the rated voltage, and the lifetime in the high temperature load test is zero defect at 1000 hours or more. The characteristics were not satisfied.
<Example II>
Each raw material powder was mixed in the ratio shown in Table 7 in the same manner as in Example 1 except that the BCT powder having a specific surface area of 6 m 2 / g was used instead of the BCT powder having a specific surface area of 4 m 2 / g. Thus, a ceramic green sheet was obtained, and the capacitor body molded body was fired at 1130 to 1160 ° C. to produce a capacitor body, and further a multilayer ceramic capacitor was produced. The obtained multilayer ceramic capacitor was evaluated in the same manner as in Example I. However, unlike the conditions of Example I (temperature: 105 ° C., voltage: 6 V, test time: 1000 hours), the high temperature load test satisfies temperature: 125 ° C., voltage: 6 V, test time: 1000 hours. Was evaluated.
Sample No. II-50 was satisfactory in high temperature load characteristics at 105 ° C. because the average crystal grain size of crystal grains exceeded 0.19 μm, but had high temperature load characteristics at 125 ° C. I'm not satisfied.
Claims (4)
- (i)チタン酸バリウムを主成分とする結晶粒子により構成され、カルシウム,マグネシウム,バナジウム,マンガンおよびテルビウムと、イットリウム,ディスプロシウム,ホルミウムおよびエルビウムから選ばれる少なくとも1種の希土類元素とを含む誘電体磁器からなる誘電体層と、(ii)内部電極層とを交互に積層して形成された積層セラミックコンデンサであって、
前記誘電体磁器が、前記チタン酸バリウムを構成するチタン100モルに対して、前記バナジウムをV2O5換算で0.02~0.2モル、前記マグネシウムをMgO換算で0.2~0.8モル、前記マンガンをMnO換算で0.1~0.5モル、イットリウム,ディスプロシウム,ホルミウムおよびエルビウムから選ばれる少なくとも1種の前記希土類元素(RE)をRE2O3換算で0.3~0.8モル、および前記テルビウムをTb4O7換算で0.02~0.2モル含有するとともに、
前記結晶粒子のカルシウムの濃度が0.4原子%以上であり、
前記該誘電体磁器のX線回折チャートにおいて、立方晶のチタン酸バリウムを示す(200)面の回折強度が、正方晶のチタン酸バリウムを示す(002)面の回折強度よりも大きく、かつキュリー温度が90~100℃である
ことを特徴とする積層セラミックコンデンサ。 (I) A dielectric composed of crystal particles mainly composed of barium titanate and containing calcium, magnesium, vanadium, manganese and terbium and at least one rare earth element selected from yttrium, dysprosium, holmium and erbium A multilayer ceramic capacitor formed by alternately laminating dielectric layers made of a ceramic body and (ii) internal electrode layers,
In the dielectric ceramic, with respect to 100 moles of titanium constituting the barium titanate, the vanadium is 0.02 to 0.2 mole in terms of V 2 O 5 and the magnesium is 0.2 to 0.00 in terms of MgO. 8 mol, 0.1 to 0.5 mol of manganese in terms of MnO, and at least one rare earth element (RE) selected from yttrium, dysprosium, holmium and erbium in an amount of 0.3 in terms of RE 2 O 3 Containing 0.8 to 0.8 mol, and 0.02 to 0.2 mol of the terbium in terms of Tb 4 O 7 ,
The crystal particles have a calcium concentration of 0.4 atomic% or more;
In the X-ray diffraction chart of the dielectric ceramic, the diffraction intensity of the (200) plane showing cubic barium titanate is larger than the diffraction intensity of the (002) plane showing tetragonal barium titanate, and the Curie A multilayer ceramic capacitor having a temperature of 90 to 100 ° C. - 前記誘電体磁器が、前記チタン酸バリウムを構成するチタン100モルに対して、前記バナジウムをV2O5換算で0.02~0.08モル、前記マグネシウムをMgO換算で0.3~0.6モル、前記マンガンをMnO換算で0.2~0.4モル、イットリウム,ディスプロシウム,ホルミウムおよびエルビウムから選ばれる少なくとも1種の前記希土類元素をRE2O3換算で0.4~0.6モル、および前記テルビウムをTb4O7換算で0.02~0.08モル含有することを特徴とする請求項1に記載の積層セラミックコンデンサ。 In the dielectric ceramic, with respect to 100 moles of titanium constituting the barium titanate, the vanadium is 0.02 to 0.08 mole in terms of V 2 O 5 and the magnesium is 0.3 to 0.00 in terms of MgO. 6 mol, 0.2 to 0.4 mol of manganese in terms of MnO, and at least one rare earth element selected from yttrium, dysprosium, holmium and erbium in an amount of 0.4 to 0.00 in terms of RE 2 O 3 . The multilayer ceramic capacitor according to claim 1, wherein 6 mol and 0.02 to 0.08 mol of terbium in terms of Tb 4 O 7 are contained.
- 前記結晶粒子の平均結晶粒径が0.22~0.28μmであることを特徴とする請求項1または2に記載の積層セラミックコンデンサ。 3. The multilayer ceramic capacitor according to claim 1, wherein an average crystal grain size of the crystal particles is 0.22 to 0.28 μm.
- 前記結晶粒子の平均結晶粒径が0.13~0.19μmであることを特徴とする請求項1または2に記載の積層セラミックコンデンサ。
3. The multilayer ceramic capacitor according to claim 1, wherein an average crystal grain size of the crystal particles is 0.13 to 0.19 μm.
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JP2011176184A (en) * | 2010-02-25 | 2011-09-08 | Kyocera Corp | Multilayer ceramic capacitor |
WO2012057216A1 (en) * | 2010-10-27 | 2012-05-03 | 京セラ株式会社 | Capacitor |
JP2016060690A (en) * | 2014-09-12 | 2016-04-25 | Tdk株式会社 | Dielectric film and dielectric element |
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JP2011176184A (en) * | 2010-02-25 | 2011-09-08 | Kyocera Corp | Multilayer ceramic capacitor |
WO2012057216A1 (en) * | 2010-10-27 | 2012-05-03 | 京セラ株式会社 | Capacitor |
JP2016060690A (en) * | 2014-09-12 | 2016-04-25 | Tdk株式会社 | Dielectric film and dielectric element |
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