WO2011162371A1 - Capacitor - Google Patents
Capacitor Download PDFInfo
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- WO2011162371A1 WO2011162371A1 PCT/JP2011/064528 JP2011064528W WO2011162371A1 WO 2011162371 A1 WO2011162371 A1 WO 2011162371A1 JP 2011064528 W JP2011064528 W JP 2011064528W WO 2011162371 A1 WO2011162371 A1 WO 2011162371A1
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- WIPO (PCT)
- Prior art keywords
- grain boundary
- boundary phase
- rare earth
- magnesium
- crystal
- Prior art date
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- 239000003990 capacitor Substances 0.000 title claims description 67
- 239000013078 crystal Substances 0.000 claims abstract description 112
- 239000000919 ceramic Substances 0.000 claims abstract description 66
- 239000002245 particle Substances 0.000 claims abstract description 62
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 27
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 74
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 43
- 229910052749 magnesium Inorganic materials 0.000 claims description 43
- 239000011777 magnesium Substances 0.000 claims description 43
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- 229910052689 Holmium Inorganic materials 0.000 claims description 9
- 229910052771 Terbium Inorganic materials 0.000 claims description 9
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 9
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 9
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 9
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 9
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 4
- 239000003985 ceramic capacitor Substances 0.000 abstract description 22
- 239000002075 main ingredient Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 50
- 239000000843 powder Substances 0.000 description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910018068 Li 2 O Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
- 230000005469 synchrotron radiation Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000010953 base metal 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding 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
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Definitions
- the present invention relates to a capacitor that is made of crystal particles mainly composed of barium titanate and can be thinned.
- barium titanate has been used as a dielectric material for multilayer ceramic capacitors because of its high relative dielectric constant, and inexpensive base metals (such as Ni) have been used for the internal electrode layers of multilayer ceramic capacitors. It is used.
- the dielectric layer mainly composed of barium titanate and the internal electrode layer are fired at the same time, it is necessary to reduce the oxygen partial pressure (for example, 0.03 Pa or less at 1300 ° C.) in order not to oxidize Ni. In this case, there is a problem that the dielectric layer is reduced and the insulating property is lowered, so that practical characteristics cannot be obtained.
- a dielectric material for example, barium titanate as a main component, rare earth element oxide, Mn , V, Cr, Mo, Fe, Ni, Cu, Co and the like, reduction-resistant dielectric ceramics to which compounds of acceptor type and donor type elements are added are used (see, for example, Patent Document 1).
- a crystal particle in which a plurality of such additive components are dissolved in barium titanate has a tetragonal core part (usually pure BaTiO 3 ) and a core part surrounding the core part. It has the core-shell structure comprised from the shell part.
- rare earth elements such as vanadium, magnesium, yttrium and manganese are added to barium titanate as dielectric ceramics that have a core-shell structure in the crystal grains mainly composed of barium titanate and satisfy the X5R characteristics of the EIA standard.
- Patent Document 2 Japanese Patent Document 1
- an object of the present invention is to provide a capacitor having a high dielectric constant while satisfying the X5R characteristic of the EIA standard.
- the dielectric layer is composed of crystal particles mainly composed of barium titanate, a crystal structure having a tetragonal core part, and a crystal structure having a cubic shell part,
- the shell portion has a thickness of 11.8 to 26.5 nm, and is made of a dielectric ceramic having an average particle size of the crystal particles of 0.15 to 0.35 ⁇ m.
- the dielectric ceramic contains vanadium, magnesium, at least one rare earth element (RE) selected from yttrium, dysprosium, holmium, terbium and ytterbium, and manganese, and titanate.
- the vanadium is 0.04 to 0.10 mol in terms of V 2 O 5
- the magnesium is 0.4 to 1.2 mol in terms of MgO
- the rare earth element (RE) is RE 2 O with respect to 100 mol of barium. It is desirable to be composed of a dielectric ceramic containing 0.12 to 0.48 mol in terms of 3 and 0.05 to 0.35 mol in terms of manganese in terms of MnO.
- the dielectric ceramic contains vanadium, magnesium, at least one rare earth element (RE) selected from yttrium, dysprosium, holmium, terbium and ytterbium, and manganese, and titanate.
- the vanadium is 0.04 to 0.10 mol in terms of V 2 O 5
- the magnesium is 0.4 to 1.2 mol in terms of MgO
- the rare earth element (RE) is RE 2 O It is desirable to contain 0.30 to 0.48 mol in terms of 3 and 0.05 to 0.35 mol of manganese in terms of MnO.
- the dielectric ceramic has a grain boundary phase between the crystal grains, and the grain boundary phase is formed by a plurality of crystal grains and an interfacial grain boundary phase and a triple point grain boundary.
- the rare earth element, magnesium and silicon, and the concentration of the rare earth element, magnesium and silicon in the interfacial grain boundary phase is C1, and the triple point grain boundary phase. It is desirable that the concentration ratio C2 / C1 of two elements among the respective elements when the respective concentrations of the rare earth element, magnesium and silicon in C are C2 is 0.8 to 1.2.
- the dielectric ceramic has a grain boundary phase between the crystal grains, and the grain boundary phase is formed by a plurality of the crystal grains and the interfacial grain boundary phase and the triple point grain boundary.
- the rare earth element, magnesium and silicon, and the concentration of the rare earth element, magnesium and silicon in the interfacial grain boundary phase is C1, and the triple point grain boundary phase. It is desirable that the concentration ratio C2 / C1 of each element is 0.8 to 1.2 when the concentration of each of the rare earth element, magnesium and silicon in C is C2.
- a capacitor having a high dielectric constant can be obtained while satisfying the X5R characteristic of the EIA standard.
- (A) is a schematic sectional drawing which shows an example of the capacitor
- (b) is an internal enlarged view. It is a cross-sectional schematic diagram which shows the internal structure of the crystal grain which has a barium titanate as a main component in the dielectric material ceramic which is a dielectric material layer which comprises the capacitor
- a dielectric ceramic that is a dielectric layer constituting the capacitor of the present embodiment a grain boundary phase between two faces and a triple point formed by a plurality of crystal grains for measuring the concentration ratio of rare earth elements, magnesium and silicon
- FIG. 1A is a schematic cross-sectional view showing an example of the capacitor of the present invention
- FIG. 1B is an enlarged view of the inside.
- FIG. 2 is a schematic cross-sectional view showing the internal structure of crystal grains mainly composed of barium titanate in a dielectric ceramic that is a dielectric layer constituting the capacitor of this embodiment.
- external electrodes 3 are formed on 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 dielectric layers 5 and internal electrode layers 7 made of dielectric porcelain.
- FIG. 1 the laminated state of the dielectric layer 5 and the internal electrode layer 7 is shown in a simplified manner, but the capacitor of this embodiment is a laminated body in which the dielectric layer 5 and the internal electrode layer 7 are several hundred layers. It has become.
- the dielectric layer 5 made of dielectric porcelain is composed of crystal grains 9 and grain boundary phases 11, and the thickness is preferably 3 ⁇ m or less, particularly 2 ⁇ m or less, thereby reducing the size and increasing the capacity of the multilayer ceramic capacitor. It becomes possible to do. If the thickness of the dielectric layer 5 is 0.5 ⁇ m or more, it becomes possible to stabilize the temperature characteristics of the capacitance.
- the internal electrode layer 7 is preferably made of nickel (Ni) in that the manufacturing cost can be suppressed even when the internal electrode layer 7 is made highly stacked, and simultaneous firing with the dielectric layer 5 can be achieved.
- the dielectric layer 5 constituting the multilayer ceramic capacitor has crystal grains in the above average particle diameter range, and the crystal structure of the crystal grains 9 is a tetragonal core portion 9a and a cubic shell portion 9b.
- the dielectric layer 5 constituting the capacitor has a relative dielectric constant of 3950 or more at room temperature (25 ° C.) and the temperature characteristics of the capacitance.
- a multilayer ceramic capacitor that satisfies the X5R characteristics of the EIA standard (with a rate of change of capacitance within ⁇ 15% with respect to 25 ° C in the temperature range of -55 to 85 ° C). it can.
- the EIA standard X5R characteristic means that the rate of change in capacitance is within ⁇ 15% with respect to 25 ° C in the temperature range of -55 to 85 ° C.
- the thickness of the shell portion 9b of the crystal particle 9 having the core-shell structure is 11.8 to 26.5 nm.
- the thickness of the shell portion 9b is less than 11.8 nm, the temperature characteristic of the capacitance becomes difficult to satisfy the X5R characteristic.
- the thickness of the shell portion 9b is greater than 26.5 nm, the relative dielectric constant is from 3950. Also lower.
- the average particle size of the crystal particles 9 constituting the dielectric ceramic that is the dielectric layer 5 is 0.15 to 0.35 ⁇ m.
- the average particle diameter of the crystal particles 9 is smaller than 0.15 ⁇ m, it becomes difficult to form a core-shell structure in the crystal particles 9, and the structure is changed to a structure in which the additive component is dissolved in the center of the crystal particles 9. For this reason, the temperature change rate of the capacitance is larger than ⁇ 15%, and the X5R characteristic of the EIA standard is not satisfied.
- the average grain size of the crystal grains 9 is larger than 0.35 ⁇ m, the temperature change rate of the capacitance is larger than ⁇ 15%, which does not satisfy the EIA standard X5R characteristics.
- the dielectric ceramic constituting the dielectric layer 5 includes vanadium, magnesium, at least one rare earth element (RE) selected from yttrium, dysprosium, holmium, terbium and ytterbium, Containing manganese, with respect to 100 mol of barium titanate, vanadium is 0.04 to 0.10 mol in terms of V 2 O 5 , magnesium is 0.4 to 1.2 mol in terms of MgO, yttrium, dysprosium, holmium , Terbium and ytterbium containing at least one rare earth element (RE) in the range of 0.12 to 0.48 mol in terms of RE 2 O 3 and manganese in the range of 0.05 to 0.35 mol in terms of MnO It is desirable to consist of.
- RE rare earth element
- the relative permittivity can be increased to 4500 or more while the temperature characteristic of the capacitance satisfies the X5R characteristic, and the AC bias characteristic is 30% or less.
- the AC bias characteristic is a ratio of a change amount of a dielectric constant when an alternating current of 1 V / um is applied to a dielectric constant when an alternating current of 0.01 V / um is applied.
- the dielectric ceramic constituting the dielectric layer 5 is composed of 0.04 to 0.10 mol of vanadium in terms of V 2 O 5 and MgO of MgO with respect to 100 mol of barium titanate.
- Dielectric porcelain containing 0.5 to 1.2 mol in terms of conversion, rare earth element (RE) 0.30 to 0.48 mol in terms of RE 2 O 3 and 0.05 to 0.35 mol in terms of manganese in terms of MnO It is desirable to consist of.
- the dielectric ceramic constituting the dielectric layer 5 has the above composition, the AC bias characteristic can be further reduced.
- a glass component and other additive components are added to the dielectric ceramic in an amount of 4% by mass or less as an aid for enhancing the sinterability as long as desired dielectric characteristics can be maintained. May be.
- the shell portion 9b surrounds the core portion 9a.
- the crystal particle 9 surrounding the core portion 9a by the shell portion 9b has a transmission electron microscope provided with an element analyzer (EDS). Confirm by analysis using.
- EDS element analyzer
- 10 to 20 crystal grains 9 in the range of ⁇ 30% of the average particle diameter are extracted from a sample produced by processing a multilayer ceramic capacitor.
- the spot size of the electron beam at the time of elemental analysis is 1 to 3 nm, and the site to be analyzed is the region from the grain boundary, which is the surface of the crystal grain 9, to the center.
- the concentration of the element is obtained every 5 to 10 nm from the grain boundary which is the surface of the crystal grain 9 to the central portion, and a graph is created with the horizontal axis representing the distance and the vertical axis representing the element concentration. .
- the concentration gradient of the element on the center side is used.
- the concentration gradient of the element on the surface layer side is 0.15 atomic% / nm or more and the concentration gradient of the element on the center side is 0.5 atomic% / nm or less, the core-shell structure is formed.
- the crystal structure of each of the core portion 9a and the shell portion 9b constituting the crystal particle 9 is obtained by an X-ray diffraction method.
- the (004) plane showing the cubic system of barium titanate appearing between the (004) plane showing the tetragonal system of barium titanate and the (400) plane (( (040) plane and (400) plane overlap)) or the diffraction intensity of any one of the (400) plane and (004) plane showing the tetragonal system of barium titanate, or It is assumed that the crystal grains 9 have tetragonal and cubic crystal structures when larger than that.
- the crystal grain 9 had the core part 9a and the shell part 9b surrounding the core part 9a, and the crystal grain 9 have a tetragonal crystal system and a cubic crystal structure Based on the result, the crystal particle 9 is determined to have a tetragonal core portion 9a and a cubic shell portion 9b surrounding the core portion 9a.
- the thickness of the shell portion of the crystal particle 9 is determined for the crystal particle 9 determined to be composed of a tetragonal core portion 9a and a cubic shell portion 9b surrounding the core portion 9a.
- the thickness of the shell portion 9b of the crystal grain 9 was determined by using the X-ray diffraction method disclosed in Japanese Patent Application Laid-Open No. 2006-137647 and J. Am. Ceram. Soc., 90 [4] 1107-1111 (2007). Based on the evaluation method, the following formula is used.
- the crystal structure of the target crystal particle 9 is compared with the reflection of a pure tetragonal crystal (hkl) or cubic crystal (h'k'l ') in the measured X-ray diffraction pattern. It is assumed that the reflection of tetragonal crystal (h k l) and cubic crystal (h ′ k ′ l ′) is included from the identification of the peak position.
- the target diffraction data are reflections of tetragonal crystals (h k l) and cubic crystals (h ′ k ′ l ′).
- the 2 ⁇ position of the peak top Parameters such as half width and peak shape function are obtained.
- peak separation is performed as necessary.
- the conditions for peak separation are as follows: background function: 0th order polynomial, synchrotron radiation: K ⁇ 1, profile function: theopsedo-Voigt function, half width: different half width for all reflections, object of profile: object, Data resolution: Sharp (minimum half-value width: about 0.1 °).
- commercially available software for example, PROFIT
- PROFIT can be used for peak separation, and the tool for peak separation is not particularly limited.
- the average particle diameter of the crystal particles 9 is measured by the following procedure. First, the fracture surface of the sample which is the capacitor body 1 after firing is polished. After this, a photograph of the internal structure is taken of the polished sample using a scanning electron microscope, a circle containing 50 to 100 crystal particles is drawn on the photograph, and crystal particles that fall within and around the circle are selected. . Next, image processing is performed on the outline of each crystal particle to determine the area of each crystal particle, and the diameter when the crystal particle is replaced with a circle having the same area is calculated and obtained from the average value.
- the composition of the dielectric ceramic is determined by using a solution obtained by dissolving a multilayer ceramic capacitor in an acid using ICP (Inductively-Coupled-Plasma) analysis and atomic absorption analysis.
- ICP Inductively-Coupled-Plasma
- the amount of oxygen is determined using the valence of each element as the valence shown in the periodic table.
- the grain boundary phase 11 forming the dielectric ceramic that is the dielectric layer 5 is formed by a plurality of crystal grains 9 between the two-sided grain boundary phase and the triple point grain boundary phase.
- the rare earth elements, magnesium and silicon contained in the dielectric ceramic are between the interfacial grain boundary phase and the triple point intergranular phase, and the rare earth elements, magnesium and silicon in the interfacial grain boundary phase.
- the respective concentrations are C1
- the respective concentrations of rare earth elements, magnesium and silicon in the triple-point grain boundary phase are C2
- the C2 / C1 of the two elements of the rare earth elements, magnesium and silicon is 0.8 to 1 .2 is desirable.
- FIG. 3 shows a two-sided surface formed by a plurality of crystal grains 9 for measuring a concentration ratio of rare earth elements, magnesium and silicon in a dielectric ceramic that is the dielectric layer 5 constituting the capacitor of the present embodiment. It is a cross-sectional schematic diagram which shows the measurement position of the grain boundary phase 11a and the triple point grain boundary phase 11b.
- the concentrations of rare earth elements, magnesium and silicon in the intergranular grain boundary phase 11a and the triple point grain boundary phase 11b are determined by an X-ray microanalyzer (XMA) attached to the transmission electron microscope.
- XMA X-ray microanalyzer
- a sample used for analysis is a thin plate-shaped dielectric ceramic cut out from the dielectric layer 5 of the capacitor and subjected to ion milling.
- the region to be analyzed is that when the two-sided grain boundary phase 11a and the triple point grain boundary phase 11b formed from the plurality of crystal grains 9 are viewed in cross section, the maximum diameter of at least three crystal grains 9 is the average grain diameter. Of crystal grains in a range within ⁇ 20%.
- XMA X-ray microanalyzer
- each of the rare earth elements, magnesium and silicon at the position S1 of the intergranular grain boundary phase 11a and the position S2 of the triple point grain boundary phase 11b respectively.
- the concentration is obtained, and the ratio C2 / C1 between the concentration C1 of each element in the interfacial grain boundary phase 11a and the concentration C2 of each element in the triple point grain boundary phase 11b is obtained.
- the position S1 of the interfacial grain boundary phase 11a to be analyzed is substantially the center of the width of the grain boundary phase 11, and the position S2 of the triple point grain boundary phase 11b is the center of the triple point grain boundary phase 11b.
- the position S1 of the interfacial grain boundary phase 11a is a position separated by 50 nm or more from the position where the position S2 of the triple point grain boundary phase 11b is determined.
- a ceramic slurry is prepared by using a ball mill or the like together with a dielectric powder, an organic resin such as polyvinyl butyral resin, a solvent such as toluene and alcohol, and then the ceramic slurry is subjected to a sheet molding method such as a doctor blade method or a die coater method.
- a ceramic green sheet is formed on the substrate.
- the thickness of the ceramic green sheet is preferably 1 to 5 ⁇ m from the viewpoint of reducing the thickness of the dielectric layer 5 to increase the capacity and maintaining high insulation.
- BT powder barium titanate powder
- Ba / Ti molar ratio is 1.001 to 1.009
- the average particle size of the BT powder is desirably 0.21 to 0.30 ⁇ m.
- the average particle size is 0.21 to 0.30 ⁇ m as the BT powder for forming the crystal particles 9 constituting the dielectric ceramic serving as the dielectric layer 5.
- the material in the range it is possible to suppress the solid solution of the additive component including the rare earth element (RE) in the BT powder and to form a shell portion having a thickness described later. This facilitates the thinning of the dielectric layer 5, and the BT powder can be made into crystal particles 9 having a high dielectric constant under the firing conditions described later and satisfying the X5R characteristics of the EIA standard.
- RE rare earth element
- the dielectric powder used in manufacturing the capacitor of this embodiment is mainly composed of barium titanate, which will be described later, and, for example, vanadium, magnesium, rare earth elements, manganese, and a predetermined amount of all components of the sintering aid. It is good to use what was coat
- the dielectric powder to be used is prepared as follows, for example. First, a suspension of barium titanate powder (BT powder) having a purity of 99.9% or more, a Ba / Ti molar ratio of 1.001 to 1.009, and an average particle diameter of 0.21 to 0.30 ⁇ m.
- BT powder barium titanate powder
- the suspension is adjusted to a pH of 6 to 8 using aqueous ammonia as a pH adjuster, and includes lithium aqueous solution, silica sol, barium carbonate aqueous solution, magnesium hydroxide aqueous solution, calcium hydroxide aqueous solution, ammonium vanadate aqueous solution, An aqueous solution of manganese acetate and an aqueous solution of at least one rare earth element selected from yttrium, dysprosium, holmium, terbium and ytterbium are added and mixed in this order to prepare a ceramic slurry.
- the purity of these raw material reagents is preferably 99.5% or more for the purpose of suppressing the mixing of impurities into the obtained dielectric ceramic and obtaining high dielectric properties.
- the ceramic slurry is put into a spray dryer equipped with a four-fluid nozzle, droplets having a diameter of 10 ⁇ m or less are generated from the four-fluid nozzle, and dried at a temperature of about 200 ° C.
- a precursor is prepared, and then the dielectric powder precursor is prepared by heat treatment at a temperature higher than the temperature of the drying treatment.
- the ammonium vanadate aqueous solution is 0.04 to 0.10 mol in terms of V 2 O 5 and the magnesium hydroxide aqueous solution is 0.5 to 0.5 in terms of MgO.
- the composition be 0.12 to 0.48 mol at this time, thereby obtaining a multilayer ceramic capacitor having a high dielectric constant, a temperature characteristic of capacitance satisfying X5R characteristics, and a low AC bias characteristic and dielectric loss. It becomes possible.
- RE rare earth element
- the amount of the sintering aid is adjusted so as to be 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the BT powder. Thereby, the sinterability of the dielectric ceramic can be further enhanced.
- the conductor paste used as the internal electrode pattern is prepared by mixing Ni or an alloy powder thereof as a main component metal, mixing ceramic powder as a co-material with this, and adding an organic binder, a solvent and a dispersant. Further, in order to eliminate the step due to the internal electrode pattern on the ceramic green sheet, it is preferable to form the ceramic pattern with substantially the same thickness as the internal electrode pattern around the internal electrode pattern. In this case, it is preferable to use the dielectric powder used for the ceramic green sheet as the ceramic component constituting the ceramic pattern in that the firing shrinkage in the simultaneous firing is the same.
- a desired number of ceramic green sheets with internal electrode patterns are stacked, and a plurality of ceramic green sheets without internal electrode patterns are stacked on top and bottom of the ceramic green sheets so that the upper and lower layers have the same number.
- the internal electrode patterns in the temporary laminate are shifted by half patterns in the longitudinal direction. By such a laminating method, the internal electrode pattern can be formed so as to be alternately exposed on the end face of the cut laminate.
- the capacitor according to the present embodiment has the internal electrode pattern formed after the ceramic green sheet is once brought into close contact with the underlying equipment.
- Printed, dried, printed and dried internal electrode patterns are stacked with a ceramic green sheet that is not printed with an internal electrode pattern, temporarily adhered, and the ceramic green sheet is adhered and the internal electrode pattern is printed sequentially. Can also be formed.
- the capacitor body molded body in which the end portions of the internal electrode patterns are exposed is formed by cutting the laminated body into a lattice shape.
- the obtained capacitor body molded body is degreased and fired.
- the firing is desirably performed in a hydrogen-nitrogen atmosphere at a maximum temperature of 1150 to 1230 ° C. and a holding time of 0.1 to 4 hours.
- the capacitor body 1 is obtained by performing re-oxidation treatment in the temperature range of 900 to 1100 ° C.
- the ridge line portion of the capacitor body 1 may be chamfered and barrel polishing may be performed to expose the internal electrode layer 7 exposed from the opposing end surface of the capacitor body 1.
- the average particle size of the crystal particles 9 constituting the dielectric layer 5 is in the range of 0.15 to 0.35 ⁇ m, and the crystal structure of the crystal particles 9 is a tetragonal core part. 9a and a cubic shell portion 9b that surrounds the core portion and in which at least one additive component of vanadium, magnesium, rare earth element (RE) and manganese is dissolved, and the thickness of the shell portion 9b is 10 to 10
- a capacitor body 1 having a thickness of 20 nm can be obtained.
- the capacitor of the present embodiment when the capacitor of the present embodiment is manufactured, after degreasing the obtained capacitor body molded body, before reaching the maximum temperature in a hydrogen-nitrogen atmosphere, once at a temperature of 900 to 1000 ° C. It is desirable to provide a heat treatment step for holding for about 5 to 3 hours. By providing such a heat treatment step, the difference in the composition of rare earth elements, magnesium and glass components in the interfacial grain boundary phase 11a and the triple-point grain boundary phase 11b of the crystal grain 9 can be reduced, and thus the capacitor Capacitance variation (CV) at a temperature (about 85 ° C.) higher than room temperature (25 ° C.) can be reduced.
- CV capacitor Capacitance variation
- the variation in capacitance (CV) is expressed by a ratio ( ⁇ / x) of an average value (x) and a standard deviation ( ⁇ ) obtained by using a measured value of the capacitance of a plurality of samples as a parameter. Is the value to be
- the capacitor according to the present embodiment is mainly composed of barium titanate to produce the dielectric layer 5, and vanadium, magnesium, rare earth element (RE), manganese, and a sintering aid.
- Crystal grains 9 having a small average thickness of the shell portion 9b can be obtained by firing the obtained raw capacitor body molded body with a predetermined amount of all components and firing the obtained raw capacitor body under firing conditions with a high heating rate. .
- an external electrode paste is applied to the opposing ends of the capacitor body 1 and baked to form the external electrodes 3.
- a plating film is formed on the surface of the external electrode 3 in order to improve mountability.
- barium titanate powder (hereinafter referred to as BT powder) having a purity of 99.9% and a Ba / Ti molar ratio of 1.005 was prepared as a raw material powder.
- the pH of the suspension of BT powder was adjusted to a range of 6 to 8 using aqueous ammonia as a pH adjuster.
- aqueous ammonia as a pH adjuster.
- An aqueous solution of rare earth elements was added and mixed in this order to prepare a ceramic slurry.
- the ceramic slurry is put into a spray dryer equipped with a four-fluid nozzle, droplets having a diameter of 10 ⁇ m or less are generated from the four-fluid nozzle, and dried at a temperature of about 200 ° C.
- a precursor is prepared, and then the dielectric powder precursor is heat-treated at 400 ° C. to cover the surface of the BT powder with a predetermined amount of all components of vanadium, magnesium, rare earth element, manganese and sintering aid.
- a dielectric powder was prepared.
- a sample was prepared by adding glass powder as a sintering aid to BT powder coated with a predetermined amount of vanadium, magnesium, rare earth element and manganese (sample No. 33).
- the obtained dielectric 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 1 mm to prepare a ceramic slurry.
- a 2 ⁇ m ceramic green sheet was prepared.
- the conductor paste for forming the internal electrode pattern was obtained by adding 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 air, and then fired at a temperature rising rate of 2000 ° C./h in hydrogen-nitrogen at a temperature shown in Table 1 to produce a capacitor body.
- This firing was performed using a roller hearth kiln.
- the sample which made the temperature increase rate 500 degreeC / h was produced (sample No. 34).
- the produced capacitor body was subsequently reoxidized at 1000 ° C. for 4 hours in a nitrogen atmosphere.
- the size of the capacitor body was 2.05 ⁇ 1.28 ⁇ 1.28 mm 3
- the thickness of the dielectric layer was 2.0 ⁇ m
- the effective area of one internal electrode layer was 1.78 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.
- these multilayer ceramic capacitors were evaluated as follows.
- the dielectric constant at room temperature (25 ° C.) was measured by using an LCR meter (manufactured by Hewlett-Packard Co.) with a capacitance of 25 ° C., a frequency of 1.0 kHz, and an AC voltage of 1.0 V / ⁇ m. And the effective area of the internal electrode layer.
- Dielectric loss was also measured using the same LCR meter under the same conditions as the capacitance. Further, the temperature characteristics of the capacitance were measured in the temperature range of ⁇ 55 to 85 ° C.
- the AC bias characteristic is that when an alternating current (AC) voltage of 0.01 V / ⁇ m is applied at a temperature of 25 ° C., a frequency of 1.0 kHz and an AC voltage of 0.01 to 3.5 V / ⁇ m, the capacitance is C1,
- the capacitance was determined from ((C2-C1) / C1) ⁇ 100 (%), where C2 was the electrostatic capacity when an AC voltage of 3.5 V / ⁇ m was applied at a temperature of 1.0 ° C.
- the average particle size of the crystal particles constituting the dielectric layer is determined by polishing the fracture surface of the sample that is the capacitor body after firing, and then taking a picture of the internal structure using a scanning electron microscope. Draw a circle that contains 30 circles, select the crystal particles that fall within and around the circle, image the outline of each crystal particle, determine the area of each particle, and replace it with a circle with the same area Was calculated from the average value.
- the crystal particles having the core part and the shell part are those in which the shell part surrounds the core part was confirmed by analysis using a transmission electron microscope provided with an element analyzer (EDS).
- EDS element analyzer
- 10 to 20 crystal particles in a range of ⁇ 30% of the average particle diameter were extracted from a TEM sample manufactured by processing a multilayer ceramic capacitor.
- the spot size of the electron beam at the time of elemental analysis was 1 to 3 nm, and the site to be analyzed was the region from the grain boundary to the center of the crystal grain surface.
- the concentration of the rare earth element was determined every 5 to 10 nm from the grain boundary, which is the surface of the crystal grain, to the central portion, and a graph was created with the horizontal axis representing the distance and the vertical axis representing the element concentration.
- the graph three points were taken in order from the measurement point closest to the grain boundary, and an approximate straight line was drawn using these three points, and the slope of the straight line was taken as the concentration gradient of the element on the surface layer side.
- three points are taken in order from the measurement point closest to the center of the crystal grain, and an approximate line is drawn from these three points, and the slope of the straight line is obtained.
- the concentration gradient of the element on the grain boundary side is 0.15 atomic% / nm or more and the concentration gradient of the element on the center side is 0.5 atomic% / nm or less, the core-shell structure is obtained. It was supposed to be.
- the crystal structure of each of the core part and the shell part constituting the crystal grain was determined by X-ray diffraction method.
- the cubic system of barium titanate appearing between the (004) plane and the (400) plane showing the tetragonal system of barium titanate is shown (004).
- the diffraction intensity of the plane (the (040) plane and (400) plane overlap) is the diffraction intensity of any one of the (400) plane and (004) plane showing the tetragonal system of barium titanate.
- the crystal grains had tetragonal and cubic crystal structures when they were equal or larger.
- the thickness of the shell portion of the crystal particle was determined by the following method for the crystal particle 9 determined to have a tetragonal core portion and a cubic shell portion surrounding the core portion.
- the shell thickness of the crystal particles was determined using the above-described Equation 1 and Equation 2.
- X′Pertpro manufactured by Panallytical was used as the X-ray diffractometer.
- the crystal structure of the target crystal particle is that the selected X-ray diffraction pattern reflects pure tetragonal (hkl) or cubic (h'k'l ') in the measured X-ray diffraction pattern.
- the spectrum was broad, and from the identification of the peak position, a crystal containing tetragonal (hkl) and cubic (h'k'l ') reflections was selected.
- the diffraction peaks were tetragonal (002), (200) and cubic (200).
- the size of the beam was 0.5 mm in the vertical direction and 5 mm in the horizontal direction.
- the wavelength was 1.54982 mm.
- the step width was 0.02 °, and the counting time per point was 5.0 seconds. Further, the number of repetitions was 10, and the integration for 10 times was defined as the diffraction intensity.
- peak separation was performed for tetragonal (002), (200), and cubic (200) from the diffraction peak using peak separation software (PROFIT) under the following conditions.
- PROFIT peak separation software
- the conditions for peak separation are as follows: background function: 0th order polynomial, synchrotron radiation: K ⁇ 1, profile function: the psedo-Voigt function, half width: different half width for all reflections, profile objectivity: object, data resolution: Sharp (minimum half width: about 0.1 °) and analysis range: 44 ° ⁇ 2 ⁇ ⁇ 47 °.
- composition analysis of the obtained sintered body sample was performed by ICP (Inductively-Coupled Plasma) analysis and 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 composition of the dielectric layer constituting the obtained multilayer ceramic capacitor matched the composition shown in Table 1.
- composition and firing conditions are shown in Table 1, and the average grain size and dielectric characteristics (relative permittivity, capacitance temperature characteristics, AC bias characteristics, dielectric loss) of the dielectric particles in the obtained multilayer ceramic capacitor ) Shows the results in Table 2.
- the vanadium is 0.04 to 0.1 mol in terms of V 2 O 5
- the magnesium is 0.5 to 1.2 mol in terms of MgO
- the rare earth element (RE) Is a dielectric ceramic layer comprising a dielectric ceramic containing 0.3 to 0.48 mol in terms of RE 2 O 3 and 0.05 to 0.35 mol in terms of MnO in terms of manganese.
- No. At I-2 to 3, I-6 to 10, I-12, I-13, I-16 to 19, I-22 to 24, I-27 to 29, I-31 and I-32, room temperature (25 The relative dielectric constant at 4 ° C. was 4500 or more, the temperature characteristic of the capacitance satisfied the X5R characteristic, the AC bias characteristic was 29.00% or less, and the dielectric loss was 5% or less.
- sample no. in I-5, I-11, I-14, I-20, I-25, I-30, and I-35 the relative dielectric constant at room temperature (25 ° C.) is 3950 or more, and the temperature characteristic of capacitance is X5R. Any of the characteristics of satisfying the characteristics was not satisfied.
- the concentrations of rare earth elements, magnesium and silicon in the interfacial grain boundary phase and triple point grain boundary phase in the dielectric ceramic were obtained by an X-ray microanalyzer (XMA) attached to the transmission electron microscope.
- XMA X-ray microanalyzer
- the sample used for the analysis was a thin plate-like dielectric ceramic cut out from the dielectric layer of the produced multilayer ceramic capacitor and subjected to ion milling.
- the region to be analyzed is from a group of crystal grains in which the maximum diameter of at least three crystal grains is within a range of ⁇ 20% of the average grain diameter when the cross-sectional view of the interfacial grain boundary phase and the triple point grain boundary phase is viewed. 5 locations were selected.
- the concentrations of rare earth elements, magnesium and silicon at the position S1 of the intergranular grain boundary phase and the position S2 of the triple point grain boundary phase are obtained,
- the average value of the ratio C2 / C1 between the element concentration C1 in the interfacial grain boundary phase and the element concentration C2 in the triple-point grain boundary phase was determined.
- the position S1 of the intergranular boundary phase to be analyzed was set to be approximately the center of the width of the grain boundary phase, and the position S2 of the triple point grain boundary phase was set to the center of the triple point boundary phase.
- the position S1 of the intergranular grain boundary phase was set at a position about 50 nm away from the position where the position S2 of the triple point grain boundary phase was determined.
- the production conditions are shown in Table 3, and the evaluation results such as dielectric properties are shown in Table 4.
- the prepared samples are all in the same ratio as that of the sample prepared by the method of Example 1 at room temperature (25 ° C.).
- the dielectric constant was 3950 or more, and the temperature characteristic of the capacitance satisfied the X5R characteristic.
- the AC bias characteristic was 30% or less, and the dielectric loss was 5% or less.
- a laminated body produced by adding a heat treatment step that is held at the temperature shown in Table 3 after degreasing the obtained capacitor body molded product during manufacturing and before reaching the maximum temperature in a hydrogen-nitrogen atmosphere.
- the ceramic capacitor samples (Sample Nos.
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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
9a コア部
9b シェル部
11 粒界相
11a 二面間粒界相
11b 三重点粒界相 DESCRIPTION OF
Claims (5)
- 誘電体層が、チタン酸バリウムを主成分とし、結晶構造が正方晶系のコア部と、結晶構造が立方晶系のシェル部とを有する結晶粒子により構成されており、前記シェル部の厚みが11.8~26.5nmであるとともに、前記結晶粒子の平均粒径が0.15~0.35μmである誘電体磁器からなることを特徴とするコンデンサ。 The dielectric layer is composed of crystal particles mainly composed of barium titanate, a crystal structure having a tetragonal core part, and a crystal structure having a cubic shell part, and the thickness of the shell part is A capacitor comprising a dielectric ceramic having an average particle diameter of 11.8 to 26.5 nm and an average particle diameter of the crystal particles of 0.15 to 0.35 μm.
- 前記誘電体磁器が、バナジウムと、マグネシウムと、イットリウム,ジスプロシウム,ホルミウム,テルビウムおよびイッテルビウムから選ばれる少なくとも1種の希土類元素(RE)と、マンガンとを含み、チタン酸バリウム100モルに対して、前記バナジウムがV2O5換算で0.04~0.10モル、前記マグネシウムがMgO換算で0.4~1.2モル、前記希土類元素(RE)がRE2O3換算で0.12~0.48モルおよびマンガンがMnO換算で0.05~0.35モル含有することを特徴とする請求項1に記載のコンデンサ。 The dielectric ceramic contains vanadium, magnesium, at least one rare earth element (RE) selected from yttrium, dysprosium, holmium, terbium and ytterbium, and manganese, Vanadium is 0.04 to 0.10 mol in terms of V 2 O 5 , magnesium is 0.4 to 1.2 mol in terms of MgO, and the rare earth element (RE) is 0.12 to 0 in terms of RE 2 O 3. 2. The capacitor according to claim 1, wherein .48 mol and manganese are contained in an amount of 0.05 to 0.35 mol in terms of MnO.
- 前記誘電体磁器が、バナジウムと、マグネシウムと、イットリウム,ジスプロシウム,ホルミウム,テルビウムおよびイッテルビウムから選ばれる少なくとも1種の希土類元素(RE)と、マンガンとを含み、チタン酸バリウム100モルに対して、前記バナジウムをV2O5換算で0.04~0.10モル、前記マグネシウムをMgO換算で0.4~1.2モル、前記希土類元素(RE)をRE2O3換算で0.30~0.48モルおよび前記マンガンをMnO換算で0.05~0.35モル含有することを特徴とする請求項1に記載のコンデンサ。 The dielectric ceramic contains vanadium, magnesium, at least one rare earth element (RE) selected from yttrium, dysprosium, holmium, terbium and ytterbium, and manganese, Vanadium is 0.04 to 0.10 mol in terms of V 2 O 5 , magnesium is 0.4 to 1.2 mol in terms of MgO, and the rare earth element (RE) is 0.30 to 0 in terms of RE 2 O 3. 2. The capacitor according to claim 1, wherein .48 mol and manganese are contained in an amount of 0.05 to 0.35 mol in terms of MnO.
- 前記誘電体磁器が前記結晶粒子間に粒界相を有し、該粒界相が複数の前記結晶粒子により形成される二面間粒界相と三重点粒界相とから構成されているとともに、前記希土類元素、前記マグネシウムおよびケイ素を含み、前記二面間粒界相における前記希土類元素、前記マグネシウムおよび前記ケイ素のそれぞれの濃度をC1、前記三重点粒界相における前記希土類元素、前記マグネシウムおよび前記ケイ素のそれぞれの濃度をC2としたときの各元素のうち2種の元素の濃度比C2/C1が0.8~1.2であることを特徴とする請求項1乃至3のうちいずれかに記載のコンデンサ。 The dielectric ceramic has a grain boundary phase between the crystal grains, and the grain boundary phase is composed of a two-sided grain boundary phase formed by a plurality of the crystal grains and a triple point grain boundary phase. The rare earth element, the magnesium and silicon, and the concentration of each of the rare earth element, the magnesium and the silicon in the interfacial grain boundary phase is C1, the rare earth element in the triple point grain boundary phase, the magnesium and 4. The concentration ratio C2 / C1 of two kinds of elements among the respective elements when the respective concentrations of silicon are C2 is 0.8 to 1.2. Capacitor described in.
- 前記誘電体磁器が前記結晶粒子間に粒界相を有し、前記粒界相が複数の前記結晶粒子により形成される二面間粒界相と三重点粒界相とから構成されているとともに、前記希土類元素、前記マグネシウムおよびケイ素を含み、前記二面間粒界相における前記希土類元素、前記マグネシウムおよび前記ケイ素のそれぞれの濃度をC1、前記三重点粒界相における前記希土類元素、前記マグネシウムおよび前記ケイ素のそれぞれの濃度をC2としたときの各元素の濃度比C2/C1がいずれも0.8~1.2であることを特徴とする請求項1乃至4のうちいずれかに記載のコンデンサ。 The dielectric ceramic has a grain boundary phase between the crystal grains, and the grain boundary phase is composed of a two-sided grain boundary phase formed by a plurality of the crystal grains and a triple point grain boundary phase. The rare earth element, the magnesium and silicon, and the concentration of each of the rare earth element, the magnesium and the silicon in the interfacial grain boundary phase is C1, the rare earth element in the triple point grain boundary phase, the magnesium and 5. The capacitor according to claim 1, wherein the concentration ratio C2 / C1 of each element is 0.8 to 1.2 when each concentration of silicon is C2. .
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KR20180076628A (en) * | 2016-12-28 | 2018-07-06 | 삼성전기주식회사 | Dielectric Powder and Multilayered Capacitor Using the Same |
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